Thermal Degradation Kinetics and Modeling Study of Ultra High Molecular Weight Polyethylene (UHMWP)/Graphene Nanocomposite

The incorporation of nanofillers such as graphene into polymers has shown significant improvements in mechanical characteristics, thermal stability, and conductivity of resulting polymeric nanocomposites. To this aim, the influence of incorporation of graphene nanosheets into ultra-high molecular weight polyethylene (UHMWPE) on the thermal behavior and degradation kinetics of UHMWPE/graphene nanocomposites was investigated. Scanning electron microscopy (SEM) analysis revealed that graphene nanosheets were uniformly spread throughout the UHMWPE’s molecular chains. X-Ray Diffraction (XRD) data posited that the morphology of dispersed graphene sheets in UHMWPE was exfoliated. Non-isothermal differential scanning calorimetry (DSC) studies identified a more pronounced increase in melting temperatures and latent heat of fusions in nanocomposites compared to UHMWPE at lower concentrations of graphene. Thermogravimetric analysis (TGA) and derivative thermogravimetric (DTG) revealed that UHMWPE’s thermal stability has been improved via incorporating graphene nanosheets. Further, degradation kinetics of neat polymer and nanocomposites have been modeled using equations such as Friedman, Ozawa–Flynn–Wall (OFW), Kissinger, and Augis and Bennett’s. The "Model-Fitting Method” showed that the auto-catalytic nth-order mechanism provided a highly consistent and appropriate fit to describe the degradation mechanism of UHMWPE and its graphene nanocomposites. In addition, the calculated activation energy (E_a) of thermal degradation was enhanced by an increase in graphene concentration up to 2.1 wt.%, followed by a decrease in higher graphene content.     

From Nef‐Isocyanide Adducts toward Functionalized 5‐Iminothiazolidines Containing Polarized CC Bonds

An efficient synthesis of alkyl 5‐(alkylimino)‐3‐aryl(alkyl)‐2‐(dicyanomethylene)‐4‐hydroxythiazolidine‐4‐carboxylates, containing polarized C?C bonds, via reaction of malononitrile, arylisothiocyanates, and the Nef‐isocyanide adducts, under basic conditions, is described.     

Influence of NO2 attachment on the nuclear magnetic shielding tensors of N and B nuclei in C30B15N15 heterofullerene: a DFT study

Adsorption of nitrogen dioxide in three different configurations on the exterior surface of C₃₀B₁₅N₁₅ is studied using density functional theory calculations. To this end, we optimized the structures of raw C₃₀B₁₅N₁₅ and nine NO₂–C₃₀B₁₅N₁₅ complexes at the B3LYP/6-31G^* level of theory and then calculated chemical shielding (CS) tensors at the GIAO-B3LYP/6-311G^** level for the optimized structures. The calculated chemical shielding isotropy (CSI), chemical shielding anisotropy (CSA), and orientation of CS tensors (Euler angles) reveal that the adsorption configurations (nitro, trans-nitrite, and cis-nitrite) have different effects on the electronic structure of C₃₀B₁₅N₁₅. Natural atomic charges based on natural population analysis (NPA) were used to justify the changes in CSI values after gas sorption.     

Synthesis,Characterization, and Catalytic Activity of Heteroleptic Rhodium Complex for C–N Couplings

Russian Journal of Coordination Chemistry - We have reported synthesis of complex [Rh(COD)(L{Me})Cl] (III), where L{Me} (II) is N-(1-methylpyridin-4(1H)-ylidene)benzamide and COD is...     

Investigation of keto–enol tautomerism in tetraketonate ligands

Molecular structure, vibration analysis, and natural bond orbital study of four derivatives of tetraketonate ligand were investigated in three different solvents using density functional theory B3LYP/6-31++G** method. The solution phase studies were carried out using an Onsager model. According to the obtained results the enol form of the ligands is more stable than keto form, even in solvents with high dielectric constant such as DMSO. This result is also confirmed experimentally using NMR studies for tetraacetylethane. Their stabilities are due to the presence of hydrogen bonding in the enol tautomers. A comparison among different possible enol forms of the substituted tetraketonate ligands demonstrated that three factors control the stability of the compounds as hydrogen bonding, steric hindrance, and charge distribution. The effectiveness of each of these factors on the stability of ligands depends on the nature of the substituent attached to the ligand.     

Separation of BTEX compounds (benzene,toluene, ethylbenzene and xylenes) from aqueous solutions using adsorption process

A commercial synthetic zeolite (Na-ZSM-5) was modified with an organic surfactant, HDTMA-Br. Then both unmodified and modified zeolite (SMZ-100) were tested to adsorb Benzene, Toluene, Ethylbenzene and Xylene (BTEX) compounds from water solution. Adsorption tests were done in batch conditions at the ambient temperature (20?°C) and pressure. Adsorbents were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N₂ adsorption-desorption isotherms and field emission scanning electron microscopy (FE-SEM) and characterization results proved the existence of surfactant on the surface of the adsorbent. In all cases, the modified zeolite sample, because of increasing the hydrophobicity of its surface, exhibited higher adsorption capacity in comparison with unmodified zeolite. Also, for each adsorbent, the adsorption capacity follows the order: E?>?X?>?T?>?B. In equilibrium experiments, Langmuir isotherm model fitted the equilibrium data better than the Freundlich model. In kinetic experiments, the pseudo-second order model described the kinetic data better than the other models.     

Benzene-1,3,5-tricarboxylic acid-functionalized MCM-41 as a novel and recoverable hybrid catalyst for expeditious and efficient synthesis of 2,3-dihydroquinazolin-4(1H)-ones via one-pot three-component reaction

Research on Chemical Intermediates - Benzene-1,3,5-tricarboxylic acid-functionalized MCM-41 (MCM-41-Pr-BTA), as a novel hybrid organosilica, was prepared and properly characterized by the...     

Improved efficacy of bio‐mineralization of human mesenchymal stem cells on modified PLLA nanofibers coated with bioactive materials via enhanced expression of integrin α2β1

Current therapeutic interventions in bone defects are mainly focused on finding the best bioactive materials for inducing bone regeneration via activating the related intracellular signaling pathways. Integrins are trans‐membrane receptors that facilitate cell‐extracellular matrix (ECM) interactions and activate signal transduction. To develop a suitable platform for supporting human bone marrow mesenchymal stem cells (hBM‐MSCs) differentiation into bone tissue, electrospun poly L‐lactide (PLLA) nanofiber scaffolds were coated with nano‐hydroxyapatite (PLLA/nHa group), gelatin nanoparticles (PLLA/Gel group), and nHa/Gel nanoparticles (PLLA/nHa/Gel group) and their impacts on cell proliferation, expression of osteoblastic biomarkers, and bone differentiation were examined and compared. MTT data showed that proliferation of hBM‐MSCs on PLLA/nHa/Gel scaffolds was significantly higher than other groups (P < .05). Alkaline phosphatase activity was also more increased in hBM‐MSCs cultured under osteogenic media on PLLA/nHa/Gel scaffolds compared to others. Gene expression evaluation confirmed up‐regulation of integrin α2β1 as well as the osteogenic genes BGLAP, COL1A1, and RUNX2. Following use of integrin α2β1 blocker antibody, the protein level of integrin α2β1 in cells seeded on PLLA/nHa/Gel scaffolds was decreased compared to control, which confirmed that most of the integrin receptors were bound to gelatin molecules on scaffolds and could activate the integrin α2β1/ERK axis. Collectively, PLLA/nHa/Gel scaffold is a suitable platform for hBM‐MSCs adhesion, proliferation, and osteogenic differentiation in less time via activating integrin α2β1/ERK axis, and thus it might be applicable in bone tissue engineering.     

Synthesis of 7-hydroxy-6H-benzo[c]chromen-6-ones based on a ‘[3+3] cyclization/domino retro-Michael-aldol-lactonization’ strategy

The TiCl₄-mediated [3+3] cyclization of 2,4-bis(trimethylsilyloxy)penta-1,3-diene with 3-silyloxyalk-2-en-1-ones afforded 2-acetylphenols, which were transformed into functionalized chromones. The Me₃SiOTf-mediated condensation of the latter with 1,3-bis(silyl enol ethers) and subsequent domino ‘retro-Michael-aldol-lactonization’ reaction afforded 7-hydroxy-6H-benzo[c]chromen-6-ones.