A single-site model for divalent transition and heavy metal adsorption over a range of metal concentrations

Metal adsorption data over a range of surface coverages typically are characterized by curvilinear metal adsorption isotherms. These isotherms generally have a slope of 1 at low surface coverage and a shallower slope at higher surface coverages. The curvature of metal adsorption isotherms with increasing surface coverage is frequently interpreted in terms of sequential adsorption onto different types of surface sites, multinuclear surface complexation, or nonideality of metal adsorption. We demonstrate that the curvature of metal adsorption isotherms can also be attributed to changes in surface charge and potential that depend on the predominant type of metal surface complex. A single-site extended triple-layer model is used to reinterpret previously studied metal adsorption isotherms and pH edges for a wide variety of metals (Cd2+, Co2+, Cu2+, Pb2+, and Zn2+) and solids (goethite, hydrous ferric oxide, corundum, and magnetite) in different electrolyte solutions (NaNO3 and NaClO4). Only metal adsorption on ferrihydrite at very low surface coverages is not consistent with the single-site triple-layer model. This discrepancy might be explained if ferrihydrite is in fact not a single phase but a mixture of two or more phases. Metal surface coverages ranging from 10(-4) to 10.2 mmol/m2 on the other minerals can be accounted for with a single-site extended triple-layer model if appropriate metal adsorption reactions are chosen. In addition, several examples suggest that, within the context of the model, surface complexation schemes can be established that describe metal adsorption over both a wide range of surface coverage and a wide range of ionic strength.     

Formation of supported size-controlled nanoparticles of sulfated zirconia

Methods of the preparation of catalysts for alkane skeletal isomerization based on uniform nanoparticles of sulfated zirconia anchored to different supports were investigated. These catalysts were characterized by using the ICP, HRTEM and BET techniques. The activities of the catalysts in the reaction of n-butane isomerization were measured and compared with those of bulk catalysts.     

2-Azabicyclo[2.2.1]heptane-3-carboxylic acid - A bicyclic proline

Diels-Alder reaction of cyclopentadiene and methyl N-carbobenzyloxy-2-iminoacetate generated in situ from methyl 2-chloro-N-carbobenzyloxyglycinate by triethylamine gave the N-carbobenzyloxy unsaturated bicyclic proline ester. This was converted in two steps to 2-azabicylo[2.2.1]heptane-3-carboxylic acid. In contrast to N-carbobenzyloxy-L-proline methyl ester, the corresponding bicyclic proline ester was resistant to hydrolysis catalyzed by carboxypeptidase Y.     

Local dense structural heterogeneities in liquid water from ambient to 300 MPa pressure: evidence for multiple liquid-liquid transitions.

Difference and double-difference near-infrared DO-D and HO-H stretching overtone (2nuOD and 2nuOH) spectroscopy and a rigorous (physically substantiated) band deconvolution technique were applied to reveal three different kinds of inherent (interstitial) structures of liquid water, which determine its high density (compared to ice lh under ambient conditions), its compressibility (under hydrostatic pressure, up to 300MPa), and its high fragility (manifested under temperature variation). Our data processing allowed the rigorous discrimination of up to six vibrational components. On the basis of an extensive comparative analysis combined with available structural data (X-ray and neutron scattering) and molecular dynamics (MD) simulations for liquid water, as well as with experimental and computed data for small non-tetrahedrally arranged water clusters, the major four components could be ascribed to: i) The basic lh icelike substructure; ii) the temperature-dependent remote interstitial "defects" due to tetrahedral displacements (primarily responsible for transport properties); iii) the interstitial "defects" most probably arranged in quasiplanar noncyclic tetramers (totally absent in the ice structure); and iv) the interstitial "defects" formed with increasing pressure, probably arranged in cubic water octamers and composed of two pairs of noncyclic and cyclic tetramer fragments. The latter structures include, essentially, bent hydrogen bonds stabilized by resonance effects.     

Fast reduction of a copper center in laccase by nitric oxide and formation of a peroxide intermediate

The rapid reduction of one of the copper atoms (type 2) of tree laccase by nitric oxide (NO) has been detected. Addition of NO to native laccase in the presence of oxygen leads to EPR changes consistent with fast reduction and slow reoxidation of this metal center. These events are paralleled by optical changes that are reminiscent of formation and decay of the peroxide intermediate in a fraction of the enzyme population. Formation of this species is only possible if the trinuclear copper cluster (type 2 plus type 3) is fully reduced. This condition can only be met if, as suggested previously, a fraction of the enzyme contains both type 3 coppers already reduced before addition of NO. Our data are consistent with this assumption. We have suggested recently that fast reduction of copper is the mechanism by which NO interacts with the oxidized dinuclear center in cytochrome c oxidase. The present experiments using laccase strongly support this view and suggest this reaction as a general mechanism by which copper proteins interact with NO. In addition, this provides an unexploited way to produce a stable peroxide intermediate in copper oxidases in which the full complement of copper atoms is present. This enables the O-O scission step in the catalytic cycle to be studied by electron addition to the peroxide derivative through the native electron entry site, type 1 copper.     

Catalytic Reduction of Hydrazine to Ammonia with MoFe(3)S(4)-Polycarboxylate Clusters. Possible Relevance Regarding the Function of the Molybdenum-Coordinated Homocitrate in Nitrogenase

The catalytic function of the previously synthesized and characterized [(L)MoFe(3)S(4)Cl(3)](2)(-)(,3)(-) clusters (L = tetrachlorocatecholate, citrate, citramalate, methyliminodiacetate, nitrilotriacetate, thiodiglycolate) and of the [MoFe(3)S(4)Cl(3)(thiolactate)](2)(4)(-) and [(MoFe(3)S(4)Cl(4))(2)(&mgr;-oxalate)](4)(-) clusters in the reduction of N(2)H(4) to NH(3) is reported. In the catalytic reduction, which is carried out at ambient temperature and pressure, cobaltocene and 2,6-lutidinium chloride are supplied externally as electron and proton sources, respectively. In experiments where the N(2)H(4) to the [(L)MoFe(3)S(4)Cl(3)](n)()(-) catalyst ratio is 100:1, and over a period of 30 min, the reduction proceeds to 92% completion for L = citrate, 66% completion for L = citramalate, and 34% completion for L = tetrachlorocatecholate. The [Fe(4)S(4)Cl(4)](2)(-) cluster is totally inactive and gives only background ammonia measurements. Inhibition studies with PEt(3) and CO as inhibitors show a dramatic decrease in the catalytic efficiency. These results are consistent with results obtained previously in our laboratory and strongly suggest that N(2)H(4) activation and reduction occur at the Mo site of the [(L)MoFe(3)S(4)Cl(3)](2)(-)(, 3)(-) clusters. A possible pathway for the N(2)H(4) reduction on a single metal site (Mo) and a possible role for the carboxylate ligand are proposed. The possibility that the Mo-bound polycarboxylate ligand acts as a proton delivery "shuttle" during hydrazine reduction is considered.     

Screening an In-House Isoquinoline Alkaloids Library for New Blockers of Voltage-Gated Na+ Channels Using Voltage Sensor Fluorescent Probes: Hits and Biases

Voltage-gated Na⁺ (Na_V) channels are significant therapeutic targets for the treatment of cardiac and neurological disorders, thus promoting the search for novel Na_V channel ligands. With the objective of discovering new blockers of Na_V channel ligands, we screened an In-House vegetal alkaloid library using fluorescence cell-based assays. We screened 62 isoquinoline alkaloids (IA) for their ability to decrease the FRET signal of voltage sensor probes (VSP), which were induced by the activation of Na_V channels with batrachotoxin (BTX) in GH3b6 cells. This led to the selection of five IA: liriodenine, oxostephanine, thalmiculine, protopine, and bebeerine, inhibiting the BTX-induced VSP signal with micromolar IC₅₀. These five alkaloids were then assayed using the Na⁺ fluorescent probe ANG-2 and the patch-clamp technique. Only oxostephanine and liriodenine were able to inhibit the BTX-induced ANG-2 signal in HEK293-hNa_V1.3 cells. Indeed, liriodenine and oxostephanine decreased the effects of BTX on Na⁺ currents elicited by the hNa_V1.3 channel, suggesting that conformation change induced by BTX binding could induce a bias in fluorescent assays. However, among the five IA selected in the VSP assay, only bebeerine exhibited strong inhibitory effects against Na⁺ currents elicited by the hNav1.2 and hNav1.6 channels, with IC₅₀ values below 10 µM. So far, bebeerine is the first BBIQ to have been reported to block Na_V channels, with promising therapeutical applications.     

Ferroelectric liquid crystal composites based on the porous stretched polyethylene films

Electro-optically active polymer–liquid crystal composites based on ferroelectric liquid crystals and stretched porous polyethylene films were developed. The alignment of ferroelectric liquid crystals incorporated into the porous polyethylene films with average porous diameter of around 200 nm was observed and studied. It was shown experimentally that these samples containing ferroelectric liquid crystals are flexible electro-optical films exhibiting a saturation electric field near 2·10⁷ Vm^?1 and a response time of about 30 μs under the action of the saturation field. A simple theoretical model of ferroelectric liquid crystal molecules' complete reorientation in electric fields inside pores of the films has been proposed and confirmed experimentally.