Laser-Treated Screen-Printed Carbon Electrodes for Electrochemiluminescence imaging.

Electrochemiluminescence (ECL) is nowadays a powerful technique widely used in biosensing and imaging, offering high sensitivity and specificity for detecting and mapping biomolecules. Screen-printed electrodes (SPEs) offer a versatile and cost-effective platform for ECL applications due to their ease of fabrication, disposability, and suitability for large-scale production. This research introduces a novel method for improving the ECL characteristics of screen-printed carbon electrodes (SPCEs) through the application of CO laser treatment following fabrication.

Electrogenerated chemiluminescence from luminol-labelled microbeads triggered by in situ generation of hydrogen peroxide.

We developed a sensing strategy that mimics the bead-based electrogenerated chemiluminescence immunoassay. However, instead of the most common metal complexes, such as Ru or Ir, the luminophore is luminol. The electrogenerated chemiluminescence of luminol was promoted by in situ electrochemical generation of hydrogen peroxide at a boron-doped diamond electrode.

Unveiling the promising anticancer activity of palladium(II)-aryl complexes bearing diphosphine ligands: a structure-activity relationship analysis.

In continuation of our previous works on the cytotoxic properties of organopalladium compounds, in this contribution we describe the first systematic study of the anticancer activity of Pd(II)-aryl complexes. To this end, we have prepared and thoroughly characterized a wide range of palladium derivatives bearing different diphosphine, aryl and halide ligands, developing, when necessary, specific synthetic protocols. Most of the synthesized compounds showed remarkable cytotoxicity towards ovarian and breast cancer cell lines, with IC values often comparable to or lower than that of cisplatin.

Rosuvastatin effect on atherosclerotic plaque metabolism: A subclinical atherosclerosis imaging study with F-NaF PET-CT.

Background And Aims: Atherosclerotic plaque fluorine-18 sodium fluoride (F-NaF) uptake on positron emission tomography with computed tomography (PET-CT) identifies active microcalcification and has been shown to correlate with clinical instability in patients with cardiovascular (CV) disease. Statin therapy promotes coronary macrocalcification over time. Our aim was to investigate rosuvastatin effect on atheroma F-NaF uptake.

Redox-mediated electrochemiluminescence enhancement for bead-based immunoassay.

Electrochemiluminescence (ECL) is a highly sensitive mode of detection utilised in commercialised bead-based immunoassays. Recently, the introduction of a freely diffusing water-soluble Ir(iii) complex was demonstrated to enhance the ECL emission of [Ru(bpy)] labels anchored to microbeads, but a comprehensive investigation of the proposed 'redox-mediated' mechanism was not carried out. In this work, we select three different water-soluble Ir(iii) complexes by virtue of their photophysical and electrochemical properties in comparison with those of the [Ru(bpy)] luminophore and the TPrA co-reactant.

Boron-Doped Diamond Electrode Outperforms the State-of-the-Art Electrochemiluminescence from Microbeads Immunoassay.

Electrochemiluminescence (ECL) is a powerful transduction technique where light emission from a molecular species is triggered by an electrochemical reaction. Application to biosensors has led to a wide range of electroanalytical methods with particular impact on clinical analysis for diagnostic and therapeutic monitoring. Therefore, the quest for increasing the sensitivity while maintaining reproducible and easy procedures has brought investigations and innovations in (i) electrode materials, (ii) luminophores, and (iii) reagents.

Chemoselective oxidative addition of vinyl sulfones mediated by palladium complexes bearing picolyl-N-heterocyclic carbene ligands.

The manifold interactions of (E)- or (Z)-1,2-ditosylethene with a palladium(0) centre bearing picolyl-NHC carbene ligands have been studied thoroughly. (E)-1,2-Ditosylethene produces the expected and stable η-olefin palladium complexes, whereas the coordination of the Z derivative alternatively promotes the isomerization of the olefin itself or an oxidative addition process depending on the steric bulkiness of carbene substituents and/or the adopted synthetic procedure. Remarkably, the oxidative addition pathway involves a selective S-vinyl (not S-aryl) breaking and produces selectively the S- rather than O-coordinated sulfinate.

Synthesis of new allyl palladium complexes bearing purine-based NHC ligands with antiproliferative and proapoptotic activities on human ovarian cancer cell lines.

A series of new palladium allyl complexes bearing purine-based carbenes derived from caffeine, theophylline and theobromine have been prepared and characterized by NMR spectroscopy, and elemental analysis and in two cases by single crystal X-ray diffraction. The cytotoxic and proapoptotic activities of compounds have been determined in vitro on human ovarian cancer A2780 and SKOV-3 cell lines. These experiments have shown that the palladium-allyl fragment induces a general cytotoxicity, but the choice of the supporting ligands is of paramount importance for achieving the best results.

Reactivity of N-heterocyclic carbene-pyridine palladacyclopentadiene complexes toward halogen addition. The unpredictable course of the reaction.

As an extension of a previously published work we have reacted some palladacyclopentadiene complexes stabilized by bidentate N-heterocyclic carbene-pyridine or monodentate N-heterocyclic carbene-pyridine and isocyanide ligands with the halogens I and Br. All the bidentate and monodentate complexes react with halogens to give at first the expected σ-coordinated butadienyl fragment. However, two of the less hindered NHC carbene-pyridine bidentate butadienyl iodo derivatives undergo a further rearrangement and novel Pd(ii) complexes characterized by a ten term coordinative ring were isolated and characterized.

Isocyanide insertion across the Pd-C bond of allenyl and propargyl palladium complexes bearing phosphoquinoline as a spectator ligand. Synthesis of a palladium complex bearing a coordinated cyclobutenyl fragment.

We have studied the insertion of p-toluenesulfonylmethyl isocyanide (TosMIC) on selected allenyl and propargyl complexes of palladium bearing diphenylphosphine quinoline as a spectator ligand. The fast process gives different products depending on the tautomer involved in the reaction. Thus, the unsubstituted allenyl species yields an insertion complex with the isocyanide coordinated between the metal and the first allenyl carbon.

The unexpected case of reactions of halogens and interhalogens with halide substituted Pd(ii) σ-butadienyl complexes.

We have experimentally studied and theoretically interpreted the addition under stoichiometric conditions of halogens or interhalogens to σ-butadienyl palladium complexes bearing the heteroditopic thioquinolines as spectator ligands. The observed reactions do not involve the expected extrusion of the butadienyl fragment but rather the unpredictable substitution of the halide coordinated to palladium and in some cases also of that bound to the terminal butadienyl carbon. We have explained this peculiar reactivity with a mechanistic hypothesis based on a sequence of selective processes of oxidative addition and reductive elimination involving Pd(iv) intermediates.

The addition of bromine and iodine to palladacyclopentadienyl complexes bearing bidentate heteroditopic P-N spectator ligands derived from differently substituted quinolinic frames. The unexpected evolution of the reaction.

We have synthesized two palladacyclopentadienyl derivatives bearing bidentate ligands heteroditopic 8-(diphenylphosphino)quinoline or 8-(diphenylphosphino)-2-methylquinoline. We have reacted the palladacyclopentadienyl complexes with Br2 and I2 to gain clues on the formation mechanism of the corresponding σ-butadienyl derivatives. We were able to obtain the pure σ-butadienyl derivative only in the case of Br2 reacting with the palladacyclopentadienyl complex bearing the unsubstituted quinoline.

Substitution reactions between bis-chelate ligands in palladium(II) alkenyl complexes: an unusual way to form unstable trans-P complexes. A study on the isomerization mechanism.

The substitution reactions between asymmetric bis-chelate ligands and alkenyl chloro derivatives of palladium(II) of the type [Pd(L-L')(Rx)Cl] (L-L' = 2-phenylsulfanylmethyl-pyridine (HN-SPh), 2-methyl-6-phenylsulfanylmethyl-pyridine (MeN-SPh), 2,2'-bipyridinyl (BiPy), Rx = -CCOOMe=CMeCOOMe (Ra), -CCOOEt=CMeCOOEt (Rb), -CCOOt-Bu=CMeCOOt-Bu (Rc), -(CCOOMe=CCOOMe)(2)Me (Rd)) with phosphoquinoline moieties (8-diphenylphosphanyl-quinoline (DPPQ), 8-diphenylphosphanyl-2-methyl-quinoline (DPPQ-Me)) usually leads to the formation of the stable geometrical isomer bearing these groups in the cis position thanks to the mutual trans influence of the alkenyl and phosphine groups. However, when the leaving group MeN-SPh and the entering ligand DPPQ are involved, the fast and quantitative substitution reaction leads to the formation of a couple of geometrical isomers [Pd(DPPQ)(Rx)Cl]-trans P and [Pd(DPPQ)(Rx)Cl]-cis P (Rx = Ra, Rb, Rc, Rd) in which the alkenyl and the phosphine groups are in mutual trans or cis position. The substrate [Pd(DPPQ)(Rx)Cl]-trans P (Rx = Ra, Rb, Rc) slowly interconverts into its thermodynamically stable -cis P counterpart while the bulky [Pd(DPPQ)(Rd)Cl]-trans P displays no tendency to isomerize, thereby allowing separation of the two geometrical forms.