Simulated autohydrolysis of aspen milled wood lignin in the presence of aromatic additives: Structural modifications

In a previous article the authors have described changes in molecular weight which occur when aspen milled wood lignin is subjecte to autocatalyzed hydrolysis (autohydrolysis) in the presence of three aromatic additives: 2-naphthol, resorcinol, and p-hydroxybenzoic acid. In the present work, the reactions of these additives have been studied from the viewpoint of their effect on the structure of the lignin. The use of milled wood lignin instead of aspen wood served to distinguish those reactions between the additives and the lignin, without involving the other wood components. The reaction products have been charactrized by elemental analysis and UV and IR spectroscopy. It was concluded that keto groups, generated on the lignin side-chain during autohydrolysis, condense with the additives, which become incorporated into the lignin. This occurs most probably through an aromatic eletrophilic substitution reaction. While 2-naphthol condensed primarily with the β-keto carbonyl groups, resorcinol attacked also the α-keto carbonyl groups. When p-hydroxybenzoic acid was the additive, its incorporation was accompanied by an increase in lignin carboxylic acid groups.     

On the second order topological asymptotic expansion

The topological derivative provides the sensitivity of a given shape functional with respect to an infinitesimal (non smooth) domain perturbation at an arbitrary point of the domain. Classically, this derivative comes from the second term of the topological asymptotic expansion, dealing only with infinitesimal perturbations. However, for practical applications, we need to insert perturbations of finite size. Therefore, we consider one more term in the expansion which is defined as the second order topological derivative. In order to present these ideas, in this work we calculate first as well as second order topological derivatives for the total potential energy associated to the Laplace’s equation, when the domain is perturbed with a hole. Furthermore, we also study the effects of different boundary conditions on the hole: Neumann and Dirichlet (both homogeneous). In the Neumann’s case, the second order topological derivative depends explicitly on higher-order gradients of the state solution and also implicitly on the point where the hole is nucleated through the solution of an auxiliary problem. On the other hand, in the Dirichlet’s case, the first order topological derivative depends explicitly on the state solution as well as implicitly through the solution of an auxiliary problem, and the second order topological derivative depends only explicitly on the solution associated to the original problem. Finally, we present two simple examples showing the influence of both terms in the second order topological asymptotic expansion for each case of boundary condition on the hole.     

A Framework and Lightweight Protocol for Multimedia Network Management

The increasing complexities of modern networks coupled with the popularity of multimedia applications have placed higher demands on network managers. This paper reviews the main requirements and challenges for effective management of multimedia networks, presents a case study of a thin-client-based multimedia system called CSL (Computer-supported Learning System) and proposes a framework for managing such networks. CSL delivers browser-based assessments and other learning materials to thousands of students at the University of Auckland. This type of demand requires more flexible schemes for the management of the network. In the framework proposed, most of the link management information will be kept in a MIB in the network and a very simple MIB will be maintained in the thin client. The MIB in the network is accessible to the network management application, and a lightweight protocol is proposed for updating of the network MIB using an agent at the thin client.     

Structural and Magnetic Properties of the New La2SrCo2FeO9 Triple Perovskite

In this work, we report synthesis and characterization of the new La₂SrCo₂FeO₉ triple perovskite material. The samples were produced by the solid-state reaction method. The analyses of the XRD patterns were made by Rietveld refinement through the GSAS code. The results reveal that the material crystallizes in an orthorhombic complex perovskite, space group Immm (#71) with lattice parameters a=5.4314(3) ?, b=5.4583(3) ? and c=7.7018(2) ?. SEM micrographs evidence a strongly diffused granular morphology with mean grain size of 2 μm and the EDX spectra show that the chemical composition of samples are in good agreement with the nominal values of the stoichiometric formula. ⁵⁷Fe Mössbauer spectroscopy recorded at 300 K reveals two sites in concordance with the X-ray diffraction measurements, and its valence state is +3, as determined from the isomer shift found. At 4.2 K magnetic ordering with canting of the Fe moments is found. Measurements of the magnetization as a function of temperature permitted us to determine the ferromagnetic characteristic of material with an effective magnetic moment of 9.7μ _B.     

Sensitivity of Simulating Hydrologic Processes to Gauge and Radar Rainfall Data in Subtropical Coastal Catchments

This research evaluated the impact of three rainfall datasets on hydrologic process simulations in two coastal catchments located in Alabama. In this study, rain gauge time series recorded by the U.S. National Oceanic and Atmospheric Administration (NOAA) and Geological Survey (USGS) along with radar precipitation data derived from NOAA National Weather Service (NWS) were input into the Hydrological Simulation Program??FORTRAN (HSPF). Automatic parameter calibration was performed using daily streamflow data recorded at USGS Fish and Magnolia River gauge stations from 07/01/2002 to 12/31/2008. HSPF parameters were optimized using the Model-Independent Parameter Estimation (PEST) program. Model parameter ranges were refined by incorporating physical characteristic of the study areas and after analyzing observed streamflow time series. This approach, in turn, helped PEST optimization tool to find the most physically-related set of parameters that can be transferred to any watershed with similar characteristics and minimum parameter calibration. On average, annual USGS and radar rainfall values were around 480?mm and 250?mm, respectively lower than NOAA precipitation records. Overall, it is found that the NOAA precipitation input data resulted in better daily flow simulations than results from radar and USGS rainfall time series. Streamflows derived from USGS rainfall time series showed the worst model performance at both catchment outlets because of missing data, low amounts, and temporal delay of peaks. This study found that annual actual evapotranspiration values were closed among rainfall time series and varied from 900 to 958?mm. Deep percolation values for Magnolia and Fish River, regardless of rainfall source, ranged from 66 to 192?mm/year. Major discrepancies were found at storm runoff values. Gauge rainfall time series yielded the closest streamflow values compared to observed flow time series at both watershed outlets. Rainfall derived from radar yielded consistent and acceptable runoff results in Fish and Magnolia River models. In both case studies, the high spatial variability of rainfall storm events was not adequately captured by any of the rainfall datasets and yielded high uncertainty in model results.     

Nafion/polyaniline/silica composite membranes for direct methanol fuel cell application

This work investigates the characterization and performance of polyaniline and silica modified Nafion membranes. The aniline monomers are synthesized in situ to form a polyaniline film, whilst silica is embedded into the Nafion matrix by the polycondensation of tetraethylorthosilicate. The physicochemical properties are studied by means of X-ray diffraction and Fourier transform infrared techniques and show that the polyaniline layer is formed on the Nafion surface and improves the structural properties of Nafion in methanol solution. Nafion loses its crystallinity once exposed to water and ethanol, whilst the polyaniline modification allows crystallinity to be maintained under similar conditions. By contrast, the proton conductivities of polyaniline modified membranes are 3–5-fold lower than that of Nafion. On a positive note, methanol crossover is reduced by over two orders of magnitude, as verified by crossover limiting current analysis. The polyaniline modification allows the membrane to become less hydrophilic, which explains the lower proton conductivity. No major advantages are observed by embedding silica into the Nafion matrix. The performance of a membrane electrode assembly (MEA) using commercial catalysts and polyaniline modified membranes in a cell gives a peak power of 8 mW cm⁻² at 20 °C with 2 M methanol and air feeding. This performance correlates to half that of MEAs using Nafion, though the membrane modification leads to a robust material that may allow operation at high methanol concentration.     

Soy protein containing isoflavones favorably influences macrophage lipoprotein metabolism but not the development of atherosclerosis in CETP transgenic mice

The possibility that soy protein containing isoflavones influences the development of experimental atherosclerosis has been investigated in ovariectomized mice heterozygous for the human CETP transgene and for the LDL-receptor null allele (LDLr^+/− CETP^+/−). After ovariectomy at 8 wk of age they were fed a fat/cholesterol-rich diet for 19 wk and divided into three experimental groups: dietary unmodified soy protein containing isoflavones (mg/g of diet), either at low-dose (Iso Low, 0.272, n=25), or at high-dose (Iso High, 0.535, n=28); and the atherogenic diet containing an isoflavone-depleted alcohol-washed soy protein as a control group (n=28). Aortic root lipid-stained lesion area (mean μm²×10³±SD) did not differ among Iso Low (12.3±9.9), Iso High (7.4±6.4), and controls (10.7±12.8). Autoantibody titers against plasma oxidized LDL did not differ among the experimental groups. Using the control mice as the reference value (100%), in vitro mouse peritoneal macrophage uptake of labeled acetylated LDL-cholesterol was lower in the Iso High (68%) than in the Iso Low (85%) group. The in vitro percent removal by exogenous HDL of labeled unesterified cholesterol from macrophages previously enriched with human [4-¹⁴C]-cholesteryl oleate acetylated LDL was enhanced in the Iso High group (50%). In spite of these in vitro potentially antiatherogenic actions, soy protein containing isoflavones did not modify the average size of lipid-stained area in the aortic root.     

Prediction of Generation of High- and Low-Angle Grain Boundaries (HAGB and LAGB) During Severe Plastic Deformation

Metallurgical and Materials Transactions A - It is well known that a balance between the generation of low-angle and high-angle grain boundaries (LABG and HAGB) is achieved in materials undergoing...