Interaction of Chlorpromazine and Trifluoperazine with Anionic Sodium Dodecyl Sulfate (SDS) Micelles: Electronic Absorption and Fluorescence Studies

The characteristics of binding of two phenothiazine antipsychothic drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), to anionic sodium dodecyl sulfate (SDS) monomers and/or micelles were investigated using electronic absorption and fluorescence spectroscopies. Binding constants K(b) and pK(a) values for the drugs in SDS micelles were estimated using the red shifts of the maximum absorption and changes in absorption upon alkalization or in the presence of surfactant. The pK(a) shift of CPZ due to its interaction with SDS micelles is about 0.7 unit to higher values, as compared to the reported value of pK(a) obtained in buffer around 9.3. For TFP the pK(a) shift is 0.4 unit to higher values compared to that in buffer, reported as 4.0. The electronic absorption spectroscopic data suggest a biphasic interaction as a function of detergent concentration which is quite dependent of the protonation states of the drugs. In the case of TFP a very strong binding takes place when the drug is fully protonated (pH 2.0) and a distinct binding takes place at stoichiometric (low) surfactant concentrations (interaction via surfactant monomers) and at higher concentrations (in the presence of micelles). Static fluorescence probe analysis using pyrene was used to study the nature of the phenothiazine-surfactant premicellar and self-aggregates. The I(3)/I(1) and I(475)/I(1) ratios associated to pyrene fluorescence vibronic bands and excimer intensities ratios, respectively, were monitored for several ratios [SDS]/[drug] and significant changes, dependent of the drug presence and its protonation state, have been observed revealing a hydrophobic microenvironment provided by TFP-SDS aggregates in comparison with CPZ both at pH 7.0 and 4.0. Static anisotropy was also used to monitor the changes of the self-aggregates and micellar packing in the presence of the phenothiazine drugs. In aqueous solutions the anisotropy of the fluorescent probe dipyridamole (DIP) is quite low, being around 0.005 at pH 7.0 and 0.025 at pH 4.0, and the addition of detergent leads to an increase in the values of anisotropy to 0.030 at pH 7.0 and 0.070 at pH 4.0. In the presence of the phenothiazine drugs, and in the premicellar detergent concentration range, the anisotropy of DIP increases to 0.134 and 0.111 (dependent on drug concentration) for CPZ and TFP, respectively, at pH 4.0. These results suggest that the presence of both phenotiazine drugs makes the premicellar aggregates more rigid by decreasing the probe mobility, and are consistent with a more polar localization of the CPZ in the micelles as compared with TFP. At pH 7.0 the anisotropy changes are smaller, suggesting a slight decrease in CMC induced by the phenothiazines. Copyright 2000 Academic Press.     

Benzamide species retained by DMSO composites at a kaolinite surface

The surface area of kaolinite-benzamide (K-Bz)6.62 m² g^–1, whichis noticeably lower than that of kaolinite-dimethyl sulphoxide (K-DMSO) 14.61m² g^–1, the co-perturbationof the inner-surface hydroxyl features at 3697 and 3650 cm^–1,and the increase of d(001) value by 7.44 Å are all related to the benzamidespecies inserted into the kaolinite structure through the replacement of theK-DMSO composites. Disappearance of the DMSO reflections and emergence ofwell-defined features at 6.04(2θ) and 11.16(2θ), 001 and 002 reflectionswith d values of 14.62 and 7.92 Å, respectively point out that the DMSOspecies were substituted efficiently by benzamide molecules. The thermal stabilityof the K-Bz derivative up to 300°C can be attributed to the slightly tiltedaromatic ring keying into the gibbsitic sheets via the –NH₂groups.     

Crosslinking‐induced morphology change of latex nanoparticles: A study of RAFT‐mediated polymerization in aqueous dispersed media using amphiphilic double‐brush copolymers as reactive surfactants

Amphiphilic double‐brush copolymers (DBCs) with each graft site quantitatively carrying both a hydrophilic poly(ethylene oxide) (PEO) graft and a hydrophobic polystyrene (PSt) graft are synthesized by sequential reversible addition‐fragmentation chain transfer (RAFT) polymerization and ring‐opening metathesis polymerization (ROMP). These DBCs are used as both surfactants and polyfunctional RAFT agents in the radical polymerization of St in aqueous dispersed media. Miniemulsions with narrowly dispersed St‐based nanodroplets are readily obtained after ultrasonication of the reaction mixtures. Without the presence of crosslinker, chain‐extension polymerization of St from the DBCs yields well‐defined polymeric latexes with narrow size distributions. However, with the presence of divinylbenzene (DVB) as the crosslinker, vesicular polymeric nanoparticles are formed as the major product. Such crosslinking‐induced change in morphology of the resulting latex nanomaterials may be ascribed to the increase of interfacial curvature in the heterophase systems during crosslinking polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3250–3259     

Influence of using nanoobjects as filler on functionality-based energy use of nanocomposites

The goal of our study was to investigate the potential benefits of reinforcing polymer matrices with nanoobjects for structural applications by looking at both the mechanical properties and environmental impacts. For determining the mechanical properties, we applied the material indices defined by Ashby for stiffness and strength. For the calculation of environmental impacts, we applied the life cycle assessment methodology, focusing on non-renewable energy use (NREU). NREU has shown to be a good indicator also for other environmental impacts. We then divided the NREU by the appropriate Ashby index to obtain the ‘functionality-based NREU’. We studied 23 different nanocomposites, based on thermoplastic and thermosetting polymer matrices and organophilic montmorillonite, silica, carbon nanotubes (single-walled and multiwalled) and calcium carbonate as filler. For 17 of these, we saw a decrease of the functionality-based NREU with increasing filler content. We draw the conclusion that the use of nanoobjects as filler can have benefits from both an environmental point of view and with respect to mechanical properties.     

Topological properties of commodities networks

This paper investigates the topological properties of the commodities networks. We have found that commodities form strong clusters and are homogeneous with relation to sector (metals, agriculture and energy). We also develop a dynamic approach suggesting that agriculture commodities are very important in the network, followed by metals and energy. Furthermore, the parameters that characterize the network seem to be changing over time.     

The expectation hypothesis of interest rates and network theory: The case of Brazil

This paper investigates the topological properties of the Brazilian term structure of interest rates network. We build the minimum spanning tree (MST), which is based on the concept of ultrametricity, using the correlation matrix for interest rates of different maturities. We show that the short-term interest rate is the most important within the interest rates network, which is in line with the Expectation Hypothesis of interest rates. Furthermore, we find that the Brazilian interest rates network forms clusters by maturity.     

Mixing Closures for Conservation Laws in Stratified Flows

A closure for shocks involving the mixing of the fluids in two-layer stratified flows is proposed. The closure maximizes the rate of mixing, treating the dynamical hydraulic equations and entropy conditions as constraints. This closure may also be viewed as yielding an upper bound on the mixing rate by internal shocks. It is shown that the maximal mixing rate is accomplished by a shock moving at the fastest allowable speed against the upstream flow. Depending on whether the active constraint limiting this speed is the Lax entropy condition or the positive dissipation of energy, we distinguish precisely between internal hydraulic jumps and bores. Maximizing entrainment is shown to be equivalent to maximizing a suitable entropy associated to mixing. By using the latter, one can describe the flow globally by an optimization procedure, without treating the shocks separately. A general mathematical framework is formulated that can be applied whenever an insufficient number of conservation laws is supplemented by a maximization principle.     

Topological properties of stock market networks: The case of Brazil

This paper investigates the topological properties of the Brazilian stock market networks. We build the minimum spanning tree, which is based on the concept of ultrametricity, using the correlation matrix for a variety of stocks of different sectors. Our results suggest that stocks tend to cluster by sector. We employ a dynamic approach using complex network measures and find that the relative importance of different sectors within the network varies. The financial, energy and material sectors are the most important within the network.     

Synthesis, spectroscopic characterization, X-ray structure, and DFT calculations of [ReOBr2(hmquin-7-COOH)(AsPh3)]

The reaction of [ReOBr₃(AsPh₃)₂] with 8-hydroxy-2-methylquinoline-7-carboxylic acid (Hhmquin-7-COOH) has been examined and the [ReOBr₂(hmquin-7-COOH)(AsPh₃)] complex has been obtained. It was characterized by IR, UV–vis spectroscopy, and single crystal X-ray analysis. The nature of the frontier orbitals and the electronic transitions involved in the absorption spectrum have been studied by means of density functional and time-dependent density functional calculations.