Energy exchange between Nd and Er centers within molecular complexes.

Developing controlled and reproducible molecular assemblies incorporating lanthanide centers is a crucial step for driving forward up- and down-conversion processes. This challenge calls for the development of strategies to facilitate the efficient segregation of different Ln metal ions into distinct positions within the molecule. The unique family of pure [LnLn'Ln] heterometallic coordination compounds previously developed by us represents an ideal platform for studying the desired Ln-to-Ln' energy transfer (ET).

Guest selectivity of [Ni] supramolecular helicates.

Two new paramagnetic supramolecular helicates with the formula (X@[NiL]) (X = Cl, or Br; L = a bis-pyrazolylpyridine ligand) have been prepared and are described. Helicates of this metal are very rare with virtually no prior examples of them acting as hosts of anionic species. The persistence of the new assemblies in solution has been demonstrated unambiguously by mass spectrometry and paramagnetic H NMR.

Engineered π⋯π interactions favour supramolecular dimers X@[FeL] (X = Cl, Br, I): solid state and solution structure.

Ditopic bis-pyrazolylpyridine ligands usually react with divalent metal ions (M) to produce dinuclear triple-stranded helicates [ML] or, π⋯π interactions, dimers of monoatomic complexes ([ML]). The introduction of an additional benzene ring at each end of ligand L increases the number of aromatic contacts within the supramolecular aggregate by 40%, driving the self-recognition process in an irreversible manner. Consequently, the mixing of new bis-pyrazolylquinoline L2 with FeX salts leads to crystallization of the tripartite high-spin assemblies (X@[Fe(L2)]) (X = Cl, Br or I).

Cooperativity and oscillations: Regulatory mechanisms of K-Ras nanoclusters.

K-Ras nanoclusters (NCs) concentrate all required molecules belonging to the extracellular signal-regulated kinase (ERK) mitogen-activated protein kinase (MAPK) pathway in a small area where signaling events take place, increasing efficiency and specificity of signaling. Such nanostructures are characterized by controlled sizes and lifetimes distributions, but there is a poor understanding of the mechanisms involved in their dynamics of growth/decay. Here, a minimum computational model is presented to analyze the behavior of K-Ras NCs as cooperative dynamic structures that self-regulate their growth and decay according to their size.

Emergence of magnetic nanoparticles in photothermal and ferroptotic therapies.

With their distinctive physicochemical features, nanoparticles have gained recognition as effective multifunctional tools for biomedical applications, with designs and compositions tailored for specific uses. Notably, magnetic nanoparticles stand out as first-in-class examples of multiple modalities provided by the iron-based composition. They have long been exploited as contrast agents for magnetic resonance imaging (MRI) or as anti-cancer agents generating therapeutic hyperthermia through high-frequency magnetic field application, known as magnetic hyperthermia (MHT).

A supramolecular helicate with two independent Fe(II) switchable centres and a [Fe(anilate)] guest.

A biphenyl-spaced bis-pyrazolylpyridine ligand interacts with ferrous ions to engender a dimetallic helical coordination cage that encapsulates an Fe tris-anilate complex. The host-guest interaction breaks the symmetry of the Fe centers causing a differential spin crossover behavior in them that can be followed in great detail crystallographically.

Distributive Nd-to-Yb Energy Transfer within Pure [YbNdYb] Heterometallic Molecules.

Facile access to site-selective hetero-lanthanide molecules will open new avenues in the search of novel photophysical phenomena based on Ln-to-Ln' energy transfer (ET). This challenge demands strategies to segregate efficiently different Ln metal ions among different positions in a molecule. We report here the one-step synthesis and structure of a pure [YbNdYb] () coordination complex featuring short Yb···Nd distances, ideal to investigate a potential distributive (, from one donor to two acceptors) intramolecular ET from one Nd ion to two Yb centers within a well-characterized molecule.

Unparalleled selectivity and electronic structure of heterometallic [LnLn'Ln] molecules as 3-qubit quantum gates.

Heterometallic lanthanide [LnLn'] coordination complexes that are accessible thermodynamically are very scarce because the metals of this series have very similar chemical behaviour. Trinuclear systems of this category have not been reported. A coordination chemistry scaffold has been shown to produce molecules of type [LnLn'Ln] of high purity, exhibiting high metal distribution ability, based on their differences in ionic radius.

A ferric guest inside a spin crossover ferrous helicate.

A designed dimetallic Fe(II) helicate made with biphenylene-bridged bispyrazolylpyridine ligands and exhibiting a process of spin crossover at temperatures above ambient is shown to encapsulate an = 5/2 tris-oxalato Fe(III) ion. The spin relaxation dynamics of this guest are strongly reduced upon encapsulation.

Designed polynuclear lanthanide complexes for quantum information processing.

The design of dissymmetric organic ligands featuring combinations of 1,3-diketone and 2,6-diacetylpyridine coordination pockets has been exploited to produce dinuclear and trinuclear lanthanide-based coordination compounds. These molecules exhibit two or more non-equivalent Ln ions, most remarkably enabling the access to well-defined heterolanthanide compositions. The site-selective disposition of each metal ion within the molecular entities allows the study of each centre individually as a spin-based quantum bit, affording unparalleled versatility for quantum gate design.

Direct Evidence of a Graded Magnetic Interface in Bimagnetic Core/Shell Nanoparticles Using Electron Magnetic Circular Dichroism (EMCD).

Interfaces play a crucial role in composite magnetic materials and particularly in bimagnetic core/shell nanoparticles. However, resolving the microscopic magnetic structure of these nanoparticles is rather complex. Here, we investigate the local magnetization of antiferromagnetic/ferrimagnetic FeO/FeO core/shell nanocubes by electron magnetic circular dichroism (EMCD).

A heterometallic [LnLn'Ln] lanthanide complex as a qubit with embedded quantum error correction.

We show that a [Er-Ce-Er] molecular trinuclear coordination compound is a promising platform to implement the three-qubit quantum error correction code protecting against pure dephasing, the most important error in magnetic molecules. We characterize it by preparing the [Lu-Ce-Lu] and [Er-La-Er] analogues, which contain only one of the two types of qubit, and by combining magnetometry, low-temperature specific heat and electron paramagnetic resonance measurements on both the elementary constituents and the trimer. Using the resulting parameters, we demonstrate by numerical simulations that the proposed molecular device can efficiently suppress pure dephasing of the spin qubits.

Could α-synuclein amyloid-like aggregates trigger a prionic neuronal invasion?

Parkinson's disease (PD), a progressive neurodegenerative disease primarily affecting voluntary and controlled movement, is characterized by abnormal accumulations of α-synuclein (α-syn) in intraneuronal Lewy bodies. In the last years, the increased number of evidences from both the in vitro and in vivo studies has shown the ability of α-syn to misfold in amyloid conformations and to spread via neuron-to-neuron transmission, suggesting a prion-like behaviour. However, in contrast to prion protein (PrP), α-syn transmission is far from neuronal invasion.

Predicting the aggregation propensity of prion sequences.

The presence of prions can result in debilitating and neurodegenerative diseases in mammals and protein-based genetic elements in fungi. Prions are defined as a subclass of amyloids in which the self-aggregation process becomes self-perpetuating and infectious. Like all amyloids, prions polymerize into fibres with a common core formed of β-sheet structures oriented perpendicular to the fibril axes which form a structure known as a cross-β structure.