bluuebunny/crossref_metadata_2025_split huggingface dataset:
Construction of 1,4‐Oxazepinones via a Cascade Aza‐Michael/SN2 Annulation of Trifluoromethyl Pyrazole‐Derived Oxadienes with a‐Bromohydroxamates
Authors: Yang Kaichuan , Li Zhengwen , Wang Yuchi , Jia Aiqiong , Zhang Xiao , Sun Wenxia , Li Qiang , Hu Yibing , Wang Ling , Ren Jing 
Published: July 2024

AbstractA highly efficient cascade aza‐MIRC (Michael Induced Ring Closure) reaction between trifluoromethylpyrazole (TFPZ)‐derived oxadienes and a‐bromohydroxamates has been developed for the construction of 1,4‐oxazepinone derivatives. The reaction proceeds smoothly under mild conditions via a cascade Aza‐Michael addition/intramolecular SN2 sequence, and features broad substrate scope, transition‐metal free, operational simplicity etc. The utility of the versatile protocol was also demonstrated by gram‐scale reaction and valuable synthetic transformations.
Introducing Indigenist Critical Policy Analysis: A rights‐based approach to analysing public policies and processes
Authors: Bryant Natalie 
Published: July 2024

AbstractInstitutional racism within Australia, grounded in the country's settler‐colonial structure, has sidelined Indigenous interests in public policymaking since federation. In an attempt to redress this, the United Nations Declaration on the Rights of Indigenous Peoples (UNDRIP) was endorsed by the Australian government in 2009. UNDRIP is an authoritative international standard that could inform the ways that governments engage with Indigenous peoples and protect their rights. This paper introduces Indigenist Critical Policy Analysis (ICPA). While mainstream policy evaluation assesses whether policies and processes have met the governments stated objectives, ICPA assesses whether they uphold or violate Indigenous rights. ICPA involves reviewing policy documents against the key principles and specific Articles of UNDRIP. Presenting a worked example of ICPA, the NSW Regional Health Strategic Plan 2022–2032 is assessed against the five phases: (1) Orientation; (2) Close examination; (3) Determination; (4) Strengthening practice; and (5) Indigenous final word. This analysis finds that the Strategic Plan is poorly aligned with UNDRIP. Specifically, there is little evidence that Indigenous values influenced or held any authority in the process. ICPA offers a practical approach to analysing policy for compatibility with Indigenous rights under international law that could be used by Indigenous organisations and policymakers.
Single‐Crystal Cage Framework with High Selectivity and Reversibility in Fullerene Binding
Authors: Huang Shaofeng , Teat Simon J. , Wayment Lacey J. , Settineri Nicholas S. , Chen Hongxuan , Lei Zepeng , Zhang Wei 
Published: July 2024

AbstractHost‐guest chemistry, a pivotal branch of supramolecular chemistry, plays an essential role in understanding and constructing complex structures through non‐covalent interactions. Organic molecular cages, characterized by their intrinsic confined cavities, can selectively bind a variety of guest molecules. Their host–guest chemistry has been well studied in the solution phase, and several attempts have been made to encode well‐defined molecular architectures into solid‐state polymeric materials. However, only limited studies have explored their potential in the solid state, where their lack of robustness and less ordered networks significantly hinder practical applications. Herein, we report the synthesis of a single‐crystal cage framework and a systematic study of its host–guest chemistry, spanning from the solution state to the solid state. Our studies reveal that the host–guest interactions inherent to the cage are successfully maintained in the solid‐state polymeric material. Furthermore, the framework's robustness allows for the guest molecules (fullerene) to be released triggered by an organic acid (trifluoroacetic acid), with subsequent regeneration of the framework through an organic base (triethylamine) treatment. Our findings represent the first synthesis of a robust, single‐crystal cage framework exhibiting highly selective and reversible host–guest chemistry, thus showing great potential towards molecular separation application.
Symmetric Electron Transfer Coordinates are Intrinsic to Bridged Systems: An ab Initio Treatment of the Creutz–Taube Ion
Authors: Šrut Adam , Lear Benjamin J. , Krewald Vera 
Published: July 2024

AbstractA long‐standing question in electron transfer research concerns the number and identity of collective nuclear motions that drive electron transfer or localisation. It is well established that these nuclear motions are commonly gathered into a so‐called electron transfer coordinate. In this theoretical study, we demonstrate that both anti‐symmetric and symmetric vibrational motions are intrinsic to bridged systems, and that both are required to explain the characteristic shape of their intervalence charge transfer bands. Using the properties of a two‐state Marcus–Hush model, we identify and quantify these two coordinates as linear combinations of normal modes from ab initio calculations. This quantification gives access to the potential coupling, reorganization energy and curvature of the potential energy surfaces involved in electron transfer, independent of any prior assumptions about the system of interest. We showcase these claims with the Creutz–Taube ion, a prototypical Class III mixed valence complex. We find that the symmetric dimension is responsible for the asymmetric band shape, and trace this back to the offset of the ground and excited state potentials in this dimension. The significance of the symmetric dimension originates from geometry dependent coupling, which in turn is a natural consequence of the well‐established superexchange mechanism. The conceptual connection between the symmetric and anti‐symmetric motions and the superexchange mechanism appears as a general result for bridged systems.
Unravelling White Phosphorus: Experimental and Computational Studies Reveal the Mechanisms of P4 Hydrostannylation
Authors: Cammarata Jose , Westermair Franz F. , Coburger Peter , Duvinage Daniel , Janssen Marvin , Uttendorfer Maria K. , Beckmann Jens , Gschwind Ruth M. , Wolf Robert , Scott Daniel J. 
Published: July 2024

AbstractThe hydrostannylation of white phosphorus (P4) allows this crucial industrial precursor to be easily transformed into useful P1 products via direct, ‘one pot’ (or even catalytic) procedures. However, a thorough mechanistic understanding of this transformation has remained elusive, hindering attempts to use this rare example of successful, direct P4 functionalization as a model for further reaction development. Here, we provide a deep and generalizable mechanistic picture for P4 hydrostannylation by combining DFT calculations with in situ 31P NMR reaction monitoring and kinetic trapping of previously unobservable reaction intermediates using bulky tin hydrides. The results offer important insights into both how this reaction proceeds and why it is successful and provide implicit guidelines for future research in the field of P4 activation.
Cycloadditions of Diazoalkenes with P4 and tBuCP: Access to Diazaphospholes
Authors: Hauer Sebastian , Reitz Justus , Koike Taichi , Hansmann Max M. , Wolf Robert 
Published: July 2024

AbstractDiazoalkenes readily react with tert‐butylphosphaalkyne (tBuCP) and white phosphorus (P4) to afford novel phosphorus heterocycles, 3H‐1,2,4‐diazamonophospholes and 1,2,3,4‐diazadiphospholes. Both species represent rare examples of neutral heterophospholes. The mechanism of formation and the electronic structures of these formal (3+2) cycloaddition products were analyzed computationally. The new phospholes form structurally diverse coordination compounds with transition metal and main group elements. Given the growing number of stable diazoalkenes, this work offers a straightforward route to neutral aza(di‐)phospholes as a new ligand class.
Atomically Dispersed Iron‐Copper Dual‐Metal Sites Synergistically Boost Carbonylation of Methane
Authors: Cheng Qingpeng , Yao Xueli , Li Guanna , Li Guanxing , Zheng Lirong , Yang Kaijie , Emwas Abdul‐Hamid , Li Xingang , Han Yu , Gascon Jorge 
Published: July 2024

AbstractThe direct liquid‐phase oxidative carbonylation of methane, utilizing abundant natural gas, offers a mild and straightforward alternative. However, most catalysts proposed for this process suffer from low acetic acid yields due to few active sites and rapid C1 oxygenate generation, impeding their industrial feasibility. Herein, we report a highly efficient 0.1Cu/Fe‐HZSM‐5‐TF (TF denotes template‐free synthesis) catalyst featuring exclusively mononuclear Fe and Cu anchored in the ZSM‐5 channels. Under optimized conditions, the catalyst achieved an unprecedented acetic acid yield of 40.5 mmol gcat−1 h−1 at 50 °C, tripling the previous records of 12.0 mmol gcat−1 h−1. Comprehensive characterization, isotope‐labeled experiments and density functional theory (DFT) calculations reveal that the homogeneous mononuclear Fe sites are responsible for the activation and oxidation of methane, while the neighboring Cu sites play a key role in retarding the oxidation process, promoting C−C coupling for effective acetic acid synthesis. Furthermore, the methyl‐group carbon in acetic acid originates solely from methane, while its carbonyl‐group carbon is derived exclusively from CO, rather than the conversion of other C1 oxygenates. The proposed bimetallic catalyst design not only overcomes the limitations of current catalysts but also generalizes the oxidative carbonylation of other alkanes, demonstrating promising advancements in sustainable chemical synthesis.
Impact of adding magnesium oxide nanoparticles on the optical and shielding characteristics of polyvinyl chloride
Authors: Salem Elsayeda F. , Abido Amr M. N. , Ali I. A. 
Published: July 2024

AbstractThis work uses pure polyvinyl chloride (PVC) with magnesium oxide (MgO) nanoparticles to enhance PVC's optical and shielding properties. The distribution of MgO nanoparticles in the PVC polymer was shown using a scanning electronic microscope, x‐ray diffraction, and Fourier transform infrared. The prepared samples' optical parameters and thermal analysis are investigated using ultraviolet (UV) spectroscopy and thermogravimetric analysis, respectively. The shielding characteristics parameters for the prepared samples were experimentally tested using a Cs‐137 point source with an energy of 0.662 MeV, and the outcomes were contrasted with what the XCOM software had calculated. Results indicated that optical constants were significantly affected by the addition of MgO wt% concentration. The linear attenuation coefficient was directly proportional to the weight concentration of MgO nanoparticle filler in the PVC matrix, and the ability to absorb UV increased. Adding MgO nanoparticle concentrations improved the PVC composite's radiation shielding behavior. It concluded that the PVC/MgO nanoparticle‐prepared samples are suitable for packaging for industrial applications and apron shielding for medical applications.
Stabilization of complex‐valued neural networks subject to semi‐Markov jumping parameters: A dynamic event‐triggered protocol
Authors: Wang Yuan , Yan Huaicheng , Li Zhichen , Wang Meng , Shi Kaibo 
Published: July 2024

AbstractFor continuous‐time complex‐valued neural networks, this paper addresses the state‐feedback stabilization issue via dynamic event‐triggered protocol. Aiming at random parameters' switching, semi‐Markov jump model surpasses the Markov jump model in terms of its generality, enabling us to effectively capture the occurrence of random abrupt alterations in both the structure and parameters of complex‐valued neural networks. To optimize packet transmission, a new dynamic event‐based protocol is introduced to judge whether the previous signal transmission continues. The design of this protocol takes into full consideration the imaginary part characteristics of the system, while also integrating the system modes and dynamic variables. Utilizing an appropriate Lyapunov functional that contains auxiliary internal dynamical variables, the desired stability is proposed. Eventually, the effectiveness of theoretical findings is ultimately validated through two numerical simulations.
How institutional pressures on green innovation are perceived by firms? The role of board social ties
Authors: Zou Hailiang , Zhang Li , Qi Guoyou 
Published: July 2024

AbstractInstitutional pressures are major driving forces for firms' green innovation. However, there is significant heterogeneity in firms' responses to these forces due to the complex information environment within the institutional field. Social ties are known to provide information and resources. This study explores how board social ties, including business and political ties, shape firms' responsiveness to formal and informal institutional forces related to green innovation. Using a dataset from Chinese listed companies in the manufacturing sector, we propose that firms' business ties strengthen the effects of various institutional pressures on green innovation. On the other hand, political ties strengthen the impact of environmental regulation on green innovation but weaken the influence of imitative pressure on green innovation. This suggests that political ties can be a double‐edged sword in firms' responses to institutional pressures. This research contributes to institutional theory and social capital theory, offering implications for green innovation strategies.
Cd(II) and Zn(II) adsorption on lignite‐derived humic substances and cattle manure biochar
Authors: Zhao Yihan , Naeth M. Anne 
Published: July 2024

AbstractExcessive industrial release of trace elements may pose a great risk to the environment. Conventional remediation treatments have considerable limitations, making less expensive new technologies an important research area. Batch experiments were conducted at room temperature to investigate the use of two lignite‐derived humic products (nano‐humus and humic powder) and a cattle manure biochar as adsorbents in the removal of cadmium and zinc from laboratory synthesized water. Nano‐humus was most effective in adsorbing Cd(II), wherein 89% adsorption was rapidly achieved in 15 min. The adsorbed amount of Cd(II) and Zn(II) both increased with initial metal ion concentrations from 25 to 125 mg L−1. Despite being produced from the same sources, nano‐humus and humic powder showed different properties and adsorption behaviors. The adsorption mechanism of nano‐humus followed the Freundlich isotherm model and pseudo‐second‐order kinetic model, indicating multilayer chemisorption. Humic powder followed the pseudo‐second‐order kinetic model, although it had a low isotherm model fit, implying chemisorption‐dominated adsorption. Cattle manure biochar followed the Freundlich isotherm and pseudo‐first‐order kinetics model, suggesting diffusion‐dominated multilayer adsorption. Of the three adsorbents tested, nano‐humus had greatest potential as an effective and inexpensive material for metal remediation.
Theoretical and Experimental Evaluation of the Electronic Relaxation Mechanisms of 2‐Pyrimidinone: The Primary UVA Absorbing Moiety of the DNA and RNA (6–4) Photolesion
Authors: Valverde Danillo , Hoehn Sean J. , Koyanagui Eduardo D. , Krul Sarah E. , Crespo‐Hernández Carlos E. , Borin Antonio Carlos 
Published: July 2024

AbstractThe (6–4) photolesion is a key photodamage that occurs when two adjacent pyrimidine bases in a DNA strand bond together. To better understand how the absorption of UVB and UVA radiation by the 2‐pyrimidinone moiety in a (6–4) lesion can damage DNA, it is important to study the electronic deactivation mechanism of its 2‐pyrimidinone chromophore. This study employs theoretical (MS‐CASPT2/cc‐pVDZ level) and experimental (steady state and femtosecond broadband spectroscopic) methods to elucidate the photochemical relaxation mechanisms of 2‐(1H)‐pyrimidinone and 1‐methyl‐2‐(1H)‐pyrimidinone in aqueous solution (pH 7.4). In short, excitation at 320 nm leads to the population of the S1 1(ππ*) state with excess vibrational energy, which relaxes to the S1 1(ππ*) minimum in one picosecond or less. A trifurcation event in the S1 1(ππ*) minimum ensued, leading to radiative and nonradiative decay of the population to the ground state or the population of the long‐lived and reactive T1 3(ππ*) state in hundreds of picoseconds. Collectively, the theoretical and experimental results support the idea that in DNA and RNA, the T1 3(ππ*) state of the 2‐pyrimidinone moiety in the (6–4) lesion can further participate in photosensitized chemical reactions increasing DNA and RNA damage.
Difluorocarbene Enables Modular Synthesis of Difluoroalkylated Bicyclopentanes
Authors: Zhang Meng‐Die , Zhao Hai‐Yang , Zhang Xingang 
Published: July 2024

AbstractA straightforward method for the synthesis of difluoroalkylated bicyclopentanes (BCPs) from [1.1.1]propellane (TCP) through a stepwise procedure has been developed. This process involves nucleophilic addition of organozinc or ArMgBr reagents to TCP, followed by reaction with difluorocarbene to generate BCP substituted difluoroalkylzinc species, which subsequently couple with electrophiles, including allyl/propargyl bromides, (hetero)aryl disulfides, and proton, to provide a wide range of difluoroalkylated BCPs that otherwise are difficult to access through conventional methods. The transformations of the resulting products demonstrate the synthetic utility of this modular synthesis.
A new, high‐resolution atmospheric dataset for southern New Zealand, 2005–2020
Authors: Kropač Elena , Mölg Thomas , Cullen Nicolas J. 
Published: July 2024

AbstractThe regional climate of New Zealand's South Island is shaped by the interaction of the Southern Hemisphere westerlies with the complex orography of the Southern Alps. Due to its isolated geographical setting in the south‐west Pacific, the influence of the surrounding oceans on the atmospheric circulation is strong. Therefore, variations in sea surface temperature (SST) impact various spatial and temporal scales and are statistically detectable down to temperature anomalies and glacier mass changes in the high mountains of the Southern Alps. To enable future studies on the processes that govern the link between large‐scale SST and local‐scale high‐mountain climate, we utilized dynamical downscaling with the Weather Research and Forecasting (WRF) model to produce a regional atmospheric modelling dataset for the South Island of New Zealand over a 16‐year period between 2005 and 2020. The 2 km horizontal resolution ensures realistic representation of high‐mountain topography and glaciers, as well as explicit simulation of convection. The dataset is extensively evaluated against observations, including weather station and satellite data, on both regional (in the inner domain) and local (on Brewster Glacier in the Southern Alps) scales. Variability in both atmospheric water content and near‐surface meteorological conditions is well captured, with minor seasonal and spatial biases. The local high‐mountain climate at Brewster Glacier, where land use and topographic model settings have been optimized, yields remarkable accuracy on both monthly and daily time scales. The data provide a valuable resource to researchers from various disciplines studying the local and regional impacts of climate variability on society, economies and ecosystems in New Zealand. The model output from the highest resolution model domain is available for download in daily temporal resolution from a public repository at the German Climate Computation Center (DKRZ) in Hamburg, Germany (Kropač et al., 2023; 16‐year WRF simulation for the Southern Alps of New Zealand, World Data Center for Climate (WDCC) at DKRZ [data set]. https://doi.org/10.26050/WDCC/NZ‐PROXY_16yrWRF).
Intermolecular interaction energies with AROFRAG–A systematic approach for fragmentation of aromatic molecules
Authors: Masoumifeshani Emran , Korona Tatiana 
Published: July 2024

AbstractIntermolecular interactions with polycyclic aromatic hydrocarbons (PAHs) represent an important area of physisorption studies. These investigations are often hampered by a size of interacting PAHs, which makes the calculation prohibitively expensive. Therefore, methods designed to deal with large molecules could be helpful to reduce the computational costs of such studies. Recently we have introduced a new systematic approach for the molecular fragmentation of PAHs, denoted as AROFRAG, which decomposes a large PAH molecule into a set of predefined small PAHs with a benzene ring being the smallest unbreakable unit, and which in conjunction with the Molecules‐in‐Molecules (MIM) approach provides an accurate description of total molecular energies. In this contribution we propose an extension of the AROFRAG, which provides a description of intermolecular interactions for complexes composed of PAH molecules. The examination of interaction energy partitioning for various test cases shows that the AROFRAG3 model connected with the MIM approach accurately reproduces all important components of the interaction energy. An additional important finding in our study is that the computationally expensive long‐range electron‐correlation part of the interaction energy, that is, the dispersion component, is well described at lower AROFRAG levels even without MIM, which makes the latter models interesting alternatives to existing methods for an accurate description of the electron‐correlated part of the interaction energy.
Knowledge, perception or disaster experience? The new determinants of household disaster preparedness behaviour in Bangladesh
Authors: Karim Azreen 
Published: July 2024

AbstractThis paper explores the relationship among education, knowledge, perception and disaster experience to investigate whether household disaster preparedness behaviour mitigates income losses. We employ instrumental variables approach and generate indigenous knowledge from a large‐scale dataset to examine responsiveness of disaster preparedness via unemployment and production. We identify disaster and climate knowledge perception as new determinant towards disaster risk reduction. Our findings suggest Disaster Preparedness Index (DPI) is almost 64% effective in mitigating household per capita net income loss in comparison with the mean via unemployment channel. We argue that informal education and community‐based training could bring more efficacies in this loss mitigation mechanism.