Article
Chemistry, Multidisciplinary
Meng Wang, Muralidharan Shanmugam, Eric J. L. McInnes, Michael P. Shaver
Summary: Polymeric frustrated radical pairs (poly(FRP)s) were synthesized by in situ photoinduction of FLP moieties, enabling single electron transfer (SET). The radical generation was confirmed by monitoring stable polymeric phosphine radical cations. These new poly(FRP)s exhibited catalytic hydrogenation and radical-mediated photocatalytic perfluoroalkylations, providing new avenues for designing novel functional polymers in catalysis and photoelectrical chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Christoph Wallach, Felix S. Geitner, Antti J. Karttunen, Thomas F. Faessler
Summary: The unique three-dimensional structure of spherical, homoatomic nine-atom germanium clusters allows for various spatial arrangement of functional groups. Recent introduction of ligands with lone pairs and addition of boranyl group to the cluster featuring a Ge-B exo-cluster bond have expanded the possibilities in cluster chemistry. Quantum-chemical calculations have revealed the frustrated Lewis pair character of the boranyl-functionalized cluster.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Zhipeng Lu, Minsoo Ju, Yi Wang, Jonathan M. Meinhardt, Jesus I. Martinez Alvarado, Elisia Villemure, Jack A. Terrett, Song Lin
Summary: This study demonstrates the functionalization of C(sp(3))-H bonds using frustrated radical pairs (FRPs) generated from disilazide donors and an N-oxoammonium acceptor. The FRPs cleave unactivated C-H bonds to provide aminoxylated products, and the reaction selectivity towards tertiary, secondary, or primary C-H bonds can be controlled by tuning the structure of the donor. Mechanistic studies confirm the formation and involvement of radical pairs in the target reaction.
Review
Biochemistry & Molecular Biology
Qiang Wan, Sen Lin, Hua Guo
Summary: This article reviews recent theoretical advances in understanding FLP-based heterogeneous catalysis in various applications, such as metal oxides, functionalized surfaces, and two-dimensional materials. It emphasizes the importance of a better understanding of the catalytic mechanism for the experimental design of novel heterogeneous FLP catalysts.
Article
Chemistry, Multidisciplinary
Chamila Manankandayalage, Daniel K. Unruh, Clemens Krempner
Summary: The intramolecular inverse frustrated Lewis pairs (FLPs) with weakly Lewis acidic boryl and strongly basic guanidino moieties were synthesized and characterized, demonstrating their capability to activate small molecules. These novel FLPs show promising potential in diverse chemical transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Multidisciplinary
Minsoo Ju, Zhipeng Lu, Luiz F. T. Novaes, Jesus I. Martinez Alvarado, Song Lin
Summary: Frustrated radical pairs (FRPs) are able to coexist in solution due to steric repulsion or weak bonding association between two distinct radicals, which would otherwise annihilate each other. They are typically formed via spontaneous single-electron transfer between two sterically encumbered precursors and exhibit orthogonal chemical properties. FRPs have been found to be capable of homolytically activating various chemical bonds and are being extensively explored in synthetic organic chemistry, including C-H bond functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Ayan Dasgupta, Emma Richards, Rebecca L. Melen
Summary: Progress in frustrated Lewis pair (FLP) chemistry has highlighted the significance of main group elements in catalysis, introducing novel approaches to synthetic chemistry. Recent studies have uncovered new reactivities of frustrated Lewis pairs involving single-electron transfer processes, leading to the formation of reactive frustrated radical pairs (FRP). Electron Paramagnetic Resonance (EPR) spectroscopy has been employed to explain the nature and stability of the observed radical species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Zhen Wan, Chengjun Wang, Chun Yang, Dongge Ma, Hongwei Ji, Chuncheng Chen, Wanhong Ma, Jincai Zhao
Summary: In this study, an unusual inverse H-transfer order is reported, where photoinduced solid In2O3-FLPs catalyze the hydrogenated dehalogenation of aryl halides. The results show that this method effectively activates the aryl halides and performs the dehalogenation reaction with high yields. By studying the H/D kinetic isotope effects and activation energies of hydrogenated dehalogenation, it is demonstrated that the initial hydride transfer mediated by photoinduced solid FLPs is more effective than common proton transfer.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Multidisciplinary
Dipendu Mandal, Ting Chen, Zheng-Wang Qu, Stefan Grimme, Douglas W. Stephan
Summary: This study investigates the properties of the products formed by the reaction between PAr3/B(C6F5)(3) and DEAD. It is found that the steric demands and electronic structures play a crucial role in determining the nature of the products.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Physical
Glory A. Russell-Parks, Thomas Gennett, Brian G. Trewyn
Summary: The rise in energy demands and environmental issues related to fossil fuels have led to a surge of interest in hydrogen as a green alternative. Hydrogen's high energy density and potential as an energy and economic power-house make it an attractive option. Significant research has been focused on material-based hydrogen storage, particularly liquid organic hydrogen carriers (LOHC) for reversible hydrogen transportation. Frustrated Lewis pair (FLP) catalysis shows promise in addressing challenges associated with LOHC technology. This review assesses recent literature on the utilization of intermolecular FLP main group catalysts for improved hydrogenation/dehydrogenation processes, highlighting potential hydrogen storage applications and knowledge gaps that require further investigations.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Engineering, Environmental
Fengfeng Wang, Qijia Ding, Jinrui Ding, Yajie Bai, Hongye Bai, Weiqiang Fan
Summary: This study introduces a ZnIn2S4/BiVO4 heterostructure with zinc vacancies for efficient chemisorption and catalytic kinetics of nitrate reduction. The formation of frustrated Lewis pairs plays a critical role in enhancing the selectivity and yield rate. These findings expand the prospect of using frustrated Lewis pairs as active sites in photoelectrochemical nitrate reduction reactions.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Physical
Ranita Pal, Manas Ghara, Pratim Kumar Chattaraj
Summary: This article provides a review of the chemistry of frustrated Lewis pair (FLP) in the activation of small molecules, hydrogenation of CO2, and unsaturated organic species. Experimental works and electronic structure theory calculations are used to gain mechanistic insights into the reactivity of FLPs. The findings can guide the design of more efficient FLP catalysts for hydrogen activation.
Article
Chemistry, Physical
Xiaoyu Liang, Xinkui Wang, Xinxin Zhang, Sisi Lin, Min Ji, Min Wang
Summary: In this study, a ZnIn2S4/In(OH)3-x (ZIOS) heterojunction was developed for visible-light-driven CO2 reduction. The ZIOS composites, fabricated via partial sulfurization of Zn-In-O oxide, exhibit a CO formation rate of 1945.5 mu mol center dot g-1 center dot h-1, which is about 2.76-fold higher than that over ZnIn2S4, and suppress hydrogen evolution, with the CO/H2 ratio increasing from 0.436 for ZnIn2S4 to 1.6 for ZIOS. This work provides insight into the design of efficient CO2 reduction photocatalysts.
Article
Chemistry, Organic
C. Li, A-D Manick, J-P Dutasta, X. Bugaut, B. Chatelet, A. Martinez
Summary: This study investigates the effects of the size and shape of molecular cavities on the frustrated behavior of Lewis/Bronsted acid-base pairs and on catalytic activities using different endohedrally functionalized cages. The results show that the shape of the inner space strongly influences these properties. A small change in the cage size can significantly affect the frustrated properties of the related systems, highlighting the importance of finding the right balance between frustrated behavior and cage flexibility for optimal catalytic applications.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Yi-Chen Chan, Yuna Bai, Wen-Ching Chen, Hsing-Yin Chen, Chen-Yu Li, Ying-Yann Wu, Mei-Chun Tseng, Glenn P. A. Yap, Lili Zhao, Hsuan-Ying Chen, Tiow-Gan Ong
Summary: By utilizing benzyl alcohol as a co-modulator, carbodicarbene is transformed into a Frustrated Lewis Pair-like reactivity, showing enhanced catalytic activity in various chemical reactions. This unique catalytic reactivity differs significantly from conventional NHC carbenes, demonstrating a new approach in diversifying FLP reactivity with the use of co-modulators.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemical Research Methods
Nane Griem-Krey, Bente Frolund, Ales Marek, Petrine Wellendorph
Summary: GHB is both an endogenously present small molecule and a clinically prescribed drug for narcolepsy. Its mechanism of action, targeting GABA(B) receptors and high-affinity binding sites, remains to be fully understood. The use of radioligands like [H-3]HOCPCA for selectively probing GHB high-affinity binding sites shows promise in drug discovery and future investigations.
JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS
(2021)
Review
Biochemical Research Methods
Veronika Prazienkova, Ales Marek, Lenka Maletinska
Summary: CART peptides are involved in food intake regulation, stress, and other physiological functions, but their receptor(s) have not been fully characterized. Previous studies have shown that CART(61-102) and its di-iodinated analogs can bind to PC12 cells and maintain biological activity.
JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS
(2021)
Article
Chemistry, Physical
Shu R. Huang, Gabriela Novakova, Ales Marek, Frantisek Turecek
Summary: The study reports the targeted synthesis of gas-phase 9-methylene(1H)adenine cation radical and its unique collision-induced dissociation and UV-vis photodissociation action spectra. Computational analysis was performed to identify the global energy minimum of the cation radical and to explain the dissociation mechanisms. Additionally, a computational study of noncanonical isomers of 2'-deoxyadenosine cation radical was conducted to investigate their stability and ion-electron recombination energies.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Biochemical Research Methods
Yue Liu, Congcong Ma, Calvin J. A. Leonen, Champak Chatterjee, Gabriela Novakova, Ales Marek, Frantisek Turecek
Summary: The study of gas-phase riboguanosine radicals with a fixed charge provides insights into the mechanism of radical generation, which is crucial for exploring reactions and processes related to nucleic acids.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2021)
Article
Biochemical Research Methods
Seiya Asai, Lenka Zakova, Irena Selicharova, Ales Marek, Jiri Jiracek
Summary: The study utilized an IR binding assay to determine insulin levels, showing comparable results to RIA kits. Arginine stimulated glucose-induced insulin secretion in MIN6 cells, while dopamine had inhibitory effects. The effects of serotonin varied with concentration levels. The IR binding assay allows for higher throughput and broader range of measurements compared to RIA kits.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2021)
Article
Chemistry, Medicinal
Marketa Pimkova Polidarova, Petra Brehova, Martin Maxmilian Kaiser, Miroslav Smola, Martin Dracinsky, Joshua Smith, Ales Marek, Milan Dejmek, Michal Sala, Ondrej Gutten, Lubomir Rulisek, Barbora Novotna, Andrea Brazdova, Zlatko Janeba, Radim Nencka, Evzen Boura, Ondrej Pav, Gabriel Birkus
Summary: In this study, the activity of 3',3'-c-di(2'F,2'dAMP) and its analogues against different STING allelic forms was evaluated. The synthesis of acyloxymethyl and isopropyloxycarbonyl phosphoester prodrugs of CDNs was described, and masking the negative charges of CDNs resulted in significantly improved activity of the prodrugs. Rapid uptake and intracellular cleavage of pivaloyloxymethyl prodrugs to the parent CDN were also observed, with peak intracellular concentration reached within 2 hours.
JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Physical
Yue Liu, Congcong Ma, Gabriela Novakova, Ales Marek, Frantisek Turecek
Summary: Cytidine ribonucleosides were studied in the gas phase with fixed-charge tags to probe the behavior of isolated nucleobase chromophores in different forms. The formation of protonated tautomers and hydrogen-adduct radical forms were observed, with the protonated forms favored under different conditions. Collision-induced dissociations of cytidine radicals were characterized by calculations of transition state structures and energies, revealing them to be more stable than previously reported adenosine and guanosine radicals.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Biochemistry & Molecular Biology
Matej Milacek, Lenka Bittova, Sarka Tumova, Ondrej Luksan, Robert Hanus, Pavlina Kyjakova, Ales Machara, Ales Marek, Marek Jindra
Summary: Juvenile hormone controls insect reproduction and development through a receptor complex consisting of Met and Tai proteins, affecting vitellogenesis in cockroaches and caste polyphenism in termites. Studies show high-affinity binding of JH III by Met proteins in cockroaches and termites, with evidence of JH receptor agonist binding in hemimetabolous species.
INSECT BIOCHEMISTRY AND MOLECULAR BIOLOGY
(2021)
Article
Biochemical Research Methods
Tian Yongsong, Bretislav Broz, Frantisek Turecek, Ales Marek
Summary: This study presents a time- and cost-efficient method for tritium late-stage labeling of compounds with a tertiary trifluoroethylsulfonamide moiety. By utilizing hydrogen-isotope exchange reactions in tertiary benzenesulfonamides and iridium catalysts, a high specific activity of the radioligand was achieved. Alternative heterogeneous catalyst conditions provided significant enrichment, but failed when repeating with tritium gas.
JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS
(2022)
Article
Biochemistry & Molecular Biology
Zuzana Honetschlagerova, Lucie Hejnova, Jiri Novotny, Ales Marek, Ludek Cervenka
Summary: The study aimed to evaluate the effects of renal denervation on heart failure, specifically looking at renal vascular responsiveness to angiotensin II and the characterization of angiotensin II receptors in the kidney. The findings suggest that maintained renal AT(1) receptor binding combined with elevated ANG II levels influence renal hemodynamics and lead to renal dysfunction. Renal denervation did not attenuate the decrease in renal blood flow or enhance renal vascular responsiveness to angiotensin II, indicating that the beneficial effects of renal denervation on heart failure mortality may not be primarily mediated by renal mechanisms.
Article
Biochemical Research Methods
Michal Kriegelstein, Ales Marek
Summary: [H-3]NAAG, a widely used substrate in research, has been successfully synthesized with high purity and activity. Due to its unavailability in the market, a reliable synthetic procedure has been developed.
JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS
(2022)
Article
Biochemical Research Methods
Bretislav Broz, Frantisek Turecek, Ales Marek
Summary: Fast and reasonable low-scale (200 nmol) syringe-made synthesis of N-15-labeled oligonucleotides representing DNA trinucleotide codons was achieved using solid-phase controlled pore glass synthesis column technique via the phosphoramidite method. The labeled oligonucleotides have acceptable yields and purity for direct applications in mass spectrometry.
JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS
(2022)
Article
Biochemical Research Methods
Jiahao Wan, Bretislav Broz, Yue Liu, Ales Marek, Shu R. Huang, Frantisek Turecek
Summary: The dissociation of DNA trinucleotide codons in gas-phase ions was investigated by mass spectrometry. The study reveals different patterns of nucleobase loss depending on the nucleobase, as well as the involvement of proton migration and neighboring group participation.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Biochemical Research Methods
Jiahao Wan, Bretislav Broz, Yue Liu, Shu R. Huang, Ales Marek, Frantisek Turecek
Summary: Sixty DNA trinucleotide cation radicals were generated by electron transfer and studied using mass spectrometry and theoretical calculations. The dissociations involved loss of nucleobase molecules, backbone cleavage, and cross-ring fragmentations. Specific features included the formation of d2+ ions, hydrogen atom migrations, and cross-ring cleavages, which depended on the nucleobase type and position.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Biochemistry & Molecular Biology
Anna Kertisova, Lenka Zakova, Katerina Machackova, Ales Marek, Pavel Sacha, Petr Pompach, Jiri Jiracek, Irena Selicharova
Summary: This study investigates the transition between inactive and active states of insulin receptor (IR) and insulin-like growth factor 1 receptor (IGF-1R) through mutation of key residues. The results show that these mutations significantly affect the binding and activation abilities of the receptors, providing further insights into the relationship between the structure and function of these receptors.
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
