Site-Specific Ubiquitination of Tau Amyloids Promoted by the E3 Ligase CHIP

Post-translational modifications of Tau are emerging as key players in determining the onset and progression of different tauopathies such as Alzheimer's disease, and are recognized to mediate the structural diversity of the disease-specific Tau amyloids. Here we show that the E3 ligase CHIP catalyzes the site-specific ubiquitination of Tau filaments both in vitro and in cellular models, proving that also Tau amyloid aggregates are direct substrate of PTMs. Transmission electron microscopy and mass spectrometry analysis on ubiquitin-modified Tau amyloids revealed that the conformation of the filaments restricts CHIP-mediated ubiquitination to specific positions of the repeat domain, while only minor alterations in the structure of the fibril core were inferred using seeding experiments in vitro and in a cell-based tauopathy model. Overexpression of CHIP significantly increased the ubiquitination of exogenous PHF, proving that the ligase can interact and modify Tau aggregates also in a complex cellular environment.     

Suitability of Different 13C Solid-state NMR Techniques in the Characterization of Humic Acids

Qualitative and quantitative analyses of humic acids (HAs) with five different ¹³C solid-state NMR techniques were assessed using HAs of various origins and locations. The NMR techniques compared are: (1) direct polarization/magic angle spinning (DP/MAS) at 13 kHz, (2) conventional cross polarization (CP)/MAS at 5 kHz, (3) ramp-CP/MAS at 8 kHz, (4) CP/total sideband suppression (TOSS) at 4.5 kHz, and (5) DP/MAS corrected by CP/spin-lattice relaxation with TOSS. The spectra from the five techniques were first compared qualitatively. Then, each spectrum was divided into eight regions for quantitative evaluation. DP/MAS spectra were used as quantitative references. Ramp-CP/MAS and CP/TOSS spectra gave consistently better results than those of the conventional CP/MAS spectra at a ¹³C frequency of 75 MHz, which were incorrect due to spinning sidebands. CP/MAS at low magnetic fields (22.6 and 50.6 MHz ¹³C frequency) indicated improved integration results but lower resolution. Correction factors calculated by comparison with DP/MAS will be useful to convert the non-quantitative peak areas in the CP/TOSS and ramp-CP/MAS spectra into more quantitative results.     

Ni-guanidine@MCM-41 NPs: a new catalyst for the synthesis of 4,4ʹ-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ols) and symmetric di-aryl sulfides

In this work, the surface of mesoporous MCM-41 was modified with guanidine, and then, Nickel particles have become immobilized on its surface (Ni-guanidine@MCM-41NPs). This heterogeneous catalyst has been identified by various techniques including: low-angle X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, inductively coupled plasma, thermal gravimetric analysis and N₂ adsorption–desorption measurement isotherms, and its catalytic application was studied in the synthesis of 4,4ʹ-(arylmethylene)-bis-(3-methyl-1-phenyl-1H-pyrazol-5-ol) derivatives and symmetric di-aryl sulfides. The prepared organometallic complex could be isolated, post-reaction, by simple filtration for several consecutive cycles without a notable change in its catalytic activity.

     

Supramolecular Peptide/Polymer Hybrid Hydrogels for Biomedical Applications

Peptides and polymers are the “elite” building blocks in hydrogel fabrication where the typical approach consists of coupling specific peptide sequences (cell adhesive and/or enzymatically cleavable) to polymer chains aiming to obtain controlled cell responses (adhesion, migration, differentiation). However, the use of polymers and peptides as structural components for fabricating supramolecular hydrogels is less well established. Here, the literature on the design of peptide/polymer systems for self‐assembly into hybrid hydrogels, as either peptide‐polymer conjugates or combining both components individually, is reviewed. The properties (stiffness, mesh structure, responsiveness, and biocompatibility) of the hydrogels are then discussed from the viewpoint of their potential biomedical applications.     

Pt–NiO–Al2O3/G derived from graphene-supported layered double hydroxide as efficient catalyst for p-nitrophenol reduction

Research on Chemical Intermediates - The present work reports the synthesis of a Pt-modified NiO–Al2O3 nanocomposite derived from graphene-supported layered double hydroxide (Pt–NiO/G)...     

Comparison of the Effect of an Organoclay,Triphenylphosphate, and a Mixture of Both on the Degradation and Combustion Behaviour of PC/ABS Blends

Summary: Polycarbonate Acrylonitrile-Butadiene-Styrene blends (PC/ABS) with flame retardants Triphenyl Phosphate (TPP), nanoclay and their mixtures were prepared in a twin- screw extruder. The morphological properties were characterized by X-ray diffractometry (XRD) which showed the intercalated structure of nanoclay in the matrix. Thermal stability of the samples was studied using Thermogravimetric Analysis (TGA), and the degradation kinetic parameters were determined using various methods including Kissinger, Flynn-Wall-Ozawa and Coats-Redfern methods. It was found that the sample containing both TPP and nanoclay has the highest activation energy. The activation energy order of PC/ABS blends with different flame retardant packages, obtained by Kissinger method agrees well with that obtained by Coats-Redfern. Cone calorimetry and limited oxygen index (LOI)/underwriters laboratory 94 (UL94) methods were used to investigate the fire behaviour and flammability of materials. The reduced mass loss rate (MLR), peak heat release rate (PHRR) and enhanced LOI of the composite containing mixture system confirmed a synergistic effect of TPP and nanoclay.     

Compositions of the seed oil of the Borago officinalis from Iran

In order to investigate the composition of borage (Borago officinalis L.) seed oil, this research was performed under the field conditions at Shahriyar and Garmsar zones, Iran during the 2012 planting year. The oil yield of borage was 31.46% and 33.7% at Shahriyar and Garmsar zone, respectively, and nine and eight fatty acids were identified in the seed oil of borage at Shahriyar and Garmsar, respectively – palmitic, linoleic, stearic and γ-linolenic acids were dominant in the seed oil of borage from both zones. Unsaturated fatty acid content was more than the saturated fatty acids in both zones. The ratio of linoleic acid and α-linolenic acid in the borage cultivated at Shahriyar and Garmsar zones was 2.13 and 2.29. The fatty acid profile of Garmsar borage, oleic and oleic/linoleic acid ratio, increased. Locations with different ecological conditions resulted in changes in both seed oil content and fatty acid profile of borage.     

Thermal decomposition of haemin chloride and related derivatives

Differential scanning calorimetry was used to study the thermal decomposition of haemin chloride and its derivatives protoporphyrin and bilirubin. Under a static air atmosphere, exothermic transitions due to degradation were recorded for the two former compounds, whereas bilirubin exhibited a higher thermal stability. Thermogravimetry indicated that the weight loss process with these compounds under an oxidizing atmosphere of oxygen was different from that under an inert atmosphere of nitrogen. Infrared spectra of these compounds were also recorded and are briefly discussed.     

Solution equilibria and stability of the complexes of pyridinecarboxylic acids: Complexation reaction of mercury(II) with 2-hydroxynicotinic acid

Summary The solution equilibria of 2-hydroxynicotinic acid (hyna) complexes with mercury(II) have been studied spectrophotometrically in 50% (v/v) ethanol at 20°C and an ionic strength of 0.1mol dm^–3 (NaClO₄). Three mercuric complexes are formed in solution in dependence on the acidity of the medium. The basic characteristics of the different complexes are determined and the analytical aspects of the complexation reaction are demonstrated. A critical investigation has also been presented of the solution equilibria and stability of the mixed complex of mercury(II) withhyna and thiosalicylic acid (tsa). The various complex transitions leading to the formation of the 1 : 1 : 1 Hg(tsa)(hyna) ternary complex in solution are investigated. The non-charged mono-ligand complex Hg(hyna) is used for UV-spectrophotometric determination of mercury atpH 4.5–5 (_max=325nm, =0.8·10⁴lmol^–1cm^–1). The system obeyed Beer's law up to 36.1 µg ml^–1 of Hg(II). The optimum concentration range (Ringbom) is between 6 and 28.5µg ml^–1. Interference caused by a number of ions was masked by the addition of fluoride ions.

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Lösungsgleichgewichte und Stabilitätskonstanten von Komplexen der Pyridincarbonsäuren: Die Komplexierungsreaktion von Quecksilber(II) mit 2-Hydroxynikotinsäure

Zusammenfassung Die Lösungsgleichgewichte von 2-Hydroxynikotinsäure (hyna) mit Hg(II) wurde spektrophotometrisch in 50% (v/v) Ethanol bei 20°C und einer Ionenstärke von 0.1 mol dm^–3 (NaClO₄) untersucht. In Abhängigkeit von der Acidität des Mediums werden drei Quecksilberkomplexe gebildet. Die grundlegenden Charakteristika der Komplexe wurden bestimmt und die analytischen Aspekte aufgezeigt. Die gemischten Komplexe von Hg(II) mithyna und Thiosalicylsäure (tsa), insbesondere die verschiedenen Komplexübergänge zum ternären 1 : 1 : 1 Hg(tsa)(hyna)-Komplex, wurden ebenfalls untersucht. Der ungeladene Monoligandenkomplex Hg(hyna) kann beipH 4.5–5 zur UV-spektroskopischen Quecksilberbestimmung eingesetzt werden (_max=325nm, =0.8·10⁴lmol^–1cm^–1). Das System gehorcht bis zu einer Hg(II)-Konzentration von 36.1µgml^–1 dem Beerschen Gesetz. Der optimale Konzentrationsbereich (Ringbom) liegt zwischen 6 und 28.5µgml^–1. Interferenzen mit einer Reihe anderer Ionen konnten durch Maskierung mit Fluoridionen umgangen werden.

     

Dimethyltin(IV) complexes with zwitterionic buffers (Mes and Mops)

Equilibrium studies in aqueous solution are reported for dimethyltin(IV) complexes of the zwitterionic buffers “Good’s buffer”, such as Mes and Mops (L). Stoichiometry and stability constants for the complexes formed were determined at different temperature and ionic strength 0.1 M NaNO₃. The results showed the best fit of the titration curves were obtained when complexes ML, MLH₋₁, MLH₋₂, and MLH₋₃ were expected beside the hydrolysis products of the dimethyltin(IV) cation. The thermodynamic parameters ΔH°, ΔS° and ΔG° calculated from the temperature dependence of the formation constant of the dimethyltin(IV)-Mes complex was investigated. The effect of dioxane as a solvent on the formation constants of dimethyltin(IV)-Mes complex was discussed. The concentration distribution of the various complex species was evaluated as a function of pH. The bonding sites of the dimethyltin(IV) complexes in solid state with Mes and Mops were characterized by means of elemental analyses and FTIR. The NMR (¹H, ¹³C) spectra of the DMT-Mes complex exhibits the strongly distorted octahedron geometry around tin atom. Also, thermal analyses (TGA and DTA) were discussed. Thermodynamic parameters such as activation energy (E_a), pre-exponential factor (A), entropy of activation (ΔS^∗) and free energy of activation (ΔG^∗) have been calculated for each step, employing integral method Coats and Redfern. The reaction enthalpy (ΔH) is obtained from DTA data.