Discovery of an all-donor aromatic [2]catenane.
Ontology highlight
ABSTRACT:
SUBMITTER: Gianga TM
PROVIDER: S-EPMC8162110 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:The template-directed synthesis of a bistable donor-acceptor [2]catenane wherein both translational isomers--one in which a tetrathiafulvalene unit in a mechanically interlocked crown ether occupies the cavity of a cyclobis(paraquat-p-phenylene) ring and the other in which a 1,5-dioxynaphthalene unit in the crown ether resides inside the cavity of the tetracationic cyclophane--exist in equilibrium in solution, has led to the isolation and separation by hand picking of single crystals colored red and green, respectively. These two crystalline co-conformations have been characterized separately at both the molecular and supramolecular levels, and also by dynamic NMR spectroscopy in solution where there is compelling evidence that the mechanically interlocked molecules are present as a complex mixture of translational, configurational, and conformational isomers wherein the isomerization is best described as being a highly dynamic and adaptable phenomenon.
| S-EPMC2922539 | biostudies-literature
Project description:The plausible role of arginine and tyrosine residues at the active side of horseradish peroxidase (HRP) in aromatic donor (guaiacol) oxidation was probed by chemical modification followed by characterization of the modified enzyme. The arginine-specific reagents phenylglyoxal (PGO), 2,3-butanedione and 1,2-cyclohexanedione all inactivated the enzyme, following pseudo-first-order kinetics with second-order rate contents of 24M(-1.)min(-1), 0.8M(-1.)min(-1) and 0.54M(-1.)min(-1) respectively. Modification with tetranitromethane, a tyrosine-specific reagent, also resulted in 50% loss of activity following pseudo-first-order kinetics with a second-order rate constant of 2.0M(-1.)min(-1). The substrate, H2O2, and electron donors such as I- and SCN- offered no protection against inactivation by both types of modifier, whereas the enzyme was completely protected by guaiacol or o-dianisidine, an aromatic electron donor (second substrate) oxidized by the enzyme. These studies indicate the involvement or arginine and tyrosine residues at the aromatic donor site of HRP. The guaiacol-protected phenylglyoxal-modified enzyme showed almost the same binding parameter (Kd) as the native enzyme, and a similar free energy change (deltaG')for the binding of the donor. Stoicheiometric studies with [7-14C]phenylglyoxal showed incorporation of 2 mol of phenylglyoxal per mol of enzyme, indicating modification of one arginine residue for complete activation. The difference absorption spectrum of the tetranitromethane-modified against the native enzyme showed a peak at 428 nm, characteristic of the nitrotyrosyl residue, that was abolished by treatment with sodium dithionite, indicating specific modification of a tyrosine residue. Inactivation stoicheiometry showed that modification of one tyrosine residue per enzyme caused 50% inactivation. Binding studies by optical difference spectroscopy indicated that the arginine-modified enzyme could not bind guaiacol at all, whereas the tyrosine-modified enzyme bound it with reduced affinity (Kd 35mM compared with 10mM for the native enzyme). Both the modified enzymes, however, retained the property of the formation of compound II (one-electron oxidation state higher than native ferriperoxidase) with H2O2, but reduction of compound II to native enzyme by guaiacol did not occur in the PGO-modified enzyme, owing to lack of binding. No non-specific change in protein structure due to modification was evident from circular dichromism studies. We therefore suggest that the active site of HRP for aromatic donor oxidation is composed of an arginine and an adjacent tyrosine residue, of which the former plays an obligatory role in aromatic donor binding whereas the latter residue plays a facilitatory role, presumably by hydrophobic interaction or hydrogen bonding.
| S-EPMC1217153 | biostudies-other
Project description:Molar mixtures (1:1) of electron-rich dialkoxynapthalene (Dan) and electron-deficient 1,4,5,8-napthalenetetracarboxylic diimide (Ndi) derivatives form highly tunable, columnar mesophases with a dark red color due to a charge transfer absorbance derived from alternating face-centered stacking. Certain Dan-Ndi mixtures undergo a dramatic color change from dark red to an almost colorless material upon crystallizing from the mesophase. Macroscopic morphology of the solid is not changed during this process. In order to investigate the origins of this interesting thermochromic behavior, Dan and Ndi side chains were systematically altered and their 1:1 mixtures were studied. We have previously speculated that the presence or absence of steric interactions due to side chain branching on the aromatic units controlled the level of color change associated with crystallization. Results from the present study further refine this conclusion including a key crystal structure that provides a structural rationale for the observed results.
| S-EPMC3274635 | biostudies-literature
Project description:We present that cationic rings can act as donor ligands thanks to suitably delocalized metal-metal bonds. This could grant parent complexes with the peculiar properties of aromatic rings that are crafted with main group elements. We assembled Pd nuclei into equilateral mono-cationic triangles with unhindered faces. Like their main group element counterparts and despite their positive charge, these noble-metal rings form stable bonding interactions with other cations, such as positively charged silver atoms, to deliver the corresponding tetranuclear dicationic complexes. Through a mix of modeling and experimental techniques we propose that this bonding mode is an original coordination-like one rather than a 4-centre-2-electron bond, which have already been observed in three dimensional aromatics. The present results thus pave the way for the use of suitable metal rings as ligands.
| S-EPMC5672843 | biostudies-literature
Project description:Transition metal-mediated templating and self-assembly have shown great potential to construct mechanically interlocked molecules. Herein, we describe the formation of the bimetallic [3]catenane and [4]catenane based on neutral organometallic scaffolds via the orthogonality of platinum-to-oxygen coordination-driven self-assembly and copper(I) template-directed strategy of a [2]pseudorotaxane. The structures of these bimetallic [3]catenane and [4]catenane were characterized by multinuclear NMR {1H and 31P} spectroscopy, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and PM6 semiempirical molecular orbital theoretical calculations. In addition, single-crystal X-ray analyses of the [3]catenane revealed two asymmetric [2]pseudorotaxane units inside the metallacycle. It was discovered that tubular structures were formed through the stacking of individual [3]catenane molecules driven by the strong π-π interactions.
| S-EPMC8710481 | biostudies-literature
Project description:A new type of neutral donor-acceptor [2]-catenane, containing both complementary units in the same ring was synthesized from a dynamic combinatorial library in water. The yield of the water soluble [2]-catenane is enhanced by increasing either building-block concentrations or ionic strength, or by the addition of an electron-rich template. NMR spectroscopy demonstrates that the template is intercalated between the 2 electron-deficient naphthalenediimide units of the catenane.
| S-EPMC2705551 | biostudies-literature
Project description:The chiral dirhodium(ii) tetracarboxylate-catalyzed enantioselective intramolecular Büchner reaction of donor/donor-carbenes was reported and a series of valuable chiral polycyclic products were synthesized. Both aryloxy enynones and diazo compounds were efficient carbene precursors for this reaction. Excellent yields (up to 99%) and outstanding enantioselectivities (up to >99% ee) were achieved under standard conditions. For furyl substituted chiral cyclohepta[b]benzofurans bearing a substituent at the C4 position on cycloheptatrienes, control reactions showed that the chiral Büchner products could slowly racemize either under dark or natural light conditions. A diradical-involved mechanism rather than a zwitterionic intermediate was proposed to explain the racemization. Furthermore, furyl substituted chiral fluorene derivatives were obtained via asymmetric aromatic substitution when biaryl enynones were employed as carbene precursors.
| S-EPMC8848862 | biostudies-literature
Project description:After earlier unsuccessful attempts, this work reports the application of covalent templating for the synthesis of mechanically interlocked molecules (MiMs) bearing no supramolecular recognition sites. Two linear strands were covalently connected in a perpendicular fashion by a central ketal linkage. After subsequent attachment of the first strand to a template via temporary benzylic linkages, the second was linked to the template in a backfolding macrocyclization. The resulting pseudo[1]rotaxane structure was successfully converted to a [2]catenane via a second macrocyclization and cleavage of the ketal and temporary linkages.
| S-EPMC7898614 | biostudies-literature
Project description:Catenated cages represent chemistry's challenging synthetic targets because a three-dimensional assembly is necessary for their formation. Herein, a cyclic bis[2]catenane is constructed through the coordination-driven self-assembly of the interlocked bis-metallacage, by the 90° Pt(II) heteroligation of the endo-functionalized double-bridged tweezer bearing pyridyl moieties and the tetra-carboxylated linker. NMR spectrometry, X-ray crystallography and mass spectrometry confirm the formation of a cyclic bis[2]catenane with "∞"-shaped topology via a 14-component self-assembly. Particularly, reversibly responsive transformation between the bis[2]catenane and the bis-metallacage can be realized by guest exchange, concentration effect and solvent effect. This work represents a novel example of a cyclic cage-based [2]catenane oligomer.
| S-EPMC7264200 | biostudies-literature
Project description:Aromatic amines in nature are typically installed with Glu or Gln as the nitrogen donor. Here we report a pathway that features glycyl-tRNA instead. During the biosynthesis of pyrroloiminoquinone-type natural products such as ammosamides, peptide-aminoacyl tRNA ligases append amino acids to the C-terminus of a ribosomally synthesized peptide. First, [Formula: see text] adds Trp in a Trp-tRNA-dependent reaction and the flavoprotein AmmC1 then carries out three hydroxylations of the indole ring of Trp. After oxidation to the corresponding ortho-hydroxy para-quinone, [Formula: see text] attaches Gly to the indole ring in a Gly-tRNA dependent fashion. Subsequent decarboxylation and hydrolysis results in an amino-substituted indole. Similar transformations are catalysed by orthologous enzymes from Bacillus halodurans. This pathway features three previously unknown biochemical processes using a ribosomally synthesized peptide as scaffold for non-ribosomal peptide extension and chemical modification to generate an amino acid-derived natural product.
| S-EPMC8758506 | biostudies-literature