Surface decorated metal carbonyl clusters: bridging organometallic molecular clusters and atomically precise ligated nanoclusters.

In this Frontier Article, the work carried out within our research group in Bologna in the field of surface decorated metal carbonyl clusters will be outlined and put in a more general context. After a short Introduction, clusters composed of a metal carbonyl core decorated on the surface by metal-ligand fragments will be analyzed. Both metal-ligand fragments behaving as Lewis acids and Lewis bases will be considered.

Atomically precise rhodium-indium carbonyl nanoclusters: synthesis, characterization, crystal structure and electron-sponge features.

In this paper we present the investigation of the reactivity of [Rh(CO)] with InCl, with the aim of expanding the more general study that allowed us to obtain, among other species, the icosahedral [RhE(CO)] ( = 4 when E = Ge or Sn; = 3 when E = Sb or Bi) family of clusters. Indeed, the study resulted in the isolation and characterization of the analogous In-centred icosahedral [RhIn(CO)] nanocluster (1), which is isoelectronic and isostructural with the [RhE(CO)] congeners. During the course of the reaction two more new species, namely the octahedral [Rh(CO)InCl] (2) and the dimeric [{Rh(CO)InCl}] (3) have also been identified.

Expression analysis of during development.

The tRNA-histidine guanylyltransferase 1-like (), also known as induced in high glucose-1 (), encodes for an essential mitochondria-associated protein highly conserved throughout evolution, that catalyses the 3'-5' addition of a guanine to the 5'-end of tRNA-histidine (tRNA). Previous data indicated that THG1L plays a crucial role in the regulation of mitochondrial biogenesis and dynamics, in ATP production, and is critically involved in the modulation of apoptosis, cell-cycle progression and survival, as well as in cellular stress responses and redox homeostasis. Dysregulations of THG1L expression play a central role in various pathologies, including nephropathies, and neurodevelopmental disorders often characterized by developmental delay and cerebellar ataxia.

Peraurated ruthenium hydride carbonyl clusters: aurophilicity, isolobal analogy, structural isomerism, and fluxionality.

The stepwise addition of increasing amounts of Au(PPh)Cl to [HRu(CO)] (1) results in the sequential formation of [HRu(CO)(AuPPh)] (2), [HRu(CO)(AuPPh)] (3), and HRu(CO)(AuPPh) (4). Alternatively, 4 can be obtained upon addition of HBF·EtO (two mole equivalents) to 3. Further addition of acid to 3 (three mole equivalents) results in the formation of the tetra-aurated cluster Ru(CO)(AuPPh) (5).

Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [RuC(CO)].

The reaction of [RuC(CO)] () with NaOH in DMSO resulted in the formation of a highly reduced [RuC(CO)] (), which was readily protonated by acids, such as HBF·EtO, to [HRuC(CO)] (). Oxidation of with [CpFe][PF] or [CH][BF] in CHCN resulted in [RuC(CO)(CHCN)] (), which was quantitatively converted into after exposure to CO atmosphere. The reaction of with a mild methylating agent such as CHI afforded the purported [RuC(CO)(COCH)] ().

[Historical events in epidemiology, at the Muñiz Hospital, Buenos Aires, Argentina].

The Muñiz hospital is an institution with historical, cultural and health heritage. A historical analysis of the different epidemics/pandemics and outbreaks is carried out here, assessing the epidemiological management (surveillance, prevention, control and emergency management) in the institution and the reason for its architecture. To this end, a systematic review of the literature on the history of the Muñiz hospital and its references was carried out, since 1980 to 2023, following the PRISMA format.

Crosslinked Chitosan Nanoparticles with Muco-Adhesive Potential for Intranasal Delivery Applications.

Intranasal drug delivery is convenient and provides a high bioavailability but requires the use of mucoadhesive nanocarriers. Chitosan is a well-established polymer for mucoadhesive applications but can suffer from poor cytocompatibility and stability upon administration. In this work, we present a method to obtain stable and cytocompatible crosslinked chitosan nanoparticles.

From M to M, M and M molecular alloy Pt-Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters.

Heterometallic Chini-type clusters [PtNi(CO)] ( = 0-6) were obtained by reactions of [Pt(CO)] with Ni-clusters such as [Ni(CO)], [Ni(CO)] and [HNi(CO)], or from [Pt(CO)] and [Ni(CO)]. The Pt/Ni composition of [PtNi(CO)] ( = 0-6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt(CO)] with [Ni(CO)] and [HNi(CO)], as well as reactions of [Pt(CO)] with [Ni(CO)], [Ni(CO)] and [HNi(CO)], afforded [PtNi(CO)] ( = 0-9) species.

Antitumor immunity induced by antibody-based natural killer cell engager therapeutics armed with not-alpha IL-2 variant.

Harnessing innate immunity is emerging as a promising therapeutic approach in cancer. We report here the design of tetraspecific molecules engaging natural killer (NK) cell-activating receptors NKp46 and CD16a, the β-chain of the interleukin-2 receptor (IL-2R), and a tumor-associated antigen (TAA). In vitro, these tetraspecific antibody-based natural killer cell engager therapeutics (ANKETs) induce a preferential activation and proliferation of NK cells, and the binding to the targeted TAA triggers NK cell cytotoxicity and cytokine and chemokine production.

2-D Molecular Alloy Ru-M (M = Cu, Ag, and Au) Carbonyl Clusters: Synthesis, Molecular Structure, Catalysis, and Computational Studies.

The reactions of [HRu(CO)] () with M(I) (M = Cu, Ag, and Au) compounds such as [Cu(CHCN)][BF], AgNO, and Au(EtS)Cl afford the 2-D molecular alloy clusters [CuRu(CO)] (), [AgRu(CO)] (), and [AuRu(CO)] (), respectively. The reactions of with PPh result in mixtures of products, among which [CuRu(CO)] (), Ru(CO)(CuPPh) (), Ru(CO)(AgPPh) (), Ru(CO)(PPh) (), and HRu(OH)(CO)(PPh) () have been isolated and characterized. The molecular structures of and have been determined by single-crystal X-ray diffraction.

Atomically Precise Platinum Carbonyl Nanoclusters: Synthesis, Total Structure, and Electrochemical Investigation of [Pt(CO)] Displaying a Defective Structure.

The molecular Pt nanocluster [Pt(CO)] () was obtained by thermal decomposition of [Pt(CO)] in tetrahydrofuran under a H atmosphere. The reaction of with increasing amounts of HBFEtO afforded the previously reported [Pt(CO)] () and [Pt(CO)] (). The new nanocluster was characterized by IR and UV-visible spectroscopy, single-crystal X-ray diffraction, direct-current superconducting quantum interference device magnetometry, cyclic voltammetry, IR spectroelectrochemistry (IR SEC), and electrochemical impedance spectroscopy.

Inverted Ligand Field in a Pentanuclear Bow Tie Au/Fe Carbonyl Cluster.

Gold chemistry has experienced in the last decades exponential attention for a wide spectrum of chemical applications, but the +3 oxidation state, traditionally assigned to gold, remains somewhat questionable. Herein, we present a detailed analysis of the electronic structure of the pentanuclear bow tie Au/Fe carbonyl cluster [Au{η-Fe(CO)}] together with its two one-electron reversible reductions. A new interpretation of the bonding pattern is provided with the help of inverted ligand field theory.

Synthesis, molecular structure and fluxional behavior of the elusive [HRu(CO)] carbonyl anion.

The elusive mono-hydride tri-anion [HRu(CO)] (4) has been isolated and fully characterized for the first time. Cluster 4 can be obtained by the deprotonation of [HRu(CO)] (2) with NaOH in DMSO. A more convenient synthesis is represented by the reaction of [HRu(CO)] (6) with an excess of NaOH in DMSO.

Enriching the Arsenal of Pharmacological Tools against MICAL2.

Molecule interacting with CasL 2 (MICAL2), a cytoskeleton dynamics regulator, are strongly expressed in several human cancer types, especially at the invasive front, in metastasizing cancer cells and in the neo-angiogenic vasculature. Although a plethora of data exist and stress a growing relevance of MICAL2 to human cancer, it is worth noting that only one small-molecule inhibitor, named CCG-1423 (1), is known to date. Herein, with the aim to develop novel MICAL2 inhibitors, starting from CCG-1423 (1), a small library of new compounds was synthetized and biologically evaluated on human dermal microvascular endothelial cells (HMEC-1) and on renal cell adenocarcinoma (786-O) cells.

Atomically Precise Ni-Pd Alloy Carbonyl Nanoclusters: Synthesis, Total Structure, Electrochemistry, Spectroelectrochemistry, and Electrochemical Impedance Spectroscopy.

The molecular nanocluster [NiPd(CO)] ( = 0.41) () was obtained from the reaction of [NMe(CHPh)][Ni(CO)] with 0.8 molar equivalent of [Pd(CHCN)][BF] in tetrahydrofuran (thf).

Inducible Pluripotent Stem Cells to Model and Treat Inherited Degenerative Diseases of the Outer Retina: 3D-Organoids Limitations and Bioengineering Solutions.

Inherited retinal degenerations (IRD) affecting either photoreceptors or pigment epithelial cells cause progressive visual loss and severe disability, up to complete blindness. Retinal organoids (ROs) technologies opened up the development of human inducible pluripotent stem cells (hiPSC) for disease modeling and replacement therapies. However, hiPSC-derived ROs applications to IRD presently display limited maturation and functionality, with most photoreceptors lacking well-developed outer segments (OS) and light responsiveness comparable to their adult retinal counterparts.

Heterometallic rhodium clusters as electron reservoirs: Chemical, electrochemical, and theoretical studies of the centered-icosahedral [RhE(CO)] atomically precise carbonyl compounds.

In this paper, we present a comparative study of the redox properties of the icosahedral [RhE(CO)] (n = 4 when E = Ge or Sn and n = 3 when E = Sb or Bi) family of clusters through in situ infrared spectroelectrochemistry experiments and density functional theory computational studies. These clusters show shared characteristics in terms of molecular structure, being all E-centered icosahedral species, and electron counting, possessing 170 valence electrons as predicted by the electron-counting rules, based on the cluster-borane analogy, for compounds with such metal geometry. However, in some cases, clusters of similar nuclearity, and beyond, may show multivalence behavior and may be stable with a different electron counting, at least on the time scale of the electrochemical analyses.

Metal carbonyl clusters of groups 8-10: synthesis and catalysis.

In this review article, we discuss advances in the chemistry of metal carbonyl clusters (MCCs) spanning the last three decades, with an emphasis on the more recent reports and those involving groups 8-10 elements. Synthetic methods have advanced and been refined, leading to higher-nuclearity clusters and a wider array of structures and nuclearities. Our understanding of the electronic structure in MCCs has advanced to a point where molecular chemistry tools and other advanced tools can probe their properties at a level of detail that surpasses that possible with other nanomaterials and solid-state materials.

Characterization of Grapevine Wood Microbiome Through a Metatranscriptomic Approach.

Grapevine trunk diseases threaten wine and table grape production worldwide, primarily by reducing yields and, in its advanced stages, causing plant death. Among those diseases, the complex etiology disease known as hoja de malvón (HDM) significantly concerns Argentinian and Uruguayan viticulture. At least four different fungi are associated with this disease, but their role and interactions with other wood microorganisms are understudied.

One-pot atmospheric pressure synthesis of [HRu(CO)].

Reductive carbonylation of RuCl3·3H2O at CO-atmospheric pressure results in the [H3Ru4(CO)12]- (1) polyhydride carbonyl cluster. The one-pot synthesis involves the following steps: heating RuCl3·3H2O at 80 °C in 2-ethoxyethanol for 2 h, addition of three equivalents of KOH, heating at 135 °C for 2 h, addition of a fourth equivalent of KOH and heating at 135 °C for 1 h. The resulting K[1] salt is transformed into [NEt4][1] upon metathesis with [NEt4]Br in H2O.