Synthesis,Characterization, and Crystal Structure of new Macromolecule Iron(III) Complex Containing Dimethyl Phosphate,Acetate, and Dimethyl sulfoxide

The reaction between a solution of [Fe₃O(μ‐OAc)₆(H₂O)₃]Cl·6H₂O ( 1 ) (OAc = acetate) and TMP (TMP = trimethyl phosphate) in absolute ethanol and DMSO (DMSO = dimethyl sulfoxide), led to the coordination macromolecule ‐[Fe₁₆(μ₃O)₈(μ₃‐OH)₄(μ‐OH)₄(μ‐DMP)₁₂(μ‐OAc)₁₂(DMSO)₄]·2DMSO·1.5H₂O ( 2 ) (DMP = dimethyl phosphate). This complex was characterized by elemental analysis, IR spectroscopy, and single‐crystal structure. Crystal data for 2 at ?153 °C: triclinic, space group , a = 18.185(2), b = 18.349(2), c = 21.976(3) Å, α = 91.633(3)°, ß = 103.833(3)° γ = 96.486(3)°, Z = 2 and R1 = 0.0655.     

COMMON FIXED POINT THEOREMS FOR THREE MAPS IN DISCONTINUOUS Gb-METRIC SPACES

In [Aghajani A, Abbas M, Roshan JR. Common fixed point of generalized weak contractive mappings in partially ordered Gb-metric spaces. Filomat, 2013, in press], using the concepts of G-metric and b-metric Aghajani et al. defined a new type of metric which is called generalized b-metric or Gb-metric. In this paper, we prove a common fixed point theorem for three mappings in Gb-metric space which is not continuous. An example is presented to verify the effectiveness and applicability of our main result.     

Common fixed point theorems for three maps in discontinuous Gb metric spaces

In [Aghajani A, Abbas M, Roshan JR. Common fixed point of generalized weak contractive mappings in partially ordered G_b-metric spaces. Filomat, 2013, in press], using the concepts of G-metric and b-metric Aghajani et al. defined a new type of metric which is called generalized b-metric or G_b-metric. In this paper, we prove a common fixed point theorem for three mappings in G_b-metric space which is not continuous. An example is presented to verify the effectiveness and applicability of our main result.     

Improved sensitivity of intensity-modulated spectroscopy using correlative signal processing

Frequency-modulation (FM) spectroscopy is known to be a sensitive spectroscopic technique capable of accurately measuring the frequency dependence of the absorption and index of refraction of narrow spectral features. The absorption and index of refraction are coupled by a form of the Kramers-Kronig (K-K) relations, and both components provide information about the spectral feature. In this Letter, we propose a processing technique based on fitting the data to a complex signal model derived from the K-K relation. By using this complex constraint and only processing a single quadrature, our model predicts significant improvement in the minimum detectable absorption compared with conventional FM spectroscopy.     

Sonochemical synthesis, size controlling and gas sensing properties of NiO nanoparticles

Nanoparticles of NiO (NP-NiO) were prepared by a novel sonochemical route from Ni acetate and sodium hydroxide without any requirement of calcinations steps at high temperature and without surfactants. Drop casting of the nanocrystals onto alumina substrates allowed the fabrication of gas sensing devices, which were tested towards NO₂ and CO and showed promising results. At low working temperature, the NiO nanoparticles based sensors are selective to nitrogen oxide; in fact a good sensitivity is shown at 200 °C at low concentration (2 ppm), while at temperature above 350 °C, high responses are obtained for carbon monoxide. The results obtained are stimulating for further developing of NP-NiO based sensor devices.     

Effect of fluids properties on non-equilibrium capillarity effects: Dynamic pore-network modeling

We have developed a Dynamic Pore-network model for Simulating Two-phase flow in porous media (DYPOSIT). The model is applicable to both drainage and imbibition processes. Employing improved numerical and geometrical features in the model facilitate a physically-based pore-scale simulator. This computational tool is employed to perform several numerical experiments (primary and main drainage, main imbibition) to investigate the current capillarity theory. Traditional two-phase flow formulations state that the pressure difference between the two phase is equal to the capillary pressure, which is assumed to be a function of saturation only. Many theoretical and experimental studies have shown that this assumption is invalid and the pressure difference between the two fluids is not only equal to the capillary pressure but is also related to the variation of saturation with time in the domain; this is referred to as the non-equilibrium capillarity effect. To date, non-equilibrium capillarity effect has been investigated mainly under drainage. In this study, we analyze the non-equilibrium capillarity theory under drainage and imbibition as a function of saturation, viscosity ratio, and effective viscosity. Other aspects of the dynamics of two-phase flow such as trapping and saturation profile are also studied.     

Quantum chemical and theoretical kinetics study of the O(3P) + CS2 reaction

The triplet potential energy surface of the O((3)P) + CS(2) reaction is investigated by using various quantum chemical methods including CCSD(T), QCISD(T), CCSD, QCISD, G3B3, MPWB1K, BB1K, MP2, and B3LYP. The thermal rate coefficients for the formation of three major products, CS + SO ((3)Σ(-)), OCS + S ((3)P) and CO + S(2) ((3)Σ(-)(g)) were computed by using transition state and RRKM statistical rate theories over the temperature range of 200-2000 K. The computed k(SO + CS) by using high-level quantum chemical methods is in accordance with the available experimental data. The calculated rate coefficients for the formation of OCS + S ((3)P) and CO + S(2) ((3)Σ(-)(g)) are much lower than k(SO + CS); hence, it is predicted that these two product channels do not contribute significantly to the overall rate coefficient.     

Metal matrix composites for sustainable lotus-effect surfaces

The lotus effect involving roughness-induced superhydrophobicity is a way to design nonwetting, self-cleaning, omniphobic, icephobic, and antifouling surfaces. However, such surfaces require micropatterning, which is extremely vulnerable to even small wear rates. This limits the applicability of the lotus effects to situations when wear is practically absent. To design sustainable superhydrophobic surfaces, we suggest using metal matrix composites (MMCs) with hydrophobic reinforcement in the bulk of the material, rather than only at its surface. Such surfaces, if properly designed, provide roughness and heterogeneity needed for superhydrophobicity. In addition, they are sustainable, since when the surface layer is deteriorated and removed due to wear, hydrophobic reinforcement and roughness remains. We present a model and experimental data on wetting of MMCs. We also conducted selected experiments with graphite-reinforced MMCs and showed that the contact angle can be determined from the model. In order to decouple the effects of reinforcement and roughness, the experiments were conducted for initially smooth and etched matrix and composite materials.     

Dinuclear copper complexes of pyridylphenylphosphine ligands: Characterization of a mixed-valence Cu/Cu dimer

Homo bi-copper complexes [Cu₂{PhP(2-py)₂}₂(NO₃)₃] (1) and [Cu₂{P(2-py)₃}₂Cl₂] (2), were synthesized from the reaction of Cu(NO₃)₂·3H₂O and CuCl₂·2H₂O with their corresponding 2-pyridylphosphine ligands. Compound 1 has a mixed valence Cu(I)-Cu(II) core with electron acceptor phosphine atoms and two NO₃⁻ anions coordinated in a monodentate fashion to Cu(I), giving it a distorted tetrahedral geometry. The environment of Cu(II) in 1 is composed of four nitrogen atoms from pyridyl and another NO₃⁻ anion in a square pyramidal geometry. This complex shows luminescence and a low energy absorption band at 969 nm corresponding to intermetallic electron transfer between the copper centers. Complex 2 was prepared from the treatment of copper(II) chloride with tris(2-pyridyl)phosphine, producing a binuclear copper complex which possesses a crystallographic inversion center. The copper geometry in this complex is distorted tetrahedral with coordination of one Cl⁻, two nitrogens from one bridging tris(2-pyridyl)phosphine ligand and one P atom from the other bridging tris(2-pyridyl)phosphine ligand, in a similar way observed in related complexes. The products have been characterized by spectroscopic methods and also by the single-crystal X-ray diffraction method.     

Optimization of dispersive liquid-liquid microextraction coupled with inductively coupled plasma-optical emission spectrometry with the aid of experimental design for simultaneous determination of heavy metals in natural waters

In this study, dispersive liquid-liquid microextraction (DLLME) combined with inductively coupled plasma optical emission spectrometry (ICP-OES) was developed for simultaneous preconcentration and trace determination of chromium, copper, nickel and zinc in water samples. Sodium diethyldithiocarbamate (Na-DDTC), carbon tetrachloride and methanol were used as chelating agent, extraction solvent and disperser solvent, respectively. The effective parameters of DLLME such as volume of extraction and disperser solvents, pH, concentration of salt and concentration of the chelating agent were studied by a (2^f−1) fractional factorial design to identify the most important parameters and their interactions. The results showed that concentration of salt and volume of disperser solvent had no effect on the extraction efficiency. In the next step, central composite design was used to obtain optimum levels of effective parameters. The optimal conditions were: volume of extraction solvent, 113 μL; concentration of the chelating agent, 540 mg L⁻¹; and pH, 6.70. The linear dynamic range for Cu, Ni and Zn was 1-1000 μg L⁻¹ and for Cr was 1-750 μg L⁻¹. The correlation coefficient (R²) was higher than 0.993. The limits of detection were 0.23-0.55 μg L⁻¹. The relative standard deviations (RSDs, C = 200 μg L⁻¹, n = 7) were in the range of 2.1-3.8%. The method was successfully applied to determination of Cr, Cu, Ni and Zn in the real water samples and satisfactory relative recoveries (90-99%) were achieved.