Some literature reports have shown the existence of short Hg(II)···d8[M] (M = Pd, Pt) contacts between linear Hg(II) and square planar d8[M] complexes that have been defined as heterometallophilic interactions. Linear L–Hg(II)–L complexes exhibit a π-hole or positive belt of electrostatic potential at the Hg atom, while late transition metals can serve as effective electron donors through their filled dz2 orbitals. This study provides compelling evidence that Hg(II)···d8[M] interactions should be more appropriately termed Spodium bonds.
Design and Synthesis of Novel 2‐Acetamido, 6‐Carboxamide Substituted Benzothiazoles as Potential BRAFV600E Inhibitors – In vitro Evaluation of their Antiproliferative Activity
The oncogenic BRAFV600E kinase leads to abnormal activation of the MAPK signaling pathway and thus, uncontrolled cellular proliferation and cancer development. Based on our previous virtual screening studies which issued 2-acetamido-1,3 benzothiazole-6-carboxamide scaffold as active pharmacophore displaying selectivity against the mutated BRAF, eleven new substituted benzothiazole derivatives were designed and synthesized by coupling of 2-acetamidobenzo[d]thiazole-6-carboxylic acid with the appropriate amines in an effort to provide even more efficient inhibitors and tackle drug resistance often developed during cancer treatment. All derived compounds bore the benzothiazole scaffold substituted at position-2 by an acetamido moiety and at position-6 by a carboxamide functionality, the NH moiety of which was further linked through an alkylene linker to a sulfonamido (or amino) aryl (or alkyl) functionality or a phenylene linker to a sulfonamido aromatic (or non-aromatic) terminal pharmacophore in the order -C6H4-NHSO2-R or reversevely -C6H4-SO2N(H)-R. These analogs were subsequently biologically evaluated as potential BRAFV600E inhibitors and antiproliferative agents in several colorectal cancer and melanoma cell lines. In all assays applied, one analog, namely 2-acetamido-N-[3-(pyridin-2-ylamino)propyl]benzo[d]thiazole-6-carboxamide (22), provided promising results in view of its use in drug development.
An Unusual Macrocyclic Hexamer of an Iso‐Tellurazole N‐Oxide Featuring CTe…O Chalcogen Bonds is Formed by κ6‐O Complexation to Fe(II) and Ni(II)
Studies of the supramolecular chemistry of iso-tellurazole N-oxides have been confined to non-polar media until now. To overcome that limitation, an iso-tellurazole N-oxide was derivatized with a primary alcohol group; the compound is soluble in polar solvents and stable in acidic to neutral aqueous media. Nickel (II) and iron (II) form macrocyclic complexes with six molecules of that isotellurazole N-oxide in a hitherto not-observed macrocyclic arrangement defined by CTe…O chalcogen bonds and κ6-O bound to the metal ion. This behaviour is in sharp contrast with the κn-Te (n = 1,2,4) complexes formed by soft metal ions.
NHC‐Stabilized Dialanes(4) of Al2Mes4
The synthesis and characterization of novel N-heterocyclic carbene (NHC) stabilized dialanes Al2Mes4 as well as first investigations concerning the reactivity of these compounds are reported. The synthesis of these compounds proceeds via the Mesityl-substituted alanes (NHC)·AlHMes2 (NHC = IMeMe3, IiPrMe4) and iodo-alanes (NHC)·AlIMes2 (NHC = IMeMe5, IiPrMe6). Metallic reduction of 5 and 6 afforded the new NHC-stabilized dialanes (NHC)2·Al2Mes4 (NHC = IMeMe7, IiPrMe8). The NHC-ligated dialanes are thermally robust and storable synthons for the dialane Al2Mes4. First reactivity studies on (IMeMe)2·Al2Mes47 towards small molecules confirm this, as 7 shows controlled and selective reactions with several substrates. Reaction with CuCl leads to oxidation of the dialane and formation of (IMeMe)·AlClMes210, reactions with pyridine N-oxide and tBu-N=C=S, respectively, gave the chalcogenide-bridged dimers ((IMeMe)·AlMes2)2-μ-E (E= O 11, S 12), and reaction with acetylene afforded the dimetallaacetylide ((IMeMe)·AlMes2)2-μ-(C≡C) 13.
Capture‐SELEX of DNA Aptamers for Sulforhodamine B and Fluorescein
While many dye binding aptamers have been reported, most of them were for light-up aptamers that can significantly enhance the quantum yield of fluorophores. Sulforhodamine B (SRhB) was used as a target previously to select both DNA and RNA aptamers, and the DNA aptamer was a G-quadruplex that can bind to a number of rhodamine analogs. In addition, the previous selections were performed by immobilizing the target molecules. In this work, we used the library immobilization method to respectively select aptamers for SRhB and fluorescein. The SRhB aptamer has a non-G-quadruplex structure with a Kd of 1.0 µM measured from isothermal titration calorimetry. Upon titration of the aptamer, the fluorescence of SRhB increased 2.5-fold, and this aptamer does not require Mg2+ for binding. Rhodamine B has even tighter binding suggesting binding through the xanthene moiety of the dyes. No binding was detected for fluorescein. For the fluorescein selection, a dominant aptamer sequence with a Kd of 147 µM was obtained. This study provides two new aptamers for two important fluorophores that can be used to study aptamer-based separation, dye detection and catalysis. Comparison of these aptamers also provide insights into the effect of functional groups on aptamer binding.
Halogen Bonding Tripodal Metallo‐receptors for Phosphate Recognition and Sensing in Aqueous containing Organic Media
The anion recognition and electrochemical anion sensing properties of halogen bonding (XB) tripodal zinc (II)-receptors strategically designed and constructed for tetrahedral anion guest binding are described. The XB tris(iodotriazole)-containing hosts exhibit high affinities and selectivities for inorganic phosphate over other more basic, mono-charged oxoanions such as acetate and the halides in a competitive CH3CN/ D2O 9:1 v/v aqueous solvent mixture. 1H NMR anion binding and electrochemical voltammetric anion sensing studies with redox-active ferrocene functionalised metallo-tripodal receptor analogues, reveal each of the XB tripods as superior anion complexants when compared to their tris(prototriazole)-containing, hydrogen bonding (HB) counterparts, not only exemplifying the halogen bond as a strong alternative interaction to the traditional hydrogen bond for molecular recognition but also providing rare evidence of the ability of XB receptors to preferentially bind the ‘harder’ phosphate oxoanion over the ‘softer’ and less hydrated halides in aqueous containing media.
Direct Synthesis of Organonitrogen Compounds from Dinitrogen Using Transition Metal Complexes: Leap from Stoichiometric Reactions to Catalytic Reactions
Organonitrogen compounds are of vital importance to our lives. For almost all organonitrogen compounds, ammonia is only the feedstock as a nitrogen source. Ammonia is produced from dinitrogen (N2) and dihydrogen (H2) by the Haber-Bosch process, which consumes an enormous amount of energy. As an alternative method to convert N2 into organonitrogen compounds under milder conditions, various stoichiometric reactions with transition metal complexes have been explored for the last 50 years. However, the field of catalytic formation of organonitrogen compounds directly from N2 with transition metal complexes is still in its infancy. This short review summarizes strategies to achieve the direct synthesis of organonitrogen compounds from N2 under mild reaction conditions using transition metal complexes ranging from stoichiometric reactions to catalytic reactions.
From Rags to Riches: Exploiting the Calvin‐Benson‐Bassham Cycle for Biomanufacturing
Industrial chemical production largely relies on fossil fuels, resulting in the unavoidable release of carbon dioxide (CO2) into the atmosphere. The concept of a circular carbon bioeconomy has been proposed to address this issue, wherein CO2 is captured and used as raw material for manufacturing new chemicals. Microbial cell factories and, in particular, autotrophic microorganisms capable of utilizing CO2 as the sole carbon source, emerged as potential catalysts for upcycling CO2 to valuable products. The Calvin-Benson-Bassham cycle (CBBc), the best-known CO2 fixation pathway, is widely distributed in Nature. While extensively studied, microbial engineering programmes based on the CBBc remains relatively underexplored. In this review, we discuss avenues towards biotechnological exploitation of the CBBc to engineer CO2-utilizing microbial cell factories, with a focus on chemically-derived electron donors. We also highlight the advantages and challenges of implementing the CBBc in heterotrophic microbial hosts and its potential to advance a true circular carbon bioeconomy. Moreover, based on the pathway’s architecture, we argue about the ideal value-added products to generate from this metabolic route. Studying and engineering the CBBc in both natural- and synthetic-autotrophs will enhance our understanding on this CO2 fixation pathway, enabling further exploration of biomanufacturing avenues with CO2 as feedstock.
Iron‐catalyzed Hydrosilylation of Secondary Carboxamides Chemoselective Access to Aldimines
This contribution described the chemoselective reduction of secondary carboxamides to aldimines. To perform such challenging transformation, we reported a catalyzed hydrosilylation using Fe(CO)4(IMes) [IMes=1,3-bis (2,4,6-trimethylphenyl) imidazol-2ylidene] as the catalyst, diphenylsilane as the reductant under UV irradiation (365 nm) at room temperature for 16 h. Aldimines were then obtained, after a basic quench, in 40-83% isolated yields. This transformation was unprecedented at iron.
Structural Analyses of DP‐1, a Protein with the Ability to Keep the Gold Nanoparticles, using Nuclear Magnetic Resonance
Gold nanoparticles (AuNPs) consisting of metallic gold are applied in various fields owing to their characteristic physical properties. Collimonas sp. D-25 (D-25) is a Gram-negative bacterium obtained from soil, compost, and other environmental materials in the Akita Prefecture. DP-1 is a water-soluble protein found in D-25 that binds specifically to AuNPs and retains the nano-sized AuNPs with high stability. This study aimed to identify the part of DP-1 interacting with AuNPs and determine its 3D structure in solution using nuclear magnetic resonance (NMR). The peptide fragments obtained by trypsin digestion were examined for their AuNP-binding capacity to determine the key Au-binding domain of DP-1. A fragment consisting of 16 amino acid residues (GHAATPEQYGVVTANK) was identified as the peptide with the highest binding activity. Structural analyses of this peptide indicated that the main chain was elongated, and negatively charged residues in the side chain were exposed on the surface by incorporating AuNPs. These results suggest that DP-1 interacts with AuNPs via negatively charged residues and extended hydrophobic residues for protein-protein interactions. The structural data also provide new insights into biomimetic technologies.