Article
Chemistry, Organic
Xinhan Li, Fuqin Zhang, Yao Zhong, Na Li, Jianbin Xu, Baomin Fan
Summary: Alkynylsilanes are important structural units used in various fields. A method for direct coupling reaction and alkynylation of hydrosilanes using a hydrogen atom transfer strategy and visible-light-driven photocatalysis was reported. The protocol also showed applicability to dihydroalkyl/aryl silanes using 4CzIPN and quinuclidine as photocatalysts.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sandip Bag, Shubham Ojha, Sreelakshmi Venugopalan, Basudev Sahoo
Summary: In this study, we present a visible-light photoredox-catalyzed alkylation/arylative cyclization reaction of N-acrylamides with ketone-derived dihydroquinazolinones. This method allows the formation of indolo- and benzimidazolo[2,1-a]isoquinolines or 2-oxindoles from 2-arylindoles, 2-arylbenzimidazoles, or N-substituted anilines. The reaction proceeds through the formal cleavage of ketone α-C-C and arene C-H bonds, leading to the incorporation of alkyl and aryl carbogenic motifs and the synthesis of cyclic structures with a quaternary stereocenter.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Nikitas G. Malliaros, Michael Orfanopoulos
Summary: An innovative and efficient method for regioselective functionalization of C-60 with 9H-fluorenes has been developed. This approach involves the use of fluorenyl radicals derived from fluorenes in a HAT process mediated by tetrabutylammoniumdecatungstate to produce [60]fullerene-fluorene dyads in a single step. Kinetic isotope effect measurements suggest a stepwise mechanism with C-H (D) bond scission as the rate-limiting step.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Environmental Sciences
Mohammed-Amine Edaala, Lekbira El Mersly, Abdelaziz Aloui Tahiri, Pascal Wong-Wah-Chung, Lahssen El Blidi, Maher M. Alrashed, Salah Rafqah
Summary: The aim of this study is to propose a successful method for the treatment of water contaminated by pharmaceutical pollutants. The method utilizes homogeneous photocatalysis in the presence of decatungstate ions to degrade the target pharmaceutical compound. The results demonstrate effective degradation of the compound under simulated solar irradiation, and optimal conditions for the degradation process are identified. The study also provides insights into the photocatalytic degradation mechanism of the compound in an aqueous solution.
Article
Chemistry, Multidisciplinary
Franz-Lucas Haut, Riccardo S. Mega, Joan V. Estornell, Ruben Martin
Summary: We describe a catalytic intramolecular decarboxylative/desulfonylative sp(3) allylation triggered by sulfinate salts under light irradiation. The reaction likely proceeds through a non-classical, radical-polar crossover mechanism, providing a rapid and reliable method to access valuable allyl architectures from readily available precursors. The protocol is characterized by its simplicity, scalability, and the use of abundant, commercially available catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Alessandro Marotta, Hao Fang, Callum E. Adams, Kailey Sun Marcus, Constantin G. Daniliuc, John J. Molloy
Summary: Operationally simple strategies using visible light and a simple Lewis base are disclosed for the facile activation of α-halo boronic esters, leading to the construction of versatile E-allylic boronic esters via intermolecular addition to styrenes. This activation method can be strategically merged with selective energy transfer catalysis for the complimentary stereodivergent synthesis of Z-allylic boronic esters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zexian Li, Minyan Wang, Zhuangzhi Shi
Summary: An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed, generating valuable multisubstituted perfluoroalkylated compounds in a single step. Mechanistically, photoinduced alkyl radical addition to an alkene leads to migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center, followed by generation of a C-radical bearing two electron-withdrawing groups and reduction by a hydrogen donor to complete the domino sequence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Nobukazu Taniguchi, Mamoru Hyodo, Lin-Wei Pan, Ilhyong Ryu
Summary: Site-selective C(sp(3))-H thiolation has been achieved using thiosulfonates as substrates and the decatungstate anion as a photocatalyst. The reaction proceeds through a cascade of double S(H)2 reactions, HAT and ArS group transfer, and PCET, allowing the recovery of the catalyst, W10O324-.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Anastasiya Krech, Viktoryia Yakimchyk, Tatsiana Jarg, Dzmitry Kananovich, Maksim Oseka
Summary: We present a methodology for photocatalytic generation of beta-ketoalkyl radicals from tertiary cyclopropanols, using TBADT as a photoredox catalyst. The method allows for redox-neutral addition of the radicals to olefins, resulting in the synthesis of distantly functionalized ketones. The reaction occurs under ambient temperature conditions and is compatible with various cyclopropanol and alkene substrates. Mechanistic investigations reveal the role of TBADT as a photoredox catalyst and the formation of electron donor-acceptor complexes between certain cyclopropanols and olefins.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ruben Canton-Vitoria, Mildred Quintana, Nikitas G. Malliaros, Nikos Tagmatarchis
Summary: This paper presents a new method for the functionalization of single-walled carbon nanotubes through a photocatalytic acylation process. The method is environmentally friendly and has great potential for various applications. It is also expected to be extended to other nanomaterials.
ADVANCED MATERIALS INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Patrick J. Sarver, Noah B. Bissonnette, David W. C. MacMillan
Summary: The study presents a method for converting strong, aliphatic C(sp(3))-H bonds into alkyl sulfinic acids using decatungstate photocatalysis, which can be applied to a variety of C(sp(3))-rich molecules for efficient synthesis of complex sulfur-containing compounds. Furthermore, the method demonstrates potential for divergent synthesis of pharmaceutically relevant molecules through diversification of the sulfinic acid products into various medicinally relevant functional groups.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Remi Canterel, Jacques Lalevee, Elodie Bourgeat-Lami, Emmanuel Lacote, Muriel Lansalot
Summary: Polystyrene particles were successfully synthesized in a mixture of ethanol and water using visible light and an optimized photoinitiating system. The addition of a base and the use of a specific stabilizer significantly improved the reproducibility and allowed for the formation of larger, narrowly distributed particles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhenda Tan, Shibo Zhu, Yangbin Liu, Xiaoming Feng
Summary: This article reports a photoinduced chemo-, site- and stereoselective alpha-C(sp(3))-H functionalization of sulfides using isatins as the photoredox reagent and coupling partner catalyzed by a chiral gallium(III)-N,N '-dioxide complex. The reaction proceeds through a verified single-electron transfer (SET) mechanism with high efficiency, excellent functional group tolerance, as well as a broad substrate scope. Importantly, this cross-coupling protocol is highly selective for the direct late-stage functionalization of methionine-related peptides, regardless of the inherent structural similarity and complexity of diverse residues.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qiang Liu, Bei-Bei Zhang, He Sheng, Sen Qiao, Zhi-Xiang Wang, Xiang-Yu Chen
Summary: The visible-light-induced photoreduction of carborane phosphonium salts under blue light irradiation provides a simple and effective method for accessing carbon-centered carboranyl radicals without the use of transition metals and photocatalysts. The utility of this method is demonstrated by the successful preparation of carborane-oxindole-pharmaceutical hybrids through radical cascade reactions. Computational and experimental studies suggest that the carbon-centered carboranyl radicals are generated through single-electron transfer of photoactive charge-transfer complexes between the salts and the additive potassium acetate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
D. Sai Reddy, Ivan M. Novitskiy, Andrei G. Kutateladze
Summary: A novel photoinduced cascade reaction has been developed to access complex nitrogen polyheterocycles. This reaction involves excited state intramolecular proton transfer in aromatic amino ketones with tethered dual unsaturated pendants, leading to the formation of four sigma bonds and setting six new stereogenic centers in a single photochemical step with significant complexity increases of up to 220 mcbit.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Tommaso Caielli, Alessandro Raffaele Ferrari, Simone Bonizzoni, Eva Sediva, Angela Capri, Mariarita Santoro, Irene Gatto, Vincenzo Baglio, Piercarlo Mustarelli
Summary: Water electrolyzers based on anion exchange membranes (AEMs) with poly(aryl piperidiniums) (PAPs) show promise for reducing the capital costs of green hydrogen production. Through optimized polymerization parameters, mechanically resistant PAP-based membranes with a thickness of 15 μm were obtained, exhibiting an impressive conductivity of 185 mS cm-1 and excellent stability in 1 M KOH solution at 80°C. These membranes outperformed a commercially available PAP-based membrane in an electrolyzer cell, demonstrating their potential as low-cost AEMs with easy synthesis.
JOURNAL OF POWER SOURCES
(2023)
Article
Chemistry, Physical
Eva Sediva, Simone Bonizzoni, Tommaso Caielli, Piercarlo Mustarelli
Summary: The progress in AEMFCs performance is driven by improved water management through electrode layer engineering. The use of DRT as a diagnostic tool has simplified the electrode optimization process and increased the peak power density of AEMFCs.
JOURNAL OF POWER SOURCES
(2023)
Article
Electrochemistry
Simone Bonizzoni, Diego Stucchi, Tommaso Caielli, Eva Sediva, Michele Mauri, Piercarlo Mustarelli
Summary: Water electrolysis is the most attractive method for producing green hydrogen, and Anion Exchange Membrane (AEM) water electrolyzers are a promising technology. However, AEMs still need improvement in terms of performance and stability. In this study, we report a simple and cost-effective chemical modification of polyketone (PK) to fabricate self-standing membranes with good ion exchange capacity. Preliminary electrolysis tests show that the PK-based membrane performs similarly to a commercial one.
Article
Energy & Fuels
Giuseppe Sportelli, Tommaso Boselli, Stefano Protti, Nick Serpone, Davide Ravelli
Summary: Light absorption by semiconducting materials generates electrons and holes, leading to charge separation for photovoltaics and photocatalysis. Recent developments in photovoltaic applications have been impressive, thanks to innovative and efficient materials. This review showcases the high performance of photovoltaic materials in photocatalytic synthetic applications, such as redox processes, C-C bond formation, and manipulation of cyclic structures. The trend highlights the importance of converting highly performing photovoltaic materials into the photocatalytic field.
Article
Electrochemistry
Shahid Khalid, Nicolo Pianta, Piercarlo Mustarelli, Riccardo Ruffo
Summary: Batteries based on organic electrolytes are unsafe due to fire/explosion accidents. Aqueous batteries are considered as a good alternative, but their main weakness lies in the decomposition of water molecules. This perspective discusses the state-of-the-art of water-in-salt (WIS) electrolytes for aqueous energy storage systems and explores strategies to improve their electrochemical stability window (ESW). Challenges and future prospects for practical aqueous energy storage systems are also highlighted.
Article
Chemistry, Applied
Alexandra Jorea, Benedetta Bassetti, Klaus Gervasoni, Stefano Protti, Alessandro Palmieri, Davide Ravelli
Summary: The hydroalkylation of nitroalkenes and beta-nitroacrylates has been optimized using a photocatalytic strategy. The decatungstate anion has been utilized as a versatile photocatalyst for the generation of alkyl radicals from various substrates, such as aliphatic heterocycles, amides, and cycloalkanes.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Alexandra Jorea, Carlotta Raviola, Mariateresa Giustiniano, Davide Ravelli
Summary: A library of unnatural a-amino acid derivatives was synthesized by hydrofunctionalization of the C=N bond in a series of compounds. Tetrabutylammonium decatungstate was used as the photocatalyst to generate C-centered radicals, leading to the formation of (protected) a-hydrazino acids as products. This methodology proved to be versatile, allowing functionalization of the herbicide safener isoxadifen-ethyl.
Article
Chemistry, Physical
Shahid Khalid, Nicolo Pianta, Simone Bonizzoni, Chiara Ferrara, Roberto Lorenzi, Alberto Paleari, Patrik Johansson, Piercarlo Mustarelli, Riccardo Ruffo
Summary: Highly concentrated aqueous binary solutions of acetate salts show potential for electrochemical applications, including energy storage. These solutions have high solubility and can reduce ion activity, leading to better stability of the electrolyte. The addition of Li+ or Na+ allows compatibility with intercalation materials, making them suitable for rechargeable alkaline-ion batteries. However, a deeper understanding of their physicochemical properties is still needed. In this study, we investigated the properties of solutions with different concentrations of CH3COONa and found that the solution with 20 mol kg(-1) CH3COOK + 7 mol kg(-1) CH3COONa achieved the best balance between transport properties and electrochemical stability.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Lorenzo Mezzomo, Nicolo Pianta, Irene Ostroman, Niv Aloni, Diana Golodnitsky, Emanuel Peled, Piercarlo Mustarelli, Riccardo Ruffo
Summary: New generation lithium batteries require better performances, improved safety, and sustainability. Deep Eutectic Solvents (DESs) made with 2,2,2-trifluoroacetamide (TFA) and LiPF6 show promise as safer and more environmentally sustainable electrolyte components. The DES composition tested against Li metal, LiFePO4 (LFP), and high voltage LiNi1-x-yMnxCoyO2 (NMC) demonstrates good electrochemical performance and improved thermal stability compared to a commercial liquid electrolyte.
JOURNAL OF POWER SOURCES
(2023)
Article
Chemistry, Multidisciplinary
Haidi Tang, Muliang Zhang, Yuchao Zhang, Penghao Luo, Davide Ravelli, Jie Wu
Summary: Researchers have developed a method for synthesizing thioesters through carbonyl thiyl radical-based reactions, using direct photocatalyzed hydrogen atom transfer. This method allows for the synthesis of complex pharmaceutical molecules from readily available commodity chemicals. The study provides a new approach for the application of thiol-ene click chemistry in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Abdullah Hamadamin, Valentina Benazzi, Carlotta Campalani, Luca Quattri, Davide Ravelli, Faiq Hussain, Alvise Perosa, Maurizio Selva, Stefano Protti
Summary: Amorphous nitrogen-doped carbon dots (a-N-CDs) were synthesized via hydrothermal conditions using citric acid and diethylenetriamine (DETA) as carbon and nitrogen sources, respectively. These materials exhibit strong absorption in the visible light region and have been successfully used as photoredox catalysts under violet LED irradiation for the 1,2-difunctionalization of olefins through an atom transfer radical addition (ATRA) process. The reported approach offers a metal-free and aqueous medium synthesis route, highlighting the potential applications of these bio-derived carbon materials in organic synthesis.
Article
Chemistry, Organic
Giovanni Preda, Andrea Arico, Chiara Botta, Davide Ravelli, Daniele Merli, Sara Mattiello, Luca Beverina, Dario Pasini
Summary: We report a facile, metal-free convergent synthesis method and characterization of novel quinacridone dyes with two triptycene units that function as end-caps and steric confinements for the quinacridone chromophore. A precise comparison between the confined dyes and known homologues reveals that the reduction of p-p interactions in triptycene-fused quinacridone dyes, compared to classical quinacridone, leads to increased solubility, processability, fluorescence quantum yield, and photostability in the solid state.
Article
Green & Sustainable Science & Technology
Pietro Cattaneo, Daniele Callegari, Daniele Merli, Cristina Tealdi, Dhanalakshmi Vadivel, Chiara Milanese, Valeriy Kapelyushko, Fiorenza D'Aprile, Eliana Quartarone
Summary: The rapid growth in demand for lithium-ion batteries (LIBs) poses challenges in EoL management and CRM supply. Collecting and recycling spent LIBs through sustainable processes and transitioning to a circular economy vision can address these challenges. These processes involve metallurgic approaches to recover critical metals and pretreatment approaches to enhance the recovery efficiency of valuable materials.
ADVANCED SUSTAINABLE SYSTEMS
(2023)
Article
Electrochemistry
Daniele Callegari, Lorenzo Airoldi, Riccardo Brucculeri, Umberto Anselmi Tamburini, Eliana Quartarone
Summary: This study reports a simple and scalable process using additive manufacturing technology to produce copper current collectors with different patterns to address the challenges of lithium metal anodes. The three-dimensional network of the current collectors stabilizes the electrodeposition of lithium and prevents dendrite growth, leading to stable battery performance and high coulombic efficiency.
BATTERIES & SUPERCAPS
(2023)
Article
Electrochemistry
Daniele Callegari, Stefania Davino, Miriam Parmigiani, Maria M. Llamas, Lorenzo Malavasi, Eliana Quartarone
Summary: This study developed a novel Janus separator with tunable properties to address crucial drawbacks of lithium-metal batteries. The results showed that the Janus separator effectively prevented self-discharge and internal short-circuiting, resulting in enhanced cell lifespan and improved capacity retention. The introduced functionalities successfully intercepted dendrite formation and exhibited higher thermal resistance compared to traditional separators.
BATTERIES & SUPERCAPS
(2023)
