Speciation of antimony using chromosorb 102 resin as a retention medium.

The selective retention of the Sb(III) chelate with ammonium pyrrolidine dithiocarbamate (APDC) on a column of Chromosorb 102 resin from a buffered sample solution including Sb(V) was used for the determination of Sb(III). The retained antimony was eluted with acetone. The retention of the Sb(III)-iodide compounds with sodium iodide on the Chromosorb 102 resin column from the same solution after reducing Sb(V) to Sb(III) by iodide in acidic solution was used to preconcentrate the total antimony. The retained antimony was eluted with 0.25 mol l(-1) HNO3. The antimony in the effluent was determined by flame atomic-absorption spectrometry. Also, the total antimony was determined directly by graphite-furnace atomic absorption spectrometry. The Sb(V) concentration could be calculated by the difference. The recoveries were > or = 95%. The detection limits of a combination of the column procedure and flame AAS for antimony were 6 - 61 microg l(-1) and comparable to 4 microg l(-1) for a direct GFAAS measurement. The relative standard deviations were <6%. The procedure was applied to the determination of Sb(III) and Sb(V) in spiked tap water, waste-water samples and a certified copper metal with the satisfactory results.     

Fam-Ti catalyzed enantioselective alkynylation of aldehydes

Ferrocenyl-substituted aziridinylmethanol (Fam-1) has been used as a chiral catalyst with titanium for enantioselective alkynylation of aromatic, heteroaromatic, aliphatic, and alpha,beta-unsaturated aldehydes to give the corresponding propargylic alcohols in up to 96% yield and 96% ee. The ligand can be prepared easily and recycled.     

Untersuchung von Schwingungen einer Zweiphasenströmung durch Druckabfall und Dichtewellen mit Hilfe finiter Differenzen

The previous experimental analysis has indicated the existence to two major modes of oscillations, i.e., Density-Wave (high frequency) and Pressure-Drop (low frequency) Oscillations in single channel, electrically heated, forced convection upflow systems. In this work the stability of such a system is investigated theoretically and the results are compared with experimental findings obtained by the authors. The Homogeneous Phase Equilibrium model is used to describe the two-phase flow characteristics. The friction between the pipe wall and the expanding fluid is modeled using the Moody friction factor assuming an effective two-phase viscosity. Gravitational forces are included and heat transfer into the fluid is assumed to be the function of the wall temperature, fluid temperature and heat transfer coefficient which is also assumed to be a function of the flow rate. Though simple, this model is found to be very satisfactory in simulating both modes of oscillations with acceptable accuracy. The physical nature of each mode is different and distinct, therefore, separate solution methods are developed for each case. The Steady-State Flow Characteristics are obtained for various heat inputs and inlet temperatures by solving the conservation equations together with the equation of state by using an Implicit Finite- Difference technique. In the analysis of low frequency oscillations it is assumed that the quasi-steady state conditions prevail in the heater. The system equations obtained with this assumption are solved under constant exit pressure and constant container pressure boundary conditions using the finite-difference technique. Two methods of approach are adapted in solving the non-linear hyperbolic equations which describe the system at low mass flow rates where the density-wave type oscillations are observed. They are the Explicit Integral Momentum method (EIM) and the Explicit Finite-Difference method (EFD). A comparison of the results with experiments and other mathematical models is discussed.     

Helical Propensity in an Intrinsically Disordered Protein Accelerates Ligand Binding

Many intrinsically disordered proteins fold upon binding to other macromolecules. The secondary structure present in the well‐ordered complex is often formed transiently in the unbound state. The consequence of such transient structure for the binding process is, however, not clear. The activation domain of the activator for thyroid hormone and retinoid receptors (ACTR) is intrinsically disordered and folds upon binding to the nuclear coactivator binding domain (NCBD) of the CREB binding protein. A number of mutants was designed that selectively perturbs the amount of secondary structure in unbound ACTR without interfering with the intermolecular interactions between ACTR and NCBD. Using NMR spectroscopy and fluorescence‐monitored stopped‐flow kinetic measurements we show that the secondary structure content in helix 1 of ACTR indeed influences the binding kinetics. The results thus support the notion of preformed secondary structure as an important determinant for molecular recognition in intrinsically disordered proteins.     

Determination of Trace Metal Ions in SeaWater by Atomic Absorption Spectrometry After Separation/Preconcentration with Calmagite on Amberlite Xad-1180

A preconcentration/separation method for the atomic absorption spectrometric determinations of Cu(II), Ni(II) and Pb(II) ions in seawater have been established by using a chromatographic column filled Amberlite XAD-1180. The recoveries of Cu(II), Ni(II) and Pb(II) ions were quantitative (> 95%) at pH 8-9. The influences of the various analytical parameters including the amount of calmagite, amount of Amberlite XAD-1180, eluent type, etc. were investigated. The influence of the seawater matrix was also examined. Simultaneous enrichment and determination of copper, nickel and lead ions in seawater are possible with satisfactory results (recoveries > 95%, RSD <9%).     

Determination of potassium, calcium and chlorine in some vegetables by EDXRF

Total concentration of potassium, calcium and chlorine was determined in the presence of each other and irrespective of the nature of their compounds, in the leaves of Urticae dioico L. and Spinacia oleracea L. (spinach) plants by EDXRF. The enhancement of potassium K X-rays due to calcium K X-rays and enhancement of chlorine K X-rays due to potassium and calcium K X-rays present in the samples were avoided by selective secondary excitation method of the samples. Our results were compared with other experimental results.     

A novel approach for determination of tin, lead and copper in biological samples and sediments by alternating current anodic stripping voltammetry

Simultaneous determination of Sn, Pb and Cu in biological samples (plants, animal tissues) and sediments is possible in methanolic 1 M HCl by alternating current anodic stripping voltammetry after digestion of the samples with Lumatom. This digesting agent eliminates some common sources of error and increases the intensity of the anodic current. With a l min pre-electrolysis time. 1 ppb Sn, Pb or Cu can easily be determined.     

Side-chain interactions form late and cooperatively in the binding reaction between disordered peptides and PDZ domains

Intrinsically disordered proteins are very common and mediate numerous protein-protein and protein-DNA interactions. While it is clear that these interactions are instrumental for the life of the mammalian cell, there is a paucity of data regarding their molecular binding mechanisms. Here we have used short peptides as a model system for intrinsically disordered proteins. Linear free energy relationships based on rate and equilibrium constants for the binding of these peptides to ordered target proteins, PDZ domains, demonstrate that native side-chain interactions form mainly after the rate-limiting barrier for binding and in a cooperative fashion. This finding suggests that these disordered peptides first form a weak encounter complex with non-native interactions. The data do not support the recent notion that the affinities of intrinsically disordered proteins toward their targets are generally governed by their association rate constants. Instead, we observed the opposite for peptide-PDZ interactions, namely, that changes in K(d) correlate with changes in k(off).     

Optically stimulated luminescence dating of Holocene alluvial fans,East Anatolian Fault System,Turkey

In this study, the optically stimulated luminescence dating technique was used to determine the time of deposition of alluvial sediment samples from the Türko?lu-Antakya segment of the East Anatolian Fault System (EAFS) in Turkey. The double-single aliquot regenerative dose protocol on fine grain samples was used to estimate equivalent doses (D_e). Annual dose rate was computed using elemental concentration of uranium (U) and thorium (Th) determined by using thick-source alpha counting and potassium (K) concentrations using X-ray fluorescence and/or atomic absorption spectroscopy. The environmental dose was measured in situ using α-Al₂O₃:C chips inside plastic tubes for a year. The two different bulk sediment samples collected from the Islahiye trench yielded ages of 4.54?±?0.28 and 2.91?±?0.23?ka. We also obtained a 2.60?±?0.18?ka age for the alluvial deposit in the K?ranyurdu trench and 2.31?±?0.14?ka age for an excavation area called Malzeme Oca??. These ages were consistent with the corresponding calibrated Carbon-14 (¹⁴C) ages of the region. The differences between the determined ages were insufficient to clearly distinguish the disturbance event from the effects of bioturbation, biological mixing, or other sources of D_e variation in the region. They provide a record of alluvial aggradation in the region and may determine undocumented historical earthquake events.