Article
Chemistry, Multidisciplinary
Matteo Cavalleri, Caterina Damiano, Gabriele Manca, Emma Gallo
Summary: Protonated commercially available porphyrin ligands can act as bifunctional catalysts for the synthesis of N-alkyl oxazolidinones by CO2 cycloaddition to aziridines. This metal-free methodology is cost effective and eco-compatible, and the protonated porphyrin can be recycled without loss in performance. DFT study provides insights into the mechanism of CO2 cycloaddition to aziridines mediated by protonated porphyrin.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Tomoya Ishizuka, Nitika Grover, Christopher J. Kingsbury, Hiroaki Kotani, Mathias O. Senge, Takahiko Kojima
Summary: This article summarizes the synthetic methods and design aspects of nonplanar porphyrin formation, the key properties and functionality of the nonplanar aromatic framework, and the scope and utility of this emerging class in addressing important scientific, industrial, and environmental issues.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Kaeden Teindl, Brian O. O. Patrick, Eva M. M. Nichols
Summary: This study investigates the contribution of proton transfer driving forces in molecular catalysts for electrochemical CO2 reduction. By synthesizing a series of catalysts with tunable pK(a) and varying acidity of exogenous acids, it is found that the kinetics of catalytic turnover are more sensitive to variations in SCS pK(a) when using more acidic exogenous acids and to variations in exogenous acid pK(a) when SCS acidity is increased.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Environmental Sciences
Yong-Ming Dai, Yan-Yun Li, Jia-Hao-Lin, Bing Yi Chen, Chiing-Chang Chen
Summary: The study demonstrated that acid-base bifunctional heterogeneous solid catalysts prepared using niobium and alkali metal oxides showed good performance in transesterification for green fuel production. The highest biodiesel yield was achieved with LiNbO3 catalyst under specific conditions, and the properties of the biodiesel produced met international standard specifications.
JOURNAL OF ENVIRONMENTAL MANAGEMENT
(2021)
Article
Chemistry, Multidisciplinary
Kai Wang, Na Liu, Jian Wei, Yang Yu, Jixin Zhang, Joshua Iseoluwa Orege, Lifei Song, Qingjie Ge, Jian Sun
Summary: The study demonstrates that CoFe/HZSM-5 catalyst significantly enhances the selectivity of C5+ hydrocarbons, paving the way for more effective CO2 utilization.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Physical
Saswati Santra, Verena Streibel, Ian D. Sharp
Summary: The transition from a global economy dependent on fossil fuels to one based on sustainable energy conversion technologies is the primary challenge of the day. Earth-abundant bifunctional transition metal catalysts, especially those based on molybdenum (Mo), show great promise in reducing cost, simplifying systems, and providing prospects for accelerated scaling and sustainable material reuse. This comprehensive review focuses on recent progress in Mo-based multifunctional catalysts, discussing various formations and structures, as well as emerging trends and opportunities in this promising materials space.
Article
Polymer Science
Lilian D. Ramirez-Valencia, Esther Bailon-Garcia, Adriana I. Moral-Rodriguez, Francisco Carrasco-Marin, Agustin F. Perez-Cadenas
Summary: Bifunctional electrocatalysts were obtained by doping carbon microspheres with Eco-graphene, enhancing the efficiency of pollutant degradation in the Electro-Fenton process.
Article
Nanoscience & Nanotechnology
Takeshi Aihara, Wataru Aoki, Shin Kiyohara, Yu Kumagai, Keigo Kamata, Michikazu Hara
Summary: In this study, perovskite oxide nanoparticles were successfully synthesized using dicarboxylic acids as reagents. The resulting SrTiO3 nanoparticles showed high catalytic activity for the cyanosilylation of carbonyl compounds, even without a heat pretreatment.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Qingqing Luo, Zhou Tian, Jie Tang, Jie Wang, Yin Tian, Cheng Peng, Gu Zhan, Bo Han
Summary: The study focuses on the design of bifunctional 4-pyrrolidinopyridines as Lewis base catalysts, which exhibited excellent efficiency and stereoselectivity in asymmetric cycloaddition reactions. The research provides strong support for the construction of chiral spiropyrazolone derivatives.
Article
Electrochemistry
Kaur Muuli, Xiang Lyu, Marek Mooste, Maike Kaarik, Barr Zulevi, Jaan Leis, Haoran Yu, David A. Cullen, Alexey Serov, Kaido Tammeveski
Summary: In this study, Fe-N-C catalysts were prepared at a kilogram scale using the commercial VariPoreTM method, and the effect of synthesis conditions on the catalyst performance at ZAB air electrode was investigated. The results showed that the PA-450-HT catalyst exhibited excellent electrocatalytic activity for the oxygen reduction reaction (ORR) and was the most suitable catalyst for primary ZAB, with a galvanostatic polarization discharge peak power density of 149 mW cm-2, outperforming commercial Pt-Ru/C catalysts. Additionally, the NCB-600-HT catalyst displayed outstanding ORR and OER reversibility, with a half-wave potential of 0.87 V vs. RHE and a Delta E value of 0.81 V, and exhibited excellent charge-discharge cycling durability similar to NCB-550-LT for the secondary ZAB. This study reported for the first time the mass production of outstanding bifunctional Fe-N-C catalysts for rechargeable ZAB.
ELECTROCHIMICA ACTA
(2023)
Article
Chemistry, Physical
Natesan Kumaresan, Pichan Karuppasamy, M. Praveen Kumar, Shaik Gouse Peera, Mohamad S. AlSalhi, Sandhanasamy Devanesan, R. V. Mangalaraja, Perumalsamy Ramasamy, Tatianne Ferreira de Oliveira, G. Murugadoss
Summary: The production of green hydrogen through water electrolysis has gained attention due to the demand for green energy technologies. Currently, Pt and RuO2-based electrocatalysts are expensive, leading to the search for efficient and cheap alternatives. In this study, biomass-derived electrocatalysts with implanted heteroatoms were synthesized and characterized. The catalyst exhibited excellent morphology, surface area, and activity for hydrogen and oxygen evolution reactions in alkaline electrolytes.
MOLECULAR CATALYSIS
(2023)
Article
Nanoscience & Nanotechnology
Huaiying Zhang, Dongyuan Cui, Tianyang Shen, Tong He, Xuejie Chen, Sai An, Bo Qi, Yu-Fei Song
Summary: In this study, a PW12@NiCo-LDH acid-base bifunctional catalyst was successfully prepared using the in-situ encapsulation-reassembly strategy. The catalyst exhibited excellent catalytic activity in the deacetalization-Knoevenagel condensation reaction, with over 99% conversion of benzaldehyde dimethyl acetal (BDMA) and over 99% yield of ethyl & alpha;-cyanocinnamate (ECC). Moreover, the catalyst could be recycled at least 10 times without significant structural changes, thanks to the stable assembly between PW12 and NiCo-LDH.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Engineering, Chemical
Fatai Alade Aderibigbe, Harvis Bamidele Saka, Sherif Ishola Mustapha, Mutiu Kolade Amosa, Suleiman Shiru, Idowu Abdulfatai Tijani, Esther Oluwabunmi Babatunde, Bisola Taibat Bello
Summary: The depletion of fossil fuels and their harmful effects on the environment has led to the search for alternative fuels, namely biofuels. Among the various biofuels, biodiesel has gained significant attention due to its ability to promote carbon neutrality. The transesterification and interesterification processes are widely used for biodiesel production. This review focuses on the performance efficiency of solid base, solid acid, and bifunctional solid acid-base catalysts for biodiesel production from waste cooking oil. The benefits of exploring biomass-derived acid-base heterogeneous bifunctional catalysts, as well as the current status and future prospects for biodiesel production from waste cooking oil, are discussed.
CHEMBIOENG REVIEWS
(2023)
Review
Chemistry, Physical
Alexis Munyentwali, He Li, Qihua Yang
Summary: This review discusses the application of bifunctional solid acid/base catalysts in sustainable biodiesel production. Compared to conventional liquid base catalysts, solid catalysts offer better environmental friendliness and cost-effectiveness, and can be produced using low-cost feedstocks.
APPLIED CATALYSIS A-GENERAL
(2022)
Article
Chemistry, Physical
Xingqiu Li, Nini Ye, Han Liu, Chongzhao Li, Yuanpeng Huang, Xuelong Zhu, Hailong Feng, Jinghang Lin, Li Huang, Jingjie Wu, Yang Liu, Chenglu Liang, Xiangfang Peng
Summary: By modifying the surface electronic states of CuS catalysts through iron doping, the catalytic activity of CuFe0.6S1.6 catalysts for overall water electrolysis in alkaline electrolytes was enhanced, with improved charge transfer efficiency. The catalyst showed satisfactory stability at high current densities, demonstrating great potential for industrial applications.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Multidisciplinary
Karolis Norvaisa, Sophie Maguire, Claire Donohoe, John E. O'Brien, Brendan Twamley, Ligia C. Gomes-da-Silva, Mathias O. Senge
Summary: Inspired by 'picket-fence' systems, this study utilized strain to introduce intramolecular tension, leading to selective compound atropisomer conversion and the formation of distinctive supramolecular nanostructures.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Biochemistry & Molecular Biology
Arno Wiehe, Mathias O. Senge
Summary: This review provides an overview of the research, development, and clinical applications of the photosensitizer 5,10,15,20-tetra(m-hydroxyphenyl)chlorin (mTHPC, temoporfin) in photodynamic (cancer) therapy (PDT) and other medical applications. The review covers the chemistry, biochemistry, pharmacology, and clinical applications of temoporfin, including the formulation development such as liposomal formulations. The literature covered spans from 2009 to early 2022 and is connected to a previous extensive review on this photosensitizer, which traces its development, approval, and clinical application.
PHOTOCHEMISTRY AND PHOTOBIOLOGY
(2023)
Article
Chemistry, Organic
Claire Donohoe, Asterios Charisiadis, Sophie Maguire, Brendan Twamley, Fabio A. Schaberle, Ligia C. Gomes-da-Silva, Mathias O. Senge
Summary: The time dependence of atropisomer interconversion has hindered the development of single atropisomer drug candidates. The instability caused by moderate interconversion energy barriers is a concern for drug stability. However, there is a recent focus on developing stable atropisomer drugs with enhanced activity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Biao Yang, Kaifeng Niu, Nan Cao, Nitika Grover, Wenchao Zhao, Alexander Riss, Jonas Bjoerk, Willi Auwaerter, Johannes V. Barth, Mathias O. Senge
Summary: In this study, the behavior of 1,3-disubstituted BCP moieties on metal surfaces was examined using low-temperature scanning tunneling microscopy/non-contact atomic force microscopy studies and density functional theory modeling. The configuration, supramolecular assembly, and thermally activated dehalogenative coupling reactions of BCP-containing precursors on Au(111) were investigated, resulting in the formation of polymeric chains. These findings provide sub-molecular insights into the behavior of BCP scaffolds on surfaces and expand the potential application of BCP derivatives in custom-designed surface architectures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nitika Grover, Maxime Cheveau, Brendan Twamley, Christopher J. Kingsbury, Cornelia M. Mattern, Mathias O. Senge
Summary: We present a two-step method for obtaining versatile bicyclo[1.1.1]pentane (BCP) derivatives using Grignard reagents. This approach allows for the incorporation of BCP units into tetrapyrrolic macrocycles, as well as the synthesis of a novel class of calix[4]pyrrole analogues by replacing bridging methylene groups with BCP units. Moreover, electron-withdrawing substituents at the BCP bridgeheads lead to the formation of a doubly N-confused system. Single-crystal X-ray diffraction analyses and 2D NMR spectroscopy reveal that the pyrrole rings in BCP-containing macrocycles exist in 1,3-alternate or alpha beta alpha beta conformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Irina Osadchuk, Hanna-Eliisa Luts, Karolis Norvaisa, Victor Borovkov, Mathias O. Senge
Summary: The determination of molecular stereochemistry and absolute configuration is important in chemistry, pharmacology, and biology. Electronic circular dichroism (ECD) is a widely used tool for chirality assignment, but the mechanisms of induced ECD in porphyrin complexes are not fully understood.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Crystallography
Harry C. Sample, Brendan Twamley, Mathias O. Senge
Summary: The crystal structures of three S-(pyridin-2-yl) benzothioesters with different para-phenyl substituents are reported. These compounds are used in the mono-acylation of pyrrolic species to produce multifunctional tetrapyrroles. The dominant interactions in the crystal packing vary from pi-pi stacking in compound 1 to exclusively C-H···O/N interactions in compound 3 as the para-phenyl motif changes from electron withdrawing to electron donating.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2023)
Article
Crystallography
Harry C. Sample, Brendan Twamley, Mathias O. Senge
Summary: The crystal structure of compound 1 (C26H24Br2N4O8S2) is presented in this study. Compound 1 was obtained as a by-product in the synthesis of geminal-dimethyl hydrodipyrrins. Unexpected enantiomeric resolution was observed in both the bulk sample and crystal of 1, with distinct C-H···O (C-methyl-H···O-nitro, C-sp3-H···O-sulfonyl) interactions present in the enantiomers, along with other interactions, forming a polymer along the c-axis direction. Little data is available on the 1,3-dinitrobutane scaffold, unlike the well-documented pyrrolic fragments.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Davide Ranieri, Alberto Privitera, Fabio Santanni, Karolina Urbanska, Grant J. Strachan, Brendan Twamley, Enrico Salvadori, Yu-Kai Liao, Mario Chiesa, Mathias O. Senge, Federico Totti, Lorenzo Sorace, Roberta Sessoli
Summary: By synthesizing and studying a VIVO-CuII porphyrin dimer, we observed measurable exchange coupling and good spin coherence, making it suitable for operating two-qubit molecular spin-based quantum gates under various conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Irina Osadchuk, Hanna-Eliisa Luts, Karolis Norvaisa, Victor Borovkov
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Multidisciplinary
Irina Osadchuk, Hanna-Eliisa Luts, Karolis Norvaisa, Victor Borovkov, Mathias O. Senge
Summary: This article features the groups of Irina Osadchuk at Tallinn University of Technology and Mathias Senge at Trinity College Dublin. The image illustrates the measurement and simulation of ECD and UV-Vis spectra of a porphyrin molecule with two guest molecules (R)-camphor sulfonic acid under UV-visible light irradiation. Read the full text of the article at 10.1002/chem.202301408.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Nan Cao, Jonas Bjoerk, Eduardo Corral-Rascon, Zhi Chen, Mario Ruben, Mathias O. Senge, Johannes V. Barth, Alexander Riss
Summary: This study investigates how aromaticity affects the reactivity of alkyne-substituted porphyrin molecules on a Au(111) surface. The experiments show that carbon atoms stabilized by aromaticity display lower reactivity, which is consistent with density functional theory calculations.
Review
Chemistry, Multidisciplinary
Tomoya Ishizuka, Nitika Grover, Christopher J. Kingsbury, Hiroaki Kotani, Mathias O. Senge, Takahiko Kojima
Summary: This article summarizes the synthetic methods and design aspects of nonplanar porphyrin formation, the key properties and functionality of the nonplanar aromatic framework, and the scope and utility of this emerging class in addressing important scientific, industrial, and environmental issues.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Karolis Norvaisa, John E. O'Brien, Irina Osadchuk, Brendan Twamley, Victor Borovkov, Mathias O. Senge
Summary: In this study, we investigated the activity and symmetry of porphyrin-based supramolecular receptors in a chiral environment through NMR analysis of atropisomeric receptors. By exploiting the hydrogen bond abilities of the exposed porphyrin inner core, we found that N-H signals in a previously underutilized region of the spectrum can detect enantiomeric compositions with three times higher sensitivity than previously reported systems.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Robby Buechner, Vinicius Vaz da Cruz, Nitika Grover, Asterios Charisiadis, Mattis Fondell, Robert Haverkamp, Mathias O. Senge, Alexander Foehlisch
Summary: Free base porphyrins, such as 5,10,15,20-tetrakis(4-carboxylatophenyl)porphyrin, are powerful photosensitizers for singlet oxygen generation and light-harvesting. The atomic level selectivity of dynamic UV pump - N K-edge probe X-ray absorption spectroscopy, combined with TD-DFT theory, provides insight into the excited molecular states within an unusual relaxation pathway. The efficient intersystem crossing is confirmed to be the result of long singlet excited state lifetime and thermal effects.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)