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Mild and Catalytic Electrocyclizations of Heptatrienyl Anions. Chem. Sci. (IF 8.4) Pub Date : 2024-04-26 Arturo Orellana, Faizan Rasheed, Andrei Nikolaev, Anmol Dhesi, Tao Zeng, You Xuan Guo, Krishna Yarkali, Samira Komijani
We report a mild synthesis of functionalized cycloheptanes by thermal electrocyclization of heptatrienyl anions. In addition, we disclose the first examples of this electrocyclization manifold conducted under catalytic conditions. Previously, electrocyclization of heptatrienyl systems required formation of anions with strong base, resulting in limited functional group compatibility. We demonstrate
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Multiconfigurational Actinide Nitrides Assisted by Double Möbius Aromaticity Chem. Sci. (IF 8.4) Pub Date : 2024-04-26 Xuhui Lin, Xiaoli Lu, Shenghui Tang, Wei Wu, Yirong Mo
Understanding the bonding nature between actinides and main-group elements remains a key challenge in actinide chemistry due to the involvement of f orbitals. Herein, we propose a unique “aromaticity-assisted multiconfiguration” (AAM) model to elucidate the bonding nature in actinide nitrides (An2N2, An= Ac, Th, Pa, U). Each planar four-membered An2N2 with equivalent An-N bonds possesses four delocalized
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A Mitochondrial-Targeted Activity-Based Sensing Probe for Ratiometric Imaging of Formaldehyde Reveals Key Regulators of the Mitochondrial One-Carbon Pool Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Chris Chang, Logan Tenney, Vanha N Pham, Thomas F. Brewer
Formaldehyde (FA) is both a highly reactive environmental genotoxin and an endogenously produced metabolite that functions as a signaling molecule and one-carbon (1C) store to regulate 1C metabolism and epigenetics in the cell. Owing to its signal-stress duality, cells have evolved multiple clearance mechanisms to maintain FA homeostasis, acting to avoid the established genotoxicity of FA while also
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Improving Electron Transportation and Operational Lifetime of Full Color Organic Light Emitting Diode Through “Weak hydrogen bonding cage” Structure Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Huayi Zhou, Tengyue Li, Mingliang Xie, Yannan Zhou, Qikun Sun, Shitong Zhang, Yujian Zhang, Wenjun Yang, Shanfeng Xue
Efficient electron-transporting materials (ETMs) are critical to achieving excellent performance of organic light-emitting diodes (OLEDs), yet developing such materials remains a major long-term challenge, particularly ETMs with high electron mobilities (μeles). Herein, we report a short conjugated ETM molecule (PICN) with a dipolar phenanthroimidazole group, which exhibits an electron mobility of
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Structural elucidation of HIV-1 G-quadruplexes in cellular environment and their ligand binding using responsive 19F-labeled nucleoside probes Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Sarupa Roy, Priyasha Majee, Sruthi Sudhakar, Satyajit Mishra, Jeet Kalia, P. I. Pradeepkumar, Seergazhi G Srivatsan
Understanding structure and recognition of highly conserved regulatory segments of the integrated viral DNA genome that forms unique topologies can greatly aid devise novel therapeutic strategies to counter chronic infections. In this study, we configured a probe system using highly environment-sensitive nucleoside analogs, 5-fluoro-2'-deoxyuridine (FdU) and 5-fluorobenzofuran-2'-deoxyuridine (FBFdU)
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Photochemical and Biological Dual-effects Enhance the Inhibition of Photosensitizer for Tumour Growth Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Hua Zhang, Huiyu Niu, Yang Liu, Yafu Wang, Yonggang Yang, Ge Wang, Tony D. James, Jonathan L. Sessler
Photosensitizers typically rely on a singular photochemical reaction to generate reactive oxygen species, which can then inhibit or eradicate lesions. However, photosensitizers often exhibit limited therapeutic efficiency due to their reliance on a single photochemical effect. Herein, we propose a new strategy that integrates the photochemical effect (Type-I photochemical effect) with a biological
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The Development of Cage Phosphine ‘DalPhos’ Ligands to Enable Nickel-Catalyzed Cross-Couplings of (Hetero)aryl Electrophiles Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Kathleen M Morrison, Mark Stradiotto
Nickel-catalyzed cross-couplings of (hetero)aryl electrophiles with a diversity of nucleophiles (nitrogen, oxygen, carbon, and other) have evolved into competitive alternatives to well-established palladium- and copper-based protocols for the synthesis of (hetero)aryl products, including (hetero)anilines and (hetero)aryl ethers. A survey of the literature reveals that the use of cage phosphine (CgP)
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Insights into mechanistic interpretation of crystalline-state reddish phosphorescence of non-planar π-conjugated organoboron compounds Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Yohei Adachi, Maho Kurihara, Kohei Yamada, Fuka Arai, Yuto Hattori, Keita Yamana, Riku Kawasaki, Joji Ohshita
Metal-free room-temperature phosphorescent (RTP) materials are attracting attention in such applications as organic light-emitting diodes and bioimaging. However, the chemical structures of RTP materials reported thus far are mostly predominantly based on π-conjugated systems incorporating heavy atoms such as bromine atoms or carbonyl groups, resulting in limited structural diversity. On the other
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Azole reagents enabled ligation of peptide acyl pyrazoles for chemical protein synthesis Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Peisi Liao, Chunmao He
Native chemical ligation (NCL) has been playing an increasingly important role in chemical protein synthesis (CPS), more efficient ligation methods that circumvent the requirement of peptidyl thioester and thiol additive—which allow the following desulfurization or refolding in one pot—are urgently needed for the synthesis of more complex protein targets and in large quantities. Herein, we discover
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Metal-free Platforms for Molecular Thin Films as High-performance Supercapacitors Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Ritu Gupta, Ankur Malik, Kusum Kumari, Saurabh Kumar Singh, Vincent Vivier, Prakash Chandra Mondal
Controlling chemical functionalization and achieving stable electrode-molecule interfaces for high-performance electrochemical energy storage applications remains a challenging task. Herein, we present a simple, controllable, scalable, and versatile electrochemical modification approach of graphite rods (GR) extracted from low-cost Eveready cells that were covalently modified with anthracene oligomers
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Directed Evolution of Escherichia coli Surface-displayed Vitreoscilla Hemoglobin as an Artificial Metalloenzyme for the Synthesis of 5-Imino-1,2,4-thiadiazoles Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Yaning Xu, Fengxi Li, Hanqing Xie, Yuyang Liu, Weiwei Han, Junhao Wu, Lei Cheng, Chunyu Wang, Zhengqiang Li, Lei Wang
Artificial metalloenzymes (ArMs) are constructed by anchoring organometallic catalysts to an evolvable protein scaffold. They present the advantages of both components and exhibit considerable potential for the in vivo catalysis of new-to-nature reactions. Herein, Escherichia coli surface-displayed Vitreoscilla hemoglobin (VHbSD-Co) that anchored the cobalt porphyrin cofactor instead of the original
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Enantioconvergent Synthesis of Chiral Fluorenols from Racemic Secondary Alcohols via Pd(II)/Chiral Norbornene Cooperative Catalysis Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Bo Ding, Qilin Xue, Han Wei, Jiangwei Chen, Ze-Shui Liu, Hong-Gang Cheng, Hengjiang Cong, Jianting Tang, Qianghui Zhou
An efficient protocol for the asymmetric synthesis of fluorenols has been developed through an enantioconvergent process enabled by Pd(II)/chiral norbornene cooperative catalysis. This approach allows facile access to diverse functionalized chiral fluorenols with constantly excellent enantioselectivities, applying readily available racemic secondary ortho-bromobenzyl alcohols and aryl iodides as the
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Electrochemical Stereoselective Synthesis of Polysubstituted 1,4-dicarbonyl Z-Alkenes via Three-Component Coupling of Sulfoxonium Ylides, Alkynes with Water Chem. Sci. (IF 8.4) Pub Date : 2024-04-25 Hao-Ran Li, Yi-An Ran, Yu-Yi Zhu, Weisi Guo, Shao-Fei Ni, Li-Rong Wen, Ming Li, Lin-Bao Zhang
The first straightforward strategy for the synthesis of 1,4-dicarbonyl Z-alkenes has been developed via an electrochemical cross-coupling reaction of sulfoxonium ylides, and alkynes with water. The metal-free protocol showed an easy-handle nature, good functional group tolerance, and a high Z-stereoselectivity, which is rare in previous cases. The proposed reaction mechanism was convincingly established
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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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Biosynthesis of the Bacterial Antibiotic 3,7-Dihydroxytropolone through Enzymatic Salvaging of Catabolic Shunt Products Chem. Sci. (IF 8.4) Pub Date : 2024-04-24 Lars Höing, Sven T. Sowa, Marina Toplak, Jakob Klaus Reinhardt, Roman P Jakob, Timm Maier, Markus A. Lill, Robin Teufel
The non-benzenoid aromatic tropone ring is a structural motif of numerous microbial and plant natural products with potent bioactivities. In bacteria, tropone biosynthesis involves early steps of the widespread CoA-dependent phenylacetic acid (paa) catabolon, from which a shunt product is sequestered and surprisingly further utilized as universal precursor for structurally and functionally diverse
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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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Materials Discovery with Extreme Properties via Reinforcement Learning-Guided Combinatorial Chemistry Chem. Sci. (IF 8.4) Pub Date : 2024-04-24 Hyunseung Kim, Haeyeon Choi, Dongju Kang, Won Bo Lee, Jonggeol Na
The goal of most materials discovery is to discover materials that are superior to those currently known. Fundamentally, this is close to extrapolation, which is a weak point for most machine learning models that learn the probability distribution of data. Herein, we develop reinforcement learning-guided combinatorial chemistry, which is a rule-based molecular designer driven by trained policy for
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Nickel/Photoredox-Catalyzed Three-Component Silylacylation of Acrylates via Chlorine Photoelimination Chem. Sci. (IF 8.4) Pub Date : 2024-04-24 Yejin Koo, Sungwoo Hong
The extensive utility of organosilicon compounds across a wide range of disciplines has sparked significant interest in their efficient synthesis. Although catalytic 1,2-silyldifunctionalization of alkenes provides a promising method for the assembly of intricate organosilicon frameworks with atom and step economy, its advancement is hindered by the requirement of an external hydrogen atom transfer
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Contracted porphyrins and calixpyrroles: synthetic challenges and ring-contraction effects Chem. Sci. (IF 8.4) Pub Date : 2024-04-24 Keita Watanabe, Narendra Nath Pati, Yasuhide Inokuma
Ring-contracted porphyrin analogues, such as subporphyrins and calix[3]pyrroles, have recently attracted considerable attention not only as challenging synthetic targets but also as functional macrocyclic compounds. Although canonical porphyrins and calix[4]pyrrole are selectively generated via acid-catalyzed condensation reactions of pyrrole monomers, their tripyrrolic analogues are always missing
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Redox regulation of Ni hydroxides with controllable phase composition towards biomass-derived polyols electro-refinery Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Yi Tang, Zhuxin Gui, Yingshuai Jia, Xianping Liao, Tianlan Yan, Boxu Gao, Wenbiao Zhang, Li Chen, Qingsheng Gao, Yahong Zhang
Electrocatalytic refinery from biomass-derived glycerol (GLY) to formic acid (FA), one of the most promising candidates of green H2 carrier, has driven widespread attention for its sustainability. Herein, we fabricated a series of monolithic Ni hydroxides-based electrocatalysts by a facile and in-situ electrochemical method through the manipulation of local pH near electrode. The as-synthesized Ni(OH)2@NF-1
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Understanding Electrochemical Interfaces through Comparing Experimental and Computational Charge Density-Potential Curves Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Nandita Mohandas, Sumit Bawari, Jani J.T. Shibuya, Soumya Ghosh, Jagannath Mondal, Tharangattu N. Narayanan, Angel Cuesta
Electrode-electrolyte interfaces play a decisive role in electrochemical charge accumulation and transfer processes. Theoretical modelling of these interfaces is critical to decipher the microscopic details of such phenomena. Different force field-based molecular dynamics protocols are compared here in a view to connect calculated and experimental charge density-potential relationships. Platinum-aqueous
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Enantioselective synthesis of α-aryl α-hydrazino phosphonates Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Saul Alberca, Javier Romero-Parra, Israel Fernandez, Rosario Fernández, Jose M. Lassaletta, David Monge
Catalysts generated in situ by the combination of pyridine-hydrazone N,N-ligands and Pd(TFA)2 have been applied to the addition of arylboronic acids to formylphosphonate-derived hydrazones, yielding α-aryl α-hydrazino phosphonates in excellent enantioselectivities (96−>99% ee). Subsequent removal of the benzyloxycarbonyl (Cbz) N-protecting group afforded key building blocks en route to appealing artificial
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Monolithic 3D nanoelectrospray emitters based on continuous fluid-assisted etching strategy for glass droplet microfluidic chip-mass spectrometry Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Yaoyao Zhao, Ziyang Guo, Yingqi Zhao, Zhao Jin, Yaran Chang, Xiayan Wang, Guangsheng Guo
Glass microfluidic chips are suitable for coupling with mass spectrometry (MS) due to their flexible design, optical transparency and resistance to organic reagents. However, due to the high hardness and brittleness of glass, there is a lack of simple and feasible technology to manufacture a monolithic nanospray ionization (nESI) emitter on a glass microchip, which hinders its coupling with mass spectrometry
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Photo-Thermal Synergistic CO2 Hydrogenation towards CO over PtRh Bimetal-Decorated GaN Nanowires/Si Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Jinglin Li, Bowen Sheng, Liang Qiu, Jiajia Yang, Ping Wang, Yixin Li, Tianqi Yu, Hu Pan, Ying Li, Muhan Li, Lei Zhu, Xinqiang Wang, Zhen Huang, Baowen Zhou
Photo-thermal-synergistic hydrogenation is a promising strategy for upcycling carbon dioxide into fuels and chemicals by maximally utilizing full-spectrum solar energy. Herein, by immobilizing Pt-Rh bimetal onto a well-developed GaN NWs/Si platform, CO2 was photo-thermo-catalytically hydrogenated towards CO under concentrated light illumination without extra energies. The as-designed architecture demonstrates
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Optoelectronic insights of lead-free layered halide perovskites Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Vishwadeepa Hazra, Arnab Mandal, Sayan Bhattacharyya
Two-dimensional organic-inorganic halide perovskites have emerged as promising candidates for a multitude of optoelectronic technologies, owing to their versatile structure and electronic properties. The optical and electronic properties are harmoniously integrated with both the inorganic metal halide octahedral slab, and the organic spacer layer. The inorganic octahedral layers can also assemble into
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1,5-Hydrogen Atom Transfer of α-Iminyl Radical Cations: A New Platform for Relay Annulation towards Pyridine Derivatives and Axially Chiral Heterobiaryls Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Yu-Qiang Zhou, Kui-Cheng He, Wei-Hao Zheng, Jing-Fang Lv, Shi-Mei He, Ning Yu, Yun-Bo Yang, Lv-Yan Liu, Kun Jiang, Ye Wei
The exploitation of new reactive species and novel transformation modes for their synthetic applications have significantly promoted the development of synthetic organic methodology, drug discovery, and advanced functional materials. α-Iminyl radical cations, a class of distonic ions, exhibit great synthetic potential towards the synthesis of valuable molecules. For their generation, radical conjugate
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Highly intense NIR emissive Cu4Pt2 bimetallic clusters featuring Pt(I)-Cu4-Pt(I) sandwich kernel Chem. Sci. (IF 8.4) Pub Date : 2024-04-23 Rui-Ru Zhong, Mo Xie, Cui-Zhou Luan, Lin-Mei Zhang, De-Bo Hao, Shang-Fu Yuan, Tao Wu
Metal nanoclusters (NCs) capable of near-infrared (NIR) photoluminescence (PL) are gaining increasing interest for their potential applications in bioimaging, cell labelling, and phototherapy. However, the limited quantum yield (QY) of NIR emission in metal NCs, especially those emitting beyond 800 nm, hinders their widespread applications. Herein, we present a bright NIR luminescence (PLQY up to 36%
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DNA-Directed Formation of Plasmonic Core-Satellite Nanostructures for Quantification of Hepatitis C Viral RNA Chem. Sci. (IF 8.4) Pub Date : 2024-04-22 Samuel Mabbott, Siddhant Jaitpal, Ka Wai Ng, Angela Michelle San Juan, Cecilia Martinez, Christian Phillips, Sayantan Tripathy
Hepatitis C virus (HCV) continues to be a significant public health challenge, affecting an estimated 71 million people globally and posing risks of severe liver diseases. Despite advancements in treatments, diagnostic limitations hinder the global elimination efforts targeted by 2030. This study introduces an innovative diagnostic approach, integrating catalytic hairpin assembly (CHA) with plasmonic
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Copper-catalyzed Remote Double Functionalization of Allenynes Chem. Sci. (IF 8.4) Pub Date : 2024-04-20 Shengming Ma, Yulong Song, Chunling Fu, Jian Zheng
Addition reactions of molecules with conjugated or non-conjugated multiple unsaturated C-C bonds are very attractive yet challenging due to the versatile issues of chemo-, regio-, and stereo-selectivities. Especially for the readily available conjugated allenynes compounds, the reactivities have not been explored. The first example of copper-catalyzed 2,5-hydrofunctionalization and 2,5-difunctionalization
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Boron-containing helicenes as new generation of chiral materials: opportunities and challenges of leaving the flatland Chem. Sci. (IF 8.4) Pub Date : 2024-04-19 Agnieszka Nowak-Krol, Patrick T. Geppert, Kenkera Rayappa Naveen
Increased interest in chiral functional dyes has stimulated activity in the field of boron-containing helicenes over the past few years. Despite the fact that the introduction of boron endows π-conjugated scaffolds with attractive electronic and optical properties, boron helicenes have long remained underdeveloped compared to other helicenes containing main group elements. The main reason was the lack
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A High-Resolution Structural Characterization and Physicochemical Study of How a Peptoid Binds to an Oncoprotein MDM2 Chem. Sci. (IF 8.4) Pub Date : 2024-04-19 Marin Yokomine, Jumpei Morimoto, Yasuhiro Fukuda, Takumi Ueda, Koh Takeuchi, Koji Umezawa, Hideo Ago, Hiroaki Matsuura, Go Ueno, Akinobu Senoo, Satoru Nagatoishi, Kouhei Tsumoto, Shinsuke Sando
Peptoids are a promising drug modality targeting disease-related proteins, but how a peptoid engages in protein binding is poorly understood. This is primarily due to a lack of high-resolution peptoid–protein complex structures and systematic physicochemical studies. Here, we present the first crystal structure of a peptoid bound to a protein, providing high-resolution structural information about
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An Adsorbate Biased Dynamic 3D Porous Framework for Inverse CO2 Sieving over C2H2 Chem. Sci. (IF 8.4) Pub Date : 2024-04-17 Nivedita Sikdar, Subhajit Laha, Rohan Jena, Anupam Dey, Faruk Ahamed Rahimi, Tapas Kumar Maji
Separating carbon dioxide (CO2) from acetylene (C2H2) is one of the most critical and complex industrial separations due to similarities in physicochemical properties and molecular dimensions. Herein, we report a novel Ni-based three-dimensional framework {[Ni4(μ3-OH)2(μ2-OH2)2(1,4-ndc)3](3H2O)}n (1,4-ndc = 1,4-naphthalenedicarboxylate) with one-dimensional pore channel (3.05 × 3.57 Å2), that perfectly
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Amorphous Conversion in Pyrolytic Symmetric Trinuclear Nickel Clusters Trigger Trifunctional Electrocatalysts Chem. Sci. (IF 8.4) Pub Date : 2024-04-16 Li Li, Huifeng Zhao, Meixing Gan, Tao Zhang, Jianing Li, Shi Tao, Jing Peng, Hai-Bin Yu, Xu Peng
The pursuit of multifunctional electrocatalysts holds significant importance due to their foundational comprehension of material chemistry. Amorphous materials are particularly appealing, yet they pose challenges in terms of rational design due to their structure disorder and thermal instability. Herein, we propose a strategy that entails the tandem (low-temperature/250-350 oC) pyrolysis of molecular
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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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Therapeutic Coordination Polymers: Tailoring Drug Release through Metal-Ligand Interactions Chem. Sci. (IF 8.4) Pub Date : 2024-04-11 Vedran Nicholas Vukotic, Jennifer Murphy, Joy-Lynn Kobti, Michelle Dao, Darcy Wear, Michael Okoko, S. Pandey
Developing tunable materials which exhibit sustained drug release is a considerable challenge. Herein, we report the concept of Therapeutic Coordination Polymers (TCPs); non-porous coordination polymers constructed from biocompatible components which demonstrate tunable zero-order drug release kinetics upon degradation of metal-ligand bonds. TCPs were constructed from three principal components: i)
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P-doped spherical hard carbon with high initial Coulombic efficiency and enhanced capacity for sodium ion batteries Chem. Sci. (IF 8.4) Pub Date : 2024-04-11 Zhengguang Liu, Jiahua Zhao, Hao Yao, Xiangxi He, Hang Zhang, Yun Qiao, Xingqiao Wu, Li Li, Shulei Chou
Hard carbon (HC) is one of the most promising anode materials for sodium-ion batteries (SIBs) due to its cost-effectiveness, and low-voltage plateau capacity. Heteroatom doping is considered as an effective strategy to improve the sodium storage capacity of HC. However, most of the previous heteroatom doping strategies are occurred at a relatively low temperature, which could not be utilized to raise
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Binding of carbon dioxide and acetylene to free carboxylic-acid sites in a metal-organic framework Chem. Sci. (IF 8.4) Pub Date : 2024-04-10 Martin Schroder, Christopher Marsh, Xue Han, Zhenzhong Lu, Ivan da Silva, Yongqiang Cheng, Luke L. Daemen, Sarah Day, Stephen Thompson, Anibal Javier Ramirez-Cuesta, Sihai Yang
The functionalisation of organic linkers in metal-organic frameworks (MOFs) to improve gas uptake is well-documented. Although the positive role of free carboxylic acid sites in MOFs for binding gas molecules has been proposed in computational studies, relatively little experimental evidence has been reported in support of this. Primarily this is because of the inherent synthetic difficulty to prepare
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Ultrafast photogeneration of a metal-organic nitrene from 1,1’-diazidoferrocene Chem. Sci. (IF 8.4) Pub Date : 2024-04-09 Frederik Scherz, Markus Bauer, Luis Domenianni, Carolin Hoyer, Jonas Schmidt, Biprajit Sarkar, Peter Vöhringer, Vera Krewald
Ferrocene and its derivatives have fascinated chemists for more than 70 years, not least due to the analogies with the properties of benzene. Despite these similarities, the obvious difference between benzene and ferrocene is the presence of an iron ion and hence the availability of d-orbitals for properties and reactivity. Phenylnitrene with its rich photochemistry can be considered an analogue of
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De novo Design of Peptides that Bind Specific Conformers of α-Synuclein Chem. Sci. (IF 8.4) Pub Date : 2024-03-30 Hailey M Wallace, Hyunjun Yang, Sophia K Tan, Henry S Pan, Rose Yang, Junyi Xu, Hyunil Jo, Carlo Condello, Nicholas F Polizzi, Bill DeGrado
Insoluble amyloids rich in cross-β fibrils are observed in a number of neurodegenerative diseases. Depending on the clinicopathology, the amyloids can adopt distinct supramolecular assemblies, termed conformational strains. However, rapid methods to study amyloid in a conformationally specific manner are lacking. We introduce a novel computational method for de novo design of peptides that tile the
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Cluster dynamics of heterometallic trinuclear clusters during ligand substitution, redox chemistry, and group transfer processes Chem. Sci. (IF 8.4) Pub Date : 2024-02-15 Cristin E. Juda, Rex Handford, Amymarie K. Bartholomew, Tamara Powers, Nina X. Gu, Elisabeth Meyers, Nikolaj Roth, Yu-Sheng Chen, Shao-Liang Zheng, Theodore Betley
Stepwise metalation of the hexadentate ligand tbsLH6 (tbsLH6 = 1,3,5-C6H9(NHC6H4-o-NHSiMe2tBu)3) affords bimetallic trinuclear clusters (tbsL)Fe2Zn(thf) and (tbsL)Fe2Zn(py). Reactivity studies were pursued to understand metal atom lability as the clusters undergo ligand substitution, redox chemistry, and group transfer processes. Chloride addition to (tbsL)Fe2Zn(thf) resulted in a mixture of species
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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