Complexation ability of kryptofix 22DD with lanthanum (III) cation in some binary mixed non-aqueous solvents

The complex formation between lanthanum (III) cation with kryptofix 22DD was studied in acetonitrile–dimethylformamide (AN–DMF), acetonitrile–methanol (AN–MeOH), acetonitrile–ethylacetate (AN–EtOAc) and acetonitrile–ethanol (AN–EtOH) binary solvent solutions at different temperatures by using conductometric method. The conductance data show that in all cases, the stoichiometry of the complex formed between the macrocyclic ligand and the metal cation is 1:1 [ML]. The stability order of (kryptofix 22DD.La)³⁺ complex in the studied binary solvent solutions at 25 °C was found to be: AN–EtOAc>AN–EtOH>AN–MeOH>AN–DMF and in the case of pure non-aqueous solvents at 25 °C was: EtOAc>EtOH>MeOH>AN>DMF. A non-linear behavior was observed for changes of logK_f of (kryptofix 22DD.La)³⁺ complex versus the composition of the binary mixed solvents, which was explained in terms of solvent–solvent interactions and also the preferential solvation of the species involved in the complexation reaction. The values of standard thermodynamic parameters (?H _c°, ?S _c°) for formation of (kryptofix 22DD.La)³⁺ complex were obtained from temperature dependence of the stability constant using the van’t Hoff plots.The results show that in most cases, the (kryptofix 22DD.La)³⁺ complex is enthalpy destabilized, but entropy stabilized and the values of these thermodynamic quantities for formation of the complex are quite sensitive to the nature and composition of the mixed solvents solution.     

“Grafting through” approach for synthesis of polystyrene/silica aerogel nanocomposites by in situ reversible addition-fragmentation chain transfer polymerization

Aerogel/polystyrene nanocomposites with mixed free and aerogel-attached polystyrene chains were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. 3-methacryloxypropyldimethylchlorosilane containing a double bond, which could be incorporated into polystyrene chains by a “grafting through” approach, was used as an aerogel modifier. Kinetics of RAFT polymerization of styrene in the presence of modified silica aerogel was studied by monitoring conversion and molar mass values. To further study, attached polymers were detached and their molecular characteristics were compared to free chains. According to results, the presence of silica aerogel particles has a sensible influence on polymerization kinetic and more aerogels result in decreased polymerization rate and conversion. The dispersity (Ð) of polymer chains increased by the addition of silica aerogel. In the case of aerogel-attached polystyrene chains, number-averaged molar mass values were slightly lower than that of free chains. Also, thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to observe the effect of loading on thermal properties of synthesized nanocomposites.     

Structure and properties of NR/BR blend/clay nanocomposites prepared by the latex method

Rubber blend/clay nanocomposites based on the 50/50 (wt %) natural rubber/butadiene rubber was prepared by the latex method via mixing the latex of 50/50 NR/BR blend with different amounts of the aqueous sodium montmorillonite (Na-MMT) dispersion and co-coagulating the mixture. XRD and TEM were used to characterize structure of the nanocomposites. It was found that fully exfoliated structure could be obtained by this method only when the low loading of layered silicate (up to 5 phr) is used. With increasing the clay content, both non-exfoliated (stacked layers) and exfoliated structures can be observed simultaneously in the nanocomposites. Nanocomposites showed mechanical properties better than the clay-free volcanizate. Moreover, modulus, tensile strength, elongation at break and tear strength increased significantly by increasing the clay amount up to 5 phr and then remained almost constant by further increasing the clay content. Improvement in the mechanical properties by increasing the clay loading up to 5 phr was attributed to the nano-reinforcement effect of Na-MMT. TGA results indicated an improvement in the main decomposition temperature by increasing the clay amount.     

Switching adaptive controllers to control fractional‐order complex systems with unknown structure and input nonlinearities

This article investigates the chaos control problem for the fractional‐order chaotic systems containing unknown structure and input nonlinearities. Two types of nonlinearity in the control input are considered. In the first case, a general continuous nonlinearity input is supposed in the controller, and in the second case, the unknown dead‐zone input is included. In each case, a proper switching adaptive controller is introduced to stabilize the fractional‐order chaotic system in the presence of unknown parameters and uncertainties. The control methods are designed based on the boundedness property of the chaotic system's states, where, in the proposed methods the nonlinear/linear dynamic terms of the fractional‐order chaotic systems are assumed to be fully unknown. The analytical results of the mentioned techniques are proved by the stability analysis theorem of fractional‐order systems and the adaptive control method. In addition, as an application of the proposed methods, single input adaptive controllers are adopted for control of a class of three‐dimensional nonlinear fractional‐order chaotic systems. And finally, some numerical examples illustrate the correctness of the analytical results. © 2014 Wiley Periodicals, Inc. Complexity 21: 211–223, 2015     

Atom-economical isocyanide-based multicomponent synthesis of 2,5-dioxopyrrolidines,spirobenzothiazinechromans and 1,5-benzothiazepines

An efficient synthesis of new pharmaceutically relevant dioxopyrrolidines, spirobenzo thiazine-2,3′-chromans, and benzothiazepines via isocyanide-based multicomponent condensation reactions at room temperature is reported. This synthesis serves as a nice addition to group-assistant-purification (GAP) chemistry in which purification via chromatography and recrystallization can be avoided, and the pure products are obtained simply by washing the crude products with 95% ethanol.     

A highly diastereoselective five-component synthesis of 1-(alkylimino)-5,5-dicyano-3a-aryloctahydro-3-oxacyclobuta[cd]pentalene-1a,2,5a,5b(2H,3aH)-tetracarboxylates

A novel one-pot, five-component synthesis of 1-(alkylimino)-5,5-dicyano-3a-aryloctahydro-3-oxacyclobuta[cd]pentalene-1a,2,5a,5b(2H,3aH)-tetracarboxylates is described. A mixture of phenacyl bromide, malononitrile, isocyanide, and two equivalents of a dialkyl acetylenedicarboxylate undergoes a novel 1:1:1:2 addition reaction at ambient temperature in absolute ethanol to produce diastereoselectively the title compounds in good yields.     

An efficient and convenient synthesis of pentasubstituted pyrroles from alkyl acetoacetates,dialkyl acetylenedicarboxylates,and amines

A simple and efficient synthesis of pentasubstituted pyrroles has been developed using a one-pot, two-step reaction. The synthesis of a series of 4-hydroxypenta-1,3-diene-tricarboxylates from alkyl acetoacetates and dialkyl acetylenedicarboxylates in the presence of K₂CO₃, followed by cyclization with amines, gave the corresponding pyrroles in excellent yields.     

Nanofluid in Hydrophilic State for EOR Implication Through Carbonate Reservoir

More than 50% of oil is trapped in petroleum reservoirs after applying primary and secondary recovery methods for removal. Thus, to produce more crude oils from these reservoirs, different enhanced oil recovery (EOR) approaches should be performed. In this research, the effect of hydrophilic nanoparticles of SiO₂ at 12 nm size, in (EOR) from carbonate reservoir is systematically investigated. Using this nanoparticle, we can increase viscosity of the injection fluid and then lower the mobility ratio between oil and nanofluid in carbonate reservoirs. To this end, a core flooding apparatus was used to determine the effectiveness and robustness of nanosilica for EOR from carbonate reservoirs. These experiments are applied on the reservoir carbonate core samples, which are saturated with brine and oil that was injected with nanoparticles of SiO₂ at various concentrations. The output results depict that, with increasing nanoparticle concentration, the viscosity of the injection fluid increases and results in decreased mobility ratio between oil and nanofluid. The results confirm that using the nanoparticle increases the recovery. Also, increasing the nanoparticle concentration up to 0.6% increases the ultimate recovery (%OOIP), but a further increase to 1.0 does not have a significant effect.     

Batch and continuous fixed-bed column biosorption of thorium(IV) from aqueous solutions: equilibrium and dynamic modeling

Biosorption of thorium(IV) from aqueous solution by Cystoseira indica alga was investigated in batch and fixed-bed column experiments. In the batch study the effects of pH and initial concentration were investigated. The optimum pH for Th(IV) biosorption was found to be 3.5. The experimental isotherms obtained at different pH conditions were analyzed using three two-parameter models and three three-parameter models. Among the two-parameter models the Langmuir model and among the three-parameter models the Redlich–Peterson model vividly described the equilibrium data. The results showed that C. indica alga is a homogeneous biosorbent and Th(IV) biosorption is a favorable and physical process. The maximum biosorption capacity from the Langmuir model was 151.3, 195.7 and 120.6 mg/g at pH 2.5, 3.5 and 4.5, respectively. The continuous isotherm obtained from the column data was modeled by the Langmuir model and the maximum biosorption capacity was 283.8 mg/g. The experimental data were fitted by the use of an analytical and a numerical model, namely Clark and mass transfer models. The results showed that the mass transfer model adequately described the experimental data. Sensitivity analysis revealed that the value of k _in has more effect than the axial dispersion coefficient (D _z) on the shape of breakthrough curve.     

Influence of polymeric coating on capillary electrophoresis of iron oxide nanoparticles

In this work, electrophoresis was successfully used to separate three different polymer-coated magnetic iron oxide nanoparticles with similar sizes (nominally 50 nm) using high-pH borate buffer system. The coating polymers were dextran, polyethylene glycol, or carboxymethyl dextran. The results showed that the migration time of carboxymethyl dextran coated nanoparticles is the longest due to relatively more negative surface charges. Investigation of the effects of buffer concentration, pH, electric field strength and the capillary temperature, on electrophoretic properties of samples was also carried out. The results showed that pH, electric field strength and the capillary temperature had indirect relations with both of the migration time and the separation resolution of three different polymer-coated nanoparticles while the buffer concentration had a direct relation.