Synergistic solvent extraction of cerium(III) with mixtures of thenoyltrifluoroacetone and dialkyl sulfoxides

Synergism in the extraction of Ce(III) from thiocyanate solutions has been investigated using mixtures of 2-thenoyltrifluoroacetone (HTTA) and bis-2-ethylhexyl sulfoxide (B2EHSO) or di-n-octyl sulfoxide (DOSO) in benzene. A very high synergistic enhancement of the order of 10⁵ has been observed. If a mixture of both dialkyl sulfoxides (B2EHSO+DOSO) is used, an additional synergistic effect is found due to the formation of a mixed, solvated complex when both reagents are added to the metal chelate. These extraction data have been analyzed theoretically with the aid of a computer by taking into account complexation of the metal in the aqueous phase by inorganic ligands and plausible complexation in the organic phase. The equilibrium constants of the various product species have been deduced by non-linear regression analysis.     

Mixed integer formulation to minimize makespan in a flow shop with batch processing machines

Batch processing machines are commonly used in wafer fabrication, kilns, and chambers used for environmental stress screening (ESS). This paper proposes two models to schedule batches of jobs on two machines in a flow shop. A set of jobs with known processing times and sizes has to be grouped, to form batches, in order to be processed on the batch processing machines. The jobs are nonidentical in size. The processing time of a batch is the longest processing time of all the jobs in that batch. Mixed integer formulations are proposed for the flow shop problem when the buffer capacity is unlimited or zero. Numerical examples are presented to demonstrate the application of our model.     

Phylogenetics of worldwide human populations as determined by polymorphic Alu insertions

Alu elements, the largest family of interspersed repeats, mobilize throughout the genomes of primates by retroposition. Alu are present in humans in an excess of 500 000 copies per haploid genome. Since some of the insertion alleles have not reached fixation, they remain polymorphic and can be used as biallelic DNA marker systems in investigations of human evolution. In this study, six polymorphic Alu insertional (PAI) loci were used as genetic markers. These markers are thought to be selectively neutral. The presence of these six PAIs was determined by a polymerase chain reaction (PCR)-based assay in 1646 individuals from 47 populations from around the world. Examination of the populations by plotting the first and second principal components, shows the expected segregation of populations according to geographical vicinity and established ethnic affinities. Centroid analysis demonstrated that sub-Sahara populations have experienced higher than average gene flow and/or represent larger populations as compared to groups in other parts of the globe and especially to known inbreed populations. This is consistent with greater heterogeneity and diversity expected of source groups. In addition, maximum likelihood (ML) analyses were performed with these 47 populations and a hypothetical ancestral group lacking the insertion in all six loci. Analysis of our data supports the Out of Africa hypothesis. African populations and admixed groups of African descent formed a single monophyletic group with a basal placement on the tree, which grouped closest to the hypothetical ancestor.     

Simultaneous determination of copper,mercury and lead by first-order derivative spectrophotometry using dithizone as reagent

A first-order derivative spectrophotometric method has been developed for the simultaneous determination of copper, mercury and lead at g/L levels using dithizone as reagent. The procedure involves the simultaneous extraction of these elements by dithizone in chloroform from weakly alkaline solutions. Linear calibration curves were obtained in the ranges 0.5–10 (Cu), 1–10 (Hg) and 1–10 (Pb) g present in 40 ml of aqueous phase with detection limits of 5 g/L (Cu) and 20 g/L (Hg and Pb). The R.S.D.s for 100 g/L of copper, mercury and lead were 2.5, 2.6 and 3.1% respectively, for 5 determinations. The method is applicable for the determination of copper and lead in marine sediment samples with good precision and accuracy.     

Second derivative spectrophotometric determination of iron by extraction of the ferroin-perchlorate ion-association complex into mesityl oxide

A highly selective and sensitive second-derivative spectrophotometric determination of iron is based on the extraction of the ferroin-perchlorate ion-association complex into mesityl oxide. A linear calibration graph is obtained for iron in the range 0.5-50 mug in 100 ml of original aqueous phase, with a detection limit of 2 ng/ml. The method is precise and reliable and has been applied to the determination of iron in high-purity rare-earth oxides.     

Surface pressure dependence of phospholipase A2 activity in lipid monolayers is linked to interfacial water activity

The specific activity of pancreatic phospholipase A2 (PLA2) was studied in two disparate systems, one involving phosphatidylcholine monolayer at various surface pressures at the air-water interface and the other involving a solid-state system exposed to various equilibrium relative humidity (ERH). The results were examined in terms of thermodynamic activity of water in the interfacial region (aws*) and in the hydrated solid phase (aw). In both these physically different systems, the specific activity versus aw and aws* profiles of PLA2 were remarkably similar. In both cases, the specific activity exhibited a maximum at aw (or aws*) approximately 0.3. These results suggested that the mechanism of control of PLA2 activity at the lipid-water interface might involve modulation of the hydration state of the enzyme through control of the thermodynamic activity of water in the interfacial region. Extension of these results to biomembranes suggests that one of the functions of lipid bilayer might be the control of local water activity at the lipid-water interface. In biological membranes, localized subtle changes in interfacial water activity may occur as a result of local stretching or compression of the membrane facilitated by conformational changes in membrane-bound receptor proteins.     

Solvent extraction of zinc/II/ with sulphoxides: Theoretical analysis of extraction behaviour

This paper describes a theoretical method for analyzing the behaviour of⁶⁵Zn during solvent extraction from ammonium thiocyanate solutions with dialkyl sulphoxides. The mechanism of extraction of Zn/II/ from thiocyanate medium by sulphoxides may be represented by the following general equation: $$xM_{aq}^{m + } + ySCN_{aq}^ - + zS_{org} \rightleftharpoons [M_x /SCN/_y ]^{mx - y} .zS_{org} $$ where M^m+ is the metal ion and S is the extractant. Expressions for the distribution coefficients were derived taking into account complexation of the metal in the aqueous phase by inorganic ligands and also the dissociation of the extracted ion-pairs in the organic phase. Using these expressions, the values of the extraction constants were determined by a least-squares fit with the experimental extraction data. From these extraction constants, the various species extracted into the organic phase were resolved. The influence of the metal concentration, temperature and the diluent on the extraction of Zn/II/ has been investigated.     

Synergic liquid-liquid extraction studies of neodymium and praseodymium with mixtures of tributyl phosphate and Aliquat-336 in nitrate media

Extraction studies of neodymium and praseodymium with mixtures of tributyl phosphate and Aliquat-336 in xylene have been carried out. From 3.0M aqueous ammonium nitrate solutions, negatively charged complexes of neodymium and praseodymium were extracted with Aliquat-336 in the presence of tributyl phosphate into the organic phase. The synergic extracted species observed was M(NO₃) ₄ ^– L⁺·TBP. The synergic extraction of lanthanide elements in nitrate media increases from lanthanum to lutetium.     

Incompatibility and Phase Separation in a Bovine Serum Albumin/beta-Casein/Water Ternary Film at the Air-Water Interface

Thermodynamic incompatibility and two-dimensional phase separation in a bovine serum albumin (BSA)/beta-casein/water ternary film at the air-water interface has been studied using an epifluorescence microscopy technique. The incompatibility between BSA and beta-casein at the air-water interface was deduced from deviation of the experimental equilibrium composition of the proteins in the mixed saturated monolayer film from that predicted by the Langmuir-type competitive adsorption model at various bulk concentration ratios. Fluorescence microscopy of the mixed monolayer film showed distinct phase-separated BSA-rich and beta-casein-rich regions coexisting with inhomogeneous mixed regions. BSA always tended to be the dispersed phase and beta-casein the continuous phase. It is suggested that because the free energy at the "interfaces" between the phase-separated regions is generally higher than at other regions of the film, they may act as zones of instability in protein-stabilized foams and possibly emulsions. Copyright 2000 Academic Press.