bluuebunny/crossref_metadata_2025 huggingface dataset:
Rational Design of Single‐Component White‐Light Emissive Molecular Copper Clusters
Authors: Rocheteau Alexia , Lemeur Lanig , Cordier Marie , Paris Michaël , Mevellec Jean‐Yves , Latouche Camille , Serier‐Brault Hélène , Perruchas Sandrine
Published: November 2024

The development of low‐cost and earth‐abundant phosphors for substituting expensive noble metals and toxic lead materials is currently of major importance for sustainable solid‐state lighting technologies. Hybrid copper halide materials are currently receiving considerable attention due to their unique and diverse structural and photophysical properties combined to their low cost and toxicity. This article reports the rational design of copper iodide compounds for developing single‐component white light emitters. By a ligand engineering strategy, the energy layout of the molecular clusters can be adjusted and the variation in the relative intensity of two emission bands can be obtained, enabling white light to be emitted. Temperature dependence of this dual‐emission feature also allows high contrast luminescence thermochromism. Thanks to their good solubility properties, the studied copper iodide clusters have been successfully incorporated within organic polymer leading to polymer materials with processability suitable for application development. Therefore, the potential applicability of these composite materials has been demonstrated in various fields as luminescence ratiometric thermometry, single‐component emitters for phosphor‐converted white‐light emitting diodes, and as ink for anticounterfeiting properties. This study highlights the power of the ligand design strategy to develop high potential multifunctional materials based on light‐emitting copper materials.
High Exciton Utilization Red Hot Exciton Electro‐Fluorescence Diodes Based on Emitters with Anti‐Kasha High‐Lying Triplet Emission
Authors: Xie Mingliang , Zhou Yannan , Ma Chenglin , Zhou Huayi , Wang Xin , Chu Lizhi , Sun Qikun , Zhang Shi‐Tong , Yang Wenjun , Xue Shanfeng
Published: November 2024

Red hot exciton emitters with high exciton utilization efficiencies (EUEs) are scarce. Herein, three red emitters, 2TPA, TPAPXZ, and TPAPXZCN, are designed and synthesized. These emitters have large rigid structures and large spin‐orbit coupling between the high‐lying triplet and adjacent singlet states. Photophysical studies show that these emitters exhibit anti‐Kasha high‐lying triplet emissions. Moreover, the MADN host is doped with 5 wt.% of these emitters, which inhibits the internal conversion (IC) rate (kICTn ∼ 108 s−1) of the high‐lying triplet state, making it similar to the high‐lying reverse intersystem crossing (hRISC) rate (khRISC ∼ 108 s−1). It provides a basis for doped devices to achieve high EUEs. Using 2TPA, TPAPXZ, and TPAPXZCN as emissive layers, the doped devices achieve red emission with emission peaks at 628, 626, and 647 nm, respectively. Notably, these devices achieve high EUEs of 43.9%, 81.0%, and 62.6%, respectively. To this knowledge, the EUE of these devices is among the highest values reported for hot exciton material devices. This study provides a novel approach for addressing low EUEs of hot exciton materials and improving their design strategies.
Rewritable Dual‐Mode Patterns Based on DASA Decorated PEG Crystal
Authors: Pan Xinyi , He Yaning
Published: November 2024

Displaying the same data in different optical modes has improved both storage capacity and information security. However, it always requires either sophisticated chemistry or expensive experimental setup to build a dual‐mode or even multi‐mode anti‐counterfeiting system. Here, a rewritable dual‐mode pattern is designed, based on the second‐generation Donor‐acceptor Stenhouse adducts decorated polyethylene glycol crystal. Uniform square crystals are obtained through a simple process of controlled solvent evaporation. Complex pattern such as words can be written on the crystals with the help of microregional irradiation. It endows the high‐resolution of the pattern that only the area exposed to light goes through the discoloration and fluorescence change. The great reversibility and fatigue resistance of the photochromism enable the crystals to be repeatedly utilized, making them qualified candidates as high‐level anti‐counterfeiting materials.
Robotic Laser Tissue Soldering for Atraumatic Soft Tissue Fusion Guided by Fluorescent Nanothermometry
Authors: Cipolato Oscar , Leuthold Tobias , Zäch Marius , Männel Georg , Aegerter Sam , Sciascia Calinda , Jessernig Alexander , von Salis Marco , Sarcevic Sima , Rosendorf Jachym , Liska Vaclav , Kundrat Dennis , Quidant Romain , Herrmann Inge K.
Published: November 2024

Minimally invasive surgical techniques, including endoscopic and robotic procedures, continue to revolutionize patient care, for their ability to minimize surgical trauma, thus promoting faster recovery and reduced hospital stays. Yet, the suturing of soft tissues ensuring damage‐free tissue bonding during these procedures remains challenging due to missing haptics and the fulcrum effect. Laser tissue soldering has potential in overcoming these issues, offering atraumatic seamless tissue fusion. To ensure the precision and safety of laser tissue soldering, the study introduces feedback‐controlled fluorescent nanothermometry‐guided laser tissue soldering using nanoparticle‐protein solders within endoscopic and robotic contexts. Temperature‐sensitive fluorescent nanoparticles embedded in the solder provide surgeons with immediate feedback on tissue temperatures during laser application, all while within the confines of minimally invasive (robotic) surgical setups. By integrating fluorescent nanothermometry‐guided laser tissue surgery into endoscopic and robotic surgery, the study paves the way for a new approach for safe and atraumatic soft tissue joining, especially in regions where traditional suturing is unfeasible.
Oblique‐Angle Damage‐Free Evaporation of Silicon Oxide Electron‐Selective Passivation Contacts for Efficient and Stable Perovskite and Perovskite/TOPCon Tandem Solar Cells
Authors: Guo Xuchao , Ying Zhiqin , Li Xin , Zhang Meili , Su Shiqian , Zheng Jingming , Du Haojiang , Sun Yihan , Wu Jun , Liu Linhui , Zeng Yuheng , Yang Xi , Ye Jichun
Published: November 2024

Inverted perovskite solar cells (IPSCs) suffer from significant non‐radiative recombination losses at the defective perovskite/C60 interface, limiting the efficiency and stability of perovskite/silicon tandem solar cells. Despite silicon oxide (SiOX) being a common passivation material in the silicon industry with higher electron selectivity than conventional atomic layer‐deposited alumina, its application in IPSCs is limited by its tendency to damage sensitive perovskite during processing. Here, an oblique angle evaporation method is developed to deposit a conformal, ultra‐thin SiOX layer without damaging the underlying perovskite. This SiOX interlayer not only chemically passivates under‐coordinated Pb2+ defects but also forms an n/n+ homojunction that provides effective field‐effect passivation, concurrently reducing recombination and enhancing electron selectivity. As a result, extending this strategy to two‐terminal monolithic perovskite/tunnel oxide passivating contact silicon tandem solar cells achieves a stabilized power conversion efficiency of 30.2%, representing one of the highest efficiencies reported for such tandems. More importantly, the robust inorganic nature of SiOX enables it to serve as a dense inner encapsulation, enhancing both light (ISOS‐L‐1) and thermal (ISOS‐D‐2I) device stabilities.
Ion Migration in Mesoscopic Perovskite Solar Cells: Effects on Electroluminescence, Open Circuit Voltage, and Photovoltaic Quantum Efficiency
Authors: Torre Cachafeiro Miguel A. , Comi Ennio Luigi , Parayil Shaji Sharun , Narbey Stéphanie , Jenatsch Sandra , Knapp Evelyne , Tress Wolfgang
Published: November 2024

Perovskite solar cells (PSCs) commonly suffer from drastic changes in performance over time, dominated by the redistribution of mobile ionic defects. Common characterization techniques for solar cells, such as electroluminescence (EL) imaging, are compromised by transient ionic effects, which makes understanding them important for the device optimization process. This study looks at the shape of EL transients in carbon‐based triple mesoscopic PSCs (CPSCs), which have emerged as a potential solution for increased stability and scalability. The slow changes in EL are explained in terms of the migration of two ionic species with different mobilities, and increased ionic densities over time. The effects of applying a forward bias in the dark and illuminating at open circuit for several hours are found to be similar, both pointing toward an increased mobile ion density which causes current collection efficiency losses without decreasing the radiative recombination yield. Current losses are found to be highly dependent on the ionic distribution, as demonstrated with measurements and simulations of the external quantum efficiency (EQE). The findings explain the commonly observed shape of the EQE in CPSCs and help to further understand the effects of ion migration. Furthermore, this study establishes an effective way to analyze ion‐dominated current losses by measuring low temperature EQE spectra with different preconditioning voltages, which enables to directly compare the effect of different ionic distributions.
Visible Light‐Mediated Radical Decarboxylative Strategies for the Synthesis of Heterocyclic Compounds
Authors: Bhuyan Kabita , Borang Lubang , Jamatia Ramen
Published: November 2024

Heterocycles are an important structural motif found in many bioactive compounds, natural products and pharmaceuticals. Heterocycles have been synthesised at large employing conventional methods which are usually associated with limitations such as the need for an external oxidant or reductant, harsh reaction conditions, lower selectivity and its unsustainable nature. To circumvent these drawbacks, visible light photocatalysis has emerged as a milder, energetically efficient and environmentally benign tool in organic synthesis. Visible light‐mediated radical decarboxylation of carboxylic acid and its derivatives has been widely explored to affect a wide range of chemical transformation reactions. Redox‐active NHPI derivatives are easily prepared from carboxylic acids which are inexpensive, non‐toxic and stable finding wide applications across various fields. Further, carboxylic acids are one of the most plentiful and renewable feedstock of our planet. Hence, this review brings forth the current developments in the area of visible light‐mediated decarboxylative strategies employing carboxylic acid and its derivatives for the synthesis of heterocyclic compounds.
Design and Synthesis of Novel Spiro [Chromane‐2,4′‐Piperidin]‐4‐One Derivatives: Anti‐Proliferative Investigation and Molecular Docking Studies
Authors: Nakka Srinuvasu , Sengar Suryansh , Sai Chaitanya Kosana , Swati  , Chandu Ala , Sankaranarayanan Murugesan , Sharma Vivek , Devunuri Nagaraju , Gowri Chandra Sekhar Kondapalli Venkata
Published: November 2024

Chemists around the globe are extensively working for remedial solutions to cancer, one of the greatest health hazards. We have synthesized twenty‐three novel spiro [chromane‐2,4′‐piperidin]‐ 4 ‐one derivatives (KBS and KMS series of analogues) as part of our ongoing research to combat this deadly disease, and confirmed their structures using 1H NMR, 13C NMR, HRMS, and FT‐IR. Furthermore, we employed single‐crystal XRD to identify the compound structures of KBS4 and KMS10. We have tested the compounds on the cell line such as MCF‐7; U87‐MG; SCC‐25; and HEK‐293T, via WST‐1 assay. Eight compounds showed IC50 values ranging 3.9–10 μM; against the cell line MCF‐7. The best compounds of all were KMS9 (IC50=3.83 μM), KMS5 (IC50=4.14 μM), and KBS8 (IC50=8.24 μM), which promoted apoptosis in MCF‐7 cells. KMS5 and KMS9 compounds showed G1 cell cycle arrest, while compound KBS8 showed G2 cell cycle arrest. Insilco ADME studies were carried out. Molecular docking and dynamics experiments showed how KMS5, KMS9, and KBS8 bind to the active region of the EGFR family – a group of receptor tyrosine kinase (RTK) proteins (PDB ID: 7JXP, 2.16 Å). Further structural modifications of the KMS5, KMS9, and KBS8 may improve their activity against breast cancer.
A scoping review of non‐binary research in “Australian” social sciences: Community, solidarity, resilience and resisting marginalisation
Authors: Nicholas Lucy , Clark Sal , Falzon Chloe
Published: November 2024

Non‐binary and genderqueer identities are increasingly discussed in public discourse and academia, but there remains a dearth of academic literature centred on non‐binary people's lives and experiences. When non‐binary people are included in research, it is frequently as an additive to explorations of trans identities and subsumed under the trans umbrella or treated as categorically indistinct. Much has been written from a clinical perspective, but the social sciences tend to discuss non‐binary identity conceptually or as a proxy in theoretical arguments. Of the emerging sociological literature on non‐binary identity, much is from the United States or the United Kingdom. Thus, this scoping review engaged with the corpus of research on non‐binary people in “Australia” to consider social change and policy needs. We found much about the negative health impacts resulting from discrimination and barriers, emphasising the structural and systemic nature of the existing gender binary. However, the majority of these papers include a focus on how non‐binary people actively participate in the collective creation of community, identity and safe spaces for affirmation. Resilience, coping strategies and solidarity were key themes and offer important insights into how the barriers identified can be ameliorated.
Retroperitoneal hemorrhage due to ruptured artery induced by median arcuate ligament syndrome in patients with COVID‐19: A case series
Authors: Okuno Nao , Maruyama Shuhei , Wada Daiki , Komemushi Atsushi , Shimazu Haruka , Kanayama Shuji , Saito Fukuki , Nakamori Yasushi , Kuwagata Yasuyuki
Published: November 2024

Background

Median arcuate ligament syndrome describes a clinical presentation associated with direct compression of the celiac artery by the median arcuate ligament. Decreased blood flow from the celiac artery and increased flow from superior mesenteric artery causes blood flow in the pancreatic arcade to increase, and aneurysms can form. We report our experience with six cases of retroperitoneal hemorrhage induced by median arcuate ligament syndrome in patients during the COVID‐19 period.

Case Presentation

The time from the onset of COVID‐19 to that of abdominal pain in the patients ranged from 3 to 9 days. None of the patients required oxygen for COVID‐19. We used contrast‐enhanced computed tomography to diagnose retroperitoneal hemorrhage and formation of a visceral pseudoaneurysm or aneurysm due to median arcuate ligament syndrome. Five patients underwent transcatheter arterial embolization. One patient suffered complications of duodenal stenosis and another suffered portal vein thrombosis.

Conclusions

Retroperitoneal hemorrhage associated with median arcuate ligament syndrome is rare. However, it might be triggered by COVID‐19 disease, resulting in arterial disruption and hemorrhage.
Polymer Design of Microwell Hydrogels Influences Epithelial–Mesenchymal Interactions During Human Bronchosphere Formation
Authors: Eiken Madeline K. , Levine Justin E. , Lee Shinyeong , Lukpat Samantha , Plaster Eleanor M. , Bala Vikram , Spence Jason R. , Loebel Claudia
Published: November 2024

Bronchospheres have emerged as a promising in vitro model toward probing questions on organ development and disease. Several organoid models, including from airway (e.g., bronchial, tracheal) cells, require three‐dimensional (3D) Matrigel, a complex mouse tumor‐derived matrix that typically leads to heterogeneous size and structures. Synthetic and naturally derived polymeric hydrogels show increased opportunities as an alternative to Matrigel culture. In addition, recent advances in hydrogel‐based microcavities (i.e., microwells) have shown improved control over organoid size, structure, and composition. Here, we build upon this approach and describe the fabrication and characterization of microwell hydrogels based on other polymers, including diacrylated poly(ethylene glycol), agarose, methacrylated gelatin, and norbornene‐modified hyaluronic acid. Using these microwell hydrogels, human bronchial epithelial cells and lung fibroblasts readily assemble into viable cyst‐like bronchospheres. The study shows that the cellular composition regulates the formation and structure of the bronchosphere which also depends on the type and adhesiveness of the hydrogel. Furthermore, both hydrogel type and cellular composition influence the amount and composition of deposited extracellular matrix within the microwells. This hydrogel fabrication platform provides an accessible in vitro culture platform for the formation and growth of bronchospheres which can be extended to the culture of other organoid systems.
Meta‐Dimethylation of Arenes via Catellani Reaction from Aryl Thianthrenium Salts
Authors: Mrozowicz Michał , Chatterjee Sagnik , Aliki Mermigki Markella , Pantazis Dimitrios A. , Ritter Tobias
Published: November 2024

Here we report the reaction of aryl thianthrenium salts that allows selective functionalization of the meta position of arenes. The combination of a site‐selective thianthrenation with a Catellani reaction provides access to 3,5‐dimethylated arenes. The developed reaction is complementary to the previously discovered reductive ipso‐alkylation of aryl thianthrenium salts and extends the possibilities for late‐stage methylation of arenes with a single aryl thianthrenium salt.
Sb‐to‐P Metathesis: A Direct Route to Structurally Constrained, Cationic PIII Compound
Authors: Bawari Deependra , Malahov Irina , Dobrovetsky Roman
Published: November 2024

Structurally constrained, cationic PIII compound [LP][SbCl4] with an OCO pincer‐type ligand (L) having a central carbene donor was directly synthesized via an Sb‐to‐P metathesis reaction between PCl3 and LSb‐Cl. [LP][SbCl4] was isolated and its reactivity with small molecules (ROH and RNH2) was studied, showing that [SbCl4]− is not an innocent counter anion, but an active participant in these reactions. When the [SbCl4]− was replaced with the [CB11H12]− ([Cb]−) anion, the reactions were redirected to [LP]+ cation only. The reactions with alcohols and amines led to the equilibrium between the products of the formal E−H (E=O, N) bond oxidative addition to the P‐center and products of the P‐center/ligand‐assisted bond activation. Remarkably, [LP]+ activated the PhO−H and PhN(H)−H bonds in a reversible, thermoneutral fashion.
Neuromorphic Nanofluidic Sense Digitalization
Authors: Duan Zu‐Ming , Xu Yi‐Tong , Li Zheng , Pang Jian‐Xiang , Xu Jing‐Juan , Zhao Wei‐Wei
Published: November 2024

Nanofluidic memristors have recently been reshaped into artificial synapses capable of mimicking many fundamental neurosynaptic patterns, while sense digitalization has been increasingly explored to link the neuromorphic devices with external equipment. By inspiration of dopaminergic nerve, here a nanofluidic nerve with sense digitalization is devised by engineering a dopamine (DA)‐specific nanofluidic synapse as mediated by PC‐12 cells to manage the robotic arm. Different from previous neuromorphic perception of DA via redox reaction, the aptamer‐based perception here is based on biological DA recognition by its receptor as indicated by the ionic signals. Various neurosynaptic patterns are emulated with DA‐dependent plasticity, based on which the digital representation of DA perception is used to control the robotic arm.
Enhancing Low‐Concentration Electroreduction of NO to NH3 via Potential‐Controlled Active Site‐Intermediate Interactions
Authors: Guo Xiaoxi , Wu Tongwei , Li Hengfeng , Chai Liyuan , Liu Min
Published: November 2024

Electronic defect states in catalysts are recognized as highly effective active sites for enhancing the low‐concentration electroreduction of NO to NH3 (NORR). Their structures dynamically evolve with applied electrode potentials, allowing the active sites to adjust interactions with intermediates, thereby improving electrocatalytic performance. However, the dynamic changes in these interactions under applied potentials remain poorly understood, hindering the design of more diverse electrocatalytic systems. Herein, we developed a strategy that unitizes electrode potential to control the interactions between active sites and intermediates over oxygen vacancy‐modified TiO2 (VO−TiO2−x) to enhance NORR performance. By combining state‐of‐the‐art constant inner potential (CIP) DFT calculations with in situ (spectro)electrochemical measurements, we investigated how the electrode potential influences these interactions in NORR. The results clearly demonstrate that applying an external potential alters the spatial symmetry of degenerate orbitals of Ti3+ to facilitate the generation of key intermediates for NO‐to‐NH3 conversion. Therefore, the VO−TiO2−x catalyst exhibited superior NORR performance with a NH3 Faradaic efficiency up to 76.4 % and a high NH3 yield rate of 632.9 μg h−1 mgcat.−1 under 1.0 vol % NO atmosphere, which is competitive with those of previously reported works under higher NO concentration (above 10 vol %). Remarkably, the NORR process achieved a record‐breaking NH3 yield of 2292.7 μg h−1 mgcat.−1 in a membrane electrode assembly (MEA) electrolyzer under the same conditions. This study opens a new avenue for enhancing electrocatalytic activity by adjusting operating conditions, thereby transcending the limitations of material design.
Thermal and self‐curing kinetics of single pack epoxy adhesive with zeolitic imidazolate framework‐8
Authors: Shi Xuetang , Zhang Caimian , Zheng Wenji , Tong Lianpeng , Luo Sijia , He Gaohong
Published: November 2024

Single pack epoxy adhesives, known for their simple operation process, combined with good reactivity at moderate temperatures and excellent storage stability, have gained extensive attention. An appropriate accelerator is crucial for enhancing their performance. This study demonstrates that the zinc zeolitic imidazolate framework ZIF‐8 (Zn(2‐methylimidazole)2) can effectively serve as an effective accelerator for the epoxy‐anhydride system, as evidenced by the complete exothermic curing curve obtained via differential scanning calorimetry (DSC) tests of the epoxy (A‐128) and anhydride (THPA) adhesive sample with ZIF‐8. The optimal addition amount of ZIF‐8 (0.9%) was determined by assessing the glass transition temperature (Tg) of the cured resin with varying ZIF‐8 weight fractions. Furthermore, the ideal curing conditions—gel temperature of 388.4 K, curing temperature of 416.7 K, and post‐treatment temperature of 441.9 K—were established by analyzing heating curves at different circumstances. The epoxy (A‐128) and anhydride (THPA) system with accelerator ZIF‐8 exhibited superior stability compared to the commercial accelerators like PN‐23 or DMP‐30. This is attributed to the steric hindrance and coordination bonds of ZIF‐8, indicated by a large pre‐exponential factor (A1 = 5.58 × 108) and low‐value reaction rate constant (k1 = 0.3461 × 10−3 s−1). In addition, the kinetic parameters, and an autocatalytic equation model for the epoxy (A‐128) and anhydride (THPA) system with accelerator ZIF‐8 have been derived through isothermal curing kinetics analysis.
Crystallization, Gas Barrier, and Mechanical Properties of Polypropylene Nanocomposites Reinforced by Graphite‐Like Carbon Nitride Nanosheets
Authors: Tan Changbin , He Haiqing , Zhao Dong , He Shan , Zheng Jia , Jiang Zhiyu , Su Jian , Liu Like , Feng Zheng , Yang Jiongye , Song Kunhao , Yang Yan
Published: November 2024

Polypropylene (PP) based nanocomposites with graphitic carbon nitride nanosheets (CNNSs) exfoliated from g‐C3N4 (CN) were fabricated via melt compounding. The detailed structure and morphology of the CNNSs were examined using X‐ray diffraction (XRD), Fourier transform infrared spectrometry (FTIR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscope (TEM), and atomic force microscopy (AFM) measurements. The effects of CNNSs on the crystalline morphology, oxygen vapor permeability, and mechanical properties of PP based nanocomposites were carefully evaluated. The CNNS not only increased the crystallization peak temperature and crystallinity, but also enhanced gas barrier properties and tensile strength of the PP nanocomposites. For PP/CNNS‐2 nanocomposites, the tensile strength was increased by 10.7%, and oxygen permeability coefficients decreased by 64.5% compared to pure PP. Therefore, PP/CNNS nanocomposite could be a potential candidate for packing application.
Racism as ontological terror and onticide
Authors: Piven Jerry S.
Published: November 2024

This paper elucidates the existential and psychological dynamics of onticide: the malicious annihilation of another's existential‐emotional being. On any given day, chances are we're going to read a new account of racist violence and injustice that is, simply put, grotesque. This cannot be adequately explained as mere ignorance or prejudice. An existential phenomenology of racism is needed to explain that disgust, malice, and disdain. What arouses such fear, hatred, loathing, and the desire to punish or humiliate? This paper explores the ways in which inner impoverishment and wounds are turned into fantasies of evil in the outer world, and how the ontological dread of annihilation and nonbeing induce the desire to harm, diminish, and annihilate the menacing other.
New Data on the Distribution of Sperm Whales in the Western Mediterranean Highlights Insufficiency of Currently Proposed Protection Measures
Authors: Brotons J.‐M. , Cerdá M. , Pirotta E. , Rendell L.
Published: November 2024

As part of ongoing efforts to protect marine megafauna, especially cetaceans, in the NW Mediterranean Sea, a ‘Particularly Sensitive Sea Area’ (PSSA) was established in July 2023 by the governments of France, Italy, Spain and Monaco through the Marine Environment Protection Committee (MEPC) of the International Maritime Organisation (IMO). This is a legal instrument by which maritime traffic can be subject to advisories or controls to protect the natural environment. While the new PSSA is a significant step forward in terms of marine wildlife protection in the region, the current area only partially includes the waters that play a key ecological role for the conservation of Mediterranean sperm whales (Physeter macrocephalus) around the Balearics Archipelago. This isolated population is currently classified as endangered by the IUCN. Survey data from 2019 to 2022 show how the current area does not include portions of habitat in which calves are more likely to be encountered and risks displacing any maritime traffic that chooses to avoid the voluntary PSSA restrictions into habitat that is sensitive for calf survival. We argue therefore that this PSSA should be augmented to incorporate waters that are an important habitat for this endangered population.
A Sandwich‐structured EVA/Cu2O/Cu Composite Current Collector to Suppress the Lithium Dendrite Growth
Authors: Huang Xianli , Yang Hui , Zuo Zhongzheng , Zhang Shunyao , He Pingting , Wang Tao , He Jianping
Published: November 2024

The proliferation of lithium dendrites has long posed a formidable hurdle in the widespread adoption of lithium metal batteries, thereby necessitating the urgent resolution of how to effectively mitigate their growth as the paramount challenge in the realm of energy storage. Herein, we have crafted a novel sandwich‐structured current collector comprising an ethylene‐vinyl acetate polymer (EVA)/Cu2O/Cu configuration, where the EVA thin film acts as a protective barrier, passivating the lithium metal anode, while the Cu2O layer fosters lithiophilic sites conducive to uniform lithium nucleation. Our experiments reveal that the EVA thin film adeptly prevents direct contact and subsequent reactions between the lithium metal and the electrolyte, enhancing the ion mobility of Li+ ions, ultimately leading to a even distribution of lithium deposition. In a Li−Cu half‐cell, the incorporation of the EVA film increases the nucleation potentials but dramatically reduces polarization potentials after 50 cycles of charge‐discharge processes. Remarkably, the Li−Cu half‐cells equipped with EVA‐coated current collectors exhibit lower electrochemical resistances, translating into significantly extended cycle lives. This work indicates the sandwich architecture (thin film/lithium metal/lithiophilic compounds) is a promising contender for achieving long‐lasting, stable lithium anodes.
Biomass‐Derived Materials in Perovskite Solar Cells: Recent Progress and Future Prospects
Authors: Rahman Md. Mahbubur , Woong Kim Tae
Published: November 2024

As a promising photovoltaic (PV) technology, perovskite solar cells (PSCs) have made significant progress in attaining high PCE, while challenges remain regarding stability and low cost. Conventional PSCs using noble metals (e. g., Au and Ag) as back electrodes and transparent conducting oxides as front electrodes contribute significantly to their high costs. PSCs comprising biomass‐derived materials, such as biocarbon as back electrodes and flexible and transparent cellulosic substrates as front electrodes, offer a promising solution to address these issues. These approaches have the potential to simultaneously improve stability and decrease manufacturing costs, making PSCs closer to commercialization. This review article furnishes a comprehensive overview of recent developments in biocarbon‐based perovskite solar cells (C‐PSCs), focusing on various biomass‐derived biocarbon materials utilized as back electrodes in different C‐PSCs device structures. This article also compiles the advancement of flexible and transparent cellulosic substrate‐based PSCs by highlighting the fundamentals of PSC and C‐PSC architectures, the basics of biomass, and the synthesis of biocarbon. Finally, this review discusses the current challenges and future research directions for optimizing biocarbon materials and cellulosic substrates in PSC technology.
N‐Protection Dependent Phosphorylation of Dehydroamino Acids to Build Unusual Phosphono‐Peptides
Authors: Kothuri Pranay , Bhumannagari Haripriya , Battula Shravani , Rekha Kolachina , Nayani Kiranmai
Published: November 2024

An efficient Mn(III)‐promoted phosphorylation of dehydroalanine (Dha) has been developed to give unusual α‐amino acids bearing phosphonates/phosphine oxides and β‐vinyl phosphonates/phosphinates depending on N‐protection of amino acid. N,N‐diprotected dehydroalanine reacted with H‐phosphonates and H‐phosphine oxides to give structurally diverse phosphorylated α‐amino acids through conjugate addition of phosphorous radical generated by Mn(OAc)3.2H2O. Whereas, a highly Z‐selective phosphorylation was observed in the case of mono N‐Boc protected dehydroalanine via cross dehydrogenative coupling to give (Z)‐ β ‐vinyl phosphono amino acid. The method is successfully applied to short peptides to derive unusual phosphono‐peptides under mild conditions.
Synthesis, Structure, Frontier Orbitals and Reactivity of Ph3GeN(SiMe3)2: Rare Crystal Structure of a Germylamine
Authors: Fortney Vanessa A. , Levescy Laura M. , Murphy Julia K. , Gembicky Milan , Weinert Charles S.
Published: November 2024

The germylamine Ph3GeN(SiMe3)2 was synthesized from Ph3GeCl and LiN(SiMe)2 and its X‐ray crystal structure was determined. This structure represents only the fourth crystallographically characterized germylamine that has been reported. The two sterically encumbering −SiMe3 groups completely encapsulate the germanium‐nitrogen bond and the geometry at the nitrogen atoms is trigonal planar rather than pyramidal. The structure of Ph3GeN(SiMe3)2 was calculated using density functional theory and it was found that the HOMO of this molecule is stabilized relative to that of Ph3GeNMe2, which has been shown to be a highly effective reagent for the amidation of acid fluorides. The steric attributes Ph3GeN(SiMe3)2, coupled with its more stable HOMO relative to Ph3GeNMe2, prevent its functioning as an amidation reagent for acid fluorides except in the case of benzoyl fluoride.
Clients' narratives of healing and harm in psychotherapy: A qualitative method
Authors: Tavallaei Seyed Vahid , Najarpourian Samaneh , Rastegar Yaser
Published: November 2024

Purpose

For decades, researchers have acknowledged the potential for negative effects in psychotherapy, highlighting the need for further investigation. However, a clear understanding of the nature and definition of harm within this context has remained elusive. Efforts were made to clarify terminology such as ‘side effects’ and ‘negative effects’, but a consensus on the extent and definition of harm has continued to evade the field. Notably, existing research on negative effects has often prioritised expert and therapist perspectives, neglecting the crucial insights offered by the client's subjective experience of harm.

Method

This study adopted an exploratory approach, employing qualitative research methods. To uncover and illuminate past experiences of harm within the therapeutic context, semi‐structured interviews were conducted with 21 participants (15 female, 6 male) who reported perceiving their psychotherapy sessions as harmful. Data analysis utilised the theoretical framework of Strauss and Corbin's grounded theory approach, facilitated by the MAXQDA2020 software.

Results

The study results offered a comprehensive examination of factors contributing to client‐perceived harm in psychotherapy, categorised as both client‐related and therapist‐related. Additionally, the definition of harm was explored through the lens of emotional and cognitive experiences. The client's reaction to perceived harm (submission, avoidance and compensation) and the therapist's course of action vs. the client's reaction (corrective and justifying) respectively, can cause consequences (strengthening the therapeutic alliance and the client's healing or individual and interpersonal impacts) from the client's perspective.

Conclusion

A significant finding was the lack of attention paid to the interpersonal nature of psychotherapy in past understandings of harm. The results highlight the potential for harm in any therapeutic relationship, regardless of the therapist. This potential appears to be particularly heightened when therapists display a lack of responsiveness to clients' internal experiences, especially through justifying comments in response to client‐reported negative experiences within the therapeutic relationship. Based on these findings, the study offers clinical recommendations for therapists to enhance their responsiveness and mitigate potential harm.
A Photo‐Caged Cross‐Linker for Identifying Protein‐Protein Interactions
Authors: Chen Xingyu , Jiménez López Cristina , Nadler André , Stengel Florian
Published: November 2024

Cross‐linking mass spectrometry (XL–MS) has seen significant improvements which have enhanced its utility for studying protein‐protein interactions (PPIs), primarily due to the emergence of novel crosslinkers and the development of streamlined analysis workflows. Nevertheless, poor membrane permeability and side reactions with water limit the extent of productive intracellular crosslinking events that can be achieved with current crosslinkers. To address these problems, we have synthesized a novel crosslinker with o‐nitrobenzyl‐based photoresponsive groups. These o‐nitrobenzyl ester (o‐NBE) groups enhance the stability and hydrophobic properties of the crosslinker and add the potential for temporal resolution, i. e. the ability to control the initiation of the crosslinking reaction. Upon exposure to UV light the resulting aldehyde product reacts with adjacent amino groups and subsequent reductive amination of the formed Schiff‐bases yields stable secondary amine linkages. This controlled activation mechanism enables precise UV‐triggered protein crosslinking. We demonstrate proof‐of principle of our o‐NBE cross‐linker to reliably detect PPIs by XL–MS using a recombinant model protein. We also demonstrate its ability to enter intact Hela cells, thereby indicating its future potential as a useful tool to study PPIs within the cellular environment.
Biochemical and Structural Characterisation of a Bacterial Lactoperoxidase
Authors: Pećanac Ognjen , Martin Caterina , Savino Simone , Rozeboom Henriette J. , Fraaije Marco W. , Lončar Nikola
Published: November 2024

Peroxidases belong to a group of enzymes that are widely found in animals, plants and microorganisms. These enzymes are effective biocatalysts for a wide range of oxidations on various substrates. This work presents a biochemical and structural characterization of a novel heme‐containing peroxidase from Cyanobacterium sp. TDX16, CyanoPOX. This cyanobacterial enzyme was successfully overexpressed in Escherichia coli as a soluble, heme‐containing monomeric enzyme. Although CyanoPOX shares relatively low sequence identity (37 %) with bovine lactoperoxidase, it displays comparable biochemical properties. CyanoPOX is most stable and active in slightly acidic conditions (pH 6–6.5) and moderately thermostable (melting temperature around 48 °C). Several compounds that are typical substrates for mammalian lactoperoxidases were tested to establish the catalytic potential of CyanoPOX. Potassium iodide showed the highest catalytic efficiency (126 mM−1 s−1), while various aromatic compounds were also readily converted. Structural elucidation of CyanoPOX confirmed the presence of a non‐covalently bound b‐type heme cofactor that is situated in the central core of the protein. Except for a highly similar overall structure, CyanoPOX also has a conserved active site pocket when compared with mammalian lactoperoxidases. Due to its catalytic properties and high expression in a bacterial host, this newly discovered peroxidase shows promise for applications.
Clinical Outcomes of Transcatheter Mitral Valve‐In‐Valve and Valve‐In‐Ring Implantation: A Systematic Review and Meta‐Analysis
Authors: Fong Khi Yung , Koh John Ming Yan , Saw Lip Wei , Anggreni Devy , Ng Ethel Zi Xie , Chan Yiong Huak , Poon Karl , Stub Dion , Sung Shih‐Hsien , Chandavimol Mann , Lee Michael Kang‐Yin , Chui Angus Shing Fung , Gopalamurugan A. B. , Nair Rajesh , Guo Yingqiang , Amanullah Mohammed Rizwan , Chao Victor Tar Toong , Ewe See Hooi , Ho Kay Woon , Yap Jonathan
Published: November 2024

Background

Transcatheter valve‐in‐valve (VIV) or valve‐in‐ring (VIR) therapies for degenerated mitral bioprosthetic valves and rings are still evolving. We aimed to characterize short‐ and long‐term outcomes of these procedures.

Methods

An electronic literature search was conducted to retrieve articles describing mitral VIV or VIR implantation with at least 10 patients. Meta‐analysis of proportions was carried out for 30‐day or in‐hospital outcomes of mortality, stroke, major bleeding, transfusion, acute kidney injury, procedural success, valve embolization, paravalvular leak, pacemaker implantation, and hospital stay. Individual patient data meta‐analysis using Kaplan‐Meier curve reconstruction was used to estimate long‐term mortality of VIV, VIR and redo surgical mitral valve replacement (SMVR).

Results

We analyzed 34 studies (7047 patients). Pooled procedural success was 94.8% in VIV and 80.5% in VIR. Pooled short‐term mortality and stroke risk was 6.4% and 1.9% respectively in VIV, 9.1% and 1.6% respectively in VIR, and 8.4% and 5.5% respectively in SMVR.

Conclusions

This study provides prognostic information on clinical outcomes for redo SMVR and transcatheter mitral VIV and VIR implantation.
Rheocarna Effectively Treats Oral Medicinal Therapy‐Resistant Cutaneous Symptoms and Renal Failure Induced by Cholesterol Crystal Embolism
Authors: Satake Akinori , Tokuda Takahiro , Ohashi Hirofumi , Nakano Yusuke , Kodama Akio , Amano Tetsuya
Published: November 2024

An 80‐year‐old man presented to our hospital with worsening renal function and ambulation difficulties due to lower extremity symptoms that included livedo reticularis, gangrene, cyanosis, and ulcers in his legs. The patient was diagnosed with a cholesterol crystal embolism. Treatment with prednisolone and rosuvastatin was initiated; however, no improvements were observed in the patient's cutaneous symptoms or renal function. Therefore, we decided to treat the patient with a new low‐density lipoprotein apheresis device (Rheocarna; Kaneka Corporation, Osaka, Japan). Following therapy, the lower extremity symptoms improved, and although dialysis was temporarily initiated, it was eventually discontinued.
Frustrated Lewis Pairs from Al−E{14} Bonds (E{14}=Ge, Sn, Pb)
Authors: Smith George W. A. , Neale Samuel E. , Evans Matthew J. , Li Xuning , Wang Junhu , Gardiner Michael G. , McMullin Claire L. , Fulton J. Robin , Coles Martyn P.
Published: November 2024

The potassium aluminyl K[Al(NON)] ([NON]2−=[O(SiMe2NDipp)2]2−, Dipp=2,6‐iPr2C6H3) reacts with group 14 chloroamidinates E{14}(Am)Cl (E{14}=Ge, Sn, Pb. [Am]−=[tBuC(NDipp)2]−) to form (NON)Al−E{14}(Am) Lewis pairs with unsupported Al−E{14} bonds, including the first structurally authenticated Al−Pb bond. Analysis using spectroscopic (NMR, UV‐vis and Mössbauer for E{14}=Sn), X‐ray diffraction and computational (DFT, QTAIM, TD‐DFT) methods conclude an Al−E{14} σ‐bond derived from a Lewis basic Al and a Lewis acidic tetrylene, with back‐donation from the E{14} s‐orbital lone pair donor NBO to acceptor NBOs on Al that are derived from s/p‐orbitals. The reaction of the Al−Ge compound with CO2 forms the dioxocarbene (NON)Al(μ‐O2C)Ge(Am), whilst under the same conditions the Al−Sn compound reacts with additional CO2 to form the carbonate, (NON)Al(μ‐CO3)Sn(Am). Addition of ethene to the Al−E{14} (E{14}=Ge, Sn) compounds introduces an ethylene bridge between the aluminium and group 14 atoms forming a frustrated Lewis pair (FLP). Reaction of the (Al/Ge) FLP with CO2 forms an activation product with new Al−O and Ge−C bonds, whilst reaction with iPrN=C=NiPr proceeds with insertion into the Al−C bond to form an aluminium amidinate.
Highlights from the Lowlands: Early Career Researchers Shine at Medicinal Chemistry Frontiers 2024
Authors: McKenna Sean M. , Borsari Chiara , Chin Chan Sean , Donckele Etienne J. , Faucher Franco F. , Grenier‐Davies Melissa C. , Haranahalli Krupanandan , Matagne Brieuc , Monastyrskyi Andrii , Petracca Rita
Published: November 2024

EFMC‐ACS MEDI Medicinal Chemistry Frontiers 2024 welcomed scientists from across Europe and the USA to share their research at a Spring meeting hosted in the Netherlands. A stellar lineup of speakers including industry luminaries and academic leaders delivered presentations on their research, encompassing a wide variety of topics in drug discovery. The event also proved to be a worthy showcase for many wonderfully talented early career researchers in medicinal chemistry and chemical biology. Presented here are some of the notable themes and activities, as well as perspectives from the event.
Absorption and Excited‐State Coherences of Cryogenically Cold Retinal Protonated Schiff Base in Vacuo
Authors: Klinkby Nikolaj , Rasmussen Anne P. , Lauridsen Anders G. S. , Andersen Lars H.
Published: November 2024

Retinal protonated Schiff base (RPSB), found in its all‐trans conformer in Bacteriorhodopsin, undergoes barrier‐controlled isomerization upon photoabsorption through polyene chain torsion. The effects of the protein environment on the active vibrations during photoabsorption and their redistribution are still not understood. This paper reports on femtosecond time‐resolved action‐absorption measurements of cryogenically cooled gas‐phase all‐trans RPSB, which exhibit two coherent vibrational oscillations, 167(14) cm
and 117(1) cm
, of the first excited state with dephasing times of
ps. The absence of the high‐frequency vibration in solution and the low‐frequency vibration in the protein indicates that these vibrations are sensitive to environments. An action‐absorption spectrum of cryogenically cold all‐trans RPSB, reveals a
 cm
active vibration when using a hole‐burning technique and 1500 cm
C=C stretching modes.
Influence of Ultrasonic Irradiation on Crystal Nucleation, Morphology and Structural Properties of Maltol Polymorphs I and II From Aqueous Solution
Authors: Srinivasan Kavipriya , Karuppannan Srinivasan
Published: November 2024

The impact of ultrasound on the nucleation control and separation of maltol polymorphs in aqueous solution has been studied for the first time. The study involved varying ultrasound parameters such as power (ranging from 75 to 225 W), pulse rate (from 10% to 50%), and insonation time (2, 4, and 6 min) at room temperature and at different supersaturation levels. In addition to the expected effects of supersaturation on induction time, nucleation, and morphology of the maltol polymorphs, ultrasound is found to have a significant influence on nucleation control and separation of the polymorphs. The results reveal that ultrasound promotes the nucleation of maltol polymorphs with shorter induction times by creating nucleation hot spots through cavitation effect, and improves the quality of the crystals. Notably, under specific conditions, ultrasound induces the nucleation of a rare metastable Form‐II polymorph of maltol in aqueous solution, while without ultrasound, only the stable Form‐I polymorph is obtained. Morphology of the nucleated polymorphs is observed using in situ optical microscopy, and their structure is confirmed through powder X‐ray diffraction (PXRD) and single crystal X‐ray diffraction (SCXRD) analyses. Furthermore, thermal stability of the grown stable Form‐I and metastable Form‐II polymorphs of maltol is verified using differential scanning calorimetry (DSC).
Growth Kinetics on KDP Crystal (101) Faces In Situ Observed by Michelson Interference
Authors: Li Xianglin , Cao Xuecheng , Li Xiaojie , Zhao Huihui , Hou Ruoxian , Wang Shenglai
Published: November 2024

The effect of rotational speeds on the growth kinetics of KDP crystal (101) faces is explored by the Michelson interference technique. The experimental results show that the growth rates rise as the rotational speed increases. The decrease in rotational speed affects the slopes of growth hillock on KDP crystal (101) faces, resulting in an overall decrease in the slopes. The kinetic coefficient of KDP crystal (101) face increases with increasing rotational speeds, and always βI, βII>βIII.
Green Electrochemical Point‐of‐Care Devices: Transient Materials and Sustainable Fabrication Methods
Authors: Batet David , Gabriel Gemma
Published: November 2024

The spread of point‐of‐care (PoC) diagnostic tests using electrochemical sensors poses a significant environmental challenge, especially in limited‐resource settings due to the lack of waste management infrastructure. This issue is expected to intensify with the emergence of the Internet of Medical Things (IoMT), necessitating eco‐friendly solutions for disposable devices. This review discusses efforts to develop green and sustainable PoC diagnostic devices, clarifying terms like biodegradability and transient electronics. It explores potential transient and biodegradable materials and fabrication technologies, emphasizing sustainable electronics with low‐energy consumption and low‐carbon footprint techniques, particularly favoring printing methods. The review highlights examples of necessary electronic components containing biodegradable materials for electrochemical PoC devices and discusses their role in device sustainability. Finally, it examines the feasibility of integrating these components and technologies into comprehensive biodegradable PoC devices, addressing the imminent need for eco‐friendly solutions in diagnostic testing. This comprehensive discussion serves as a guide for researchers and developers striving to mitigate the environmental impact of PoC testing in the era of IoMT and personalized medicine.