bluuebunny/crossref_metadata_2025 huggingface dataset:
[5]Helicene Based π‐Conjugated Macrocycles with Persistent Figure‐Eight and Möbius Shapes: Efficient Synthesis, Chiral Resolution and Bright Circularly Polarized Luminescence
Authors: Zhou Qifeng , Yuan Wei , Li Yunfei , Han Yi , Bao Lintao , Fan Wei , Jiao Liuying , Zhao Yanli , Ni Yong , Zou Ya , Yang Hai‐Bo , Wu Jishan
Published: October 2024

π‐Conjugated chiral shape‐persistent molecular nanocarbons hold great potential as chiroptical materials, though their synthesis remains a considerable challenge. Here, we present a simple approach using Suzuki coupling of a [5]helicene building block with various aromatic units, enabling the one‐pot synthesis of a series of chiral macrocycles with persistent figure‐eight and Möbius shapes. Single‐crystal structures of 7 compounds were solved, and 22 enantiomers were separated by preparative chiral HPLC. A notable pyrene‐bridged figure‐eight macrocycle, with its rigid, fully π‐conjugated and overcrowded structure, exhibited pure excimer emission and outstanding circularly polarized luminescence (CPL) properties, including a large dissymmetric factor (|glum|=3.8×10−2) and significant CPL brightness (BCPL=710.5 M−1cm−1). This method provides a versatile synthetic platform for producing various chiral D2‐symmetric figure‐eight macrocycles and singly or triply twisted Möbius macrocycles with C2 and D3 symmetry, offering tunable chiroptical properties for CPL applications.
In Situ Synthesis of MoO3 by Surface Oxidation of Mo2C (MXene) for Stable Near‐Surface Reactions in Aqueous Aluminum‐Ion Battery
Authors: Wang Yi , Wu Tanci , Lu Yong , Zhang Wenming , Li Zhanyu
Published: October 2024

Molybdenum trioxide (MoO3) is a promising positive electrode material for aqueous aluminum‐ion batteries (AAIBs) due to its high theoretical capacity. However, MoO3 faces several challenges in an aqueous electrolyte, such as easy dissolution of reaction products, volume expansion, and low conductivity, which severely limit its application in aqueous batteries. In this work, we effectively increased the overall conductivity of the electrode by in situ growing MoO3 on the Mo2C MXene layer. MXene can effectively inhibit the dissolution and structural loss of MoO3 reaction products. Additionally, the coordination effect of Mo2C and MoO3 achieves a stable near‐surface reaction on the MXene laminates, resulting in the Mo2C/MoO3 composite exhibiting excellent aluminum storage properties (123.5 mAh/g after 200 cycles at 0.4 A/g). The energy storage mechanism of H+/Al3+ co‐insertion/extraction was elucidated through ex situ characterization, and the promotion effect of Mo2C on MoO3 reaction kinetics was verified by density functional theory (DFT) calculations. This work provides new insights into improving the stability of AAIBs cathodes and extends the application of Mo‐based MXene in aqueous batteries.
The Fatal Mushroom Neurotoxin Muscarine is Released from a Harmless Phosphorylated Precursor upon Cellular Injury
Authors: Dörner Sebastian , Trottmann Felix , Jordan Paul M. , Rogge Kai , Bartels Benjamin , Werz Oliver , Hertweck Christian , Hoffmeister Dirk
Published: October 2024

l‐(+)‐Muscarine (1)‐producing mushrooms pose a severe threat to human health as ingestion can result in circulatory collapse or even death. However, their metabolic profile is surprisingly poorly understood, including knowledge of poison release and potentially toxic congeners. In the mycelium of the 1‐producing fool's funnel mushroom Clitocybe rivulosa, we identified 4’‐phosphomuscarine (2) as the major natural product. Its structure was elucidated by high‐resolution mass spectrometry, nuclear magnetic resonance spectroscopy and by comparison with a synthesized reference. We also detected this previously overlooked phosphorylated compound in the fiber cap mushrooms Pseudosperma spectrale and Inocybe nitidiuscula. Studies on the activation of the muscarinic acetylcholine receptor M3 indicate only weak affinity of 2 to this target. Furthermore, we present biological evidence that muscaridine (3), a quaternary amine congener related to and co‐occurring with 1, does not activate the muscarinic acetylcholine receptor M3 on human embryonic kidney cells. Our work provides important insight into the metabolic profile and the pharmacology of some of the most poisonous mushrooms. As the harmless 2 can liberate the potentially fatal 1 by unspecific enzymatic ester cleavage, these results are highly relevant for emergency medicine to estimate the true toxicity of these mushrooms.
Synthesis, Structural Characterization, Optical Properties, and Biological Potency of Co(II), Cu(II), and Cd(II) Complexes With Heterocyclic Thiosemicarbazide Ligand: Insights From Molecular Docking Studies
Authors: El‐Nahass Marwa N. , Gaber Mohamed , Elnadry Yasmen A. , Abu El‐Reash Gaber M. , El‐Gamil Mohammed M.
Published: October 2024

A novel heterocyclic thiosemicarbazide ligand, [(Z)‐N‐(2‐oxoindolin‐3‐ylidene)nicotinohydrazide] (H2L), and its Co(II), Cu(II), and Cd(II) metal chelates were synthesized and characterized using a variety of analytical methods, including elemental analysis, FT‐IR, UV–Visible spectroscopy, EI‐mass, fluorescence spectroscopy, X‐ray powder diffraction, and TGA. The structures and geometries of the complexes were determined using these methods as [Co2(H2L)2Cl2(H2O)4]·2H2O, [Cu(H2L)2Cl2(H2O)2]·2H2O, and [Cd(H2L)2Cl2(H2O)2], all having octahedral geometry. The particulate diameters for [Co2(H2L)2Cl2(H2O)4]·2H2O, [Cu(H2L)2Cl2(H2O)2]·2H2O, and [Cd(H2L)2Cl2(H2O)2] were 192.68, 68.48, and 192.74 nm, respectively using Debye–Scherrer equation and FWHM approach. The corresponding FWHM values were 0.0078, 0.0217, and 0.0075, whereas the crystal strain was calculated as (ε) = 0.0018, 0.0056, and 0.0054, and the dislocation density (δ) as 2.69 × 10−5, 2.13 × 10−4, 2.69 × 10−5 Å−2. Quantum chemical calculations for the ligand and its solid metal complexes were carried out utilizing DFT with the DMOL3 module. Furthermore, the optical sensing response of the free ligand H2L to Co(II), Cu(II), and Cd(II) ions was investigated, revealing that the presence of these metal ions enhanced the fluorescence spectra of the ligand. Additionally, the antibacterial effects of these compounds, as well as their cytotoxicity in human cancer cells, were investigated. Compared to its metal complexes, the ligand, H2L exhibits increased antibacterial activity against various bacteria. Tests on HepG‐2 and MCF‐7 cells were conducted to evaluate the compounds' anticancer efficacy against the standard, Doxorubicin. The ligand, H2L, demonstrated greater cytotoxicity against the HepG‐2 cell line than its metal complexes. Docking experiments were conducted to assess the interaction of the ligand and its complexes with HepG‐2 (PDB ID: 2OH4) and MCF‐7 (PDB ID: 3W2S) cells, using the XP glide technique and Schrödinger suite software.
BiOBr/SnO2/ZnO Catalyst With Interfacial Effect Enhanced Photocatalytic Degradation of Organic Dye
Authors: Deng Lihan , Chen Pengfei , Li Jin
Published: October 2024

BiOBr nanosheets were loaded onto SnO2 quantum dots, ZnO nanosheets, and SnO2/ZnO‐2 (SZ‐2) to form different heterojunction photocatalysts by sonochemistry, respectively. The photocatalytic activity of the prepared photocatalysts was evaluated by degrading the target dye Rhodamine B (RhB). The results showed that the degradation efficiency of BiOBr/SnO2/ZnO (BSZ) for RhB reached 97.5% at 80 min. The significant increase in catalytic activity of BSZ was attributed to the synergistic and interfacial effects among the three materials. Combined with the radical trapping experiments, it can be concluded that the catalytic mechanism of BSZ as a dual Z‐type heterojunction.
Curing kinetics of block copolymerization thermoset polyurethane by non‐isothermal DSC method
Authors: Li Tianqi , Xu Junjie , An Mengjing , Wang Teng , Ma Yuzhi , Luo Yunjun
Published: October 2024

Polyurethanes consist of hard and soft segments, with the hard segments typically comprising blocks containing isocyanate groups, while the soft segments often consist of chains terminated with hydroxyl groups. The hard segments contribute to the mechanical properties of polyurethanes, while the soft segments provide elasticity and flexibility. The essence of curing lies in the mixing of hard and soft segments and subjecting the system to high temperatures. The curing kinetics of PEG/PCL/IPDI/N100 in‐situ block copolymers were investigated using dynamic isothermal differential scanning calorimetry (DSC). Key curing parameters were obtained from non‐isothermal DSC curves, and these parameters were incorporated into an n‐order reaction model to determine the reaction type and apparent activation energy, thus deriving the reaction equation. The curing kinetics of PEG/PCL/IPDI/N100 in‐situ block copolymers follows an n‐th order autocatalytic reaction, where n is 1, and the activation energy is approximately 52.79 kJ/mol. Based on the reaction equation, the curing process conditions, namely the initial curing temperature (Ti), the peak exothermic temperature (Tp), and the finishing temperature (Tf), were deduced. Studying the curing kinetics of thermosetting polyurethanes can deepen our understanding of the interactions and reaction mechanisms between reactants under different conditions, thereby enhancing our grasp of the curing process. Furthermore, research into curing kinetics can provide a basis for optimizing preparation processes.
How Two‐Dimensional Heterocovariance Spectroscopy and Data Fusion Level out the Inadequacies of Compact Spectrometers
Authors: Mahler Lukas , Mayer Christian , Jaeger Martin
Published: October 2024

Over the past decade, sensors and compact spectrometers have emerged as a powerful means for real‐time monitoring of chemical and biochemical processes in the field of process analytical technologies (PATs). This is largely attributed to cost‐efficiency and their robustness in near‐line applications. In comparison to more sophisticated laboratory instruments, these devices exhibit limited sensitivity and resolution. In this study, a combination of near‐infrared, low‐field 1H nuclear magnetic resonance and compact Raman spectrometers were employed for the process monitoring of the acid‐catalyzed esterification of isoamyl alcohol and acetic acid to isoamyl acetate. The resulting real‐time data were transformed and visualized for interpretation using two‐dimensional heterocovariance spectroscopy. The data were also subjected to pretreatment, concatenation, and multivariate analysis in accordance with low‐ and mid‐level data fusion. The spectral interpretation derived from heterocovariance spectroscopy provided support for the data pretreatment during data fusion. By applying these computational techniques, the inherent limitations of sensitivity and resolution associated with compact spectroscopic instruments could be overcome, thereby facilitating the interpretation of data and yielding further insights into the process under study. A comparison of the process parameters resulting from the applied methods indicated that consistent data could be obtained. This study demonstrates that heterocovariance spectroscopy and data fusion allow to enhance compact, less expensive analytical instruments for process monitoring and to acquire process knowledge. This, in turn, enables material, financial, and energy resources to be conserved.
Alleviating Voltage Hysteresis by Interconnecting Truncated Octahedral LiNi0.5Mn1.5O4 Cathode Particles Using Exfoliated Graphene
Authors: Nadia Suryadi Putri , Karunawan Jotti , Bityasmawan Abdillah Oktaviardi , Floweri Octia , Puji Santosa Sigit , Wibowo Arie , Iskandar Ferry
Published: October 2024

High‐voltage spinel LiNi0.5Mn1.5O4 (LNMO) has been highlighted as one of the most promising cathode materials for next‐generation Li‐ion batteries. However, its performance is known to have shortcomings, i. e., voltage hysteresis induced by the increasing impedance of LNMO during electrochemical cycling at high voltage operation. This paper demonstrates an innovative design of LNMO cathode materials to alleviate voltage hysteresis by combining unique characteristics of truncated octahedral LNMO with 2D exfoliated graphene (EG). The exposed (100) plane of truncated LNMO particles is known to have superior Li+ ion conduction. Meanwhile, the (111) plane is known to have excellent resistance to metal dissolution. Moreover, it was revealed that the presence of the EG framework as an interconnection aide could significantly improve the charge transfer process, helping to alleviate the voltage polarization. The sample with optimum LNMO‐EG composition shows a stable electrochemical performance with a capacity retention of 86.56 % after 300 cycles of charge‐discharge measurement at 1 C while exhibiting almost 3 times lower voltage hysteresis (0.233 mV/cycle) compared to the pristine LNMO (0.678 mV/cycle). This result demonstrates that combining the uniqueness of truncated LNMO and 2D EG can be a promising strategy to improve the electrochemical performance of LNMO cathode materials for next‐generation batteries.
Driving sustainable competitive advantage in banking: The role of transformational leadership and digital transformation in organizational agility and corporate resiliency
Authors: Probojakti Wiweko , Utami Hamidah Nayati , Prasetya Arik , Riza Muhammad Faisal
Published: October 2024

Objectives

Continuous adaptation and innovation are critical for sustaining a competitive edge in the dynamic and technology‐driven banking sector. This study explores the impacts of transformational leadership and digital transformation on organizational agility and corporate resiliency, and how these factors contribute to sustainable competitive advantage in the banking sector.

Methodology

A quantitative approach utilizing a survey method was implemented for the research, which included a sample of 185 units comprising the head office, branch offices, and sub‐branch offices of Regional Banks in Indonesia. Data analysis was conducted using PLS‐SEM with second‐order constructs.

Findings

The results reveal that transformational leadership significantly enhances organizational agility but does not significantly impact corporate resiliency or sustainable competitive advantage. Digital transformation significantly improves both organizational agility and corporate resiliency, yet its effect on sustainable competitive advantage is insignificant. Moreover, organizational agility significantly influences both corporate resiliency and sustainable competitive advantage. Additionally, corporate resiliency makes a significant contribution to sustainable competitive advantage.

Conclusion

The study underscores the critical role of transformational leadership and digital transformation in enhancing organizational agility and resiliency. These elements are pivotal in sustaining competitive advantages in the rapidly evolving banking industry.

Implications

This research underscores the strategic importance of banks investing in leadership development and digital initiatives to enhance organizational agility and corporate resiliency, which are crucial for maintaining a sustainable competitive advantage.
Enhancing colorectal cancer screening in high‐risk population through fecal immunochemical test surveillance: Results from a surveillance program
Authors: Qin Hai , Zhang Mingqing , Zhang Guanglu , Zhao Lizhong , Zhang Huan , Zhang Weituo , Wang Yijia , Zhang Xipeng , Xie Li , Qian Biyun
Published: October 2024

Background

Current guidelines recommend colonoscopy‐based surveillance to decrease the risk of colorectal cancer (CRC) among these participants with above‐average risk. The fecal immunochemical test (FIT) holds promise as a viable alternative surveillance tool, but the existing evidence regarding the use of settings remains limited. Therefore, our aim is to evaluate the CRC incidence rates in individuals with above‐average CRC risk and the relationship between FIT surveillance and CRC incidence.

Methods

The retrospective cohort study was performed based on the CRC screening program between January 2012 and December 2022, in Tianjin, China. This cohort study included 12,515 participants aged 40–74 years with above‐average risk. The primary outcomes were the incidence rates of CRC and advanced colorectal neoplasia which were expressed as the number of events per 100,000 person‐years. Hazard ratios (HRs) and 95% confidence intervals (CIs) were calculated using Cox proportional hazards models.

Results

We included 12,515 participants aged 40–74 years, of whom 4980 received subsequent FIT surveillance during the study period. Among these participants, 51 CRC cases occurred in the non‐FIT surveillance group (incidence rate, 233.88 per 100,000 person‐years) and there were 29 cases of CRC in the FIT surveillance group (incidence rate, 184.85 per 100,000 person‐years), resulting in an incidence rate ratio (IRR) of 0.58 (95% CI, 0.37–0.91). Meanwhile, 428 advanced colorectal neoplasia cases were reported in the non‐FIT surveillance group, while 269 cases occurred in the FIT surveillance group, with significantly lower incidence of advanced colorectal neoplasia in the FIT surveillance group (IRR: 0.64; 95% CI, 0.55–0.74). Compared with the non‐FIT surveillance group, the FIT surveillance group had a 54% decreased risk of developing CRC (HR, 0.46; 95% CI, 0.29–0.74) and a 45% decreased risk of developing advanced colorectal neoplasia (HR, 0.55; 95% CI, 0.47–0.64).

Conclusions

In this retrospective cohort study, above‐average risk individuals who received subsequent FIT in the intervals between colonoscopies were associated with a reduction of CRC and advanced colorectal neoplasia incidence, which indicated the value and utility of FIT in the surveillance program.
Unlocking the Potential of Disulfidptosis‐Related LncRNAs in Lung Adenocarcinoma: A Promising Prognostic LncRNA Model for Survival and Immunotherapy Prediction
Authors: Nie Xin , Ge Hong , Wu Kongming , Liu Ru , He Chunyu
Published: October 2024

Objective

Disulfidptosis was stimulated in high SLC7A11 expression cells starving to glucose. We attempted to identify disulfidptosis‐related lncRNAs (DRLs), built a prognostic model to predict survival, and analyzed the tumor microenvironment.

Methods

The TCGA database was utilized to procure the pertinent data. By utilizing both Cox regression and the least absolute shrinkage and selection operator (LASSO) method, a risk model based on DRLs was formulated for prognostic evaluation. The ability of survival prediction was validated by multiple approaches. The biological functions were screened through GO, KEGG, and GSEA. Various methods were employed to evaluate the tumor immune environment, which included ESTIMATE, tumor mutation burden (TMB) score, CIBERSORT algorithm, and tumor immune dysfunction and exclusion (TIDE) score.

Results

Ninety‐one DRLs were recognized, and lncRNA AC092718.4, AL365181.2, AL606489.1, EMSLR, and ENTPD3‐AS1 were involved in the risk model. The GEO database was used to verify the influence of these lncRNAs on survival. The following analyses showed that survival could be predicted excellently by the DRLs risk model. The results of enrichment analyses pointed toward the involvement of the cell cycle and IgA production pathways. In the low‐risk patient group, there was a notable surge in stromal, immune, and ESTIMATE scores, while the TMB scores took a tumble. Conversely, the high‐risk patient group displayed a converse trend. Notably, the group of patients with lower risk scores and higher TMB scores showed the most favorable survival outcomes, underscoring the importance of considering both risk score and TMB in predicting the response to immune checkpoint blockade therapy. Furthermore, patients classified as high‐risk might display resistance to both chemotherapy and targeted therapy. Cellular biological experiments proved that lncRNA AC092718.4 promoted invasion, migration, and proliferation abilities in vitro. These results provided valuable insights into the role of DRLs in LUAD and presented a possible effective treatment approach for LUAD.

Conclusions

We developed a disulfidptosis‐related risk model with 5 lncRNAs that enables survival prediciton for LUAD patients and aids cilinical decisions by forecasting the TME, TMB, and drug sensitivity, making it a valuable tool for outcomes prediction.
Porous Carbon‐Supported Catalysts for Proton Exchange Membrane Fuel Cells
Authors: Song Pengyu , Chen Jiajun , Yin Zicheng , Yang Ziyi , Wang Lu
Published: October 2024

Proton exchange membrane fuel cells (PEMFCs) are crucial for the efficient utilization of hydrogen. Currently, their efficiency is mainly limited by the slow kinetics of the cathode oxygen reduction reaction (ORR) and the poisoning effect between ionomers and catalytic sites, particularly with Pt‐based catalysts. Recent works suggest that the emerging porous carbon‐supported catalysts hold promise in mitigating these challenges by ensuring fast kinetics while alleviating the poisoning. This review examines porous carbon‐supported catalysts for PEMFC cathodes, covering synthesis methods, structure and performance evaluation, and future prospects, with an emphasis on the influence of porous carbon support on PEMFC performance. On one hand, the rational design of pore structure in carbon support can help optimize the location of the active sites and enhance mass transfer. On the other hand, diverse pore structures provide a platform for gaining a deeper understanding of the mechanisms behind microscale mass transfer and reaction at the three‐phase boundaries. This review aims to inspire innovative strategies for the precise synthesis of porous carbon‐supported catalysts with various pore structures to further boost PEMFC performance.
Organic Compound Modified Cu‐Based Catalysts for the Hydrogenation of Esters
Authors: Cui Kai , Jing Yuli , Li Xiaohong
Published: October 2024

Cu/SiO2 catalysts are widely applied to the hydrogenation of dimethyl oxalate and ethylene carbonate to the corresponding ethylene glycol and methanol simultaneously, whereas ethylene glycol and methanol are important bulk commodities and raw materials for the production of oxygen‐containing chemicals and fuels. However, Cu particles usually aggregate or sinter to deactivate and the ratio of surface Cu0/Cu+ species is also difficult to control under the reaction conditions, so that the catalyst activity and stability is still a big challenge. It was found that modification of Cu‐based catalysts with certain organic compound inhibited the agglomeration of Cu particles, regulated the ratio of surface Cu0/Cu+ species, and even generated carbon layers to protect the Cu particles, which definitely improved the stability of the catalyst along with the enhanced catalytic performance. In this review, recent developments in ester hydrogenation over organic compound‐modified Cu/SiO2 catalysts were summarized and the issues to be further clarified are discussed as well.
Extractive Distillation of Isobutyl Alcohol and Isobutyl Acetate Using Dimethyl Sulfoxide: Process Design and Intensification
Authors: Yildirim Rumeysa , Unlusu Betul
Published: October 2024

We have designed a separation process of isobutyl alcohol (52.0 mol%) and isobutyl acetate (48.0 mol%) mixture using conventional extractive distillation (ED) and extractive dividing‐wall column (E‐DWC) with the solvent dimethyl sulfoxide (DMSO). The binary mixture exhibits a minimum boiling azeotrope that is sensitive to pressure. Thermodynamic analyses have shown that the vacuum pressures work better compared to the atmospheric pressure when DMSO is the solvent. Based on the separation with a purity of 99.9 mol%, the E‐DWC process has resulted in 9.6 % and 4.8 % reductions in the total annual cost and CO2 emission rates, respectively, in comparison to the conventional method. After further intensification using the heat pump technique, the E‐DWC process with the solvent DMSO has provided more than 40.0 % reduction in energy consumption compared to the ED systems studied in the literature using the solvents butyl propionate and dimethylformamide.
Elucidating the Performance Limitations of a 25 cm2 Pure‐Water‐Fed Non‐Precious Metal Anion Exchange Membrane Electrolyzer Cell
Authors: Lemcke Michelle Sophie , Loos Stefan , Menzel Nadine , Bron Michael
Published: October 2024

Anion exchange membrane (AEM) water electrolysis has emerged as a promising technology for producing hydrogen in a carbon‐neutral economy. To advance its industrial application, performance evaluations of non‐precious metal AEM electrolyzers with electrode areas of 25 cm2 were conducted. The focus was on pure water operation, achieving a current density of 0.26 A cm−2 at a voltage of 2.2 V. To gain a better understanding, the AEM electrolyzer was also operated in aqueous KOH, yielding 1.2 A cm−2 at 2.2 V. By adding a liquid electrolyte and by varying cell components, causes of the occurring performance limitations and ways to improve the AEM electrolyzer were identified. Electrochemical impedance analysis showed that the activation loss at the anode due to sluggish OER kinetics was the limiting factor at low current densities. At higher current densities, which is the operating range of interest for industrial application, the ohmic resistance from the membrane was the dominant factor limiting high performance in pure water operation.
Photoelectrochemical Hydrogen Production from Water Using Copper‐based Chalcopyrite Thin Films
Authors: Ikeda Shigeru , Ishizuka Shogo
Published: October 2024

Copper (Cu)‐based chalcopyrite compounds are promising photoabsorber materials not only for solar cells but also for photoelectrochemical (PEC) systems for conversion of sunlight energy into chemical energy. PEC water splitting to generate hydrogen (H2) is one of the most advanced technologies in a PEC system for the use of Cu‐based chalcopyrite compounds. In this review, we firstly introduce crystallographic/energetic structures of Cu‐based chalcopyrite compounds in view of their applications to PEC water splitting. Explanations for the operation of PEC water splitting using semiconductor materials are then overviewed. Based on these backgrounds, studies on PEC H2 evolution over photocathodes based on CuInS2 and CuGaSe2 thin films that we have developed are reviewed in detail. For realizing efficient PEC H2 evolution over these thin films, surface modifications with an n‐type layer such as CdS and a catalytic site such as Pt deposit were found to be indispensable. Precise controls of p‐n heterointerfaces formed by introducing an n‐type layer should also be required to enhance PEC performance. Although PEC water splitting has not reached the required efficiency to be useful, effective combinations of appropriate surface and interface modifications should lead to further improvements of properties to be close to practical applications.
A Uniform Conductive Carbon Coating of Nitrogen‐Doped Carbon Improves the Electrochemical Performance of LiMn0.7Fe0.3PO4 Cathode Material for Lithium‐ion Batteries
Authors: Xiong Hesen , Zhang Zongliang , Dai Jiaxin , Zhao Pei , He Kai , Gao Jie , Wu Qiang , Wang Baofeng
Published: October 2024

The practical application of LiMn1−xFexPO4 as a cathode material is hindered considerably by its poor electronic conductivity and slow lithium‐ion diffusion. In the present study, a uniform nitrogen‐doped carbon coating on LiMn0.7Fe0.3PO4 (LiMn0.7Fe0.3PO4@NC) was achieved using ethylene diamine tetraacetic acid (EDTA) as a chelating agent and carbon source. The nitrogen‐doped carbon layer enhanced the electronic conductivity and ionic diffusion of the LiMn0.7Fe0.3PO4 cathode. Furthermore, the uniform carbon layer prevented metal ion dissolution and stabilized the crystal structure. The resulting LiMn0.7Fe0.3PO4@NC‐2 sample demonstrated superior performance with a specific capacity of 152.5 mAh g−1 at 0.1 C and preserved 93.7 % of this capacity over 200 cycles at 1 C. Meanwhile, the LiMn0.7Fe0.3PO4@NC‐2 sample demonstrated a high Li+ diffusion coefficient (3.98×10−11 cm2 s−1) and electrical conductivity (1.47×10−2 S cm−1). This study presents a novel approach to designing high‐performance cathode materials using a cost‐effective and straightforward process.
Ag108(PEt3)24Cl6: A Hexagonal Prismatic Metalloid Cluster
Authors: Kordan Mike Alexander , Schrenk Claudio , Schnepf Andreas
Published: October 2024

The ligands used for the protection of metalloid clusters heavily influence the resulting structure and shape. For silver, thiolate and alkynyl ligands are commonly used, while phosphines usually play a minor role as co‐ligands. Herein, we report the synthesis and structural characterization of Ag108(PEt3)24Cl6 (1), the largest structurally characterized metalloid silver cluster with phosphines and halides as sole ligands. Instead of the frequently observed spherical shape of metalloid clusters, 1’s structure resembles a hexagonal prism. The highly light and temperature sensitive compound features many similarities to its smaller congener Ag64(PnBu3)16Cl6, though there are distinct structural and electronic differences present. Within 1, a Ag64 subunit can be found, which identifies these clusters as molecular seeds for the formation of faceted nanoparticles.
True and false discoveries with independent and sequential e‐values
Authors: Vovk Vladimir , Wang Ruodu
Published: October 2024

In this article, we use e‐values in the context of multiple hypothesis testing, assuming that the base tests produce independent, or sequential, e‐values. Our simulation and empirical studies, as well as theoretical considerations, suggest that, under this assumption, our new algorithms are superior to the known algorithms using independent p‐values and to our recent algorithms designed for e‐values without the assumption of independence.
Biosourced Au(III) Complexes from D‐Xylose: Synthesis and Biological Evaluation
Authors: Pascual Laura M. H. , Devy Jérôme , Colin Marius , Chazée Lise , Guillaneuf Alexandra , Marin Béatrice , Plantier‐Royon Richard , Gatard Sylvain
Published: October 2024

A series of xylose‐based ligands was obtained using a convenient approach, in a few steps from D‐xylose. The complexation properties of these ligands towards Au3+ cations have been studied through different methods (multinuclear NMR, mass spectrometry, elemental analysis). The biological properties (antibacterial and anti‐tumoral) of all the isolated xyloside Au(III) complexes were investigated in vitro. The xyloside Au(III) complexes gave the highest activities against E. coli (vs P. aeruginosa, S. aureus and S. epidermidis). The study also revealed that the nature of the sugar may play an important role in determining the selectivity of the antibacterial effect. Preliminary anti‐tumoral evaluations showed that one complex containing a polyamine chain, exhibited interesting anti‐proliferative activities on breast tumor cell lines MDA‐MB‐231 and BT‐20. The anti‐migratory effect of this complex also showed an average 35 % reduction in cell migration on the same two cancer cell lines.
Video Documented Upscaled Synthesis of Salts of the Parent Carbaborate Ion [CB11H12]−, its Undecafluorinated Form [CHB11F11]− and Useful Starting Materials for its Introduction
Authors: Kulenkampff Jan , Armbruster Christian , Drolshagen Johanna , Regnat Celine , Wienold Tina , Spari Luisa , Fix Jana , Sterbak Tabea , Scherer Harald , Krossing Ingo
Published: October 2024

In this work, we present our improved protocols for the single batch syntheses of approximately 32 g of [NHMe3][CB11H12] and 10 g of Na[CHB11F11] as well as salt metathesis reactions, granting access to useful starting materials to introduce the [CHB11F11]− anion. This includes the trityl cation [Ph3C]+ and the bis‐1,2‐difluorobenzene‐silver(I)‐complex [Ag(odfb)2]+, as well as some applications of the shown compounds. The described methodology allows the synthesis of large amounts of both the [CB11H12]− and the [CHB11F11]− anion and therefore making them accessible for further reactions. To facilitate the reproducibility, we present video tutorials of the synthetic steps towards Na[CHB11F11].
Multi‐Layer Kesterite‐Based Photocathodes for NH3 Photosynthesis from N2 Reduction Reaction
Authors: Ferreira de Brito Juliana , Medina Marina , Sousa Santos Hugo Leandro , dos Santos Araujo Mileny , Santana Andrade Marcos Antônio , Helena Mascaro Lucia
Published: October 2024

The necessity of new methods to substitute the Haber‐Bosch process in the NH3 synthesis, generating fewer greenhouse gases, and dispensing less energy, drove the investigation of the photoelectrocatalytic approach in the N2 reduction reaction (N2RR). For that, this work presents the synthesis and characterization of the layered CZTSSe/CdS/TiO2 photocathode decorated with Pt nanoparticles for application in NH3 production using the photoelectrocatalysis technique. The CZTSSe/CdS/TiO2‐Pt characterization showed a well‐designed and stable photocatalyst synthesized layer by layer with an important contribution of the Pt nanoparticles for the catalyst performance, improving the photocurrent density and the charge transfer. The N2RR in a two‐compartment photochemical cell with 0.1 mol L−1 Na2SO3 and 0.05 mol L−1 H2SO4 in the cathodic and anodic chamber, respectively, using CZTSSe/CdS/TiO2‐Pt and under 1 sun of light incidence and applied potential of −0.4 VAg/AgCl reached 0.22 mmol L−1 cm−2 NH3, a value 28 folds higher than using the catalyst without Pt modification. The superiority of N2RR under the photoelectrocatalysis technique was demonstrated compared to photocatalytic and electrocatalytic techniques, together with the investigation of the supporting electrolyte influence in the cathodic compartment. Additionally, that is the first time a kesterite‐based photocathode has been applied to NH3 photosynthesis, showing excellent photoconversion capability.
Sensitivity of Capacity Fade in Vanadium Redox Flow Battery to Electrolyte Impurity Content
Authors: Pichugov Roman , Loktionov Pavel , Verakso Darya , Pustovalova Alla , Chikin Dmitry , Antipov Anatoly
Published: October 2024

The gradual capacity decrease of vanadium redox flow battery (VRFB) over long‐term charge‐discharge cycling is determined by electrolyte degradation. While it was initially believed that this degradation was solely caused by crossover, recent research suggests that oxidative imbalance induced by hydrogen evolution reaction (HER) also plays a significant role. In this work by using vanadium pentoxides with different impurities content, we prepared three grades of vanadium electrolyte. By measuring electrochemical properties on carbon felt electrode in three‐electrode cell and VRFB membrane‐electrode assembly we evaluate the influence of impurity content on battery polarization and rate of side reactions which is indicated by the increase of average oxidation state (AOS) during charge‐discharge tests and varies from 0.061 to 0.027 day−1 for electrolytes made from 99.1 and 99.9 wt % V2O5. We found that increase of AOS correlates with the increase of open‐circuit voltage of VRFB in the discharged state ranging from 9.6 to 14.9 mV day−1 for highest and lowest electrolyte purity levels, respectively. While AOS increase is significant, it does not solely determine capacity fade. It is demonstrated that the presence of vanadium crossover decreases capacity fade, i. e. levels the contribution of side reactions on capacity drop.
High‐Efficiency Deep‐Blue Solution‐Processed Organic Light‐Emitting Diodes Using Carbazole Dendrons Modified Hybridized Local and Charge‐Transfer Emitters
Authors: Chantanop Nuttapong , Saenubol Atthapon , Itsoponpan Teerapat , Prakanpo Nipanan , Wongkaew Praweena , Loythaworn Thidarat , Waengdongbung Wijitra , Sudyodsuk Taweesak , Promarak Vinich
Published: October 2024

In the pursuit of efficient and cost‐effective organic light‐emitting diodes (OLEDs), the development of solution‐processed hybridized local and charge transfer (HLCT) emitters presents a promising approach. HLCT materials uniquely integrate the advantages of both singlet and triplet excitons, surpassing the traditional spin statistical limit of 25 % while offering high photoluminescence efficiency and balanced charge transport properties. Herein, we report the synthesis and characterization of two new deep blue, solution‐processable HLCT fluorophores, G1FTPI and G2FTPI. These compounds incorporate fluorenyl carbazole dendron units into the HLCT luminogenic triphenylamine‐phenanthroimidazole (TPI) molecule. Their HLCT and photoluminescence (PL) properties were experimentally and theoretically investigated using solvation effects and density functional theory (DFT) calculations. The molecules exhibit deep blue emission with a high solid‐state fluorescence quantum yield, good solution‐processed film‐forming quality, and high hole mobility values of 2.18–2.61×10−6 cm2 V−1 s−1. Both compounds were successfully employed as non‐doped emissive layers in solution‐processed OLEDs, demonstrating excellent electroluminescent (EL) performance. Notably, the G2FTPI‐based device emitted a deep blue light at 432 nm with CIE coordinates of (0.158, 0.098) and achieved a maximum current efficiency (CEmax) of 3.13 cd A−1 and a maximum external quantum efficiency (EQEmax) of 5.30 %.
Real‐Time Implementation of Unknown Input Observer‐Based State and Unknown Disturbance Estimation for Series Active Filters
Authors: Kiran Nagulapati , Naidu I. E. S.
Published: October 2024

Series active filter (SAF) is generally utilized in compensating harmonic voltage source‐type loads. In this paper, a combined action of controller and observer is proposed for SAF. Full state feedback (SFB) and linear quadratic regulator (LQR) controllers are posited in order to estimate states, and fault. SFB utilizes the pole placement method, whereas LQR utilizes the tuning of matrices by Bryson's rule. Luenberger observer (LO), proportional–integral observer (PIO), and unknown input observer (UIO) were also designed. The efficacy of this scheme is illustrated through the simulations, in the presence of faults. The state dynamics of SFB‐ and LQR‐based control of SAF with LO, PIO, and UIO in different faulty cases are compared. It can be clearly seen through simulations that the state dynamic response of LQR‐based control of SAF is faster when compared to SFB‐based control of SAF in both cases. Further, LO and PIO established a steady‐state error between the actual state and its estimate, with reference to desired input, in the presence of a fault. UIO perfectly tracked the desired input, even in the presence of various unknown fault, when compared to LO and PIO. Furthermore, UIO also estimates the unknown faults better when compared to PIO. Finally, in a dynamic operating scenario, the effectiveness of the suggested control strategy has been assessed and verified using MATLAB/SIMULINK and the output of a real‐time simulator (OPAL‐RT OP4510).
Heatwave‐Induced Paternal Effects Have Limited Adaptive Benefits in Offspring
Authors: Irish Sara D. , Sutter Andreas , Pinzoni Livia , Sydney Mabel C. , Travers Laura , Murray David , de Coriolis Jean‐Charles , Immler Simone
Published: October 2024

As the threat of climate change and associated heatwaves grows, we need to understand how natural populations will respond. Inter‐generational non‐genetic inheritance may play a key role in rapid adaptation, but whether such mechanisms are truly adaptive and sufficient to protect wild populations is unclear. The contribution of paternal effects in particular is not fully understood, even though the male reproductive system may be highly sensitive to heatwaves. We used the zebrafish Danio rerio to investigate the effects of heatwaves on male fertility and assess potential adaptive benefits to their offspring in a number of large‐scale heatwave experiments. Heatwave conditions had negative effects on male fertility by reducing gamete quality and fertilisation success, and we found indications of an adaptive effect on hatching in offspring produced by heatwave‐exposed males. Our findings highlight the importance of including male and female fertility when determining species ability to cope with extreme conditions and suggest that parental effects provide limited adaptive benefits.
Dinuclear Copper(II) Complex with Intramolecular O−H⋅⋅⋅O Hydrogen Bonding: Magneto‐Structural Correlation for Acylhydrazone‐Based Phenoxido Bridged Copper(II) Complexes
Authors: Böhme Michael , Mohanty Monalisa , Lima Sudhir , Buchholz Axel , Görls Helmar , Dinda Rupam , Plass Winfried
Published: October 2024

The μ‐phenoxido‐bridged dinuclear copper(II) complex, [Cu2(L1)2(dmso)(MeOH)] (1), has been synthesized using N′‐(4‐(diethylamino)‐2‐hydroxybenzylidene)‐1‐naphthohydrazide (H2L1) as ligand. The structural analysis of 1 reveals that the coordination geometry at the copper ions is best described as a square pyramidal with a Cu⋅⋅⋅Cu distance in the dinuclear complex of 303 pm which is supported by hydrogen bonding between the two apical oxygen donor ligands (O⋅⋅⋅O 277 pm). Magnetic studies indicate that 1 exhibits a strong antiferromagnetic interaction between the two copper(II) ions with a coupling constant of J=−450 cm−1 (
). The magnetic exchange is transmitted through the central [Cu2(OR)2]2+ core, a fragment for which different magneto‐structural correlations have been reported depending on the substituent at the bridging oxygen atom. However, the properties of complex 1 cannot be explained by any of the established correlations. Nevertheless, complex 1, together with the series of compounds based on an acylhydrazone ligand framework reported so far, shows a magneto‐structural correlation as a function of the Cu−O−Cu bridging angle that significantly differs from all previously reported.
A Dehydrocoupling Approach Towards Titanocene Iminophosphane Complexes
Authors: Petrov Andrey , Hering‐Junghans Christian
Published: October 2024

Dehydrocoupling reactions represent a powerful tool for element‐element bond formation upon H2 elimination. It was shown that transition metals (in low oxidation states or in the form of hydrides) can be coupled with two equivalents of primary pnictanes (R–PnH2; Pn=P, Sb) providing direct access to otherwise elusive η2‐dipnictene (R–Pn=Pn–R) complexes. Herein, we report on the reactivity of the common group IV metallocene precursors Cp2Ti(btmsa) and Cp2Zr(btmsa)(pyridine) (btmsa=C2(SiMe3)2) towards primary pnictanes (R–PnH2 (Pn=P or N) and secondary aminophosphanes (R'P(H)–N(H)R). We found that Cp2Ti(btmsa) reacts with secondary aminophosphanes (R'P(H)–N(H)R) to give η2‐iminophosphane titanocene complexes. The molecular and electronic structure of the new compounds were thoroughly investigated spectroscopically, crystallographically and computationally.
Computation‐Guided Scope Exploration of a Conjugate Addition/Truce‐Smiles Cascade Reaction for Scaffold Diversification
Authors: Horst Brendan , Gabella Carena Leopoldo J. , Doppert Michael T. , Ham Rens , Hansen Thomas , Ruijter Eelco
Published: October 2024

Based on the successful application of a nitroaryl transfer cascade reaction in the total synthesis of various monoterpene indole alkaloids proceeding via fused bicyclic intermediate, we investigated analogous cascade reactions involving spiro, bridged, and alternatively fused bicyclic intermediates. Unfortunately, none of these was found to afford the desired nitroaryl transfer product. DFT studies of the original cascade process revealed that the Truce‐Smiles rearrangement is the rate‐determining step. In addition, we found that the subsequent SO2 extrusion is accompanied by retro‐Mannich ring opening, resulting in a stabilized enolate that only recyclizes after activation of the cyclic imine moiety. Computation of the reaction profiles of the proposed alternative cascade reactions showed that the barrier for the Truce‐Smiles rearrangement is unreasonably high for the bridged and alternatively fused systems, but only moderately higher for the five‐membered spiro system. Reasoning that even more electron‐deficient arenesulfonamides should have a lower barrier for the Truce‐Smiles rearrangement, we synthesized the corresponding 2,4‐dinitrobenzenesulfonamide precursor and found that it indeed smoothly undergoes the nitroaryl transfer cascade at room temperature. In this case, however, the cascade reaction produces a cyclic imine product, as the intermediate 2,4‐dinitrophenyl‐substituted enolate is insufficiently nucleophilic to undergo the Mannich cyclization.
Photocatalytic Regioselective Tandem Cyclization Protocol to Trifluoromethylated Pyrrolidones
Authors: Wang Panpan , Leng Yuting , Sui Kaixia , Jiang Shiliang , Ma Ning , Wu Yangjie
Published: October 2024

A new environmentally friendly and efficient strategy for preparing trifluoromethylated pyrrolidones has been developed. The process involves using visible light to induce radical cyclization of 1,5‐dienes with CF3SO2Na, resulting in excellent regioselectivity. This method uses less expensive and easy‐to‐store trifluoromethylation reagents, making it an attractive option. Additionally, the resulting trifluoromethylated pyrrolidones can be easily modified and preliminary mechanistic studies have been presented.
Rhodium(II)‐Catalyzed Denitrogenative Transformations of N‐Sulfonyl‐1,2,3‐Triazoles
Authors: Doraghi Fatemeh , Hossein Morshedsolouk Mohammad , Ghofrani Samaneh , Larijani Bagher , Mahdavi Mohammad
Published: October 2024

N‐Sulfonyl‐1,2,3‐triazoles are valuable precursors for the generation of α‐imino carbene intermediates in the presence of the metal catalysts, especially rhodium(II) complexes. Due to the presence of electrophilic carbene and nucleophilic nitrogen, these reactive intermediates can easily be incorporated into many annulations, cycloadditions, C−H or O/N/S−H bond insertions and functionalization reactions. A large number of pharmaceutically important nitrogen‐based building blocks can be constructed via this direct and atom‐economical carbene strategy. In this review, we have described the transformations of N‐sulfonyl‐1,2,3‐triazoles based on α‐imino rhodium(II) carbene intermediates.
Aging damage characteristics of acid‐etched sandstone samples
Authors: Zhao Aohan , Ma Yankun , Zhang Tong , Zhang Xi
Published: October 2024

To investigate the erosive damage effect of the acidic solution on sandstone, experiments were conducted to examine the macro‐ and micro‐characteristics of sandstone samples under different acid etching times. Microscopic morphology changes, pore structure characteristics, mineral composition changes, and mechanical response characteristics were obtained before and after acid etching. Finally, a comprehensive evaluation index for acid etching damage was proposed. The results show that: (1) Acidic solution will erode the sandstone skeleton and cause the sandstone to collapse. The etched surface appears “flocculent” and yellow sediment is produced. (2) The pores in sandstone samples are mainly micro‐ and mesopores, and the total porosity increases exponentially with the duration of acid etching. The volume fraction of micropores can reach up to 81.5%. (3) The acid etching process of sandstone samples includes physical diffusion and chemical dissolution, which can be divided into four stages and three regions from the outside to the inside. After acid etching, the uniaxial compression failure mode of the sample changes from shear to mixed shear‐tensile failure. (4) The comprehensive evaluation index based on three failure modes generated during the loading process shows good consistency with the overall changes of characteristics parameters such as elastic modulus, peak stress, and peak strain. The research findings of this paper can provide theoretical support for the assessment of rock mass stability and disaster prevention in acidic environments.