bluuebunny/crossref_metadata_2025_split huggingface dataset:
Sequence‐Defined Synthesis Enabled by Fast and Living Anionic Monoaddition of Vinyl Monomers
Authors: Okamoto Kazuhiro , Yoo Dong‐eun , Yoshioka Rikako , Nakasato Ryohei , Ashikari Yosuke , Kitayama Kenji , Nagaki Aiichiro 
Published: October 2024

AbstractThe selective monoaddition of polymerizable vinyl monomers like styrenes and methacrylates in a living manner has been achieved for the flash‐flow preparation of molecules in a defined sequence with high selectivity. We demonstrated the sequence‐defined synthesis of multifunctional molecules using an initiator, functionalized styrenes, diarylethylenes, various methacrylates, and an electrophilic trapping reagent at the living terminus (six‐component sequential connection at maximum) without any intermediate purification steps. The anionic living terminus of the vinyl monomers in the flow system described herein is active for polymerization, such that the styrene or methacrylate sequence can be expanded to afford highly dispersed oligomers without affecting other single units, which means that the unequivocal sequences were successfully inserted into the internal or terminal positions. The methodology described herein provides an adaptable method for the construction of new molecular spaces based on unimolecular sequence control and pinpoint functionalization.
Dual Signature of Chirality Induced Spin Selectivity through Spontaneous Resolution of 2D Metal–Organic Frameworks
Authors: Garg Rabia , Bisht Pravesh Singh , Sahoo Subash Chandra , Mondal Amit Kumar 
Published: October 2024

AbstractThe Chiral‐Induced Spin Selectivity (CISS) effect has emerged as a fascinating phenomenon within the realm of electron's spin manipulation, showcasing a unique interplay between electron's spin and molecular chirality. Subsequent to its discovery, researchers have been actively involved in exploring the new chiral molecules as effective spin filters. In the realm of observing the CISS effect, the conventional approach has mandated the utilization of two distinct enantiomers of chiral molecules. However, this present study represents a significant advancement by demonstrating the ability to control both spin states of electrons in a single system. In this work, we have demonstrated the preparation of chiral metal–organic frameworks (MOFs) via a “spontaneous resolution” process, obviating the requirement for chiral sources. This resulted in the production of chiral crystals exhibiting opposite handedness (1P and 1M) and these crystals were subsequently employed as a new class of spin filters based on CISS effect. Remarkably, this work signifies the first instance of achieving dual signature of spin selectivity from a single and exclusively achiral system through a spontaneous resolution process. This holds immense potential as it facilitates the production of two distinct spin‐filtering materials from a unified system. Furthermore, we investigated the contact potential differences (CPD) of these chiral crystals and, for the first time, associated it with the preferential spin transport properties. Our findings revealed a correlation between the CPD and the chirality of the crystals, as well as the magnetization orientations of the ferromagnetic substrate, which can be elucidated by the CISS effect. In overall, the significant findings achieved using these robust and easily synthesized MOF crystals without the requirement for chiral medium represent a crucial advancement in enhancing the effectiveness of spin filtering materials to produce spintronic devices.
Photochemical Deracemization of N‐Carboxyanhydrides En Route to Chiral α‐Amino Acid Derivatives
Authors: Iglhaut Maximilian , Freund Philip , Bach Thorsten 
Published: October 2024

AbstractReadily accessible, racemic N‐carboxyanhydrides (NCAs) of α‐amino acids underwent a deracemization reaction upon irradiation at λ=366 nm in the presence of a chiral benzophenone catalyst. The enantioenriched NCAs (up to 98 % ee) serve as activated α‐amino acid surrogates and, due to their instability, they were directly converted into consecutive products. N‐Protected α‐amino acid esters were obtained after reaction with MeOH and N‐benzoylation (14 examples, 70 %‐quant., 82–96 % ee). Other consecutive reactions included amide (ten examples, 65 %‐quant., 90–98 % ee) and peptide (three examples, 75–89 %, d. r.=97/3 to 94/6) bond formation. Limitations of the method relate for some NCAs to issues with solubility, photooxidation, and high configurational lability.
Scalable Electro‐Biosynthesis of Ectoine from Greenhouse Gases
Authors: Guo Shuqi , Li Chengbo , Su Yuehang , Huang Xiaohan , Zhang Chenyue , Dai Yizhou , Ji Yuan , Fu Rongzhan , Zheng Tingting , Fei Qiang , Fan Daidi , Xia Chuan 
Published: October 2024

AbstractConverting greenhouse gases into valuable products has become a promising approach for achieving a carbon‐neutral economy and sustainable development. However, the conversion efficiency depends on the energy yield of the substrate. In this study, we developed an electro‐biocatalytic system by integrating electrochemical and microbial processes to upcycle CO2 into a valuable product (ectoine) using renewable energy. This system initiates the electrocatalytic reduction of CO2 to methane, an energy‐dense molecule, which then serves as an electrofuel to energize the growth of an engineered methanotrophic cell factory for ectoine biosynthesis. The scalability of this system was demonstrated using an array of ten 25 cm2 electrochemical cells equipped with a high‐performance carbon‐supported isolated copper catalyst. The system consistently generated methane at the cathode under a total partial current of approximately −37 A (~175 mmolCH4 h−1) and O2 at the anode under a total partial current of approximately 62 A (~583 mmolO2 h−1). This output met the requirements of a 3‐L bioreactor, even at maximum CH4 and O2 consumption, resulting in the high‐yield conversion of CO2 to ectoine (1146.9 mg L−1). This work underscores the potential of electrifying the biosynthesis of valuable products from CO2, providing a sustainable avenue for biomanufacturing and energy storage.
Zipper‐Like Dynamic Switching of Coordination Bonds Gives a Polar Bimetallic Halide Toward Self‐Driven X‐Ray Detection
Authors: Li Wenjing , Ma Yu , Liu Yi , Fan Qingshun , Xu Haojie , Guo Wuqian , Tang Liwei , Rong Hao , Sun Zhihua , Luo Junhua 
Published: October 2024

AbstractPolar molecular crystals hold a promise for controlling bulk physical properties originated in their unique switchable polarity via structural transformation. However, the mechanisms for switching polarization are mainly limited to displacive and disorder‐order phase transitions, which rarely involve the reconstruction of chemical bonds. Here, we have switched and tuned electric polarization in a bimetallic halide, (Neopentylammonium)4AgBiBr8 (1), as verified by light‐excited pyroelectric effect. Most notably, its Ag−Br coordination bonds show a zipper‐like dynamic switching behavior from the ‘locked’ to ‘unlocked’ state, namely, reconstruction of chemical bonds. Coupling with the dynamic ordering of organic cations, this bond‐switching transition makes a contribution to switchable polarization of 1. As expected, its polarity creates pyroelectric effect for self‐driven X‐ray detection with high sensitivity (3.8×103 μC Gy−1 cm−2) and low limit of detection (4.8 nGy s−1). This work on the bond‐switching mechanism provides an avenue to design polar molecular candidate for smart optoelectronic devices.
Fe‐Catalyzed α‐C(sp3)−H Amination of N‐Heterocycles
Authors: Geraci Andrea , Baudoin Olivier 
Published: October 2024

AbstractNitrogen‐heterocycles are privileged structures in both marketed drugs and natural products. On the other hand, C−H amination reactions furnish unconventional and straightforward approaches for the construction of C−N bonds. Yet, most of the known methods rely on precious metal catalysts. Herein we report a site‐selective intermolecular C(sp3)−H amination of N‐heterocycles, catalyzed by inexpensive FeCl2, which allows the functionalization of a wide range of pharmaceutically relevant cyclic amines. The C−H amination occurs site‐selectively in α‐position to the nitrogen atom, even when weaker C−H bonds are present, and furnishes Troc‐protected aminals or amidines. The method employs the N‐heterocycle as limiting reagent and is applicable to the late‐stage functionalization of complex molecules. Its synthetic potential was further illustrated through the derivatization of α‐aminated products and the application to a concise total synthesis of the reported structure for senobtusin. Mechanistic studies allowed to propose a plausible reaction mechanism involving a turnover‐limiting Fe‐nitrene generation followed by fast H atom transfer and radical rebound.
Independent LUMO Reactivity in Mesoionic N‐Heterocyclic Thiones: Synthesis of a Stable Radical Anion
Authors: Maji Subir , Gope Biplab , Sharma Madhur , Das Arpan , Jose Anex , Biswas Amit , Bhattacharyya Kalishankar , Mandal Swadhin K. 
Published: October 2024

AbstractMesoionic compounds, with positive and negative charges, are expected to have dual‐site highest occupied molecular orbital (HOMO, donor) and lowest unoccupied molecular orbital (LUMO, acceptor) reactivity. Herein, we report a novel class of air‐stable mesoionic N‐heterocyclic thiones (mNHTs) synthesized from abnormal N‐heterocyclic carbenes (aNHCs). DFT studies revealed a highly polarized exocyclic thione moiety and computed Fukui function analysis suggests the dual‐site HOMO/LUMO reactivity of mNHTs predicting donor property at the negatively charged ‘S’ center while acceptor property at the cationic imidazole ring. The independent LUMO reactivity of the mNHT was realized by its chemical reduction to an elusive radical anion, which was characterized by a single crystal X‐raydiffraction study. Further, we explore the reactivity of radical anion for the activation of SO2 gas, C−Br bonds of aryl bromide and photocatalytic functionalization of C−X (X = F, Br) bonds. This work unlocks the independent LUMO reactivity of a mesoionic compound.
Vinylene‐Linking of Polycyclic Aromatic Hydrocarbons to π‐Extended Two‐Dimensional Covalent Organic Framework Photocatalyst for H2O2 Synthesis
Authors: Chi Xu , Zhang Zixing , Li Mengqi , Jiao Yang , Li Xiaomeng , Meng Fancheng , Xue Bai , Wu Dongqing , Zhang Fan 
Published: October 2024

AbstractPolycyclic aromatic hydrocarbons (PAHs) hold the predominant role either as individual molecules or building blocks in the field of organic semiconductors or nanocarbons. Connecting PAHs via sp2‐carbon bridges to form high‐crystalline π‐extended structures is highly desired not only for enlarging the regimes of two‐dimensional materials but also for achieving exceptional properties/functions. In this work, we developed 5,10‐dimethyl‐4,9‐diazapyrene as a key monomer, whose two methyl groups at the positions adjacent to nitrogen atoms, can helpfully increase the solubility, and serve as the active connection sites. In the presence of organic acids, this monomer enables smoothly conducting Knoevenagel condensation to form two vinylene‐linked PAH‐cored COFs, which show high‐crystalline honeycomb structures with large surface areas up to 1238 m2 g−1. Owing to the direct connection mode of PAH building blocks with vinylene, the as‐prepared COFs possess spatially extended π‐conjugation and substantial semiconducting properties. Consequently, their visible‐light photocatalysis with exceptional activity and durability was manifested to generate H2O2 up to 3820 μmol g−1 h−1 in pure water, and even 17080 μmol g−1 h−1 using benzyl alcohol as a hole sacrificial agent.
Synthesis and DFT Calculation of Hg2+ Fluorescence Chemosensor Based on a New Hybrid Organic–Inorganic Nanoporous Material of SBA‐Pr‐Is‐Hy
Authors: Panahande Zahra , Mohammadi Ziarani Ghodsi , Feizi‐Dehnayebi Mehran , Badiei Alireza , Abu‐Dief Ahmed M. 
Published: October 2024

ABSTRACTIn this study, a new hybrid organic–inorganic nanoporous material of SBA‐Pr‐Is‐Hy was synthesized by modification of SBA‐15 with (3‐chloropropyl)triethoxysilane to get SBA‐Pr‐Cl, which was reacted with isatin hydrazone to obtain SBA‐Pr‐Is‐Hy. This new compound was characterized by different FT‐IR, TGA, SEM, EDX, XRD, and BET techniques. Fluorescence spectroscopy of SBA‐Pr‐Is‐Hy was studied. According to the results, it can detect the Hg2+ ion with a detection limit of 3.5 × 10−7 M among the other metal cations. Hg2+ ion is toxic and dangerous; it is very important to identify it with simple and efficient methods. DFT calculations, including molecular electrostatic potential (MEP) surface, geometry optimization, HOMO–LUMO analysis, and quantum chemical descriptors, were investigated utilizing the B3LYP/6‐311G(d,p)/LANL2DZ method. The DFT calculation verifies the experimental mechanism of interaction between the ligand and Hg2+.
Tin(IV) Complexes With 2‐Formylpyridine Thiosemicarbazones: Structural and Cytotoxic Activity Studies on Bacterial, Fungal, and Cancer Cells
Authors: Ibrahim Ahmed B. M. , Cordes David B. , Slawin Alexandra M. Z. , Abbas S. M. 
Published: October 2024

ABSTRACTTin complexes, Sn(IV)‐TSC 1·MeOH and Sn(IV)‐TSC 2, with thiosemicarbazones possessing an N2S ligation system [TSC 1 = 4‐(4‐nitrophenyl)‐1‐((pyridin‐2‐yl)methylene)thiosemicarbazide and TSC 2 = 4‐(2‐methoxyphenyl)‐1‐((pyridin‐2‐yl)methylene)thiosemicarbazide] were prepared and structurally characterized. These complexes are found in the space groups P and P21/n, respectively, with their tin atoms in octahedral environments established by three chlorine atoms and an anionic thiosemicarbazone ligand. All compounds (20 mg/mL in DMSO) were tested for their antibacterial [against Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa] and antifungal [against Aspergillus flavus and Candida albicans] properties. The ligand TSC 2 displayed inhibitions in the S. aureus and E. coli cultures (with zones of 11 and 10 mm, respectively), whereas Sn(IV)‐TSC 1·MeOH and Sn(IV)‐TSC 2 inhibited all bacteria with 11–15 and 14–16 mm, respectively. In the fungal cultures, only Sn(IV)‐TSC 1·MeOH (10 mm) showed an inhibition zone against A. flavus. The ligands' antiproliferative activities were determined against human cancer cells of the lung, breast, liver, and colon, and both ligands afforded the highest activity against the breast MCF‐7 cells. The complexation enhanced the ligands' activities as TSC 1, TSC 2, Sn(IV)‐TSC 1·MeOH, and Sn(IV)‐TSC 2 afforded respective IC50 values of 52.4, 153.7, 18.3, and 63.9 μM. However, against normal baby hamster kidney (BHK) cells, these compounds showed IC50 data of 54.8, 82.7, 16.1, and 15.3 μM, respectively.
A new parasite discovery in Micronesia: eggs of the nematodeToxocara canisat archaeological sites on Ebon Atoll, Marshall Islands extend the known dog presence by c.600 years
Authors: Horrocks Mark , Weisler Marshall I. , Hua Quan , Presswell Bronwen 
Published: October 2024

ABSTRACTLittle is known of helminth parasites in Micronesia in archaeological contexts. This study presents a parasitological analysis of soil and sediment samples from Ebon Atoll in the Marshall Islands, eastern Micronesia. Microscopic eggs of the dog (Canis lupus familiaris) nematodeToxocara canis, which could have adversely affected the health of local people as well as their dogs, were found at two sites, in one example in habitation layers dated to 1830–1625 calBP (95% CI), extending the date for the known presence of dogs in the Marshall Islands by at least 600 years. This study represents the first confirmed evidence of pre‐European helminth parasites in Micronesia. As similar Melanesian and Polynesian studies have previously been reported, the study also completes the initial, pre‐contact helminth record for the three main island regions of Oceania.
The Duck 1000 Genomes Project: Achievements and perspectives
Authors: Fan Wenlei , Hou Shuisheng , Zhou Zhengkui 
Published: October 2024

AbstractThe duck (Anas platyrhynchos) is not only a vital farm animal but also an excellent model for genetic dissection of economic traits. The integration of multiomics data provides a powerful approach to elucidate the genetic basis of domestication and phenotype variation. Since its inception in 2014, the Duck 1000 Genomes Project has aimed to uncover the genetic foundation of key economic traits in ducks by combining multiomics data including genomic, transcriptomic, and metabolomic from various natural and segregating populations. This paper summarizes the strategies and achievements of the Duck 1000 Genomes Project, highlighting the reference genome assembly, genome evolution analysis, and the identification of genes and causative mutations responsible for key economic traits in ducks. We also discuss perspectives and potential challenges in functional genomic studies that could further accelerate duck molecular breeding.
A slide into obscurity? The current state of histology education in Australian and Aotearoa New Zealand medical curricula in 2022–2023
Authors: Meyer Amanda J. , Chapman Jamie A. 
Published: October 2024

AbstractAustralia and Aotearoa New Zealand (AANZ) medical schools have been impacted by curricular changes and the introduction of virtual microscopy (VM). No survey has explicitly described the outcome of these events on histology education in AANZ. This study provides a cross‐sectional overview of histology education in accredited medical schools across AANZ in 2022–2023. Responses were received from 83% (19/23) of Australian medical schools, and 50% (1/2) of medical schools in Aotearoa New Zealand. VM, either exclusively (42%) or combined with traditional microscopy (37%), emerged as the preferred mode for delivering histology education. Common instructional methods included face‐to‐face lectures (26%) and synchronous online live lectures (26%). A significant proportion (84%) of educators supplemented resources with virtual microscopy websites. Integration of histology education was prevalent (79%), primarily with pathology (32%) or gross anatomy (26%). On average, medical students in the region spent a maximum of 21 ± 17 h in face‐to‐face histology laboratories throughout their degree. Histology education was predominantly taught by academics with a PhD degree. This study also examined the similarities and differences in histology education between AANZ and the global landscape. Through this examination, the present study positions AANZ within the broader context of histology education worldwide discusses key factors impacting histology education, and advocates for action to mitigate a looming shortage of pathologists in AANZ. In light of these findings, AANZ medical schools should integrate histology and pathology, establish a core curriculum, and promote flexible teaching modalities.
3D Ternary Hybrid of VSe2/e‐MXene/CNT with a Promising Energy Storage Performance for High Performance Asymmetric Supercapacitor
Authors: Siddu Pavithra , K A Sree Raj , Radhakrishnan Sithara , Mun Jeong Sang , Sekhar Rout Chandra 
Published: October 2024

AbstractMXene and TMDs are two of the emerging electrode materials for supercapacitors owing to their unique physicochemical properties such as high conductivity, large surface area, and rich redox active sites. However, sheet restacking, volume expansion and oxidation hinder these materials from being used in practical applications. In this work, a 3D ternary hybrid structure of metallic VSe2, Ti3C2Tx MXene and carbon nanotube was designed to address some of the challenges in 2D materials‐based electrodes for supercapacitor application. The exfoliated MXene and CNT decorated VSe2 3D structure showed excellent synergy between each component to deliver promising energy storage and cycling performance. The ternary hybrid structure also can suppress the surface oxidation of MXene sheets during the hydrothermal reaction. Furthermore, an asymmetric supercapacitor fabricated with VSe2/e‐MXene/CNT and MoS2/MXene delivered the highest energy density of 35.91 Wh/kg at a power density of 1280 W/kg and a remarkable cycle life.
Reshaping the substrate‐binding pocket of acyl‐ACP reductase to enhance the production of sustainable aviation fuel in Escherichia coli
Authors: Han Jiahu , Matsumoto Takuya , Yamada Ryosuke , Ogino Hiroyasu 
Published: October 2024

AbstractTo reduce carbon emissions and address environmental concerns, the aviation industry is exploring the use of sustainable aviation fuel (SAF) as an alternative to traditional fossil fuels. In this context, bio‐alkane is considered a potentially high‐value solution. The present study focuses on the enzymes acyl‐acyl carrier protein [ACP] reductase (AAR) and aldehyde‐deformylating oxygenase (ADO), which are crucial enzymes for alka(e)ne biosynthesis. By using protein engineering techniques, including semi‐rational design and site‐directed mutagenesis, we aimed to enhance the substrate specificity of AAR and improve alkane production efficiency. The co‐expression of a modified AAR (Y26G/Q40M mutant) with wild‐type ADO in Escherichia coli significantly increased alka(e)ne production from 28.92 mg/L to 167.30 mg/L, thus notably demonstrating a 36‐fold increase in alkane yield. This research highlights the potential of protein engineering in optimizing SAF production, thereby contributing to the development of more sustainable and efficient SAF production methods and promoting greener air travel.
The challenges that remain: The role of innovation intermediary‐led training in implementing circular business models
Authors: Hartmann Marie Luise Elisabeth , Long Thomas B. 
Published: October 2024

AbstractCircular business model innovation is critical in the transition to the circular economy, often requiring businesses to undergo significant internal changes. One intervention to better support businesses in this process is circularity training, often provided by an innovation intermediary. However, little is known of the impact on internal barriers and drivers for circular business model innovation after circularity training has been completed.This research tackles this question through a qualitative exploratory approach, using a multiple‐case study, collecting semi‐structured data from businesses after their completion of a circular training course. We find that even after the circular training, a range of barriers continue to influence circular business model innovation, including issues related to the availability of resources, company acceptance, and technology.The research concludes with recommendations for future training programs and the role of innovation intermediaries, based on the internal barriers and drivers that the companies encountered when working toward circularity implementation and circular business model innovation.