Phase diagrams of a CTAB/organic solvent/buffer system applied to extraction of enzymes by reverse micelles

A partial pseudo-ternary phase diagram has been studied for the cethyltrimethylammonium bromide/isooctane:hexanol:butanol/potassium phosphate buffer system, where the two-phase diagram consisting of the reverse micelle phase (L-2) in equilibrium with the solvent is indicated. Based on these diagrams two-phase systems of reverse micelles were prepared with different compositions of the compounds and used for extraction and recovery of two enzymes, and the percentage of enzyme recovery yield monitored. The enzymes glucose-6-phosphate dehydrogenase (G6PD) and xylose redutase (XR) obtained from Candida guilliermondii yeast were used in the extraction procedures. The recovery yield data indicate that micelles having different composition give selective extraction of enzymes. The method can thus be used to optimize enzyme extraction processes. (c) 2007 Elsevier B.V. All rights reserved.

Crystal and molecular structures of dichloro((Z)-2-chloro-2-phenylvinyl)(organo)tellurium(IV) for organo = n-butyl and phenyl

In each of the title compounds, R[Ph(Cl)C=(H)C]TeCl(2), R = nBu (1) and Ph (2), the primary geometry about the Te(IV) atom is a pseudo-trigonal-bipyramidal arrangement, with two Cl atoms in apical positions, and the lone pair of electrons and C atoms in the equatorial plane. As the Te(IV) is involved in two, an intra- and an inter-molecular, Te center dot center dot center dot Cl interactions the coordination geometry might be considered as a Psi-pentagonal bipyramid in each case. In addition, in (2) there is a hint of a Te center dot center dot center dot pi interaction (Te center dot center dot center dot C = 3.911(3) A). The key feature in the crystal structure of both compounds is the formation of supramolecular chains mediated by Te center dot center dot center dot Cl contacts. (1): C(12)H(15)Cl(3)Te, triclinic, P (1) over bar, a = 5.9471 (11), b = 10.7826(22), c = 11.7983(19) angstrom, alpha = 75.416(12), beta = 78.868(13), gamma = 80.902(14)degrees, V = 713.6(2) angstrom(3), Z = 2, R(1) = 0.021; (2): C14HIIC13Te, orthorhombic, Pcab, a=7.7189(10), b=17.415(2), c=21.568(3)angstrom, V = 2899.3(6) angstrom(3), Z = 8, R(1) = 0.027.

In situ gelling hexagonal phases for sustained release of an anti-addiction drug

In this study, fluid precursor formulations for subcutaneous injection and in situ formation of hexagonal phase gels upon water absorption were developed as a strategy to sustain the release of naltrexone, a drug used for treatment of drug addiction. Precursor formulations were obtained by combining BRIJ 97 with propylene glycol (PG, 5-70%, w/w). To study the phase behavior of these formulations, water was added at 10-90% (w/w), and the resulting systems were characterized by polarized light microscopy. Two precursor formulations containing BRIJ:PG at 95:5 (w/w, referred to as BRIJ-95) and at 80:20 (w/w, referred to as BRIJ-80) were chosen. Naltrexone was dissolved at 1% or suspended at 5% (w/w). Precursor formulations were transformed into hexagonal phases when water content exceeded 20%. Water uptake followed second-order kinetics, and after 2-4 h all precursor formulations were transformed into hexagonal phases. Drug release was prolonged by the precursor formulations (compared to a drug solution in PBS), and followed pseudo-first order kinetics regardless of naltrexone concentration. The release from BRIJ-80 was significantly higher than that from BRIJ-95 after 48 h. The relative safety of the precursor formulations was assessed in cultured fibroblasts. Even though BRIJ-95 was more cytotoxic than BRIJ-80, both precursor formulations were significantly less cytotoxic than sodium lauryl sulfate (considered moderate-to-severe irritant) at the same concentration (up to 50 mu g/mL). These results suggest the potential of BRIJ-based precursor formulations for sustained naltrexone release. (C) 2011 Elsevier By. All rights reserved.

Microparticles as a Strategy for Low-Molecular-Weight Heparin Delivery

The aims of this work were preparation and physical-chemical characterization of a microparticulate release system for delivery of enoxaparin sodium (ENX), a low-molecular-weight heparin, as a potential vehicle for optimization of deep venous thrombosis therapy. Microparticles (MPs) containing ENX were prepared from polylactide-co-glycolic acid [PLGA; (50: 50)] by a double emulsification/solvent evaporation method. The preparation parameters, such as proportion ENX/PLGA, surfactant concentration, type, time, and speed of stirring, were evaluated. The encapsulation efficiency and yield process were determined and optimized, and the in vitro release profile was analysed at 35 days. The MPs showed a spherical shape with smooth and regular surfaces. The size distribution showed a unimodal profile with an average size of 2.0 +/- 0.9 mu m. The low encapsulation efficiency (< 30%), characteristic of hydrophilic macromolecules was improved, reaching 50.2% with a procedure yield of 71.3%. The in vitro profile of ENX release from the MPs was evaluated and showed pseudo-zero-order kinetics. This indicated that diffusion was the main drug release mechanism. (C) 2010 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 100:1783-1792, 2011

The Equilibrium Flux Method for the calculation of flows with non-equilbrium chemical reactions

The Equilibrium Flux Method [1] is a kinetic theory based finite volume method for calculating the flow of a compressible ideal gas. It is shown here that, in effect, the method solves the Euler equations with added pseudo-dissipative terms and that it is a natural upwinding scheme. The method can be easily modified so that the flow of a chemically reacting gas mixture can be calculated. Results from the method for a one-dimensional non-equilibrium reacting flow are shown to agree well with a conventional continuum solution. Results are also presented for the calculation of a plane two-dimensional flow, at hypersonic speed, of a dissociating gas around a blunt-nosed body.

The importance of wet-powder dynamic mechanical properties in understanding granulation

Granule impact deformation has long been recognised as important in determining whether or not two colliding granules will coalesce. Work in the last 10 years has highlighted the fact that viscous effects are significant in granulation. The relative strengths of different formulations can vary with strain rate. Therefore, traditional strength measurements made at pseudo-static conditions give no indication, even qualitatively, of how materials will behave at high strain rates, and hence are actually misleading when used to model granule coalescence. This means that new standard methods need to be developed for determining the strain rates encountered by granules inside industrial equipment and also for measuring the mechanical properties of granules at these strain rates. The constitutive equations used in theoretical models of granule coalescence also need to be extended to include strain-rate dependent components.

Emotion and attribution of intentionality in leader–member relationships

In this article, we present a model of emotions and attributions of intentionality within the leader–member relationship. The model is predicated on two central ideas. The first is that leadership is intrinsically an emotional process, where leaders display emotion and attempt to evoke emotion in their members. The second is that leadership is a process of social interaction and is therefore appropriately defined in terms of social, psychological theories such as the attribution theory. Our focus is on the perspective of members, not the leaders. Specifically, members' attributions about their leader's intentions influence how the members evaluate, interpret, and eventually label the leader's influence attempts as either “true” or “pseudo” transformational leadership. These attributions are determined by and themselves influence the members' emotions. We describe each of the elements of the model and conclude with a discussion of the implications of the model for theory, research, and practice.

A master equation model for bimolecular reaction via multi-well isomerization intermediates

A reversible linear master equation model is presented for pressure- and temperature-dependent bimolecular reactions proceeding via multiple long-lived intermediates. This kinetic treatment, which applies when the reactions are measured under pseudo-first-order conditions, facilitates accurate and efficient simulation of the time dependence of the populations of reactants, intermediate species and products. Detailed exploratory calculations have been carried out to demonstrate the capabilities of the approach, with applications to the bimolecular association reaction C3H6 + H reversible arrow C3H7 and the bimolecular chemical activation reaction C2H2 +(CH2)-C-1--> C3H3+H. The efficiency of the method can be dramatically enhanced through use of a diffusion approximation to the master equation, and a methodology for exploiting the sparse structure of the resulting rate matrix is established.

Bifurcation in growth patterns for arrays of parallel Griffith, edge and sliding cracks

This paper presents the recent finding by Muhlhaus et al [1] that bifurcation of crack growth patterns exists for arrays of two-dimensional cracks. This bifurcation is a result of the nonlinear effect due to crack interaction, which is, in the present analysis, approximated by the dipole asymptotic or pseudo-traction method. The nonlinear parameter for the problem is the crack length/ spacing ratio lambda = a/h. For parallel and edge crack arrays under far field tension, uniform crack growth patterns (all cracks having same size) yield to nonuniform crack growth patterns (i.e. bifurcation) if lambda is larger than a critical value lambda(cr) (note that such bifurcation is not found for collinear crack arrays). For parallel and edge crack arrays respectively, the value of lambda(cr) decreases monotonically from (2/9)(1/2) and (2/15.096)(1/2) for arrays of 2 cracks, to (2/3)(1/2)/pi and (2/5.032)(1/2)/pi for infinite arrays of cracks. The critical parameter lambda(cr) is calculated numerically for arrays of up to 100 cracks, whilst discrete Fourier transform is used to obtain the exact solution of lambda(cr) for infinite crack arrays. For geomaterials, bifurcation can also occurs when array of sliding cracks are under compression.

Modeling ex vivo hematopoiesis using chemical engineering metaphors

Ex vivo hematopoiesis is increasingly used for clinical applications. Models of ex vivo hematopoiesis are required to better understand the complex dynamics and to optimize hematopoietic culture processes. A general mathematical modeling framework is developed which uses traditional chemical engineering metaphors to describe the complex hematopoietic dynamics. Tanks and tubular reactors are used to describe the (pseudo-) stochastic and deterministic elements of hematopoiesis, respectively. Cells at any point in the differentiation process can belong to either an immobilized, inert phase (quiescent cells) or a mobile, active phase (cycling cells). The model describes five processes: (1) flow (differentiation), (2) autocatalytic formation (growth),(3) degradation (death), (4) phase transition from immobilized to mobile phase (quiescent to cycling transition), and (5) phase transition from mobile to immobilized phase (cycling to quiescent transition). The modeling framework is illustrated with an example concerning the effect of TGF-beta 1 on erythropoiesis. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Derivatives of 1,3,5-triamino-1,3,5-trideoxy-cis-inositas versatile pentadentate ligands for protein labeling with Re-186/188. Prelabeling, biodistribution, and X-ray structural studies

The pentadentate H(3)bhci [1,3,5-trideoxy-1,3-bis((2-hydroxybenzyl)amino)-cis-inistol] and its bifunctionalized analogue H(3)bhci-glu-H [1,3,5-trideoxy-1,3-bis((2-hydroxybenzyl)amino)-5-glutaramido-cis-inositol] were synthesized, and their coordination chemistry was investigated with inactive rhenium, with no carrier added Re-188 and with carrier added Re-186. The neutral Re(V) complexes [ReO-(bhci)] and [ReO(bhci-glu-H)] are formed in good yields starting from [ReOCl3(P(C6H5)(3))(2)] or in quantitative yield directly from [(ReO4)-Re-186/188](-) in aqueous solution by reduction with Sn(II) or Sn(0). The X-ray structures of [ReO(bhci)] and [ReO(bhci-glu-H)] were elucidated revealing pentadentate side on coordination of the ligands to the Re=O core. The basic cyclohexane frame adopts a chair form in the case of [ReO(bhci)] and a twisted boat form in the case of [ReO(bhci-glu-H)]. [ReO(bhci)] crystallizes in the monoclinic space group C2/c with a = 27.425(3), b = 14.185(1), c = 19.047(2) Angstrom, and beta = 103.64(2)degrees and [ReO(bhci-glu-H)] in the monoclinic space group P2(1)/c with a = 13.056(3), b = 10.180(1), c = 22.378(5) Angstrom and beta = 98.205(9)degrees Both Re-188 complexes are stable in human serum for at least 3 days without decomposition. After injection into mice, [ReO(bhci-glu)](-) is readily excreted through the intestines, while [ReO(bhci)] is excreted by intestines, liver, and the kidneys. TLC investigations of the urine showed exclusively the complexes [ReO(bhci-glu-H)] and [ReO(bhci)], respectively, and no decomposition products. For derivatization of antibodies, the carboxylic group of [ReO(bhci-glu-H)] was activated with N-hydroxysuccinimide, which required unusually vigorous reaction conditions (heating). The anti colon cancer antibody mAb-35 [IgG and F(ab')(2) fragment] was labeled with [(ReO)-Re-186/188(bhci-glu)] to a specific activity of up to 1.5 mCi/mg (55 MBq/mg) with full retention of immunoreactivity. Labeling yields followed pseudo-first-order kinetics in antibody concentration with the ratio of rates between aminolysis and hydrolysis being about 2. Biodistributions of Re-186-labeled intact mAb-35 as well as of its F(ab')(2) fragment in tumor-bearing nude mice revealed good uptake by the tumor with only low accumulation of radioactivity in normal tissue.

Search for time variation of the fine structure constant

An order of magnitude sensitivity gain is described for using quasar spectra to investigate possible time or space variation in the fine structure constant alpha. Applied to a sample of 30 absorption systems, spanning redshifts 0.5 < z < 1.6, we derive limits on variations in alpha over a wide range of epochs. For the whole sample, Delta alpha/alpha = (-1.1 +/- 0.4) x 10(-5). This deviation is dominated by measurements at z > 1, where Delta alpha/alpha = (-1.9 +/- 0.5) x 10(-5). For z < 1, Delta alpha/alpha = (-0.2 +/- 0.4) x 10(-5). While this is consistent with a time-varying alpha, further work is required to explore possible systematic errors in the data, although careful searches have so far revealed none.

The effect of Al2O3 on liquidus temperatures of fayalite slags

The effect of alumina on the liquidus temperatures of fayalite slags at iron saturation has been investigated experimentally. Equilibrated synthetic slags were quenched, and the samples were subsequently examined using optical microscopy and electron probe microanalysis (EPMA). The isotherms in the fayalite primary field and boundary lines were determined, and the results were presented in the form of pseudo-ternary phase diagrams of FeO-CaO-SiO2 with 0, 2, 4, and 6 wt pet Al2O3 in the slag. The experimental results show that the alumina addition expands the fayalite primary phase field and decreases the liquidus temperatures in the fayalite primary phase field.

Sedimentologic, petrographic, and sulfur isotope constraints on fine-grained pyrite formation at Mount Isa Mine and environs, Northwest Queensland, Australia

Fine-grained pyrite is the earliest generation of pyrite and the most abundant sulfide within the Urquhart Shale at Mount Isa, northwest Queensland. The pyrite is intimately interbanded with ore-grade Pb-Zn miner alization at the Mount Isa mine but is also abundant north and south of the mine at several stratigraphic horizons within the Urquhart Shale. Detailed sedimentologic, petrographic, and sulfur isotope studies of the Urquhart Shale, mostly north of the mine, reveal that the fine-grained pyrite (delta(34)S = -3.3 to +26.3 parts per thousand) formed by thermochemical sulfate reduction during diagenesis. The sulfate source was local sulfate evaporites, pseudo morphs of which are present throughout the Urquhart Shale (i.e., gypsum, anhydrite, and barite). Deep-burial diagenetic replacement of these evaporites resulted in sulfate-bearing ground waters which migrated parallel to bedding. Fine-grained pyrite formed where these fluids infiltrated and then interacted with carbon-rich laminated siltstones. Comparison of the sulfur isotope systematics of fine-grained pyrite and spatially associated base metal sulfides from the Mount Isa Pb-Zn and Cu orebodies indicates a common sulfur source of ultimately marine origin for all sulfide types. Different sulfur isotope ratio distributions for the various sulfides are the result of contrasting formation mechanisms and/or depositional conditions rather than differing sulfur sources. The sulfur isotope systematics of the base metal and associated iron sulfide generations are consistent with mineralization by reduced hydrothermal fluids, perhaps generated by bulk reduction of evaporite-sourced sulfate-bearing waters generated deeper in the Mount Isa Group, the sedimentary sequence which contains the Urquhart Shale. The available sulfur isotope data from the Mount Isa orebodies are consistent with either a chemically and thermally zoned, evolving Cu-Pb-Zn system, or discrete Cu and Pb-Zn mineralizing events linked by a common sulfur source.

Coupled experimental and thermodynamic modeling studies for metallurgical smelting and coal combustion slag systems

An extensive research program focused on the characterization of various metallurgical complex smelting and coal combustion slags is being undertaken. The research combines both experimental and thermodynamic modeling studies. The approach is illustrated by work on the PbO-ZnO-Al2O3-FeO-Fe2O3-CaO-SiO2 system. Experimental measurements of the liquidus and solidus have been undertaken under oxidizing and reducing conditions using equilibration, quenching, and electron probe X-ray microanalysis. The experimental program has been planned so as to obtain data for thermodynamic model development as well as for pseudo-ternary Liquidus diagrams that can be used directly by process operators. Thermodynamic modeling has been carried out using the computer system FACT, which contains thermodynamic databases with over 5000 compounds and evaluated solution models. The FACT package is used for the calculation of multiphase equilibria in multicomponent systems of industrial interest. A modified quasi-chemical solution model is used for the liquid slag phase. New optimizations have been carried out, which significantly improve the accuracy of the thermodynamic models for lead/zinc smelting and coal combustion processes. Examples of experimentally determined and calculated liquidus diagrams are presented. These examples provide information of direct relevance to various metallurgical smelting and coal combustion processes.