Late-Stage Hydrocarbon Conjugation and Cyclisation in Synthetic Peptides and Proteins

The conventional S-alkylation of cysteine relies upon using activated electrophiles. Here we demonstrate high-yielding and selective S-alkylation and S-lipidation of cysteines in unprotected synthetic peptides and proteins by using weak electrophiles and a Zn²⁺ promoter. Linear or branched iodoalkanes can S-alkylate cysteine in an unprotected 38-residue Myc peptide fragment and in a 91-residue miniprotein Omomyc, thus highlighting selective late-stage synthetic modifications. Metal-assisted cysteine alkylation is also effective for incorporating dehydroalanine into unprotected peptides and for peptide cyclisation via aliphatic thioether crosslinks, including customising macrocycles to stabilise helical peptides for enhanced uptake and delivery to proteins inside cells. Chemoselective and efficient late-stage Zn²⁺-promoted cysteine alkylation in unprotected peptides and proteins promises many useful applications.     

[2.2]Paracyclophane-Based TCN-201 Analogs as GluN2A-Selective NMDA Receptor Antagonists

Recent studies have shown the involvement of GluN2A subunit-containing NMDA receptors in various neurological and pathological disorders. In the X-ray crystal structure, TCN-201 ( 1 ) and analogous pyrazine derivatives 2 and 3 adopt a U-shape (hairpin) conformation within the binding site formed by the ligand binding domains of the GluN1 and GluN2A subunits. In order to mimic the resulting π/π-interactions of two aromatic rings in the binding site, a [2.2]paracyclophane system was designed to lock these aromatic rings in a parallel orientation. Acylation of [2.2]paracyclophane ( 5 ) with oxalyl chloride and chloroacetyl chloride and subsequent transformations led to the oxalamide 7 , triazole 10 and benzamides 12 . The GluN2A inhibitory activities of the paracyclophane derivatives were tested with two-electrode voltage clamp electrophysiology using Xenopus laevis oocytes expressing selectively functional NMDA receptors with GluN2A subunit. The o-iodobenzamide 12 b with the highest similarity to TCN-201 showed the highest GuN2A inhibitory activity of this series of compounds. At a concentration of 10 μM, 12 b reached 36 % of the inhibitory activity of TCN-201 ( 1 ). This result indicates that the [2.2]paracyclophane system is well accepted by the TCN-201 binding site.     

Response of Corn Seedlings (Zea mays L.) to Different Concentrations of Nitrogen in Absence and Presence of Silicon

Silicon - Corn plants are highly demanding of nitrogen and the application of silicon has been studied because it minimizes stress from different natures, and for the better utilization of some...     

Microwave hybrid fast sintering of red clay ceramics

This work aimed to examine the performance of the hybrid sintering of clay ceramic in a microwave furnace, compared to the sintering process in a conventional furnace. The raw materials were subjected to X-ray fluorescence, loss on ignition (LOI), X-ray diffraction, particle size distribution, real specific mass, and thermogravimetric analyses. The red clay ceramic mass was prepared, extruded, pre-sintered in a conventional furnace at 600°C/60 min, and sintered at temperatures between 700 °C and 1100 °C. The sintering conventional (resistive oven) was carried out for 60 min with a heating rate of 10°C/min. In the microwave furnace, the sintering times were 5, 10, and 15 min, with a heating rate of 50°C/min, with a sintering chamber coated with silicon carbide (susceptor). The sintered specimens were characterized according to linear shrinkage, water absorption, apparent porosity, apparent specific mass, X-ray diffraction, Raman spectroscopy analysis, spectroscopy analysis in the ultraviolet and visible regions, microhardness, and scanning electron microscopy. The results showed that microwave sintering promoted an increase in the microhardness and apparent specific mass, and reduction in water absorption and apparent porosity values, due to greater densification in the microstructure. The best results occurred for specimens sintered at 1100°C.     

Effect of height on the corrosion of steel and galvanized steel in nontropical coastal marine environments

In this study, the behavior of carbon steel and galvanized steel in nontropical coastal marine environments was evaluated. Evaluation was carried out with specimens with dimensions of 10 cm × 10 cm × 0.3 cm. These specimens were exposed to four testing stations (Iquique, Mejillones, Los Vilos, and San Vicente), where racks were installed both at ground level (ground), as well as in the upper zone of electrical transmission towers (tower). In each station, 24 specimens of A36 carbon steel and galvanized steel were placed (12 each). The corrosivity of the environment was measured using the ISO 9223, 9225, and 9226 standards. The specimens were evaluated on-site, monthly, through visual inspection and photographic record. Once withdrawn, the corrosion rate was determined and the corrosion products were analyzed through Raman and Fourier-transform infrared. The results show that, in all cases, the corrosion rate is greater in the tower than on the ground. However, even though the Los Vilos station is located farther from the sea (3,500 vs. ≈500 m), the corrosion rate of steel in the tower is the highest. This is caused by the generation of HCl from the transformation of lepidocrocite into goethite, in the presence of low chloride content, which acidifies the steel/corrosion product interface. In the case of galvanized steel, the corrosion rate is a function of the chloride content in the atmosphere, obtaining an excellent correlation between both parameters.     

Combined application of electrolysed water and ultrasound to improve the sanitation of knives in the meat industry

This study investigated the effect of the combination of basic electrolysed water (BEW) and slightly acid electrolysed water (SAEW) with ultrasound (US) for cleaning and sanitation of the knives used in slaughtering processes. The knives were sonicated in a US bath using two modes of operation (normal and sweep) in two steps: (i) 5 min with BEW and (ii) 10 min with SAEW at 35 °C. The microbiological counts and the possible changes in the physical structure of the knives were evaluated. The association BEW + SAEW + US, in the sweep mode, provided lower mesophilic, enterobacterial, Staphylococcus aureus and yeast counts when compared to the values recommended by the international legislation. In addition, these conditions removed all organic residues from the knife blades and promoted the highest migration rate of the residues to the US water bath (12.35 mg/L·min), without modifications in the knife blades. Thus, cleaning and sanitation of knives was feasible with the association of BEW + SAEW + US, which could be a useful alternative for the meat industry.     

Studies on spinel cobaltites,MCo2O4 (M = Mn,Zn, Fe,Ni and Co) and their functional properties

Optimization of electrodes for charge storage with appropriate processing conditions places significant challenges in the developments for high performance charge storage devices. In this article, metal cobaltite spinels of formula MCo₂O₄ (where M = Mn, Zn, Fe, Ni and Co) are synthesized by oxalate decomposition method followed by calcination at three typical temperatures, viz. 350, 550, and 750 °C and examined their performance variation when used as anodes in lithium ion batteries. Phase and structure of the materials are studied by powder x-ray diffraction (XRD) technique. Single phase MnCo2O4,ZnCo2O4 and Co3O4 are obtained for all different temperatures 350 °C, 550 °C and 750 °C; whereas FeCo₂O₄ and NiCo₂O₄ contained their constituent binary phases even after repeated calcination. Morphologies of the materials are studied via scanning electron microscopy (SEM): needle-shaped particles of MnCo₂O₄ and ZnCo₂O₄, submicron sized particles of FeCo₂O₄ and agglomerated submicron particle of NiCo₂O₄ are observed. Galvanostatic cycling has been conducted in the voltage range 0.005–3.0 V vs. Li at a current density of 60 mA g^?1 up to 50 cycles to study their Li storage capabilities. Highest observed charge capacities are: MnCo₂O₄ – 365 mA h g^?1 (750 °C); ZnCo₂O₄ – 516 mA h g^?1 (550 °C); FeCo₂O₄ – 480 mA h g^?1 (550 °C); NiCo₂O₄ – 384 mA h g^?1 (750 °C); and Co₃O₄ – 675 mA h g^?1 (350 °C). The Co₃O₄ showed the highest reversible capacity of 675 mA h g^?1; the NiO present in NiCo₂O₄ acts as a buffer layer that results in improved cycling stability; the ZnCo₂O₄ with long needle-like shows good cycling stability.