New Group 6 metal carbonyl derivatives of 2-(2'(-pyridyl)benzimidazole: synthesis and spectroscopic studies

Reaction of Cr(CO)(6) with 2-(2'-pyridyl)benzimidazole (pbiH) under reduced pressure resulted in the formation of the dinuclear complex [Cr(2)(CO)(6)(pbiH)(2)]. Infra-red (IR) spectroscopy revealed the presence of terminal and bridge Cr-CO bonds. Interaction of M(CO)(6), M=Cr, Mo and W, with pbiH in the presence of 2,2'-bipyridine (bpy) gave the tetracarbonyl complexes [M(CO)(4)(pbiH)].bpy. Spectroscopic studies of the complexes indicated the presence of hydrogen bonding between the bpy nitrogen and the NH group of pbiH. Reactions of M(CO)(6) with pbiH in the presence of PPh(3) gave the tricarbonyl monosubstituted derivatives [M(CO)(3)(PPh(3))(pbiH)]. The spectroscopic studies of the complexes suggested the proposed structures.     

Intrinsic adsorption properties of CO2 on 5A and 13X zeolite

Data for the adsorption of CO₂ on 5A (CaA) and 13X (NaX) zeolite are critically evaluated. In addition, fresh data for the adsorption of CO₂ on 13X zeolite is reported. Three intrinsic properties are examined: q _max , the saturation loading, K _H , the Henry constant, and (?ΔH) _q , the isosteric heat of sorption. Below a reduced temperature T _r , of 0.9, the q _max values for both 5A and 13X zeolites are similar to theoretical values that may be derived using zeolitic crystallographic properties and the sorbate density calculated using the Rackett equation. For the region 0.9 ≤ Tr ≤ 1.0, the calculated q _max values exceed the theoretical values similarly calculated, indicating that the molecules have a smaller molar volume than in a similar liquid phase. This is a similar result to that observed in ionic liquids. Linear regressed equations are derived for q _max for the region 0.9 ≤ Tr ≤ 1.25. The Henry constant values for 5A are remarkably consistent for the five studies examined, with a correlation coefficient, R, of 0.999 for the van’t Hoff equation, but for the seven studies examined in 13X the data is more disperse as indicated by a correlation coefficient R of 0.899 for the van’t Hoff equation. The values of (?ΔH) _q , the isosteric heat of sorption are in agreement with the literature. An explanation is advanced for the discrepancy between the higher heats of sorption values obtained calorimetrically from those obtained from isosteric adsorption studies. Finally, the fresh data is observed to fit the Toth model with regression coefficients of 0.999. However, the parameters obtained for the Toth equation by regression are significantly different from the intrinsic properties derived earlier, indicating the difficulty of deriving intrinsic parameters from isotherm fits.     

Bulk polymer nanoparticles containing a tetrakis(3-hydroxyphenyl)porphyrin for fast and highly selective separation of mercury ions

We report on the synthesis of polymeric nanoparticles (PNPs) containing a tetrakis(3-hydroxyphenyl)porphyrin, and their use for the separation of mercury(II) ion. The PNPs were prepared by bulk polymerization from methacrylic acid (the monomer), ethyleneglycol dimethacrylate (the cross-linker), 2,2′-azobisisobutyronitrile (the radical initiator) and the mercury(II) complex of 5,10,15,20-tetrakis(3-hydroxyphenyl)-porphyrin. The Hg(II) ion was then removed by treatment with dilute hydrochloric acid. The PNPs were characterized by colorimetry, FT-IR spectroscopy, and scanning electron microscopy. The material is capable of binding Hg(II) from analyte samples. Bound Hg(II) ions can be eluted with dilute nitric acid and then quantified by cold vapor AAS. The extraction efficiency, the effects of pH, preconcentration and leaching times, sample volume, and of the nature, concentration and volume of eluent were investigated. The maximum adsorption capacity of the PNPs is 249 mg g^?1, the relative standard deviation of the AAS assay is 2.2 %, and the limit of detection (3σ) is 8 ng.L^?1. The nanoparticles exhibit excellent selectivity for Hg(II) ion over other metal ions and were successfully applied to the selective extraction and determination of Hg(II) ion in spiked water samples.

Inhibition effect of horehound (Marrubium vulgare L.) extract towards C38 steel corrosion in HCl solution

The corrosion inhibition properties of horehound (Marrubium vulgare L.) extract (HE) in 1 M hydrochloric acid medium was carried out using electrochemical methods (polarization curve and electrochemical impedance spectroscopy). Experiments were performed by concentration of the inhibitor and temperature effect. The results showed variation in inhibition performance of this plant extract. The Langmuir model was tested to describe the adsorption behavior of the inhibitor on the C38 steel surface. Some thermodynamic functions of dissolution processes were also determined.     

Synthesis of two-dimensional gallium nitride via spin coating method: influences of nitridation temperatures

This paper reports the synthesis and characterization of gallium nitride (GaN) thin films deposited on p-type silicon (100) substrates by using low cost spin coating method under various nitridation temperatures. This work demonstrated that spin coating with the new prepared precursor solution can be used as a versatile method for the successfully growth of GaN thin films. Furthermore, the influence of varying nitridation temperatures on the structural, morphological, and optical properties of synthesized GaN thin films were studied in this work. The GaN thin films were characterized by X-ray diffraction, field-emission scanning electron microscopy, atomic force microscopy, photoluminescence and Raman spectroscopy. All the characteristics of the GaN thin films were effectively improved with the increasing of the nitridation temperatures from 750 to 950 °C and degraded at temperature of 1,050 °C. The measured results show that nitridation temperature plays an important role in improving the crystalline quality of the GaN thin films and the most efficient nitridation temperature was at 950 °C.     

Comparison of HPLC and MEEKC for Miconazole Nitrate Determination in Pharmaceutical Formulation

A simple solid phase extraction (SPE) method coupled with high performance liquid chromatography (HPLC) using UV detector and microemulsion electrokinetic chromatography (MEEKC) has been developed and compared for the quantitative determination of miconazole nitrate in pharmaceutical formulation. For HPLC method, two parameters were optimized, namely, the wavelength and the mobile phases. The optimized condition was at the 225 nm wavelength and the mobile phase of ACN:MeOH (90:10 v/v). There are seven MEEKC parameters that were optimized, in this research, which were applied to voltage, temperature, wavelength, sodium dodecyl sulfate (SDS) concentration, buffer pH, buffer concentration and butan-1-ol concentration. The optimum MEEKC condition was obtained using 86.35 % (w/w) 2.5 mM borate buffer pH 9, 0.25 % (w/w) SDS, 0.8 % (w/w) ethyl acetate, 6.6 % w/w butan-1-ol and 6.0 % (w/w) acetonitrile. The combination of SPE using a diol column with HPLC–UV and the MEEKC methods were successfully applied for the determination of miconazole nitrate in a pharmaceutical formulation with the recovery percentage of 98.35 and 92.50 %, respectively.     

Preparation of activated carbon filled epoxy nanocomposites

Activated carbon derived from oil palm empty fruit bunch (AC-EFB), bamboo stem (AC-BS), and coconut shells (AC-CNS) were obtained by pyrolysis of agricultural wastes using two chemical reagents (H₃PO₄ or KOH). The AC-EFB, AC-BS and AC-CNS were used as filler in preparation of epoxy nanocomposites. Epoxy nanocomposites prepared at 1, 5 and 10 % activated carbons filler loading using KOH and H₃PO₄ chemical agents. Transmission electron microscopy confirms better dispersion of the nano-activated carbons in the epoxy matrix at 5 % activated carbon. The presence of 5 % AC-CNS in the epoxy matrix using H₃PO₄ chemical reagent resulted in an improvement of the thermal stability of epoxy matrix. KOH treated AC filled epoxy nanocomposites were slightly better in thermal stability as compared to H₃PO₄ treated AC filled epoxy nanocomposites, may be due to better interaction of filler with epoxy matrix. Thermal analysis results showed that thermal stability of the activated carbon filled epoxy nanocomposites improved as compared to the neat epoxy matrix. The degree of crystallinity of epoxy matrix was improved by adding the activated carbon due to interfacial interaction between AC and epoxy matrix rather than loading of AC alone. Developed nanocomposites from biomass (agricultural wastes) materials will help to reduce the overall cost of the materials for its demanding applications as insulating material.     

Evaluating the residence time for cesium removal from simulated Hanford tank wastes using SuperLig® 644 resin

Batch contact and column experiments were performed to evaluate the effect of residence time on cesium removal from two simulated Hanford tank wastes using SuperLig^® 644 resin. The two waste simulants mimic the compositions of tanks 241-AZ-102 and 241-AN-107 at the U.S. Department of Energy (DOE) Hanford site. A single column made of glass tube (2.7-cm i.d.), which contained ~100 ml of H-form SuperLig^® 644 resin was used in the column experiments. The experiments each consisted of loading, elution, and regeneration steps were performed at flow rates ranging from 0.64 to 8.2 BV/h for AZ-102 and from 1.5 to 18 BV/h for AN-107 simulant. The lowest flow rates of 0.64 and 1.5 BV/h were selected to evaluate less than optimal flow conditions in the plant. The range of the flow rates is consistent with the River Protection Project design for the waste treatment plant (WTP) columns, which will operate at a flow rate between 1.5 to 3 BV/h. Batch contact experiments were also performed for two batches of SuperLig^® 644 to determine the equilibrium distribution coefficients (K _d) as a function of Cs concentration. The column experiments revealed that adequate column loading for Cs on SuperLig^® 644 (50% breakthrough at 100 bed volumes) can be achieved for the two simulated Hanford tank wastes at the nominal plant flow rates of 1.5 and 3 BV/h (residence times 40 and 20 minutes). The column performance was marginally improved at flow rates below the nominal rates. At flow rates higher than the nominal, the Cs loading deteriorated significantly. The SuperLig^® 644 was eluted effectively with 0.5M nitric acid. The elution required approximately 15 BVs to reduce Cs concentration to below 1% of initial Cs concentration in the feeds.     

A new flavonol glycoside and other flavonoids from the aerial parts of Taverniera aegyptiaca

Isolation of flavonoids from the aerial parts of Taverniera aegyptiaca Bioss. (Fabaceae) led to identification of one new flavonol glycoside, isorhamnetin-3-O-α-l-rhamnopyranosyl-(1→2)-α-l-arabinopyranoside (1), along with eleven compounds, which previously have not been isolated from this plant quercetin-3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (2), isorhamnetin-3-O-α-l-arabinopyranoside (3), quercetin-3-O-α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside (4), isorhamnetin-3-O-α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside (7), isorhamnetin 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (8), isorhamnetin 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside] (9), kaempferol 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (10), isorhamnetin (11), 4,4′-dihydroxy-2′-methoxychalcone (12), formononetin (13) and calycosin (15)] and some compounds already known from this plant [quercetin-3-O-robinobioside (5), isorhamnetin-3-O-robinobioside (6), afrormosin (14) and odoratin (16)].     

Dearomatization of 3-Nitroindoles with Highly γ-Functionalized Allenoates in Formal (3+2) Cycloadditions

3-Nitroindoles are easily reacted with highly substituted γ-allenoates in the presence of a commercially available phosphine catalyst. For instance, allenoates derived from biomolecules such as amino and deoxycholic acids are combined for the first time with 3-nitroindole. The corresponding dearomatized (3+2) tricyclic cycloadducts are obtained as α-regioisomers exclusively. DFT computations shed light on this multi-step reaction mechanism and on the selectivities observed in the sequence.