Surface passivation of MgAl2O4 spinel powder by chemisorbing H3PO4 for easy aqueous processing

A stoichiometric MgAl 2O 4 spinel (MAS) powder was synthesized by heat treating at 1400 degrees C for 2 h a compacted mixture of alpha-Al 2O 3 and calcined caustic MgO, followed by crushing and milling. The surface of this powder was then passivated against hydrolysis with H 3PO 4 and Al(H 2PO 4) 3 in an ethanol solution. The as-passivated powder could then be dispersed in water using tetramethylammonium hydroxide (TMAH) and an ammonium salt of poly(acrylic acid) (Duramax D-3005) as dispersing agents and gelcast to form green consolidates with relatively high strength (>15 MPa). The good dispersing behavior of the passivated powder in water was confirmed by the low viscosity of its suspension containing 41-45 vol % solids, demonstrating the viability of replacing organic solvents by water in colloidal processing of MAS-based ceramics. The Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and energy dispersive X-ray (EDAX) studies revealed that only negligible amounts of phosphate ions at the surface are required to effectively protect the powder from reacting with water.     

Lectins and/or xyloglucans/alginate layers as supports for immobilization of dengue virus particles

Formation of stable thin films of mixed xyloglucan (XG) and alginate (ALG) onto Si/SiO(2) wafers was achieved under pH 11.6, 50mM CaCl(2), and at 70 degrees C. XG-ALG films presented mean thickness of (16+/-2)nm and globules rich surface, as evidenced by means of ellipsometry and atomic force microscopy (AFM), respectively. The adsorption of two glucose/mannose-binding seed (Canavalia ensiformis and Dioclea altissima) lectins, coded here as ConA and DAlt, onto XG-ALG surfaces took place under pH 5. Under this condition both lectins present positive net charge. ConA and DAlt adsorbed irreversibly onto XG-ALG forming homogenous monolayers approximately (4+/-1)nm thick. Lectins adsorption was mainly driven by electrostatic interaction between lectins positively charged residues and carboxylated (negatively charged) ALG groups. Adhesion of four serotypes of dengue virus, DENV (1-4), particles to XG-ALG surfaces were observed by ellipsometry and AFM. The attachment of dengue particles onto XG-ALG films might be mediated by (i) H bonding between E protein (located at virus particle surface) polar residues and hydroxyl groups present on XG-ALG surfaces and (ii) electrostatic interaction between E protein positively charged residues and ALG carboxylic groups. DENV-4 serotype presented the weakest adsorption onto XG-ALG surfaces, indicating that E protein on DENV-4 surface presents net charge (amino acid sequence) different from E proteins of other serotypes. All four DENV particles serotypes adsorbed similarly onto lectin films adsorbed. Nevertheless, the addition of 0.005mol/L of mannose prevented dengue particles from adsorbing onto lectin films. XG-ALG and lectin layers serve as potential materials for the development of diagnostic methods for dengue.     

Aflatoxin B(1) adsorption by natural and copper modified montmorillonite

Adsorption of aflatoxin B(1) (AFB1) by natural montmorillonite (MONT) and montmorillonite modified with copper ions (Cu-MONT) was investigated. Both MONTs were characterized using the X-ray powder diffraction (XRPD) analysis, thermal analysis (DTA/TGA) and scanning electron miscroscopy/electron dispersive spectroscopy (SEM/EDS). The results of XRPD and SEM/EDS analyses of Cu-MONT suggested partial ion exchange of native inorganic cations in MONT with copper occurred. Investigation of AFB1 adsorption by MONT and Cu-MONT, at pH 3, 7 or 9, showed that adsorption of this toxin by both MONTs was high (over 93%). Since AFB1 is nonionizable, no differences in AFB1 adsorption by both MONTs, at different pHs, were observed, as expected. Futhermore, it was determined that adsorption of AFB1 by both MONTs followed a non-linear (Langmuir) type of isotherm, at pH 3. The calculated maximum adsorbed amounts of AFB1 by MONT (40.982mg/g) and Cu-MONT (66.225mg/g), derived from Langmuir plots of isotherms, indicate that Cu-MONT was much effective in adsorbing AFB1. Since, the main cation in an exchangeable position in MONT is calcium, and in Cu-MONT both calcium and copper, the fact that ion exchange of inorganic cations in MONT with copper increases adsorption of AFB1 suggests that additional interactions between AFB1 and copper ions in Cu-MONT caused greater adsorption.     

Physical immobilization of Rhizopus oryzae lipase onto cellulose substrate: activity and stability studies

Rhizopus oryzae lipase (ROL) was immobilized by adsorption onto oxidized cellulose fibers and regenerated films. The maximum adsorption level increases with the raise in the amount of carboxylic groups on cellulose surface confirming that adsorption is being governed mainly by electrostatic interaction between the enzyme and the substrate. This hypothesis was further confirmed by zeta-potential measurements showing a decrease in the zeta-potential of the fibers after enzyme adsorption. XPS analysis showed an intensification of the N 1s peak attesting the presence of the enzyme on the surface. The effect of temperature, pH and solvent polarity on the immobilized enzyme activity and stability was investigated. The catalytic esterification of oleic acid with n-butanol has been carried on using hexane as an organic solvent. A high conversion yield was obtained (about 80%) at 37 degrees C with a molar ratio of oleic acid to butanol 1:1 and 150IU immobilized lipase. The adsorption achieved two successive cycles with the same efficiency, and started to lose its activity during the third cycle.     

Physico-chemical and electrical properties of activated carbon cloths: Effect of inherent nature of the fabric precursor

Five different cellulose-based fabrics were used to prepare activated carbon cloths (ACCs) by phosphoric acid activation at pre-established experimental conditions, in an attempt to explore the effect of the precursor's nature on properties of the resulting ACCs. Characterization by elemental analysis, nitrogen (77 K) adsorption, and scanning electron microscopy was carried out. Electrical properties of the developed ACCs were investigated to examine the possibility of regenerating the ACCs by direct electrical heating. Thermal behavior of the raw precursor and of one of the acid-treated fabrics was also studied by thermogravimetric analysis and noticeable differences due to the precursors’ characteristics and acid impregnation were detected, respectively. The ACCs derived from a denim precursor showed BET surface area (784 m² g⁻¹) and total pore volume (0.40 cm³ g⁻¹) lower than those obtained from the four other precursors (1058–1183 m² g⁻¹, 0.55–0.67 cm³ g⁻¹), whereas carbon content and yield for the former were higher. Morphology and physical appearance of the ACCs were dependent on the raw fabric employed, with most of the samples presenting well-preserved fibres integrity. Besides, the denim-derived ACCs also showed the lowest electrical resistivity (8.10⁻³ Ωm). It was properly correlated with the elemental carbon content and total pore volume of the developed ACCs.     

Metal-catalysed oxidation processes in thiosemicarbazones: new complexes with the ligand N-{2-([4-N-ethylthiosemicarbazone]methyl)phenyl}-p-toluenesulfonamide

The coordination behaviour of a new thiosemicarbazone Schiff-base building block, N-{2-([4-N-ethylthiosemicarbazone]methyl)phenyl}-p-toluenesulfonamide, H2L1 (1), incorporating a bulky tosyl group, towards Mn II, Fe II, Co II, Ni II, Cu II, Zn II, Cd II, Ag I, Sn II, and Pb II has been investigated by means of an electrochemical preparative procedure. Most metal complexes of L1 have the general formula [M(L1)]2.nX (M=Mn, Fe, Co, Ni, Cu, Cd, Pb; n=0-4, X=H2O or CH3CN), as confirmed by the structure of [Pb(L1)]2 (15), in which the lone pair on lead is stereochemically active. This lead(II) complex shows an intense fluorescence emission with a quantum yield of 0.13. In the case of silver, the complex formed was found to possess a stoichiometry of [Ag2(L1)]2.3H2O. During reactions with manganese and copper metals, interesting catalysed processes have been found to take place, with remarkable consequences regarding the ligand skeleton structure. In synthesising the manganese complex, we obtained an unexpected dithiolate thiosemicarbazone tosyl ligand, H2L2, as a side-product, which has been fully characterised, including by X-ray diffraction analysis. In the case of copper, the solid complex has the formula [CuL1]2, but the crystallised product shows the copper atoms coordinated to a new cyclised thiosemicarbazone ligand, H2L3, as in the structures of the complexes [Cu(L3)]2.CH3CN (8) and [Cu(L3)(H2O)]2.CH3CN.H2O (9). The zinc complex [Zn(L1)]4 (12) displays a particular tetranuclear zeolite-type structure capable of hosting small molecules or ions, presumably through hydrogen bonding.     

Sigma-borane complexes of iridium: synthesis and structural characterization

Reaction of NaBH4 with (tBuPOCOP)IrHCl affords the previously reported complex (tBuPOCOP)IrH2(BH3) (1) (tBuPOCOP = kappa(3)-C6H3-1,3-[OP(tBu)2]2). The structure of 1 determined from neutron diffraction data contains a B-H sigma-bond to iridium with an elongated B-H bond distance of 1.45(5) A. Compound 1 crystallizes in the space group P1 (Z = 2) with a = 8.262 (5) A, b = 12.264 (5) A, c = 13.394 (4) A, and V = 1256.2 (1) A(3) (30 K). Complex 1 can also be prepared by reaction of BH3 x THF with (tBuPOCOP)IrH2. Reaction of (tBuPOCOP)IrH2 with pinacol borane gave initially complex 2, which is assigned a structure analogous to that of 1 based on spectroscopic measurements. Complex 2 evolves H2 at room temperature leading to the borane complex 3, which is formed cleanly when 2 is subjected to dynamic vacuum. The structure of 3 has been determined by X-ray diffraction and consists of the (tBuPOCOP)Ir core with a sigma-bound pinacol borane ligand in an approximately square planar complex. Compound 3 crystallizes in the space group C2/c (Z = 4) with a = 41.2238 (2) A, b = 11.1233 (2) A, c = 14.6122 (3) A, and V = 6700.21 (19) A(3) (130 K). Reaction of (tBuPOCOP)IrH2 with 9-borobicyclononane (9-BBN) affords complex 4. Complex 4 displays (1)H NMR resonances analogous to 1 and exists in equilibrium with (tBuPOCOP)IrH2 in THF solutions.     

Design, synthesis, and biological evaluation of platensimycin analogues with varying degrees of molecular complexity

The molecular design, chemical synthesis, and biological evaluation of two distinct series of platensimycin analogues with varying degrees of complexity are described. The first series of compounds probes the biological importance of the benzoic acid subunit of the molecule, while the second series explores the tetracyclic cage domain. The biological data obtained reveal that, while the substituted benzoic acid domain of platensimycin is a highly conserved structural motif within the active compounds with strict functional group requirements, the cage domain of the molecule can tolerate considerable structural modifications without losing biological action. These findings refine our present understanding of the platensimycin pharmacophore and establish certain structure-activity relationships from which the next generation of designed analogues of this new antibiotic may emerge.     

Coacervative extraction of Ochratoxin A in wines prior to liquid chromatography/fluorescence determination

Coacervates made up of reverse micelles of decanoic acid were assessed as a new strategy for the simplification of wine sample treatment in the determination of Ochratoxin A (OTA). Simultaneous extraction/concentration of this contaminant was based on both hydrophobic and hydrogen bond OTA:coacervate interactions. Parameters affecting extraction efficiency and concentration factors were studied. Concentrations of decanoic acid and tetrahydrofuran (THF) were the most influential parameters, being 0.5% of acid and 5% of THF the selected ones. The procedure was very robust, so that the extractions were not influenced by the pH and the nature or concentration of matrix components. OTA recoveries from different types of wines (white, rosé and red) ranged between 85 and 100% and the actual concentration factors varied from 105 to 125 for sample volumes of 15 mL. The detection limits for OTA, after liquid chromatography/fluorimetry (LC/FL) analysis of the coacervate (20 microL), were 4.5 ng L(-1) in white and rosé wines and 15 ng L(-1) in red wines, values which were far below the threshold limit established for OTA by EU directives (2.0 microg L(-1)). No clean-up of the extracts was required for any of the samples analysed. The overall sample treatment took about 15-20 min and several samples could be simultaneously treated using conventional lab equipment. The precision of the method, expressed as relative standard deviation, was about 5%. The approach developed was successfully applied to the determination of OTA in different wine samples from the South of Spain. The concentrations found ranged between 0.015 and 0.091 microg L(-1).