Article
Chemistry, Multidisciplinary
Cristobal Quintana, Juan C. Ahumada, Guillermo Ahumada, Yaroslav Sobolev, Minju Kim, Atabay Allamyradov, Bartosz A. Grzybowski
Summary: The paper describes a method to investigate cooperative mechanisms by varying the probabilities of catalytic units being proximal using a nanoparticle-based platform, independently of their volume concentration. The method, based on geometrical considerations, can distinguish between cooperative and non-cooperative mechanisms.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Angus C. G. Shephard, Safaa H. Ali, Jun Wang, Zhifang Guo, Murray S. Davies, Glen B. Deacon, Peter C. Junk
Summary: A series of rare earth biphenolate complexes were synthesized via redox transmetallation/protolysis method, with the yttrium complex yielding two solvates during crystallization. The rare earth metal is six coordinate with one chelating biphenolate mbmp(2-) ligand and one unidentate monophenolate mbmpH(-) ligand.
DALTON TRANSACTIONS
(2021)
Review
Chemistry, Physical
Wasifa Asim, Azal Shakir Waheeb, Masar Ali Awad, Afaf Murtada Kadhum, Asjad Ali, Shaimaa Hassan Mallah, Muhammad Adnan Iqbal, Mustafa M. Kadhim
Summary: Due to the increasing demand for polymers, selecting an appropriate catalytic system is crucial for achieving desired properties. This review summarizes various strategies for synthesizing organometallic complexes of zirconium involving carbon bonding and their catalytic applications in polymerization reactions from 2011 to 2019.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Multidisciplinary
Tianyu Lan, Na Zhang, Liduo Chen, Cuiqin Li, Jun Wang
Summary: The dendritic salicylaldehyde imide ligand with substituent hindrance and its titanium catalyst were synthesized for ethylene polymerization, showing good catalytic performance. Characterization of the synthesized products was conducted using various techniques. Additionally, the polyethylene samples obtained were identified as ultrahigh-molecular-weight polyethylene through analysis of their microstructure, thermal properties, and viscoelastic state using specialized equipment.
Article
Chemistry, Multidisciplinary
Jingming Zhao, Ying Zhuo, Daniel E. Diaz, Muralidharan Shanmugam, Abbey J. Telfer, Peter J. Lindley, Daniel Kracher, Takahiro Hayashi, Lisa S. Seibt, Florence J. Hardy, Oliver Manners, Tobias M. Hedison, Katherine A. Hollywood, Reynard Spiess, Kathleen M. Cain, Sofia Diaz-Moreno, Nigel S. Scrutton, Morten Tovborg, Paul H. Walton, Derren J. Heyes, Anthony P. Green
Summary: A protective pathway is identified in the active sites of copper-dependent lytic polysaccharide monooxygenases (LPMOs), which prevents oxidative damage during uncoupled turnover. This pathway involves the formation of transient high-valent intermediates and ferromagnetically coupled copper-tyrosyl radical pairs.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Matthieu Regnacq, Denis Lesage, Marte S. M. Holmsen, Karinne Miqueu, Didier Bourissou, Yves Gimbert
Summary: The study demonstrates the remarkable catalytic ability of (P,C)-cyclometalated Au(iii) complexes in the intermolecular hydroarylation of alkynes. The previous evidence of an outer-sphere mechanism is confirmed through the analysis of experimental data and DFT calculations. The evaluation of critical energies of dissociation of Au(iii) complexes with different substrates using energy-resolved mass spectrometry experiments and kinetic modeling supports the collisional model and its application to particularly fragile adducts.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Eva Guillamon, Ivan Sorribes, Vicent S. Safont, Andres G. Algarra, M. Jesus Fernandez-Trujillo, Elena Pedrajas, Rosa Llusar, Manuel G. Basallote
Summary: By using a cuboidal [Mo3S4H3(dmpe)(3)](+) hydride cluster as the catalyst, formic acid (FA) can be transformed into hydrogen gas and CO2 without the need for any additives. Compared to other molybdenum compounds, our catalyst has shown higher activity and selectivity. Kinetic studies, reaction monitoring, and DFT calculations have revealed the mechanism of FA dehydrogenation, which involves the formation of a dihydrogen-bonded species and subsequent release of hydrogen gas and coordination of formate. The complete cycle, including the release of CO2 and closure of the catalytic cycle, occurs at higher temperatures.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Matthieu Regnacq, Denis Lesage, Marte S. M. Holmsen, Karinne Miqueu, Didier Bourissou, Yves Gimbert
Summary: In this study, the mechanism of (P,C)-cyclometalated Au(iii) complexes catalyzing the intermolecular hydroarylation of alkynes is confirmed through experimental data and theoretical calculations, as well as energy-resolved mass spectrometry experiments and kinetic modeling. The results support the previously proposed collisional model and provide insights into the application of this model on fragile adducts.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Vikramjeet Singh, Abhishek Kundu, Kirti Singh, Debashis Adhikari
Summary: Formazan ligands have long been investigated as redox-noninnocent backbones, but their catalytic efficiency governed by redox noninnocence remains elusive. In this study, we report an iron-formazanate molecule that can efficiently prepare alpha-keto amides through a tightly regulated reductive cleavage of the substrate molecule by the electron donation from the formazanate, in a reversible manner.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Wiebke Wackerow, Zeynabou Thiam, Edy Abou-Hamad, Walid Al Maksoud, Mohamed N. Hedhili, Jean-Marie Basset
Summary: The article discusses the unique catalytic properties of tungsten-hydrides supported on oxide supports, suggesting that supported tungsten-hydride complexes coexist on the support as bis-hydride and tris-hydride species.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Metallurgy & Metallurgical Engineering
Hongyang He, Fei Xu, Qiaolei Li, Panfei Dong, Jian Zheng, Chenjie Wu, Zhengyan He, Jun Qu, Zhigao Xu, Ruan Chi, Ming Wu
Summary: In this study, the extraction and separation of Hf from Zr using Cyanex572 as extractant in HNO3 solution was successfully achieved. It was found that HfO2+ can be extracted into the organic phase through two routes, with the dominant mechanism being cation exchange and the subordinate mechanism involving coordination with P=O in Cyanex572. The research demonstrated the potential for developing an effective solvent extraction system to separate Hf from Zr by utilizing Cyanex572.
Article
Chemistry, Physical
Chengming Wu, Ting Wu, Jifan Li, Chun-Ling Liu, Wen-Sheng Dong
Summary: A series of zirconium phosphates (ZrP-x) with various P/Zr ratios were prepared and showed excellent catalytic performance in the synthesis of p-xylene (PX) from 2,5-dimethylfuran (DMF) and ethylene. The catalyst ZrP-2.5 exhibited a high PX yield of 89.2% and a productivity of 72.3 mmol(PX).g(cat)(-1).h(-1) at 250 degrees C with a small amount of catalyst. The excellent catalytic performance was attributed to the synergy between acidic sites, balanced acidity, and abundant mesopores.
APPLIED CATALYSIS A-GENERAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Lyudmila Parfenova, Pavel Kovyazin, Olesia Mukhamadeeva, Pavel Ivchenko, Ilya E. Nifant'ev, Leonard M. Khalilov, Usein M. Dzhemilev
Summary: A series of zirconocenes were studied as catalysts in reactions involving alkenes and AlEt3, showing a dependence on ligand structure and solvent properties. NMR spectroscopy was used to investigate alkyl exchange in triethylaluminum, revealing a solvent effect on exchange parameters. The formation of intermediates and the role of ligand structure and solvent in determining intermediate ratios were also explored.
DALTON TRANSACTIONS
(2021)
Article
Multidisciplinary Sciences
Md. Ataur Rahman, Torsten Cellnik, Brij Bhushan Ahuja, Liang Li, Alan R. Healy
Summary: The aldol reaction is an important carbon-carbon bond-forming transformation in organic chemistry. Researchers have been working to develop direct catalytic variants of the aldol reaction for constructing chiral building blocks. In this study, a decarboxylative aldol reaction was developed that can produce all four possible stereoisomers of the aldol product from identical reactants in one step. The reaction is mild, can be performed on a large scale, and generates carbon dioxide as the only by-product. The method is compatible with a wide range of substrates and produces chiral beta-hydroxy thioester products with practical applications.
Article
Chemistry, Multidisciplinary
Hojae Lee, Joohyouck Park, Nayoung Kim, Wongu Youn, Gyeongwon Yun, Sang Yeong Han, Duc Tai Nguyen, Insung S. Choi
Summary: This research describes a strategy for imparting living cells with extrinsic catalytic capability through nanoencapsulation, allowing cells to acquire new biochemical functions and enhancing their biological functions. This has important implications for catalytic bioempowerment of living cells.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Elizabeth M. Bolitho, James P. C. Coverdale, Hannah E. Bridgewater, Guy J. Clarkson, Paul D. Quinn, Carlos Sanchez-Cano, Peter J. Sadler
Summary: The cellular stability of a metallodrug complex catalyzing the reduction of pyruvate to lactate in cells was investigated, with the ligand being displaced by endogenous thiols and translocated to the nucleus while the metal fragment is exported from the cells. The efficiency of catalysis is low due to this phenomenon, suggesting that it could be optimized by developing thiol resistant analogues. This work also provides a new way for the delivery of ligands which are inactive when administered on their own.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Adetola C. Oladipo, Adedibu C. Tella, Victoria T. Olayemi, Vincent O. Adimula, Tendai O. Dembaremba, Adeniyi S. Ogunlaja, Hadley S. Clayton, Guy J. Clarkson, Richard I. Walton
Summary: A novel Zn(II) mixed-ligand complex was synthesized and characterized, showing good adsorption capacity for EY dye. Results from DFT studies indicated that the adsorption mechanism is mainly attributed to electrostatic, hydrogen bonding, and pi-pi interactions.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2021)
Article
Chemistry, Organic
Vijyesh K. Vyas, Guy J. Clarkson, Martin Wills
Summary: Compounds containing bicyclo[1.1.1]pentane (BCP) adjacent to a chiral center can be prepared with high enantiomeric excess through asymmetric transfer hydrogenation (ATH) of adjacent ketones. The reduction method is applied to the synthesis of a BCP analogue of the antihistamine drug neobenodine.
Article
Chemistry, Physical
Ye Zheng, Jaime A. Martinez-Acosta, Mohammed Khimji, Luiz C. A. Barbosa, Guy J. Clarkson, Martin Wills
Summary: Aromatic ketones with ortho-substituents showed high enantioselectivity under asymmetric transfer hydrogenation conditions, while N-methylimidazole-containing ketones exhibited unexpected enantioselectivity switches upon variation of the opposing aromatic group. Pyrrole-containing ketones were found to be resistant to reduction in this study.
Article
Biochemistry & Molecular Biology
Jaroslav Malina, Hana Kostrhunova, Vojtech Novohradsky, Peter Scott, Viktor Brabec
Summary: The design of efficient and safe gene delivery vehicles remains a major challenge for gene therapy. Metal complexes with high affinity for nucleic acids are emerging as an attractive option for gene delivery systems. Certain metallohelices have been discovered to act as nonviral DNA delivery vectors capable of mediating efficient gene transfection, forming globular DNA particles that protect the DNA from degradation, and successfully being processed by cells.
NUCLEIC ACIDS RESEARCH
(2022)
Article
Chemistry, Organic
Jonathan Barrios-Rivera, Yingjian Xu, Guy J. Clarkson, Martin Wills
Summary: The application of enantiomerically-pure ruthenium(II) catalysts containing N - functionalised TsDPEN ligand to the asymmetric transfer hydrogenation of 15 examples of alpha-heterocyclic acetophenone derivatives is reported, with products of up to 99% ee formed. (C) 2021 Elsevier Ltd. All rights reserved.
Article
Chemistry, Multidisciplinary
Adedibu C. Tella, Adetola C. Oladipo, Victoria T. Olayemi, Allen Gordon, Adeniyi S. Ogunlaja, Lukman O. Alimi, Stephen P. Argent, Robert Mokaya, Guy J. Clarkson, Richard I. Walton
Summary: Two calcium coordination compounds were grown at room temperature and characterized. The structures of the compounds are stabilized by a network of hydrogen bonds. Compound 1 exhibits high excitation energies and chemical hardness, making it a better electron acceptor. Compound 2 is softer with better polarizability and reactivity.
STRUCTURAL CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Satarupa Das, Jinfang Zhang, Thomas W. Chamberlain, Guy J. Clarkson, Richard I. Walton
Summary: CO2 epoxidation to cyclic carbonates under mild, solvent-free conditions is a promising pathway for sustainable CO2 utilization. However, previous metal-organic frameworks (MOFs) used for this purpose are not suitable for commercial utilization due to the nonrenewable ligands used. This study presents new yttrium MOFs based on renewable 2,5-furandicarboxylate (FDC) ligands, which exhibit high catalytic activity and conversion efficiency for CO2 epoxidation reactions.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Guy J. Clarkson, Stefan Roesner
Summary: An efficient methodology for the synthesis of benzofuropyridines and dibenzofurans from fluoropyridines or fluoroarenes and 2-bromophenyl acetates is presented. The streamlined one-pot procedure involves four-step directed ortho-lithiation, zincation, Negishi cross-coupling, and intramolecular nucleophilic aromatic substitution, enabling the easy assembly of a diverse set of fused benzofuro heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhi Du, Chun Liu, Zhenqi Liu, Hualong Song, Peter Scott, Xiubo Du, Jinsong Ren, Xiaogang Qu
Summary: This study reveals that a pair of chiral metallohelices can selectively modulate Aβ aggregation, leading to improved cognitive function in Alzheimer's disease. The metallohelices also serve as functional modules for visualization and modification of Aβ through click reactions, offering new insights into AD therapy.
Article
Chemistry, Multidisciplinary
Zhenqi Liu, Dongqin Yu, Hualong Song, Miles Lewis Postings, Peter Scott, Zhao Wang, Jinsong Ren, Xiaogang Qu
Summary: Targeted protein degradation has made significant progress in modulating protein homeostasis. Lysosome targeting chimeras have been developed for intracellular protein degradation, and metallohelix-based degraders have shown promise in degrading extracellular proteins. This study demonstrates that a chiral metallohelix can successfully deliver extracellular human islet amyloid polypeptide (hIAPP) to lysosomes for degradation, preventing hIAPP aggregation. Furthermore, the metallohelix-based degraders can also facilitate hIAPP clearance through the asialoglycoprotein receptor in liver cells.
Article
Chemistry, Multidisciplinary
Jiangping Liu, Andrew W. Prentice, Guy J. Clarkson, Jack M. Woolley, Vasilios G. Stavros, Martin J. Paterson, Peter J. Sadler
Summary: This study reports a Ru(II) polypyridyl prodrug, RuAzNM, functionalized with azo and nitrogen mustard, which exhibits multimodal theranostic properties towards hypoxic cancer cells. Reduction of the azo group in hypoxic cell microenvironments leads to the generation of reactive oxygen species and mtDNA crosslinking, while the resulting phosphorescent RuNH2 serves as a diagnostic signal and activates phototherapy. This unique strategy allows controlled multimodal theranostics to be realized in hypoxic cells, making RuAzNM a highly selective and effective cancer-cell-selective theranostic agent.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Inorganic & Nuclear
J. P. C. Coverdale, H. Kostrhunova, L. Markova, H. Song, M. Postings, H. E. Bridgewater, V. Brabec, N. J. Rogers, P. Scott
Summary: Self-assembled enantiomers of a di-iron metallohelix showed different antiproliferative activities against HCT116 colon cancer cells, with the ?-helicity compound being more potent than the Delta compound. The accumulation and localization studies suggest that the ? enantiomer undergoes carrier-mediated efflux, while the Delta enantiomer undergoes equilibrative process. The binding of the ? metallohelix to DNA and inhibition of tubulin and actin networks contribute to its G(2)/M arrest effect on cells.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Noha Khamis, Guy J. Clarkson, Martin Wills
Summary: The synthesis of a variety of N-(heterocyclesulfonyl)-functionalized Noyori-Ikariya catalysts was described in this study. These complexes were prepared from C2-symmetric 1,2-diphenylethylene-1,2-diamine (DPEN) and characterized using multiple methods including X-ray crystallography. The complexes exhibited catalytic activity in the asymmetric transfer hydrogenation (ATH) of various acetophenone derivatives, yielding products with high enantioselectivity in most cases, especially for ortho-substituted acetophenones.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Feng Chen, Isolda Romero-Canelon, Abraha Habtemariam, Ji-Inn Song, Samya Banerjee, Guy J. Clarkson, Lijiang Song, Ivan Prokes, Peter J. Sadler
Summary: We synthesized a series of novel substituted sulfonyl ethylenediamine (en) Ru-II arene complexes, which showed antiproliferative activity against cancer cells and exhibited catalytic activity in transfer hydrogenation reactions and reactions with thiols.
DALTON TRANSACTIONS
(2022)