Fluorescent Properties of a Hybrid Cadmium Sulfide-Dendrimer Nanocomposite and its Quenching with Nitromethane

A fluorescent hybrid cadmium sulphide quantum dots (QDs) dendrimer nanocomposite (DAB-CdS) synthesised in water and stable in aqueous solution is described. The dendrimer, DAB-G5 dendrimer (polypropylenimine tetrahexacontaamine) generation 5, a diaminobutene core with 64 amine terminal primary groups. The maximum of the excitation and emission spectra, Stokes’ shift and the emission full width of half maximum of this nanocomposite are, respectively: 351, 535, 204 and 212 nm. The fluorescence time decay was complex and a four component decay time model originated a good fit (χ = 1.20) with the following lifetimes: τ ₁ = 657 ps; τ ₂ = 10.0 ns; τ ₃ = 59.42 ns; and τ ₄ = 265 ns. The fluorescence intensity of the nanocomposite is markedly quenched by the presence of nitromethane with a dynamic Stern-Volmer constant of 25 M⁻¹. The quenching profiles show that about 81% of the CdS QDs are located in the external layer of the dendrimer accessible to the quencher. PARAFAC analysis of the excitation emission matrices (EEM) acquired as function of the nitromethane concentration showed a trilinear data structure with only one linearly independent component describing the quenching which allows robust estimation of the excitation and emission spectra and of the quenching profiles. This water soluble and fluorescent nanocomposite shows a set of favourable properties to its use in sensor applications.     

Surface‐enhanced Raman scattering and density functional theory studies of bis(4‐aminophenyl)sulfone

Raman and surface‐enhanced Raman scattering (SERS) spectra of dapsone by using colloidal silver nanoparticles have been recorded. Density functional theory was used for the optimization of ground state geometries and simulation of the vibrational spectrum of this molecule. The SERS spectrum with a large silver cluster as a model metallic surface was simulated for the first time. Taking into account the experimental and calculated Raman as well as the SERS normal modes and the corresponding assignments, along with the modeling of the free dapsone and the one in the presence of the colloidal silver nanoparticles, the importance of the sulfone group on the SERS effect in dapsone was inferred. Copyright © 2009 John Wiley & Sons, Ltd.     

Quadrature formulas for the Laplace and Mellin transforms

A discrete Laplace transform and its inversion formula are obtained by using a quadrature of the integral Fourier transform which is given in terms of Hermite polynomials and its zeros. This approach yields a convergent discrete formula for the two-sided Laplace transform if the function to be transformed falls off rapidly to zero and satisfies given conditions of integrability, achieving convergence also for singular functions. The inversion formula becomes a quadrature formula for the Bromwich integral. The use of asymptotic formulae yields an algorithm to compute the discrete Laplace transform by using only exponentials.     

Heuristic solution approaches for the maximum minsum dispersion problem

The Maximum Minsum Dispersion Problem (Max-Minsum DP) is a strongly NP-Hard problem that belongs to the family of equitable dispersion problems. When dealing with dispersion, the operations research literature has focused on optimizing efficiency-based objectives while neglecting, for the most part, measures of equity. The most common efficiency-based functions are the sum of the inter-element distances or the minimum inter-element distance. Equitable dispersion problems, on the other hand, attempt to address the balance between efficiency and equity when selecting a subset of elements from a larger set. The objective of the Max-Minsum DP is to maximize the minimum aggregate dispersion among the chosen elements. We develop tabu search and GRASP solution procedures for this problem and compare them against the best in the literature. We also apply LocalSolver, a commercially available black-box optimizer, to compare our results. Our computational experiments show that we are able to establish new benchmarks in the solution of the Max-Minsum DP.     

Determination of arsenic in diesel, gasoline and naphtha by graphite furnace atomic absorption spectrometry using microemulsion medium for sample stabilization

A procedure for the determination of As in diesel, gasoline and naphtha at μg L⁻¹ levels by GFAAS is proposed. Sample stabilization was achieved by the formation of three component solutions prepared by mixing appropriate volumes of the samples propan-1-ol and nitric acid aqueous solution. This mixture resulted in a one-phase medium, which was indefinitely stable. No changes in the analyte signals were observed over several days in spiked samples, proving long-term stabilization ability. The use of conventional (Pd) and permanent (Ir) modification was investigated and the former was preferred. Central composite design multivariate optimization defined the optimum microemulsion composition as well as the temperature program. In this way, calibration using aqueous analytical solutions was possible, since the same sensitivity was observed in the investigated microemulsion media and in 0.2% v/v HNO₃. Coefficients of correlation larger than 0.999 and an As characteristic mass of 22 pg were observed. Recoveries (n=4) obtained from spiked samples were 98±4, 99±3 and 103±5%, and the limits of detection in the original samples were 1.8, 1.2 and 1.5 μg L⁻¹ for diesel, gasoline and naphtha, respectively. Validation was performed by the analysis of a set of commercial samples by independent comparative procedures. No significant difference (Student’s t-test, p<0.05) was observed between comparative and proposed procedure results. The total determination cycle lasted 4 min for diesel and 3 min for gasoline and naphtha, equivalent to a sample throughput of 7 h⁻¹ for diesel and 10 h⁻¹ for gasoline and naphtha.     

Hierarchical Functionalized Polymeric‐Ceramic Coatings on Mg‐Ca Alloys for Biodegradable Implant Applications

Magnesium‐based implants present several advantages for clinical applications, in particular due to their biocompatibility and degradability. However, degradation products can affect negatively the cell activity. In this work, a combined coating strategy to control the implant degradation and cell regulation processes is evaluated, including plasma electrolytic oxidation (PEO) that produces a 13 µm‐thick Ca, P, and Si containing ceramic coating with surface porosity, and breath figures (BF) approach that produces a porous polymeric poly(ε‐caprolactone) surface. The degradation of PCL‐PEO‐coated Mg hierarchical scaffold can be tailored to promote cell adhesion and proliferation into the porous structure. As a result, cell culture can colonize the inner PEO‐ceramic coating structure where higher amount of bioelements are present. The Mg/PEO/PCL/BF scaffolds exhibit equally good or better premyoblast cell adhesion and proliferation compared with Ti CP control. The biological behavior of this new hierarchical functionalized scaffold can improve the implantation success in bone and cardiovascular clinical applications.     

Viscometric and sorption equilibrium studies on n-alkane-butanone-poly-(dimethylsiloxane) systems

Intrinsic viscosities, [η], second virial coefficients, A₂, and preferential solvation coefficients, λ, for the ternary systems n-alkane (l)-butanone (2)-poly(dimethylsiloxane) (PDMS) (3), with n-alkane = n-hexane, n-heptane, n-nonane and n-undecane, have been determined at 20°. The K and a constants of the Mark-Houwink equation have been evaluated over the whole composition range of the binary solvent mixtures. Polymer (mixed solvent) interaction parameters and unperturbed dimensions have been evaluated both from A₂ and [η] data, the feasibility of A₂ evaluation from [η] experimental data or vice versa being discussed. Experimental and calculated (through Dondos and Patterson theory) excess free energies, G^E, follow similar trends with composition; large numerical discrepancies, however, arise between both sets of G^E. Maxima in [η], in a and in A₂ are accompanied by inversion points in λ. The solvent mixture composition range in which PDMS is preferentially solvated by n-alkane, as well as the extent of solvation, decrease with increasing number of carbon atoms in the n-alkane.     

Polymeric Gene Carriers Bearing Pendant β‐Cyclodextrin: The Relevance of Glycoside Permethylation on the “In Vitro” Cell Response

The incorporation of cyclodextrins (CDs) to nonviral cationic polymer vectors is very attractive due to recent studies that report a clear improvement of their cytocompatibility and transfection efficiency. However, a systematic study on the influence of the CD derivatization is still lacking. In this work, the relevance of β‐CD permethylation has been addressed by preparing and evaluating two series of copolymers of the cationic N‐ethyl pyrrolidine methacrylamide (EPA) and styrenic units bearing pendant hydroxylated and permethylated β‐CDs (HCDSt and MeCDSt, respectively). For both cell lines, CDs permethylation shows a strong influence on plasmid DNA complexation, “in vitro” cytocompatibility and transfection efficiency of the resulting copolymers over two murine cell lines. While the incorporation of the hydroxylated CD moiety increased the cytotoxicity of the copolymers in comparison with their homopolycationic counterpart, the permethylated copolymers have shown full cytocompatibility as well as superior transfection efficiency than the controls. This behavior has been related to the different chemical nature of both units and tentatively to a different distribution of units along the polymeric chains. Cellular internalization analysis with fluorescent copo­lymers supports this behavior.

     

Validation of new methodology for the definition of tolerance limits of critical properties in fuels handled in terminals and pipelines—giveaway: compliance with the specification

Accreditation and Quality Assurance - In any commercial transaction, the presence of tolerances from specification limits is essential to ensure that the true value of the property of interest is...