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Sulphur-Atom Positional Engineering in Perylenimide: Structure-Property Relationships and H-aggregation Directed Type-I Photodynamic Therapy Chem. Sci. (IF 8.4) Pub Date : 2024-05-10 Mst Nasima Khatun, Satyendu Nandi, Hirakjyoti Roy, Siddhartha Sankar Ghosh, Sachin Kumar, Parameswar K. Iyer
An innovative design strategy of placing sulfur (S)-atoms within the pendant functional groups and at carbonyl positions in conventional perylenimide (PNI-O) has been demonstrated to investigate the condensed state structure-property relationship and potential photodynamic therapy (PDT) application. Incorporation of simply S-atoms at the peri-functionalized perylenimide (RPNI-O) leads to aggregation-induced
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High-order layered self-assembled multicavity metal-organic capsules and anti-cooperative host-multi-guest chemistry Chem. Sci. (IF 8.4) Pub Date : 2024-05-08 Kaixiu Li, Zhenguang Li, Jie Yuan, Mingzhao Chen, He Zhao, Zhiyuan Jiang, Jun Wang, Zhilong Jiang, Yiming Li, Yi-Tsu Chan, Pingshan Wang, Die Liu
The construction and application of metal-organic cages with accessible internal cavity have witnessed rapid development, however, the precise synthesis of complex metal-organic capsules with multiple cavities and achievement of multi-guest encapsulation, and further in-depth comprehension of host-multi-guest recognition remains of great challenge. Just like building LEGO blocks, herein, we have constructed
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Periodic table screening for enhanced positive contrast in MRI and in vivo uptake in glioblastoma Chem. Sci. (IF 8.4) Pub Date : 2024-05-08 Aitor Herraiz, Maria del Puerto Morales, Lydia Martínez-Parra, Nuria Arias-Ramos, Pilar Lopez-Larrubia, Lucia Gutierrez, Jesús Mejías, Carlos Díaz-Ufano, Jesús Ruiz-Cabello, Fernando Herranz
The quest for nanomaterial-based imaging probes that can provide positive contrast in MRI is fueled by the necessity of developing novel diagnostic applications with potential for clinical translation that current gold standard probes cannot provide. Although interest in nanomaterials for positive contrast has increased in recent years, their study is less developed than that of traditional negative
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Aromatization-driven deconstructive functionalization of spiro dihydroquinazolinones via dual photoredox/nickel catalysis Chem. Sci. (IF 8.4) Pub Date : 2024-05-08 Hongjie Miao, Jin-Hua Zhang, Wenke Li, Wenpeng Yang, Hong Xin, Pin Gao, Xin-Hua Duan, Li-Na Guo
Aromatization-driven deconstruction and functionalization of spiro dihydroquinazolinones via dual photoredox/nickel catalysis is developed. The aromatization effect was introduced to synergistically drive the unstrained cyclic C-C bond cleavage, with the aim of overcoming the ring-size limitation of nitrogen-centered radical induced deconstruction of carbocycles. Herein, we demonstrate the synergistic
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Future Prospects of High-Entropy Alloys as Next-Generation Industrial Electrode Materials Chem. Sci. (IF 8.4) Pub Date : 2024-05-08 Saikat Bolar, Yoshikazu Ito, Takeshi Fujita
The rapid advancement of electrochemical processes in industrial applications has increased the demand for high-performance electrode materials. High-entropy alloys (HEAs), a class of multicomponent alloys with unique properties, have emerged as potential electrode materials owing to their enhanced catalytic activity, superior stability, and tunable electronic structures. This review explores contemporary
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Quinoxaline-based Y-type acceptors for organic solar cells Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Meiling Xie, Zhixiang Wei, Kun Lu
Minimizing energy loss plays a critical role in the quest for high-performance organic solar cells (OSCs). However, the origin of large energy loss in OCSs is complicated, involving the strong exciton binding energy of organic semiconductors, nonradiative charge-transfer state decay, defective molecular stacking network, and so on. The recently developed quinoxaline (Qx)-based acceptors have attracted
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Site-directed Conjugation of Single-Stranded DNA to Affinity Proteins: Quantifying the Importance of Conjugation Strategy Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Andres Rocha Tapia, Fabrice Abgottspon, Johan Nilvebrant, Per- Åke Nygren, Sarah Duclos Ivetich, Andres Javier Bello Hernandez, Ioanna Thanasi, Peter Szijj, Ghali Sekkat, François M Cuenot, Vijay Chudasama, Nicola Aceto, Andrew deMello, Daniel Ashley Richards
Affinity protein–oligonucleotide conjugates are increasingly being explored as diagnostic and therapeutic tools. Despite growing interest, these probes are typically constructed using outdated, non-selective chemistries, and little has been done to investigate how conjugation to oligonucleotides influences the function of affinity proteins. Herein, we report a novel site-selective conjugation method
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CoH-Catalyzed Asymmetric Remote Hydroalkylation of Heterocyclic Alkenes: A Rapid Approach to Chiral Five-Membered S- and O-Heterocycles Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Lingzi Zhao, Feipeng Liu, Yan Zhuang, Mengyang Shen, Jing Xue, Xuchao Wang, Yuting Zhang, Zi-Qiang Rong
Saturated heterocycles, which incorporate S and O heteroatoms, serve as fundamental frameworks in a diverse array of natural products, bioactive compounds, and pharmaceuticals. Herein, we describe a unique cobalt-catalyzed approach integrated with a desymmetrization strategy, facilitating precise and enantioselective remote hydroalkylation of unactivated heterocyclic alkenes. This method delivers hydroalkylation
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Synergistic Interface and Structural Engineering for High Initial Coulombic Efficiency and Stable Sodium Storage in Metal Sulfides Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Chunrong Ma, Zhengguang Fu, Yanchen Fan, Hui Li, Zi-Feng Ma, Wei Jiang, Guangshuai Han, Haoxi Ben, Hui Claire Xiong
Transition metal sulfides (TMS) have gained significant attention as potential anode materials for sodium ion batteries (SIBs) due to their high theoretical capacity and abundance in nature. Nevertheless, their practical use has been impeded by challenges such as large volume changes, unstable solid electrolyte interphase (SEI), and low initial Coulombic efficiency (ICE). To address these issues and
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Organocatalytic diastereo- and atroposelective construction of eight-membered bridged (hetero)biaryls via asymmetric intramolecular [3+2] cycloaddition Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Baomin Wang, Yue Wang, Yue Huang, Xiaoze Bao, Xingfu Wei, Shiqiang Wei, Jingping Qu
An unprecedented and straightforward route for the asymmetric construction of privileged atroposelective bridged (hetero)biaryl eight-membered scaffolds has been accomplished through chiral phosphoric acid catalyzed asymmetric intramolecular [3+2] cycloaddition of innovative (hetero)biaryl aldehydes with 3-aminooxindole hydrochloride. A class of eight-membered bridged (hetero)biaryl lactones fused
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Non-fibril Amyloid Aggregation at the Air/Water Interface: Self-adaptive Pathway Resulting in a 2D Janus Nanofilm Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Hao Ren, Huan Chen, Yu Kang, Wei Liu, Yongchun Liu, Fei Tao, Shuting Miao, Yingying Zhang, Qian Liu, Mingdong Dong, Yonggang Liu, Bing Liu, Peng Yang
Amyloid states of proteins are implicated in several neurodegenerative diseases and bioadhesion processes. However, the classical amyloid fibrillization mechanism fails to adequately explain the formation of polymorphic aggregates and their adhesion to various surfaces. Herein, we report a non-fibril amyloid aggregation pathway, with disulfide-bond-reduced lysozyme (R-Lyz) as a model protein under
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Photophysics of Fluorescent Nanoparticles Based on Organic Dyes – Challenges and Design Principles Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Stine Grønfeldt Stenspil, Bo W. Laursen
Fluorescent nanoparticles has become attractive for bioanalysis and imaging, due to their high brightness and photostability. Many different optical materials have been applied in fluorescent nanoparticles with a broad range of properties and characteristica. One apealing approach is the incorperation of molecular organic fluorophores in nanoparticles with the intention of transferring their known
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Charge-Regulated Fluorescent Anchors Enable High-Fidelity Tracking of Plasma Membrane Dynamics During Biological Events Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Jiaqi Zuo, Aohui Peng, Penglei Wu, Junyi Chen, Chuangye Yao, Junjun Pan, Engao Zhu, Yingye Weng, Kewei Zhang, Hui Feng, Zhi-Gang Jin, Zhaosheng Qian
Many biological processes generally require long-term visualization tools for time-scale dynamic changes of the plasma membrane, but there is still a lack of design rules for such imaging tools based on small-molecule fluorescent probe. Herein, we revealed the key regulatory roles of charge number and species of fluorescent dyes on the anchoring ability of the plasma membrane, and found that the introduction
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Copper-Catalyzed Asymmetric Allylic Substitution of Racemic/meso Substrates Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Jun Li, Junrong Huang, Yan Wang, Yuexin Liu, yuxiang zhu, Hengzhi You, Fener Chen
The synthesis of enantiomerically pure compounds is a pivotal subject in the field of chemistry. Enantioselective catalysis currently stands as the primary approach for delivering a singular enantiomer. Among these strategies, Cu-catalyzed asymmetric allylic substitution (AAS) is significant and irreplaceable, especially when it comes to use non-stabilized nucleophiles (pKa > 25). Although Cu-catalyzed
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Mechanistic investigations of the Fe(II) mediated synthesis of squaraines Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Yu Liu, Nathan Thomas Coles, Nathalia Cajiao, Laurence John Taylor, Edward Stephen Davies, Alistair Barbour, Patrick Morgan, Kevin Butler, Ben Pointer-Gleadhill, Stephen Argent, Jonathan McMaster, Michael L. Neidig, David Robinson, Deborah Lorraine Kays
The scission and homologation of CO is a fundamental process in the Fischer-Tropsch reaction. However, given the heterogeneous nature of the catalyst and forcing reaction conditions, it is difficult to determine the intermediates of this reaction. Here we report detailed mechanistic insight into the scission/homologation of CO by two-coordinate iron terphenyl complexes. Mechanistic investigations,
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Insulated π-Conjugated 2,2’-Bipyridine Transition-Metal Complexes: Enhanced Photoproperties in Luminescence and Catalysis Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Tomohiro Iwai, Shinsuke Abe, Shin-ya Takizawa, Hiroshi Masai, Jun Terao
2,2'-Bipyridine has been identified as a privileged ligand scaffold for photofunctional transition metal complexes. We herein report on the synthesis and photoproperties of an insulated π-conjugated 2,2’-bipyridine with a linked rotaxane structure consisting of permethylated α-cyclodextrin (PM α-CD) and oligo(p-phenylene ethynylene). The insulated π-conjugated 2,2’-bipyridine exhibited enhanced ligand
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Rapid Flow-Based Synthesis of Post-Translationally Modified Peptides and Proteins: A Case Study on MYC’s Transactivation Domain Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Elyse T. Williams, Kevin Schiefelbein, Matthias Schuster, Ikhlas M. M. Ahmed, Marije De Vries, Rebecca Beveridge, Oliver Zerbe, Nina Hartrampf
Protein-protein interactions of c-Myc (MYC) are often regulated by post-translational modifications (PTMs), such as phosphorylation, and crosstalk thereof. Studying these interactions requires proteins with unique PTM patterns, which are challenging to obtain by recombinant methods. Standard peptide synthesis and native chemical ligation can produce such modified proteins, but are time-consuming and
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Visible Light-Driven Dearomative Ring Expansion of (Aza)arenes to Access Dihydrofuran-based Polycyclic Compounds Chem. Sci. (IF 8.4) Pub Date : 2024-05-07 Linghong Zhang, Mengdi You, Xu Ban, Xiaowei Zhao, Yanli Yin, Shanshan Cao, Zhiyong Jiang
The dearomative expansion of aromatic rings has long been pursued by chemists due to its potential to provide tractable approaches for synthesizing valuable non-aromatic molecules. To circumvent the conventional use of hazardous and unstable diazo compounds, photochemical synthesis has recently emerged as a promising platform. However, protocols that can effentively handle both arenes and azaarenes
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A Nine-Ring Fused Terrylene Diimide Exhibits Switching between Red TADF and Near-IR Room Temperature Phosphorescence Chem. Sci. (IF 8.4) Pub Date : 2024-05-06 Shivangee Jha, Kundan Singh Mehra, MANDIRA DEY, S. Sujesh, Debashree Ghosh, Pradip Kumar Mondal, Maurizio Polentarutti, Sankar Jeyaraman
Herein, we report the first example of a terrylene diimide derivative that switches emission between thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) in the red region. By design, the molecule TDI-cDBT boasts a symmetrical, consecutively fused nine-ring motif with a kite-like structure. The rigid core formed by the annulated dibenzothiophene moiety favoured
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Bifunctional primitive strategy induces enhancements of large second harmonic generation and wide UV transmittance in rare-earth borates containing [B5O10] groups Chem. Sci. (IF 8.4) Pub Date : 2024-05-06 Shuaifeng Li, Weiming Li, Xiang Li, Guangsai Yang, Ning Ye, Zhanggui Hu, Yicheng Wu, Conggang Li
Strong second-harmonic generation (SHG) and short ultraviolet (UV) cutoff edge are two crucial yet often conflicting parameters that must be finely tuned in the exploration of nonlinear optical (NLO) materials. In this study, two new rare earth borate NLO crystals, K7BaSc2B15O30 (KBSBO) and Rb21Sr3.8Sc5.2B45O90 (RSSBO), were rationally designed through a bifunctional primitive strategy to achieve an
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Nanoscale and Chiral Metal–Organic Framework for Asymmetric Reactions in Water: Bridging Lewis Acid Catalysis to Biological Systems Chem. Sci. (IF 8.4) Pub Date : 2024-05-06 Watchara Srimontree, Taku Kitanosono, Yasuhiro Yamashita, Shu Kobayashi
Nowadays, stereoselective control over the sheer variety of chemical transformations benefits from the multipotency of chiral Lewis acids. Their use under biocompatible conditions has long posed a challenge because profuse amounts of biogenic nucleophiles readily deactivate them. To bridge a gap between chiral Lewis acid catalysis and biocompatible chemistry, the conversion of UiO(BPY)-type nanosized
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The importance of understanding (pre)catalyst activation in versatile C−H bond functionalisations catalysed by [Mn2(CO)10] Chem. Sci. (IF 8.4) Pub Date : 2024-05-03 Jonathan B. Eastwood, Thomas J Burden, Lars Anders Hammarback, Chris S. Horbaczewskyj, Theo Tanner, Ian P Clark, Gregory M Greetham, Michael Towrie, Ian J. S. Fairlamb, Jason Martin Lynam
Mn-catalysed reactions offer great potential in synthetic organic and organometallic chemistry and the success of Mn carbonyl complexes as (pre)catalysts hinges on their stabilisation by strong field ligands enabling Mn(I)-based, redox neutral, catalytic cycles. The mechanistic processes underpinning the activation of the ubiquitous Mn(0) (pre)catalyst [Mn2(CO)10] in C–H bond functionalisation reactions
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Investing in Entropy: The Strategy of Cucurbit[n]urils to Accelerate the Intramolecular Diels-Alder Cycloaddition Reaction of Tertiary Furfuryl Amines Chem. Sci. (IF 8.4) Pub Date : 2024-05-03 Pablo Ballester, Karen de la Vega-Hernández, Marcos G. Suero
Cucurbit[n]urils, renowned for their host-guest chemistry, are becoming versatile biomimetic receptors. Herein, we report that cucurbit[7]uril (CB[7]) accelerates the intramolecular Diels-Alder (IMDA) reaction for previously elusive and unreactive tertiary N-methyl-N-(homo)allyl-2-furfurylamines up to 4 orders of magnitude under mild conditions. Using 1H NMR titrations and ITC experiments, we characterize
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Hydroalkylation of styrenes enabled by boryl radical mediated halogen atom transfer Chem. Sci. (IF 8.4) Pub Date : 2024-05-03 Serena Pillitteri, Rajat Walia, Erik V Van der Eycken, Upendra K. Sharma
In this study, we present an inexpensive, stable, and easily available boryl radical source (NaBPh4) employed in a Halogen Atom Transfer (XAT) methodology. This mild and convenient strategy unlocks the use of not only alkyl iodides as radical precursors but also of the more challenging alkyl and aryl bromides to generate C-centered radicals. The generated radicals were further engaged in the anti-Markovnikov
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Clinically used drug arsenic trioxide targets XIAP and overcomes apoptosis resistance in an organoid-based preclinical cancer model Chem. Sci. (IF 8.4) Pub Date : 2024-05-03 Liwa Shi, Jing Lu, Xin Xia, Xue Liu, Hongyan Li, Xinghua Li, Zhu Jun, Xiaofeng Li, Hongzhe Sun, Xinming Yang
Drug resistance in tumor cells remains a persistent clinical challenge in the pursuit of effective anticancer therapy. XIAP, a member of inhibitor of apoptosis proteins (IAPs) family, suppresses apoptosis via its Baculovirus IAP Repeat (BIR) domains and is responsible for drug resistance in various human cancers. Therefore, XIAP has attracted significant attention as a potential therapeutic target
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AN ANTHROPOCENE-FRAMED TRANSDISCIPLINARY DIALOG AT THE CHEMISTRY-ENERGY NEXUS Chem. Sci. (IF 8.4) Pub Date : 2024-05-02 mathieu prevot, Valeria Finelli, Xavier Carrier, Gabriele Deplano, Margherita Cavallo, Elsje Alessandra Alessandra Quadrelli, Juliette Michel, Marie-Hélène Pietraru, Clément Camp, Giulia Forghieri, Anna Gagliardi, Sebastian Seidel, Antoine Missemer, Bertrand Reuillard, Barbara Centrella, Silvia Bordiga, Maria Grace Salamanca González, Vincent Artero, Keanu V. A. Bierkelbach, Niklas Von Wolff
At the energy-chemistry nexus, key molecules include carbon dioxide (CO2), hydrogen (H2), methane (CH4), and ammonia (NH3). The position of these four molecules and that of the more general family of synthetic macromolecular polymer blends (found in plastics) were cross-analyzed with the Planetary Boundary framework, and as part of five scientific policy roadmaps for the energy transition. According
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Advances and challenges in electrochemical reduction of carbon dioxide Chem. Sci. (IF 8.4) Pub Date : 2024-05-02 Jingyi Han, Xue Bai, Xiaoqin Xu, Xue Bai, Anaer Husile, Siying Zhang, Luoluo Qi, Jingqi Guan
Electrocatalytic reduction of carbon dioxide (ECO2RR) is a promising way to realize the transformation of waste into treasure, which can not only meet the environmental goal of reducing carbon emissions, but also obtain clean energy and valuable industrial products simultaneously. Herein, we first introduce the complex CO2RR mechanisms according to the number of carbons in the product. Since the coupling
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Adamantane-Type Clusters: Compounds with a Ubiquitous Architecture but a Wide Variety of Compositions and Unexpected Materials Properties Chem. Sci. (IF 8.4) Pub Date : 2024-05-02 Stephanie Dehnen, Niklas Rinn, Irán Rojas-León, Benjamin Peerless, Saravanan Gowrisankar, Ferdinand Ziese, Nils Wilhelm Rosemann, Wolf-Christian Pilgrim, Simone Sanna, Peter R Schreiner
The research of adamantane-type compounds has gained momentum in recent years, yielding remarkable new applications for this class of materials. In particular, organic adamantane derivatives (AdR4) or inorganic adamantane-type compounds of the general formula [(RT)4E6] (R: organic substituent; T: group 14 atom C, Si, Ge, Sn; E: chalcogenide atom S, Se, Te or CH2) were shown to exhibit strong non-linear
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Achieving Pure Room Temperature Phosphorescence (RTP) in Phenoselenazine-Based Organic Emitters Through Synergism among Heavy Atom Effect, Enhanced n → π* Transition and Magnified Electron Coupling by the A-D-A Molecular Configuration Chem. Sci. (IF 8.4) Pub Date : 2024-05-02 Daokun Zhong, Siqi Liu, Ling Yue, Zhao Feng, Hongyan Wang, Peng Yang, Bochao Su, Xiaolong Yang, Yuanhui Sun, Guijiang Zhou
The weak spin-orbit coupling (SOC) in metal-free organic molecules poses a challenge in achieving phosphorescent emission. To attain pure phosphorescence in RTP organic emitters, a promising molecular design concept has been proposed. This involves incorporating n → π* transition and leveraging heavy atomic effect within the spin-orbit charge transfer-induced intersystem crossing (SOCT−ISC) mechanism
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Structural characterization of PHOX2B and its DNA interaction shed lights into the molecular basis of the + 7Ala variant pathogenicity in CCHS Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Donatella Diana, Luciano Pirone, Luigi Russo, Gianluca D'Abrosca, Manoj Madheswaran, Roberta Benfante, Simona Di Lascio, Laura Caldinelli, D. Fornasari, Clementina Acconcia, Andrea Corvino, Nataliia Ventserova, Loredano Pollegioni, Carla Isernia, Sonia Di Gaetano, Gaetano Malgieri, Emilia Pedone, Roberto Fattorusso
An expansion of poly-alanine up to +13 residues in the C-terminus of the transcription factor PHOX2B underlies the onset of congenital central hypoventilation syndrome (CCHS). Recent studies demonstrated that the alanine tract expansion influences PHOX2B folding and activity. Therefore, structural information on PHOX2B is an important target for obtaining clues to elucidate the insurgence of the alanine
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Highly Chemoselective Oxidative Dimerization of Indolosesquiterpene Alkaloids: Biomimetic Approach to Dixiamycin Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Alakesh Bisai, Mintu Munda, Ayan Mondal, Nanda Kishore Roy, Ranjit Murmu, Sovan Niyogi
Dimeric indolosesquiterpene alkaloids typically N-N- and C-N-linked xiamycin dimers feature pentacyclic framework with four contiguous stereogenic centers at the periphery of a trans-decalin scaffold to which a carbazole unit is attached. In comparison with the actual biosynthetic dixiamycin derivatives, we designed the C-C-linked xiamycin dimers, aiming to serve as a powerful tool to create unique
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Carbonyl Mediated Fluorescence in Aceno[n]helicenones and Fluoreno[n]helicenes Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Michal Šámal, Ludmilla Sturm, Marzena Banasiewicz, Irena Deperasińska, Boleslaw Kozankiewicz, Olaf Morawski, Yuuya Nagata, Pierre Dechambenoit, Harald Bock, Amandine Rossel, Milos Budesinsky, Anthony Boudier, Andrej Jancarik
Helicenes are very attractive chiral non-planar polycyclic aromatic hydrocarbons possessing strong chiroptical properties. However, most of the helicenes absorb light mainly in the ultraviolet region, with only a small segment in the blue part of the visible spectrum. Furthermore, carbo[n]helicenes exhibit only weak luminescence that limits their utilization. Herein, we demonstrate that peripheral
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Emerging high voltage V4+/V5+ redox reaction in Na3V2(PO4)3-based cathode for sodium-ion batteries Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Meng Zhou, Xunzhu Zhou, Lin Li, Xiang Chen, Zhen-An Qiao, Shulei Chou
Na3V2(PO4)3 (NVP) cathode materials with the advantages of long cycle life and superior thermal stability have been considered promising cathode candidates for SIBs. However, the unsatisfied energy density derived from low theoretical capacity and operating voltage (3.35 V vs. Na+/Na, based on V3+/V4+ redox couple) inevitably limits their practical application. Therefore, the activation of V4+/V5+
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Thermal Control over Phosphorescence or Thermally Activated Delayed Fluorescence in a Metal–Organic Framework Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Huili Sun, Qiang-Sheng Zhang, Liuli Meng, Zhonghao Wang, Yanan Fan, Marcel Mayor, Mei Pan, Cheng-Yong Su
By integrating a tailor-made donor-acceptor (D-A) ligand in a metal-organic framework (MOF), a material with unprecedented features emerges. The ligand combines a pair of cyano groups as acceptor with four sulfanylphenyls as donors, which expose each a carboxylic acid as coordination sites. Upon treatment with zinc nitrate in a solvothermal synthesis, the MOF is obtained. The new material combines
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Near-Infrared Photocatalysis with Cyanines: Synthesis, Applications and Perspectives Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Jean-Philippe Goddard, Nicolas Sellet, Johanna Frey, Morgan Cormier
Cyanine are organic dyes bearing two Aza-heterocycles linked by a polymethine chain. Excited states, fluorescence, redox activity, and energy transfer are interesting properties which have been used by chemists. Moreover, they are easily accessible and highly tunable. For all these reasons, cyanines are often selected for applications like fluorescent probes, phototherapy and photovoltaic. However
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A C–H Functionalization Approach to Diverse Nitrogenous Scaffolds Through Conjugate Addition of Catalytic Allyliron Nucleophiles Chem. Sci. (IF 8.4) Pub Date : 2024-05-01 Sarah G. Scrivener, Yiming Wang
Cyclopentadienyliron(II) dicarbonyl complexes capable of coordinating to and enhancing the acidity of a range of unsaturated substrates have emerged as a new class of base-metal derived catalysts for C–H functionalization. In this manuscript, the iron-catalyzed C–H functionalization of allylic C(sp3)−H bonds using nitrogen containing α,β-unsaturated carbonyl compounds as coupling partners is reported
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Highly Acidic N-Triflylphosphoramides as Chiral Brønsted Acid Catalysts: The Effect of Weak Hydrogen Bonds and Multiple Acceptors on Complex Structures and Aggregation Chem. Sci. (IF 8.4) Pub Date : 2024-04-29 Markus Hecht, Philipp Dullinger, Wagner Silva, Dominik Horinek, Ruth Maria Gschwind
N-Triflylphosphoramides (NTPAs) represent an important catalyst class in asymmetric catalysis due to their multiple hydrogen bond acceptor sites and acidity, which is increased by several orders of magnitude compared to conventional chiral phosphoric acids (CPAs). Thus, NTPAs allow for several challenging transformations, which are not accessible with CPAs. However, detailed evidence on their hydrogen
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β-Terrecyclene synthase constructs the quadrane backbone in terrecyclic acid biosynthesis Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Yongxiang Song, Wengui Wang, Jiafan Yang, De-Wei Gao, John M Billingsley, Songtao Wang, Yiguang Zhu, Junfeng Wang, Jianhua Ju, Yan Yan, Yi Tang
Quadrane sesquiterpenes featuring a distinctive tricyclic skeleton exhibit potent antimicrobial and anticancer activities. Although extensive studies have attempted to reveal the multistep carbocation rearrangement involved in the formation of the tricyclic quadrane scaffold, the exact biosynthetic pathway and chemical logic to generate the quadrane structure remains mysterious. Here we identified
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De-epimerizing DyKAT of β-Lactones Generated by Isothiourea-Catalysed Enantioselective [2+2] Cycloaddition Chem. Sci. (IF 8.4) Pub Date : 2024-04-24 Aífe Conboy, Alister S. Goodfellow, Kevin Kasten, Joanne Dunne, David Bradford Cordes, Michael Buehl, Andrew D Smith
Moderate diastereoselectivity (typically 70:30 dr) is observed in the isothiourea-catalysed [2+2]-cycloaddition of C(1)-ammonium enolates with pyrazol-4,5-diones to generate spirocyclic β lactones, but subsequent ring-opening with morpholine generatesβ hydroxyamide products with enhanced stereoselectivity (up to >95:5 dr). Stereoconvergence is observed in the ring-opening of diastereoisomeric β lactones
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¬The impact of earth-abundant metals as a replacement for Pd in cross coupling reactions Chem. Sci. (IF 8.4) Pub Date : 2024-04-16 Michael U. Luescher, Fabrice Gallou, Bruce H. Lipshutz
Substitution of one metal catalyst for another is not straightforward as simply justifying this change based on the availability and/or cost of the metals. A life cycle-like assessment was performed leading to the conclusion that the commonly held view that use of earth-abundant metals (and in this case study, Ni) are replacements for palladium most notably in cross coupling reactions, and Suzuki-Miyaura
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Local Solvation Structures Govern the Mixing Thermodynamics of Glycerol-Water Solutions Chem. Sci. (IF 8.4) Pub Date : 2023-06-16 Debasish Das Mahanta, Dennis Robinson Brown, Simone Pezzotti, Gerhard Schwaab, Songi Han, M. Scott Shell, Martina Havenith
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Fe2(MoO4)3 assembled by cross-stacking of porous nanosheets enables a high-performance aluminum-ion battery Chem. Sci. (IF 8.4) Pub Date : 2022-11-12 Hongsen Li, Huanyu Liang, Yongshuai Liu, Fengkai Zuo, Cunliang Zhang, Li Yang, Linyi Zhao, Yuhao Li, Yifei Xu, Tiansheng Wang, Xia Hua, Yue Zhu
Rechargeable aluminum-ion batteries have attracted increasing attention owing to the advantageous multivalent ion storage mechanism thus high theoretical capacity as well as inherent safety and low cost of using aluminum. However, their development has been largely impeded by the lack of suitable positive electrodes to provide both sufficient energy density and satisfactory rate capability. Here we
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Anode Optimization Strategies for Aqueous Zinc-ion Batteries Chem. Sci. (IF 8.4) Pub Date : 2022-10-30 Yiyang Zhang, Xiaobo Zheng, Nana Wang, Wei-Hong Lai, Yong Liu, Shulei Chou, Huakun Liu, Shi Xue Dou, Yunxiao Wang
Zinc-ion batteries (ZIBs) have received much research and attention due to their advantages of safety, non-toxicity, simple manufacture, and element abundance. Nevertheless, serious problems still remain for their anodes, with dendrite development, corrosion, passivation, and the parasitic hydrogen evolution reaction due to their unique aqueous electrolyte system constituting the main issues that must
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Fast Predictions of Liquid-Phase Acid-Catalyzed Reaction Rates Using Molecular Dynamics Simulations and Convolutional Neural Networks Chem. Sci. (IF 8.4) Pub Date : 2020-10-19 Alex K. Chew, Shengli Jiang, Weiqi Zhang, Victor M Zavala, Reid C Van Lehn
The rates of liquid-phase, acid-catalyzed reactions relevant to the upgrading of biomass into high-value chemicals are highly sensitive to solvent composition and identifying suitable solvent mixtures is theoretically and experimentally challenging. We show that the complex atomistic configurations of reactant-solvent environments generated by classical molecular dynamics simulations can be exploited
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Cobalt-Catalyzed Intramolecular Decarbonylative Coupling of Acylindoles and Diarylketones through the Cleavage of C−C Bonds Chem. Sci. (IF 8.4) Pub Date : 2020-10-16 Tian-Yang Yu, Wenhua Xu, Hong Lu, Hao Wei
We report here cobalt−N-heterocyclic carbene catalytic systems for the intramolecular decarbonylative coupling through the chelation-assisted C−C bond cleavage of acylindoles and diarylketones. The reaction tolerates a wide range of functional groups such as alkyl, aryl, and heteroaryl groups, giving the decarbonylative products in moderate to excellent yields. This transformation involves the cleavage
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Access to Substituted Cyclobutenes by Tandem [3,3]-Sigmatropic Rearrangement/[2+2] Cycloaddition of Dipropargylphosphonates under Ag/Co Relay Catalysis Chem. Sci. (IF 8.4) Pub Date : 2020-10-16 Qijian Ni, Xiaoxiao Song, Chin Wen Png, Yongliang Zhang, Yu Zhao
We present herein an unconventional tandem [3,3]-sigmatropic rearrangement/[2+2] cycloaddition of simple dipropargylphosphonates to deliver a range of bicyclic polysubstituted cyclobutenes and cyclobutanes under Ag/Co relay catalysis. An interesting switch from allene-allene to allene-alkyne cycloaddition was observed based on the substitution of the substrates, which further diversified the range
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Iron-Catalyzed α-C–H functionalization of π-Bonds: Cross-Dehydrogenative Coupling and Mechanistic Insights Chem. Sci. (IF 8.4) Pub Date : 2020-10-16 Yidong Wang, Jin Zhu, Rui Guo, Haley Lindberg, Yiming Wang
The deprotonation of propargylic C–H bonds for subsequent functionalization typically requires stoichiometric metal alkyl or amide reagents. In addition to the undesirable generation of stoichiometric metallic waste, these conditions limit the functional group compatibility and versatility of this functionalization strategy and often result in regioisomeric mixtures. In this Article, we report the
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Photoresponsive molecular tools for emerging applications of light in medicine Chem. Sci. (IF 8.4) Pub Date : 2020-10-15 Ilse M. Welleman, Mark W. H. Hoorens, Ben L Feringa, Hendrikus H. Boersma, Wiktor Szymanski
Light-based therapeutic and imaging modalities, which emerge in clinical applications, rely on molecular tools, such as photocleavable protecting groups and photoswitches, that respond to photonic stimulus and translate it into a biological effect. However, optimisation of their key parameters (activation wavelength, band separation, fatigue resistance and half-life) is necessary to enable application
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Efficient Cleavage of Tertiary Amide Bonds via Radical-Polar Crossover Using a Copper(II) Bromide/Selectfluor Hybrid System Chem. Sci. (IF 8.4) Pub Date : 2020-10-14 Zhe Wang, Akira Matsumoto, Keiji Maruoka
A novel approach for the efficient cleavage of the amide bonds in tertiary amides is reported. Based on the selective radical abstraction of a benzylic hydrogen atom by a CuBr2/Selectfluor hybrid system followed by a selective cleavage of an N–C bond, an acyl fluoride intermediate is formed. This intermediate may then be derivatized in a one-pot fashion. The reaction proceeds under mild conditions
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Synthesis, crystal structure and charge transport characteristics of stable peri-tetracene analogues Chem. Sci. (IF 8.4) Pub Date : 2020-10-14 Masashi Mamada, Ryota Nakamura, Chihaya Adachi
Peri-acenes have shown great potential for use as functional materials because of their open-shell singlet biradical character. However, only a limited number of peri-acene derivatives larger than peri-tetracene have been synthesized to date, presumably owing to the low stability of the target compounds in addition to the complicated synthesis scheme. Here, a very simple synthesis route for the tetrabenzo[a
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Photocatalytic Redox-Neutral Hydoxyalkylation of N-Heteroaromatics with Aldehydes Chem. Sci. (IF 8.4) Pub Date : 2020-10-12 Hiromu Fuse, Hiroyasu Nakao, Yutaka Saga, Arisa Fukatsu, Mio Kondo, Shigeyuki Masaoka, Harunobu Mitsunuma, Motomu Kanai
A hydroxyalkylation of N-heteroaromatics with aldehydes was achieved using a binary hybrid catalyst system comprising an acridinium photoredox catalyst and a thiophosphoric acid organocatalyst. The reaction proceeded through the following sequence: 1) photoredox-catalyzed single-electron oxidation of a thiophosphoric acid catalyst to generate a thiyl radical, 2) cleavage of the formyl C‒H bond of the
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Aromatic foldamers as scaffolds for metal second coordination sphere design Chem. Sci. (IF 8.4) Pub Date : 2020-10-12 Antoine Meunier, Michael Singleton, Brice Kauffmann, Thierry Granier, Guillaume Lautrette, Yann Ferrand, Ivan Huc
As metalloproteins exemplify, the chemical and physical properties of metal centers depend not only on their first but also on their second coordination sphere. Installing arrays of functional groups around the first coordination sphere of synthetic metal complexes is thus highly desirable, but it remains a challenging objective. Here we introduce a novel approach to produce tailored second coordination
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Enhancing the ROS Generation Ability of a Rhodamine-Decorated Iridium(III) Complex by Ligand Regulation for Endoplasmic Reticulum-Targeted Photodynamic Therapy Chem. Sci. (IF 8.4) Pub Date : 2020-10-12 Lihua Zhou, Keith Man-Chung Wong, Lintao Cai, Ping Gong, Pengfei Zhang, Chunbin Li, Chuangjun Liu, Jingjing Xiang, Fangfang Wei, Hongfeng Li
The endoplasmic reticulum (ER) is a very important organelle responsible for crucial biosynthetic, sensing, and signalling functions in eukaryotic cells. In this work, we established a strategy of ligand regulation to enhance the singlet oxygen generation capacity and subcellular organelle localization ability of a rhodamine-decorated iridium(III) complex by variation of the cyclometallating ligand
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Bis[Pyrrolyl Ru(II)] Triads: a New Class of Photosensitizers for Metal-Organic Photodynamic Therapy Chem. Sci. (IF 8.4) Pub Date : 2020-10-06 Deborah A. Smithen, Susan Monro, Mitch A. Pinto, John A Roque III, Roberto Diaz-Rodriguez, Huimin Yin, Colin G. Cameron, Alison Thompson, Sherri Ann McFarland
A new family of ten dinuclear Ru(II) complexes based on the bis[pyrrolyl Ru(II)] triad scaffold, where two Ru(bpy)2centers are separated by a variety of organic linkers, was prepared to evaluate the influence of the organic chromophore on the spectroscopic and in vitro photodynamic therapy (PDT) properties of the compounds. The bis[pyrrolyl Ru(II)] triads absorbed strongly throughout the visible region
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Shaping non-noble metal nanocrystals via colloidal chemistry Chem. Sci. (IF 8.4) Pub Date : 2020-10-05 Valeria Mantella, Laia Castilla i Amoròs, Raffaella Buonsanti
Non-noble metal nanocrystals with well-defined shapes have been attracting increasingly more attention in the last decade as potential alternatives to noble metals, by virtue of their Earth abundance combined with intriguing physical and chemical properties relevant for both fundamental studies and technological applications. Nevertheless, their synthesis is still primitive when compared to noble metals
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Unveiling the molecular mechanism of SARS-CoV-2 main protease inhibition from 137 crystal structures using algebraic topology and deep learning Chem. Sci. (IF 8.4) Pub Date : 2020-09-30 Duc Nguyen, Kaifu Gao, Jiahui Chen, Rui Rui Wang, Guowei Wei
Currently, there is no effective antiviral drugs nor vaccine for coronavirus disease 2019 (COVID-19)caused by acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Due to its high conservativeness andlow similarity with human genes, SARS-CoV-2 main protease (Mpro) is one of the most favorable drug targets.However, the current understanding of the molecular mechanism of Mpro inhibition is limited by
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Inorganic nanocrystal-dynamic porous polymer assemblies with effective energy transfer for sensitive diagnosis of urine copper Chem. Sci. (IF 8.4) Pub Date : 2020-09-23 Xujiao Ma, Yajie Yang, Rongchen Ma, Yunfeng Zhang, Xiaoqin Zou, Shoujun Zhu, Xin Ge, Ye Yuan, Wei Zhang, Guangshan Zhu
Despite the remarkable mechanical/optical/electrical properties, the inorganic particles and dynamic polymer assemblies encountered the difficulties in compatibility with structural order and complexity. Here, covalent organic frameworks (COFs) constructed through reversible coupling reactions were exploited as dynamic porous polymers to prepare the inorganic nanocrystal-polymer assemblies. Experiencing
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Modulating the ground state, stability and charge transport in OFETs of biradicaloid Hexahydro-diindenopyrene derivatives and a proposed method to estimate the biradical character Chem. Sci. (IF 8.4) Pub Date : 2020-09-16 Tanguy Jousselin-Oba, Masashi Mamada, Atsushi Okazawa, Jérome Marrot, Takayuki Ishida, Chihaya Adachi, Abderrahim Yassar, Michel Frigoli
Biradicaloid compounds with an open-shell ground state have been the subject of intense research in the past decade. Although diindenoacenes are one of the most developed families, only few examples have been reported as active layer in organic field-effect transistors (OFETs) with charge mobility of around 10−3 cm2 V−1 s−1 due to a steric disadvantage of the mesityl group to kinetically stabilize
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Oxygen accelerated scalable synthesis of highly fluorescent sulfur quantum dots Chem. Sci. (IF 8.4) Pub Date : 2019-11-27 Yiheng Song, Jisuan Tan, Guan Wang, Pengxiang Gao, Jiehao Lei, Li Zhou
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Single electron transfer events and dynamical heterogeneity in the small protein azurin from Pseudomonas aeruginosa Chem. Sci. (IF 8.4) Pub Date : 2019-11-27 Biswajit Pradhan, Christopher Engelhard, Sebastiaan Van Mulken, Xueyan Miao, Gerard W. Canters, Michel Orrit