bluuebunny/crossref_metadata_2025 huggingface dataset:
Ethers as Building Blocks for the Synthesis and Modification of N‐Heterocycles
Authors: Grishin Sergey S. , Mulina Olga M. , Lv Leiyang , Vil Vera A. , Li Zhiping , Terent'ev Alexander O.
Published: October 2024

The use of C−H compounds as reactive partners in a variety of transformations represents the state of the art in synthetic methodology. In this review, we have summarized the main achievements in using ethers as building blocks for the construction and modification of one of the basic platforms of organic chemistry, nitrogen‐containing heterocycles. Ethers, previously considered mainly as solvents, are excellent CH‐partners, capable of generating radical or cationic reactive species under the action of HAT agents and oxidants. The challenge in this field is the still limited number of heterocyclic systems and other starting reagents, with which the processes can be carried out selectively due to closer bond dissociation energies and oxidation potentials of heterocycles, reactive intermediates and ethers. However, the fine‐tuning of the reaction system using electro‐ and photochemical approaches and a deep understanding of the reaction pathways make the use of ethers as C−H reagents a promising synthetic strategy.
Artificial intelligence–assisted oculo‐gait measurements for cognitive impairment in cerebral small vessel disease
Authors: Chen Huimin , Du Hao , Yi Fang , Wang Tingting , Yang Shuo , Pan Yuesong , Yan Hongyi , Liu Dandan , Zhou Mengyuan , Chen Yiyi , Zhao Mengxi , Pi Jingtao , Yang Yingying , Fan Xiangmin , Cai Xueli , Qiu Ziyu , Zhang Jipeng , Liu Yawei , Gu Wenping , Wang Yilong
Published: October 2024

INTRODUCTION

Oculomotor and gait dysfunctions are closely associated with cognition. However, oculo‐gait patterns and their correlation with cognition in cerebral small vessel disease (CSVD) remain unclear.

METHODS

Patients with CSVD from a hospital‐based cohort (n = 194) and individuals with presumed early CSVD from a community‐based cohort (n = 319) were included. Oculo‐gait patterns were measured using the artificial intelligence (AI) –assisted ‘EyeKnow’ eye‐tracking and ‘ReadyGo’ motor evaluation systems. Multivariable linear and logistic regression models were employed to investigate the association between the oculo‐gait parameters and cognition.

RESULTS

Anti‐saccade accuracy, stride velocity, and swing velocity were significantly associated with cognition in both patients and community dwellers with CSVD, and could identify cognitive impairment in CSVD with moderate accuracy (area under the curve [AUC]: hospital cohort, 0.787; community cohort, 0.810) after adjusting for age and education.

DISCUSSION

The evaluation of oculo‐gait features (anti‐saccade accuracy, stride velocity, and swing velocity) may help screen cognitive impairment in CSVD.

Highlights

Oculo‐gait features (lower anti‐saccade accuracy, stride velocity, and swing velocity) were associated with cognitive impairment in cerebral small vessel disease (CSVD).

Logistic model integrating the oculo‐gait features, age, and education level moderately distinguished cognitive status in CSVD.

Artificial intelligence–assisted oculomotor and gait measurements provide quick and accurate evaluation in hospital and community settings.
Li2MoO4 Tailored Anion‐enhanced Solvation Sheath Layer Promotes Solution‐phase Mediated Li‐O2 Batteries
Authors: Zhang Fengling , Hu Zhengqiang , Lai Jingning , Faiza Arshad , Hu Xin , Sun Wen , Zhou Anbin , Wang Huirong , Chen Yi , Xue Tianyang , Ye Yusheng , Chen Nan , Li Li , Wu Feng , Chen Renjie
Published: October 2024

The high overpotential of Li‐O2 batteries (LOBs) is primarily triggered by sluggish charge transfer kinetics at the reaction interfaces. A typical LiBr redox mediator (RM) catalyst can effectively reduce the battery's overpotential. However, it is prone to shuttling and corroding the Li anode, leading to RM loss and reduced energy efficiency. To address these challenges, we introduced Li2MoO4 into the LiBr‐containing electrolyte to promote the solution‐phase mediated LOBs. This addition tailors the anion‐enhanced Li+ solvation sheath layer and forms a robust anion‐derived solid electrolyte interphases (SEI) on the Li anode. The robust SEI effectively mitigates the corrosion of soluble Br3−/Br2 and attacks by highly reactive oxygen species. Additionally, the dispersed and high‐density Li2MoO4 exhibits strong adsorption capabilities for O2/LiO2 and Br‐related species during the discharge/charge process, thereby promoting the growth and decomposition of Li2O2 in the solution phase and inhibiting the shuttle effect of Br‐related species in LOBs. Consequently, the LOBs demonstrate exceptional cycling stability (415 cycles) and high energy efficiency (86.2 %), paving the way for the sustainable development and practical application of these battery systems.
Organic Room Temperature Phosphorescence from BN‐Substituted Xanthene Derivatives
Authors: Watson Alexander E. R. , Tao Si Yuan , Siemiarczuk Alex , Boyle Paul D. , Ragogna Paul J. , Gilroy Joe B.
Published: October 2024

Emissive organic materials are predominantly fluorescent and there is significant interest in realizing and understanding examples that defy this paradigm and exhibit phosphorescence under ambient conditions. Organic room temperature phosphorescence (ORTP) offers the long‐lived excited states and bathochromically‐shifted emission maxima of phosphorescence without the use of potentially toxic and expensive transition metals. Most ORTP materials rely on well‐studied structural motifs that include aryl carbonyls, sulfones, and heavy main group elements. We report the unexpected ORTP of a series of heavy atom‐free BN‐substituted xanthene derivatives. The creation of heteroatom‐rich scaffolds, combined with stabilizing C−H⋅⋅⋅F interactions in the solid‐state, resulted in oxygen‐tolerant heavy atom‐free organic phosphorescence without relying on the use of cryogenic temperatures, polymer matrices, or host–guest interactions. The observation of ORTP in these simple systems sets a blueprint for the further development of heavy atom‐free organic phosphors.
Oxygen Plasma Triggered Co−O−Fe Motif in Prussian Blue Analogue for Efficient and Robust Alkaline Water Oxidation
Authors: Guan Xu Hao , Zhu Chen , Yang Lin Hao , Kai Liu Ji , Xiao Wu Yi , Qin Fu Huai , Yu Zhang Xin , Mao Fangxin , Yang Yuan Hai , Sun Chenghua , Fei Liu Peng , Gui Yang Hua
Published: October 2024

In the context of oxygen evolution reaction (OER), the construction of high‐valence transition metal sites to trigger the lattice oxygen oxidation mechanism is considered crucial for overcoming the performance limitations of traditional adsorbate evolution mechanism. However, the dynamic evolution of lattice oxygen during the reaction poses significant challenges for the stability of high‐valence metal sites, particularly in high‐current‐density water‐splitting systems. Here, we have successfully constructed Co−O−Fe catalytic active motifs in cobalt‐iron Prussian blue analogs (CoFe‐PBA) through oxygen plasma bombardment, effectively activating lattice oxygen reactivity while sustaining robust stability. Our spectroscopic and theoretical studies reveal that the Co−O−Fe bridged motifs enable a unique double‐exchange interaction between Co and Fe atoms, promoting the formation of high‐valence Co species as OER active centers while maintaining Fe in a low‐valence state, preventing its dissolution. The resultant catalyst (CoFe‐PBA‐30) requires an overpotential of only 276 mV to achieve 1000 mA cm−2. Furthermore, the assembled alkaline exchange membrane electrolyzer using CoFe‐PBA‐30 as anode material achieves a high current density of 1 A cm−2 at 1.76 V and continuously operates for 250 hours with negligible degradation. This work provides significant insights for activating lattice oxygen redox without compromising structure stability in practical water electrolyzers.
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

The 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

The 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

Readily 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

Converting 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

Polar 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

Nitrogen‐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

Mesoionic 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

Polycyclic 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

In 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

Tin 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

Little 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

The 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

Australia 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

MXene 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

To 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

Circular 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.
Negotiating Prejudice and Equality: Analysing Gender and Sexuality Discourse Among Supporters of Populist Radical Right Message in Switzerland and Finland
Authors: Tormis Helenor , Mabrouk Mariman , Pettersson Katarina , Sakki Inari
Published: October 2024

Research on gender, sexuality and the populist radical right has revealed the contradictory positions of such parties and politicians regarding gender issues. However, less is known about the perspective of laypeople on these matters. This study focuses on supporters of a radical right populist message and analyses how prejudice is constructed in populist gender discourse. Analysing interview material from two countries, Finland (n = 55) and Switzerland (n = 33), this study adopts a discursive–rhetorical approach and identifies six key discursive practices: radical supporters of gender equality, privileged gender and sexual minorities, assimilating individuals as exceptions, sexual minorities excluded from normality, the unprejudiced self distanced from the discriminating party and the self aligned with the rational party. First, this study sheds light on supporters' constructions of equality, gender and feminism in contemporary discourse. Second, our discursive–rhetorical analysis shows how different categorisation strategies are used in negotiating prejudice. Third, the study further complements existing research on gender populism by examining gender issues from the demand side, illustrating the appeal of radical right populist ideology among voters. We conclude that discursive category constructions and exceptions allow including, excluding and delegitimising gender and sexual minorities and their supporters while distancing and aligning oneself with (un)prejudiced positions in gender discourse. Please refer to the Supporting Information section to find this article's Community and Social Impact Statement.
Training Climbing Roses by Constrained Graph Search
Authors: Umezawa Wataru , Mukai Tomohiko
Published: October 2024

Cultivated climbing roses are skillfully shaped by arranging their stems manually against support walls to enhance their aesthetic appeal. This study introduces a procedural technique designed to replicate the branching pattern of climbing roses, simulating the manual training process. The central idea of the proposed approach is the conceptualization of tree modeling as a constrained path‐finding problem. The primary goal is to optimize the stem structure to achieve the most impressive floral display. The proposed method operates iteratively, generating multiple stems while applying the objective function in each iteration for maximizing coverage on the support wall. Our approach offers a diverse range of tree forms employing only a few parameters, which eliminates the requirement for specialized knowledge in cultivation or plant ecology.
Breaking the Loop: A Meta‐Analysis on the Bidirectional Effects of Materialism on Social Well‐Being Outlining Future Research Directions
Authors: Moldes Olaya , Zaleskiewicz Tomasz , Gąsiorowska Agata
Published: October 2024

This meta‐analysis examines correlational and experimental research linking materialism—broadly understood as an excessive focus on acquiring wealth and possessions that convey status—and social well‐being—characterised by healthy interpersonal relationships and a sense of social support and integration. We identified 55 reports containing 72 independent studies and 123 effect sizes (N = 44,376). Meta‐analytic calculations yielded a pooled effect of r = −0.18, suggesting that the effects of materialism on social well‐being (e.g., loneliness or relationship satisfaction) may be greater than the effects of materialism on individual well‐being (e.g., self‐esteem or life satisfaction). Moderation analyses revealed that the effects are bi‐directional, consistent across genders and cultures and significantly stronger in children and adolescents. These findings emphasise the universal and reciprocal link between materialism and social well‐being and highlight the particular vulnerability of younger populations. Based on the results, we propose suggestions for further research to address the existing gaps and strengthen the current evidence, and recommend a sample size of 240 participants for correlational studies and 50 participants per group for experimental research. This work calls for targeted interventions and policies to tackle the adverse social effects of materialism, particularly among young populations.
I Know I Am Ugly, but Please Listen to My Story First: An Examination of How Storytelling Can Impact Consumers' Valuation of Unattractive Produce
Authors: Pai Chu‐Yen , Young Kai‐Yi , Liska Luke Ingalls , Laverie Debra
Published: October 2024

In a world where food insecurity and food waste paradoxically coexist, the rejection of aesthetically imperfect yet edible produce significantly contributes to food waste. This study examines the application of compelling storytelling to alter consumer perceptions and behaviors toward unattractive produce, a perspective largely overlooked in sustainability research. We address this gap by exploring how storytelling can mitigate cognitive biases against such produce, thereby enhancing consumer acceptance through improved perceived taste. In Study 1, we examine the effect of unattractive produce on produce valuation and the mediation of perceived taste. In Study 2, we investigate the moderating role of storytelling in enhancing consumers' perceived taste of unattractive food. Through two experimental studies, we confirm that combining storytelling with marketing tactics, such as coupons, significantly increases consumers' consumption of unattractive produce. We recommend retailers utilize storytelling in marketing unattractive produce to optimize marketing effectiveness and promote sustainable food consumption. Our findings advance storytelling, visual marketing, and unattractive produce literature and offer practical insights for reducing food waste, contributing to sustainability efforts and social welfare. By employing a storytelling strategy, we support social good by encouraging the consumption of “ugly” produce.
Combined antegrade and retrograde dissection and re‐entry techniques: A two‐in‐one chronic total occlusion procedure
Authors: Low Randal Jun Bang , Marciniak Maciej , Kaier Thomas , Pavlidis Antonis
Published: October 2024

Treatment of chronic total occlusions (CTOs) by percutaneous coronary intervention (PCI) is technically challenging, with exponential difficulty in the presence of specific anatomical features. We present a complex case where procedural success was achieved by sequential PCIs to two separate CTOs in a ‘two‐in‐one’ procedure.
Prussian Blue Analogue‐Based Materials: Synthesis and Their Application in Peroxymonosulfate Activation for Wastewater Treatment
Authors: Zhang Ting , Zhang Chi , Zhang Hui
Published: October 2024

Peroxymonosulfate‐(PMS) based advanced oxidation processes (AOPs) are effective in degrading refractory organic pollutants in water. The unique internal chemical tunability of Prussian blue analogues (PBAs), a type of metal–organic framework materials (MOFs), makes them promising catalysts for PMS‐AOPs. However, the pristine PBA is limited in practical application due to its structural instability and easy leaching of metal ions. To this end, various methods have been developed to enhance the recycling and catalytic performance of PBAs. In this paper, the recent advances in the modification and composite strategies of PBA catalysts are systematically reviewed. PBA modification by the regulation of synthesis conditions and postsynthesis treatment, along with composite strategy involving metal and nonmetal‐based materials are introduced. The structural morphology improvement, physical and chemical property adjustment, vacancy design, and crystal surface modulation of PBAs induced by these modification and composite strategies are discussed in depth. In addition, the performance of the modified and composite catalysts to activate PMS for organic pollutant degradation is demonstrated. The radical pathway via SO4•−, •OH, and O2•−, nonradical pathway through 1O2, electron transfer process and high‐valent metal–oxo species, or a combination of radical and nonradical pathways are revealed in PMS‐AOPs with PBAs and their derivatives as catalysts.
Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide
Authors: Jain Nimisha , Houard Félix , Marchal Rémi , Cordier Marie , Le Guennic Boris , Suffren Yan , Sarazin Yann , Bernot Kevin
Published: October 2024

We are reporting on the use of a low‐coordinate YbIII amide with near‐ideal planar trigonal [Yb{N(SiMe3)2}3] (1) and on a bipyramidal trigonal derivative [Yb{N(SiMe2H)2}3 ⋅ (thf)2] (2) that constitute quintessential cases to investigate luminescent and magnetic properties otherwise usually blurred on less symmetrical compounds. These compounds represent the first experimental objects that allow for the confirmation of the recent conjecture about best‐performing SMM built on the archetypal prolate lanthanide ion. We have performed a combined theoretical, luminescent, and magnetic study on these molecules. For 1, a spectacular split of the 2F7/2 ground state of 1312 cm−1 is measured by low‐temperature near‐infra‐red luminescence as well as the calculated pure wavefunction composition of the low‐lying Kramers doublets, making this complex a textbook example of a prolate SMM. These results are corroborated by comparison with 2, that exhibits as expected a 50 % decrease of the ground state splitting compared to 1. Yet, we show that these remarkable features are insufficient to promote SMM behavior, and Orbach relaxation is unlikely to occur even on such an ideal low‐coordinate SMM without control of spin‐phonon coupling.
Electrochemical Decarboxylation Coupling Reactions
Authors: Liu Jiaxiu , Li Haoran , Guo Weisi , Cai Zhihua , Li Ming , Zhang Lin‐Bao
Published: October 2024

Carboxylic acids are attractive synthetic feedstocks with stable, non‐toxic, and inexpensive properties that can be easily obtained from natural sources or through synthesis. Carboxylic acids have long been considered environmentally friendly coupling agents in various organic transformations. In recent years, electrochemically mediated decarboxylation reactions of decarboxylic acids and their derivatives (NHPI) have emerged as effective new methods for constructing carbon‐carbon or carbon‐heterocarbon chemical bonds. Compared with transition metal and photochemistry‐mediated catalytic reactions, which do not require the addition of oxidants and strong bases, electrochemically‐mediated decarboxylative transformations are considered a sustainable strategy. In addition, various functional groups tolerate the electrochemical decarboxylation conversion strategy well. Here, we summarize the recent electrochemical decarboxylation reactions to better elucidate the advantages of electrochemical decarboxylation reactions.
O‐p‐Methoxyphenyl α‐Hydroxycarboxylic Acids as Versatile Hydroxyalkylation Agents for Photocatalysis
Authors: Nopper Christoph , Veith Adrian , Himmelsbach Felix , Söhner Luca , Breit Bernhard
Published: October 2024

Reliable radical precursors are crucial for photocatalytic processes. In particular, heteroatom‐stabilized radicals have attracted considerable research interest in photocatalysis. Among them, α‐amino radicals have received the most attention, while the research on α‐hydroxy radicals is much less developed. Herein, we present O‐PMP α‐hydroxycarboxylic acids as novel precursors for the formation of oxygen‐stabilized radicals. These radicals have been successfully used as building blocks in Pd‐catalyzed allylation reactions, Ni‐catalyzed arylation and alkenylation reactions, and Giese reactions. A subsequent deprotection step liberates the corresponding hydroxyalkylation products.
An Intelligent Triple Assisted Gold Cluster‐Based Nanosystem for Enhanced Tumor Photodynamic Therapy
Authors: Gao Fangli , Liu Yanru , Zhu Liang , Zhang Jie , Chang Yi , Gao Weihua , Ma Guanglei , Ma Xiaoming , Guo Yuming
Published: October 2024

Comprehensive Summary

Photodynamic therapy (PDT) has been attracted a surge of research interest. However, there are several obstacles to limit the efficacy of PDT, such as hypoxic tumor microenvironment (TME), overexpressed glutathione (GSH), inefficient reactive oxygen species (ROS) generation, and so on. Herein, a smart responsive nanosystem was constructed, which was composed of Au25 modified with triphenylphosphine (Au25‐TPP), catalase (CAT) and GSH‐responsive diselenide‐bridged mesoporous silica nanoparticles (Se‐MSN). When the nanosystem arrived at tumor site, Se‐MSN was degraded by the intracellular overexpressed GSH to release Au25‐TPP and CAT. The Au25‐TPP was targeted to mitochondria and generated ROS under the 808 nm NIR laser irradiation to kill tumor cells. Simultaneously, CAT could catalyze hydrogen peroxide to provide oxygen for relieving the hypoxia of TME. Besides, GSH was consumed by the diselenide bond to diminish the ROS loss. The above tactics (mitochondria targeting, hypoxia relieving and GSH consuming) jointly enhanced the PDT efficacy. The nanosystem showed distinct in vitro anticancer effect significantly stronger than other groups containing one or two assistance. Moreover, the in vivo results suggested that the tumors could be restrained obviously. The current study provides a new inspiration for constructing novel inorganic nanomedicines with multiple enhancement effect of PDT efficacy.
Unusual Presentation of Metastatic Medullary Thyroid Cancer Involving Bone Marrow, Kidneys, and Adrenal Gland: A Literature Review Based on a Case Report
Authors: Ebrahimi Pouya , Payab Moloud , Shariati Alireza , Alipour Neda , Nozheh Aysan , Tavangar Seyed Mohammad , Taheri Homa , Ebrahimpur Mahbube
Published: October 2024

Background

Medullary thyroid cancer (MTC) is one of the rare neuroendocrine malignancies. This cancer is hereditary in approximately 20% of cases. Although lymph node (LN) metastasis is prevalent in MTC, distant metastasis is not commonly seen in these patients. The most common locations for metastasis are the lungs, liver, and bones. This study presents an extremely rare MTC metastasis to bone marrow (BM) and adrenal gland, which has not been reported before.

Case

The patient was a 50‐year‐old man with a diagnosis of MTC and total thyroidectomy 2 months before his presentation. He came to the emergency department (ED) complaining of dyspnea, diffuse bone pain, nonbloody diarrhea, and abdominal cramps starting in the last month before. Initial treatment with intravenous fluid infusion and loperamide, due to the provisional diagnosis of infectious diarrhea, was ineffective. Further assessments revealed severe pancytopenia and a massive tumor above the left kidney. Bone marrow aspiration (BMA) and biopsy (BMB) led to the diagnosis of invasive metastasis of the MTC to the BM and the left adrenal gland. In the initial evaluations, his COVID‐19 test became positive, and despite all efforts, his condition deteriorated, and he died 5 days after admission due to respiratory distress.

Conclusion

Most MTC cases present with thyroid nodules in the initial steps and are confined to the thyroid gland or the adjacent LNs. These cases are mostly cured by thyroidectomy and LN dissection. This neuroendocrine cancer infrequently becomes aggressive and involves other parts of the body. However, involving BM or adrenal gland has been scarcely reported. Due to ineffective red and white blood cell production, BM metastasis can cause pancytopenia and, consequently, pallor, fatigue, dyspnea, and susceptibility to infections. High calcitonin levels can also cause diarrhea. The initial diagnosis is mostly with neck ultrasound (US) and fine needle aspiration (FNA). Total thyroidectomy is the main therapeutic option for these patients. Calcitonin and carcinoembryonic antigen (CEA) are sensitive indicators of recurrence or remaining tumors, which might be helpful for the initial diagnosis and postoperation follow‐up. Although extremely rare, invasive metastasis of MTC might involve unusual body organs such as the BM or adrenal glands. In cases of unjustifiable pancytopenia or adrenal dysfunction in MTC‐positive patients, these possibilities should be considered and ruled out by some specific evaluations, such as bone marrow biopsy and contrast‐enhanced imaging.