Computational explorations to gain insight into the structural features of TNF-α receptor I inhibitors

TNF-α is a crucial cytokine in the process of inflammatory diseases. The adverse effect of TNF-α is mostly mediated by interaction of TNF-α with TNF-α receptor type I (TNFR1); therefore, discovery of molecules which can bind to TNFR1 preventing TNF-α-receptor complex formation would be of great interest. In the current study, using GRID/GOLPE program, a 3D-QSAR study was conducted on a series of synthetic TNFR1 binders, which resulted in a 3D-QSAR model with appropriate power of predictivity in internal (r²?=?0.94 and q²_LOO?=?0.74) and external (r²?=?0.66 and SDEP?=?0.42) validations. The structural features of TNFR1 inhibitors essential for exerting activity were explored by analyzing the contour maps of the 3D-QSAR model showing that steric interactions and hydrogen bonds are responsible for exerting TNFR1 inhibitory activity. To propose potential chemical entities for TNFR1 inhibition, PubChem database was searched and the selected compounds were virtually tested for anti-TNFR1 activity using the generated model, resulting in two potential anti-TNFR1 compounds. Finally, the possible interactions of the compounds with TNFR1 were investigated using docking studies. The findings in the current work can pave the way for designing more potent anti-TNFR1 inhibitors.     

Electrocatalytic oxidation of salicylic acid at a carbon paste electrode impregnated with cerium-doped zirconium oxide nanoparticles as a new sensing approach for salicylic acid determination

Cerium-doped zirconium oxide (Ce/ZrO₂) was introduced as a highly efficient electrocatalyst for electrooxidation of salicylic acid (SA). The electrocatalyst material was synthesized via co-precipitation of cerium and zirconium ions, and then the resulting solid was heat-treated at high temperature to create crystallized cerium-doped zirconium oxide nanoparticles. The obtained material was characterized by scanning electron microscopy and X-ray diffraction methods. The Ce/ZrO₂-modified carbon paste electrode (Ce/ZrO₂-CPE) exhibited a distinct oxidative peak for SA, whereas no signal was observed for SA at unmodified carbon paste electrode at the same experimental conditions. Cyclic voltammetry and electrochemical impedance spectroscopy were applied to investigate the electrocatalytic performance of the electrode and SA electrooxidation mechanism. Square wave voltammetry was used to capture the analytical signal of SA. The electrode composition was optimized to increase the SA signal. Using the optimized electrode, it became possible to determine SA in the concentration range of 5.0–1000.0 μM with detection limit of 1.1 μM (3S_b/m). The electrode showed very high sensitivity of 1013.5 μA mM^?1 cm^?2 which is remarkably better than the previously reported SA sensors. The proposed method was successfully applied for the determination of SA in human serum, milk, and pharmaceutical samples.     

Experimental determination of acetamiprid pesticide residue in three different types of pistachio by ion mobility spectrometry and using QuEChERS method in the different temperatures and in the presence of ammonia as dopant gas

In this project, Ion Mobility Spectrometer (IMS) instrument in the positive mode and with corona ionization source was utilized to determine the residue of acetamiprid pesticide in three different types of pistachio (Akbari, Fandoghi and Kalachuchi). The QuEChERS method, notable because of easy and quick preparation of sample and using lower amounts of organic solvents with harmful environmental effects and high costs, was used in this study. Many experiments were performed in the different temperatures in order to obtain optimum temperature for cell and injection. Ammonia and acetone were considered as dopant substances and it turned out that the ammonia gas, contrary to acetone, increased significantly the signal intensity and sensitivity and avoided the overlap of desired peaks. The LOD of device for acetamiprid pesticide was estimated to be 0.5 μg g^?1 and the LOQ of instrument was obtained as 1.66 μg g^?1. The calibration curve was in the dynamic range between 0.5–11.5 μg g^?1 and the Correlation Coefficient was 0.998. Also, the ion mobility and the reduced ion mobility were calculated for acetamiprid ion. After analysis of five samples with IMS instrument, the acetamiprid residue was determined and it turned out that it was under allowed limit in all three types of pistachio. In addition, the amount of acetamiprid residue was higher for Akbari type relative to Fandoghi and Kalachuchi ones. The reason for this observation is the higher vulnerability of Akbari trees to insects and pests and this in turn causes more pesticide to be consumed.     

Crystal Structure and Hirshfeld Surface Analysis of Bis(3-thienoyl) Disulfide

The spectroscopic characterization (¹H, ¹³C{¹H} NMR, UV–Vis) and single-crystal X-ray diffraction (scXRD) analysis accomplished by inspection of the Hirshfeld surface of bis(3-thienoyl) disulfide (1) is described. The title compound 1 crystallizes in the monoclinic space group P2₁/n. The unit cell parameters are a?=?7.9959(3) Å, b?=?6.4348(3) Å, c?=?22.4924(9) Å, β?=?100.108(4)°, V?=?1139.32(8) ų, Z?=?4, R_gt(F)?=?0.0278, wR_ref(F²)?=?0.0667. The packing of 1 is dominated by S?O and S?S interactions, giving a 2D layer structure parallel to (101). The X‐ray crystal structure analysis revealed the packing of 1 is dominated by S?O and S?S interactions, giving a 2D layer structure parallel to (101). The intermolecular interactions in 1 were analyzed using the Hirshfeld surface method including 2D fingerprint plots and enrichment ratios (E), which shows that the most favored intermolecular contacts are the O?H and C?S indicated by E values above 1.30. The interaction energies between molecular pairs revealed the importance of the weak O?H and C?S interactions in stabilizing the molecular structure of 1.

Graphic Abstract

Single crystal X-ray structure analysis, DFT calculations and Hirshfeld surface analysis to identify intermolecular interactions within the solid state structure of bis(3-thienoyl) disulfide (1).

     

Stereoselective synthesis of helical dihydrodipyrrolophenanthroline and hindrance hexa tert‐butyl carboxylatodipyrrolophenanthroline from reaction between 1,10‐phenanthroline and dialkyl acetylenedicarboxylates

High hindrance Hexa tert‐butoxy carbonyl dipyrrolophenanthroline and helical dihydropyrrolophen‐anthroline compounds were prepared from reactions between di tert‐butyl acetylenedicarboxylate and 1,10‐phenanthroline in polar solvents media.     

Detection of acetone in the human breath as diabetes biomarker based on PPy/WO3 nanocomposite sensor by FFT continuous cyclic voltammetry method

This research represents a novel detection method of acetone level in the exhaled breath samples (RH=88 %) based on polypyrrole/tungsten oxide (PPy/WO₃) nanocomposite sensor. The PPy/WO₃ sensor was fabricated by the deposition of nanocomposite on/between interdigitated electrodes (IDEs) through electrospray coating and was then characterized by FE-SEM imaging. In this detection method, the coulometric signal of the sensor was calculated using Fast Fourier Continuous Cyclic Voltammetry (FFTCCV), where cyclic voltammetry (CV) was applied to the sensor in the defined potential rang and then charge changes of the sensor was obtained by integration of the current in all scanned potential ranges. FFTCCV method enhances the sensitivity of the sensor when exposed to the gas mixtures containing acetone. In addition to its fast coulometric response time (≤5 s) in the two linear ranges of 0.7–2.8 ppm and 2.8–28.2 ppm (R²=0.99), FFTCCV method provides the low detection limit of 70 ppb, and high sensitivity toward acetone at the optimum values of the parameters. The fabricated sensor showed great selectivity toward acetone when exposed to humid air and some exhaled gas like carbon dioxide, ammonia, methanol, ethanol and alkyl amines. The results were very satisfying as the sensor was capable to detect different acetone levels in human exhaled breath as non-invasive diagnosis of diabetes with a good correlation (R²≃0.9) to the routine blood sugar test taken by different commercial glucometers results.     

Indirect Determination of Trace Copper(II) by Adsorptive Stripping Voltammetry with Zincon at a Carbon Paste Electrode

Traces of copper(II) can be determined by adsorptive stripping voltammetry using 2‐carboxy‐2′‐hydroxy‐5′‐sulfoformazyl benzene (Zincon) as complex forming reagent. First in phosphate buffer pH 6.4, copper(II)‐Zincon complex was adsorbed on carbon paste electrode (CPE) with an accumulation potential of 0.6 V. Following this, adsorbed complex was oxidized and detected by differential pulse voltammetric (DPV) scan from 0.6 to 1.0 V. The effective parameters in sensor response were examined. The detection limit (DL) of copper(II) was 1.1 μg/L and relative standard deviations (RSDs) for 10 and 200 μg/L Cu(II) were 1.81 and 1.03%, respectively. The calibration curve was linear for 2–220 μg/L copper(II). The resulting CPE does not use mercury and therefore, has a positive environmental benefit. The method, which is reasonably sensitive and selective, has been successfully applied to the determination of trace amount of copper in water and human hair samples.     

Reaction parameters influence on the catalytic performance of copper-silica aerogel in the methanol steam reforming

Steam reforming of methanol was carried out on the copper-silica aerogel catalyst.The effects of reaction temperature,feed rate,water to methanol molar ratio and carrier gas flowrate on the H_2 production rate and CO selectivity were investigated.M ethanol conversion was increased considerably in the range of about 240-300,after which it increased at a slightly lower rate.The used feed flowrate,steam to methanol molar ratio and carrier gas flowwere 1.2-9.0 m L/h,1.2-5.0 and 20-80 m L/min,respectively.Reducing the feed flowrate increased the H_2 production rate.It was found that an increase in the water to methanol ratio and decreasing the carrier gas flowrate slightly increases the H2production rate.Increasing the water to methanol ratio causes the lowest temperature in which CO formation was observed to rise,so that for the ratio of 5.0 no CO formation was detected in temperatures lower than 375℃.In all conditions,by approaching the complete conversion,increasing the main product concentration,increasing the temperature and contact time,and decreasing the steam to methanol ratio,the CO selectivity was increased.These results suggested that CO was formed as a secondary product through reverse water-gas shift reaction and did not participate in the methanol steam reforming reaction mechanism.     

On the stability of a radical cubic functional equation in quasi-$${\beta}$$-spaces

In this paper, we introduce and solve the radical cubic functional equation

$$f\left({\sqrt[3]{x^{3} + y^{3}}}\right)= f(x) + f(y).$$

We also establish stability in quasi-\({\beta}\)-Banach spaces, and then the stability by using subadditive and subquadratic functions for the radical cubic functional equation in (\({\beta}\), p)-Banach spaces is given.

     

Ruthenium(II) complexes of azoimine and α-diimine ligands: synthesis,spectroscopic and electrochemical properties,crystal structures and DFT calculations

Five octahedral ruthenium(II) complexes with azoimine–quinoline (Azo) and α-diimine (L) ligands having the general formula [Ru^II(L)(Azo)Cl](PF₆) (1–5) {Azo: PhN=NC(COMe)=NC₉H₆N, L = 4,4′-dimethoxy-2,2′-bipyridine (dmeb) (1), 4,4′-di-tertbutyl-2,2′-bipyridine (dtb) (2), 1,10-phenanthroline (phen) (3), 5-chlorophenanthroline (Clphen) (4), or 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) (5)} were prepared by stepwise addition of the tridentate azoimine (H₂Azo) and α-diimine (L) pro-ligands to RuCl₃ in refluxing EtOH. The tridentate azoimine–quinoline ligands coordinate to ruthenium via the Azo-N′, N′-imine and N″-quinolone nitrogen atoms. The spectroscopic properties (IR, UV/Vis, ¹H, ¹³C and ¹⁹F NMR) and electrochemical behavior of complexes 1–5 and the X-ray crystal structures of complexes 2 and 3 are presented. The coordination of Ru(II) to these strong π-acceptor ligands (Azo and L) results in a large anodic shift for the Ru(III/II) couples of 1.63–1.72 V versus NHE. The electronic spectra in MeCN and IR spectra in CH₂Cl₂ for complex 3 in its oxidized 3 ⁺ and reduced 3 ^? forms were investigated. The calculated absorption spectrum of 3 in MeCN was used to assign the UV–Vis absorption bands.