Article
Biochemistry & Molecular Biology
Anurag Noonikara-Poyil, Alvaro Munoz-Castro, H. V. Rasika Dias
Summary: This study describes the isolation and full characterization of a thermally stable, copper(I) acetylene complex using a highly fluorinated bis(pyrazolyl)borate ligand support, as well as the details of a related copper(I) complex. Raman data show significant red-shifts in C equivalent to C stretch of different alkynes bound to copper(I), with computational analysis indicating that the interaction is primarily of the electrostatic character. The study also highlights the catalytic activity of a mononuclear copper complex in [3 + 2] cycloadditions and compares its effectiveness with a trinuclear copper catalyst.
Article
Chemistry, Physical
Dilip K. Pandey, Eugene Khaskin, Shrinwantu Pal, Robert R. Fayzullin, Julia R. Khusnutdinova
Summary: We describe an efficient semihydrogenation of terminal alkynes using a modified tetramethylated PNP pincer Fe hydride complex. The modified complex shows different reactivity compared to a classical PNP Fe hydride complex with CH2 arms, which predominantly catalyzes terminal alkyne dimerization even in the presence of H-2. The modified PNP ligand allows for selective alkene formation, eliminating dimerization side products and minimizing overreduction.
Article
Chemistry, Multidisciplinary
Maria Galiana-Cameo, Raul Romeo, Asier Urriolabeitia, Vincenzo Passarelli, Jesus J. Perez-Torrente, Victor Polo, Ricardo Castarlenas
Summary: The dinuclear complex [Rh(eta-C1)(eta(2)-coe)(IPr)](2) serves as an efficient catalyst for the O-selective Markovnikov-type addition of 2-pyridones to terminal alkynes. DFT calculations suggest a hydride-free pathway involving intramolecular oxidative protonation of a pi-alkyne by a kappa N-1-hydroxypyridine ligand. The release of the alkenyl ether is considered the rate-determining step in the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Eliezer Ortiz, Madeline M. Evarts, Zachary H. Strong, Jonathan Z. Shezaf, Michael J. Krische
Summary: The first metal-catalyzed oxidative alkynylations of primary alcohols or aldehydes to form alpha,beta-acetylenic ketones (ynones) are reported. Deuterium labelling studies support a novel reaction mechanism in which alkyne hydroruthenation induces the formation of a transient vinylruthenium complex, which then deprotonates the terminal alkyne to produce an active alkynylruthenium nucleophile.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Mayur I. Morja, Prakashsingh M. Chauhan, Kishor H. Chikhalia
Summary: This study introduces a novel strategy for Iron(II)-catalyzed alkynylation of thiohydantoins with terminal alkyne, showcasing its tolerance to various functional group transformations. The optimized method provides a unified approach to access alkynylated thiohydantoins in moderate to higher yields via C(sp(3))-C(sp) bond formation.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Applied
Jiajie Li, Xin Xu, Zhenli Luo, Zhen Yao, Ji Yang, Xin Zhang, Lijin Xu, Peng Wang, Qian Shi
Summary: Cp*Rh(III)-catalyzed regioselective C-H annulation and alkenylation of 2-pyridones with terminal alkynes has been developed, providing efficient access to diversified compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Nanoscience & Nanotechnology
Minkang Li, Lina Zhang, Zhongzheng Zhang, Jialin Shi, Yuefeng Liu, Jiansong Chen, Nannan Sun, Wei Wei
Summary: The study successfully prepared xAg@SiO2 catalysts with excellent activity, stability, and productivity using a reversed microemulsion method, which were applied in carboxylation reactions under CO2. The prepared catalysts showed extraordinary performance and wide substrate scope, enriching the toolbox for enhancing metal catalyst performance through specially fabricated structures.
ACS APPLIED NANO MATERIALS
(2021)
Article
Chemistry, Multidisciplinary
Fan Yang, Juan-Juan Xue, Guang-Ping Lei, Wen-Yan Zhang, Guo-Ping Yang, Yao-Yu Wang
Summary: Using the dual-ligand strategy, a microporous Zn-based MOF 1 with nitro and amino groups was successfully synthesized. The activated interconnected pores of 1 showed high C2H2 uptake capacity and selective adsorption behavior for C2H2 over CO2, as confirmed by experiments and simulations. This study presents a novel approach to design and synthesize MOFs with desired structures and properties by optimizing their pore environment.
CHEMICAL COMMUNICATIONS
(2023)
Article
Biochemistry & Molecular Biology
Carlo Diaferia, Elisabetta Rosa, Enrico Gallo, Giovanni Smaldone, Mariano Stornaiuolo, Giancarlo Morelli, Antonella Accardo
Summary: Peptide-based hydrogels, specifically the Fmoc derivatives of series K, are capable of self-assembly and gelation in aqueous solutions, with Fmoc-K3 hydrogel showing potential for tissue engineering applications by supporting cell adhesion, survival, and duplication. The gelification process is dependent on the balance of aggregation forces within the peptide sequences, such as van der Waals, hydrogen bonding, and pi-pi stacking.
Review
Chemistry, Organic
Arti Ramani, Bhargav Desai, Monak Patel, Togati Naveen
Summary: This review presents the recent advances in the functionalization of alkynes, including substrate scope, limitations, regioselectivity control, and applications. Alkyne functionalization reactions are important for the synthesis of organic intermediates and natural products, and have significant research and application value.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Rong-Hua Wang, Jiang-Fei Li, Yue Li, Shao-Long Qi, Tao Zhang, Yu-Xin Luan, Mengchun Ye
Summary: A selective C(sp(3))-H cleavage of N-formyl enamides without modifying the backbone to synthesize 2-pyridones in good yields was reported in this study. The use of a bifunctional phosphine oxide ligand-bridging Ni-Al bimetallic catalyst played a key role in the reaction.
Article
Chemistry, Applied
Shanhong Wan, Zhenli Luo, Xin Xu, Haiyang Yu, Jiajie Li, Yixiao Pan, Xin Zhang, Lijin Xu, Rui Cao
Summary: A Mn(I)-catalyzed chelation-assisted direct C6-H alkenylation of 2-pyridones with both terminal and internal alkynes has been developed, leading to high yields of the products. Mechanistic studies indicate the involvement of a five-membered organomanganese as the key intermediate.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Hongyu Guo, Sheng Zhang, Xiaoqiang Yu, Xiujuan Feng, Yoshinori Yamamoto, Ming Bao
Summary: Palladium and acid cooperative catalysis was proposed as a strategy for the [3 + 2] cycloaddition of acceptor/donor-type diazo compounds with terminal alkynes, resulting in high yields of 2,3,5-trisubstituted furans. This method provides an efficient pathway to prepare furan-containing organosilane and organoboron reagents, while preserving important functional groups during the cycloaddition reaction.
Article
Multidisciplinary Sciences
Siyao Wang, Qingqing Zhou, Xiaoping Chen, Rong-Hua Luo, Yunxue Li, Xinliang Liu, Liu-Meng Yang, Yong-Tang Zheng, Ping Wang
Summary: The study presents a convenient strategy for protein modification via a biomimetic quinone-mediated oxidation at the N-terminus, highlighting an efficient and complementary approach to existing strategies for N-terminal modification of proteins. The selective and fast method for N-terminal modification of proteins based on quinone-mediated oxidation of the alpha-amine to aldehyde or ketone is applied to diverse proteins.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Sourav Kumar, Jaswant Kumar, Tahira Naqvi, Shabnam Raheem, Masood Ahmad Rizvi, Bhahwal Ali Shah
Summary: A photoredox mediated approach for the synthesis of (E)beta-iodovinyl sulfones at room temperature using simple alkynes and thiols as coupling partners is reported. The method involves the direct conversion of thiols into sulfones by introducing C-I and C-S bonds with the use of SeO2 as an oxidizing agent. It is applicable to a wide range of alkynes and thiols, offers mild conditions and high yields. Furthermore, beta-iodovinyl sulfones can be used as starting materials to access various beta-functionalized sulfone derivatives.
Article
Chemistry, Multidisciplinary
Anna Lisa Semrau, Philip M. Stanley, Dominik Huber, Michael Schuster, Bauke Albada, Han Zuilhof, Mirza Cokoja, Roland A. Fischer
Summary: The study presents the development of surface-anchored nanometer-sized metal-organic framework based microfluidic devices for vectorial catalysis applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Anna Lisa Semrau, Philip M. Stanley, Dominik Huber, Michael Schuster, Bauke Albada, Han Zuilhof, Mirza Cokoja, Roland A. Fischer
Summary: Vectorial catalysis, controlling multi-step reactions in a programmed sequence with defined spatial localization, is a challenging goal in bio-inspired catalysis research. This study demonstrates the integration of two different surface-anchored nanometer-sized metal-organic frameworks in a microfluidic device for modeling vectorial catalysis, achieving full conversion and high turnover frequencies in a two-step cascade reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Biochemistry & Molecular Biology
Jordi F. Keijzer, Bauke Albada
Summary: This review discusses the use of DNA in protein modification to achieve concentration of reactants, selectivity, and enhancement of reactions.
Article
Chemistry, Multidisciplinary
Dianna Truong, Nelson Y. S. Lam, Meder Kamalov, Mie Riisom, Stephen M. F. Jamieson, Paul W. R. Harris, Margaret A. Brimble, Nils Metzler-Nolte, Christian G. Hartinger
Summary: The study presents a novel approach for selectively anchoring transition metal half-sandwich complexes onto peptides with high purity using solid support synthesis. The metalated peptides were evaluated for their anticancer properties against human cancer cell lines, showing no cytotoxic activity but potential for site-selective peptide labelling and ligand design in transition metal catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Marion Graf, Hans-Christian Boettcher, Nils Metzler-Nolte, Sugina Thavalingam, Peter Mayer
Summary: This study describes the synthesis and characterization of eight new bis-cyclometalated compounds. The cytotoxic properties of these compounds were evaluated against prominent cancer cell lines, and it was found that the compounds with 5-chloro-substituted phenanthroline ligands showed the highest cytotoxicity.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2022)
Article
Chemistry, Multidisciplinary
Daniel Obitz, Karmel S. Gkika, Marvin Heller, Tia E. Keyes, Nils Metzler-Nolte
Summary: A lanthanide(iii) complex connected to a light harvesting antenna was synthesized and tested as a potential photosensitizer in photodynamic therapy. The complex showed significant phototoxic activity on cancer cells upon irradiation, with ROS production identified as the compound's phototoxic mode of action. In cell viability assays, a 10-fold decrease in IC50 value was observed compared to the dark control.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
James W. Southwell, Reyme Herman, Daniel J. Raines, Justin E. Clarke, Isabelle Boeswald, Thorsten Dreher, Sophie M. Gutenthaler, Nicole Schubert, Jana Seefeldt, Nils Metzler-Nolte, Gavin H. Thomas, Keith S. Wilson, Anne-Kathrin Duhme-Klair
Summary: This study investigates the use of siderophore-linked ruthenium catalysts for the activation of antibacterial prodrugs within cells. It demonstrates that moxifloxacin-based prodrugs can be activated under anaerobic, biologically relevant conditions with the help of these catalysts. Conjugates containing siderophore units based on catechol and azotochelin are found to be the most promising for intracellular prodrug activation.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Marion Graf, Jasmine Ochs, Nils Metzler-Nolte, Peter Mayer, Hans-Christian Bottcher
Summary: This paper describes the synthesis and characterization of six new organometallic half-sandwich iridium(III) compounds with modified bipyridine ligands. The cytotoxic properties of the compounds against two cancer cell lines were evaluated, and compound 3 showed the most remarkable biological activity with significantly enhanced toxicity compared to cisplatin.
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2023)
Article
Biochemical Research Methods
Boudewijn Hollebrands, Jos A. Hageman, Jasper W. van de Sande, Bauke Albada, Hans-Gerd Janssen
Summary: Peptides play a significant role in determining the taste of food products, with their taste impressions depending on the amino acids present and their sequence. Identifying short peptides in foods is challenging, but a method was developed to accurately predict retention times of short peptides using reversed phase separation. By training a model using a combination of peptide descriptors and a newly derived set of amino acid index derived sequence-specific peptide descriptors, the model achieved a high accuracy in predicting retention times and elution order for 93% of the short peptides.
ANALYTICAL AND BIOANALYTICAL CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Bauke Albada
Summary: Bioconjugation of chemical entities to biologically active proteins has provided valuable insights into cellular processes and yielded innovative therapeutic agents. However, a current challenge lies in efficiently generating uniform conjugates of native proteins in their natural environment. By combining various features of protein-modifying enzymes, artificial constructs have been developed. This review evaluates the current status of this approach, with a focus on the protein-binding anchor, modification chemistry, linker, and suggests the incorporation of trigger-responsive switches for regulating protein modification.
Article
Chemistry, Multidisciplinary
Johannes A. M. Damen, Jorge Escorihuela, Han Zuilhof, Floris L. van Delft, Bauke Albada
Summary: The rates of reaction between strained cycloalkynes and cycloalkenes with 1,2-quinone were studied using stopped flow UV-Vis spectroscopy and computational analysis. The results showed that strained alkyne BCN OH 3 reacted over 150 times faster than strained alkene TCO-OH 5, and the introduction of a carbamate derivative reduced the rate constant by almost half. Additionally, the 8-membered strained alkyne BCN OH 3 reacted 16 times faster than the more strained 7-membered THS 2. Thermodynamic activation parameters were determined using the linearized Eyring equation, providing valuable insights into these rapid click reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Jasper W. van de Sande, Bauke Albada
Summary: The researchers reported the total synthesis of post-translationally modified peptides, including beta-1,2-linked L-arabinosylated Fmoc-protected hydroxyproline building blocks and sulfated tyrosine and hydroxyproline, which are important regulating molecules for living organisms. Clean glycopeptides were obtained by removing acetyl groups from the L-arabinose and neopentyl-protected sulfated tyrosine before deprotection.
Review
Biochemistry & Molecular Biology
Jaccoline Zegers, Maartje Peters, Bauke Albada
Summary: This article summarizes the importance of stabilizing guanine quadruplexes (G4s) for cancer treatment and explores the methods and techniques for stabilizing G4s using metal complexes. By analyzing the G4-stabilizing capacity and bioactivity data of 74 metal-based ligands, guidelines for future studies in this field are proposed.
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Karolina Kaminska, Andrzej Mular, Evgenia Olshvang, Nils Metzler Nolte, Henryk Kozlowski, Elzbieta Wojaczynska, Elzbieta Gumienna-Kontecka
Summary: Siderophores are specific iron chelators produced and secreted by organisms under iron deficiency conditions. These molecules have high affinity and specificity for Fe3+ and other metal ions, and have potential applications in antibiotics delivery. Total synthesis of siderophores is necessary due to their low natural concentrations.
Correction
Chemistry, Multidisciplinary
Christine N. Morrison, Kathleen E. Prosser, Ryjul W. Stokes, Anna Cordes, Nils Metzler-Nolte, Seth M. Cohen
Summary: The study introduces a novel approach using metallofragments as 3D scaffolds for fragment-based drug discovery. This method has great potential in the field of medicinal chemistry and provides a new direction for drug development.
