An assessment of pure,hybrid, meta,and hybrid‐meta GGA density functional theory methods for open‐shell systems: The case of the nonheme iron enzyme 8R–LOX

The performance of a range density functional theory functionals combined in a quantum mechanical (QM)/molecular mechanical (MM) approach was investigated in their ability to reliably provide geometries, electronic distributions, and relative energies of a multicentered open‐shell mechanistic intermediate in the mechanism 8R–Lipoxygenase. With the use of large QM/MM active site chemical models, the smallest average differences in geometries between the catalytically relevant quartet and sextet complexes were obtained with the B3LYP^* functional. Moreover, in the case of the relative energies between ⁴II and ⁶II , the use of the B3LYP^* functional provided a difference of 0.0 kcal mol^–1. However, B3LYP^± and B3LYP also predicted differences in energies of less than 1 kcal mol^–1. In the case of describing the electronic distribution (i.e., spin density), the B3LYP^*, B3LYP, or M06‐L functionals appeared to be the most suitable. Overall, the results obtained suggest that for systems with multiple centers having unpaired electrons, the B3LYP^* appears most well rounded to provide reliable geometries, electronic structures, and relative energies. © 2012 Wiley Periodicals, Inc.     

A valence bond model for aqueous Cu(II) and Zn(II) ions in the AMOEBA polarizable force field

A general molecular mechanics (MM) model for treating aqueous Cu²⁺ and Zn²⁺ ions was developed based on valence bond (VB) theory and incorporated into the atomic multipole optimized energetics for biomolecular applications (AMOEBA) polarizable force field. Parameters were obtained by fitting MM energies to that computed by ab initio methods for gas‐phase tetra‐ and hexa‐aqua metal complexes. Molecular dynamics (MD) simulations using the proposed AMOEBA‐VB model were performed for each transition metal ion in aqueous solution, and solvent coordination was evaluated. Results show that the AMOEBA‐VB model generates the correct square‐planar geometry for gas‐phase tetra‐aqua Cu²⁺ complex and improves the accuracy of MM model energetics for a number of ligation geometries when compared to quantum mechanical (QM) computations. On the other hand, both AMOEBA and AMOEBA‐VB generate results for Zn²⁺–water complexes in good agreement with QM calculations. Analyses of the MD trajectories revealed a six‐coordination first solvation shell for both Cu²⁺ and Zn²⁺ ions in aqueous solution, with ligation geometries falling in the range reported by previous studies. © 2012 Wiley Periodicals, Inc.     

Study and Modeling of Metal Oxide Solubilization in (w/o) Microemulsions

Water-in-oil (w/o) microemulsions are very appealing reaction media due to their ability to provide huge surface of contact between water-soluble and oil-soluble reactants. Their application as reaction media, including the preparation of nanoparticles, is, however, limited to water soluble precursors. In this study, we present a first step scheme in a two-step process for the preparation of metal oxide nanoparticles starting from their water-insoluble metal oxide bulk powder. This step involves solubilizing the metal oxide in the water pools of the microemulsion with the aid of a solubilizing agent. The variables affecting the solubilizing capacity of iron and copper oxides, as examples of important metal oxides, in single HCl-containing AOT/water/isooctane microemulsions were investigated. The effect of the following variables on the solubilization capacity is reported, namely, mixing time, surfactant concentration, water to surfactant mole ratio (R), and the nominal concentration of HCl in the water pool. At 300-rpm, time-invariant concentration of the metals in the microemulsions was achieved in about 6 hours. These values were quoted as the solubilization capacity of the metal oxide at the corresponding conditions. Solubilization capacity increased linearly with the surfactant concentration and R, and portrait a power function with the nominal concentration of HCl in the water pool. A mathematical model previously derived to describe nanoparticle uptake by single microemulsion accurately accounted for the effect of the aforementioned variables on the solubilization capacity.     

Studies on the Uptake of Rare Earth Elements on Polyacrylamidoxime Resins from Natural Concentrate Leachate Solutions

Synthesis of poly(acrylamidoxime) resin from polyacrylonitrile performed with different crosslinking ratios 2, 5, and 10 wt% of divinylbenzene as crosslinking agent, using methylbenzoate and dioctylphthalate as pore producing solvent, the reaction mixture occurred under nitrogen. Studies carried out on diluted solution from rare earth elements (REEs) concentrate contains impurities as Cu²⁺, Ni²⁺, Zn²⁺, Fe³⁺, Al³⁺, Si⁴⁺, Th⁴⁺, U⁶⁺, Ca²⁺, and K⁺. Changing some parameters as pH of the solution, time of feeding and type of acid as HCl, HNO₃, H₂SO₄. The adsorption efficiency of resin is in the order pH 6 > pH 5 > pH 4 > pH 2 with excluding pH 6 due to the precipitation of some of REEs with the impurities and complete precipitation of Dy ion during pH adjustment, the adsorption in HNO₃ > HCl > H₂SO₄ media.     

Micellar Effects on Alkaline Hydrolysis of 3,5-Dinitro-2-chloro Benzotriflouride and 2,4-Dinitrochloro Benzene in Aqueous-Acetonitrile Mixtures

Reaction rate for alkaline hydrolysis of the substrates 3,5-dinitro-2-chloro benzotriflouride (DNCBTF) (1) at 30°C and 2,4-dinitrochloro benzene (DNCB) (2) at 50°C separetely with NaOH as nucleophile is carried out spectrophotometrically in mixed aqueous-acetonitrile solvents. In each system, cationic surfactant as dodecyltrimethyl ammonium bromide (DoTAB), or anionic one as sodium dodecyle sulfate (SDS) is used in wide range of concentrations to study the effect of micelle on the reaction rate. The micellar effect is explained in term of modified pseudo phase ion exchange model. Pseudo first order rate constant, k_obs is obtained for each of the nucleophile and for both substrates 1 and 2 at all range of X_AN · k_obs at given [OH^?] and in presence of any substrate is found to increase with the increase of DoTAB,while decrease with the increase of SDS as micellar phases. Critical micelle concentrations (CMCs) in similar trend are observed to increase in DoTAB while decrease in SDS systems by increasing acetonitrile (AN) content. Micellar binding constant (K_S) between any type of given substrate and the formed micelle, is found to decrease in presence of DoTAB and increase in SDS micellar phases by increasing AN content. Finally, the ratios between pseudo first order rate constants for hydrolysis in micellar phase k_M to that in the bulk phase k_w for DoTAB and SDS systems are found to be greater than and smaller than unity respectively at any given X_AN where the data indicated for (1) is always higher than those for (2). The results concluded that micelle DoTAB is working as a catalyst for the reaction rate, while that for SDS is considered as an inhibitor.     

Comparative Study of Biosorption of Heavy Metals Using Living Green Algae Scenedesmus quadricauda and Neochloris pseudoalveolaris: Equilibrium and Kinetics

The biosorption of several heavy metals such as cobalt(II), chromium(III), lead(II), cadmium(II), nickel(II), and manganese(II) from aqueous systems on living microalgae cultures, Scenedesmus quadricauda and Neochloris pseudoalveolaris were studied under laboratories conditions. The kinetic and statistical parameters were calculated by using the data obtained from batch cultivation and well fitted a pseudo-first-order rate equation. The initial metal concentrations in solution were about 5–40 mg · L^?1. According to the pseudo-second-order model, the biosorption capacities of Scenedesmus quadricauda for Co(II), Cr(III), Pb(II), Cd(II), Ni(II), and Mn(II) ions were found in the ranges of 2.14–52.48, 1.98–81.98, 8.05–4.26, 7.81–24.96, 2.17–55.71, and 3.54–75.20 mg g^?1, respectively. Kinetic studies revealed that the metal uptake capacity of each living green algae was rather fast. It was also observed that the biosorption kinetic rate decreased with increasing concentration for both microalgae. The application of diffusion-controlled models to the experimental results indicated that the contribution of intraparticle diffusion to the overall sorption kinetics was not very important. Results showed that Co(II), Cr(III), Pb(II), Cd(II), Ni(II), and Mn(II) ions could effectively be absorbed by using living microalga cultures from aqueous solutions.     

湖南辰溪特高有机硫煤的稀土元素特征及其成因

采用高分辨率电感耦合等离子质谱(HR-ICP-MS)技术测定辰溪晚二叠世高有机硫(7.75%)煤中的稀土元素(REEs)。辰溪煤中∑REE变化较大,从38.84 μg/g至305.85 μg/g,加权平均值为104.57 μg/g,高于世界煤均值,与中国煤相近。辰溪煤中有明显的Ce负异常(δCe=0.74~0.84)和Eu的负异常(δEu=0.55~0.69)。煤层剖面上稀土元素含量和分布模式的变化反映了成煤环境的波动,从底板到顶板陆源物质的影响减弱,而海水的影响增强。沉积环境的阶段性变化是导致剖面上下有机硫与黄铁矿硫比值相差悬殊的原因。辰溪煤中稀土元素与铁呈现了显著的正相关性(n=11,r=0.95),说明其物质来源和富集条件有一定相似性,即陆源物质和海水共同影响的结果。稀土元素的分布模式以及∑REE与灰分、Si、Al的相关性说明了其主要来源于陆源物质;辰溪煤中δCe与δEu在剖面上变化很小,说明海水对煤中的稀土元素存在重新改造的作用。     

Rapid conversion of cellulose to 5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid

Direct conversion of cellulose into 5-hydroxymethylfurfural(HMF) was performed by using single or combined metal chloride catalysts in 1-ethyl-3-methylimidazolium chloride(Cl) ionic liquid.Our study demonstrated formation of 2-furyl hydroxymethyl ketone(FHMK),and furfural(FF) simultaneously with the formation of HMF.Various reaction parameters were addressed to optimize yields of furan derivatives produced from cellulose by varying reaction temperature,time,and the type of metal chloride catalyst.Catalytic reaction by using FeCl3 resulted in 59.9% total yield of furan derivatives(HMF,FHMK,and FF) from cellulose.CrCl3 was the most effective catalyst for selective conversion of cellulose into HMF(35.6%) with less concentrations of FHMK,and FF.Improving the yields of furans produced from cellulose could be achieved via reactions catalyzed by different combinations of two metal chlorides.Further optimization was carried out to produce total furans yield 75.9% by using FeCl3/CuCl2 combination.CrCl3/CuCl2 was the most selective combination to convert cellulose into HMF(39.9%) with total yield(63.8%) of furans produced from the reaction.The temperature and time of the catalytic reaction played an important role in cellulose conversion,and the yields of products.Increasing the reaction temperature could enhance the cellulose conversion and HMF yield for short reaction time intervals(5~20 min).     

Novel mesophases in fluorine substituted banana-shaped mesogens

A new homologous series of achiral banana-shaped mesogens ('Dn') has been synthesized and studied by the classical techniques (optical microscopy, differential scanning calorimetry, X-ray diffraction, miscibility studies and electro-optic investigations). The short homologues (D6-D8) exhibit a two-dimensional phase 'B1_x' different from a B1 phase with a rectangular lattice. The longer homologues (D9-D14) present a mesophase which displays the defects of the B7 phase of the PIMB-NO₂ compounds. Nevertheless the D9-D14 mesophase is not miscible with the B7 phase, and contrary to B7, exhibits a bistable behaviour ('ferroelectric' type) suggesting at least a B7 variant.     

Cleansing contaminated seawaters using marine cyanobacteria: evaluation of trace metal removal from the medium

The use of microbial biomass in biosorption is already being studied as a potential alternative to (or combined with) conventional processes, where several algae and microorganisms have already shown promising ability to uptake metals. Cyanobacteria (blue-green algae) are widespread organisms, with specific properties, such as high nutrient removal capacity and tolerance to highly variable conditions which make them well-suited for wastewater and remediation purposes. The main aim of this work was to evaluate the use of a marine cyanobacterium LEANCYA 21 (Synechocystis sp.), collected from the Portuguese southern border, for the removal of selected trace metals when in natural seawater culture medium. It was observed, for the first time, that this particular strain is capable of uptaking Pb, Ni and Zn (at nM levels) from seawater solutions using small amounts of biomass. Uptake values for Pb were up to 90% (0.75 mg g^?1 biomass) in 6 h. The specific biosorption curves of Ni and Zn showed that these metals follow a first order kinetics biosorption in batch conditions. Solutions containing multimetals have revealed that Ni uptake is affected by the presence of Pb and Zn. The calculated specific absorption values were high enough to predict a possible application in aquaculture where such low levels of metals may inhibit microalgae growth.