Unanticipated Heterocyclization from Reaction of Hydrazine Hydrate and/or Hydrazine Dihydrochloride with 1‐Ethyl‐4‐hydroxyquinolin‐2(1H)‐one

Unexpectedly, the reaction of 1‐ethyl‐4‐hydroxyquinolin‐2(1H)‐one ( 1 ) with hydrazine hydrate and/or hydrazine dihydrochloride led to three different products. In addition to the expected quninolinylhydrazine, two heteropentacycles, diquinopyrrole and diquinopyridazine, were afforded, depending on reaction conditions. The structure of the new products was established upon their spectral and analytical data.     

Substituted quinolinones. 31. Some new pyrano[3,2‐c]quinoline‐3‐carboxamides and their antioxidant activity

1‐Ethyl‐4‐hydroxy‐2‐oxo‐1,2‐dihydroquinoline‐3‐carbaldehyde ( 1 ) was annulated using malonic acid and/or its ethyl ester to furnish pyrano[3,2‐c]quinoline‐3‐carboxylic acid 2 and its ester 3 . Interconversions between acid 2 and ester 3 were successfully carried out. The anticipated pyrano[3,2‐c]quinoline‐3‐carboxamides 5–12 were conveniently attained via condensation of ester 3 with the proper amine. Surprisingly, treatment of ester 3 with dimethylformamide (DMF) in acidic media led to the carboxamide 5 . All attempts to convert ester 3 to its corresponding acid hydrazides by interaction with the proper hydrazine derivative led to formation of pyrazolidinediones 15 and 17 . Ester 3 underwent cyclo‐condensation with malononitrile dimer affording pyrido[3′,4′:5,6]pyrano[3,2‐c]quinoline derivative 18 . The new compounds revealed significant antioxidant effect, which suggests that most of them are possible potent antioxidant agents.     

Unusual behavior of 3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one towards some phosphorus reagents: Synthesis of novel diethyl 2-phosphonochromone,diethyl 3-phosphonopyrone and 1,3,2-oxathiaphosphinines

The chemical reactivity of 3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one (1) towards some phosphorus reagents was studied. The enaminone 1 was cyclized into diethyl 2-phosphonochromone 2 via its treatment with diethyl phosphite in basic medium. However, its reaction with triethoxy phosphonoacetate gave the substituted pyrone phosphonate 3. In addition, two novel examples of 4-(dimethylamino)-6-(2-hydroxyphenyl)-2-sulfido-4H-1,3,2-oxathia-phosphinines 6 and 7 were obtained from treatment of enaminone 1 with O,O-diethyl dithiophosphoric acid and Lawesson’s reagent. When enaminone 1 was also treated with phosphorus decasulfide, it was turned into 4H-thiochromene-4-thione while its treatment with phosphorus tribromide, phosphorus oxychloride, or phenylphosphonic dichloride, 4H-4-oxo-chromene was isolated in all cases. The possible reaction mechanisms of the formation of these products were discussed. The structures of newly isolated products were established by elemental analysis and spectral tools.     

Properties of ethylene propylene diene rubber/white and black filler composites cured by gamma radiation in presence of sorbic acid

The effect of incorporating sorbic acid (SA), an echo-friendly curing agent, and silica or carbon black (CB) filler, as well as gamma irradiation on the physico-chemical, mechanical and thermal properties of ethylene propylene diene monomer rubber (EPDM) was investigated. The results indicated that the developed composites revealed improvement in the studied parameters over the untreated samples. Filler incorporation into rubber matrix has been proven a key factor in enhancing the swelling resistance, tensile strength and thermal properties of the fabricated composites. The improvement in tensile strength and modulus was attributed to better interfacial bonding via SA. Alternatively, a comparison was established between the performance of the white and black fillers. The utmost mechanical performance was reported for the incorporated ratios 10 phr SA and 40 phr white filler into a 50 kGy irradiated composite. Meanwhile, the incorporation of CB yielded better thermally stable composites than those filled with silica at similar conditions.     

Efficient catalytic degradation of single and binary azo dyes by a novel triple nanocomposite of Mn3O4/Ag/SiO2

The strategy of structurally integrating noble metal and metal oxides is expected to offer exceptional opportunities toward emerging functions of all. We report the creation of an efficient hetero-structured nanocatalyst consisting of Mn₃O₄ core, SiO₂ shell impregnated with noble Ag nanoparticles. The triple nanocatalyst Mn₃O₄/Ag/SiO₂ was synthesized by using a facile three-step approach to disperse Ag nanoparticles between the surfaces of functionalized Mn₃O₄ and SiO₂. The physicochemical structural characterization was performed by XRD and FTIR. The surface morphologies were observed by SEM and TEM. The EDX measurements confirmed the composition of the composite. The nanocomposite has been used as a catalyst for the degradation of Direct blue 78 in the presence of sodium borohydride (NaBH₄). It has a drastic catalytic effect as compared to Mn₃O₄/Ag and Mn₃O₄. The rate constant of Direct blue 78 reduction followed the order: Mn₃O₄/Ag/SiO₂ (0.25166 min⁻¹) > Mn₃O₄/Ag (0.07971 min⁻¹) > Mn₃O₄ (0.00947 min⁻¹). The effects of different reaction conditions of the catalytic reaction have been determined. The catalytic activity of the as- synthesized nanocomposite was examined for the binary dyes system by incorporation of an additional dye (Sunset yellow). Its influence on the degradation rate and efficiency of Direct blue 78 was investigated. The nanocatalyst exhibited excellent catalytic activity towards the complete degradation of both the Direct blue 78 and Sunset yellow. The degradation percentage for these dyes reached 99.33 and 94.68%, respectively. The recovery and reusability of the Mn₃O₄/Ag/SiO₂ nanocomposite was studied in the reduction reaction of Direct blue 78. Five consecutive recovery reaction cycles were performed. They revealed high stability and constant efficiency of the catalyst for four cycles.     

High speed hydrophilic interaction liquid chromatographic method for simultaneous determination of selected pharmaceuticals in wastewater using a cyano-bonded silica column

In this work, a fast analytical method based on hydrophilic interaction liquid chromatographic-Ultraviolet detection (HILIC-UV) using a short narrow bore cyano-bonded silica column packed with fully porous sub-2?µm particles has been developed for simultaneous determination of eight pharmaceuticals in wastewater. The method involved pre-concentration and clean-up by solid phase extraction using Oasis HLB extraction cartridges. The analytes were separated using a mobile phase consisted of acetonitrile and 5?mM ammonium acetate buffer (95:5?v/v) with a flow rate of 0.6?mL/min. The chromatographic separation was optimized in order to achieve short analysis time and good resolution for all analytes in a single run. Each analyte was detected at its maximum wavelength for higher sensitivity. All analytes could be separated in 5.7?min with resolution ≥2.7. The optimized method was validated based on linearity, precision, detection and quantification limits, selectivity and accuracy. The detection limits of the studied pharmaceuticals ranged from 0.6 to 3?µg/L, while limits of quantification were in the range from 2 to 10?µg/L with UV detection. The developed method is fast, reliable, cost-effective and could be used for the analysis of the studied analytes in other matrices such as food, pharmaceutical preparations and biological fluids.     

Impact of Thermal Fluctuations on Logarithmic Corrected Massive Gravity Charged Black Hole

We investigate the influence of the first-order correction of entropy caused by thermal quantum fluctuations on the thermodynamics of a logarithmic corrected charged black hole in massive gravity. For this black hole, we explore the thermodynamic quantities, such as entropy, Helmholtz free energy, internal energy, enthalpy, Gibbs free energy and specific heat. We discuss the influence of the topology of the event horizon, dimensions and nonlinearity parameter on the local and global stability of the black hole. As a result, it is found that the holographic dual parameter vanishes. This means that the thermal corrections have no significant role to disturb the holographic duality of the logarithmic charged black hole in massive gravity, although the thermal corrections have a substantial impact on the thermodynamic quantities in the high-energy limit and the stability conditions of black holes.     

Design,synthesis and structural diversity in coordination polymers

The fundamental precept of crystal engineering is that all the information necessary for the design of a network is already stored in the molecular building blocks used. Coordination polymers represent an example of how crystal engineering has become a paradigm for the synthesis of new architectures and compositions. We report herein ten structures that are supramolecular isomers of one another. The structures are prepared from the same building blocks under mild reaction conditions. The modularity of coordination polymers imparts structural diversity that otherwise would not be possible.     

Generalized Ghost Pilgrim Scalar Field Models of Dark Energy

We assume generalized ghost Pilgrim dark energy (GGPDE) model in the presence of cold dark matter in flat FRW universe. With suitable choice of interaction term between GGPDE and cold dark matter, we investigate the nature of equation of state parameter for GGPDE. Also, we investigate the natures of dynamical scalar field models (such as quintessence, tachyon, k-essence, and dilaton dark energy) and concerned potentials through the correspondence phenomenon between GGPDE and these models.     

Spectrofluorimetric Determination of Fluvoxamine in Dosage Forms and Plasma Via Derivatization with 4-Chloro-7-Nitrobenzo-2-Oxa-1,3-Diazole

A highly sensitive and simple spectrofluorimetric method has been developed and validated for the determination of the antidepressant fluvoxamine (FXM) in its dosage forms and plasma. The method was based on nucleophilic substitution reaction of FXM with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole in an alkaline medium (pH 8) to form a highly fluorescent derivative that was measured at 535 nm after excitation at 470 nm. The factors affecting the reaction was carefully studied and optimized. The kinetics of the reaction was investigated, and the reaction mechanism was presented. Under the optimized conditions, linear relationship with good correlation coefficient (0.9995) was found between the fluorescence intensity and FXM concentration in the range of 65–800 ng ml⁻¹. The limits of detection and quantitation for the method were 21 and 64 ng ml⁻¹, respectively. The precision of the method was satisfactory; the values of relative standard deviations did not exceed 2.17%. The proposed method was successfully applied to the determination of FXM in its pharmaceutical tablets with good accuracy; the recovery values were 97.8–101.4 ± 1.08–2.75%. The results obtained by the proposed method were comparable with those obtained by the official method. The high sensitivity of the method allowed its successful application to the analysis of FXM in spiked human plasma. The proposed method is superior to the previously reported spectrofluorimetric method for determination of FXM in terms of its simplicity. The proposed method is practical and valuable for its routine application in quality control and clinical laboratories for analysis of FXM.