Anisotropic singularities in modified gravity models

We show that the common singularities present in generic modified gravity models governed by actions of the type S = integral d(4)x root-gf(R, phi, X). with X = -1/2 g(ab)partial derivative(a)phi partial derivative(b)phi, are essentially the same anisotropic instabilities associated to the hypersurface F(phi) = 0 in the case of a nonminimal coupling of the type F(phi)R, enlightening the physical origin of such singularities that typically arise in rather complex and cumbersome inhomogeneous perturbation analyses. We show, moreover, that such anisotropic instabilities typically give rise to dynamically unavoidable singularities, precluding completely the possibility of having physically viable models for which the hypersurface partial derivative f/partial derivative R = 0 is attained. Some examples are explicitly discussed.

Fluoride-modified electrical properties of lead borate glasses and electrochemically induced crystallization in the glassy state

Lead fluoroborate glasses were prepared by the melt-quenching technique and characterized in terms of (micro)structural and electrical properties. The study was conducted on as prepared as well as temperature- and/or electric field-treated glass samples. The results show that, in the as-prepared glassy-state materials, electrical conductivity improved with increasing the PbF(2) glass content. This result involves both an increase of the fluoride charge carrier density and, especially, a decrease of the activation energy from a glass structure expansion improving charge carrier mobility. Moreover, for the electric field-treated glass samples, surface crystallization was observed even below the glass transition temperature. As previously proposed in literature, and shown here, the occurrence of this phenomenon arose from an electrochemically induced redox reaction at the electrodes, followed by crystallite nucleation. Once nucleated, growth of beta-PbF(2) crystallites, with the indication of incorporating reduced lead ions (Pb(+)), was both (micro)structurally and electrically detectable and analyzed. The overall crystallization-associated features observed here adapt well with the floppy-rigid model that has been proposed to further complete the original continuous-random-network model by Zachariasen for closely addressing not only glasses' structure but also crystallization mechanism. Finally, the crystallization-modified kinetic picture of the glasses' electrical properties, through application of polarization/depolarization measurements originally combined with impedance spectroscopy, was extensively explored. (c) 2008 American Institute of Physics.

Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

Hybrid layer-by-layer assembly based on animal and vegetable structural materials: multilayered films of collagen and cellulose nanowhiskers

Layer-by-layer (LBL) assembly was used to combine crystalline rod-like nanoparticles obtained from a vegetable source, cellulose nanowhiskers (CNWs), with collagen, the main component of skin and connective tissue found exclusively in animals. The film growth of the multilayered collagen/CNW was monitored by UV-Vis spectroscopy and ellipsometry measurements, whereas the film morphology and surface roughness were characterized by SEM and AFM. UV-Vis spectra showed the deposition of the same amount of collagen, 5 mg m(-2), in each dipping cycle. Ellipsometry data showed an increment in thickness with the number of layers, and the average thickness of each bilayer was found to be 8.6 nm. The multilayered bio-based nanocomposites were formed by single layers of densely packed CNWs adsorbed on top of each thin collagen layer where the hydrogen bonding between collagen amide groups and OH groups of the CNWs plays a mandatory role in the build-up of the thin films. The approach used in this work represents a potential strategy to mimic the characteristics of natural extracellular matrix (ECM) which can be used for applications in the biomedical field.

Continuous monitoring of ascorbate transport through neuroblastoma cells with a ruthenium oxide hexacyanoferrate modified microelectrode

The uptake of ascorbate by neuroblastoma cells using a ruthenium oxide hexacyanoferrate (RuOHCF)-modified carbon fiber disc (CFD) microelectrode (r = 14.5 mu m) was investigated. By use of the proposed electrochemical sensor the amperometric determination of ascorbate was performed at 0.0 V in minimum essential medium (MEM, pH = 7.2) with a limit of detection of 25 mu mol L(-1). Under the optimum experimental conditions, no interference from MEM constituents and reduced glutathione (used to prevent the oxidation of ascorbate during the experiments) was noticed. The stability of the RuOHCF-modified electrode response was studied by measuring the sensitivity over an extended period of time (120 h), a decrease of around 10% being noticed at the end of the experiment. The rate of ascorbate uptake by control human neuroblastoma SH-SY5Y cells, and cells transfected with wild-type Cu,Zn-superoxide dismutase (SOD WT) or with a mutant typical of familial amyotrophic lateral sclerosis (SOD G93A), was in agreement with the level of oxidative stress in these cells. The usefulness of the RuOHCF-modified microelectrode for in vivo monitoring of ascorbate inside neuroblastoma cells was also demonstrated.

Sisal cellulose acetates obtained from heterogeneous reactions

In the present work, cellulose obtained from sisal, which is a source of rapid growth, was used. Cellulose acetates were produced in heterogeneous medium, using acetic anhydride as esterifying agent and iodine as catalyst, to check if the procedure described in the literature for commercial cellulose also is adequate to sisal cellulose. The results indicated that iodine is an excellent catalyst to obtain sisal cellulose acetates, but the reaction is so fast as described in the literature when, instead of sisal, lower average molar weight cellulose (microcrystalline) is used. The crystallinity index (I(c)) of sisal cellulose acetates diminished compared to sisal cellulose, but there was no direct correlation between their degree of substitution (DS) and I(c). Probably acetyl groups were introduced more homogeneously along the short chains of microcrystalline cellulose, when compared to sisal cellulose, and then for microcrystalline cellulose acetates the Ic decreases as DS increases. Using the linear correlation that was found between degree of substitution (DS) and time reaction is possible to control the DS of sisal cellulose acetates, considering a large interval of degrees of substitution (0.3-2.8).

Ethanol electrooxidation onto stepped surfaces modified by Ru deposition: electrochemical and spectroscopic studies

Oxidation of ethanol on ruthenium-modified Pt(775) and Pt(332) stepped electrodes has been studied using electrochemical and FTIR techniques. It has been found that the oxidation of ethanol on these electrodes takes place preferentially on the step sites yielding CO(2) as the major final product. The cleavage of the C-C bond, which is the required step to yield CO(2), occurs only on this type of site. The presence of low ruthenium coverages on the step sites promotes the complete oxidation of ethanol since it facilitates the oxidation of CO formed on the step from the cleavage of the C-C bond. However, high ruthenium coverages have an important inhibiting effect since the adatoms block the step sites, which are required for the cleavage of the C-C bond. Under these conditions, the oxidation current diminishes and the major product in the oxidation process is acetic acid, which is the product formed preferentially on the (111) terrace sites.

Electrochemical and spectroscopic studies of ethanol oxidation on Pt stepped surfaces modified by tin adatoms

Ethanol oxidation on platinum stepped surfaces vicinal to the (111) pole modified by tin has been studied to determine the role of this adatom in the oxidation mechanism. Tin has been slowly deposited so that the initial stages of the deposition take place on the step, and deposition on the terrace only occurs when the step has been completely decorated. Voltammetric and chronoamperometric experiments demonstrate that tin on the step catalyzes the oxidation. The maximum enhancement is found when the step is completely decorated by tin. FTIR experiments using normal and isotopically labeled ethanol have been used to elucidate the effect of the tin adatoms in the mechanism. The obtained results indicate that the role of tin is double: (i) when the surface has sites capable of breaking the C-C bond of the molecule, that is, when the step sites are not completely covered by tin, it promotes the oxidation of CO formed from the molecular fragments to CO(2) through a bifunctional mechanism and (ii) it catalyzes the oxidation of ethanol to acetic acid.

Sequence-specific electrochemical detection of Alicyclobacillus acidoterrestris DNA using electroconductive polymer-modified fluorine tin oxide electrodes

This study outlines the quantification of low levels of Alicyclobacillus acidoterrestris in pure cultures, since this bacterium is not inactivated by pasteurization and may remain in industrialized foods and beverages. Electroconductive polymer-modified fluorine tin oxide (FTO) electrodes and multiple nanoparticle labels were used for biosensing. The detection of A. acidoterrestris in pure cultures was performed by reverse transcription polymerase chain reaction (RT-PCR) and the sensitivity was further increased by asymmetric nested RT-PCR using electrochemical detection for quantification of the amplicon. The quantification of nested RT-PCR products by Ag/Au-based electrochemical detection was able to detect 2 colony forming units per mL (CFU mL(-1)) of spores in pure culture and low detection and quantification limits (7.07 and 23.6 nM, respectively) were obtained for the target A. acidoterrestris on the electrochemical detection bioassay.

Multifractal regime transition in a modified minority game model

The search for more realistic modeling of financial time series reveals several stylized facts of real markets. In this work we focus on the multifractal properties found in price and index signals. Although the usual minority game (MG) models do not exhibit multifractality, we study here one of its variants that does. We show that the nonsynchronous MG models in the nonergodic phase is multifractal and in this sense, together with other stylized facts, constitute a better modeling tool. Using the structure function (SF) approach we detected the stationary and the scaling range of the time series generated by the MG model and, from the linear (non-linear) behavior of the SF we identified the fractal (multifractal) regimes. Finally, using the wavelet transform modulus maxima (WTMM) technique we obtained its multifractal spectrum width for different dynamical regimes. (C) 2009 Elsevier Ltd. All rights reserved.

Correlation of Modified Natural Rubber Properties by Artificial Neural Networks

Natural rubber (NR) is a raw material largely used by the modern industry; however, it is common that chemical modifications must be made to NR in order to improve properties such as hydrophobicity or mechanical resistance. This work deals with the correlation of properties of NR modified with dimethylaminoethylmethacrylate or methylmethacrylate as grafting agents. Dynamic-mechanical behavior and stress/strain relations are very important properties because they furnish essential characteristics of the material such as glass transition temperature and rupture point. These properties are concerned with different physical principles; for this reason, normally they are not related to each other. This work showed that they can be correlated by artificial neural networks (ANN). So, from one type of assay, the properties that as a rule only could be obtained from the other can be extracted by ANN correlation. POLYM. ENG. SCI., 49:499-505, 2009. (c) 2009 Society of Plastics Engineers

EFFECT OF CULTIVATION CONDITIONS ON GLUCOSE-6-PHOSPHATE DEHYDROGENASE PRODUCTION BY GENETICALLY MODIFIED Saccharomyces cerevisiae

The objective of this research was to improve Glucose-6-phosphate dehydrogenase (G6PD) production by Saccharomyces cerevisiae W303-181, which carry the plasmid YEpPGK-G6PD, by varying the following cultivation conditions: pH value (4.8, 5.7 and 6.6); inoculum concentration (0.1, 0.6 and 1.1 g/L) and initial glucose concentration (20.0, 30.0 and 40.0 g/L). The effect of those variables on G6PD production capability was studied by the application of response surface statistical analysis. The results showed that the highest G6PD production (1594.2 U/L), specific activity (1189.7 U/g(cell)) and productivity (45.6 U/L.h) occurred at pH 4.8, inoculum concentration of 0.1 g/L and initial glucose concentration of 20.0 g/L, under agitation of 150 rpm at 30 degrees C after 36 h. In this work, the strain expressed about 21 fold more activity than the wild S. cerevisiae strain, being an attractive and promising new source of this enzyme.

The effect of agitation speed, enzyme loading and substrate concentration on enzymatic hydrolysis of cellulose from brewer`s spent grain

Brewer`s spent grain components (cellulose, hemicellulose and lignin) were fractionated in a two-step chemical pretreatment process using dilute sulfuric acid and sodium hydroxide solutions. The cellulose pulp produced was hydrolyzed with a cellulolytic complex, Celluclast 1.5 L, at 45 degrees C to convert the cellulose into glucose. Several conditions were examined: agitation speed (100, 150 and 200 rpm), enzyme loading (5, 25 and 45 FPU/g substrate), and substrate concentration (2, 5 and 8% w/v), according to a 2(3) full factorial design aiming to maximize the glucose yield. The obtained results were interpreted by analysis of variance and response surface methodology. The optimal conditions for enzymatic hydrolysis of brewer`s spent grain were identified as 100 rpm, 45 FPU/g and 2% w/v substrate. Under these conditions, a glucose yield of 93.1% and a cellulose conversion (into glucose and cellobiose) of 99.4% was achieved. The easiness of glucose release from BSG makes this substrate a raw material with great potential to be used in bioconversion processes.

Effect of hemicellulose and lignin on enzymatic hydrolysis of cellulose from brewer`s spent grain

Enzymatic hydrolysis of brewer`s spent grain in three different forms: original (untreated), pretreated by dilute acid (cellulignin), and pretreated by a sequence of dilute acid and dilute alkali (cellulose pulp), was studied to verify the effect of hemicellulose and lignin on cellulose conversion into glucose. The hydrolysis was carried out using a commercial cellulase concentrate (Celluclast 1.5 L) in an enzyme/substrate ratio of 45 FPU/g, 2% (w/v) substrate concentration, 45 degrees C for 96 h. According to the results, the cellulose hydrolysis was affected by the presence of hemicellulose and/or lignin in the sample. The cellulose conversion ratio (defined as glucose yield + cellobiose yield) from cellulignin was 3.5-times higher than that from untreated sample, whereas from cellulose pulp such value was 4-times higher, correspondent to 91.8% (glucose yield of 85.6%). This best result was probably due to the strong modification in the material structure caused by the hemicellulose and lignin removal from the sample. As a consequence, the cellulose fibers were separated being more susceptible to the enzymatic attack. It was concluded that the lower the hemicellulose and lignin contents in the sample, the higher the efficiency of cellulose hydrolysis. (C) 2007 Elsevier Inc. All rights reserved.

Hydrogen peroxide bleaching of cellulose pulps obtained from brewer`s spent grain

Brewer`s spent grain (BSG) was evaluated for bleached pulp production. Two cellulose pulps with different chemical compositions were produced by soda pulping: one from the original raw material and the other from material pretreated by dilute acid. Both of them were bleached by a totally chlorine-free sequence performed in three stages, using 5% hydrogen peroxide in the two initial, and a 0.25 N NaOH solution in the last one. Chemical composition, kappa number, viscosity, brightness and yield of bleached and unbleached pulps were evaluated. The high hemicellulose (28.4% w/w) and extractives (5.8% w/w) contents in original BSG affected the pulping and bleaching processes. However, soda pulping of acid pretreated BSG gave a cellulose-rich pulp (90.4% w/w) with low hemicellulose and extractives contents (7.9% w/w and < 3.4% w/w, respectively), which was easily bleached achieving a kappa number of 11.21, viscosity of 3.12 cp, brightness of 71.3%, cellulose content of 95.7% w/w, and residual lignin of 3.4% w/w. Alkaline and oxidative delignification of acid pretreated BSG was found as an attractive approach for producing high-purity, chlorine-free cellulose pulp.