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Iwamoto, Sora; Nakano, Reki; Sasaki, Keiji; Kobayashi, Shoichiro; Taira, Yuki; Takei, Koya; Kawakita, Reiji; Tokuyama, Ayako; Nakamura, Haruto; Tomoike, Manato; Kawahara, Ryota; Murase, Akari; Simizu, Siro; Chida, Noritaka; Okamura, Toshitaka; Sato, Takaaki
doi: 10.1002/anie.202508062pmid: 40326370
The total synthesis of isodaphlongamine H based on a lactam strategy, which enables quick access to complex cyclic amines, is described. The strategy begins with alkylation of a chiral lactam and subsequent N‐oxidation via an imino ether to afford the N‐hydroxylactam. For the key transformation to functionalize the amide carbonyl, an iridium‐catalyzed reductive [3 + 2] cycloaddition of the N‐hydroxylactam provides a tricyclic isoxazolidine in a one‐pot process. After the coupling reaction with an allylic silane fragment, the total synthesis is accomplished through intramolecular Hosomi–Sakurai allylation to construct a pentacyclic core. The deoxygenated pentacyclic intermediate shows higher cytotoxicity against HeLa and U937 cell lines than isodaphlongamine H, and might become a lead compound for further biological study.
Sturm, Hunter; Teufel, Jonas; Isfeld, Kaitlin A.; Friederich, Pascal; Davis, Rebecca L.
doi: 10.1002/anie.202503259pmid: 40384591
Herein, we present the application of multi‐channel graph attention network (MEGAN), our explainable AI (xAI) model, for the identification of small colloidally aggregating molecules (SCAMs). This work offers solutions to the long‐standing problem of false positives caused by SCAMs in high‐throughput screening for drug discovery and demonstrates the power of xAI in the classification of molecular properties that are not chemically intuitive based on our current understanding. We leverage xAI insights and molecular counterfactuals to design alternatives to problematic compounds in drug screening libraries. Additionally, we experimentally validate the MEGAN prediction classification for one of the counterfactuals and demonstrate the utility of counterfactuals for altering the aggregation properties of a compound through minor structural modifications. The integration of this method in high‐throughput screening approaches will help combat and circumvent false positives, providing better lead molecules more rapidly and thus accelerating drug discovery cycles.
Chen, Zijian; Li, Zhizhi; Tian, Yingrui; Liu, Denghui; Yang, Zhihai; Li, Mengke; Su, Shi‐Jian
doi: 10.1002/anie.202507626pmid: 40345985
Selenium‐containing multiple resonance thermally activated delayed fluorescence (MR‐TADF) materials with ultra‐fast reverse intersystem crossing (RISC) have emerged as a promising solution for mitigating efficiency roll‐off in organic light‐emitting diodes (OLEDs). In this work, we introduce DBSeBN, the first MR‐TADF emitter incorporating a rigid five‐membered dibenzoselenophene unit. This design simultaneously achieves a narrow full width at half maximum of 23 nm across a wide range of doping concentrations in films, along with an ultra‐fast RISC rate of 1.1 × 107 s−1, which is two orders higher than that of its sulfur‐containing counterpart, DBTBN, due to the enhanced spin‐orbit coupling via the heavy atom effect of selenium. As an OLED emitter, DBSeBN demonstrates exceptional performance, achieving a maximum external quantum efficiency of 31.6% and retaining 23.3% at 1000 cd m−2, surpassing DBTBN in suppressing efficiency roll‐off. Its remarkably fast RISC and insensitivity to doping concentration enable unprecedented versatility in advanced OLED architectures. As a sensitizer in sensitized green‐fluorescent OLEDs, it surpasses Ir‐based complex sensitizers in reducing efficiency roll‐off. As a blue emitter in bi‐color white OLEDs, it effectively harnesses high‐energy triplet excitons to minimize efficiency roll‐off. DBSeBN thus expands the scope of MR‐TADF materials across various kinds of OLED applications while suppressing efficiency roll‐off.
Ma, Xin‐Yue; Wang, Xiao‐Xue; Guan, De‐Hui; Miao, Cheng‐Lin; Wang, Huan‐Feng; Zhu, Qing‐Yao; Xu, Ji‐Jing
doi: 10.1002/anie.202504767pmid: 40377653
Solid‐state electrolytes (SSEs) have emerged as high‐priority materials for ensuring the safe operation of solid‐state lithium (Li) batteries. However, current SSEs still face challenges of balancing stability and ionic conductivity, which limits their practical applications in solid‐state Li batteries. Here, we report a general strategy for achieving high‐performance SSEs by constructing a Li+‐conducted polymeric metal–organic nanocapsule (PolyMONC(Li)) network through molecular design. With the unique cage structure and pore size, metal–organic nanocapsule (MONC) can achieve excellent anion confinement effects. The PolyMONC(Li) network with continuous Li+ conduction pathways serves as a solid electrolyte exhibiting a high ionic conductivity (0.18 mS cm−1 at 25 °C) and a high Li+ transference number (0.83). Combining the two superiorities of optimal balance between mechanical strength and excellent Li+ conductivity, the PolyMONC(Li) can still restrain the dendrite growth and prevent Li symmetric batteries from short‐circuiting even over 900 h cycling. The PolyMONC(Li)‐based SSEs Li‐metal batteries achieved a higher specific capacity than common polymer electrolytes such as polyethylene oxide‐based SSE. Additionally, taking advantage of the PolyMONC(Li) electrode binder, the solid‐state Li–O2 battery achieves a stable cycling over 400 cycles. This work provides a comprehensive guideline for developing porous solids from molecule design to practical application.
Zhang, Chu; Zhou, Quan; Li, Zeyu; Yan, Chunshuang; Liu, Hengjie; Liu, Daobin; Song, Li; Yan, Qingyu; Lv, Chade
doi: 10.1002/anie.202507869pmid: 40355377
Electrocatalytic coupling of CO2 and NO3− offers a sustainable approach for urea production. However, the limited supply of active hydrogen (*H) hinders the formation of the key carbon‐ and nitrogen‐containing intermediates, thus impeding the selective C─N coupling. Herein, we developed copper molybdate (Cu3Mo2O9) nanorods, which could serve as “active hydrogen pump” catalysts by regulating the water dissociation and hydrogen adsorption. Such electrocatalyst would guarantee a steady *H supply for intermediates hydrogenation, hence boosting the generation of *CO and *NH2 intermediates for selective C‒N coupling and urea production. In a CO2‐saturated 0.1 M KNO3 solution, Cu3Mo2O9 achieved a maximum urea yield rate of 177 mmol h−1 g−1 with a urea‐producing FE of 40% in a flow cell configuration, outperforming most reported electrocatalysts. This study underscores the crucial role of *H, which may guide the exploration of advanced catalysts for expediting the sustainable synthesis of indispensable chemicals requiring rapid intermediates hydrogenation.
Ding, Ning; Jiang, Yaoyukun; Ge, Robbie; Shao, Qianzhen; Shin, Wook; Ran, Xinchun; Yang, Zhongyue J.
doi: 10.1002/anie.202505991pmid: 40272877
Cold‐adapted bidomain enzymes have the potential to foster industrial sustainability by reducing energy consumption and greenhouse gas emissions. Despite their allure, these benefits are unattainable, as the molecular basis of cold adaptation remains elusive, and there are no strategies to guide the acquisition of this behavior. To uncover principles of cold adaptation, we selected the cold‐adapted Saccharophagus degradans amylase (sdA) and mesophilic Pseudomonas saccharophila amylase (psA) as model systems. Through molecular dynamics (MD) simulations and biochemical assays, we found that sdA exhibits significantly greater interdomain separation between its catalytic domain (CD) and carbohydrate‐binding module (CBM) at low temperatures. Therefore, we introduce the domain separation index metric to guide the in silico screening of 120 psA variants using high‐throughput enzyme modeling. The highest‐ranked variant, psA121, shows a 3‐fold increase in relative activity over the wild type at 0 °C. MD simulations suggest that psA121 achieves cold adaptation via helical linkers, which induce interdomain separation and enhance flexibility of the active site and binding loops via dynamic allostery, promoting substrate recruitment, binding, and catalysis at lower temperatures. This study highlights how domain separation contributes to cold adaptation in bidomain amylases and offers strategies for introducing such cold adaptation to other systems.
doi: 10.1002/anie.202504895pmid: 40323713
Understanding the types and locations of interactions between atoms or molecules within a chemical system is a fundamental concern in chemistry. In the field of theoretical and computational chemistry, wavefunction analysis offers various methods based on functions defined in 3D real space, enabling the visual representation of both covalent and noncovalent interactions. These methods provide researchers with an intuitive understanding of molecular interactions and are gaining increasing attention. This review systematically introduces various widely adopted and distinctive visualization methods, such as the noncovalent interaction (NCI) method, the independent gradient model based on Hirshfeld partition of molecular density (IGMH), the interaction region indicator (IRI), the electrostatic potential (ESP), the electron localization function (ELF), and deformation density. Additionally, numerous application examples are provided to help readers recognize the significant practical value of these methods. Also the computer program Multiwfn, which effectively implemented all the introduced methods, is briefly mentioned.
Hu, Wenting; Libérioux, Valérian; Rossignol, Julien; Pembouong, Gaëlle; Derat, Etienne; Ménand, Mickaël; Bouteiller, Laurent; Sollogoub, Matthieu
doi: 10.1002/anie.202507069pmid: 40372984
Linking a cyclodextrin (CD) host to a hydrophobic guest can result in two distinct conformations: an introverted form (in), in which the guest is self‐included within the CD cavity, and an extraverted form (out), which enables intermolecular interactions and thus the formation of a supramolecular polymer. In this study, we demonstrate that a subtle variation of the linker enables interconversion between these two conformations, the in conformer being thermodynamically the most stable in water. At basic pH (>8) the out conformer is instantly converted into the in. In contrast, at acidic pH (<2), the out monomer can be kinetically trapped and can self‐assemble into a supramolecular polymer. DFT calculations reveal that the interconversion mechanism is governed by a key hydrogen bond that locks the conformational states. Furthermore, we show that pH provides fine kinetic control over the interconversion rate and, consequently, the polymerization process. The system can then be reset toward the out conformation by using DMSO. This system stands in contrast to known transient supramolecular polymerization processes, which rely on metastable (non‐assembled) monomers. Here, it is the kinetic trapping of the assembling monomer that allows control over the lifetime of the transient supramolecular polymer via a pH‐responsive mechanism.
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