Biolabeling with nanoparticles based on Y2O3: Nd and luminescence detection in the near-infrared

Neodymium based fluorescence presents several advantages in comparison to conventional rare earth or enzyme-substrate based fluorescence emitting sources (e.g.Tb, HRP) . Based on this fact we have herein explored a Nd-based fluoroimmunoassay. We efficiently detected the presence of an oxidized low-density lipoprotein (oxLDL) in human plasma a well-known marker for cardiovascular diseases, which causes around 30% of deaths worldwide. Conventional fluoroimmunoassay uses time-resolved luminescence techniques, with detection in the visible range, to eliminate the fluorescence background from the biological specimens. By using an immunoassay based on functionalized Y₂O₃:Nd³⁺ nanoparticles, where the excitation and emission processes in the Nd³⁺ ion occur in the near-infrared (NIR) region, we have succeeded in eliminating the interferences from the biological fluorescence background, avoiding the use of time-resolved techniques. This yields higher emission intensity from the Nd³⁺-nanolabels and efficient detection of anti-oxidized low-density lipoproteins (anti-oxLDL) by Y₂O₃:Nd³⁺-antibody-antigen conjugation, leading to a novel biolabeling method.     

Endo-cavity Complexes between Calix[6]arene Dianions and Aliphatic Ammonium Cations: Structure of a Hexylammonium Complex by X-ray Crystallography

The interactions of calix[6]arene and p-tert-butylcalix[6]arene with aliphatic amines in acetonitrile solution were studied by spectrophotometric titrations in the UV region and ¹H NMR spectrometry. Calix[6]arenes can undergo two deprotonations by aliphatic amines and the extent of the second proton transfer is mainly governed by the size of the α-substituent of the amine. ¹H NMR spectra show that the macrocycle adopts a 1,2,3-alternate conformation and that the α-hydrogens of the ammonium ions are shielded by the π-clouds of the aromatic rings. The X-ray crystal structure of the dihexylammonium complex of the p-tert-butylcalix[6]arene dianion, reported here, confirms the 1,2,3-alternate conformation and shows one of the two ammonium moieties encapsulated in the inner cavity of the macrocycle.     

Molecular Recognition of Aromatic Nitro Compounds at Cyclodextrin Dithiocarbamate-modified Electrodes

Silver electrodes were modified by the adsorption of α-, β-, and γ-cyclodextrin dithiocarbamates (2α–γ) and characterized by reductive desorption experiments. Their molecular recognition properties were studied by cyclic voltammetry using three families of positional isomers of aromatic nitro compounds. Electrodes modified with 2α and 2β were selective for meta and para isomers while 2γ showed little selectivity. These observations are explained in terms of cavity sizes and guest structure. Computational studies suggest that the main reason for the observed selectivity is the different position of the NO² group in ortho and para isomers with respect to the CD cavity.