Pathogenic Mutations Shift the Equilibria of α‐Synuclein Single Molecules towards Structured Conformers

α‐synuclein (α‐Syn) is an abundant brain protein whose mutations have been linked to early‐onset Parkinson's disease (PD). We recently demonstrated, by means of a single‐molecule force spectroscopy (SMFS) methodology, that the conformational equilibrium of monomeric wild‐type (WT) α‐Syn shifts toward β‐containing structures in several unrelated conditions linked to PD pathogenicity. Herein, we follow the same methodology previously employed for WT α‐Syn to characterize the conformational heterogeneity of pathological α‐Syn mutants A30P, A53T, and E46K. Contrary to the bulk ensemble‐averaged spectroscopies so far employed to this end by different authors, our single‐molecule methodology monitored marked differences in the conformational behaviors of the mutants with respect to the WT sequence. We found that all the mutants have a much higher propensity than the WT to adopt a monomeric compact conformation that is compatible with the acquiring of β structure. Mutants A30P and A53T show a similar conformational equilibrium that is significantly different from that of E46K. Another class of conformations, stabilized by mechanically weak interactions (MWI), shows a higher variety in the mutants than in the WT protein. In the A30P mutant these interactions are relatively stronger, and therefore the corresponding conformations are possibly more structured. The more structured and globular conformations of the mutants can explain their higher propensity to aggregate with respect to the WT.     

Intrinsic surface depression of the order parameter under mixed (s+id)-wave pair symmetry and its effect on the critical current of high-Tc SIS Josephson junctions

An intrinsic gap depression at the superconductor-insulator interface due to the very short value of the coherence length in high-T _c superconductors [HTS] is considered in the framework of a mixed (s+id)-wave pair symmetry for the order parameter ranging from pures to pured-wave. This gap depression acts as the main physical agent causing the relevant reduction ofI _c (T)R _n (T) values with respect to BCS expectations in HTS SIS Josephson junctions. Good agreement with various experimental data is obtained with both pures-wave and pured-wave symmetries of the order parameter, but with amounts of gap depression depending on the pair symmetry adopted. Regardless of the apir symmetry considered, these results prove the importance of the surface order-parameter depression in the correct interpretation of theI _c (T)R _n (T) data in HTS SIS junctions. In the case of a planar YBCO-based junction the use of the de Gennes condition allowed us to tentatively obtain an upper limit for the amount ofd-wave present in the gap of YBCO.     

Spectral and chemical evidence for the direct formation of carboxylic groups in aerobically oxidised water-soluble fullerenes

The synthesis of oxidised water-soluble fullerenes, prepared by chemically-induced aerobic oxidation, yields functionalised carbon cluster structures, which are oxidised by the covalent insertion of different oxygen units. Their strictly pH-dependent behaviour in aqueous solutions appears to be properly ascribed to the existence of directly attached carboxylic moieties. The presence of these groups, which are usually neglected and underestimated, has been thoroughly investigated. Several concurrent spectral (UV-VIS, XPS, solid-state ¹³C CPMAS NMR, FT-IR, Raman, EDAX, TGA-MS, ESI-MS) and chemical (acid-base behaviour, salt precipitation by metal-complexation, carboxylic functionalisation) methods have provided a definitive set of consistent evidence, indicating for the first time the direct linkage of carboxylic groups on water-soluble fullerenes prepared in this manner.     

Evaluation of gamma rays influence on some biochemical and microbiological aspects in black truffles

The effects of two gamma-ray doses (1.5 kGy and 2.0 kGy) on some biochemical aspects and on the microbiological profile of black truffles was monitored, immediately after treatment and after 30 days of storage at 4 °C. Electrophoretic and chromatographic analyses of proteins and peptides, just like monitoring of polyphenol content, peroxides formation and microbial profile, allowed for the first time a better understanding of the mechanisms responsible for biochemical alterations and bacterial pattern in black truffles during their storage. Treatment at 1.5 kGy appeared to better preserve the characteristics of the fresh product. In 2.0 kGy-samples, the protein profile was characterised by a 20 kDa-polypeptide, which could be considered as an useful marker of the irradiation treatment and of the storage time of the product. MALDI-TOF mass spectrometry analysis did not permit a correct identification from tryptic peptides in databases, although the nano-ES/MS/MS analyses performed on the 10 kDa tryptic digest peptides showed an amino acidic sequence entirely contained in a protein of filamentous fungus Neurospora crassa.     

Controlled filling and external cleaning of multi-wall carbon nanotubes using a wet chemical method

A controlled, material-independent and adaptable cold wet chemical procedure is described. It allows organic and inorganic compounds to be confined inside multi-wall carbon nanotubes. The procedure mainly consists of a lyophilization process to fill multi-wall carbon nanotubes (MWCNTs), and a washing method to clean their outer surface without removing the encapsulated material. The technique was tested by synthesizing CdS crystals inside the nanotubes. Morphological and structural studies of the CdS crystals demonstrated a complete control of the synthesis process, and the possibility of maximizing the crystal size and the filling efficiency that approached 70% of open-ended nanotubes.     

Chemical and Structural Properties of Nickel Hydroxide Xerogels Obtained by the Sol-Gel Procedure in the Presence of Acetic Acid

The sol-gel route to glasses and ceramics has attracted an increasing amount of scientific and technological interest recently. In this process, sols with different concentrations are used as precursors for xerogels and to produce materials that consist of fine oxide particles. In the present work, nickel hydroxide gels have been obtained via the hydrolysis of a molecular precursor in the presence of acetic acid. The chemical aspects of the material transformation have been studied by using Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) for different acetic acid contents and several heat-treatment temperatures. The carboxylic acid acts as a ligand at a molecular level in the precursor, therefore modifying the entire hydrolysis and condensation process. Small-angle X-ray scattering (SAXS) studies and density measurements have been performed for the structural characterization of the xerogels. A denser, final oxide material is obtained when a higher acetic acid concentration is used. The porosity of the dry gels coarsens when they are heat-treated up to a temperature of ∼400°C and its density decreases. The material that has been heat-treated up to a temperature of 800°C densifies and exhibits a finer porosity. The chemical properties at a molecular level satisfactorily explain and are well correlated with the structural characteristics of the studied material.     

Lithiated short side chain perfluorinated sulfonic ionomeric membranes: Water content and conductivity

In view of possible applications as single-ion electrolyte for lithium batteries, some aspects of the lithium form of Hyflon Ion ionomer, a sulfonic short side chain (SSC) electrolyte, have been investigated. The synthesis of the ionomer and the successive membrane preparation is reported. An appropriate methodology for the direct salification of the ionomeric membrane from the SO₂F form to lithium salt, using lithium hydroxide in absence of organic solvent has been found. Utilizing these SSC lithium ionomer membranes and though a particular methodology for the dehydration of the lithium ion membrane in non-aqueous media, it has been possible to achieve an ionic conductivity of 10⁻³ S cm⁻¹ at room temperature [W. Navarrini, S. Panero, B. Scrosati, A. Sanguineti, European Patent 1,403,958 A1 (2003)]. Surprisingly it was observed that the membrane ionic conductivity depends on the dehydration methodologies adopted.     

Modeling of gas transport through a tubular solid oxide fuel cell and the porous anode layer

A design model is a necessary tool to understand the gas transport phenomena that occurs in a tubular solid oxide fuel cell (SOFC). This paper describes a computational model, which studies the gas flow through an anode-supported tubular SOFC and the subsequent diffusion of gas through its porous anode. The model is a numerical solution for the gas flow through a plug flow reactor with a diffusion layer, which includes the activation, ohmic, and concentration polarizations. Gas diffusion is modeled using the dusty-gas equations which include Knudsen diffusion. Mercury intrusion porosimetry (MIP) is used to experimentally determine micro-structural parameters such as porosity, tortuosity and effective diffusion coefficients, which are used in the diffusion equations for the porous anode layer. It was found that diffusion in the anode plays a key role in the performance of a tubular SOFC. The concentration gradient of hydrogen and water results in a lower concentration of hydrogen and a higher concentration of water at the reactive triple phase boundary (TPB) than in the fuel stream which both lead to a lower cell voltage. The gas diffusion determines the limiting current density of the cell where a higher concentration drop of hydrogen results in a lower limiting current density. The model validates well with experimental data and is used to improve micro-tubular solid oxide fuel cell designs.     

Increase of trans-resveratrol in typical Sicilian wine using β-Glucosidase from various sources

β-Glucosidase (EC 3.2.1.21) (β-G) from different sources were tested to increase the trans-resveratrol in some Sicilian wines by hydrolysing resveratrol glucoside. β-G from Aspergillus niger mould was tested as a crude and purified enzyme, and compared with the same enzyme from Saccharomyces cerevisiae yeast. Specific purification served to eliminate collateral enzyme activities so that β-G could be used simply and economically. Aspergillus niger β-G produced trans-resveratrol increases of up to 75%, with no change in physico-chemical properties and bouquet, and an increase in health and nutritional properties. S. cerevisiae β-G raised free-terpenol levels, but impaired wine colour due to anthocyanase activity.     

Ultraviolet curable epoxy acrylic resins — network flexibilization in the presence of reactive diluents

Different reactive diluents suitable for inducing network flexibilization of a typical ultraviolet curable epoxy resin based on bisphenol-A-diglycidyl-ether-diacrylate (BGEDA) were investigated. Firstly the influence of some monoacrylic reactive diluents, e.g. 2-ethylhexyl-acrylate (EHA) and 4-hydrocybutil-acrylate (HBA) and of a bis-acrylic diluent, polyethylene-glycol-diacrylate (PEGDA) was examined. Subsequently a systematic study was carried out on the properties of coatings resulting from mixtures of BGEDA and a poly(diethylene-glycol-carbonate) diacrylate (PGCDA) as reactive diluent. The main mechanical, dynamic-mechanical and technological properties of both free films and films coated on steel sheets, were evaluated. Interesting network flexibilization properties were observed when PGCDA was used as reactive diluent of BGEDA. The formulations investigated allowed us to obtain a broad range of flexibility for the resulting ultraviolet cured resins and to correlate the coating flexibility with other fundamental properties such asT _g, elastic modulus, abrasion resistance, hardness, adhesion, impact resistance, accelerated ageing and resistance to chemicals.