Effects of anionic additives on the rheological behavior of aqueous calcium montmorillonite suspensions

Three different experimental measurements, namely, rheology, particle sizing, and x-ray diffraction (XRD), were used to study the effect of anionic additives on the properties of bentonite suspensions. The three additives were sodium carboxymethylcellulose, xanthan gum, and sodium dodecyl sulfate. Flow curves were obtained from shear stress–shear rate measurements, and the viscoelastic properties were determined from oscillatory and transient measurements. Mineralogical data were evaluated by XRD and the particle size analysis performed by light scattering technique. The presence of the surfactant modifies the face-to-face interactions and yields changes of the mixtures rheological behavior at low deformation rates. Polymers act by coating each clay particle and prevent their agglomeration. Therefore, the additives are responsible for the mechanisms of destructuration and structure reorganization as well as the mixtures viscous and viscoelastic behavior.     

S-Storage Operators

In 1990, J. L. Krivine introduced the notion of storage operator to simulate, for Church integers, the “call by value” in a context of a “call by name” strategy. In the present paper we define for every λ-term S which realizes the successor function on Church integers the notion of S-storage operator. We prove that every storage operator is an S-storage operator. But the converse is not always true.     

Anisotropic Lithium Ion Conductivity in Single‐Ion Diblock Copolymer Electrolyte Thin Films

Well‐defined single‐ion diblock copolymers consisting of a Li‐ion conductive poly(styrenesulfonyllithium(trifluoromethylsulfonyl)imide) (PSLiTFSI) block associated with a glassy polystyrene (PS) block have been synthesized via reversible addition fragmentation chain transfer polymerization. Conductivity anisotropy ratio up to 1000 has been achieved from PS‐b‐PSLiTFSI thin films by comparing Li‐ion conductivities of out‐of‐plane (aligned) and in‐plane (antialigned) cylinder morphologies at 40 °C. Blending of PS‐b‐PSLiTFSI thin films with poly(ethylene oxide) homopolymer (hPEO) enables a substantial improvement of Li‐ion transport within aligned cylindrical domains, since hPEO, preferentially located in PSLiTFSI domains, is an excellent lithium‐solvating material. Results are also compared with unblended and blended PSLiTFSI homopolymer (hPSLiTFSI) homologues, which reveals that ionic conductivity is improved when thin films are nanostructured.

     

Acoustics and dynamics of coaxial interacting vortex rings

Using a contour dynamics method for inviscid axisymmetric flow we examine the effects of core deformation on the dynamics and acoustic signatures of coaxial interacting vortex rings. Both “passage” and “collision” (head-on) interactions are studied for initially identical vortices. Good correspondence with experiments is obtained. A simple model which retains only the elliptic degree of freedom in the core shape is used to explain some of the calculated features.     

Determination of Imidacloprid in Tomato Grown in Greenhouse Based on Copper(II) Phthalocyanine Modified Carbon Ceramic Electrode by Differential Pulse Voltammetry

A new sol‐gel derived electrocatalytic carbon ceramic electrode was prepared by incorporating copper(II) phthalocyanine (CuPc) in a carbon ceramic network. This electrode was used as a sensitive electrochemical sensor for determination of the insecticide Imidacloprid (1‐(6‐chloro‐3‐pyridylmethyl)‐N‐nitro‐imidazolidin‐2‐ylideneamine) by differential pulse voltammetry (DPV). The resulting modified electrode exhibits a cathodic peak potential shifted positively and an increasing in cathodic peak current in comparison with unmodified electrode. The redox properties of this modified electrode at various pH values and CuPc percentage were investigated. The catalytic current obtained from differential pulse voltammetry is linearly dependent on Imidacloprid concentration over the two linear ranges of 0.67‐17 μM and 17‐93 μM with correlation coefficient of R² = 0.9999 and R² = 0.990, respectively. The detection limit for Imidacloprid was found to be 0.28 μM according to lower linear range. Possible interferences from several common pesticides were also evaluated. The inherent stability, high sensitivity, low detection limit and low cost for each preparation are advantages of this sensor. Determination of Imidacloprid in commercial formulation and residual Imidacloprid in tomato grown in greenhouse (protected cultivation) was also conducted. The results obtained from commercial formulation were completely consistent with those obtained through the standard high‐performance liquid chromatography (HPLC) method.     

Eu(3+)-mediated polymerization of benzenetetracarboxylic acid studied by spectroscopy, temperature-dependent calorimetry, and density functional theory

Thermodynamic parameters for the complexation of Eu(3+) with pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid, BTC) as a model system for polymerizable metal-complexing humic acids were determined using temperature-dependent time-resolved laser-induced fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC). At low metal and ligand concentrations (<50 μM Eu(3+), <1 mM BTC), a 1:1 monomeric Eu-BTC complex was identified in the range of 25-60 °C. At elevated concentrations (>500 μM Eu(3+) and BTC) a temperature-dependent polymerization was observed, where BTC monomers are linked via coordinating shared Eu(3+) ions. The two methods lead to comparable thermodynamic data (ΔH = 18.5 ± 1.5/16.5 ± 0.1 kJ mol(-1); ΔS = 152 ± 5/130 ± 5 J mol(-1) K(-1); TRLFS/ITC) in the absence of polymerization. With the onset of polymerization, TRLFS reveals the water coordination number of the lanthanide, whereas calorimetry is superior in determining the thermodynamic data in this regime. Evaluating the heat uptake kinetics, the monomer and polymer formation steps could be separated by "time-resolved" ITC, revealing almost identical binding enthalpies for the sequential reactions. Structural features of the complexes were studied by Fourier-transform infrared (FTIR) spectroscopy in combination with density functional theory (DFT) calculations showing predominantly chelating coordination with two carboxylate groups in the monomeric complex and monodentate binding of a single carboxylate group in the polymeric complex of the polycarboxylate with Eu(3+). The data show that pyromellitic acid is a suitable model for the study of metal-mediated polymerization as a crucial factor in determining the effect of humic acids on the mobility of heavy metals in the environment.     

Friedel-Craft acylation of ar-himachalene: synthesis of acyl-ar-himachalene and a new acyl-hydroperoxide

Friedel-Craft acylation at 100 °C of 2,5,9,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocycloheptene [ar-himachalene], a sesquiterpenic hydrocarbon obtained by catalytic dehydrogenation of α-, β- and γ-himachalenes, produces a mixture of two compounds: (3,5,5,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocyclohepten-2-yl)-ethanone (2, in 69% yield), with a conserved reactant backbone, and 3, with a different skeleton, in 21% yield. The crystal structure of 3 reveals it to be 1-(8-ethyl-8-hydroperoxy-3,5,5-trimethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-ethanone. In this compound O-H…O bonds form dimers. These hydrogen-bonds, in conjunction with weaker C-H…O interactions, form a more extended supramolecular arrangement in the crystal.     

Ni(0)-CMC-Na - nickel colloids in sodium carboxymethyl-cellulose: catalytic evaluation in hydrogenation reactions

A recyclable catalyst, Ni(0)-CMC-Na, composed of nickel colloids dispersed in a water soluble bioorganic polymer, sodium carboxymethylcellulose (CMC-Na), was synthesized by a simple procedure from readily available reagents. The catalyst thus obtained is stable and highly active in alkene hydrogenations.