A model for doped-oxide-source diffusion with a chemical reaction at the silicon-silicon dioxide interface

A mathematical model for doped-oxide-source diffusion is proposed. In this model the concept of segregation of impurity at the silicon-silicon dioxide is used and also a constant of “rate limitation” is introduced through a chemical reaction at the interface.

Recovery responses of acidified Finnish lakes under declining acid deposition

The present work provides a regional-scale assessment of the changes in acidifying deposition in Finland over the past 30 years and the current pattern in the recovery of acid-sensitive lakes from acidification in relation to changes in sulphate deposition. This information is needed for documenting the ecosystem benefits of costly emission reduction policies and further actions in air pollution policy. The development of sulphate deposition in Finland reflects that of European SO2 emissions. Before the 1990s, reductions in sulphur emissions in Europe had been relatively small and sulphate deposition showed no consistent trends. Due to emission reduction measures that were then taken, sulphate deposition started to clearly decline from the late 1980s. The bulk deposition of sulphate has declined 40-60% in most parts of the country during 1990-2003. The decline in sulphate deposition exceeded the decline of base cation deposition, which resulted in a decrease in acidity and acidifying potential of deposition over the 1990s. Nitrogen deposition also decreased since the late 1980s, but less than that of sulphate, and levelling off during the 1990s. Sulphate concentrations in all types of small lakes throughout Finland have declined from the early 1990s. The relative decrease in lake sulphate concentrations (average 40-50%) during 1990-2003 was rather similar to the decline in sulphate deposition, indicating a direct response to the reduction in deposition. There are presently no indications of elevated nitrate concentrations in forested headwater lakes. Base cation concentrations are still declining in many lakes, especially in south Finland, but to a lesser extent than sulphate allowing buffering capacity (alkalinity) to increase, being significant in 60% of the study lakes. Chemical recovery is resulting in biological recovery with populations of acid-sensitive fish species increasing. The recovery has been strongest in lakes in which sulphate has been the major acidifying agent, and recovery has been the strongest and most consistent in lakes in south Finland. The recovery of lakes in central Finland and north Finland is not as widespread and strong as observed in south. Many catchments, particularly in central Finland, have a high proportion of peatlands and therefore high TOC concentrations in lakes, and runoff-induced surges of organic acids have been an important confounding factor suppressing the recovery of pH and alkalinity in these lakes. Chemical recovery is progressing even in the most acidified lakes, but the buffering capacity of many lakes is still low and still sensitive to acidic input. Further reduction in sulphur emissions are needed for the alkalinity to increase in the acidified lakes. Increasing total organic carbon (TOC) concentrations are indicated in small forest lakes in Finland. The trends appear to be related to decreasing sulphate deposition and improved acid-base status of the soil, and the rise in TOC is integral to recovery from acidification. A new challenge is climate change with potential trends in temperature, precipitation and runoff, which are expected to affect future chemical and biological recovery from acidification. The potential impact on the mobilization and leaching of organic acids may become particularly important in Finnish conditions. Long-term environmental monitoring has evidently shown the success of international emission abatement strategies. The importance and value of integrated monitoring approach including physical, chemical and biological variables is clearly indicated, and continuous environmental monitoring is needed as a scientific basis for further actions in air pollution policy.

A conditional random field-based downscaling method for assessment of climate change impact on multisite daily precipitation in the Mahanadi basin

Downscaling to station-scale hydrologic variables from large-scale atmospheric variables simulated by general circulation models (GCMs) is usually necessary to assess the hydrologic impact of climate change. This work presents CRF-downscaling, a new probabilistic downscaling method that represents the daily precipitation sequence as a conditional random field (CRF). The conditional distribution of the precipitation sequence at a site, given the daily atmospheric (large-scale) variable sequence, is modeled as a linear chain CRF. CRFs do not make assumptions on independence of observations, which gives them flexibility in using high-dimensional feature vectors. Maximum likelihood parameter estimation for the model is performed using limited memory Broyden-Fletcher-Goldfarb-Shanno (L-BFGS) optimization. Maximum a posteriori estimation is used to determine the most likely precipitation sequence for a given set of atmospheric input variables using the Viterbi algorithm. Direct classification of dry/wet days as well as precipitation amount is achieved within a single modeling framework. The model is used to project the future cumulative distribution function of precipitation. Uncertainty in precipitation prediction is addressed through a modified Viterbi algorithm that predicts the n most likely sequences. The model is applied for downscaling monsoon (June-September) daily precipitation at eight sites in the Mahanadi basin in Orissa, India, using the MIROC3.2 medium-resolution GCM. The predicted distributions at all sites show an increase in the number of wet days, and also an increase in wet day precipitation amounts. A comparison of current and future predicted probability density functions for daily precipitation shows a change in shape of the density function with decreasing probability of lower precipitation and increasing probability of higher precipitation.

Thiol-Disulfide Interchange Mediated Reversible Dendritic Megamer Formation and Dissociation

We report the formation of dynamic, reversible cross-linked dendritic megamers and their dissociation to monomeric dendrimers, through a thiol-disulfide interchange reaction. For this study, poly(alkyl aryl ether) dendrimers up to three-generations presenting thiol functionalities, were prepared. The series from zero to three generations of dendrimers were installed with 3, 6, 12, and 24 thiol functionalities at their peripheries. Upon synthesis, cross-linking of the dendrimer was accomplished through disulfide bond formation. The cross-linking of dendrimers was monitored through optical density changes at 420 nm. Dense cross-linking led to visible precipitation of dendritic megamers and the morphologies of the megamers were characterized by transmission electron microscopy. The disulfide cross-links between megamer monomers could be dissociated readily upon reduction of disulfide bond by dithiothreitol reagent. Preliminary studies show that dendritic megamers encapsulate C-60 and the efficiency of encapsulation increased with increasing generation of dendritic megamer.

Modeling of Freezing Phenomena Induced by Chemical Reactions

Spatial variations in the concentration of a reactive solute in solution are often encountered in a catalyst particle, and this leads to variation in the freezing point of the solution. Depending on the operating temperature, this can result in freezing of the solvent oil a portion of catalyst, rendering that part of the active area ineffective Freezing call occur by formation of a sharp front or it mush that separates the solid and fluid phases. In this paper, we model the extent of reduction in the active area due to freezing. Assuming that the freezing point decreases linearly with solute concentration, conditions for freezing to occur have been derived. At steady state, the ineffective fraction of catalyst pellet is found to be the same irrespective of the mode of freezing. Progress of freezing is determined by both the heat of reaction and the latent heat of fusion Unlike in freezing of alloys where the latter plays a dominant role, the exothermicity of the reaction has a significant effect on freezing in the presence of chemical reactions. A dimensionless group analogous to the Stefan number could be defined to capture the combined effect of both of these.

Ferrous iron oxidation by foam immobilized Acidithiobacillus ferrooxidans: Experiments and modeling

Ferrous iron bio-oxidation by Acidithiobacillus ferrooxidans immobilized on polyurethane foam was investigated. Cells were immobilized on foams by placing them in a growth environment and fully bacterially activated polyurethane foams (BAPUFs) were prepared by serial subculturing in batches with partially bacterially activated foam (pBAPUFs). The dependence of foam density on cell immobilization process, the effect of pH and BAPUF loading on ferrous oxidation were studied to choose operating parameters for continuous operations. With an objective to have high cell densities both in foam and the liquid phase, pretreated foams of density 50 kg/m3 as cell support and ferrous oxidation at pH 1.5 to moderate the ferric precipitation were preferred. A novel basket-type bioreactor for continuous ferrous iron oxidation, which features a multiple effect of stirred tank in combination with recirculation, was designed and operated. The results were compared with that of a free cell and a sheet-type foam immobilized reactors. A fivefold increase in ferric iron productivity at 33.02 g/h/L of free volume in foam was achieved using basket-type bioreactor when compared to a free cell continuous system. A mathematical model for ferrous iron oxidation by Acidithiobacillus ferrooxidans cells immobilized on polyurethane foam was developed with cell growth in foam accounted by an effectiveness factor. The basic parameters of simulation were estimated using the experimental data on free cell growth as well as from cell attachment to foam under nongrowing conditions. The model predicted the phase of both oxidation of ferrous in shake flasks by pBAPUFs as well as by fully activated BAPUFs for different cell loadings in foam. Model for stirred tank basket bioreactor predicted within 5% both transient and steady state of the experiments closely for the simulated dilution rates. Bio-oxidation at high Fe2+ concentrations were simulated with experiments when substrate and product inhibition coefficients were factored into cell growth kinetics.

Single layer graphene film by ethanol chemical vapor deposition: Highly efficient growth and clean transfer method

The choice of ethanol (C2H5OH) as carbon source in the Chemical Vapor Deposition (CVD) of graphene on copper foils can be considered as an attractive alternative among the commonly used hydrocarbons, such as methane (CH4) [1]. Ethanol, a safe, low cost and easy handling liquid precursor, offers fast and efficient growth kinetics with the synthesis of fullyformed graphene films in just few seconds [2]. In previous studies of graphene growth from ethanol, various research groups explored temperature ranges lower than 1000 °C, usually reported for methane-assisted CVD. In particular, the 650–850 °C and 900 °C ranges were investigated, respectively for 5 and 30 min growth time [3, 4]. Recently, our group reported the growth of highly-crystalline, few-layer graphene by ethanol-CVD in hydrogen flow (1– 100 sccm) at high temperatures (1000–1070 °C) using growth times typical of CH4-assisted synthesis (10–30 min) [5]. Furthermore, a synthesis time between 20 and 60 s in the same conditions was explored too. In such fast growth we demonstrated that fully-formed graphene films can be grown by exposing copper foils to a low partial pressure of ethanol (up to 2 Pa) in just 20 s [6] and we proposed that the rapid growth is related to an increase of the Cu catalyst efficiency due weak oxidizing nature of ethanol. Thus, the employment of such liquid precursor, in small concentrations, together with a reduced time of growth and very low pressure leads to highly efficient graphene synthesis. By this way, the complete coverage of a copper catalyst surface with high spatial uniformity can be obtained in a considerably lower time than when using methane.

Surfactant-Mediated Synthesis of Functional Metal Oxide Nanostructures Via Microwave Irradiation-Assisted Chemical Synthesis

In the present work we report a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant (cationic, anionic, non ionic and polymeric), without the use of any templates. The method is simple, inexpensive, and helps one to prepare nanostructures in quick time, measured in seconds and minutes. This method has been applied successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with changes in different process parameters, such as microwave power, irradiation time, identity of solvent, type of surfactant, and its concentration.

The effect of horizontal resolution on simulation of very extreme US precipitation events in a global atmosphere model

We investigate the ability of a global atmospheric general circulation model (AGCM) to reproduce observed 20 year return values of the annual maximum daily precipitation totals over the continental United States as a function of horizontal resolution. We find that at the high resolutions enabled by contemporary supercomputers, the AGCM can produce values of comparable magnitude to high quality observations. However, at the resolutions typical of the coupled general circulation models used in the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, the precipitation return values are severely underestimated.

H N.M.R. studies of protected alpha-aminoisobutyric acid containing peptides. Chemical shift nonequivalence of benzyloxycarbonyl methylene protons

The benzylic methylene protons in a large number of benzyloxycarbonyl alpha-aminoisobutyric acid (Z-Aib) containing peptides, show chemical shift nonequivalence. The magnitude of the geminal nonequivalence is correlated with the involvement of the urethane carbonyl group, in an intramolecular hydrogen bond. Studies of the model compounds Z-Aib-Aib-Ala-NHMe, and Z-Aib-Aib-Aib-Pro-OMe clearly establish the presence of intramolecular hydrogen bonds, involving the urethane CO group. In both compounds marked anisochrony of the benzylic methylene protons is demonstrated. In Z-Aib-Aib-Pro-OMe, where a 4 leads to 1 hydrogen bonded beta-turn is not possible, the benzylic-CH2-protons appear as a singlet in CDCl3 and have a very small chemical shift difference in (CD3)2SO. The observation of such nonequivalence is of value in establishing whether the amino terminal Aib-Pro beta-turn is retained in large peptide-fragments of alamethicin.

Sinteractivity, proton conductivity and chemical stability of BaZr 0.7In0.3O3-δ for solid oxide fuel cells (SOFCs)

In3+ was used as dopant for BaZrO3 proton conductor and 30 at%-doped BaZrO3 samples (BaZr0.7In 0.3O3-δ, BZI) were prepared as electrolyte materials for proton-conducting solid oxide fuel cells (SOFCs). The BZI material showed a much improved sinteractivity compared with the conventional Y-doped BaZrO 3. The BZI pellets reached almost full density after sintering at 1600 °C for 10 h, whereas the Y-doped BaZrO3 samples still remained porous under the same sintering conditions. The conductivity measurements indicated that BZI pellets showed smaller bulk but improved grain boundary proton conductivity, when compared with Y-doped BaZrO3 samples. A total proton conductivity of 1.7 × 10-3 S cm -1 was obtained for the BZI sample at 700 °C in wet 10% H 2 atmosphere. The BZI electrolyte material also showed adequate chemical stability against CO2 and H2O, which is promising for application in fuel cells.

Chemical modifications of natural triterpenes—glycyrrhetinic and boswellic acids: evaluation of their biological activity

Synthetic analogues of naturally occurring triterpenoids; glycyrrhetinic acid, arjunolic acid, and boswellic acids, by modification of A-ring with a cyano- and enone-functionality, have been reported. A novel method of synthesis of α-cyanoenones from isoxazoles is reported. Bioassays using primary mouse macrophages and tumor cell lines indicate potent anti-inflammatory and cytotoxic activities associated with cyano-enones of boswellic acid and glycyrrhetinic acid.

Dynamics of Barrierless and Activated Chemical Reactions in a Dispersive Medium within the Fractional Diffusion Equation Approach

Barrierless chemical reactions have often been modeled as a Brownian motion on a one-dimensional harmonic potential energy surface with a position-dependent reaction sink or window located near the minimum of the surface. This simple (but highly successful) description leads to a nonexponential survival probability only at small to intermediate times but exponential decay in the long-time limit. However, in several reactive events involving proteins and glasses, the reactions are found to exhibit a strongly nonexponential (power law) decay kinetics even in the long time. In order to address such reactions, here, we introduce a model of barrierless chemical reaction where the motion along the reaction coordinate sustains dispersive diffusion. A complete analytical solution of the model can be obtained only in the frequency domain, but an asymptotic solution is obtained in the limit of long time. In this case, the asymptotic long-time decay of the survival probability is a power law of the Mittag−Leffler functional form. When the barrier height is increased, the decay of the survival probability still remains nonexponential, in contrast to the ordinary Brownian motion case where the rate is given by the Smoluchowski limit of the well-known Kramers' expression. Interestingly, the reaction under dispersive diffusion is shown to exhibit strong dependence on the initial state of the system, thus predicting a strong dependence on the excitation wavelength for photoisomerization reactions in a dispersive medium. The theory also predicts a fractional viscosity dependence of the rate, which is often observed in the reactions occurring in complex environments.

Synthesis of multiwall carbon nanotubes by chemical vapor deposition of ferrocene alone

Multiwall carbon nanotubes (MWNTs) filled with Fe nanoparticles (NPs) have been synthesized by thermal chemical vapor deposition of ferrocene alone as the precursor. The MWNTs were grown at different temperatures: 980 and 800 degrees C. Characterization of as-prepared MWNTs was done by scanning and transmission electron microscopy, and X-ray diffraction. The transmission electron microscopy study revealed that Fe NPs encapsulated in MWNTs grown at 980 and 800 degrees C are spherical and rod shaped, respectively. Room-temperature vibrating sample magnetometer studies were done on the two samples up to a field of 1T. The magnetization versus magnetic field loop reveals that the saturation magnetization for the two samples varies considerably, almost by a factor of 4.6. This indicates that Fe is present in different amounts in the MWNTs grown at the two different temperatures. (C) 2009 Elsevier Ltd. All rights reserved.

Synthesis of BaSO4 nanoparticles by precipitation method using sodium hexa metaphosphate as a stabilizer

We describe the synthesis and structure of Barium sulfate nanoparticles by precipitation method in the presence of water soluble inorganic stabilizing agent, sodium hexametaphosphate, (NaPO3)(6). The structural parameters were refined by the Rietveld refinement method using powder X-ray diffraction data. Barium sulfate nanoparticles were crystallized in the orthorhombic structure with space group Pbnm (No. 62) having the lattice parameters a = 7.215(1) (angstrom), b = 8.949(1) (angstrom) and c = 5.501 (1) (angstrom) respectively. Transmission electron microscopy study reveals that the nanoparticles are size range, 30-50 nm. Fourier transform infrared spectra showed distinct absorption due to the SO42- moiety at 1115 and 1084 cm(-1) indicating formation of barium sulfate nanoparticles free from the phosphate group from the stabilizer used in the synthesis. (C) 2009 Elsevier Ltd. All rights reserved.