Calcium sulfate precipitation in the presence of water-soluble polymers

The effect of four different polymers on the precipitation of calcium sulfate was investigated in the present work. The degree of inhibition was estimated from measurements of the calcium ion activity and from specific solution conductivity measurements in the supersaturated solutions during the course of the precipitation process. The effects of polyacrylic acid (PAA, three different polymers with average molecular weight 2000, 50,000, and 240,000, respectively) and of a co-polymer of PAA with polystyrene sulfonic acid (PSA, average molecular weight<20,000) were investigated with respect to their effect on the kinetics of spontaneous precipitation of calcium sulfate salts. The results of the kinetics experiments suggested that the spontaneous precipitation from supersaturated calcium sulfate solutions at 25 degrees C yielded exclusively calcium sulfate dihydrate (gypsum) both in the absence and in the presence of the polymeric additives. The induction times, preceding the formation of the solid increased in all cases in the presence of the polymeric additives. Polymer concentrations as low as 2.0 ppm increased induction time from practically zero to 10 min. The rates of precipitation were reduced according to the solutions content in the polymers added and precipitation was completely suppressed in the presence of 6.0 ppm of the polymers tested, depending on their molecular weight. The lower the molecular weight of PAA, the more efficient was the threshold inhibition and the stronger the reduction of the rates of spontaneous precipitation. PSA yielded the poorest inhibition efficiency in comparison with the PAA, possibly because of the relatively lower affinity of the sulfonate groups for the calcium ions of the surface of the solid forming. The kinetics results analysis assuming Langmuir-type adsorption of the polymeric molecules on the growing supercritical gypsum nuclei showed different affinity for the polymers tested in agreement with the respective inhibition efficiency, in the order: PAA1>PAA2>PSA>PAA3. The presence of the polymers in the supersaturated solutions resulted in modification of the precipitated gypsum crystals morphology.     

Design, synthesis, and computational studies of inhibitors of Bcl-XL

One of the primary objectives in the design of protein inhibitors is to shape the three-dimensional structures of small molecules to be complementary to the binding site of a target protein. In the course of our efforts to discover potent inhibitors of Bcl-2 family proteins, we found a unique folded conformation adopted by tethered aromatic groups in the ligand that significantly enhanced binding affinity to Bcl-XL. This finding led us to design compounds that were biased by nonbonding interactions present in a urea tether to adopt this bioactive, folded motif. To characterize the key interactions that induce the desired conformational bias, a series of substituted N,N'-diarylureas were prepared and analyzed using X-ray crystallography and quantum mechanical calculations. Stabilizing pi-stacking interactions and destabilizing steric interactions were predicted to work in concert in two of the substitution patterns to promote the bioactive conformation as a global energy minimum and result in a high target binding affinity. Conversely, intramolecular hydrogen bonding present in the third substitution motif promotes a less active, extended conformer as the energetically favored geometry. These findings were corroborated when the inhibition constant of binding to Bcl-XL was determined for fully elaborated analogues bearing these structural motifs. Finally, we obtained the NMR solution structure of the disubstituted N,N'-diarylurea bound to Bcl-XL demonstrating the folded conformation of the urea motif engaged in extensive pi-interactions with the protein.     

Influence of the organic compounds on the ecotoxicity in the treatment of foundry sludge and olive mill waste

The study of the ecotoxicity in two industrial waste materials and the relationships with the organic parameters has been conducted. Foundry sludge and olive mill waste have been used as industrial waste materials with organic or mixed character. Stabilisation/solidification (S/S) and advanced oxidation (AOP) processes have been carried out in order to treat both foundry sludge and olive mill waste. Analysis of ecotoxicity, total organic carbon, COD and phenol index have been evaluated in the untreated waste and end-products. The results of the treated samples allow obtaining the best formulations in both processes. The best formulations in the immobilisation process have been obtained with Portland cement and black carbon, activated carbon or foundry sand ashes. In the AOP process, ozone concentrations above 35 mg/l and reaction times equal to 120 minutes have been the optimal variables. The relationships between the organic parameters and the ecotoxicity of the samples have been studied in this paper. Furthermore, the global organic parameters have been studied in relation to the phenolic compounds. Lineal and logarithmic expressions have been obtained between the total organic carbon and phenol index and the ecotoxicity of the samples related to the organic parameters, respectively. Ecotoxicity of the samples with Vibrio fischeri is recommended as a very promising biotest for the study of the characterisation and the evaluation of the treatment of organic and mixed character waste and total organic carbon is recommended as global organic parameter in the treatment of foundry sludge.     

Frequency-switching inversion-recovery for severely hyperfine-shifted NMR: evidence of asymmetric electron relaxation in high-spin Co(II)

A new method for reliably measuring longitudinal relaxation rates for severely hyperfine-shifted NMR signals in aqueous solutions is presented. The method is illustrated for a well-defined cobalt tetracysteinate, with relevance to cobalt-substituted metalloproteins. The relaxation measurements are indicative of asymmetric electronic relaxation of the high-spin Co(II) ion.     

On cyclic strings avoiding a pattern

We count the number of cyclic strings over an alphabet that avoid a single pattern under two different assumptions. In the first case, we assume that the symbols of the alphabet are on numbered positions on a circle, while in the second case we assume that the symbols can be freely rotated on the circle (i.e., we deal with necklaces). In each case, we provide a generating function, and we explain how these two cases are related. For the situation of avoiding more than one pattern, we formulate a general conjecture for the first case, and a conditional result for the second case. We also explain the differences between our theory and the theory of Edlin and Zeilberger (2000) by emphasizing how we modified the definition of the enumeration of cyclic strings that avoid one or more patterns when their lengths are less than the length of the longest pattern.     

Enantioselective methylalumination of α-olefins

The ability of various enantiopure zirconocenes to catalyze the asymmetric methylalumination of allylbenzene has been tested. The enantioselectivity of an ethylene(Ind)₂ZrCl₂/MAO system is the same as that of authentic methyl cation generated with Ph₃C⁺ from ethylene(Ind)₂ZrMe₂, confirming that the methyl cation is the active catalyst from ethylene(Ind)₂ZrCl₂/MAO.     

Glafka 2004: Spacetime Topology from the Tomographic Histories Approach I: Non-Relativistic Case

The tomographic histories approach is presented. As an inverse problem, we recover in an operational way the effective topology of the extended configuration space of a system. This means that from a series of experiments we get a set of points corresponding to events. The difference between effective and actual topology is drawn. We deduce the topology of the extended configuration space of a non-relativistic system, using certain concepts from the consistent histories approach to Quantum Mechanics, such as the notion of a record. A few remarks about the case of a relativistic system, preparing the ground for a forthcoming paper sequel to this, are made in the end.     

600-mJ,double-pulse 2-microm laser

An efficient double-pulse Ho:Tm:YLF 2-microm laser with total Q-switched output energy of 600 mJ has been demonstrated. A double-pulse pair is obtained per pump pulse. By operation of the laser in a double-pulse format, the residual energy stored among the Tm ions is transferred to the Ho atoms that were de-excited by the extraction of the first Q-switched pulse. Thus, the overall laser efficiency is increased by 61%.