Interactions of phospholipase D with 1,2 diacyl-sn-glycerol-3-phosphorylcholine,dodecylsulfate, and Ca2+

Some properties of the pure, soluble phospholipase D (phosphatidycholine phosphatido hydrolase, EC 3.1.4.4) interactions with phosphatidyl choline (1,2 diacyl-sn-glycerol-3-phosphoryl choline) in a system also containing dodecylsulfate and Ca²⁺ ions were studied. Concentrations of Ca²⁺ greater than 50 mM were necessary both for activity and adsorption of the enzyme to the “supersubstrate.” Ethylenediamine tetraacetic acid caused inhibition of activity, greater than one would expect from its chelating capacity. A nonlinear increase in activity with the increase of enzyme protein was observed, suggesting a subunit aggregation into a higher mol wt protein, catalytically more active. Upon centrifugation of the supersubstrate-enzyme complex at 4.5×10⁵ g·min at 30 C, most of the substrate molecules sedimented regardless of the pH. The reverse was true when centrifugation was done at 1 C. Phospholipase D hydrolyzed phosphatidylcholine molecules present in the supersubstrate at temperatures around 0 C at a rate 1/5 that of a maximal value measured at 30C. The Arrhenius plot was linear in the range from 0 to 30 C, and at that temperature the curve broke with a smaller slope. Activation energy of 9.1 Kcal/mol, below 30 C, was calculated. Adsorption of the enzyme to the sedimentable supersubstrate occurred at pH 8.0, regardless of temperature. At pH 5.6, a considerable portion of phosphatidylcholine was degraded at 30 C, thus minimizing the capacity of the supersubstrate to adsorb the enzyme. Although Mg²⁺ could replace Ca²⁺ in the formation of sedimentable supersubstrate, it neither assists in adsorption of the enzyme nor in activation of the phosphatidylcholine hydrolysis.     

Polymerized high internal‐phase emulsions: Properties and interaction with water

The synthesis and characterization of novel polymerized high internal‐phase emulsions (polyHIPE) materials are described. Homogeneous, highly porous, low‐density, open‐cell crosslinked copolymers were prepared by polymerizing the continuous phase of HIPE containing styrene and varying amounts of 2‐ethylhexyl methacrylate. The glass transition temperatures (T_gs) of the homopolymers were similar to the literature values, but the copolymer T_gs were lower than expected. These results indicate that the copolymer composition is richer in 2‐ethylhexyl methacrylate than the feed composition. The homopolymer moduli, calculated from the foam moduli, were similar to the literature values. The influence of composition and surface treatment on the water absorbed by the foams was investigated. For example, washing a polyHIPE based on poly(ethylhexyl acrylate) in water at 70°C increased water absorption because of the removal of the residual salt. Adding a fluorinated comonomer to the HIPE reduced hydrophilicity and, thus, water absorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2018–2027, 2002; DOI 10.1002/app.10555     

Effects of axial stretching on the resistivity of carbon black filled silicone rubber

The resistance and resistivity of Ketjenblack EC/silicone rubber compounds were studied as function of strain in constant strain rate experiments. Both strain and rate of strain affect the electrical resistivity of the compounds. Such effects are carbon black concentration dependent. Ketjenblack EC, a low structure black, is shown to behave differently than other blacks of high structure in the electrical resistivity-strain experiments. The resistivity in the straining experiments is determined by the transient distribution of the conductive particle array.     

Development and characterization of reactively extruded PVC/polystyrene blends

PVC/PS blends are obtained through a reactive extrusion–polymerization method by the absorption of a solution of styrene monomer, initiator, and a crosslinking agent in commercial suspension‐type porous polyvinyl chloride (PVC) particles, forming a dry‐blend with a relatively high monomer content. These PVC/styrene dry‐blends are reactively polymerized in a twin‐screw extruder in the melt state. They do not contain monomer residues as detected by GC. The transparency, fracture surface morphology, thermal stability, rheology and static and dynamic mechanical properties of these blends are compared to physical PVC/PS blends at similar compositions. Owing to the high polymerization temperature (180°C), short PS chains are formed in the reactive extrusion process. These short chains are dispersed both as a separate phase of ～2 μm particles (recognized by SEM) and also as molecularly dispersed chains enhancing plasticization and compatibilization. The molecularly dispersed short PS chains tend to plasticize the PVC phase, reducing its melt viscosity and glass transition temperature. The content of the short PS chains forming the dispersed separate PS particles is too low for DMTA to detect a separate T_g. Thus, reactively extruded PVC/PS blends exhibit single T_g transitions at lower temperatures compared with the neat PVC. Migration of the PVC's low‐molecular‐weight additives (lubricants and thermal stabilizer) to the PS phase is observed in the physical PVC/PS blends, causing antiplasticization of the PS phase. This results in both reduction of the T_g and an increase in the thermal stability of the PS phase in the physical PVC/PS blends. Comparing TGA thermograms of reactively extruded and physical PVC/PS indicates that the PS formed in the extruder is different from the commercial PS. This can stem from various chemical reactions that can take place in the studied reactive polymerization process. Polym. Eng. Sci. 44:1473–1483, 2004. © 2004 Society of Plastics Engineers.     

Study of interactions between single-wall carbon nanotubes and surfactant using molecular simulations

Carbon nanotubes (CNT) exhibit interesting electrical and mechanical properties. However, the insolubility of CNT in either water or organic solvents, poses serious obstacles to their future applications. The main problems are strong van der Waals attractive interactions and CNT tendency to form bundles which are very difficult to disrupt. In this study, molecular dynamics and quantum mechanics simulations were conducted to investigate the interactions between a carbonaceous nanoparticle and surfactants. It was found that a benzoic ring in the surfactant molecule improves its binding to the graphitic surface. It was shown that a structure of two stacked graphene layers causes a significant straightening of the aliphatic tail of the surfactant molecule adsorbed on the outer graphene layer. Binding energy calculations showed the effect of surfactant structure and CNT diameter on their interaction intensity.     

Synthesis of Lead Nickel Niobate–Lead Zirconate Titanate Solid Solutions by a B-site Precursor Method

A modified processing method for lead nickel niobate–lead zirconate titanate (Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃, PNN–PZT) solid solutions is presented. This method is based on the high-temperature synthesis of a precursor that contains all the B-site cations (Ti, Zr, Ni, and Nb). This synthesis yields a diphasic mixture that contains a ZrTiO₄-like phase and a rutile-like phase. Both phases exhibit a cationic valence of 4; thus, it is concluded that the mixing of Ni and Nb cations is adequate for the preparation of PNN–PZT solid solutions. Indeed, a pure perovskite phase has been obtained after calcination with lead oxide for compositions that contain 40 and 50 mol% PNN. Moreover, their electromechanical properties have been shown to be superior to values reported for standard columbite routes. This conclusion has been interpreted in terms of enhanced chemical homogeneity.     

Towards interval techniques for model validation

Most physical models are approximate. It is therefore important to find out how accurate are the predictions of a given model. This can be done by validating the model, i.e., by comparing its predictions with the experimental data. In some practical situations, it is difficult to directly compare the predictions with the experimental data, since models usually contain (physically meaningful) parameters, and the exact values of these parameters are often not known. One way to overcome this difficulty is to get a statistical distribution of the corresponding parameters. Once we substitute these distributions into a model, we get statistical predictions—and we can compare the resulting probability distribution with the actual distribution of measurement results. In this approach, we combine all the measurement results, and thus, we are ignoring the information that some of these results correspond to the same values of the parameters—e.g., they come from measuring the same specimen under different conditions. In this paper, we propose an interval approach that takes into account this important information. This approach is illustrated on the example of a benchmark thermal problem presented at the Sandia Validation Challenge Workshop (Albuquerque, New Mexico, May 2006).     

Synthesis of product-driven coordination controllers for a class of discrete-event manufacturing systems

A synthesis approach is proposed for discrete-event coordination architectures applied to a class of automated manufacturing systems (AMS) in which a clear separation is established between equipment control activities and product manufacturing procedures. Manufacturing procedures are modeled by regular languages constructed with a class of control commands named imperative. Equipment controllers are synthesized as a standard discrete-event supervisors dealing only with operational and safety issues of equipment groupings. The control of equipment modules is carried out following the imperative control commands sequences. Conditions are established to guarantee that the manufacturing procedure of a given product can be achieved using the synthesized supervisors in a particular AMS. Therefore, equipment controllers are not needed to be modified to consider the manufacturing of different products, whilst the construction of achievable manufacturing procedures becomes an “ad hoc” simple process using a reduced set of procedural blocks. The approach is illustrated with an experimental AMS.     

Niobium Doping and Dielectric Anomalies in Bismuth Titanate

A study of the complex permittivity in bismuth titanate was conducted to reveal the nature of an anomaly in the real part of the permittivity, which occurs below the Curie temperature. This anomaly is frequency dependent and is caused by a combination of two relaxation phenomena that appear in the imaginary part of the permittivity. One of the relaxations showed classic characteristics of an ion-jump process. Niobium doping suppressed this relaxation and eliminated the nonferroelectric anomaly in permittivity. Niobium is proposed to affect the ion-jump relaxation through a decrease in the concentration and possibly the mobility of oxygen vacancies.