Synthesis, characterization, and bactericidal properties of composites based on crosslinked resins containing silver

Two different commercial crosslinked resins (Amberlite GT73 and Amberlite IRC748) were employed for anchoring silver. The -SH and -N(CH2COOH)2 groups, respectively, present on these resins were used for Ag+ chelation from an aqueous solution. The Ag+ ions were reduced with three different reductants: hydrazine, hydroxylamine, and formaldehyde (under an alkaline pH). The produced composites were characterized with thermogravimetry/differential thermogravimetry and scanning electron microscopy combined with a backscattered scanning electron detector. Energy-dispersive X-ray spectroscopy coupled to scanning electron microscopy allowed the observation of submicrometer particles of silver, and chemical microanalysis of emitted X-rays revealed the presence of metal on the internal and external surfaces of the composite microspheres. The amount of incorporated silver was determined by titration. The antibacterial activity of the silver/resin composites was determined toward 10(3)-10(7) cells/mL dilutions of the auxotrophic AB1157 Escherichia coli strain; the networks containing anchored submicrometer silver particles were completely bactericidal within a few minutes because of the combined action of silver and functional groups of the resins. (c) 2007 Wiley Periodicals, Inc.

Thermal properties of amphiphilic biodegradable triblock copolymer of l,l-lactide and ethylene glycol

Samples of poly(l,l-lactide)-block-poly(ethylene glycol)-block-poly(l,l-lactide) (PLLA-PEG-PLLA) were synthesized from l,l-lactide polymerization using stannous 2-ethylhexanoate, Sn(Oct)(2) as initiator and di-hydroxy-terminated poly(ethylene glycol) (PEG) (M (n) = 4000 g mol(-1)) as co-initiator. The chemical linkage between the PEG segment and the PLA segments was characterized by Fourier transform infrared spectroscopy (FTIR). Thermogravimetry analysis (TG) revealed the copolymers composition and was capable to show the deleterious effect of an excess of Sn(Oct)(2) in the polymer thermal stability, while Differential Scanning Calorimetry (DSC) allowed the observation of the miscibility between the PLLA and PEG segments in the different copolymers.

Controlling the luminescence properties of poly(p-phenylene vinylene) entrapped in Langmuir and Langmuir-Blodgett films of stearic acid

Properties of hybrid films can be enhanced if their molecular architecture is controlled. In this paper, poly (p-phenylene vinylene) was mixed with stearic acid in order to form stable hybrid Langmuir monolayers. Surface properties of these films were investigated with measurements of surface pressure, and also with polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). The films were transferred from the air-water interface to solid supports through the Langmuir-Blodgett technique, and the viability of the film as optical device was investigated with fluorescence spectroscopy. Comparing the fluorescent spectra for the polymer in solution, as a casting film, and as an LB film, the emission bands for LB films were narrower and appeared at lower wavelengths. The interactions between the film components and the design for the LB film may take advantage of the method to immobilize luminescent polymers in mixed ultrathin films adsorbed in solid matrices. (C) 2011 Elsevier B.V. All rights reserved.

Novel blue emitters based on pi-conjugated block copolymers

A series of new phenyl-based conjugated copolymers has been synthesized and investigated by vibrational and photoluminescence spectroscopy (PL). The materials are: poly( 1,4-phenylene-alt-3,6-pyridazine) (COP-PIR), poly(9,9-dioctylfluorene)-co-quaterphenylene (COP-PPP) and poly[(1,4-phenylene-alt-3,6-pyridazine)-co-(1,4-phenylene-alt-9,9-dioctylfluorene)] (COP-PIR-FLUOR), with 3.5% of fluorene. COP-PPP and COP-PIR-FLUOR have high fluorescence quantum yields in solution. Infrared and Raman spectra were used to check the chemical structure of the compounds. The copolymers exhibit blue emission ranging front 2.8 to 3.6 eV when excited at E(exc)=4.13 eV. Stokes-shift Values were estimated on pristine samples in their condensed state from steady-state PL-emission and PL-excitation spectra. They suggest a difference in the torsional angle between the molecular configuration of the polymer blocks at the absorption and PL transitions and also in the photoexcitation diffusion. Additionally, the time-resolved PL of these materials has been investigated by using 100 fs laser pulses at E(exc)=4.64 eV and a streak camera. Results show very fast biexponential kinetics for the two fluorene-based polymers with decay times below 300 ps indicating both intramolecular, fast radiative recombination and migration of photogenerated electron-hole pairs. By contrast, the PL of COP-PIR is less intense and longer lived, indicating that excitons are confined to the chains in this polymer. (C) 2008 Elsevier B.V. All rights reserved.

Thermal and mechanical characteristics of polyurethane/curaua fiber composites

Polyurethane composites reinforced with curaua fiber at 5, 10 and 20% mass/mass proportions were prepared by using the conventional melt-mixing method. The influence of curaua fibers on the thermal behavior and polymer cohesiveness in polyurethane matrix was evaluated by dynamic mechanical thermal analysis (DMTA) and by differential scanning calorimetry (DSC). This specific interaction between the fibers and the hard segment domain was influenced by the behavior of the storage modulus E` and the loss modulus EaEuro(3) curves. The polyurethane PU80 is much stiffer and resistant than the other composites at low temperatures up to 70A degrees C. All samples were thermoplastic and presented a rubbery plateau over a wide temperature range above the glass transition temperature and a thermoplastic flow around 170A degrees C.

Preparation and characterization of crosslinked resins containing ferrite particles

Micrometer-sized magnetic particles hosted on network material were successfully prepared by a simple chemical process (ion exchange followed by co-precipitation) from commercial styrene-divinylbenzene copolymers. Energy dispersive X-ray spectroscopy (EDS) coupled to scanning electron microscopy (SEM) allowed the observation of submicron particles. All the produced spherical beads have presented metallic particles (NiFe2O4, CuFe2O4, CoFe2O4, or MnFe2O4), either as isolated particles or agglomerates, located on their external and internal (within pores) The thermal stability of the composites, evaluated by thermogravimetric techniques, were found to be dependent on the amount of ferrite particles incorporated into them.

Synthesis, characterization and evaluation of phosphorylated resins in the removal of Pb(2+) from aqueous solutions

Phosphinic-derivative poly(styrene-co-divinylbenzene)-based on PS-DVB copolymers with different porosity degrees have been prepared by aromatic electrophilic substitution reaction using PCl(3)/AlCl(3) followed by base-promoted hydrolysis. The phosphorylation reaction was analyzed by infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetry (TG/DTG). In addition, the phosphorous content of the phosphorylated copolymers was determined by spectrophotometry using the method based on sodium molybdate reactant so that the extension of that modification could be assessed. The performance of the phosphorylated resins in the extraction of Pb(2+) from aqueous solutions in a batch system was also evaluated. The Pb(2+) content was determined by atomic absorption spectrometry (AAS). These materials presented excellent extraction capacity under the contact time of 30 min and pH 6.

Biodegradable nanosize particles of poly(L,L-lactide)-b-poly(ethylene glycol)-b-poly(L,L-lactide)

Two series of poly(L,L-lactide-b-ethylene glycol-b-L,L-lactide) copolymers, PLA-PEO-PLA, were synthesized by polymerization Of L,L-lactide using a dihydroxy-terminated poly(ethylene glycol) (PEG) (M-n = 4000 or 600 g/mol) as coinitiator and stannous 2-ethylhexanoate, Sn(Oct)(2), as initiator. The synthesized copolymers have shown high stereoregularity as observed by C-13 NMR analyses. The nanoparticles were prepared by using a solvent diffusion method and the self-assemblage process and were characterized by NMR and SEM. It was possible to conclude that the self-assembled particles presented a core-shell structure characterized by a hydrophobic PLA core and a hydrophilic PEG shell, thus the NMR of the aqueous solutions indicated a quasi-solid behavior for the particles` interior. The diameters of the spherical particles as observed by SEM were in the 50-250 nm range, depending on the copolymer composition and the preparation procedure.

Magnetic loss, permeability dispersion, and role of eddy currents in Mn-Zn sintered ferrites

Magnetic energy losses and permeability have been investigated in laboratory prepared and commercial Mn-Zn sintered ferrites from quasi-static conditions up to 10 MHz. The mechanisms leading to energy dissipation, either due to domain wall displacements or magnetization rotations, have been quantitatively assessed and their respective roles have been clarified. Domain wall processes dissipate energy by pure relaxation effects, while rotations display resonant absorption of energy over a broad range of frequencies. Their specific contributions to the permeability and its frequency dispersion are thus identified and separately evaluated. It is shown that eddy currents are always too weak to appreciably contribute to the losses over the whole investigated frequency range and that rotations are the dominant magnetization and loss producing mechanisms on approaching the MHz range, as predicted by the Landau-Lifshitz-Gilbert equation with distributed anisotropy fields. (C) 2008 Elsevier B.V. All rights reserved.

Infinite horizon MPC with non-minimal state space feedback

In the MPC literature, stability is usually assured under the assumption that the state is measured. Since the closed-loop system may be nonlinear because of the constraints, it is not possible to apply the separation principle to prove global stability for the Output feedback case. It is well known that, a nonlinear closed-loop system with the state estimated via an exponentially converging observer combined with a state feedback controller can be unstable even when the controller is stable. One alternative to overcome the state estimation problem is to adopt a non-minimal state space model, in which the states are represented by measured past inputs and outputs [P.C. Young, M.A. Behzadi, C.L. Wang, A. Chotai, Direct digital and adaptative control by input-output, state variable feedback pole assignment, International journal of Control 46 (1987) 1867-1881; C. Wang, P.C. Young, Direct digital control by input-output, state variable feedback: theoretical background, International journal of Control 47 (1988) 97-109]. In this case, no observer is needed since the state variables can be directly measured. However, an important disadvantage of this approach is that the realigned model is not of minimal order, which makes the infinite horizon approach to obtain nominal stability difficult to apply. Here, we propose a method to properly formulate an infinite horizon MPC based on the output-realigned model, which avoids the use of an observer and guarantees the closed loop stability. The simulation results show that, besides providing closed-loop stability for systems with integrating and stable modes, the proposed controller may have a better performance than those MPC controllers that make use of an observer to estimate the current states. (C) 2008 Elsevier Ltd. All rights reserved.

A Functional Verification Methodology Based on Parameter Domains for Efficient Input Stimuli Generation and Coverage Modeling

Modern Integrated Circuit (IC) design is characterized by a strong trend of Intellectual Property (IP) core integration into complex system-on-chip (SOC) architectures. These cores require thorough verification of their functionality to avoid erroneous behavior in the final device. Formal verification methods are capable of detecting any design bug. However, due to state explosion, their use remains limited to small circuits. Alternatively, simulation-based verification can explore hardware descriptions of any size, although the corresponding stimulus generation, as well as functional coverage definition, must be carefully planned to guarantee its efficacy. In general, static input space optimization methodologies have shown better efficiency and results than, for instance, Coverage Directed Verification (CDV) techniques, although they act on different facets of the monitored system and are not exclusive. This work presents a constrained-random simulation-based functional verification methodology where, on the basis of the Parameter Domains (PD) formalism, irrelevant and invalid test case scenarios are removed from the input space. To this purpose, a tool to automatically generate PD-based stimuli sources was developed. Additionally, we have developed a second tool to generate functional coverage models that fit exactly to the PD-based input space. Both the input stimuli and coverage model enhancements, resulted in a notable testbench efficiency increase, if compared to testbenches with traditional stimulation and coverage scenarios: 22% simulation time reduction when generating stimuli with our PD-based stimuli sources (still with a conventional coverage model), and 56% simulation time reduction when combining our stimuli sources with their corresponding, automatically generated, coverage models.

Synthesis and characterization of semiconductor polymers having different phenylene-vinylene conjugation lengths

We have synthesized phenylene-vinylene (PV) polymers containing segments with different conjugation lengths interspaced by random distributed aliphatic segments. Infrared (IR) and ultraviolet-visible (UV-vis) spectroscopies, hydrogen nuclear magnetic resonance ((1)H NMR) spectrometry and differential scanning calorimetry (DSC) were used to characterize the prepared copolymers` structures. Polymers molecular weights were determined by gel permeation chromatography (GPC). The effect of polymer structure and composition on emission properties was studied by fluorescence (PL) spectroscopy under different irradiation wavelength. The emission energy shift due to segments with longer conjugation lengths was minor owed to the low polymerization degree achieved.

A generalized multi-period mean-variance portfolio optimization with Markov switching parameters

In this paper, we deal with a generalized multi-period mean-variance portfolio selection problem with market parameters Subject to Markov random regime switchings. Problems of this kind have been recently considered in the literature for control over bankruptcy, for cases in which there are no jumps in market parameters (see [Zhu, S. S., Li, D., & Wang, S. Y. (2004). Risk control over bankruptcy in dynamic portfolio selection: A generalized mean variance formulation. IEEE Transactions on Automatic Control, 49, 447-457]). We present necessary and Sufficient conditions for obtaining an optimal control policy for this Markovian generalized multi-period meal-variance problem, based on a set of interconnected Riccati difference equations, and oil a set of other recursive equations. Some closed formulas are also derived for two special cases, extending some previous results in the literature. We apply the results to a numerical example with real data for Fisk control over bankruptcy Ill a dynamic portfolio selection problem with Markov jumps selection problem. (C) 2008 Elsevier Ltd. All rights reserved.

Toward sustainable soil and water resources use in China`s highly erodible semi-arid loess plateau

The water-wind crisscross region of the Loess Plateau in China is comprised of 17.8 million hectares of highly erodible soil under limited annual rainfall. This requires a sustainable water balance for the restoration of dryland ecosystems to reduce and manage soil erosion. In this region, alfalfa has been one of the main legumes grown to minimize soil erosion. However, alfalfa yields were significantly lower in years of reduced rainfall suggesting that high water use and deep rooting alfalfa make it an unsustainable crop due to the long-term decline in soil water storage and productivity. Our objectives in this Study were to evaluate the soil water balance of Loess Plateau soils during vegetative restoration and to evaluate practices that prevent soil desiccation and promote ecosystem restoration and sustainability. Field observations of soil moisture recovery and soil erosion were carried out for five years after alfalfa was replaced with different crops and with bare soil. Soil water content changes in cropland, rangeland, and bare soil were tracked over several years, using a water balance approach. Results indicate that growing forages significantly reduced runoff and sediment transport. A forage-food-crop rotation is a better choice than other cropping systems for achieving sustainable productivity and preventing soil erosion and desiccation. However, economic considerations have prevented its widespread adoption by local farmers. Alternatively, this study recommends consideration of grassland crops or forest ecosystems to provide a sustainable water balance in the Loess Plateau of China. (C) 2009 Elsevier B.V. All rights reserved.

Time stability of soil water storage measured by neutron probe and the effects of calibration procedures in a small watershed

The knowledge of soil water storage (SWS) of soil profiles is crucial for the adoption of vegetation restoration practices. With the aim of identifying representative sites to obtain the mean SWS of a watershed, a time stability analysis of neutron probe evaluations of SWS was performed by the means of relative differences and Spearman rank correlation coefficients. At the same time, the effects of different neutron probe calibration procedures were explored on time stability analysis. mean SWS estimation. and preservation of the spatial variability of SWS. The selected watershed, with deep gullies and undulating slopes which cover an area of 20 ha, is characterized by an Ust-Sandiic Entisol and an Aeolian sandy soil. The dominant vegetation species are bunge needlegrass (Stipa bungeana Trim) and korshinsk peashrub (Carugano Korshinskii kom.). From June 11, 2007 to July 23,2008, SWS of the top1 m soil layer was evaluated for 20 dates, based on neutron probe data of 12 sampling sites. Three calibration procedures were employed: type 1, most complete, with each site having its own linear calibration equation (TrE); type II. with TrE equations extended over the whole field: and type III, with one single linear calibration curve for the whole field (UnE) and also correcting its intercept based on site specific relative difference analysis (RdE) and on linear fitting of data (RcE), both maintaining the same slope. A strong time stability of SWS estimated by TrE equations was identified. Soil particle size and soil organic matter content were recognized as the influencing factors for spatial variability of SWS. Land use influenced neither the spatial variability nor the time stability of SWS. Time stability analysis identified one site to represent the mean SWS of the whole watershed with mean absolute percentage errors of less than 10%, therefore. this site can be used as a predictor for the mean SWS of the watershed. Some equations of type II were found to be unsatisfactory to yield reliable mean SWS values or in preserving the associated soil spatial variability. Hence, it is recommended to be cautious in extending calibration equations to other sites since they might not consider the field variability. For the equations with corrected intercept (type III), which consider the spatial variability of calibration in a different way in relation to TrE, it was found that they can yield satisfactory means and standard deviation of SWS, except for the RdE equations, which largely leveled off the SWS values in the watershed. Correlation analysis showed that the neutron probe calibration was linked to soil bulk density and to organic matter content. Therefore, spatial variability of soil properties should be taken into account during the process of neutron probe calibration. This study provides useful information on the mean SWS observation with a time stable site and on distinct neutron probe calibration procedures, and it should be extended to soil water management studies with neutron probes, e.g., the process of vegetation restoration in wider area and soil types of the Loess Plateau in China. (C) 2009 Elsevier B.V. All rights reserved.