Effect of macropore convection on mass transfer in a bidisperse adsorbent particle

The importance of adsorption induced convection in the macropores of a bidisperse adsorbent particle is studied for a step change in mole fraction or total pressure at the surface of the particle. Material balance equations for a binary gas mixture are written for both the macropores and the macropores with allowance for convection in the macropores, which is described by Darcy's law. The coupled set o1' partial differential equations is solved by orthogonal collocation. The enhancement in mass transfer as a result of convection is assessed by comparing the fractional uptake curves obtained with and without allowance for convection. Both equilibrium-based and kinetic-based separation processes are considered. The effect of the presence of convection in determining the controlling diffusional resistance (macropore or micropore) is also examined. Due to inclusion of convection no single non-dimensional group alone can determine the relative importance of macropore and micropore resistances. Results show that convection can significantly affect the performance of an equilibrium-based macropore diffusion controlled process and that the enhancement in mass transfer is more for a particle with a high value of Darcy permeability.     

Bifunctional Lewis acid-nucleophile-based asymmetric catalysis: mechanistic evidence for imine activation working in tandem with chiral enolate formation in the synthesis of beta-lactams

We report a mechanistically based study of bifunctional catalyst systems in which chiral nucleophiles work in conjunction with Lewis acids to produce beta-lactams in high chemical yield, diastereoselectivity, and enantioselectivity. Chiral cinchona alkaloid derivatives work best when paired with Lewis acids based on Al(III), Zn(II), Sc(III), and, most notably, In(III). Homogeneous bifunctional catalysts, in which the catalyst contains both Lewis acidic and Lewis basic sites, were also studied in detail. Mechanistic evidence allows us to conclude that the chiral nucleophiles form zwitterionic enolates that react with metal-coordinated imines. Alternative scenarios, which postulated metal-bound enolates, were disfavored on the basis of our observations.     

The potential of inductively coupled plasma-mass spectrometric detection for capillary electrophoretic analysis of pesticides

In this work, the potential of inductively coupled plasma-mass spectrometry (ICP-MS) coupled to capillary electrophoresis (CE) to determine organophosphorus pesticides (OPPs) is demonstrated. Element specific detection of (31)P with ICP-MS is performed for the detection of OPPs. Three common OPPs, including glyphosate, glufosinate, and aminomethylphosphonic acid (AMPA), were analyzed by CE-ICP-MS to demonstrate its applicability for the analysis of OPPs. The advantages of using ICP-MS with respect to other common detectors, such as flame photometric detection (FPD), for CE analysis of OPPs are shown. Additionally, different CE separation conditions were studied to achieve complete baseline separation of the pesticide compounds in short migration times. Two CE buffer systems were evaluated for the separation of OPPs using ICP-MS detection. A buffer solution containing 40 mmol.L(-1) ammonium acetate at pH 9.0 and an applied voltage of +20 kV were finally selected leading to a separation time of 10.0 min. Both migration time and area relative standard deviations (%RSD) were evaluated and their respective values were in the intervals of 1.1-3.3% and 2.7-5.3%. Detection limits obtained with the CE-ICP-MS system were in the range of 0.11-0.19 mg.L(-1) (as compound) yielding an enhancement of 130- to 230-fold with respect to FPD. The proposed methodology was finally applied for the determination of the OPPs mentioned above in natural river water samples.     

Synthesis and pharmacological activity of 4-(4'-(chlorophenyl)-4-hydroxypiperidine) derivatives

A new series of 4-(4'-chlorophenyl)-4-hydroxypiperidine derivatives (2-5), substituted at nitrogen, were synthesized and tested as potential analgesic compounds as well as evaluated for their effect on hypotensive activity. Results showed that all the derivatives exhibit significant analgesic activity in male Wistar rats at a dose of 50 mg/kg of body weight after intramuscular injection, when tested by thermal stimuli (tail flick test). Pethidine was used as reference drug. Compounds 2, 3 and 5 produced reduction in blood pressure in normotensive rat.     

A Novel Anti-Inflammatory d-Peptide Inhibits Disease Phenotype Progression in an ALS Mouse Model

Amyotrophic lateral sclerosis (ALS) is a progressive neurodegenerative disease characterised by selective neuronal death in the brain stem and spinal cord. The cause is unknown, but an increasing amount of evidence has firmly certified that neuroinflammation plays a key role in ALS pathogenesis. Neuroinflammation is a pathological hallmark of several neurodegenerative disorders and has been implicated as driver of disease progression. Here, we describe a treatment study demonstrating the therapeutic potential of a tandem version of the well-known all-d-peptide RD2 (RD2RD2) in a transgenic mouse model of ALS (SOD1*G93A). Mice were treated intraperitoneally for four weeks with RD2RD2 vs. placebo. SOD1*G93A mice were tested longitudinally during treatment in various behavioural and motor coordination tests. Brain and spinal cord samples were investigated immunohistochemically for gliosis and neurodegeneration. RD2RD2 treatment in SOD1*G93A mice resulted not only in a reduction of activated astrocytes and microglia in both the brain stem and lumbar spinal cord, but also in a rescue of neurons in the motor cortex. RD2RD2 treatment was able to slow progression of the disease phenotype, especially the motor deficits, to an extent that during the four weeks treatment duration, no significant progression was observed in any of the motor experiments. Based on the presented results, we conclude that RD2RD2 is a potential therapeutic candidate against ALS.     

Blends of starch with ethylene vinyl alcohol copolymers: effect of water,glycerol, and amino acids as plasticizers

Blends of thermoplastic starch with poly(ethylene‐co‐vinyl alcohol) copolymer (EVOH) were melt extruded with water/glycerol as plasticizer and a series of amino acid additives. The biggest factor in end‐use mechanical properties proved to be the relative humidity (RH) during storage. Plasticized starch‐EVOH blends stored at 0 and 50% RH changed significantly over time, with, for example, the tensile strength (TS) of the glycerol‐plasticized blend increasing from 4.7 to 26.3 MPa over 8 weeks when maintained at 0% RH. In contrast, the TS of this same sample stored at 75% RH remained unchanged for 8 weeks. Amino acids provided relatively minor, but significant changes in mechanical properties with time. Based on TS, elongation‐to‐break, and modulus, it may be concluded that β‐alanine, sarcosine, and L ‐proline were more effective than glycerol at maintaining strong flexible blends. Increases in crystallinity and changes in morphology with time, as described by modulated DSC were correlated to these changes in mechanical properties. Published in 2007 by John Wiley & Sons, Ltd.     

Environmentally degradable bio-based polymeric blends and composites

Blends and composites based on environmentally degradable-ecocompatible synthetic and natural polymeric materials and fillers of natural origin have been prepared and processed under different conditions. Poly(vinyl alcohol) (PVA) was used as the synthetic polymer of choice by virtue of its capability to be processed from water solution or suspension as well as from the melt by blow extrusion and injection molding. Starch and gelatin were taken as the polymeric materials from renewable resources. The fillers were all of natural origin, as waste from food and agro-industry consisted of sugar cane bagasse (SCB), wheat flour (WF), orange peels (OR), apple peels (AP), corn fibres (CF), saw dust (SD) and wheat straw (WS). All the natural or hybrid formulations were intended to be utilized for the production of: a) Environmentally degradable mulching films (hydro-biomulching) displaying, in some cases, self-fertilizing characteristics by in situ spraying of water solutions or suspensions; b) Laminates and containers to be used in agriculture and food packaging by compression and injection molding followed by baking. Some typical prototype items have been prepared and characterized in relation to their morphological and mechanical properties and tested with different methodology for their propensity to environmental degradation and biodegradation as ultimate stage of their service life. A relationship between chemical composition and mechanical properties and propensity to biodegradation has been discussed in a few representative cases.     

Sorptive potential of sunflower stem for Cr(III) ions from aqueous solutions and its kinetic and thermodynamic profile

The sorptive potential of sunflower stem (180-300 μm) for Cr(III) ions has been investigated in detail. The maximum sorption (≥85%) of Cr(III) ions (70.2 μM) has been accomplished using 30 mg of high density sunflower stem in 10 min from 0.001 M nitric and 0.0001 M hydrochloric acid solutions. The accumulation of Cr(III) ions on the sorbent follows Dubinin-Radushkevich (D-R), Freundlich and Langmuir isotherms. The isotherm yields D-R saturation capacity X_m = 1.60 ± 0.23 mmol g⁻¹, β = −0.00654 ± 0.00017 kJ² mol⁻², mean free energy E = 8.74 ± 0.12 kJ mol⁻¹, Freundlich sorption capacity K_F = 0.24 ± 0.11 mol g⁻¹, 1/n = 0.90 ± 0.04 and of Langmuir constant K_L = 6800 ± 600 dm³ mol⁻¹ and C_m = 120 ± 18 μmol g⁻¹. The variation of sorption with temperature (283-323 K) gives ΔH = −23.3 ± 0.8 kJ mol⁻¹, ΔS = −64.0 ± 2.7 J mol⁻¹ K⁻¹ and ΔG_298k = −4.04 ± 0.09 kJ mol⁻¹. The negative enthalpy and free energy envisage exothermic and spontaneous nature of sorption, respectively. Bisulphate, Fe(III), molybdate, citrate, Fe(II), Y(III) suppress the sorption significantly. The selectivity studies indicate that Cr(III), Eu(III) and Tb(III) ions can be separated from Tc(VII) and I(I). Sunflower stem can be used for the preconcentration and removal of Cr(III) ions from aqueous medium. This cheaper and novel sorbent has potential applications in analytical and environmental chemistry, in water decontamination, industrial waste treatment and in pollution abatement. A possible mechanism of biosorption of Cr(III) ions onto the sunflower stem has been proposed.     

Determination of <Superscript>241</Superscript>Am/<Superscript>243</Superscript>Am ratios

Determination of ²⁴¹Am/²⁴³Am ratios is required for vanous purposes including assay of Am by isotope dilution techniques. Alpha-spectrometry on electrodeposited sources is a preferred technique for this determination. However, there is an inherent problem of tail contribution which necessitates the use of suitable algorithms to account for the same. Recently, in the frame of a Coordinated Research Program (CRP) of the International Atomic Energy Agency (IAEA), WinALPHA software has been developed which is a combination of an asymmetrical Gaussian for the main part of the peak and a low energy function. Therefore, it was of interest to compare the use of this algorithm with the routinely used method, in our laboratory, based on geometric progression (G. P.) decrease. Since, there are no reference materials available commercially for ²⁴¹Am/²⁴³Am ratios, synthetic mixtures covening a wide range (0.3 to 2.0) of ²⁴¹Am/²⁴³Am α-activity ratios were used and un-ignited electrodeposited sources were prepared for α-spectrometry. The α-spectra obtained using PIPS detector, were evaluated using the two algonthms The ²⁴¹Am/²⁴³Am α-activity ratios obtained were also compared with those determined by thermal ionization mass spectrometry (TIMS). An agreement of about 1% was obtained in the ²⁴¹Am/²⁴³Am ratios determined by the two methods and also by using the two algorithms for α-spectrum evaluation.     

Preconcentration and Determination of Chromium Species Using Octadecyl Silica Membrane Disks and Flame Atomic Absorption Spectrometry

A novel and selective method for the fast determination of trace amounts of chromium species in water samples has been developed. The procedure is based on the selective formation of chromium diethyldithiocarbamate complexes at different pH in the presence of Mn(II) as an enhancement agent of chromium signals followed by elution with organic eluents and determination by atomic flame absorption spectrometry. The maximum capacity of the employed disks was found to be (396±3) µg and (376±2) µg for Cr(III) and Cr(VI), respectively. The detection limit of the proposed method is 49 and 43 ng·L^?1 for Cr(III) and Cr(VI), respectively. The proposed method was successfully applied for determination of chromium species Cr(III) and Cr(VI) in different water samples.