Ultrasound assisted dehydrogenation of 2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxamides

Dehydrogenation of various 2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxamides (THPMs) to 2-oxo-1,2-dihydropyrimidine-5-carboxamides (DHPMs) using tetrabutylammonium peroxydisulfate (TBAPS) as an efficient oxidizing agent under thermal and sono-thermal conditions has been investigated. In contrast to the thermal reaction, a decrease of the amount of oxidant and an increase of the rate of reaction are observed by simultaneously applying heat and ultrasound. The nature of both C-4 and C-5 substituents on the heterocyclic ring influences the rate of reaction under both conditions. The proposed electron-transfer-induced dehydrogenation in this study is supported by conductometric studies.     

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.     

A mechanophysical phase transition provides a dramatic example of colour polymorphism: the tribochromism of a substituted tri(methylene)tetrahydrofuran-2-one

Background

Derivatives of fulgides have been shown to have interesting photochromic properties. We have synthesised a number of such derivatives and have found, in some cases, that crystals can be made to change colour on crushing, a phenomenon we have termed “tribochromism”. We have studied a number of derivatives by X-ray crystallography, to see if the colour is linked to molecular structure or crystal packing, or both, and our structural results have been supported by calculation of molecular and lattice energies.

Results

A number of 5-dicyanomethylene-4-diphenylmethylene-3-disubstitutedmethylene-tetrahydrofuran-2-one compounds have been prepared and structurally characterised. The compounds are obtained as yellow or dark red crystals, or, in one case, both. In two cases where yellow crystals were obtained, we found that crushing the crystals gave a deep red powder. Structure determinations, including those of the one compound which gave both coloured forms, depending on crystallisation conditions, showed that the yellow crystals contained molecules in which the structure comprised a folded conformation at the diphenylmethylene site, whilst the red crystals contained molecules in a twisted conformation at this site. Lattice energy and molecular conformation energies were calculated for all molecules, and showed that the conformational energy of the molecule in structure IIIa (yellow) is marginally higher, and the conformation thus less stable, than that of the molecule in structure IIIb (red). However, the van der Waals energy for crystal structure IIIa, is slightly stronger than that of structure IIIb – which may be viewed as a hint of a metastable packing preference for IIIa, overcome by the contribution of a more stabilising Coulomb energy to the overall more favourable lattice energy of structure IIIb.

Conclusions

Our studies have shown that the crystal colour is correlated with one of two molecular conformations which are different in energy, but that the less stable conformation can be stabilised by its host crystal lattice.

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Graphical abstract Graphical representation of the structural and colour change in the tribochromic compound (III).

     

Gamma-irradiation effects on the electrical conductivity of pure and Co-doped MgAl2O4 spinel

The electrical conductivity of pure and Co-doped MgAl₂O₄ spinels was measured at 700–1100 K. The results of both pure and doped spinels were found to be fitted with an exponential expression with two different activation-energy parameters, in two ranges of temperature. The effect of -irradiation on the electrical conductivity of pure and doped spinels was also studied. The kinetic parameters of the isothermal annealing of the induced irradiation damages in the spinels were determined. All the results were found to be consistent with the ionic conduction which was suggested to be due to the motion of the cation vacancy.     

A combined genetic algorithm-fuzzy logic controller (GA–FLC) in nonlinear programming

This paper presents a combined genetic algorithm-fuzzy logic controller (GA–FLC) technique for constrained nonlinear programming problems. In the standard Genetic algorithms, the upper and lower limits of the search regions should be given by the decision maker in advance to the optimization process. In general a needlessly large search region is used in fear of missing the global optimum outside the search region. Therefore, if the search region is able to adapt toward a promising area during the optimization process, the performance of GA will be enhanced greatly. Thus in this work we tried to investigate the influence of the bounding intervals on the final result. The proposed algorithm is made of classical GA coupled with FLC. This controller monitors the variation of the decision variables during process of the algorithm and modifies the boundary intervals to restart the next round of the algorithm. These characteristics make this approach well suited for finding optimal solutions to the highly NLP problems. Compared to previous works on NLP, our method proved to be more efficient in computation time and accuracy of the final solution.     

Physical properties of hexafluoroacetone

The vapour pressure of hexafluoroacetone has been determined from 58°C to the critical point. The critical temperature and pressure were also measured. Densities of the liquid and saturated vapour were determined between - 50°C and the critical point. Using this information the rectilinear diameter line and the heats of vaporization have been determined.     

Development of Organochlorine Pesticide Electrochemical Sensor Based on Fe3O4 Nanoparticles@indium Tin Oxide Electrode

Monitoring food quality and safety need the development of highly sensitive and accurate techniques. Organochlorine pesticides (OCPs) are a widely used category of pesticides. The high toxicity and high stability of OCPs pesticides made their detection the target of several research studies. Chloridazon, one of the wide used OCPs pesticides, and its major degradation product (chloridazon-desphenyl) have shown high harmful effects. Here, a specific OCPs electrochemical sensor was developed. Fe₃O₄ nanostructures decorated indium tin oxide (ITO) electrode showed high specificity towards the OCPs because of the capability of chlorine atoms, to interact with the iron oxide NPs. The chemical composition and the morphology of the modified nanosensor were investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), vibrating sample magnetometer (VSM), energy dispersive x-ray (EDX), and Raman spectroscopy techniques. The results showed the formation of two morphologies, including spongy agglomerated NPs with100 nm in diameter and nanofibers with 20 nm in thickness. The modified electrode exhibited a high sensitivity with a detection limit of 0.9 μmol L⁻¹. Also, chloridazon was detected in the presence of various interferences, including isoproturon pesticide and urea. Furthermore, chloridazon pesticide was also detected in a surface water sample.     

Stability indicating methods for the determination of some anti-fungal agents using densitometric and RP-HPLC methods

Two chromatographic methods were developed for the determination of some anti-fungal drugs in the presence of either their degradation products or cortisone derivatives. The densitometric method determined mixtures of each of ketoconazole (KT), clotrimazole (CL), miconazole nitrate (MN) and econazole nitrate (EN) with the degradation products of each one. Mixtures of MN with hydrocortisone (HC) and of EN with triamcinolone acetonide (TA) were also successfully separated and determined by this technique. For KT and CL, a mixture of methanol:water:triethylamine (70:28:2 v/v) was used as a developing system and the spots were scanned at 243 nm and 220 nm for KT and CL, respectively. For MN and EN, a mixture of hexane:isopropyl alcohol:triethylamine (80:17:3 v/v) was used as a developing system and the spots were scanned at 225 nm for both drugs. The HPLC method determined mixtures of CL or EN with their degradation products which were separated and quantified on a Zorbax C8 column. Elution was carried out using methanol:phosphate buffer pH 2.5 (65:35 v/v) as a mobile phase at a flow rate of 1.5 ml/min and UV detection at 220 nm for CL. For EN, a mixture of methanol:water containing 0.06 ml triethylamine pH 10 (75:25 v/v) was used as a mobile phase at a flow rate of 1.5 ml/min and UV detection at 225 nm. The methods were also used to separate mixtures of CL with betamethasone dipropionate (BD) and EN with TA in a laboratory prepared mixture and in pharmaceutical preparations. The methods were sensitive, precise and applicable for determination of the drugs in pharmaceutical dosage forms.     

Cure kinetics, dynamic mechanical and morphological properties of epoxy resin-Im6NiBr2 system

The aim of this study was to examine effects of a catalyst of Nickel-imidazole, i.e. Im₆NiBr₂ on the cure reaction and network properties of diglycidyl ether of bisphenol A. DSC and FT-IR measurements are carried out on the epoxy resin loaded with 5, 15, and 30 phr of nickel salt to get some insights into the storage stability. It has been concluded that the storage stability has mainly depended on the epoxy composition and was the lowest for the highest level of curing agent. Kinetics of the cure has been described by applying iso-conversional method of Ozawa to scanning DSC data demonstrating that the studied cure reaction is autocatalytic in nature. The Kamal phenomenological approach has been utilized to fit the experimental isothermal DSC data. The model showed a satisfactory fitting of the experimental results at either early stages or at the final steps of the studied cure reaction. Further, the model did not provide a reasonable fitting in the propagation step of polymerization, 0.3 < α < 0.5, possibly due to existence of the additional reaction/s which did not consider in the used model. DMTA is used to find the optimum cure schedule. It has been shown that the sample with a postcure treatment offers the highest value of glass transition temperature (T_g) in the tan δ peak. SEM and X-ray analyses are employed to investigate the fracture surface morphology and to understand the distribution of nickel in the cured samples exhibiting that the nickel is scattered in the continuous phase homogenously. Flexural properties of the sample cured at optimum conditions are also determined.