Volume 232, Issue 4

The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca) 2 ] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χ m T are in general agreement for [Co(dpzca) 2 ], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca) 2 ] at 15 K.

The complexes have been synthesized from Cu (II) soaps of groundnut ( Arachis hypogaea ) and sesame ( Sesamum indicum ) oils, with ligand containing nitrogen and sulfur atoms like 2-amino-6-methyl benzothiazole. The complexes were greenish brown in color. In order to study TGA, first characterized them by elemental analysis, and spectroscopic technique such as IR, NMR and ESR. From the analytical data, the stoichiometry’s of the complexes have been observed to be 1:1 (metal:ligand). These complexes have been thermally analyzed using TGA techniques to determine their energy of activation. These complexes show three step thermal degradation corresponding to fatty acid components of the edible oils and each complex has three decomposition steps in the range of 439–738 K. Various equations like Coats–Redfern (CR), Horowitz–Metzger (HM) and Broido equations (BE) were applied to evaluate the energy of activation. The values of energy of activation are observed to be in the following order for both copper groundnut benzothiazole (CGB) and copper sesame benzothiazole (CSeB) complexes: CGB > CSeB. CGB is observed to be more stable than CSeB due to its higher activation energy. The above studies would provide significant information regarding the applications of synthesized agrochemicals and their safe removal through parameters obtained in degradation curves and its relation with energy.

Mesoporous diatomite particles were employed to prepare different poly(styrene-co-butyl acrylate)/diatomite nanocomposites. Diatomite nanoplatelets were used for in situ copolymerization of styrene and butyl acrylate by SR&NI ATRP to synthesize well-defined poly(styrene-co-butyl acrylate) nanocomposites. Nitrogen adsorption/desorption isotherm is applied to examine surface area and structural characteristics of the diatomite nanoplatelets. Evaluation of pore size distribution and morphological studies were also performed by SEM and TEM. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography respectively. Addition of 3 wt% pristine mesoporous diatomite nanoplatelets leads to increase of conversion from 73 to 89%. Molecular weight of poly(styrene-co-butyl acrylate) chains increases from 17,115 to 20,343 g·mol −1 by addition of 3 wt% pristine mesoporous diatomite; however, polydispersity index values increases from 1.14 to 1.37. Increasing thermal stability of the nanocomposites is demonstrated by TGA. Differential scanning calorimetry shows an increase in glass transition temperature from 35.26 to 39.61°C by adding 3 wt% of mesoporous diatomite nanoplatelets.

This study reports adsorption of Cr(VI) ions from aqueous solution using activated carbon that was prepared from stems of Leucas aspera . Eight hundred and fifty watts power of microwave radiation, 12 min of radiation time, 60% of ZnCl 2 solution and 24 h of impregnation time are the optimal parameters to prepare efficient carbon effective activated carbon. It was designated as MWLAC (Microwave assisted Zinc chloride activated Leucas aspera carbon). Various adsorption characteristics such as dose of the adsorbent, agitation time, initial Cr(VI) ion concentration, pH of the solution and temperature on adsorption were studied for removal of Cr(VI) ions from aqueous solution by batch mode. Also the equilibrium adsorption was analyzed by the Langmuir, Freundlich, Tempkin and D-R isotherm models. The order of best describing isotherms was given based on R 2 value. The pseudo-second-order kinetic model best fitted with the Cr(VI) adsorption data. Thermodynamic parameters were also determined and results suggest that the adsorption process is a spontaneous, endothermic and proceeded with increased randomness.

In the present research work the degradation of acid yellow 17 (AY 17) by H 2 O 2 /Fe 2+ was investigated. The effect of various conditions such as pH value, temperature, conc. of H 2 O 2 , Fe 2+ , conc. of AY 17 were studied. Additionally the scavenging effects of various anions such as Cl − , SO 4 2− , CO 3 2− and HCO 3 − , on percent degradation of AY 17 were examined. It was found that these anions decrease percent degradation as well as rate of degradation reaction. The optimum conditions were determined as [AY 17]=[Fe 2+ ]=0.06 mM [H 2 O 2 ]=0.9 mM, and pH 3.0 for 60 min of reaction time. It was found that at optimum conditions 89% degradation of AY17 was achieved. The degradation kinetics of AY17 followed pseudo-first-order reaction kinetics. Thermodynamic studies under natural conditions showed positive value of ∆H (enthalpy) which indicates the degradation process is endothermic.

The ability of green micro algae Chlorella vulgaris for biosorption of Cu(II) ions from an aqueous solution was studied. The biosorption process was affected by the solution pH, contact time, temperature and initial Cu(II) concentration. Experimental data were analyzed in terms of pseudo-first order, pseudo-second order and intra particle diffusion models. Results showed that the sorption process of Cu(II) ions followed pseudo-second order kinetics. The sorption data of Cu(II) ions are fitted to Langmuir, Freundlich, and Redlich–Peterson isotherms, and the Temkin isotherm. The thermodynamic study shows the Cu(II) biosorption was exothermic in nature. The Cu(II) ions were recovered effectively from Chlorella vulgaris biomass using 0.1 M H 2 SO 4 with up to 90.3% recovery, allowing for recycling of the Cu. Green algae from freshwater bodies showed significant potential for Cu(II) removal and recovery from industrial wastewater.

This study presents the incorporation of Al and Ni cations onto the surface of TiO 2 nanoparticles used as photoelectrode in dye sensitized solar cells (DSSCs). The incorporation of these cations was performed using the chemical bath deposition (CBD) technique. This process was applied up to three times to evaluate the semiconductors’ properties with respect to the amount of Al and Ni. The M(Al,Ni)-TiO 2 -based semiconductors were widely characterized using techniques such as X-ray fluorescence, X-ray diffraction, Raman spectroscopy, UV-Vis spectroscopy and X-ray photoelectron spectroscopy. The presence of (hydr)oxide species of Al(III) and Ni(II) was confirmed and anatase was the predominant crystalline phase obtained. Moreover, for both elements, a decrease in the band gap energy was observed, this being more pronounced after the incorporation of Ni. Furthermore, the use of the M(Al,Ni)-TiO 2 -based semiconductors as photoelectrodes in DSSCs led to an increase in the open-circuit voltage of up to 22% and 10% for the incorporation of Al and Ni, respectively. This increase can be reasonably explained by the negative shift of the flat band potential of the photoelectrodes. EIS measurements were performed to study the electron transport kinetics in the photoelectrode and the internal resistance in the DSSCs to understand the photocurrent density values obtained.

Using density functional theory (DFT), noncovalent interactions and four mechanisms of covalent functionalization of melphalan anticancer drug onto γ-Fe 2 O 3 nanoparticles have been studied. Quantum molecular descriptors of noncovalent configurations were investigated. It was specified that binding of melphalan onto γ-Fe 2 O 3 nanoparticles is thermodynamically suitable. Hardness and the gap of energy between LUMO and HOMO of melphalan are higher than the noncovalent configurations, showing the reactivity of drug increases in the presence of γ-Fe 2 O 3 nanoparticles. Melphalan can bond to γ-Fe 2 O 3 nanoparticles through NH 2 ( k 1 mechanism), OH ( k 2 mechanism), C=O ( k 3 mechanism) and Cl ( k 4 mechanism) groups. The activation energies, the activation enthalpies and the activation Gibbs free energies of these reactions were calculated. Thermodynamic data indicate that k 3 mechanism is exothermic and spontaneous and can take place at room temperature. These results could be generalized to other similar drugs.