bluuebunny/crossref_metadata_2025_split huggingface dataset:
How the planarity of two dimensional covalent organic frameworks affect gas adsorption and diffusion: A data mining, simulation, and experiment united study
Authors: Ma Xue , Yang Shuna , Ma Nan , Zhang Yuan , Ding Zijun , Pan Rongyu , Chen Guojian , Long Zhouyang , Ying Yunpan , Tong Minman 
Published: August 2024

AbstractThe planarity of two‐dimensional covalent organic frameworks (2D‐COFs) was demonstrated to show a significant and complex impact on their gas adsorption performance. However, the intrinsic mechanism underlying the intricate phenomenon remains unclear. Herein, a machine learning‐assisted data mining, simulation, and experiment combined study was performed to elucidate the complex impact of planar features of 2D‐COFs on gas adsorption and diffusion properties. A workflow was established for automatically assessing the planarity of 2D‐COFs. Compared with the flat configuration, the twisted and wavy configurations enhance the van der Waals interactions, promoting the adsorption of most nonpolar gases. Meanwhile, both the twisted and wavy configurations demonstrated an improved effect on gas diffusion. Gas adsorption and kinetic measurements on 2D‐COFs with similar physical and chemical properties but different planar features verified the theoretical finding. This work provides original insights and opens a new research paradigm for the study on the planarity of 2D‐COFs.
Platinum‐Metformin Conjugates Acting as Promising PD‐L1 Inhibitors through the AMP‐Activated Protein Kinase Mediated Lysosomal Degradation Pathway
Authors: Liu Bin , Liang Bing‐Bing , Cao Wan‐Di , Su Xu‐Xian , Cao Qian , Mao Zong‐Wan 
Published: August 2024

AbstractWith the development of metalloimmunology, the potential of platinum drugs in cancer immunotherapy has attracted extensive attention. Although immunochemotherapy combining PD‐1/PD−L1 antibodies with platinum drugs has achieved great success in the clinic, combination therapy commonly brings new problems. Herein, we have developed a platinum‐metformin conjugate as a promising alternative to antibody‐based PD−L1 inhibitors, not only disrupting PD‐1/PD−L1 axis on cell surface but also down‐regulating the total PD−L1 levels in non‐small cell lung cancer (NSCLC) cells comprehensively, thus achieving highly efficient immunochemotherapy by a single small molecule. Mechanism studies demonstrate that Pt‐metformin conjugate can selectively accumulate in lysosomes, promote lysosomal‐dependent PD−L1 degradation via the AMPK‐TFEB pathway, and modulate the upstream regulatory proteins related to PD−L1 expression (e.g. HIF‐1α and NF‐κB), eventually decreasing the total abundance of PD−L1 in NSCLC, overcoming tumor hypoxia, and activating anti‐tumor immunity in vivo. This work suggests an AMPK‐mediated lysosomal degradation pathway of PD−L1 for the first time and provides a unique design perspective for the development of novel platinum drugs for immunochemotherapy.
High‐Energy Ball Milling Enables an Ultra‐Fast Wittig Olefination Under Ambient and Solvent‐free Conditions
Authors: Templ Johanna , Schnürch Michael 
Published: August 2024

Abstract30 Seconds to success!—The Wittig reaction, a fundamental and extensively utilized reaction in organic chemistry, enables the efficient conversion of carbonyl compounds to olefins using phosphonium salts. Traditionally, meticulous reaction setup, including the pre‐formation of a reactive ylide species via deprotonation of a phosphonium salt, is crucial for achieving high‐yielding reactions under classical solution‐based conditions. In this report, we present an unprecedented protocol for an ultra‐fast mechanically induced Wittig reaction under solvent‐free and ambient conditions, often eliminating the need for tedious ylide pre‐formation under strict air and moisture exclusion. A range of aldehydes and ketones were reacted with diverse phosphonium salts under high‐energy ball milling conditions, frequently giving access to the respective olefins in only 30 seconds.
Exploring Aqueous Solution‐Processed Pseudohalide Rare‐Earth Double Perovskite Ferroelectrics toward X‐Ray Detection with High Sensitivity
Authors: Wang Chang‐Feng , Yang Ye , Hu Yu , Ma Chuang , Ni Hao‐Fei , Liu Pei‐Guo , Lu Hai‐Feng , Zhang Zhi‐Xu , Wang Jianguo , Zhang Yujian , Fu Da‐Wei , Zhao Kui , Zhang Yi 
Published: August 2024

AbstractThree‐dimensional (3D) pseudohalide rare‐earth double perovskites (PREDPs) have garnered significant attention for their versatile physical properties, including ferroelectricity, ferroelasticity, large piezoelectric responses, and circularly polarized luminescence. However, their potential for X‐ray detection remains unexplored, and the low Curie temperature (TC) limits the performance window for PREDP ferroelectrics. Here, by applying the chemical regulation strategies involving halogen substitution on the organic cation and Rb/Cs substitution to the PREDP [(R)‐M3HQ]2RbEu(NO3)6 [(R)‐M3HQ=(R)‐N‐methyl‐3‐hydroxylquinuclidinium] with a low TC of 285 K, a novel 3D PREDP ferroelectric [(R)‐CM3HQ]2CsEu(NO3)6 [(R)‐CM3HQ=(R)‐N‐chloromethyl‐3‐hydroxylquinuclidinium] are successfully synthesized, for which the TC reaches 344 K. More importantly, such a strategy endowed [(R)‐CM3HQ]2CsEu(NO3)6 with notable X‐ray detection capabilities. Centimeter‐sized [(R)‐CM3HQ]2CsEu(NO3)6 single crystals fabricated from aqueous solutions demonstrated a sensitivity of 1307 μC Gyair−1 cm−2 and a low detectable dose rate of 152 nGyair s−1, the highest sensitivity reported for hybrid double perovskite ferroelectric detectors. This work positions PREDPs as promising candidates for the next generation of eco‐friendly optoelectronic materials and also offers substantial insights into the interaction between structure, composition, and functionality in ferroelectric materials.
Ontogeny of the malleus in Mesocricetus auratus (Mammalia, Rodentia): Systematic and functional implications for the muroid middle ear
Authors: Fritzsche Franziska , Maier Wolfgang , Ruf Irina 
Published: August 2024

AbstractThe three mammalian auditory ossicles enhance sound transmission from the tympanic membrane to the inner ear. The anterior anchoring of the malleus is one of the key characters for functional classification of the auditory ossicles. Previous studies revealed a medial outgrowth of the mallear anterior process, the processus internus praearticularis, which serves as an anchor for the auditory ossicle chain but has been often missed due to its delicate nature. Here we describe the development and morphology of the malleus and its processus internus praearticularis in the cricetine rodent Mesocricetus auratus, compared to selected muroid species (Cricetus cricetus, Peromyscus maniculatus, and Mus musculus). Early postnatal stages of Mesocricetus show the formation of the malleus by fusion of the prearticular and mallear main body. The processus internus praearticularis forms an increasing broad lamina fused anteriorly to the ectotympanic in adult stages of all studied species. Peromyscus and Mus show a distinct orbicular apophysis that increases inertia of the malleus and therefore these species represent the microtype of auditory ossicles. In contrast, the center of mass of the malleus in the studied Cricetinae is close to the anatomical axis of rotation and their auditory ossicles represent the transitional type. The microtype belongs to the grundplan of Muroidea and is plesiomorphic for Cricetidae, whereas the transitional type evolved several times within Muroidea and represents an apomorphic feature of Cricetinae.
Feasibility and acceptability of a caregiver‐mediated early support program, delivered online, for infants at elevated familial likelihood for autism: A feasibility randomized controlled trial
Authors: Meera Shoba S. , Srikar Malavi , Raju Reny , Swaminathan Divya , Johnson Rachel Elizabeth , Watson Linda R. , Nair Deepa Bhat , Kommu John Vijay Sagar , Chopra‐McGowan Jo , Vasuki Prathyusha P. 
Published: August 2024

AbstractPreliminary evidence indicates potential benefit of providing caregiver‐mediated intervention, prior to diagnosis, for infants at elevated familial likelihood for autism and related developmental delays including language delay (EL‐A). However, delivering such interventions online and in low‐resource settings like India has not been reported. This study aimed to evaluate the feasibility and acceptability of delivering a novel manualized caregiver‐mediated early support program, the “LiL' STEPS,” online in India, for EL‐A infants. LiL' STEPS stands for Language development & Intervention Lab's (LiL') Supporting Early social‐communication and language by Promoting caregiver Sensitive responsiveness (STEPS). The program comprised 14 sessions with a focus on social‐communication and language, conducted over 12‐weeks using demonstration and video feedback. Families of 36 EL‐A infants aged 9 to 15‐months participated in this feasibility randomized controlled trial (RCT). Families were randomized in a 2:1 ratio (n = 24 LiL' STEPS and n = 12 care as usual groups). Information on feasibility and acceptability was collated following a mixed methods approach from caregiver interviews, fidelity forms, session notes, and study register. Findings indicated the LiL' STEPS study trial as feasible and acceptable with recruitment rate of 4 per month, 100% willingness for randomization, 8.3% attrition, and 3.03% loss of blinding. Interventionist and caregiver fidelity was maintained above 80%. Despite challenges like interruptions during sessions, 100% families found the program acceptable and satisfactory, 86% said they would recommend the program to others, and 71% preferred online modality. Caregivers' perspectives on beneficial components and experience attending the program have been described. Accordingly, recommendations for future definitive RCTs have been presented.
Implementing circular business models for the second‐life battery of electric vehicles: Challenges and enablers from an ecosystem perspective
Authors: Toorajipour Reza , Chirumalla Koteshwar , Johansson Glenn , Dahlquist Erik , Wallin Fredrik 
Published: August 2024

AbstractThis study adopts an ecosystem perspective to provide a detailed understanding of key challenges and enablers for implementing circular business models for electric vehicle battery second life. Although academia and practitioners believe electric vehicle (EV) batteries' second life is a potential solution, the commercial implementations are still far away. A crucial step toward such implementations is to identify the key challenges and enablers of circular business models. The criticality of this step is even more evident when approaching second life business models from an ecosystem perspective, where multiple stakeholders are involved in the creation, capture, and delivery of value. This research conducts an explorative study with 15 companies in the EV battery ecosystem and identifies nine categories of key challenges and seven categories of key enablers. Based on priority dimensions (short/long term) and the responsible entity (firm/ecosystem related), the study proposes a guiding framework to address challenges and enablers. The study contributes to the circular business model innovation and ecosystems literature related to the EV battery second life.
Synthesis, Anti‐Oomycete and Anti‐Fungal Activities of Anhydride Derivatives of Oleanolic Acid
Authors: Wang Ruiguang , Li Yuanhao , Yin Wanying , Sun Huilu , Xu Shaobin , Shuang Shaoyan , Tian Yuee , Huang Xiaobo , Chen Genqiang , Che Zhiping 
Published: August 2024

AbstractOleanolic acid is a pentacyclic triterpenoid extracted and isolated from the fruit of plants in the Ligustrum lucidum Ait. in the family Oleaceae. To discover biorational natural product‐based pesticides, a series of oleanolic acid derivatives containing anhydride active skeletons were prepared by ingeniously introducing an active acyloxy group at its C‐28 carboxyl position, and their structures were well characterized by 1H‐NMR, 13C NMR, HRMS, and m.p. The stereochemical configuration of compound 8 e was confirmed using single‐crystal X‐ray diffraction. Furthermore, bioactivities of these compounds as anti‐oomycete and anti‐fungal agents against two serious agricultural pests, Phytophthora capsici (P. capsici) and Fusarium graminearum (F. graminearum) we assessed. Amongst evaluated compounds, 1) Compounds 8 h and 8 j displayed significant anti‐oomycete against P. capsici, with EC50 values of 54.73 and 65.15 mg/L, respectively. 2) The target compounds have obvious selectivity, and their anti‐oomycete activity is significantly better than their anti‐fungal activity. 3) Interestingly, there are significant differences in the structure‐activity relationship of different substituents or the same substituent at different positions anti‐oomycete and anti‐fungal against P. capsici and F. graminearum, respectively. The study provides an idea for further exploring the bioactivities of 28‐acyloxyoleanolic acid derivatives, and develops the application of 28‐acyloxyoleanolic acid derivatives containing anhydride in agriculture.
On‐Purpose Production of Light Olefins Through Oxidative Dehydrogenation: An Overview of Recent Developments
Authors: Mukherjee Arpan , Samanta Chanchal , Bordoloi Ankur 
Published: August 2024

AbstractProducts made from light olefins play an important role in our daily lives. Traditional light olefins production based on steam cracking and fluid catalytic cracking suffer from high energy consumption and CO2 emissions. Thereby, the continually increasing demand for light olefins needs to be met through more environmentally sustainable procedures. On‐purpose production routes are preferred choice among petrochemicals manufacturers, being energy efficient and having lower carbon footprint. Among them, oxidative dehydrogenation (ODH) of light paraffins is a thermodynamically favourable exothermic process as compared to non‐oxidative routes. They can be operated at lower temperatures and have propensity of low coke deposition on catalyst, thereby resisting rapid catalyst deactivation. Herein, we have analysed various catalytic systems utilised in the oxidative dehydrogenation process. We have reviewed role of support, chemical composition of catalyst, presence of dopant, oxidation state of active metal, controlled surface modification by oxidative and reductive pretreatments, and reaction factors for each system. The performance of various catalytic systems for ODH of ethane, propane and butane in the presence of O2, CO2, N2O and special oxidants have been reviewed. A short critical overview on emerging on‐purpose routes for the production of renewable 1,3 butadiene has also been discussed.
Plant health effects of fungicides alone and in combination with plant growth regulator on improving summer turf performance in annual bluegrass
Authors: McBride Sean , Murphy James A. , Huang Bingru 
Published: August 2024

AbstractAnnual bluegrass (Poa annua L.) is sensitive to high‐temperature stress, and approaches that can improve plant growth during summer months are important for golf courses managing P. annua putting greens. The objective of this 2‐year field trial was to determine plant health benefits for selected fungicides and the combination with a plant growth regulator (PGR), trinexapac‐ethyl (TE) on P. annua growth under putting green conditions during summer months. The following treatments were foliar sprayed at 14‐day intervals from June to September in 2020 and 2021: (1) untreated control with water, (2) Daconil Action, (3) Appear II, (4) Daconil Action and Appear II, and (5) Daconil Action, Appear II, and Primo Maxx (TE). Applying individual and combination treatments resulted in significant improvements on P. annua summer performance, as manifested by increased visual turf quality and other vegetation indices evaluated using multispectral radiometer (normalized difference vegetation index, leaf area index, and stress index or digital camera [percent canopy cover and dark green color index]) in both years. The combined treatment programs, Daconil Action and Appear II or Daconil Action, Appear II, and Primo Maxx were more effective than the untreated control and each individual treatment. The results suggest that there existed synergistic effects of multiple fungicides and PGR, which could be particularly useful in promoting plant health of P. annua under heat stress conditions.
Two‐Coordinate Dinuclear Donor‐Gold(I)‐Acceptor Complexes Exhibiting Multiple Excitation Wavelength Dependent Phosphorescence
Authors: Xiong Jinfan , Song Jia‐Xi , Chang Xiaoyong , Song Xiu‐Fang , Li Kai , Chen Yong 
Published: August 2024

AbstractTwo‐coordinate Au(I) complexes with a donor‐metal‐acceptor (D‐M‐A) structure have shown rich luminescent properties. However, charge‐neutral dinuclear donor‐metal‐acceptor type Au(I) complexes featuring aurophilic interactions have been seldom explored. Herein, we describe the structures and photoluminescence properties of two dinuclear Au(I) complexes, namely DiAu‐Ph and DiAu‐Me. Single crystal X‐ray structural analysis of DiAu‐Ph reveals a short intramolecular Au‐Au distance of 3.224 Å. In dilute solution and doped films, excitation wavelength dependent multiple phosphorescence phenomena were observed for these dinuclear complexes. Theoretical calculations reveal that the aurophilic interaction causes increased contribution of the Au d orbital to the highest occupied molecular orbitals. Thus, the gap between singlet and triplet excited states (ΔEST) is enlarged, which disables the thermally activated delayed fluorescence (TADF). Moreover, the large energy separation (0.45–0.52 eV) and the different orbital configurations between the various excited states result in an inefficient internal conversion, accounting for their multiple phosphorescence properties.
Pd/C–Catalyzed Selective N‐Monomethylation by Transfer Hydrogenation of Urea Derivatives using Methanol as H2 and C1 Sources
Authors: Kamaraj Kiruthigadevi , H. Dixneuf Pierre , Sundaram Ganesh Babu , Reek Joost N. H. , Beromeo Bheeter Charles 
Published: August 2024

AbstractN‐monomethyl amines are useful intermediates in drugs, natural products, paints. Yet their synthesis is a tremendous challenge due to their high reactivity, typically leading to overmethylation. In this contribution, a highly selective catalytic N‐methylation methodology is reported, converting urea derivatives to monomethylated amines, using a commercially available heterogeneous Pd/C catalyst and methanol as unique reagent. Methanol provides a sustainable alternative protocol for the selective preparation of mono‐methylated derivatives as it acts as both H2 and C1 sources. In addition, several control experiments were performed to provide a proposal for the mechanism, namely dehydrogenation of methanol and subsequent hydrogenation of urea derivatives, followed by reduction of the in situ formed methyl imine. Importantly, the approach is simple, highly productive and enables novel synthetic procedures for the preparation of monomethylamines from urea derivatives.
Amplifying Reactivity of Bio‐Inspired [FeFe]‐Hydrogenase Mimics by Organic Nanotubes
Authors: Ahmed Md Estak , Das Puspendu , Ahamed Sk Mustak , Chattopadhyay Samir , Nayek Abhijit , Mondal Mintu , Malik Sudip , Dey Abhishek 
Published: August 2024

AbstractA bio‐inspired FeFe hydrogenase model which catalyses hydrogen evolution reaction (HER) in acidic solutions is immobilized in polyaniline (PANI)‐based nanotubes. A combination of analytical techniques reveals that this construct maintains both the molecular signatures of the bio‐inspired complex and the material properties of PANI. The amine and imine‐rich environment of the PANI chain amplifies the inherent HER activity of the bio‐inspired complex, allowing electrocatalytic HER at neutral pH, with lower overpotentials and higher current densities compared to the bio‐inspired complex alone. This construct retains the oxygen stability of the bio‐inspired complex and remains stable through several hours of aerobic electrolysis, producing only 6.5 % H₂O₂ from the competing oxygen reduction reaction (ORR).
Synthesis, Reactivity, and Bonding Analysis of a Tetracoordinated Nickel Carbene
Authors: Pérez‐García Pablo M. , Sansores‐Paredes María L. G. , Fonseca Guerra Célia , Vermeeren Pascal , Moret Marc‐Etienne 
Published: August 2024

AbstractNickel carbenes are key reactive intermediates in the catalytic cyclopropanation of olefins and other reactions, but isolated examples are scarce and generally rely on low coordination numbers (≤3) to stabilize the metal−ligand multiple bond. Here we report the isolation and characterization of a stable tetracoordinated nickel carbene bearing a triphosphine pincer ligand. Its nucleophilic character is evidenced by reaction with acids, and it can transfer the carbene fragment to CO to form a ketene. A computational study of the Ni=C chemical bond sheds light on the role of the third phosphine in the pincer framework to the stabilization of the nickel carbene fragment.
“Catch the CO2” – Carbon dioxide absorption in a school experiment as an example for gas absorption experiments in the classroom
Authors: Mauch Julian , Rubner Isabel 
Published: August 2024

AbstractDie Absorption von Kohlenstoffdioxid (CO2) ist aus nachhaltigen Gründen von großer Bedeutung. In diesem Experiment wird der Prozess anschaulich dargestellt, wobei relevante Einflussfaktoren berücksichtigt werden. Ein neu entwickeltes Messsystem ermöglicht es Schüler:innen, den Absorptionsvorgang von CO2 aus der Luft eigenständig durchzuführen und quantitativ zu erfassen. Dabei werden Parameter chemischer Reaktionen, wie der Einfluss von Temperatur und Konzentration, untersucht. Durch den Vergleich dieser Faktoren und deren Auswirkungen auf die Reaktionsgeschwindigkeit werden die Einflussfaktoren bei chemischen Gleichgewichtsreaktionen behandelt. Zur präzisen Messung wird ein hochwertiger CO2‐Sensor verwendet, dessen Auswerteelektronik als Bausatz selbst angefertigt werden kann. Die Auswertung der Messdaten erfolgt über ein Tabellenkalkulationsprogramm. Dieses Experiment und die Sensorik verdeutlichen das interdisziplinäre Arbeiten zwischen den Fächern Naturwissenschaft und Technik (NwT) sowie Chemie.