Prospects and Current Challenges of Extracellular Vesicle-Based Biomarkers in Cancer.

Cancer continues to impose a substantial global health burden, particularly among the elderly, where the ongoing global demographic shift towards an ageing population underscores the growing need for early cancer detection. This is essential for enabling personalised cancer care and optimised treatment throughout the disease course to effectively mitigate the increasing societal impact of cancer. Liquid biopsy has emerged as a promising strategy for cancer diagnosis and treatment monitoring, offering a minimally invasive method for the isolation and molecular profiling of circulating tumour-derived components.

A Well-Defined Magnesium Complex of C .

Controlling and understanding charge state and metal coordination in carbon nanomaterials is crucial to harnessing their unique properties. Here we describe the synthesis of the well-defined fulleride complex [{(nacnac)Mg}C], 2, (nacnac)=HC(MeCNMes), Mes=2,4,6-MeCH, from the reaction of the β-diketiminate magnesium(I) complex [{(nacnac)Mg}] with C in aromatic solvents. The molecular structure of complex 2 was determined, providing the first high-quality structural study of a complex with the C ion.

A molecular aluminium fulleride.

The reaction of alumylene [(nacnac)Al] (1) with C fashions the first example of a structurally characterised aluminium-fulleride complex, [{(nacnac)Al}C] (2), in which the Al centres are covalently bound to significantly elongated 6 : 6 bonds. Hydrolysis of 2 yields CH and the reaction of 2 with [{nacnac)Mg}] cleaved off the Al fragments by affording the fulleride [{nacnac)Mg}C].

Synthesis of a Hexameric Magnesium 4-pyridyl Complex with Cyclohexane-like Ring Structure via Reductive C-N Activation.

The reaction of [{(nacnac)Mg}] (nacnac = HC{MeC(NAr)}, Ar = 2,6-diisopropylphenyl, Dip, or 2,6-diethylphenyl, Dep) with 4-dimethylaminopyridine (DMAP) at elevated temperatures afforded the hexameric magnesium 4-pyridyl complex [{(nacnac)Mg(4-CHN)}] via reductive cleavage of the DMAP C-N bond. The title compound contains a large -block organometallic cyclohexane-like ring structure comprising tetrahedral (nacnac)Mg nodes and linked by linear 4-pyridyl bridging ligands, and the structure is compared with other ring systems. [(nacnac)Mg(DMAP)(NMe)] was structurally characterised as a by-product.

Hydrocarbon-soluble, hexaanionic fulleride complexes of magnesium.

The reaction of the magnesium(i) complexes [{(nacnac)Mg}], (nacnac = HC(MeCNAr), Ar = Dip (2,6-iPrCH), Dep (2,6-EtCH), Mes (2,4,6-MeCH), Xyl (2,6-MeCH)) with fullerene C afforded a series of hydrocarbon-soluble fulleride complexes [{(nacnac)Mg} C], predominantly with = 6, 4 and 2. C{H} NMR spectroscopic studies show both similarities ( = 6) and differences ( = 4, 2) to previously characterised examples of fulleride complexes and materials with electropositive metal ions. The molecular structures of [{(nacnac)Mg} C] with = 6, 4 and 2 can be described as inverse coordination complexes of [(nacnac)Mg] ions with C anions showing predominantly ionic metal-ligand interactions, and include the first well-defined and soluble complexes of the C ion.

Mechanistic insights of anionic ligand exchange and fullerene reduction with magnesium(i) compounds.

Ligand exchange reactions between combinations of the complexes [{(nacnac)Mg}], where Ar = 2,6-iPrCH (Dip), 2,6-EtCH (Dep), 2,4,6-MeCH (Mes), and 2,6-MeCH (Xyl), [({PhP(NDip)}Mg)], [(nacnac)Li], where Ar = Mes or Xyl, and [{PhP(NDip)}Li] were studied in deuterated aromatic and aliphatic solvents, and tetrahydrofuran. The reactions afforded product mixtures with asymmetrically substituted dimagnesium(i) complexes [(nacnac)MgMg(nacnac)], where Ar, Ar' = Dip, Dep, Mes, Xyl and [{PhP(NDip)}MgMg(nacnac)], where Ar = Mes or Xyl, and suggest that the exchange of anionic ligands on the Mg ion proceeds via an associative mechanism and is strongly dependent on ligand sterics and ligand shape, and can be very rapid. The activation reaction of fullerene C by dimagnesium(i) complexes [{(nacnac)Mg}] and [({PhP(NDip)}Mg)] to fulleride complexes is similarly dependent on ligand sterics and ligand shape, but likely does not involve direct coordination of the fullerene to the Mg centre in dimagnesium(i) compounds prior to its reduction.

PNacPNacE: (E = Ga, In, Tl) - monomeric group 13 metal(i) heterocycles stabilized by a sterically demanding bis(iminophosphoranyl)methanide.

The salt metathesis reaction of the sterically demanding bis(iminophosphoranyl)methanide alkali metal complexes LM (L = HC(PhP[double bond, length as m-dash]NDip), Dip = 2,6-PrCH; M = Li, Na, K) with "GaI", InBr or TlBr afforded the monomeric group 13 metal(i) complexes LE:, E = Ga (1), In (2) and Tl (3) in moderate yields, and small quantities of LGaI4 in the case of Ga, respectively. The molecular structures of LE: 1-3 from X-ray single crystal diffraction show them to contain puckered six-membered rings with N,N'-chelating methanide ligands and two-coordinated metal(i) centres. Reduction reactions of LAlI5, prepared by iodination of LAlMe, were not successful and no aluminium(i) congener could be prepared so far.