Aluminium(III) as a promoter of cellular oxidation

Aluminium has been known as a neurotoxic agent to experimental animals since the last century (Arch. Exp. Pharmacol. 40 (1897) 98). However, great interest arose in it bioinorganic chemistry as well biology when it was demonstrated to be the causative agent in pathologies related to the long-term dialysis treatment of uremic subjects with renal failure (Life Chem. 11 (1994) 197), and as a potential etiopathogenic cofactor for several neurodegenerative diseases. The inorganic biochemistry of aluminium is still largely to be discovered. In this review the pro-oxidative property of aluminium toward biological membrane will be presented and its implications in involvement in human pathology will be discussed in an interdisciplinary frame from the bioinorganic point of view.     

Siloxane-Based Nanobuilding Blocks by Reaction Between Silanediol and Trifunctional Silicon Alkoxides

The preparation of nanostructured organic-inorganic materials by assembling of nanobuilding blocks allows controlling the extent of phase interaction, which in its turn governs structure-properties relationships. We present here the synthesis of siloxane-based nanobuilding blocks prepared by reacting diphenylsilanediol with vinyltriethoxysilane and triethoxysilane. The reaction products were obtained by non-hydrolytic condensation between silanediol and ethoxide groups in inert atmosphere, in the presence of pyridine, triethylamine or butyl lithium. Different synthetic conditions were examined by means of ATR-FTIR and NMR spectroscopies, showing the formation of siloxane bonds. In the case of triethoxysilane the reaction carried out in the presence of pyridine leads to Si–H bond preservation in the final product. Air stable products with improved Si–O–Si hydrolytic stability can be obtained by removal of the base after the reaction completion. The condensation products can be described as a mixture of siloxane rings involving difunctional and trifunctional silicon units.     

Die Kristallstruktur des l, 6-8, 13-Bis-oxido-[14]-annulens

Crystals of 1,6-8, 13-bis-oxido-[14]-annulene are monoclinic, a = 9,29, b = 9,74, c = 11,46 Å, β = 90,0°, space group P 2₁/c, with 4 molecules in the unit cell. The structure has been solved by direct methods and refined by full-matrix least-squares analysis of three-dimensional intensity data. The cis-configuration of the two oxygen bridges is confirmed, and the observed molecular parameters are in full accord with the aromatic properties of the molecule.     

Selection theorems,based on generalized variation and oscillation

In this paper we prove selection theorems for everywhere and almost everywhere convergent subsequences, based on the notion of uniformly limited oscillation, ofA, Λ-oscillation and ofA, Λ-variation, whereA is a system of intervals and Λ a sequence of reals. By this, we generalize and strengthen the selection theorems of Schrader (for oscillation) and of Waterman (for Λ-variation).     

Effect of core size on the partition of organic solutes in the monolayer of water-soluble nanoparticles: an ESR investigation

ESR spectroscopy has been used to study the interaction of para-pentylbenzyl hydroxyalkyl nitroxide with the monolayer of water-soluble protected gold clusters having a core diameter ranging from 1.6 to 5.3 nm. The solubilization of the nitroxide probe in the more hydrophobic environment of the monolayer strongly depends on the size of the gold core. In particular, the partition equilibrium constant increases as the nanoparticle diameter decreases. These results have been attributed to the different packing of the chains in the monolayer resulting from the different radius of curvature of the investigated nanoparticles. This represents, to the best of our knowledge, the first report demonstrating that the core size of metallic nanoparticles affects the solvating properties of the protective organic monolayer.     

Reversible immobilization of engineered molecules by Ni-NTA chelators

Electrochemical synthesis of nickel-nitrilotriacetic acid (Ni-NTA) chelators, for subsequent immobilization of (His)(6)-tagged proteins (Photosystem II (PSII) as model molecule), on Au or Au-graphite electrodes is compared to chemical synthesis. Results show: (i) higher Ni-NTA surface density, (ii) shorter treatment time (1-12 min vs. 16 h normally needed for self-assembled monolayer (SAM)), (iii) possibility of addressing the chelator to only one Au electrode, in a sensor micro-array.     

DNA-mediated coordinative assembly of upconversion hetero-nanostructures for targeted dual-modality imaging of cancer cells

We reported a simple and universal strategy for DNA-mediated assembly of CdTe quantum dots (QDs) and lanthanide-doped upconversion nanoparticles (UCNPs). Such DNA-QD/UCNPs heterostructures not only maintains both fluorescent properties of QDs and upconversion luminescence behaviors of UCNPs, but also offers a polyvalent DNA surface, allowing for targeted dual-modality imaging of cancer cells using an aptamer     

Sequestration within biomolecular condensates inhibits Aβ-42 amyloid formation

Biomolecular condensates are emerging as an efficient strategy developed by cells to control biochemical reactions in space and time by locally modifying composition and environment. Yet, local increase in protein concentration within these compartments could promote aberrant aggregation events, including the nucleation and growth of amyloid fibrils. Understanding protein stability within the crowded and heterogeneous environment of biological condensates is therefore crucial, not only when the aggregation-prone protein is the scaffold element of the condensates but also when proteins are recruited as client molecules within the compartments. Here, we investigate the partitioning and aggregation kinetics of the amyloidogenic peptide Abeta42 (Aβ-42), the peptide strongly associated with Alzheimer''s disease, recruited into condensates based on low complexity domains (LCDs) derived from the DEAD-box proteins Laf1, Dbp1 and Ddx4, which are associated with biological membraneless organelles. We show that interactions between Aβ-42 and the scaffold proteins promote sequestration and local increase of the peptide concentration within the condensates. Yet, heterotypic interactions within the condensates inhibit the formation of amyloid fibrils. These results demonstrate that biomolecular condensates could sequester aggregation-prone proteins and prevent aberrant aggregation events, despite the local increase in their concentration. Biomolecular condensates could therefore work not only as hot-spots of protein aggregation but also as protective reservoirs, since the heterogenous composition of the condensates could prevent the formation of ordered fibrillar aggregates.

Biomolecular condensates sequester an aggregation-prone peptide and prevent its aggregation, showing that heterotypic interactions within the condensates can prevent the formation of amyloid fibrils, despite the local increase in concentration.     

Electronic spectral and photophysical properties of some p-phenylenevinylene oligomers in solution and thin films

A comprehensive photophysical and spectroscopic study of a new class of p-phenylenevinylene oligomers (PPV-trimers) possessing different alkyl and alkyloxy sidechain substituents and different end groups (aldehyde, CC, phenylene and anthracene units) was undertaken in solution at room temperature (293 K), low temperature (77 K) and in thin films. The study comprises absorption, emission and triplet–triplet absorption spectra, together with quantitative measurements of quantum yields (fluorescence, intersystem crossing, internal conversion and singlet oxygen formation) and lifetimes. The data allow the determination of rate constants for all decay processes. From these, several conclusions could be drawn. Changing from alkyl to alkyloxy substituents does not change fluorescence and internal conversion yields but decreases the (already small) intersystem crossing yield. The introduction of anthracene at the terminal ends of the PPV-trimers leads to the lowest fluorescence yield reported in this study. Of particular importance is the fact that the fluorescence quantum yields in films are of the same order of magnitude as those in solution, which suggests the potential for use of these oligomers for light-emitting device applications. With one of the alkyloxy derivatives, a more detailed study of the early part of the fluorescence decay was made, and it was found that upon excitation a fast conformational relaxation process of the initially excited oligomer occurs, leading to a more planar conjugation segment.