Correction: Selective binding and fluorescence sensing of Zn(II)/Cd(II) using macrocyclic tetra-amines with different fluorophores: insights into the design of selective chemosensors for transition metals.

Correction for 'Selective binding and fluorescence sensing of Zn(II)/Cd(II) using macrocyclic tetra-amines with different fluorophores: insights into the design of selective chemosensors for transition metals' by Giammarco Maria Romano , , 2025, https://doi.org/10.1039/d4dt02415j.

Development of a multi-targeted chemotherapeutic approach based on G-quadruplex stabilisation and carbonic anhydrase inhibition.

A novel class of compounds designed to hit two anti-tumour targets, G-quadruplex structures and human carbonic anhydrases (hCAs) IX and XII is proposed. The induction/stabilisation of G-quadruplex structures by small molecules has emerged as an anticancer strategy, disrupting telomere maintenance and reducing oncogene expression. hCAs IX and XII are well-established anti-tumour targets, upregulated in many hypoxic tumours and contributing to metastasis.

Old Acquaintances and Novel Complex Structures for the Ni(II) and Cu(II) Complexes of -Chelate Oxime-Amide Ligands.

In the process of systematically studying the methylhydroxyiminoethaneamide -chelate ligands with polymethylene spacers of different lengths, L1-L3, and their transition metal complexes, a number of new Ni(II) and Cu(II) species have been isolated, and their molecular and crystal structures were determined using single-crystal X-ray diffraction. In all of these compounds, the divalent metal is coordinated by the ligand donor atoms in a square-planar arrangement. In addition, a serendipitously discovered new type of neutral Ni(II) complex, where the propane spacer of ligand L2 underwent oxidation to the propene spacer, and one of the amide groups was oxidised to the ketoimine, is also reported.

Oxygen reduction reaction (ORR) in alkaline solution catalysed by an atomically precise catalyst based on a Pd(II) complex supported on multi-walled carbon nanotubes (MWCNTs). Electrochemical and structural considerations.

A new atomically precise, single-ion catalyst (MWCNT-LPd) for ORR (oxygen reduction reaction), consisting of a Pd(II) complex of a tetraazacycloalkane anchored on multiwalled carbon nanotubes, has been prepared through a supramolecular approach ensuring a uniform distribution of catalytic centres on the support surface. A tetraazacycloalkane was chosen to saturate the four coordination sites of the typical square planar coordination geometry of Pd(II) with the aim of ascertaining whether the metal ion must have free coordination sites to function effectively in the ORR or whether, as predicted by quantum mechanical calculations, the catalytic effect can be originated from an interaction of O in the fifth coordinative position. The results clearly demonstrated that tetracoordination of Pd(II) does not influence its catalytic capacity in the ORR.

A Norbornadiene-Based Molecular System for the Storage of Solar-Thermal Energy in an Aqueous Solution: Study of the Heat-Release Process Triggered by a Co(II)-Complex.

It is urgent yet challenging to develop new environmentally friendly and cost-effective sources of energy. Molecular solar thermal (MOST) systems for energy capture and storage are a promising option. With this in mind, we have prepared a new water-soluble (pH > 6) norbornadiene derivative (HNBD1) whose MOST properties are reported here.

Crystal engineering of high explosives through lone pair-π interactions: Insights for improving thermal safety.

In this high-risk/high-reward study, we prepared complexes of a high explosive anion (picrate) with potentially explosive -tetrazine-based ligands with the sole purpose of advancing the understanding of one of the weakest supramolecular forces: the lone pair-π interaction. This is a proof-of-concept study showing how lone pair-π contacts can be effectively used in crystal engineering, even of high explosives, and how the supramolecular architecture of the resulting crystalline phases influences their experimental thermokinetic properties. Herein we present XRD structures of 4 novel detonating compounds, all showcasing lone pair-π interactions, their thermal characterization (DSC, TGA), including the correlation of experimental thermokinetic parameters with crystal packing, and explosion properties.

6-Substituted Triazolyl Benzoxaboroles as Selective Carbonic Anhydrase Inhibitors: Design, Synthesis, and X-ray Crystallography.

Benzoxaborole is currently a scaffold of great relevance in medicinal chemistry. In 2016, it was reported to be a new and valuable chemotype for designing carbonic anhydrase (CA) inhibitors. Herein, using an design, we report the synthesis and characterization of substituted 6-(1-1,2,3-triazol-1-yl)benzoxaboroles.

Inorganic anion recognition in aqueous solution by coupling nearby highly hydrophilic and hydrophobic moieties in a macrocyclic receptor.

Receptor L, composed of a tripropylenetetramine chain linking the 2 and 7 positions of an acridine unit methylene bridges, behaves as a pentaprotic base in aqueous solution. The first four protonation steps occur on the tetra-amine chain, while the acridine nitrogen protonates only below pH 4. The penta-protonated receptor assumes a folded conformation, resulting in a cleft delimited by the aliphatic tetramine and acridine moieties, in which anions of appropriate size can be hosted.

Probing the Efficiency of 13-Pyridylalkyl Berberine Derivatives to Human Telomeric G-Quadruplexes Binding: Spectroscopic, Solid State and In Silico Analysis.

The interaction between the series of berberine derivatives - (NAX071, NAX120, NAX075, NAX077 and NAX079) and human telomeric G-quadruplexes (G4), which are able to inhibit the Telomerase enzyme's activity in malignant cells, was investigated. The derivatives bear a pyridine moiety connected by a hydrocarbon linker of varying length ( = 1-5, with number of aliphatic carbon atoms) to the C13 position of the parent berberine. As for the G4s, both bimolecular 5'-TAGGGTTAGGGT-3' (Tel12) and monomolecular 5'-TAGGGTTAGGGTTAGGGTTAGGG-3' (Tel23) DNA oligonucleotides were considered.

Noncovalent Assembly and Catalytic Activity of Hybrid Materials Based on Pd Complexes Adsorbed on Multiwalled Carbon Nanotubes, Graphene, and Graphene Nanoplatelets.

Green catalysts with excellent performance in Cu-free Sonogashira coupling reactions can be prepared by the supramolecular decoration of graphene surfaces with Pd(II) complexes. Here we report the synthesis, characterization, and catalytic properties of new catalysts obtained by the surface decoration of multiwalled carbon nanotubes (MWCNTs), graphene (G), and graphene nanoplatelets (GNPTs) with Pd(II) complexes of tetraaza-macrocyclic ligands bearing one or two anchor functionalities. The decoration of these carbon surfaces takes place under environmentally friendly conditions (water, room temperature, aerobic) in two steps: (i) π-π stacking attachment of the ligand via electron-poor anchor group 6-amino-3,4-dihydro-3-methyl-5-nitroso-4-oxo-pyrimidine and (ii) Pd(II) coordination from PdCl.

Computationally enhanced X-ray diffraction analysis of a gold(III) complex interacting with the human telomeric DNA G-quadruplex. Unravelling non-unique ligand positioning.

The crystal structure of the human telomeric DNA Tel24 G-quadruplex (Tel24 = TAG(TAG)T) in complex with the novel [AuL] species (with L = 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine - TPymT-α) was solved by a novel joint molecular mechanical (MM)/quantum mechanical (QM) innovative approach. The quantum-refinement crystallographic method (crystallographic refinement enhanced with quantum mechanical calculation) was adapted to treat the [AuL]/G-quadruplex structure, where each gold complex in the binding site was found spread over four equally occupied positions. The four positions were first determined by docking restrained to the crystallographically determined metal ions' coordinates.

Novel cyclen-polyiodide complexes: a reappraisal of I-I covalent and secondary bond limits.

Supramolecular stabilization of polyiodides and iodine-dense phases is of high interest: this study explores the possibilities offered in this sense by diprotonated cyclen, affording two novel crystal structures. One of them contains at least one peculiar I⋯I interatomic distance (3.305(1) Å), falling well below the region commonly described by secondary bonding (3.

Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles.

Polyiodide networks are currently of great practical interest for the preparation of new electronic materials. The participation of metals in the formation of these networks is believed to improve their mechanical performance and thermal stability. Here we report the results on the construction of polyiodide networks obtained using Cu(II) complexes of a series of pyridinol-based tetraazacyclophanes as countercations.

Correction to "Pyridine Derivative of the Natural Alkaloid Berberine as Human Telomeric G-DNA Binder: A Solution and Solid-State Study".

[This corrects the article DOI: 10.1021/acsmedchemlett.9b00516.

Stabilisation of Exotic Tribromide (Br) Anions via Supramolecular Interaction with A Tosylated Macrocyclic Pyridinophane. A Serendipitous Case.

Tetraaza-macrocyclic pyridinophane L-Ts, decorated with a -toluenesulfonyl (tosyl; Ts) group, appear to be a useful tool to provide evidence on how the interplay of various supramolecular forces can help stabilise exotic anionic species such as tribromide (Br) anions. Indeed, crystals of (HL-Ts)(Br)(NO) unexpectedly grew from an acidic (HNO) aqueous solution of L-Ts in the presence of Br anions. The crystal structure of this compound was determined by single crystal XRD analysis.

Halogenated isophthalamides and dipicolineamides: the role of the halogen substituents in the anion binding properties.

A novel family of amide-based receptors is herein described. Specifically, the role of the halogen substituents at the aryl moieties in the anion binding properties of a series of halogenated isophthalamides and dipicolineamides (L1-L6) was investigated both in solution and in the solid state in order to evaluate the incidence of all possible different and combined weak host-guest interactions. Only L5 and L6 bearing pentafluorophenyl rings as substituents have some affinities for the set of anions studied.

Pyridine Derivative of the Natural Alkaloid Berberine as Human Telomeric G-DNA Binder: A Solution and Solid-State Study.

Telomerase is an enzyme deputed to the maintenance of eukaryotic chromosomes; however, its overexpression is a recognized hallmark of many cancer forms. A viable route for the inhibition of telomerase in malignant cells is the stabilization of G-quadruplex structures (G) at the 3' overhang of telomeres. Berberine has shown in this regard valuable G binding properties together with a significant anticancer activity and telomerase inhibition effects.

Sensing Zn in Aqueous Solution with a Fluorescent Scorpiand Macrocyclic Ligand Decorated with an Anthracene Bearing Tail.

Synthesis of the new scorpiand ligand L composed of a [9]aneN macrocyclic ring bearing a CHCHNHCH-anthracene tail is reported. L forms both cation (Zn) and anion (phosphate, benzoate) complexes. In addition, the zinc complexes of L bind these anions.

Porous Frameworks Based on Supramolecular Ball Joints: Bringing Flexibility to Ordered 3D Lattices.

XOFs-type materials (X=M, C, S, that is, metal-organic frameworks, covalent organic frameworks and supramolecular organic frameworks, respectively) share a common unifying feature: mutual spatial orientation of constituting components is strictly directional and unchanging by design. Herein, we illustrate an alternate design for porous architectures, as rigid joints constituted by coordinative (MOFs), covalent (COFs), or hydrogen-donor/acceptor (SOFs) bonds, are replaced by supramolecular ball joints, which confer unprecedented flexibility, especially angular, to porous networks. The obtained frameworks remain highly organized but are also permutable: lacking a forced convergence towards an immutable minimum energy structure, these systems remain able to adjust depending on external conditions.

Solution Studies and Crystal Structures of Heteropolynuclear Potassium/Copper Complexes with Phytate and Aromatic Polyamines: Self-Assembly through Coordinative and Supramolecular Interactions.

Phytate (L ) is a relevant natural product. It interacts strongly with biologically relevant cations, due to the high negative charge exhibited in a wide pH range. The synthesis and crystal structures of the mixed-ligand Cu(II) polynuclear complexes K(H tptz) [Cu(H L)(tptz)] ⋅ 3.

Infinite supramolecular pseudo-polyrotaxane with poly[3]catenane axle: assembling nanosized rings from mono- and diatomic I and I tectons.

Mono- and diatomic I and I building blocks, despite their simplicity, can be used to generate complex hierarchical self-assembled architectures. Herein, the construction of a modular supramolecular poly[3]catenane and its conversion into the axle of an infinite supramolecular pseudo-polyrotaxane were achieved in a seamless process from the starting materials. The unique structural features, directionality, and iodine density of the obtained crystals demonstrate the benefits of a supramolecular design for polyiodide networks intended as solid-state conductors.

Solid State and Solution Study on the Formation of Inorganic Anion Complexes with a Series of Tetrazine-Based Ligands.

Four molecules (L1-L4) constituted by an s-tetrazine ring appended with two identical aliphatic chains of increasing length bearing terminal morpholine groups were studied as anion receptors in water. The basicity properties of these molecules were also investigated. Speciation of the anion complexes formed in solution and determination of their stability constants were performed by means of potentiometric (pH-metric) titrations, while further information was obtained by NMR and isothermal titration calorimetry (ITC) measurements.

Tales of the Unexpected: The Case of Zirconium(IV) Complexes with Desferrioxamine.

The Zr complexes with desferrioxamine (HDFO) and its derivatives are the only Zr-based imaging agents for proton emission tomography (PET) that have been used so far in clinical trials. Nevertheless, a complete speciation of the Zr/HDFO system in solution has never been performed and the stability constants of the relevant complexes are still unknown. Here we report, for the first time, the speciation of this system in water, performed by potentiometric titrations, and the determination of the stability constants of all complexes formed in the pH range 2.

Effect of structure levels on surface-enhanced Raman scattering of human telomeric G-quadruplexes in diluted and crowded media.

Human telomeric G-quadruplexes are emerging targets in anticancer drug discovery since they are able to efficiently inhibit telomerase, an enzyme which is greatly involved in telomere instability and immortalization process in malignant cells. G-quadruplex (G4) DNA is highly polymorphic and can adopt different topologies upon addition of electrolytes, additives, and ligands. The study of G-quadruplex forms under various conditions, however, might be quite challenging.