Synthesis and reactivity in salt metathesis reactions of trivalent [La(Tp(Me2))(2)X] (X = Cl, I) complexes: crystal structures of [La(Tp(Me2))(2)Cl] and [La(Tp(Me2))(2)(kappa(2)-pz(Me2))]

Reaction of LaX3(THF)(n) (X = Cl, 1) with two equiv. of K(Tp(Me2)) gave good yields of the bis-Tp complexes [La(Tp(Me2))(2)X] (X = Cl (1); I (3)). However, the formation of 1 and 3 is always accompanied by significant amounts of La(Tp(Me2))(2)(kappa(2)-pz(Me2)) ([pz(Me2)](-) = 3,5-dimethyl-pyrazolato) (2). The pyrazolato complex 2, which presumably arises from decomposition of the [Tp(Me2)](-) moiety during salt metathesis, was independently prepared in good yield from 1 and in situ generated [pz(Me2)](-). The solid-state structures of 1 and 2 were determined by single-crystal X-ray diffraction studies. Subsequent reactions of halogeno-Tp(Me2) complexes 1 and 3 with various alkali metal salts MR (M = Li, R = CH2SiMe3, Ph, N(SiMe3)(2); M = K, R = OAr) gave M(Tp(Me2)) as the major product. Alternatively, the mono-Tp bis(aryloxide) derivatives [Ln(Tp(Me2))(OC6H2-2,6-'Bu-4-Me)(2)] (Ln = La (4); Nd (5)) were obtained in high yields by salt metathesis of [Ln(OC6H2-2,6-'Bu-4-Me)(3)] with one equiv. of K(Tp(Me2)). (C) 2004 Elsevier Ltd. All rights reserved.

Cleavage of the dimeric cyclopalladated [Pd(N,C-dmba)(mu-X)](2), (dmba = N,N-dimethylbenzylamine; X = SCN and NCO) by diphosphines. Palladium(II) compounds with distinct structures in the solid-state and in solution

The reactions of the pseudohalide-bridged dimer [Pd(N,C-dmba)(mu -SCN)](2) (1) (dmba = N,N-dimethylbenzylamine) with cis-Ph2PCH=CHPPh2 (cis-dppet) (1:1 molar ratio) and of [Pd(N,C-dmba)(mu -NCO)](2) (2) with Ph2PCH2CH2PPh2 (dppe) (1:2 molar ratio) gave mononuclear [Pd(C-dmba)(SCN)(cis-dppet)].H2O (1a) and [Pd(C-dmba)(NCO)(dppe)] (2a), respectively, with the diphosphines acting as chelating ligands. Reaction of (2) with Fe(C5H4PPh2)(2) (dppf) (1:1 molar ratio) yielded [{Pd(N,C-dmba)(NCO)}(2)(mu -dppf)] (2b), a bimetallic species containing two palladium atoms bridged by the diphosphine, whereas reaction in a 1:2 molar ratio gave the mononuclear [Pd(N,C-dmba)(dppf)][NCO]. CH2Cl2 (2c), with the diphosphine acting as a chelating ligand. The compounds have been characterized by elemental analysis, i.r., P-31{H-1}, C-13- and H-1-n.m.r. spectroscopies. Conductivity measurements together with spectroscopic data showed that (1a) and (2a) do not have the same structure in the solid state and in MeCl solution, whereas for compounds (2b) and (2c) no structural changes were observed when the solids were dissolved in MeCl.

Niobium to alcohol mol ratio control of the concurring esterification and etherification reactions promoted by NbCl5 and Al2O3 catalysts under microwave irradiation

Alcohols and acids can be switched to produce ethers or esters by varying the alcohol to catalyst mol ratio, in a new etherification and esterification method using NbCl5/Al2O3 catalyst under "solvent free" conditions and promoted by MW (microwave) irradiation. A "two sites" mechanism for the reaction is proposed, in an attempt to clarify the tendency of the catalyst to be dependent on the alcohol alone during the esterification process. (c) 2008 Elsevier B.V. All rights reserved.

Solid mass falling into the reservoirs shallow water equations validity from the engineering point of view

Water waves generated by a solid mass is a complex phenomenon discussed in this paper by numerical and experimental approaches. A model based on shallow water equations with shocks (Saint Venant) has developed. It can reproduce the amplitude and the energy of the wave quite well, but because it consistently generates a hydraulic jump, it is able to reproduce the profile, in the case of high relative thickness of slide, but in the case of small relative thickness it is unable to reproduce the amplitude of the wave. As the momentum conservation is not verified during the phase of wave creation, a second technique based on discharge transfer coefficient α, is introduced at the zone of impact. Numerical tests have been performed and validated this technique from the experimental results of the wave's height obtained in a flume.

Use of the paired samples (cerebrospinal fluid and serum) in immunodiagnostic of active and inactive human neurocysticercosis

Paired samples of cerebrospinal fluid (CSF) and serum of 30 patients - 10 with active, 10 with inactive neurocysticercosis (NCC), and 10 control subjects - were evaluated by enzyme-linked immunosorbent assay (ELISA) using two Taenia crassiceps metacestode extracts as antigen in order to detect IgG antibodies. In active NCC, high levels of IgG were detected (p < 0.05). The CSF samples showed 80% (CI 72-88) of reactivity in the saline extract (S) and 90% (CI 84-95) in sodium dodecyl sulphate (SDS) and the serum samples were reactive in 90% (CI 84-95) and 100% (CI 98-100) in the S and SDS antigenic extracts, respectively. The use of the paired samples of CSF and serum in active NCC showed equivalent results suggesting that the serum samples could be used as a screening in those patients whose CSF puncture is counter-indicated.

Development of a supercritical fluid extraction method for simultaneous determination of organophosphorus, organohalogen, organonitrogen and pyretroids pesticides in fruit and vegetables and its comparison with a conventional method by GC-ECD and GC-MS

The aim of this paper was to apply a multiresidue method using Supercritical Fluid Extraction (SFE) and capillary gas chromatography with electron capture and mass spectrometry detections in the analysis of the levels of pesticide residues in fruits and vegetables. Single laboratory validation of both solid-liquid and supercritical fluid extraction methods was carried out for 32 compounds selected from four pesticide classes (organochlorine, organonitrogen, organophosphorus and pyretroid) in blank and fortified samples of fresh lettuce, potato, apple and tomato. Recoveries for the majority of pesticides from fortified samples at fortification level of 0.04-0.10 mg kg -1 ranged 74-96% for both methods and confirmation of pesticide identity was performed by gas-chromatography-mass spectrometry in a selected-ion monitoring mode. Both methods showed good limits of detection (less 0.01 mg kg-1, depending on the pesticide and matrix) and the SFE method minimized environmental concerns, time, and laboratory work. ©2005 Sociedade Brasileira de Química.

PEGylation of SPIONs by polycondensation reactions: A new strategy to improve colloidal stability in biological media

In this study, we report on a new route of PEGylation of superparamagnetic iron oxide nanoparticles (SPIONs) by polycondensation reaction with carboxylate groups. Structural and magnetic characterizations were performed by X-ray diffractometry (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and vibrating sample magnetometry (VSM). The XRD confirmed the spinel structure with a crystallite average diameter in the range of 3.5-4.1 nm in good agreement with the average diameter obtained by TEM (4.60-4.97 nm). The TGA data indicate the presence of PEG attached onto the SPIONs' surface. The SPIONs were superparamagnetic at room temperature with saturation magnetization (M S) from 36.7 to 54.1 emu/g. The colloidal stability of citrate- and PEG-coated SPIONs was evaluated by means of dynamic light scattering measurements as a function of pH, ionic strength, and nature of dispersion media (phosphate buffer and cell culture media). Our findings demonstrated that the PEG polymer chain length plays a key role in the coagulation behavior of the Mag-PEG suspensions. The excellent colloidal stability under the extreme conditions we evaluated, such as high ionic strength, pH near the isoelectric point, and cell culture media, revealed that suspensions comprising PEG-coated SPION, with PEG of molecular weight 600 and above, present steric stabilization attributed to the polymer chains attached onto the surface of SPIONs. © 2013 Springer Science+Business Media Dordrecht.

Influence of inoculum on performance of anaerobic reactors for treating municipal solid waste

The influence of bovine rumen fluid inoculum during anaerobic treatment of the organic fraction of municipal solid waste (MSW) was studied in this work. The parameters adopted for evaluation were the biostabilization constant of total volatile solids (TVs) and the biostabilization time of the chemical oxygen demand (COD) applied to the reactors. The work was realized in four anaerobic batch reactors of 20 1 capacity each, during a period of 365 days. The proportions between MSW/inoculum loaded in the reactors were Reactor A (100%/0%), Reactor B (95%/5%), Reactor C (90%/10%) and Reactor D (85%/15%). The necessary time for biostabilization of half of the applied COD was 459, 347, 302 and 234 days and the average of methane concentration in the biogas produced was 3.6%, 13.0%, 25.0% and 42.6% for Reactors A, B, C and D, respectively. The data obtained affirm that the inoculum used substantially improved the performance of the process. (C) 2004 Elsevier Ltd. All rights reserved.

Effect of short training on vaginal fluid microscopy (wet mount) learning

Objective: Is it feasible to learn the basics of wet mount microscopy of vaginal fluid in 10 hours?Materials and Methods: This is a pilot project wherein 6 students with different grades of education were invited for being tested on their ability to read wet mount microscopic slides before and after 10 hours of hands-on training. Microscopy was performed according to a standard protocol (Femicare, Tienen, Belgium). Before and after training, all students had to evaluate a different set of 50 digital slides. Different diagnoses and microscopic patterns had to be scored. kappa indices were calculated compared with the expert reading. Results: All readers improved their mean scores significantly, especially for the most important types of altered flora (p < .0001). The mean increase in reading concordance (kappa from 0.64 to 0.75) of 1 student with a solid previous experience with microscopy did not reach statistical significance, but the remaining 5 students all improved their scores from poor performance (all kappa < 0.20) to moderate (kappa = 0.53, n = 1) to good (kappa > 0.61, n = 4) concordance. Reading quality improved and reached fair to good concordance on all microscopic items studied, except for the detection of parabasal cells and cytolytic flora. Conclusions: Although further improvement is still possible, a short training course of 10 hours enables vast improvement on wet mount microscopy accuracy and results in fair to good concordance of the most important variables of the vaginal flora compared to a reference reader.

Analysis of energy dissipation in stirred suspension polymerisation reactors using computational fluid dynamics

This work evaluates the spatial distribution of normalised rates of droplet breakage and droplet coalescence in liquidliquid dispersions maintained in agitated tanks at operation conditions normally used to perform suspension polymerisation reactions. Particularly, simulations are performed with multiphase computational fluid dynamics (CFD) models to represent the flow field in liquidliquid styrene suspension polymerisation reactors for the first time. CFD tools are used first to compute the spatial distribution of the turbulent energy dissipation rates (e) inside the reaction vessel; afterwards, normalised rates of droplet breakage and particle coalescence are computed as functions of e. Surprisingly, multiphase simulations showed that the rates of energy dissipation can be very high near the free vortex surfaces, which has been completely neglected in previous works. The obtained results indicate the existence of extremely large energy dissipation gradients inside the vessel, so that particle breakage occurs primarily in very small regions that surround the impeller and the free vortex surface, while particle coalescence takes place in the liquid bulk. As a consequence, particle breakage should be regarded as an independent source term or a boundary phenomenon. Based on the obtained results, it can be very difficult to justify the use of isotropic assumptions to formulate particle population balances in similar systems, even when multiple compartment models are used to describe the fluid dynamic behaviour of the agitated vessel. (C) 2011 Canadian Society for Chemical Engineering

Using Fluid Bed Granulation to Improve the Dissolution of Poorly Water-Soluble Drugs

In this study, fluid bed granulation was applied to improve the dissolution of nimodipine and spironolactone, two very poorly water-soluble drugs. Granules were obtained with different amounts of sodium dodecyl sulfate and croscarmellose sodium and then compressed into tablets. The dissolution behavior of the tablets was studied by comparing their dissolution profiles and dissolution efficiency with those obtained from physical mixtures of the drug and excipients subjected to similar conditions. Statistical analysis of the results demonstrated that the fluid bed granulation process improves the dissolution efficiency of both nimodipine and spironolactone tablets. The addition of either the surfactant or the disintegrant employed in the study proved to have a lower impact on this improvement in dissolution than the fluid bed granulation process.

Evidence of the participation of electronic excited states in the mechanism of positronium formation in substitutional Tb1-xEux(dpm)(3) solid solutions studied by optical and positron annihilation spectroscopies

Positronium formation in the bimary molecular solid solutions Tb1-xEux (dpm)(3) (dpm = dipivaloylmethanate) has been investigated. A strong linear correlation between the D-5(4) Tb(III) energy level excited state lifetime and the positronium formation probability has been observed. This correlation indicates that the ligand-to-metal charge transfer LMCT states act in both luminescence quenching and positronium formation inhibition, as previously proposed. A kinetic mechanism is proposed to explain this correlation and shows that excited electronic states have a very important role in the positronium formation mechanism.

Effect of aqueous extracts from Ceriporiopsis subvermispora-biotreated wood on the decolorization of Azure B by Fenton-like reactions

Aqueous extracts from wood biotreated with the white-rot fungus Ceriporiopsis subvermispora were evaluated for their Fe3+- and Cu2+-reducing activities and their anti- or prooxidant properties in Fenton-like reactions to decolorize the recalcitrant dye Azure B. The decolorization of Azure B was strongly inhibited in the presence of 10% (v/v) wood extracts. Only 0.1% (v/v)-diluted extracts provided some enhancement of the Azure B decolorization. The iron-containing reactions decolorized more Azure B and consumed substantially more H2O2 than the reactions containing copper. This study demonstrates that water-soluble wood phenols exert anti- or prooxidant effects that depend on their concentration in the reactions and on the type of cation, Fe3+ or Cu2+, used to convert H2O2 to OH radicals. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.

Linking origin of the electric field-assisted beta-PbF2 crystallization in lead oxyfluoroborate glasses below T (g) to simultaneous cathode/anode-compensated electrochemical reactions

Full validation of the electrochemical mechanisms so far postulated as driving force of electric field-assisted non-spontaneous crystallization development in given glasses has suffered experimental restrictions. In this work, we looked into origin of this phenomenon in lead oxyfluoroborate glasses, resulting in beta-PbF2 growth even below the corresponding glass transition temperatures, through achieving a systematic study of not only Pt,Ag/Glass/Ag,Pt- but also Pt,Ag/Glass/YSZ:PbF2/Ag,Pt-type cells, where YSZ:PbF2 represents a two-phase system (formed by Y2O3-doped ZrO2 and PbF2). It is demonstrated that crystallization induction in these glasses involves Pb2+ ions reduction at the cathode, the phenomenon being, however, confirmed only when the F- ions were simultaneously also able to reach the anode for oxidation, after assuring either a direct glass-anode contact or percolation pathways for free fluoride migration across the YSZ:PbF2 mixtures. A further support of this account is that the electrochemically induced beta-PbF2 phase crystallizes showing ramified-like microstructure morphology that arises, accordingly, from development of electroconvective diffusion processes under electric field action.

(18O,16O) Two-neutron transfer reactions for spectroscopic studies.

A systematic study of the response of different nuclei to the (18O, 16O) two-neutron transfer reaction at 84 MeV incident energy was pursued at the INFN-LNS in Catania (Italy). The experiments were performed using several solid targets from light (9Bc, 11 B, 12,13C, 16O, 28Si) to heavier ones (58,64Ni, 120Sn, 208Pb). The 16O ejectiles were detected at forward angles by the MAGNEX magnetic spectrometer and identified without the need of time of flight measurements. Exploiting the large momentum (≈ 25%) and angular (50 msr) acceptance of the spectrometer, energy spectra were obtained with a relevant yield up to about 20 MeV excitation energy. A common feature of the light nuclei spectra is the strong population of states with well known configuration of two-particle over a core and the appearance of unknown resonant structures in the continuum. These latter can reveal the excitation of a collective mode connected with the transfer of a pair. For the heavier nuclei as 66Ni a completely different behaviour is observed indicating the presence of more dissipative processes in the reaction mechanisms that hide the spectroscopic information.