bluuebunny/crossref_metadata_2025 huggingface dataset:
Liquid Metal Composites‐Enabled Real‐Time Hand Gesture Recognizer with Superior Recognition Speed and Accuracy
Authors: Chen Yi , Tao Zhe , Chang Ruizhe , Cao Yudong , Yun Guolin , Li Weihua , Zhang Shiwu , Sun Shuaishuai
Published: January 2024

Prosthetic hands play a vital role in restoring forearm functionality for patients who have suffered hand loss or deformity. The hand gesture intention recognition system serves as a critical component within the prosthetic hand system. However, accurately and swiftly identifying hand gesture intentions remains a challenge in existing approaches. Here, a real‐time motion intention recognition system utilizing liquid metal composite sensor bracelets is proposed. The sensor bracelet detects pressure signals generated by forearm muscle movements to recognize hand gesture intent. Leveraging the remarkable pressure sensitivity of liquid metal composites and the efficient classifier based on the optimized recognition algorithm, this system achieves an average offline and real‐time recognition accuracy of 98.2% and 92.04%, respectively, with an average recognition speed of 0.364 s. Thus, this wearable system shows advantages in superior recognition speed and accuracy. Furthermore, this system finds applications in master‐slave control of prosthetic hands in unmanned scenarios, such as electrically powered operations, space exploration, and telemedicine. The proposed system promises significant advances in next‐generation intent‐controlled prosthetic hands and robots.
When Machine Learning Meets 2D Materials: A Review
Authors: Lu Bin , Xia Yuze , Ren Yuqian , Xie Miaomiao , Zhou Liguo , Vinai Giovanni , Morton Simon A. , Wee Andrew T. S. , van der Wiel Wilfred G. , Zhang Wen , Wong Ping Kwan Johnny
Published: January 2024

The availability of an ever‐expanding portfolio of 2D materials with rich internal degrees of freedom (spin, excitonic, valley, sublattice, and layer pseudospin) together with the unique ability to tailor heterostructures made layer by layer in a precisely chosen stacking sequence and relative crystallographic alignments, offers an unprecedented platform for realizing materials by design. However, the breadth of multi‐dimensional parameter space and massive data sets involved is emblematic of complex, resource‐intensive experimentation, which not only challenges the current state of the art but also renders exhaustive sampling untenable. To this end, machine learning, a very powerful data‐driven approach and subset of artificial intelligence, is a potential game‐changer, enabling a cheaper – yet more efficient – alternative to traditional computational strategies. It is also a new paradigm for autonomous experimentation for accelerated discovery and machine‐assisted design of functional 2D materials and heterostructures. Here, the study reviews the recent progress and challenges of such endeavors, and highlight various emerging opportunities in this frontier research area.
Spatiotemporally Precise Optical Manipulation of Intracellular Molecular Activities
Authors: Dong Bin , Mahapatra Shivam , Clark Matthew G. , Carlsen Mark S. , Mohn Karsten J. , Ma Seohee , Brasseale Kent A. , Crim Grace , Zhang Chi
Published: January 2024

Controlling chemical processes in live cells is a challenging task. The spatial heterogeneity of biochemical reactions in cells is often overlooked by conventional means of incubating cells with desired chemicals. A comprehensive understanding of spatially diverse biochemical processes requires precise control over molecular activities at the subcellular level. Herein, a closed‐loop optoelectronic control system is developed that allows the manipulation of biomolecular activities in live cells at high spatiotemporal precision. Chemical‐selective fluorescence signals are utilized to command lasers that trigger specific chemical processes or control the activation of photoswitchable inhibitors at desired targets. This technology is fully compatible with laser scanning confocal fluorescence microscopes. The authors demonstrate selective interactions of a 405 nm laser with targeted organelles and simultaneous monitoring of cell responses by fluorescent protein signals. Notably, blue laser interaction with the endoplasmic reticulum leads to a more pronounced reduction in cytosolic green fluorescent protein signals in comparison to that with nuclei and lipid droplets. Moreover, when combined with a photoswitchable inhibitor, microtubule polymerization is selectively inhibited within the subcellular compartments. This technology enables subcellular spatiotemporal optical manipulation over chemical processes and drug activities, exclusively at desired targets, while minimizing undesired effects on non‐targeted locations.
Using Cu‐Based Metal–Organic Framework as a Comprehensive and Powerful Antioxidant Nanozyme for Efficient Osteoarthritis Treatment
Authors: Yu Bo , Sun Wei , Lin Juntao , Fan Chaoyu , Wang Chengxinqiao , Zhang Zhisen , Wang Yupeng , Tang Yonghua , Lin Youhui , Zhou Dongfang
Published: January 2024

Developing nanozymes with effective reactive oxygen species (ROS) scavenging ability is a promising approach for osteoarthritis (OA) treatment. Nonetheless, numerous nanozymes lie in their relatively low antioxidant activity. In certain circumstances, some of these nanozymes may even instigate ROS production to cause side effects. To address these challenges, a copper‐based metal–organic framework (Cu MOF) nanozyme is designed and applied for OA treatment. Cu MOF exhibits comprehensive and powerful activities (i.e., SOD‐like, CAT‐like, and •OH scavenging activities) while negligible pro‐oxidant activities (POD‐ and OXD‐like activities). Collectively, Cu MOF nanozyme is more effective at scavenging various types of ROS than other Cu‐based antioxidants, such as commercial CuO and Cu single‐atom nanozyme. Density functional theory calculations also confirm the origin of its outstanding enzyme‐like activities. In vitro and in vivo results demonstrate that Cu MOF nanozyme exhibits an excellent ability to decrease intracellular ROS levels and relieve hypoxic microenvironment of synovial macrophages. As a result, Cu MOF nanozyme can modulate the polarization of macrophages from pro‐inflammatory M1 to anti‐inflammatory M2 subtype, and inhibit the degradation of cartilage matrix for efficient OA treatment. The excellent biocompatibility and protective properties of Cu MOF nanozyme make it a valuable asset in treating ROS‐related ailments beyond OA.
Innate Immune Training Initiates Efferocytosis to Protect against Lung Injury
Authors: Kang Yoon‐Young , Kim Dong‐Young , Lee Sang‐Yong , Kim Hee‐Joong , Kim Taehawn , Cho Jeong A. , Lee Taewon , Choi Eun Young
Published: January 2024

Innate immune training involves myelopoiesis, dynamic gene modulation, and functional reprogramming of myeloid cells in response to secondary heterologous challenges. The present study evaluates whether systemic innate immune training can protect tissues from local injury. Systemic pretreatment of mice with β‐glucan, a trained immunity agonist, reduces the mortality rate of mice with bleomycin‐induced lung injury and fibrosis, as well as decreasing collagen deposition in the lungs. β‐Glucan pretreatment induces neutrophil accumulation in the lungs and enhances efferocytosis. Training of mice with β‐glucan results in histone modification in both alveolar macrophages (AMs) and neighboring lung epithelial cells. Training also increases the production of RvD1 and soluble mediators by AMs and efferocytes. Efferocytosis increases trained immunity in AMs by stimulating RvD1 release, thus inducing SIRT1 expression in neighboring lung epithelial cells. Elevated epithelial SIRT1 expression is associated with decreased epithelial cell apoptosis after lung injury, attenuating tissue damage. Further, neutrophil depletion dampens the effects of β‐glucan on macrophage accumulation, epigenetic modification in lung macrophages, epithelial SIRT1 expression, and injury‐mediated fibrosis in the lung. These findings provide mechanistic insights into innate immune training and clues to the potential ability of centrally trained immunity to protect peripheral organs against injury‐mediated disorders.
Strong Photon‐Magnon Coupling Using a Lithographically Defined Organic Ferrimagnet
Authors: Xu Qin , Cheung Hil Fung Harry , Cormode Donley S. , Puel Tharnier O. , Pal Srishti , Yusuf Huma , Chilcote Michael , Flatté Michael E. , Johnston‐Halperin Ezekiel , Fuchs Gregory D.
Published: January 2024

A cavity‐magnonic system composed of a superconducting microwave resonator coupled to a magnon mode hosted by the organic‐based ferrimagnet vanadium tetracyanoethylene (V[TCNE]x) is demonstrated. This work is motivated by the challenge of scalably integrating a low‐damping magnetic system with planar superconducting circuits. V[TCNE]xhas ultra‐low intrinsic damping, can be grown at low processing temperatures on arbitrary substrates, and can be patterned via electron beam lithography. The devices operate in the strong coupling regime, with a cooperativity exceeding 1000 for coupling between the Kittel mode and the resonator mode at T≈0.4 K, suitable for scalable quantum circuit integration. Higher‐order magnon modes are also observed with much narrower linewidths than the Kittel mode. This work paves the way for high‐cooperativity hybrid quantum devices in which magnonic circuits can be designed and fabricated as easily as electrical wires.
Insight of Synthesis of Single Crystal Ni‐Rich LiNi1−x−yCoxMnyO2 Cathodes
Authors: Wu Yingqiang , Wu Hanfeng , Deng Jiushuai , Han Zhiding , Xiao Xiang , Wang Li , Chen Zonghai , Deng Yida , He Xiangming
Published: January 2024

Single‐crystal Ni‐rich LiNi1−x−yCoxMnyO2 (NCM) cathodes have garnered widespread attention in the lithium‐ion battery community due to their unique advantages in mechanical performance and their ability to minimize interfacial electrochemical side reactions. The synthesis of single‐crystal materials with monodisperse and appropriate size, minimal lattice defects, and highly ordered structures is the key for high‐performance batteries. However, achieving this goal poses challenges due to the lack of in‐depth understanding regarding specific experimental parameters and the solid reaction mechanism during the synthesis process. In this review, the aim is to provide an in‐depth analysis of the critical process parameters involved in the synthesis and their impact on crystal morphology, structure, and electrochemical performance. Consequently, the first section focuses on the effect of the precursor morphology, lithium salt, atmosphere, and sintering procedure. In the second section, the study delves into an in‐depth discussion of the solid reaction and crystal growth mechanism. Lastly, it is concluded by highlighting the prospects and challenges associated with the synthesis and application of single‐crystal Ni‐rich NCM cathodes.
A 3 µm‐Ultrathin Hybrid Electrolyte Membrane with Integrative Architecture for All‐Solid‐State Lithium Metal Batteries
Authors: Liu Kexin , Cheng Hui , Wang Zhuyi , Zhao Yin , Lv Yingying , Shi Liyi , Cai Xuesong , Cheng Zhongling , Zhang Haijiao , Yuan Shuai
Published: January 2024

Ultrathin all‐solid‐state electrolytes with an excellent Li+ transport behavior are highly desirable for developing high‐energy‐density solid‐state lithium metal batteries. However, how to balance the electrochemical performance and their mechanical properties remains a huge challenge. Herein, an ultrathin solid electrolyte membrane with a thickness of only 3 µm and a weight of 11.7 g m−2 is well constructed by integrating individual functionalized organic with inorganic modules. Impressively, the optimized hybrid electrolyte membrane shows a set of merits including a high room‐temperature ionic conductivity of 1.77 × 10−4 S cm−1, large Li+ transference number of 0.65, and strong mechanical strength (strength of 29 MPa, elongation of 95%), as well as negligible thermal shrink at 180 °C. The analysis results reveal that the lithium sulfonate‐functionalized mesoporous silica nanoparticles in the membrane play a crucial role in the selective transport of Li+ through anion trapping and cation exchange. The pouch full cell is further assembled with a high‐voltage NCM cathode and thin lithium anode, which exhibits excellent long‐term cycling stability, outstanding rate performance at room temperature, and high safety against abused conditions. The current work provides an innovative strategy for achieving lithium metal batteries with ultrathin all‐solid‐state electrolytes.
Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries
Authors: Sim Richard , Manthiram Arumugam
Published: January 2024

Gas evolution from high‐nickel layered oxide cathodes (>90% Ni) remains a major issue for their practical application. Gaseous species, such as CO2, O2, and CO, that are evolved at high states of charge (SOC) worsen the overall safety of batteries, as pressure build‐up within the cell may lead to cell rupture. Since these gasses are produced during cathode degradation, tracking the formation of gasses is also important in diagnosing cathode failure. Online electrochemical mass spectrometry (OEMS) is a powerful in situ technique to study gas evolution from the cathode during high‐voltage charge. However, the differences in the OEMS experimental setups between different groups make it challenging to compare results between groups. In this perspective, the various factors that influence gas evolution based on the OEMS results collected in this group are presented. The focus is on the conditions that lead to gas release, with a particular emphasis on reactive oxygen formation and subsequent chemical reactions with the electrolyte. Promising strategies, such as electrolytes, compositional tuning, and surface coatings that are effective at suppressing gas evolution from the cathode are highlighted. Critical insights into mitigating cathode degradation and gas evolution are provided to guide the development of safer, high‐energy batteries.
Decoding Polymeric Additive‐Driven Self‐Healing Processes in Perovskite Solar Cells from Chemical and Physical Bonding Perspectives
Authors: Nam Jeong‐Seok , Choi Jin‐Myung , Lee Jang Woo , Han Jiye , Jeon Il , Kim Hyung Do
Published: January 2024

This review addresses the self‐healing effects in perovskite solar cells (PSCs), emphasizing the significance of chemical and physical bonding as core mechanisms. Polymeric additives play a vital role in inducing self‐healing phenomena along with the intrinsic properties of perovskite materials, both of which are discussed herein. As a relatively underexplored area, the self‐healing effect induced by polymeric additives in PSCs is reviewed from a chemical perspective. The chemical bonds involved in self‐healing include isocyanate, disulfide, and carboxylic acid groups. The physical bonds related to self‐healing effects are primarily hydrogen bonding and chelation. Self‐healing in flexible perovskite devices extends their lifespan and improves their mechanical robustness against environmental and mechanical stressors. This discussion delves into the initiation methods for self‐healing, the conditions required, and the recovery‐rate profiles. This review not only catalogs various approaches to self‐healing, but also considers the fundamental limitations and potential of this phenomenon in PSCs. In addition, insights and an outlook on self‐healing in perovskite‐based optoelectronics are provided, offering guidance for future research and applications.
Toward Air Stability of Efficient Filter‐Free Band‐Selective Organic Photodetectors Based on Bulk Heterojunction: Avoiding Environmental Degradation with Atomic Layer Deposition Encapsulation
Authors: Eynaud Quentin , Kramdi Mohamed el Amine , Kannampalli Vyshnav , Koganezawa Tomoyuki , Yoshimoto Noriyuki , Santinacci Lionel , Ackermann Jörg , Videlot‐Ackermann Christine
Published: January 2024

To detect the band‐specific optical signals used in many fields, it is necessary to develop spectrally selective photodetection. For such wavelength‐selective photodetection or color discrimination, organic photodetectors (OPDs) can offer significant benefits as low temperature and solution processability, chemical versatility, and specific spectral detection range. However, to avoid commonly used filters, the design of a narrowing approach that simultaneously achieves a selective detection range with a bandwidth of less than 50 nm and a spectral response of over 20% remains a challenge. OPDs based on charge‐collection‐narrowing principle can provide these features. In this approach, the detection window can be selected to match the absorption onset of the junction materials used in the bulk heterojunction layer. Herein, filter‐free band‐selective OPDs are realized based on PM6:PC70BM blends as state of the art. Fine adjustment over a bandwidth of 42 nm to be highly selective at 677 nm with a quantum efficiency of 48.4% under an inverse low bias of −2 V is reached. In addition, using a noninvasive and nondestructive encapsulation technique, it is demonstrated that these OPDs fully retain their high selective peak after 30 days storage in air.
All‐Inorganic Perovskite Solar Cells: Modification Strategies and Challenges
Authors: Li Xin‐Yi , Sun Qi , Xie Yue‐Min , Fung Man‐Keung
Published: January 2024

Cesium‐based all‐inorganic wide‐bandgap perovskite solar cells (AIWPSCs) have been demonstrated with exceptional optoelectronic properties such as intrinsic optical wide‐bandgap and high thermal stability, which make them suitable candidates for the front sub‐cells of tandem solar cells (TSCs). Passivation of perovskite surface and interface is a matter of common interest in this community since all‐inorganic perovskites always suffer from non‐ideal crystallization such as phase impurity, high defect density, and non‐uniform morphology. Despite these shortcomings, numerous efforts have been devoted in recent years to pursuing high‐performance AIWPSCs, which exhibit an abruptly increased power conversion efficiency (PCE) from 2.9% to over 21.0%. In view of not having a thorough summary about the advancements on AIWPSCs, herein, a comprehensive review is given to highlight the recent device performance progress of AIWPSC, particularly focusing on the strategies to passivate the defects of all‐inorganic perovskite, namely, additive engineering, solvent engineering, interface modification, and the exploration of new charge transport materials (CTMs) for improving the phase stability and PCE of AIWPSCs. Finally, a conclusive outlook on AIWPSCs will be given to provide our perspectives aiming to inspire the further development of AIWPSCs.
The current multidisciplinary management of rectal cancer
Authors: Bhutiani Neal , Peacock Oliver , Uppal Abhineet , You Y. Nancy , Bednarski Brian K. , Skibber John M. , Messick Craig , White Michael G. , Chang George J. , Konishi Tsuyoshi
Published: January 2024

Multidisciplinary management of rectal cancer has rapidly evolved over the last several years. This review describes recent data surrounding total neoadjuvant therapy, organ preservation, and management of lateral pelvic lymph nodes. It then presents our treatment algorithm for management of rectal cancer at The University of Texas MD Anderson Cancer Center in the context of this and other existing literature. As part of this discussion, the review describes how we tailor management based upon both patient and tumor‐related factors in an effort to optimize patient outcomes.
Nanotechnology‐Empowered Combination Cancer Immunotherapies: Mechanisms, Synergies, and Perspectives
Authors: Pan Yuqing , Xue Xiangdong , Liang Xing‐Jie
Published: January 2024

This review is aiming to systematically elucidate the unique role of nanotechnology in optimizing therapeutic modalities for combinatorial cancer immunotherapy, which enables the synergistic integration of multiple treatment strategies. In particular, nanotechnology has enabled the synergistic combination of immunotherapy with physical therapies, chemotherapy, metal therapy, and nucleic acid therapy. In each combination regimen, nanocarriers play multifaceted roles by achieving targeted codelivery of different therapeutics and optimizing each individual treatment modality. This offers new paradigms to guide precision medicine in cancer treatment. Immunotherapy alone is unlikely to achieve personalized precision medicine for cancer, and new treatment modalities are needed in the future. To overcome technical bottlenecks and realize precise regulation of the tumor microenvironment for personalized cancer treatment, it is crucial to develop novel nanosystems with integrated sensing, targeting, and therapeutic functionalities.
Leveraging Expertise in Thermal Catalysis to Understand Plasma Catalysis
Authors: Lefferts Leon
Published: January 2024

Best practices in testing heterogeneous catalysts are translated to plasma‐catalytic experiments. Independent determination of plasma‐catalytic and plasma‐chemical contributions is essential. Non‐porous catalyst particles are preferred because active sites inside sub‐micron pores cannot contribute. Temperature variation is needed to determine kinetics, despite the complexity of thermal effects in plasma. Rigorous checks on catalyst deactivation and mass balance are needed. Plasma enhanced reversed reactions should be minimized by keeping conversion low and far from thermodynamic equilibrium, preventing underestimation of the rate of forward reaction. In contrast, plasma‐catalytic studies often aim at conversions surpassing thermodynamic equilibrium, not obtaining any information on kinetics. Calculation of catalyst activity per active sites (turn‐over‐frequency) requires also appropriate characterization to determine the number of active sites. The relationship between kinetics and thermodynamics for plasma‐catalysis is discussed using endothermic decomposition of CO2 and exothermic synthesis of ammonia from N2 and H2 as examples. Assuming Langmuir–Hinshelwood and Eley‐Rideal mechanisms, the effect of excitation of reactant molecules on activation barriers and surface coverages are discussed, influencing reaction rates. The consequences of reversed reactions are considered. Plasma‐catalysis with catalysts applied for thermal catalysis at much higher temperature should be avoided, as adsorbed species are bonded too strongly resulting in low rates.
Water‐Degradable Oxygen‐Rich Polymers with AB/ABB Units from Fast and Selective Copolymerization
Authors: Zhang Xun , Xia Yanni , Sun Yue , Zhang Chengjian , Zhang Xinghong
Published: January 2024

Researchers have been chasing plastics that can automatically and fully degrade into valuable products under natural conditions. Here, we develop a series of water‐degradable polymers from the first reported fast and selective cationic copolymerization of formaldehyde (B) with cyclic anhydrides (A). In addition to readily accessible monomers, the method is performed at industrially relevant temperatures (~100 °C), takes tens or even minutes, and uses common acid as the catalyst. Interestingly, such polymers possess tunable AB/ABB‐type repeating units, which are considered to be thermodynamic and kinetic products, respectively, resulting in low carbon content ([O] : [C] up to 1 : 1). Notably, the polymers can completely degrade to valuable diacids within 150 days in water at ambient temperature owing to the incorporation of carboxyl terminals and acid‐responsive acetal units. By washing with aqueous sodium carbonate, the polymers are relatively stable over several months.
Enhanced Directed Evolution in Mammalian Cells Yields a Hyperefficient Pyrrolysyl tRNA for Noncanonical Amino Acid Mutagenesis
Authors: Jewel Delilah , Kelemen Rachel E. , Huang Rachel L. , Zhu Zeyu , Sundaresh Bharathi , Malley Kaitlin , Pham Quan , Loynd Conor , Huang Zeyi , van Opijnen Tim , Chatterjee Abhishek
Published: January 2024

Heterologous tRNAs used for noncanonical amino acid (ncAA) mutagenesis in mammalian cells typically show poor activity. We recently introduced a virus‐assisted directed evolution strategy (VADER) that can enrich improved tRNA mutants from naïve libraries in mammalian cells. However, VADER was limited to processing only a few thousand mutants; the inability to screen a larger sequence space precluded the identification of highly active variants with distal synergistic mutations. Here, we report VADER2.0, which can process significantly larger mutant libraries. It also employs a novel library design, which maintains base‐pairing between distant residues in the stem regions, allowing us to pack a higher density of functional mutants within a fixed sequence space. VADER2.0 enabled simultaneous engineering of the entire acceptor stem of M. mazei pyrrolysyl tRNA (tRNAPyl), leading to a remarkably improved variant, which facilitates more efficient incorporation of a wider range of ncAAs, and enables facile development of viral vectors and stable cell‐lines for ncAA mutagenesis.
Selective C−H Halogenation of Alkenes and Alkynes Using Flavin‐Dependent Halogenases
Authors: Jiang Yuhua , Kim Ahram , Olive Cahmlo , Lewis Jared C.
Published: January 2024

Single component flavin‐dependent halogenases (FDHs) possess both flavin reductase and FDH activity in a single enzyme. We recently reported that the single component FDH AetF catalyzes site‐selective bromination and iodination of a variety of aromatic substrates and enantioselective bromolactonization and iodoetherification of styrenes bearing pendant carboxylic acid or alcohol substituents. Given this inherent reactivity and selectivity, we explored the utility of AetF as catalyst for alkene and alkyne C−H halogenation. We find that AetF catalyzes halogenation of a range of 1,1‐disubstituted styrenes, often with high stereoselectivity. Despite the utility of haloalkenes for cross‐coupling and other applications, accessing these compounds in a stereoselective manner typically requires functional group interconversion processes, and selective halogenation of 1,1′‐disubstituted olefins remains rare. We also establish that AetF and homologues of this enzyme can halogenate terminal alkynes. Mutagenesis studies and deuterium kinetic isotope effects are used to support a mechanistic proposal involving covalent catalysis for halogenation of unactivated alkynes by AetF homologues. These findings expand the scope of FDH catalysis and continue to show the unique utility of single component FDHs for biocatalysis.
π‐Radical Cascade to a Chiral Saddle‐Shaped Peropyrene
Authors: Bernhardt Annika , Čavlović Daniel , Mayländer Maximilian , Blacque Olivier , Cruz Carlos M. , Richert Sabine , Juríček Michal
Published: January 2024

Reactions of open‐shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π‐magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via formation of multiple bonds and rings in a single step. Here, we explore the feasibility of using this “undesired” reaction of phenalenyl to build up strain and provide access to non‐planar polycyclic aromatic hydrocarbons. To this end, we designed and synthesized a biradical system with two phenalenyl units linked via a biphenylene backbone. The design facilitates an intramolecular cascade reaction to a helically twisted saddle‐shaped product, where the key transformations—ring‐closure and ring‐fusion—occur within one reaction. The negative curvature of the final peropyrene product, induced by the formed eight‐membered ring, was confirmed by single‐crystal X‐ray diffraction analysis and the helical twist was validated via resolution of the product's enantiomers that display circularly polarized luminescence and high configurational stability.
Spirobifluorene‐Based Porous Organic Salts: Their Porous Network Diversification and Construction of Chiral Helical Luminescent Structures
Authors: Okubo Kohei , Oka Kouki , Tsuchiya Keiho , Tomimoto Atsunori , Tohnai Norimitsu
Published: January 2024

Porous organic salts (POSs) are organic porous materials assembled via charge‐assisted hydrogen bonds between strong acids and bases such as sulfonic acids and amines. To diversify the network topology of POSs and extend its functions, this study focused on using 4,4′,4′′,4′′′‐(9,9′‐spirobi[fluorene]‐2,2′,7,7′‐tetrayl)tetrabenzenesulfonic acid (spiroBPS), which is a tetrasulfonic acid comprising a square planar skeleton. The POS consisting of spiroBPS and triphenylmethylamine (TPMA) (spiroBPS/TPMA) was constructed from the two‐fold interpenetration of an orthogonal network with pts topology, which has not been reported in conventional POSs, owing to the shape of the spirobifluorene backbone. Furthermore, combining tris(4‐chlorophenyl)methylamine (TPMA‐Cl) and tris(4‐bromophenyl)methylamine (TPMA‐Br), which are bulkier than TPMA owing to the introduction of halogens at the p‐position of the phenyl groups with spiroBPS allows us to construct novel POSs (spiroBPS/TPMA‐Cl and spiroBPS/TPMA‐Br). These POSs were constructed from a chiral helical network with pth topology, which was induced by the steric hindrance between the halogens and the curved fluorene skeleton. Moreover, spiroBPS/TPMA‐Cl with pth topology exhibited circularly polarized luminescence (CPL) in the solid state, which has not been reported in hydrogen‐bonded organic frameworks (HOFs).
Chiral CpxRhodium(III)‐Catalyzed Enantioselective Aziridination of Unactivated Terminal Alkenes
Authors: Wang Juanjuan , Luo Mu‐Peng , Gu Yi‐Jie , Liu Yu‐Ying , Yin Qin , Wang Shou‐Guo
Published: January 2024

Chiral cyclopentadienyl‐rhodium(III) CpxRh(III) catalysis has been demonstrated to be competent for catalyzing highly enantioselective aziridination of challenging unactivated terminal alkenes and nitrene sources. The chiral CpxRh(III) catalysis system exhibited outstanding catalytic performance and wide functional group tolerance, yielding synthetically important and highly valuable chiral aziridines with good to excellent yields and enantioselectivities (up to 99 % yield, 93 % ee). This protocol presents a novel and effective strategy for synthesizing enantioenriched aziridines from simple alkenes. Various transformations were performed on the aziridine products, illustrating the versatility and synthetic potential of this protocol for constructing highly functionalized compounds.
Engineering Hydroxylase Activity, Selectivity, and Stability for a Scalable Concise Synthesis of a Key Intermediate to Belzutifan
Authors: Cheung‐Lee Wai Ling , Kolev Joshua N. , McIntosh John A. , Gil Agnieszka A. , Pan Weilan , Xiao Li , Velásquez Juan E. , Gangam Rekha , Winston Matthew S. , Li Shasha , Abe Kotoe , Alwedi Embarek , Dance Zachary E. X. , Fan Haiyang , Hiraga Kaori , Kim Jungchul , Kosjek Birgit , Le Diane N. , Marzijarani Nastaran Salehi , Mattern Keith , McMullen Jonathan P. , Narsimhan Karthik , Vikram Ajit , Wang Wei , Yan Jia‐Xuan , Yang Rong‐Sheng , Zhang Victoria , Zhong Wendy , DiRocco Daniel A. , Morris William J. , Murphy Grant S. , Maloney Kevin M.
Published: January 2024

Biocatalytic oxidations are an emerging technology for selective C−H bond activation. While promising for a range of selective oxidations, practical use of enzymes catalyzing aerobic hydroxylation is presently limited by their substrate scope and stability under industrially relevant conditions. Here, we report the engineering and practical application of a non‐heme iron and α‐ketoglutarate‐dependent dioxygenase for the direct stereo‐ and regio‐selective hydroxylation of a non‐native fluoroindanone en route to the oncology treatment belzutifan, replacing a five‐step chemical synthesis with a direct enantioselective hydroxylation. Mechanistic studies indicated that formation of the desired product was limited by enzyme stability and product overoxidation, with these properties subsequently improved by directed evolution, yielding a biocatalyst capable of >15,000 total turnovers. Highlighting the industrial utility of this biocatalyst, the high‐yielding, green, and efficient oxidation was demonstrated at kilogram scale for the synthesis of belzutifan.
Palladium‐Catalyzed Deuteration of Arylketone Oxime Ethers
Authors: Wang Zhen‐Yu , Zhang Xu , Chen Wen‐Qing , Sun Guo‐Dong , Wang Xing , Tan Lin , Xu Hui , Dai Hui‐Xiong
Published: January 2024

We report herein the development of palladium‐catalyzed deacylative deuteration of arylketone oxime ethers. This protocol features excellent functional group tolerance, heterocyclic compatibility, and high deuterium incorporation levels. Regioselective deuteration of some biologically important drugs and natural products are showcased via Friedel–Crafts acylation and subsequent deacylative deuteration. Vicinal meta‐C−H bond functionalization (including fluorination, arylation, and alkylation) and para‐C−H bond deuteration of electro‐rich arenes are realized by using the ketone as both directing group and leaving group, which is distinct from aryl halide in conventional dehalogenative deuteration.
Preparation of thermally stable and flame‐retardant sugarcane bagasse‐ammonium dihydrogen phosphate/epoxy composites and their performance
Authors: Liu Shang‐Hao , Kuan Chen‐Feng , Ke Cing‐Yu , Shen Ming‐Yuan , Chiang Chin‐Lung
Published: January 2024

Epoxy resin was often applied in fiber‐reinforced composite materials, adhesives, and encapsulation materials. However, epoxy was easily flammable and limited its usage in certain applications. The study recycled and reused agricultural waste sugarcane bagasse to prepare a halogen‐free bio‐based intumescent flame retardant and then mixed with epoxy resin to prepare a composite containing polymer with improved thermal properties and flame retardancy of the materials. The work followed the concept of circular economy and sustainability. Bagasse‐ammonium dihydrogen phosphate (ADP) flame retardant was added to an epoxy resin to prepare epoxy/bagasse‐ADP composites, an effective flame‐retarding composite material through hydrothermal method. Adding bagasse‐ADP increased the thermal stability and flame retardancy of the composite materials compared with that of pure epoxy. For the material with 30 wt% added bagasse‐ADP, the char yield was 32.3 wt%, which was 18.2 wt% higher than that of pure epoxy (14.1 wt%) through thermogravimetric analysis. In addition, the limiting oxygen index increased from 21% to 30%, and the UL‐94 classification improved from “Fail” to “V‐0.” This performance was attributed to the nitrogen, phosphorus, and silicon content of the flame retardant.
Compositae‐ParaLoss‐1272: A complementary sunflower‐specific probe set reduces paralogs in phylogenomic analyses of complex systems
Authors: Moore‐Pollard Erika R. , Jones Daniel S. , Mandel Jennifer R.
Published: January 2024

Premise

A family‐specific probe set for sunflowers, Compositae‐1061, enables family‐wide phylogenomic studies and investigations at lower taxonomic levels, but may lack resolution at genus to species levels, especially in groups complicated by polyploidy and hybridization.

Methods

We developed a Hyb‐Seq probe set, Compositae‐ParaLoss‐1272, that targets orthologous loci in Asteraceae. We tested its efficiency across the family by simulating target enrichment sequencing in silico. Additionally, we tested its effectiveness at lower taxonomic levels in the historically complex genus Packera. We performed Hyb‐Seq with Compositae‐ParaLoss‐1272 for 19 Packera taxa that were previously studied using Compositae‐1061. The resulting sequences from each probe set, plus a combination of both, were used to generate phylogenies, compare topologies, and assess node support.

Results

We report that Compositae‐ParaLoss‐1272 captured loci across all tested Asteraceae members, had less gene tree discordance, and retained longer loci than Compositae‐1061. Most notably, Compositae‐ParaLoss‐1272 recovered substantially fewer paralogous sequences than Compositae‐1061, with only ~5% of the recovered loci reporting as paralogous, compared to ~59% with Compositae‐1061.

Discussion

Given the complexity of plant evolutionary histories, assigning orthology for phylogenomic analyses will continue to be challenging. However, we anticipate Compositae‐ParaLoss‐1272 will provide improved resolution and utility for studies of complex groups and lower taxonomic levels in the sunflower family.
The redescription of Malerisaurus robinsonae (Archosauromorpha: Allokotosauria) from the Upper Triassic lower Maleri Formation, Pranhita‐Godavari Basin, India
Authors: Sengupta Saradee , Ezcurra Martín D. , Bandyopadhyay Saswati
Published: January 2024

Allokotosauria, a clade of non‐archosauriform archosauromorphs with a broad diversity of body plans, plays a crucial role in better understanding the evolutionary history of early diverging stem‐archosaurs. Here we provide a detailed redescription of Malerisaurus robinsonae, a malerisaurine allokotosaur from the middle Carnian—lowermost Norian lower Maleri Formation, Pranhita‐Godavari Basin, India. The new anatomical information available from recently discovered and well‐preserved skeletons of various allokotosaurs, such as Azendohsaurus madagaskarensis, Shringasaurus indicus, Puercosuchus traverorum, and Malerisaurus‐like taxa, and their comparison with Malerisaurus robinsonae enriches our understanding of the anatomy of this species. To reassess the phylogenetic relationships of Malerisaurus robinsonae, we revised its scorings and included eight additional allokotosaurian species to the already most comprehensive phylogenetic dataset focused on Permo‐Triassic archosauromorphs. We modified 70 scorings for Malerisaurus robinsonae and the new analysis recovered this species at the base of Malerisaurinae and this group as the earliest branch of Azendohsauridae. Pamelaria dolichotrachela is found as the earliest diverging non‐malerisaurine azendohsaurid and sister taxon to the Shringasaurus indicus + Azendohsaurus spp. clade. Trilophosaurid interrelationships are well resolved, with Teraterpeton hrynewichorum, Coelodontognathus ricovi, and Rutiotomodon tytthos as their successive earliest‐branching species. The position of Anisodontosaurus greeri as a sister taxon to Variodens inopinatus bolsters long ghost lineages in the Late Triassic trilophosaurid record. A disparity analysis of tooth crown morphology shows that Allokotosauria is the most disparate Permo‐Triassic archosauromorph clade, exploring the almost complete range of basic crown morphologies. Trilophosaurids occupy an area of the dental morphospace unique among archosauromorphs.
Recent Advances in Hydrogenation of CO2 to CO with Heterogeneous Catalysts Through the RWGS Reaction
Authors: Zhang Wenting , Sun Jiashu , Wang Hongli , Cui Xinjiang
Published: January 2024

With the continuous increase in CO2 emissions, primarily from the combustion of coal and oil, the ecosystem faces a significant threat. Therefore, as an effective method to minimize the issue, the Reverse Water Gas Shift (RWGS) reaction which converts CO2 towards CO attracts much attention, is an environmentally‐friendly method to mitigate climate change and lessen dependence on fossil fuels. Nevertheless, the inherent thermodynamic stability and kinetic inertness of CO2 is a big challenge under mild conditions. In addition, it remains another fundamental challenge in RWGS reaction owing to CO selectivity issue caused by CO2 further hydrogenation towards CH4. Up till now, a series of catalysis systems have been developed for CO2 reduction reaction to produce CO. Herein, the research progress of the well‐performed heterogeneous catalysts for the RWGS reaction were summarized, including the catalyst design, catalytic performance and reaction mechanism. This review will provide insights into efficient utilization of CO2 and promote the development of RWGS reaction.
Brain glutathione and GABA+ levels in autistic children
Authors: Song Yulu , Hupfeld Kathleen E. , Davies‐Jenkins Christopher W. , Zöllner Helge J. , Murali‐Manohar Saipavitra , Mumuni Abdul Nashirudeen , Crocetti Deana , Yedavalli Vivek , Oeltzschner Georg , Alessi Natalie , Batschelett Mitchell A. , Puts Nicolaas A. J. , Mostofsky Stewart H. , Edden Richard A. E.
Published: January 2024

Autism spectrum disorder (ASD) is a neurodevelopmental condition characterized by social communication challenges and repetitive behaviors. Altered neurometabolite levels, including glutathione (GSH) and gamma‐aminobutyric acid (GABA), have been proposed as potential contributors to the biology underlying ASD. This study investigated whether cerebral GSH or GABA levels differ between a cohort of children aged 8–12 years with ASD (n = 52) and typically developing children (TDC, n = 49). A comprehensive analysis of GSH and GABA levels in multiple brain regions, including the primary motor cortex (SM1), thalamus (Thal), medial prefrontal cortex (mPFC), and supplementary motor area (SMA), was conducted using single‐voxel HERMES MR spectroscopy at 3T. The results revealed no significant differences in cerebral GSH or GABA levels between the ASD and TDC groups across all examined regions. These findings suggest that the concentrations of GSH (an important antioxidant and neuromodulator) and GABA (a major inhibitory neurotransmitter) do not exhibit marked alterations in children with ASD compared to TDC. A statistically significant positive correlation was observed between GABA levels in the SM1 and Thal regions with ADHD inattention scores. No significant correlation was found between metabolite levels and hyper/impulsive scores of ADHD, measures of core ASD symptoms (ADOS‐2, SRS‐P) or adaptive behavior (ABAS‐2). While both GSH and GABA have been implicated in various neurological disorders, the current study provides valuable insights into the specific context of ASD and highlights the need for further research to explore other neurochemical alterations that may contribute to the pathophysiology of this complex disorder.
Preconditioning Operation of Membraneless Vanadium Micro Redox Flow Batteries
Authors: Oraá‐Poblete Beatriz , Perez‐Antolin Daniel , Maurice Ange A. , Palma Jesus , Kjeang Erik , Quintero Alberto E.
Published: January 2024

Invited for this month's cover picture is the R&D Department of B5tec lead by Dr. Alberto Quintero. The cover picture shows the first membraneless micro flow battery prototype. Read the full text of the Research Article at 10.1002/batt.202300367.
The positioning tensions between early career teachers’ and mentors’ perceptions of the mentor role
Authors: Curtis Elizabeth , Nguyen Hoa Thi Mai , Larsen Ellen , Loughland Tony
Published: January 2024

Early career teacher (ECT) mentoring has never been so important with escalating levels of attrition reported in numerous countries, including Australia, the US and the UK. However, inconsistent understanding of what a mentor can or should do continues to compromise the ways in which early career teachers experience this support. While previous research has reported on mentors’ differing perspectives on their role, we take a unique approach to this issue. In this paper, we explore the ways in which both mentors and ECTs understand the mentor role. We argue that where mentor and ECT understandings are in tension, the productive outcomes of mentoring for both the mentor and ECT are undermined. Drawing on Positioning Theory we report findings from the thematic analysis of 31 online interviews with 16 mentors and 15 ECTs in Australia. We found that while ECTs and mentors hold some common positionings, some significant differences were noted. These findings highlight the need to extend opportunities to learn about the mentoring role to include ECTs.
Development of novel carbon‐based biomedical platforms for intervention in xenotoxicant‐induced Parkinson's disease onset
Authors: Kumar Jyotish , Varela‐Ramirez Armando , Narayan Mahesh
Published: January 2024

Chronic exposure to herbicides, weedicides, and pesticides is associated with the onset and progress of neurodegenerative disorders such as Parkinson's disease (PD), Alzheimer's disease (AD), and Amyotrophic Lateral Sclerosis (ALS). Here, we have investigated whether quinic‐ and chlorogenic‐acid‐derived Carbon Quantum Dots (QACQDs and ChACQDs, respectively) protect against a (pesticide) paraquat‐insult model of PD. Our results indicated that both types of CQDs intervened in the soluble‐to‐toxic transformation of the amyloid‐forming model protein Hen Egg White Lysozyme (HEWL). Furthermore, QACQDs and ChACQDs demonstrated antioxidant activity while remaining biocompatible in a human neuroblastoma‐derived cell line (SH‐SY5Y) up to 5 mg/ml and protected the cell line from the environmental neurotoxicant (paraquat). Importantly, both CQDs were found to protect dopaminergic neuronal ablation in a paraquat model of Parkinson's disease using the nematode C. elegans. Our results are significant because both plant‐derived organic acids cross the blood–brain barrier, making them attractive for developing CQD architectures. Furthermore, since the synthesis of these CQDs was performed using green chemistry methods from precursor acids that cross the BBB, these engineered bionanomaterial platforms are tantalizing candidates for preventing neurodegenerative disorders associated with exposure to environmental neurotoxicants.
In Situ Preparation of Dehydrodieugenol‐Loaded Silver Nanoparticles and their Antischistosomal Activity
Authors: Oliveira Larissa V. F. , Camilo Fernanda F. , Soares Marisi G. , Cajas Rayssa A. , Cirino Maria E. , de Moraes Josué , Lago João Henrique G.
Published: January 2024

Schistosomiasis is a major neglected disease that imposes a substantial worldwide health burden, affecting approximately 250 million people globally. As praziquantel is the only available drug to treat schistosomiasis, there is a critical need to identify new anthelmintic compounds, particularly from natural sources. To enhance the activity of different natural products, one potential avenue involves its combination with silver nanoparticles (AgNP). Based on this approach, a one‐step green method for the in situ preparation of dehydrodieugenol (DHDG) by oxidation coupling reaction using silver and natural eugenol is presented. AgNP formation was confirmed by UV‐Vis spectroscopy due to the appearance of the surface plasmon resonance (SPR) band at 430 nm which is characteristic of silver nanoparticles. The nanoparticles were spherical with sizes in the range of 40 to 50 nm. Bioassays demonstrated that the silver nanoparticles loaded with DHDG exhibited significant anthelmintic activity against Schistosoma mansoni adult worms without toxicity to mammalian cells and an in vivo animal model (Caenorhabditis elegans), contributing to the development of new prototypes based on natural products for the treatment of schistosomiasis.