Electrostatic Interactions Are Not Sufficient to Account for Chitosan Bioactivity

Recent studies involving chitosan interacting with phospholipid monolayers that mimic cell membranes have brought molecular-level evidence for some of the physiological actions of chitosan, as in removing a protein from the membrane. This interaction has been proven to be primarily of electrostatic origin because of the positive charge OF chitosan in low pH solutions, but indirect evidence has also appeared of the presence of hydrophobic interactions. In this study, we provide definitive proof that model membranes are not affected merely by the charges in the amine groups of chitosan. Such a proof was obtained by comparing surface pressure and surface potential isotherms of dipalmitoyl phosphatidyl choline (DPPC) and dipalmitoyl phosphatidyl glycerol (DPPG) monolayers incorporating either chitosan or poly(allylamine hydrochloride) (PAH). As the latter is also positively charged and With the same charged Functional group as chitosan, similar effects should be observed in case the electrical charge was the only relevant parameter. Instead, we observed a large expansion in the surface pressure isotherms upon interaction with chitosan, whereas PAH had much smaller effects. Of particular relevance for biological implications, chitosan considerably reduced the monolayer elasticity, whereas PAH had almost no effect. it is clear therefore that chitosan action depends strongly either on its functional uncharged groups and/or on its specific conformation in solution.

Orbitally driven east-west antiphasing of South American precipitation

The variations of tropical precipitation are antiphased between the hemispheres on orbital timescales. This antiphasing arises through the alternating strength of incoming solar radiation in the two hemispheres, which affects monsoon intensity and hence the position of the meridional atmospheric circulation of the Hadley cells(1-4). Here we compare an oxygen isotopic record recovered from a speleothem from northeast Brazil for the past 26,000 years with existing reconstructions of precipitation in tropical South America(5-8). During the Holocene, we identify a similar, but zonally oriented, antiphasing of precipitation within the same hemisphere: northeast Brazil experiences humid conditions during low summer insolation and aridity when summer insolation is high, whereas the rest of southern tropical South America shows opposite characteristics. Simulations with a general circulation model that incorporates isotopic variations support this pattern as well as the link to insolation-driven monsoon activity. Our results suggest that convective heating over tropical South America and associated adjustments in large-scale subsidence over northeast Brazil lead to a remote forcing of the South American monsoon, which determines most of the precipitation changes in the region on orbital timescales.

Computational aspects of harmonic wavelet Galerkin methods and an application to a precipitation front propagation model

This article is dedicated to harmonic wavelet Galerkin methods for the solution of partial differential equations. Several variants of the method are proposed and analyzed, using the Burgers equation as a test model. The computational complexity can be reduced when the localization properties of the wavelets and restricted interactions between different scales are exploited. The resulting variants of the method have computational complexities ranging from O(N(3)) to O(N) (N being the space dimension) per time step. A pseudo-spectral wavelet scheme is also described and compared to the methods based on connection coefficients. The harmonic wavelet Galerkin scheme is applied to a nonlinear model for the propagation of precipitation fronts, with the front locations being exposed in the sizes of the localized wavelet coefficients. (C) 2011 Elsevier Ltd. All rights reserved.

Deciphering the role of the electrostatic interactions in the alpha-tropomyosin head-to-tail complex

Skeletal alpha-tropomyosin (Tm) is a dimeric coiled-coil protein that forms linear assemblies under low ionic strength conditions in vitro through head-to-tail interactions. A previously published NMR structure of the Tin head-to-tail complex revealed that it is formed by the insertion of the N-terminal coiled-coil of one molecule into a cleft formed by the separation of the helices at the C-terminus of a second molecule. To evaluate the contribution of charged residues to complex stability, we employed single and double-mutant Tm fragments in which specific charged residues were changed to alanine in head-to-tail binding assays, and the effects of the mutations were analyzed by thermodynamic double-mutant cycles and protein-protein docking. The results show that residues K5, K7, and D280 are essential to the stability of the complex. Though D2, K6, D275, and H276 are exposed to the solvent and do not participate in intermolecular contacts in the NMR structure, they may contribute to head-to-tail complex stability by modulating the stability of the helices at the Tm termini.

Electrostatic and Hydrophobic Interactions Involved in CNT Biofunctionalization with Short ss-DNA

This work is aimed at studying the adsorption mechanism of short chain 20-mer pyrimidinic homoss-DNA (oligodeoxyribonucleotide, ODN: polyC(20) and polyT(20)) onto CNT by reflectometry. To analyze the experimental data, the effective-medium theory using the Bruggemann approximation represents a Suitable optical model to account for the surface properties (roughness, thickness, and optical constants) and the size of the adsorbate. Systematic information about the involved interactions is obtained by changing the physicochemical properties of the system. Hydrophobic and electrostatic interactions are evaluated by comparing the adsorption oil hydrophobic CNT and oil hydrophilic silica and by Modulating the ionic Strength With and without Mg(2+). The ODN adsorption process oil CNT is driven by hydrophobic interactions only when the electrostatic repulsion is Suppressed. The adsorption mode results in ODN molecules in a side-on orientation with the bases (nonpolar region) toward the surface. This unfavorable orientation is partially reverse by adding Mg(2+). On the other hand, the adsorption oil silica is dominated by the strong repulsive electrostatic interaction that is screened at high ionic strength or mediated by Mg(2+). The cation-mediated process induces the interaction of the phosphate backbone (polar region) with the surface, leaving the bases free for hybridization. Although the general adsorption behavior of the pyrimidine bases is the same, polyC(20) presents higher affinity for the CNT Surface due to its acid-base properties.

Electrostatic layer-by-layer and electrophoretic depositions as methods for electrochromic nanoparticle immobilization

The present paper describes the immobilization of nanoparticles onto conducting substrates by using both electrostatic layer-by-layer and electrophoretic deposition (EPD) methods. These two techniques were compared in high-performance electrochromic electrodes based on mixed nickel hydroxide nanoparticles. In addition to easy handling, EPD seems to be the most suitable method for the immobilization of nanoparticles, leading to higher electrochromic efficiencies, lower response times and higher stability upon coloration and bleaching cycling. (C) 2008 Elsevier Ltd. All rights reserved.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

A method for Ca, Fe, Ga, Na, Si and Zn determination in alumina by inductively coupled plasma optical emission spectrometry after aluminum precipitation

In this present work a method for the determination of Ca, Fe, Ga, Na, Si and Zn in alumina (Al(2)O(3)) by inductively coupled plasma optical emission spectrometry (ICP OES) with axial viewing is presented. Preliminary studies revealed intense aluminum spectral interference over the majority of elements and reaction between aluminum and quartz to form aluminosilicate, reducing drastically the lifetime of the torch. To overcome these problems alumina samples (250 mg) were dissolved with 5 mL HCl + 1.5 mLH(2)SO(4) + 1.5 mL H(2)O in a microwave oven. After complete dissolution the volume was completed to 20 mL and aluminum was precipitated as Al(OH)(3) with NH(3) (by bubbling NH(3) into the solution up to a pH similar to 8, for 10 min). The use of internal standards (Fe/Be, Ga/Dy, Zn/In and Na/Sc) was essential to obtain precise and accurate results. The reliability of the proposed method was checked by analysis of alumina certified reference material (Alumina Reduction Grade-699, NIST). The found concentrations (0.037%w(-1) CaO, 0.013% w w(-1) Fe(2)O(3), 0.012%w w(-1)Ga(2)O(3), 0.49% w w(-1) Na(2)O, 0.014% w w(-1) SiO(2) and 0.013% w w(-1) ZnO) presented no statistical differences compared to the certified values at a 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.

Influence of neodymium ions on photocatalytic activity of TiO(2) synthesized by sol-gel and precipitation methods

Titanium dioxide with and without the addition of neodymium ions was prepared using sol-gel and precipitation methods. The resulting catalysts were characterized by thermal analysis, X-ray diffraction and BET specific surface area. Neodymium addition exerted a remarkable influence on the phase transition temperature and the surface properties of the TiO(2) matrix. TiO(2) samples synthesized by precipitation exhibit an exothermic event related from the amorphous to anatase phase transition at 510 degrees C, whereas in Nd-doped TiO(2) this transition occurred at 527 degrees C. A similar effect was observed in samples obtained using sol-gel method. The photocatalytic reactivity of the catalysts was evaluated by photodegradation of Remazol Black B (RB) under ultraviolet irradiation. Nd-doped TiO(2) showed enhanced photodegradation ability compared to undoped TiO(2) samples, independent of the method of synthesis. In samples obtained by sol-gel, RB decoloration was enhanced by 16% for TiO(2) doped with 0.5% neodymium ions. (C) 2010 Elsevier B.V. All rights reserved.

Modeling precipitation and its effect on recrystallization during hot strip rolling of niobium steels

Using a physically based model, the microstructural evolution of Nb microalloyed steels during rolling in SSAB Tunnplåt’s hot strip mill was modeled. The model describes the evolution of dislocation density, the creation and diffusion of vacancies, dynamic and static recovery through climb and glide, subgrain formation and growth, dynamic and static recrystallization and grain growth. Also, the model describes the dissolution and precipitation of particles. The impeding effect on grain growth and recrystallization due to solute drag and particles is accounted for. During hot strip rolling of Nb steels, Nb in solid solution retards recrystallization due to solute drag and at lower temperatures strain-induced precipitation of Nb(C,N) may occur which effectively retard recrystallization. The flow stress behavior during hot rolling was calculated where the mean flow stress values were calculated using both the model and measured mill data. The model showed that solute drag has an essential effect on recrystallization during hot rolling of Nb steels.

Homogenization of Precipitation Hardening Nickel Based Superalloys

Allvac 718 Plus and Haynes 282 are relatively new precipitation hardening nickel based superalloys with good high temperature mechanical properties. In addition, the weldability of these superalloys enhances easy fabrication. The combination of high temperature capabilities and superior weldability is unmatched by other precipitation hardening superalloys and linked to the amount of the γ’ hardening precipitates in the materials. Hence, it is these properties that make Allvac 718 Plus and Haynes 282 desirable in the manufacture of hot sections of aero engine components. Studies show that cast products are less weldable than wrought products. Segregation of elements in the cast results in inhomogeneous composition which consequently diminishes weldability. Segregation during solidification of the cast products results in dendritic microstructure with the segregating elements occupying interdendritic regions. These segregating elements are trapped in secondary phases present alongside γ matrix. Studies show that in Allvac 718Plus, the segregating phase is Laves while in Haynes 282 the segregating phase is not yet fully determined. Thus, the present study investigated the effects of homogenization heat treatments in eliminating segregation in cast Allvac 718 Plus and Haynes 282. Paramount to the study was the effect of different homogenization temperatures and dwell time in the removal of the segregating phases. Experimental methods used to both qualify and quantify the segregating phases included SEM, EDX analysis, manual point count and macro Vickers hardness tests. Main results show that there is a reduction in the segregating phases in both materials as homogenization proceeds hence a disappearance of the dendritic structure. In Allvac 718 Plus, plate like structures is observed to be closely associated with the Laves phase at low temperatures and dwell times. In addition, Nb is found to be segregating in the interdendritic areas. The expected trend of increase in Laves as a result of the dissolution of the plate like structures at the initial stage of homogenization is only detectable for few cases. In Haynes 282, white and grey phases are clearly distinguished and Mo is observed to be segregating in interdendritic areas.

Average Annual Precipitation in Maine

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Combining Satellite And Gauge Precipitation Data With Co-Kriging Method For Jakarta Region

Jakarta is vulnerable to flooding mainly caused by prolonged and heavy rainfall and thus a robust hydrological modeling is called for. A good quality of spatial precipitation data is therefore desired so that a good hydrological model could be achieved. Two types of rainfall sources are available: satellite and gauge station observations. At-site rainfall is considered to be a reliable and accurate source of rainfall. However, the limited number of stations makes the spatial interpolation not very much appealing. On the other hand, the gridded rainfall nowadays has high spatial resolution and improved accuracy, but still, relatively less accurate than its counterpart. To achieve a better precipitation data set, the study proposes cokriging method, a blending algorithm, to yield the blended satellite-gauge gridded rainfall at approximately 10-km resolution. The Global Satellite Mapping of Precipitation (GSMaP, 0.1⁰×0.1⁰) and daily rainfall observations from gauge stations are used. The blended product is compared with satellite data by cross-validation method. The newly-yield blended product is then utilized to re-calibrate the hydrological model. Several scenarios are simulated by the hydrological models calibrated by gauge observations alone and blended product. The performance of two calibrated hydrological models is then assessed and compared based on simulated and observed runoff.

Taking Advantage of Electrostatic Interactions To Grow Langmuir-Blodgett Films Containing Multilayers of the Phospholipid Dipalmitoylphosphatidylglycerol

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)