bluuebunny/crossref_metadata_2025 huggingface dataset:
Investigations on the Structure, Mechanical Property, Wear and Oxidation Resistances of TiAlSiN Coatings by Tailoring Al/(Al + Ti) Ratios
Authors: He Jin , Liu Gang , Ren Haoxiong , Liu Jing , Wang Hao , Qiu Longshi , Hu Xiaogang
Published: July 2024

Previous studies have broadly dealt with TiAlSiN coatings that exhibit promising characteristics as surface protective layers for antiwear and antioxidation applications. In this regard, revealing the correlations among coating composition, structure, and properties is vitally important for developing advanced TiAlSiN coatings. The present work addresses the issue by studying the structure and properties of TiAlSiN coatings by tailoring Al/(Al + Ti) ratios. To this end, TiAlSiN coatings are produced by arc deposition with the Al/(Al + Ti) ratios of 0.31, 0.42, 0.51, and 0.62, respectively. The results show that, when the Al/(Al + Ti) ratio ranges from 0.31 to 0.51, the phase structure is mainly TiN phase, and the hardness, wear resistance and oxidation resistance of the films are increased with the rise in the Al/(Al + Ti) ratio. When the Al/(Al + Ti) ratio reaches 0.62, the oxidation resistance of the coating does not improve significantly, while the mechanical and wear properties of the coating are deceased due to the formation of w‐AlN phase. Therefore, the appropriate Al/(Al + Ti) ratio at 0.51 provides overall improvements including mechanical properties, and wear and oxidation resistances under operation conditions. These findings show that optimizing the Al/(Al + Ti) ratio is a promising way to develop TiAlSiN coatings with advanced structure and properties.
Self‐Healing Waterborne Polyurethanes as a Sustainable Gel Electrolyte for Flexible Electrochromic Devices
Authors: Kim Eunji , Choi Jae Won , Sun Fayong , Eom Soo Yeon , Choi Ye Won , Jeong Beomjin , Park Jong S.
Published: July 2024

Self‐healing polymers are promising for diverse applications in wearable technology and electronic skin. Polyurethanes are versatile polymers that can incorporate various monomer structures. Waterborne polyurethanes (WPUs) emerge as an environmentally conscious choice due to water usage instead of organic solvents, thereby minimizing the generation of volatile organic compounds. This study introduces a novel approach to enhance the self‐healing properties of WPUs by integrating disulfide bonds. These dynamic disulfide bonds undergo exchange reactions upon heating, facilitating the renewal of cross‐links on damaged film surfaces. Self‐healing WPUs with a low glass transition temperature achieve excellent self‐healing efficiency under mild conditions. Self‐healing adhesives applied to various flexible substrates retain stable peel strength, which confirms their potential as self‐healing solutions. Furthermore, the WPU hydrogel electrolyte is prepared with dihydroxyhexyl viologen (DHHV), and the prepared electrochromic gel exhibits good ionic conductivity while maintaining high transparency. The flexible electrochromic device exhibited excellent performances, including low coloration voltage, high coloration efficiency, and long‐term stability. The transmittance difference is exceptional, with over 99%, and no decay after repeated bending cycles is observed. The current results demonstrate the feasibility of self‐healing WPUs in improving the operation and durability of high‐performance flexible electrochromic devices.
Effects of Different Zinc Content on Solidification, Microstructure, and Mechanical Properties in Tin–Bismuth Alloy
Authors: de Carvalho Cássia Carla , Sobral Bruno Silva , de Sousa Raí Batista , Paixão Jeverton Laureano , de Araújo Dantas Suylan Lourdes , Spinelli José Eduardo , Silva Bismarck Luiz
Published: July 2024

The present aims to evaluate the effect of adding Zn (0.5% and 9.0% in wt%) on phase transformation temperatures, microstructure coarsening, solidification parameters (cooling rate‐L and growth rate‐VL), macrosegregation, and mechanical properties of directionally solidified Sn‐34wt%Bi‐xZn alloys. The samples have been characterized by optical microscopy, scanning electron microscopy, X‐ray fluorescence, and X‐ray diffraction, in addition to Vickers microhardness and tensile tests. The CALPHAD method has been used for thermodynamic computations via Thermo‐calc software, in order to obtain thermodynamic data. The microstructure of Sn–Bi–Zn alloys is mainly dendritic, composed of a Sn‐rich matrix (β‐Sn) with Bi precipitates inside and surrounded by a Sn+Bi eutectic mixture of phases, predominantly observed at the coarse scale. Coarse Zn needles are also observed in the Sn‐34wt%Bi‐9wt%Zn alloy due to the high Zn content. On the whole, Zn provoked a coarsening of the dendritic arrangement. Moreover, Zn additions cause inverse segregation of Bi, as compared to the rather constant macrosegregation profile observed in the binary Sn–Bi alloy. On the whole, both additions of Zn (0.5 and 9.0) promoted increase in Vickers microhardness, yield strength (σY), and ultimate tensile strength (σu), however, causing an overall reduction in elongation‐to‐fracture (δ).
Smart Fabrics with Integrated Pathogen Detection, Repellency, and Antimicrobial Properties for Healthcare Applications
Authors: Abu Jarad Noor , Prasad Akansha , Rahmani Sara , Bayat Fereshteh , Thirugnanasampanthar Mathura , Hosseinidoust Zeinab , Soleymani Leyla , Didar Tohid F.
Published: July 2024

Healthcare textiles serve as key reservoirs for pathogen proliferation, demanding an urgent call for innovative interventions. Here, a new class of Smart Fabrics (SF) is introduced with integrated “Repel, Kill, and Detect” functionalities, achieved through a blend of hierarchically structured microparticles, modified nanoparticles, and an acidity‐responsive sensor. SF exhibit remarkable resilience against aerosol and droplet‐based pathogen transmission, showcasing a reduction exceeding 99.90% compared to uncoated fabrics across various drug‐resistant bacteria, Candida albicans, and Phi6 virus. Experiments involving bodily fluids from healthy and infected individuals reveal a significant reduction of 99.88% and 99.79% in clinical urine and feces samples, respectively, compared to uncoated fabrics. The SF's colorimetric detection capability coupled with machine learning (96.67% accuracy) ensures reliable pathogen identification, facilitating accurate differentiation between healthy and infected urine and fecal contaminated samples. SF holds promise for revolutionizing infection prevention and control in healthcare facilities, providing protection through early contamination detection.
Native Defects Hybridization and Electronic Transport in Cu2Se‐CuGaSe2 Hierarchical Composites
Authors: Yin Zhixiong , Zhang Yinying , Huang Yiqiao , Schwarz Johnathan , Xi Zhucong , Uher Ctirad , Hovden Robert , Qi Liang , Poudeu Pierre F. P.
Published: July 2024

Engineering the energy distribution of electronic defects in semiconductors can afford the coexistence of degenerate and nondegenerate transport behavior. By leveraging native defects in Cu2Se and CuGaSe2 phases, the tunability of the concentration and energy distribution of active electronic defects in hierarchical (1‐x)Cu2Se‐(x)CuGaSe2 composites is demonstrated. This study found that the electrical conductivity of various composites decreases with rising temperature indicating degenerate semiconducting behavior, whereas the carrier density increases with temperature, which is consistent with non‐degenerate semiconductivity. Remarkably, this study found that while the carrier density and electrical conductivity drop with the increasing CuGaSe2 content for samples with x ≤ 0.45 is consistent with an increase in the activation energy of “active” electronic defects, the sudden increase by 140% in the electrical conductivity and by 109% in the carrier density for near equimolar composition suggests the formation of a large density of electronic defects with lower activation energy. This unusual behavior is understood within the context of the hybridization of coexisting native electronic defects to form degenerate hybrid acceptor states with lower activation energy. The reported unique electronic transport can be leveraged for the development of more versatile electronic and optoelectronic devices with superior performance.
Anisotropic Heterobimetallic Nanomaterials with Controlled Composition for Efficient Oxygen Reduction at Ultralow Loading
Authors: Ming Siyi , Cobb Samuel J. , Rahaman Motiar , Sammy Nicholas , Reisner Erwin , Wheatley Andrew E. H.
Published: July 2024

Hydrogen fuel cells represent a leading technology in developing green energy targeting net‐zero emissions goals by mid‐century. However, the sluggish kinetics of the oxygen reduction reaction (ORR) have hitherto demanded substantial quantities of expensive platinum (Pt) group metals. Advances in catalyst design, including the controllable fabrication of highly branched morphologies to increase the surface area‐to‐volume ratio, intermixing Pt with more affordable transition metals, and controlling composition, offer solutions that can further enhance activity and reduce expense. In this context, Pt/M (M = Fe, Ni, Co) nanopods and nanodendrites with precise composition control using more affordable starting materials are designed and crafted. The method is highly efficient, taking only 30 min and avoiding the need for high‐pressure equipment, making it highly scalable. These catalysts show superior ORR performance at an electrode loading as low as 0.0022 mgPt cm−2. One, nanodendritic Pt/Ni, achieves a mass activity of at 0.9 V versus RHE, making it 87 times more efficient in terms of Pt‐content than a commercial 10 wt% Pt/C nanoparticle standard. These findings provide new opportunities for developing next‐generation, cost‐efficient Pt‐based catalysts, by potentially advancing hydrogen fuel cell technology through performance enhancement and addressing cost challenges through catalyst design.
Dried Blood Matrix as a New Material for the Detection of DNA Viruses
Authors: Lim Jongwon , Hwang Joanne , Min Hyegi , Wester Matthew , Kim Chansong , Valera Enrique , Kong Hyun Joon , Bashir Rashid
Published: July 2024

The gold standard for diagnosing viruses such as the Hepatitis B Virus has remained largely unchanged, relying on conventional methods involving extraction, purification, and polymerase chain reaction (PCR). This approach is hindered by limited availability, as it is time‐consuming and requires highly trained personnel. Moreover, it suffers from low recovery rates of the nucleic acid molecules for samples with low copy numbers. To address the challenges of complex instrumentation and low recovery rate of DNA, a drying process coupled with thermal treatment of whole blood is employed, resulting in the creation of a dried blood matrix characterized by a porous structure with a high surface‐to‐volume ratio where it also inactivates the amplification inhibitors present in whole blood. Drawing on insights from Brunauer–Emmett–Teller (BET)‐ Barrett–Joyner–Halenda (BJH) analysis, scanning electron microscopy (SEM), and fluorescence recovery after photobleaching (FRAP), detection assay is devised for HBV, as a demonstration, from whole blood with high recovery of DNA and simplified instrumentation achieving a limit of detection (LOD) of 10 IU mL−1. This assay can be completed in <1.5 h using a simple heater, can be applied to other DNA viruses, and is expected to be suitable for point‐of‐care, especially in low‐resource settings.
Cascaded Heteroporous Nanocomposites for Thermo‐Adaptive Passive Radiation Cooling
Authors: Tang Weiming , Zhan Yaohui , Yang Jingrun , Meng Xue , Zhu Xingyue , Li Yong , Lin Tianyi , jiang Lei , Zhao Ziguang , Wang Shutao
Published: July 2024

Passive radiative cooling is a promising technology for heat dissipation that does not consume energy. However, current radiative cooling materials can only exhibit subambient cooling under atmospheric conditions and struggle to process specific heat accumulation. Thus, a passive thermal regulation mechanism adapted to wide‐temperature‐range applications is required to match device heating systems. Herein, a heteroporous nanocomposite film (HENF) with thermo‐adaptive radiation cooling performance is reported. Compared to conventional porous cooling films with limited scattering efficiencies, the HENFs with multistage scattering have a strong emissivity of 96.5% (8–13 µm) and a high reflectivity of 97.3% (0.3–2.5 µm), resulting in an ultrahigh cooling power of 114 W m−2. In such HENFs, theoretical analyses have confirmed the spectrum management superiority of the heteroporous unit in terms of the scattering efficiency strength, with their cascading effect enhancing the overall film‐cooling efficiency. The high mechanical performance, phase‐transition features, and environmental adaptive properties of HENFs are also exhibited. Importantly, HENFs synergistically couple thermal dissipation and absorption to effectively process heat accumulation and counteract thermal shock in heating devices. It is anticipated that thermo‐adaptive HENFs will act as a promising platform for device surface thermal regulation over a wide temperature range.
Vertical Thermal Emission from Optical Antennas on an Epsilon‐Near–Zero Substrate
Authors: Khan Irfan , Palei Milan , Dominguez Owen , Simmons Evan , Podolskiy Viktor A. , Hoffman Anthony J.
Published: July 2024

This work presents a novel approach to achieve directional and normal thermal emission from epsilon‐near–zero (ENZ) materials. ENZ materials exhibit near–zero permittivity at the ENZ point, resulting in some unique properties compared to conventional optical materials including infinite wavelength, constant phase distribution, and decoupling of spatial and temporal fields inside the ENZ material. These properties are used to engineer the far‐field thermal emission from optical antennas fabricated on ENZ film in the mid‐infrared. By coupling the antenna resonance mode with the Berreman mode of the ENZ material, highly directional and normal emission is demonstrated. This approach could have significant implications for thermal management, energy conversion, and sensing applications.
Absolute Quantum Efficiency Measurements of Electrochemiluminescent Devices Through Electrical Impedance Spectroscopy
Authors: Moon Chang‐Ki , Gather Malte C.
Published: July 2024

AC‐operating electrochemiluminescent devices (ECLDs) have recently shown a substantial increase in brightness, making them potentially relevant for applications in lighting and displays. To further improve the performance of these liquid‐state light‐emitting devices, it is essential to reliably assess the absolute quantum efficiency of electrochemiluminescence and the electrochemical reactions leading to exciton formation. However, significant non‐faradaic currents occurring under the AC operation schemes make it challenging to quantify the number of charges involved in the electrochemical reactions. Here, faradaic and non‐faradaic currents in sandwich‐type ECLDs are analysed by electric impedance spectroscopy and to assess the absolute quantum efficiency of the electrochemiluminescence (ΦECL). An equivalent circuit model enables analysis of the current at different voltage amplitudes and operating frequencies. The analysis reveals that non‐faradaic currents stem primarily from capacitive currents associated with the formation of electric double‐layers near liquid/electrode interfaces. Their contribution to the total current increases at high operating frequencies and low voltages. For ECLDs operating based on an exciplex‐formation and energy transfer pathway, the estimated ΦECL and resulting exciton formation efficiency are 0.53% and 27%, respectively. Reverse redox reactions are identified as a significant loss factor, thus indicating potential avenues for future improvements.
High‐Performance P‐N Junction Heterostructure with Carbon Quantum Dot and Nitrogen Self‐Doped Graphitic Carbon Nitride for Visible Light Photodetection
Authors: Zandi Pegah , Phani Arindam , Kim Seonghwan
Published: July 2024

Organic photodetectors (OPDs) hold immense promise for optoelectronic applications. Here a zero‐biased, high‐performance organic photodetector employing a 2D organic heterostructure is introduced. The structure combines carbon quantum dots (CQDs) with nitrogen self‐doped graphitic carbon nitride (g‐C3N4+) and is tested for alternating current (AC) photodetection on an interdigitated electrode platform. The study reveals extraordinary performance driven by the synergistic effects of efficient charge excitation, separation, and emission within the 2D/2D CQD/g‐C3N4+ heterostructure, leveraging mechanisms of photoconduction, photogating, and fluorescence. A unique convergence to similar rise and decay times in the order of 2.9 ms is observed at higher frequencies in the visible (Vis) spectrum. Benchmarking against state‐of‐the‐art OPDs shows ultrahigh specific detectivity (4.60 × 1018 Jones), ultrahigh responsivity (1.43 × 107 A W−1), high external quantum efficiency  (43 × 107%) at an optical intensity of 3.56 × 10−4 mW cm−2 and a wavelength of 405 nm while delivering competitive performance at 532 and 635 nm as well. Moreover, a large linear dynamic range of 86–162 dB in the Vis spectrum is obtained. These enhancements promise development of a new generation of OPDs to advance light sensing and imaging applications at high frequency, marking a significant milestone in optoelectronic device engineering.
Supramolecular Light‐Harvesting Nanoarchitectonics Toward Self‐Locked Logic Gates
Authors: Wang Xuanyu , Gao Zhao , Tian Wei
Published: July 2024

Supramolecules are considered a promising approach for molecular logic gates due to their inherent dynamic responsiveness driven by non‐covalent forces. However, the lack of input sequence dependence in these logic gates may lead to misinterpretation of outputs, compromising their reliability. This study proposes an efficient universal supramolecular Förster resonance energy transfer (FRET) platform for logic gates with self‐locking features. Specifically, well‐designed naphthalene‐based monomers serve as energy donors, while dyes such as eosin Y (EY), rhodamine B (RhB), and sulforhodamine 101 (SR101), spanning from yellow to red, are employed as energy acceptors. Leveraging large exciton migration rates (1.21 × 1014 to 1.36 × 1014 L mol−1 s−1) between donor and acceptors, FRET processes are effectively facilitated. Building upon this framework, supramolecular logic gates with self‐locking features are successfully constructed. Notably, in these logic gates, even with the correct truth table, any deviation in the order of inputs can lead to alterations in the original outputs.
Low‐Temperature Atomic Layer Deposition of Hole Transport Layers for Enhanced Performance and Scalability in Textured Perovskite/Silicon Tandem Solar Cells
Authors: Zhu Zhengjie , Yuan Shaojie , Mao Kaitian , Meng Hongguang , Cai Fengchun , Li Tieqiang , Feng Xingyu , Guo Huitian , Tang Lianyou , Xu Jixian
Published: July 2024

Perovskite tandem solar cells on textured silicon hold potential for surpassing single‐junction limits and industrial compatibility. However, integrating hole‐transporting layers (HTLs) onto textured silicon poses challenges in conformal coating, low‐temperature fabrication, and perovskite solution process compatibility. Here, an atomic layer deposition (ALD) copper‐doping process is introduced to fabricate low‐temperature NiOx HTLs (ALD Cu:NiOx), tailored for textured tandems. Copper‐doping reduces hydroxyl group content and Ni3+ defects, addressing the challenge of enhancing hole conductivity while mitigating recombination loss. This advancement enables to lower the post‐annealing temperature from >300 to 200 °C, achieving compatibility with silicon heterojunction (SHJ) cells and boosting the power‐conversion efficiency (PCE) of 1.65‐eV p–i–n perovskite solar cells to 22.47%. Integrating ALD Cu:NiOx beneath conventional self‐assembled monolayer HTL on textured SHJ leads to notable PCE enhancements, from 28.6% to 30.5% for 1‐cm2 tandems (certified stabilized PCE of 30.04%) and from 23.9% to 26.4% for 8.89‐cm2 tandems. Following 1000 h of maximum‐power‐point (MPP) tracking, tandems maintain 95% of initial efficiency. Notably, losses in open‐circuit voltage and PCE due to area upscaling reduced by over 20%, attributed to ALD Cu:NiOx’s ability to enhance perovskite film wettability and minimize shunting on silicon pyramid texture, underscoring its impacts for textured tandem upscaling.
Genomic Analysis Identifies Risk Factors in Restless Legs Syndrome
Authors: Akçimen Fulya , Chia Ruth , Saez‐Atienzar Sara , Ruffo Paola , Rasheed Memoona , Ross Jay P. , Liao Calwing , Ray Anindita , Dion Patrick A. , Scholz Sonja W. , Rouleau Guy A. , Traynor Bryan J.
Published: July 2024

Objective

Restless legs syndrome (RLS) is a neurological condition that causes uncomfortable sensations in the legs and an irresistible urge to move them, typically during periods of rest. The genetic basis and pathophysiology of RLS are incompletely understood. We sought to identify additional novel genetic risk factors associated with RLS susceptibility.

Methods

We performed a whole‐genome sequencing and genome‐wide association meta‐analysis of RLS cases (n = 9,851) and controls (n = 38,957) in 3 population‐based biobanks (All of Us, Canadian Longitudinal Study on Aging, and CARTaGENE).

Results

Genome‐wide association analysis identified 9 independent risk loci, of which 8 had been previously reported, and 1 was a novel risk locus (LMX1B, rs35196838, OR 1.14, 95% CI 1.09–1.19, p value = 2.2 × 10−9). Furthermore, a transcriptome‐wide association study also identified GLO1 and a previously unreported gene, ELFN1. A genetic correlation analysis revealed significant common variant overlaps between RLS and neuroticism (rg = 0.40, se = 0.08, p value = 5.4 × 10−7), depression (rg = 0.35, se = 0.06, p value = 2.17 × 10−8), and intelligence (rg = −0.20, se = 0.06, p value = 4.0 × 10−4).

Interpretation

Our study expands the understanding of the genetic architecture of RLS, and highlights the contributions of common variants to this prevalent neurological disorder. ANN NEUROL 2024;96:994–1005
DNA Dissipative System for Controlled Release of Immunostimulatory CpG Oligodeoxynucleotides
Authors: Ishaqat Aman , Zhang Xiaofeng , Herrmann Andreas
Published: July 2024

Herein, a dissipative system tailored for the controlled loading and release of CpG oligodeoxynucleotides (CpG ODNs), known for their pharmacological immunostimulatory properties, is reported. The approach involves multiple cycles of deactivation and activation of the CpG ODNs via its hybridization with a complementary fuel strand, followed by its selective release mediated by the enzymatic activity of T7 exonuclease. The autonomous and temporal behavior of this dissipative system can be tuned by three factors: the design of the fuel strand and its concentration that governs the kinetics of the forward hybridization reaction, as well as the concentration of T7 exonuclease, which regulates the backward energy dissipation reaction. Furthermore, the enzyme's tolerance toward waste accumulation is demonstrated, and the system's robust performance when utilizing various fuel strands in alternating fashion is showcased. The findings underscore the potential of this approach for precise and programmable delivery of therapeutic nucleic acids in multiple cycles, with implications for enhancing immunotherapeutic strategies in which controlled kinetics of the nucleic acid is highly desired.
High‐Voltage Single‐Ion Covalent Organic Framework Electrolytes Enabled by Nitrile Migration Ladders for Lithium Metal Batteries
Authors: Li Weiping , Han Shantao , Xiao Chenxi , Yan Jingying , Wu Baifei , Wen Peng , Lin Jun , Chen Mao , Lin Xinrong
Published: July 2024

The poor electrochemical stability window and low ionic conductivity in solid‐state electrolytes hinder the development of safe, high‐voltage, and energy‐dense lithium metal batteries. Herein, taking advantage of the unique electronic effect of nitrile groups, we designed a novel azanide‐based single‐ion covalent organic framework (CN−iCOF) structure that possesses effective Li+ transport and high‐voltage stability in lithium metal batteries. Density functional theory (DFT) calculations and molecular dynamics (MD) revealed that electron‐withdrawing nitrile groups not only resulted in an ultralow HOMO energy orbital but also enhanced Li+ dissociation through charge delocalization, leading to a high tLi+ of 0.93 and remarkable oxidative stability up to 5.6 V (vs. Li+/Li) simultaneously. Moreover, cyanation leveraging Strecker reaction transformed reversible imine‐linkage to a stable sp3‐carbon‐containing azanide anion, which facilitated contorted alignment of transport “ladders” along the one‐dimensional anionic channels and the ionic conductivity could reach 1.33×10−5 S cm−1 at ambient temperature without any additives. As a result, CN−iCOF allowed operation of solid‐state lithium metal batteries with high‐voltage cathodes such as LiNi0.8Mn0.1Co0.1O2 (NCM811), demonstrating stable lithium deposition up to 1,100 h and reversible battery cycling at ambient temperature up to 4.5 V, shedding light on the importance of discovering new functionality for forthcoming high‐performance batteries.
Ligand‐Enabled Pd‐Catalyzed sp3 C−H Macrocyclization: Synthesis and Evaluation of Macrocyclic Sulfonamide for the Treatment of Parkinson's Disease
Authors: Bi Tongyu , Cui Yunxia , Liu Shuai , Yu Haiyue , Qiu Weirong , Hou Ke‐Qiang , Zou Jiaqi , Yu Zhipeng , Zhang Feili , Xu Zhongliang , Zhang Jian , Xu Xiaojun , Yang Weibo
Published: July 2024

The development of simplified synthetic strategy to create structurally and functionally diverse pseudo‐natural macrocyclic molecules is highly appealing but poses a marked challenge. Inspired by natural scaffolds, herein, we describe a practical and concise ligand‐enabled Pd(II)‐catalyzed sp3 C−H alkylation, olefination and arylation macrocyclization, which could offer a novel set of pseudo‐natural macrocyclic sulfonamides. Interestingly, the potential of ligand acceleration in C−H activation is also demonstrated by an unprecedented enantioselective sp3 C−H alkylation macrocyclization. Moreover, a combination of in silico screening and biological evaluation led to the identification of a novel spiro‐grafted macrocyclic sulfonamide 2 a, which showed a promising efficacy for the treatment of Parkinson's disease (PD) in a mouse model through the activation of silent information regulator sirtuin 3 (SIRT3).
Coordination Environment and Distance Optimization of Dual Single Atoms on Fluorine‐Doped Carbon Nanotubes for Chlorine Evolution Reaction
Authors: Shao Xiaodong , Maibam Ashakiran , Cao Fengliang , Jin Haiyan , Huang Shiqing , Liang Mengfang , Gyu Kim Min , My Tran Kim , Jadhav Amol R. , Seung Jung Hyun , Babarao Ravichandar , Lee Hyoyoung
Published: July 2024

The chlorine evolution reaction (CER) is a crucial anode reaction in the chlor‐alkali industrial process. Precious metal‐based dimensionally stable anodes (DSA) are commonly used as catalysts for CER but are constrained by their high cost and low selectivity. Herein, a Pt dual singe‐atom catalyst (DSAC) dispersed on fluorine‐doped carbon nanotubes (F‐CNTs) is designed for an efficient and robust CER process. The prepared Pt DSAC demonstrates excellent CER activity with a low overpotential of 21 mV to achieve a current density of 10 mA cm−2 and a remarkable mass activity of 3802.6 A gpt−1 at an overpotential around 30 mV, outperforming those of commercial DSA and Pt single‐atom catalyst. The excellent CER performance of Pt DSAC is attributed to the high atomic utilization and improved intrinsic activity. Notably, introducing fluorine atoms on CNTs increases the oxidation and chlorination resistance of Pt DSAC, and reduces the demetalization ratio of Pt atoms, resulting in excellent long‐term CER stability. Theoretical calculations reveal that several Pt DSAC configurations with optimized first‐shell ligands and interatomic distance display lower energy barriers for Cl intermediates generation and weaker ionic Pt−Cl bond interaction, which are favorable for the CER process.
Direct Asymmetric Synthesis of α‐Aminoimines from 1,2‐Bis‐N‐Sulfinylimines by Using Allyl Boronic Acids
Authors: Bhunia Susanta , Karan Ganesh , Snehil Shubham , Maji Modhu Sudan
Published: July 2024

A unique direct asymmetric synthesis of α‐aminoimines is realized, through rapid and exclusive mono‐allylation of chiral bis‐N‐sulfinylimines using allylboronic acids. The highly selective allylation was possible as electrophilic imine functional group in the product α‐aminoimines remained unreactive towards allyl boronic acid nucleophiles. Notably, by varying the geometry and chiral auxiliary, all four isomers of the α‐aminoimines were accessed from readily available precursors. A range of allyl nucleophiles, which are tricky to generate by other means possessing highly reactive functional groups also took part in this reaction, expanding the scope further. The applicability of the products α‐aminoimines were further demonstrated by accessing a range of structurally diverse chiral cyclic and acyclic 1,2‐diamines bearing adjacent stereocenters through addition of a second nucleophile or Prins‐type cyclization by exploiting the nucleophilicity of the tethered alkene moiety. Moreover, the leaving group aptitude of sulfinyl auxiliary attached to imine, was exploited to access valuable chiral α‐aminonitriles under thermal conditions without employing any reagents. Detailed DFT calculation revealed a chair‐like transition state, arising from corresponding allylboroxine species, likely operating for the allylboration reaction across imine.
The Fate of the Formic Acid Proton on the Anatase TiO2(101) Surface
Authors: Fallacara Erika , Finocchi Fabio , Cazzaniga Marco , Chenot Stéphane , Stankic Slavica , Ceotto Michele
Published: July 2024

As a prototype adsorption reaction of gas Brønsted acid on oxides, we study the adsorption of formic acid on anatase. We perform infrared spectroscopy measurements of adsorbed HCOOH and HCOOD on TiO2 nanopowders, from 13 K up to room temperature in an ultra‐high vacuum chamber. We assign the IR signals via computed spectra from nuclear quantum dynamics simulations using our divide‐and‐conquer semiclassical ab initio molecular dynamics method. The acid proton forms an extraordinarily short and strong hydrogen bond with the surface oxygen. The strength of this hydrogen bond, that compares to H bonds in ice at high pressures, is at the root of a substantial redshift with respect to the typical free OH stretching frequency, which eludes its straightforward detection.
Increased threat of strong typhoons along the Pacific coast of Japan: Combined effect of track change and seasonal advance
Authors: Shen Zheng‐Qin , Gu Jian‐Feng , Wang Qi‐Wei , Qiu Xin
Published: July 2024

This study analyses the landfall intensity of tropical cyclones (TCs) affecting the Pacific coast of Japan and found that the proportion of strong typhoons increased significantly in the second 22 years from 1977 to 2020. With an objective cluster analysis of TC tracks, one could isolate a cluster of TCs originating from the southeastern part of the western North Pacific (WNP), which plays a dominant role in increasing landfalls of strong typhoons. These TCs are characterized by a long‐recurving track and could achieve significantly higher intensity and larger size. Further analysis of TC trajectories and the environmental steering flow show a greater tendency for TCs originating from the southeastern WNP to approach the Pacific coast of Japan, even though there was a dramatic decrease in TC genesis number during autumn. Meanwhile, a notable earlier onset of strong typhoons occurred within this cluster of TCs due to more favorable atmospheric and oceanic conditions in summer. The results of this study emphasize the impacts of TC track change and seasonal advance of strong typhoons on the variation of intensity and potential destructiveness of landfalling TCs.
MTML: An Efficient Multitrait Multilocus GWAS Method Based on the Cauchy Combination Test
Authors: Guo Hongping , Li Tong , Shi Yao , Wang Xiao
Published: July 2024

Genome‐wide association study (GWAS) by measuring the joint effect of multiple loci on multiple traits, has recently attracted interest, due to the decreased costs of high‐throughput genotyping and phenotyping technologies. Previous studies mainly focused on either multilocus models that identify associations with a single trait or multitrait models that scan a single marker at a time. Since these types of models cannot fully utilize the association information, the powers of the tests are usually low. To potentially address this problem, we present here a multitrait multilocus (MTML) modeling framework that implements in three steps: (1) simplify the complex calculation; (2) reduce the model dimension; (3) integrate the joint contribution of single markers to multiple traits by Cauchy combination. The performances of MTML are evaluated and compared with other three published methods by Monte Carlo simulations. Simulation results show that MTML is more powerful for quantitative trait nucleotide detection and robust for various numbers of traits. In the meanwhile, MTML can effectively control type I error rate at a reasonable level. Real data analysis of Arabidopsis thaliana shows that MTML identifies more pleiotropic genetic associations. Therefore, we conclude that MTML is an efficient GWAS method for joint analysis of multiple quantitative traits. The R package MTML, which facilitates the implementation of the proposed method, is publicly available on GitHub https://github.com/Guohongping/MTML.
Berberine chloride loaded nano‐PEGylated liposomes attenuates imidacloprid‐induced neurotoxicity by inhibiting NLRP3/Caspase‐1/GSDMD‐mediated pyroptosis
Authors: El Gazzar Walaa Bayoumie , Farag Amina A. , Samir Mohamed , Bayoumi Heba , Youssef Heba S. , Marei Yasmin Mohammed , Mohamed Shimaa K. , Marei Azza M. , Abdelfatah Reham M. , Mahmoud Manal Moustafa , Aboelkomsan Elshaimaa Ahmed Fahmy , Khalfallah Eman Kamel M. , Anwer Hala Magdy
Published: July 2024

Concerns have been expressed about imidacloprid (IMI), one of the most often used pesticides, and its potential neurotoxicity to non‐target organisms. Chronic neuroinflammation is central to the pathology of several neurodegenerative disorders. Hence, exploring the molecular mechanism by which IMI would trigger neuroinflammation is particularly important. This study examined the neurotoxic effects of oral administration of IMI (45 mg/kg/day for 30 days) and the potential neuroprotective effect of berberine (Ber) chloride loaded nano‐PEGylated liposomes (Ber‐Lip) (10 mg/kg, intravenously every other day for 30 days) using laboratory rat. The histopathological changes, anti‐oxidant and oxidative stress markers (GSH, SOD, and MDA), proinflammatory cytokines (IL1β and TNF‐α), microglia phenotype markers (CD86 and iNOS for M1; CD163 for M2), the canonical pyroptotic pathway markers (NLRP3, caspase‐1, GSDMD, and IL‐18) and Alzheimer's disease markers (Neprilysin and beta amyloid [Aβ] deposits) were assessed. Oral administration of IMI resulted in apparent cerebellar histopathological alterations, oxidative stress, predominance of M1 microglia phenotype, significantly upregulated NLRP3, caspase‐1, GSDMD, IL‐18 and Aβ deposits and significantly decreased Neprilysin expression. Berberine reduced the IMI‐induced aberrations in the measured parameters and improved the IMI‐induced histopathological and ultrastructure alterations brought on by IMI. This study highlights the IMI neurotoxic effect and its potential contribution to the development of Alzheimer's disease and displayed the neuroprotective effect of Ber‐Lip.
Unlocking sustainable project management: The role of project managers' competencies in resource bricolage from a stakeholder engagement perspective
Authors: Al‐Nimer Munther , Khattak Muhammad Sualeh , Wu Qiang , Ullah Rizwan
Published: July 2024

Sustainable project management practices have garnered increasing attention in recent years. Consequently, in the age of digitalization and globalization, numerous studies extensively explore the relationship between digitalization and sustainable practice. While optimism abounds, there is insufficient research into how and what types of project managers effectively manage resources to enhance the sustainability of projects when stakeholders are engaged. Therefore, we aim to address this gap by analyzing a sample of 211 Chinese project managers involved in the China‐Pakistan Economic Corridor (CPEC). Our findings indicate that project managers with digital literacy and experience are effective at managing existing resources to promote sustainable project management practices, while project managers with financial literacy do not directly exhibit sustainable practices. Furthermore, digitally literate managers are more likely to engage in bricolage (effective resource management), whereas experienced project managers are less likely to do so in the presence of stakeholder engagement. Moreover, stakeholder engagement does not appear to moderate the relationship between project manager financial literacy and bricolage. Based on these findings, our research recommends that organizations focus on employing digitally literate and experienced project managers to effectively manage their limited resources for sustainable project management. Further practical implications are discussed.
Biodiversity reporting by United Kingdom (UK)‐listed companies: A review of extent, content and readability of disclosures
Authors: Maroun Warren , Ecim Dusan
Published: July 2024

This study examines biodiversity reporting by UK‐listed companies. An instrument is developed, based on earlier research, and used to analyse biodiversity‐related disclosures as either policy considerations or actions taken to conserve biodiversity. A mixed design is employed. The extent of reporting, information content of disclosures and their readability are used to provide an overarching perspective on how firms internalise biodiversity. Outliers are identified and their reports are examined interpretively to identify how leading reporters understand biodiversity as a policy imperative and factor it into their operational and managerial performances. This qualitative analysis highlights best practices that can be used by other entities interested in developing the accounting and management infrastructure necessary for reporting comprehensively on biodiversity. Best practices are, however, isolated and stand in stark contrast with how organisations are dealing with biodiversity on average. At the policy level, there is little on how biodiversity is defined and the rationale for wanting to protect biodiversity. When it comes to performance, few organisations are setting detailed biodiversity‐related targets linked clearly to operational plans, risk assessments and key performance indicators. Post‐implementation reviews of conservation initiatives are seldom conducted and biodiversity is not being factored into valuations, cost assessments and project appraisals. Understanding these limitations is timely given the international community's recent efforts to develop standards for extra‐financial reporting. The results will be relevant for regulators, scholars and practitioners interested in advancing the quality of biodiversity reporting and factoring biodiversity into mainstream business discourses.
A novel hybrid decision‐making framework for measuring Industry 4.0‐driven circular economy performance for textile industry
Authors: Ali Sadia Samar , Torğul Belkız , Paksoy Turan , Luthra Sunil , Kayikci Yasanur
Published: July 2024

The sustainability strategy focuses on conscious production and consumption, with the circular economy (CE) as an innovative approach to maximize resource value and minimize waste. Industry 4.0 technologies like AI, robotics, and blockchain play a significant role in enhancing the competitiveness of businesses pursuing the CE. These advanced technologies help organizations achieve their sustainability goals, particularly within the CE framework. The study analyses how Industry 4.0‐driven CE practices impact sustainable business performance, using the Indian textile industry as a case study. The researchers developed a three‐stage hybrid decision‐making framework, integrating various methods to assess sustainable performance. A novel three‐stage hybrid decision‐making framework was developed by integrating Kendall's agreement test (Kendall's W), fuzzy Delphi, best–worst method (BWM), full consistency method (FUCOM), and combined compromise solution (CoCoSo) methods. The findings highlight positive outcomes such as enhanced incentives, government support, greener logistics, and improved monitoring of emissions, waste, and pollution. However, there is room for further improvements to address market demand and increase the profitability of green products.
Condensation Domain Editing of the FR900359 Assembly Line Yields a Novel Analog Amenable to Late‐Stage Functionalization
Authors: Pistorius Dominik , Richard Etienne , Buntin Kathrin , Dresen Kathrin , Wollbrett Séverine , Weber Eric , Haberkorn Anne , Manchado Eusebio , Petersen Frank
Published: July 2024

The natural product FR900359 (FR) has generated significant attention lately, due to its characteristics as potent and selective inhibitor of Gq/11 mediated signal transduction of associated G protein‐coupled receptors (GPCRs). This makes FR both a widely used pharmacological tool compound and a lead molecule for targeted cancer therapy. The exploration of structure‐activity‐relationship (SAR) of the scaffold by total synthesis has been complicated by its structural complexity and its incompatibility with standard approaches of solid‐phase peptide synthesis. Options for late‐stage functionalization of FR are limited due to a lack of tractable functional groups. Here we present a mixed approach combining (i) genetic engineering of the FR‐assembly line in Chromobacterium vaccinii, to obtain a novel FR analog featuring a primary amine, with (ii) its subsequent synthetic modification and biological profiling for further SAR exploration of the FR scaffold.
Strain‐Modulated Hydrogen Production Performance in Monolayer MoS2 Electrocatalysis Nanodevices
Authors: Niu Baokang , Wang Ningyu , Shen Ruizhao , Liao Xiaobin , Mai Liqiang
Published: July 2024

The integration of flexible micro‐ and nanodevices plays a pivotal role in investigating stress‐enhanced performances and underlying intrinsic mechanisms for two‐dimensional materials. This study presents the fabrication of single‐crystal flexible devices using monolayer MoS2 and its catalytic activities for the hydrogen evolution reaction under stress conditions. A metallic conductive layer was deposited on the photoresist surface via magnetron sputtering, overcoming the challenges associated with lithography on insulating substrates using electron beam lithography (EBL). The results demonstrate optimal etch patterns with a metal modification layer thickness of 10.97 nm. Leveraging this flexible device fabrication process, a single‐layer MoS2 single‐nanosheet flexible micro/nano device was developed and subsequently strain‐modulated (stretched along the zigzag lattice direction with the armchair lattice direction as the axis). A significant enhancement is observed in the electrocatalytic hydrogen evolution performance as the strain increases from 0 % to 0.40 %. Notably, the onset overpotential decreased from 155.6 to 95.7 mV, and the Tafel slope decreased from 175.3 to 98.6 mV dec−1. This study provides new insights into the design and performance of strain devices for two‐dimensional (2D) monocrystalline/polycrystalline materials.
New Twists in the Chemistry of Thioureas: 1,3‐Thiazolidines as a Vector of Sustainability
Authors: Canudo‐Barreras Guillermo , Herrera Raquel P. , Concepción Gimeno M.
Published: July 2024

This study introduces a sustainable and pioneering cascade synthesis of 1,3‐thiazolidine derivatives under eco‐friendly conditions. The methodology transcends traditional approaches yielding complex novel compounds with unique N,S‐heterocyclic structures. By operating at room temperature, utilizing green solvents, and minimizing excess of reactants, this procedure offers an innovative pathway for sustainable chemical development. Notably, this method not only prioritizes sustainability but also delivers high‐purity products with exceptional yields. The simplicity of the process, requiring only a simple filtration and featuring short reaction times, underscores its efficiency and utility.
Why Are Some Pnictogen(III) Pincer Complexes Planar and Others Pyramidal?
Authors: Hannah Tyler J. , Kirsch Tamina Z. , Chitnis Saurabh S.
Published: July 2024

Geometrically‐constrained pnictogen pincer complexes have emerged in recent years as platforms for unique stoichiometric and catalytic chemical transformations. These complexes feature dynamic conformations ranging from fully planar at the pnictogen centre to distorted‐pyramidal geometries, as well as variation between phases. Although the valued reactivity of pnictogen pincer complexes is ascribed to their geometries, there is no unified model to explain the observed conformational outcomes across different ligands and pnictogen centres. Here we propose such a model through computational analysis of more than 1300 structures across 64 complexes (16 ligands and 4 heavy pnictogens), explaining the experimental observations and making new predictions. By looking at signatures of bond stability (bond lengths, Wiberg bond indices) and delocalization (NPA charges, Hirshfeld charges), our framework posits a pnictogen‐based σ‐bonding effect that favours pyramidalization and exists in competition with a ligand‐based π‐bonding effect that favours planarity. Variations in structure as a function of pnictogen identity, ligand tethering, electronics, and aromaticity can be reconciled with reference to a balance between these two opposing forces. Careful consideration of the σ/π‐bonding effects may aid in the rational design of future pnictogen pincer complexes with predictable geometries and reactivities.
Structural Investigations of Cargo Molecules Inside Icosahedrally Symmetric Encapsulin by VUVCD Spectroscopic Measurements
Authors: Kumamoto Shiori , Yamamoto Akima , Shiratsuchi Yu , Matsuo Koichi , Higashiura Akifumi , Hira Daisuke
Published: July 2024

Prokaryotes organize intracellular compartments with protein‐based organelles called encapsulins. Encapsulins with icosahedral symmetry can encapsulate specific cargo proteins mediated by targeting peptides or encapsulation‐mediating domains. Encapsulins have been used in eukaryotic cells for bioengineering, vaccine development, and nanoparticle alignment. Their versatility makes them attractive for research; however, detailed structural information on encapsulins is crucial for further applied research. However, cargo proteins are randomly oriented inside the icosahedral encapsulins. The random orientation of cargo proteins presents a challenge for structural analysis that relies on averaging processes such as x‐ray crystallography and cryo‐electron microscopy (cryo‐EM) single‐particle imaging. Therefore, we aimed to accurately estimate the secondary structure content and elucidate the structure of cargo proteins inside the particle by measuring the circular dichroism (CD) spectra using vacuum ultraviolet circular dichroism (VUVCD) spectroscopy. Thus, the structure of the cargo protein inside encapsulin was evaluated. This approach could potentially set a standard for evaluating cargo proteins inside particles in future applied research on encapsulins.