Platinum(VI) dihydroxo tetramesitylporphyrin; characterization and chemical reactivity

Tetramesitylporphyrin platinum(VI) dihydroxo complex, TMPPt(OH)₂ · 2 benzoate was synthesized by addition of two equivalent of meta-chloroperbenzoic acid molecules to the tetramesitylporphyrin platinum(II). This complex was characterized by X-ray diffraction and spectroscopic methods, and is capable to convert two molecules of triphenylphosphine to triphenylphosphine oxide.     

The isoxazolidines: the effects of steric factor and hydrophobic chain length on the corrosion inhibition of mild steel in acidic medium

Several new isoxazolidines having varying degree of steric environment and hydrophobic chain length, prepared efficiently using single-step nitrone cycloaddition reactions, are tested for corrosion inhibition of mild steel in 1 M and 5 M HCl at 50-70 °C range by gravimetric and electrochemical methods. All compounds have shown very good corrosion inhibition efficiency (IE%) in acidic solution. Steric crowding around the nitrogen centres and hydrophobic chain lengths as well as increase in temperature (in the presence of the inhibitor in the higher concentration range 100-400 ppm) are found to increase the inhibition efficiency of the isoxazolidines. Thermodynamic parameters (ΔG°_ads, ΔH°_ads, ΔS°_ads) for the adsorption process and kinetic parameters for the metal dissolution (or hydrogen evolution) reaction in the presence of one of the isoxazolidines were determined. Experimental results agree with the Temkin adsorption isotherm. The inhibition of corrosion in 1 M HCl, influenced by both physi- and chemi-sorption, was found to be under mixed control, but predominantly under cathodic control.     

A Methionine Chemical Shift Based Order Parameter Characterizing Global Protein Dynamics

Coupling of side chain dynamics over long distances is an important component of allostery. Methionine side chains show the largest intrinsic flexibility among methyl-containing residues but the actual degree of conformational averaging depends on the proximity and mobility of neighboring residues. The ¹³C NMR chemical shifts of the methyl groups of methionine residues located at long distances in the same protein show a similar scaling with respect to the values predicted from the static X-ray structure by quantum methods. This results in a good linear correlation between calculated and observed chemical shifts. The slope is protein dependent and ranges from zero for the highly flexible calmodulin to 0.7 for the much more rigid calcineurin catalytic domain. The linear correlation is indicative of a similar level of side-chain conformational averaging over long distances, and the slope of the correlation line can be interpreted as an order parameter of the global side-chain flexibility.     

CaDHN3, a Pepper (Capsicum annuum L.) Dehydrin Gene Enhances the Tolerance against Salt and Drought Stresses by Reducing ROS Accumulation

Dehydrins (DHNs) play an important role in abiotic stress tolerance in a large number of plants, but very little is known about the function of DHNs in pepper plants. Here, we isolated a Y₁SK₂-type DHN gene “CaDHN3” from pepper. To authenticate the function of CaDHN3 in salt and drought stresses, it was overexpressed in Arabidopsis and silenced in pepper through virus-induced gene silencing (VIGS). Sub-cellular localization showed that CaDHN3 was located in the nucleus and cell membrane. It was found that CaDHN3-overexpressed (OE) in Arabidopsis plants showed salt and drought tolerance phenotypic characteristics, i.e., increased the initial rooting length and germination rate, enhanced chlorophyll content, lowered the relative electrolyte leakage (REL) and malondialdehyde (MDA) content than the wild-type (WT) plants. Moreover, a substantial increase in the activities of antioxidant enzymes; including the superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), ascorbate peroxidase (APX), and lower hydrogen peroxide (H₂O₂) contents and higher O₂^•− contents in the transgenic Arabidopsis plants. Silencing of CaDHN3 in pepper decreased the salt- and drought-stress tolerance, through a higher REL and MDA content, and there was more accumulation of reactive oxygen species (ROS) in the CaDHN3-silenced pepper plants than the control plants. Based on the yeast two-hybrid (Y2H) screening and Bimolecular Fluorescence Complementation (BiFC) results, we found that CaDHN3 interacts with CaHIRD11 protein in the plasma membrane. Correspondingly, the expressions of four osmotic-related genes were significantly up-regulated in the CaDHN3-overexpressed lines. In brief, our results manifested that CaDHN3 may play an important role in regulating the relative osmotic stress responses in plants through the ROS signaling pathway. The results of this study will provide a basis for further analyses of the function of DHN genes in pepper.     

Effect of Iron sulfate as electrolyte additive on plasma electrolytic oxidation of aluminum alloy

This study has been carried out to investigate the incorporation of Iron(II) sulfate as an additive of electrolyte on formed AA1010 aluminum alloy, using plasma electrolytic oxidation method in silicate-based electrolytes containing Iron(II) sulfate. In order to fabricate nanocomposite coating, silicon nitride nanopowder was added to electrolyte. The effects of iron(II) sulfate additive on the voltage-time trend, microstructure, compositions, wear, and corrosion resistances of PEO coatings were investigated. In addition, current density and concentration of additive were studied as parameters that were effective on coating. Results showed that although FeSO₄ enters to the coating structure, but it does not develop a new phase. The corrosion and wear behavior of coated samples with FeSO₄ indicate an improvement as compared to those without additive.     

The Ablation and Oxidation Behaviors of SiC Coatings on Graphite Prepared by Slurry Sintering and Pack Cementation

SiC coatings were generated on graphite using slurry sintering (SS) and pack cementation (PC). The samples’ ablation features were assessed by an oxyacetylene torch. The rates of mass ablation of the PC–SiC and SS–SiC coatings were approximated 2.17?×?10^?3 and 9.52?×?10^?3 g s^?1, respectively, decreased by 84.1 and 29.6% compared to the uncoated samples. It was mainly attributed to the formation of a SiO₂ layer on the surface. The continuous SiO₂ molten film formed via the PC–SiC oxidation generates a sealing mechanism which can be an obstacle against the oxygen diffusion and hinder more ablation. This is while discontinuous SiO₂ film formed from the thin SS–SiC cannot protect the graphite effectively. The non-isothermal oxidation test shows that without the SiC coating, the sample weight is lost largely from 25 to 1500 °C, and its weight loss was 2.2% after the TGA. However, after coating, the samples possessed excellent oxidation protection and weight losses of SS–SiC and PC–SiC coatings are down to 1.3 and 0.6%, respectively. The more oxidation of the graphite substrate occurred due to the formation of macrocracks in the coating during the TGA and also the formation of holes on SiO₂ glass layer owing to release of CO or CO₂.     

通过双级固溶热处理制备新型高强Al−10.5Si−3.4Cu−0.2Mg合金

通过析出硬化提高Al?Si?Cu合金的力学性能.这些合金对时效硬化的反应非常缓慢.为了解决这一问题,在Al?10.5Si?3.4Cu合金中分别加入0.2％、0.4％和0.7％(质量分数)的镁.该新型合金在固溶处理阶段经过两种不同的析出硬化过程.结果表明,添加不同含量的镁可加速该合金对时效处理的响应,提高其硬度和强度.双...     

Glassy carbon electrodes modified with a film of nanodiamond-graphite/chitosan: Application to the highly sensitive electrochemical determination of Azathioprine

A novel modified glassy carbon electrode with a film of nanodiamond-graphite/chitosan is constructed and used for the sensitive voltammetric determination of azathioprine (Aza). The surface morphology and thickness of the film modifier are characterized using atomic force microscopy. The electrochemical response characteristics of the electrode toward Aza are investigated by means of cyclic voltammetry. The modified electrode showed an efficient catalytic role for the electrochemical reduction of Aza, leading to a remarkable decrease in reduction overpotential and enhancement of the kinetics of the electrode reaction with a significant increase of peak current. The effects of experimental variables, such as the deposited amount of modifier suspension, the pH of the supporting electrolyte, the accumulation potential and time were investigated. Under optimal conditions, the modified electrode showed a wide linear response to the concentration of Aza in the range of 0.2-100 μM with a detection limit of 65 nM. The prepared modified electrode showed several advantages: simple preparation method, high stability and uniformity in the composite film, high sensitivity, excellent catalytic activity in physiological conditions and good reproducibility. The modified electrode can be successfully applied to the accurate determination of trace amounts of Aza in pharmaceutical and clinical preparations.     

Experimental investigation on the effect of surface characterization of electrodes on the gas bubble dynamics in electrolyte flow and performance of FLA batteries by using PIV

In the flooded lead_acid batteries (FLAB), gas bubbles are initially formed on the surface of the electrodes, which are produced by electrochemical reactions, and then released into the electrolyte. In the present investigation, the effect of surface characterization of electrodes of FLAB on the gas bubble dynamic parameters in the electrolyte flow at different charging/discharging rates (C-rates) are studied utilizing particle image velocimetry (PIV) method. The results show that the capacity of FLAB have a linear behav-ior due to changes in each of the two parameters of the surface characterization of electrodes and the C-rate. At all State of charges (SOCs) of FLAB cells in different tests, increasing average roughness (Ra) and average wavelength of the roughness (ka) in the electrode surfaces, results in an increase in average bub-ble diameter and bubble rising velocity. Nevertheless, a sharp decrease in the void fraction of bubbles within the electrolyte was observed due to the increment in ka and Ra. Also, the effect of the rising move-ment of gas bubbles within the electrolyte on the average electrolyte velocity pattern in the gap between the electrodes by changing the surface characterization of electrodes are investigated in detail.     

Effect of hexagonal structure nanoparticles on the morphological performance of the ceramic scaffold using analytical oscillation response

Porous bony scaffolds are utilized to manage the growth and migration of cells from adjacent tissues to a defective position. In the current investigation, the effect of titanium oxide (TiO₂) nanoparticles on mechanical and physical properties of porous bony implants made of polymeric polycaprolactone (PCL) is studied. The bio-nanocomposite scaffolds are prepared with composition of nanocrystalline hydroxyapatite (HA) and TiO₂ powder using the freeze-drying technique for different weight fractions of TiO₂ (0 wt%, 5 wt%, 10 wt%, and 15 wt%). In order to identify the microstructure and morphology of the fabricated porous bio-nanocomposites, the X-ray diffraction (XRD), atomic force microscope (AFM) and scanning electron microscopy (SEM) are employed. Also, the biocompatibility and biodegradability of the manufactured scaffolds are examined by placing them in a simulated body fluid (SBF) for 21 days, their weight and pH changes are measured. The rate of degradation of the PCL-HA scaffold can be controlled by varying the percentage of its constituent components. Due to an increasing growth and activity of bone cells and the apatite formation on the free surface of the fabricated bio-nanocomposite implants as well as their reasonable mechanical properties, they have the potential to be used as a bone substitute. Additionally, with the aid of the experimentally extracted mechanical properties of the scaffolds, the vibrational characteristics of a beam-type implant made of the proposed porous bio-nanocomposites are explored. The results obtained from SEM image indicate that the scaffolds produced by the employed method have high total porosity (70%–85%) and effective porosity. The pore size is obtained between 60 and 200 μm, which is desirable for the growth and propagation of bone cells. Also, it is revealed that the addition of TiO₂ nanoparticles leads to reduce the rate of dissolution of the fabricated bio-nanocomposite scaffolds.