Kinetics of Alkaline Decomposition and Cyaniding of Argentian Rubidium Jarosite in NaOH Medium

NASA Astrophysics Data System (ADS)

Rodríguez, Eleazar Salinas; Sáenz, Eduardo Cerecedo; Ramírez, Marius; Cardona, Francisco Patiño; Labra, Miguel Pérez

2012-10-01

The alkaline decomposition of Argentian rubidium jarosite in NaOH media is characterized by an induction period and a progressive conversion period in which the sulfate and rubidium ions pass to the solution, leaving an amorphous iron hydroxide residue. The process is chemically controlled and the order of reaction with respect to hydroxide concentration in the range of 1.75 and 20.4 mol OH- m-3 is 0.94, while activation energy in the range of temperatures of 298 K to 328 K (25 °C to 55 °C) is 91.3 kJ mol-1. Cyaniding of Argentian rubidium jarosite in NaOH media presents a reaction order of 0 with respect to NaCN concentration (in the range of 5 to 41 mol m-3) and an order of reaction of 0.62 with respect to hydroxide concentration, in the range of 1.1 and 30 mol [OH-] m-3. In this case, the cyaniding process can be described, as in other jarosites, as the following two-step process: (1) a step (slow) of alkaline decomposition that controls the overall process followed by (2) a fast step of silver complexation. The activation energy during cyaniding in the range of temperatures of 298 K to 333 K (25 °C to 60 °C) is 43.5 kJ mol-1, which is characteristic of a process controlled by chemical reaction. These results are quite similar to that observed for several synthetic jarosites and that precipitated in a zinc hydrometallurgical plant (Industrial Minera México, San Luis Potosi).

Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Favaro, Marco; Ross, Philip N.

Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assessmore » the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.« less

Catalytic actions of alkaline salts in reactions between 1,2,3,4-butanetetracarboxylic acid and cellulose: II. Esterification.

PubMed

Ji, Bolin; Tang, Peixin; Yan, Kelu; Sun, Gang

2015-11-05

1,2,3,4-Butanetetracarboxylic acid (BTCA) reacts with cellulose in two steps with catalysis of alkaline salts such as sodium hypophosphite: anhydride formation and esterification of anhydride with cellulose. The alkali metal ions were found effective in catalyzing formation of BTCA anhydride in a previous report. In this work, catalytic functions of the alkaline salts in the esterification reaction between BTCA anhydride and cellulose were investigated. Results revealed that acid anions play an important role in the esterification reaction by assisting removal of protons on intermediates and completion of the esterification between cellulose and BTCA. Besides, alkaline salts with lower pKa1 values of the corresponding acids are more effective ones for the reaction since addition of these salts could lead to lower pH values and higher acid anion concentrations in finishing baths. The mechanism explains the results of FTIR and wrinkle recovery angles of the fabrics cured under different temperatures and times. Copyright © 2015 Elsevier Ltd. All rights reserved.

Substrate inhibition: Oxidation of D-sorbitol and D-mannitol by potassium periodate in alkaline medium

NASA Astrophysics Data System (ADS)

Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

2014-05-01

In the oxidation of D-sorbitol and D-mannitol by potassium periodate in alkaline media, substrate inhibition was observed with both substrates, i.e., a decrease in the rate of the reaction was observed with an increase in the concentration of substrate. The substrate inhibition was attributed to the formation of stable complex between the substrate and periodate. The reactions were found to be first order in case of periodate and a positive fractional order with hydroxide ions. Arrhenius parameters were calculated for the oxidation of sorbitol and mannitol by potassium periodate in alkali media.

Homogeneous-heterogeneous reactions in curved channel with porous medium

NASA Astrophysics Data System (ADS)

Hayat, T.; Ayub, Sadia; Alsaedi, A.

2018-06-01

Purpose of the present investigation is to examine the peristaltic flow through porous medium in a curved conduit. Problem is modeled for incompressible electrically conducting Ellis fluid. Influence of porous medium is tackled via modified Darcy's law. The considered model utilizes homogeneous-heterogeneous reactions with equal diffusivities for reactant and autocatalysis. Constitutive equations are formulated in the presence of viscous dissipation. Channel walls are compliant in nature. Governing equations are modeled and simplified under the assumptions of small Reynolds number and large wavelength. Graphical results for velocity, temperature, heat transfer coefficient and homogeneous-heterogeneous reaction parameters are examined for the emerging parameters entering into the problem. Results reveal an activation in both homogenous-heterogenous reaction effect and heat transfer rate with increasing curvature of the channel.

Reaction-Based Off-On Near-infrared Fluorescent Probe for Imaging Alkaline Phosphatase Activity in Living Cells and Mice.

PubMed

Tan, Yi; Zhang, Ling; Man, Ka Ho; Peltier, Raoul; Chen, Ganchao; Zhang, Huatang; Zhou, Liyi; Wang, Feng; Ho, Derek; Yao, Shao Q; Hu, Yi; Sun, Hongyan

2017-03-01

Alkaline phosphatases are a group of enzymes that play important roles in regulating diverse cellular functions and disease pathogenesis. Hence, developing fluorescent probes for in vivo detection of alkaline phosphatase activity is highly desirable for studying the dynamic phosphorylation in living organisms. Here, we developed the very first reaction-based near-infrared (NIR) probe (DHXP) for sensitive detection of alkaline phosphatase activity both in vitro and in vivo. Our studies demonstrated that the probe displayed an up to 66-fold fluorescence increment upon incubation with alkaline phosphatases, and the detection limit of our probe was determined to be 0.07 U/L, which is lower than that of most of alkaline phosphatase probes reported in literature. Furthermore, we demonstrated that the probe can be applied to detecting alkaline phosphatase activity in cells and mice. In addition, our probe possesses excellent biocompatibility and rapid cell-internalization ability. In light of these prominent properties, we envision that DHXP will add useful tools for investigating alkaline phosphatase activity in biomedical research.

Nickel as a catalyst for the electro-oxidation of methanol in alkaline medium

NASA Astrophysics Data System (ADS)

Abdel Rahim, M. A.; Abdel Hameed, R. M.; Khalil, M. W.

The use of Ni as a catalyst for the electro-oxidation of methanol in alkaline medium was studied by cyclic voltammetry. It was found that only Ni dispersed on graphite shows a catalytic activity towards methanol oxidation but massive Ni does not. Ni was dispersed on graphite by the electro-deposition from acidic NiSO 4 solution using potentiostatic and galvanostatic techniques. The catalytic activity of the C/Ni electrodes towards methanol oxidation was found to vary with the amount of electro-deposited Ni. The dependence of the oxidation current on methanol concentration and scan rate was discussed. It was concluded from the electro-chemical measurements and SEM analysis that methanol oxidation starts as Ni-oxide is formed on the electrode surface.

Controllable Surface Reorganization Engineering on Cobalt Phosphide Nanowire Arrays for Efficient Alkaline Hydrogen Evolution Reaction.

PubMed

Xu, Kun; Cheng, Han; Lv, Haifeng; Wang, Jingyu; Liu, Linqi; Liu, Si; Wu, Xiaojun; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2018-01-01

Developing highly efficient hydrogen evolution reaction (HER) catalysts in alkaline media is considered significant and valuable for water splitting. Herein, it is demonstrated that surface reorganization engineering by oxygen plasma engraving on electocatalysts successfully realizes a dramatically enhanced alkaline HER activity. Taking CoP nanowire arrays grown on carbon cloth (denoted as CoP NWs/CC) as an example, the oxygen plasma engraving can trigger moderate CoO x species formation on the surface of the CoP NWs/CC, which is visually verified by the X-ray absorption fine structure, high-resolution transmission electron microscopy, and energy-dispersive spectrometer (EDS) mapping. Benefiting from the moderate CoO x species formed on the surface, which can promote the water dissociation in alkaline HER, the surface reorganization of the CoP NWs/CC realizes almost fourfold enhanced alkaline HER activity and a 180 mV decreased overpotential at 100 mA cm -2 , compared with the pristine ones. More interestingly, this surface reorganization strategy by oxygen plasma engraving can also be effective to other electrocatalysts such as free-standing CoP, Co 4 N, O-CoSe 2 , and C-CoSe 2 nanowires, which verifies the universality of the strategy. This work thus opens up new avenues for designing alkaline HER electrocatalysts based on oxygen plasma engraving. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid, general synthesis of PdPt bimetallic alloy nanosponges and their enhanced catalytic performance for ethanol/methanol electrooxidation in an alkaline medium.

PubMed

Zhu, Chengzhou; Guo, Shaojun; Dong, Shaojun

2013-01-14

We have demonstrated a rapid and general strategy to synthesize novel three-dimensional PdPt bimetallic alloy nanosponges in the absence of a capping agent. Significantly, the as-prepared PdPt bimetallic alloy nanosponges exhibited greatly enhanced activity and stability towards ethanol/methanol electrooxidation in an alkaline medium, which demonstrates the potential of applying these PdPt bimetallic alloy nanosponges as effective electrocatalysts for direct alcohol fuel cells. In addition, this simple method has also been applied for the synthesis of AuPt, AuPd bimetallic, and AuPtPd trimetallic alloy nanosponges. The as-synthesized three-dimensional bimetallic/trimetallic alloy nanosponges, because of their convenient preparation, well-defined sponge-like network, large-scale production, and high electrocatalytic performance for ethanol/methanol electrooxidation, may find promising potential applications in various fields, such as formic acid oxidation or oxygen reduction reactions, electrochemical sensors, and hydrogen-gas sensors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface

DOE PAGES

Liu, Shizhong; White, Michael G.; Liu, Ping

2016-06-30

Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e – or 4e – transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H 2O)-mediated mechanism including 4e – transfers is identified,more » where the reduction steps via *H 2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH –(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O 2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O 2 binding is strong enough to enable the ORR via the 4e – transfer mechanism.« less

Dispersion Polymerization of Polystyrene Particles Using Alcohol as Reaction Medium

NASA Astrophysics Data System (ADS)

Cho, Young-Sang; Shin, Cheol Hwan; Han, Sujin

2016-02-01

In this study, monodisperse polystyrene nanospheres were prepared by dispersion polymerization using alcohol as reaction medium to prepare colloidal clusters of the latex beads. Polyvinylpyrrolidone (PVP) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (MTC) were used as dispersion stabilizer and comonomer, respectively. The particle size could be controlled by adjusting the reactant compositions such as the amount of stabilizer, comonomer, and water in the reactant mixture. The size and monodispersity of the polymeric particles could be also controlled by changing the reaction medium with different alcohols other than ethanol or adjusting the polymerization temperature. The synthesized particles could be self-organized inside water-in-oil emulsion droplets by evaporation-driven self-assembly to produce colloidal clusters of the polymeric nanospheres.

Constraining in-medium nucleon-nucleon interactions via nucleus-nucleus reactions

NASA Astrophysics Data System (ADS)

Sammarruca, Francesca; White, Larz

2010-11-01

The nuclear equation of state is a broadly useful tool. Besides being the main input of stellar structure calculations, it allows a direct connection to the physics of nuclei. For instance, an energy functional (such as a mass formula), together with the energy/particle in nuclear matter, can be used to predict nuclear energies and radii [1]. The single-particle properties are also a key point to link infinite nuclear matter and actual nuclei. The parameters of the single-particle potential, in particular the effective mass, enter the calculations of, for instance, in-medium effective cross sections. From the well-known Glauber reaction theory, the total nucleus-nucleus reaction cross section is expressed in terms of the nuclear transparency, which, in turn, depends on the overlap of the nuclear density distributions and the elementary nucleon-nucleon (NN) cross sections. We explore the sensitivity of the reaction calculation to medium modifications of the NN cross sections to estimate the likelihood of constraining the latter through nuclear reactions. Ultimately, we wish to incorporate isospin asymmetry in the reaction model, having in mind connections with rare isotopes. [1] F. Sammarruca, arXiv:1002.00146 [nucl-th]; International Journal of Modern Physics, in press.

Synthesis of Benzannulated Medium-ring Lactams via a Tandem Oxidative Dearomatization-Ring Expansion Reaction.

PubMed

Guney, Tezcan; Wenderski, Todd A; Boudreau, Matthew W; Tan, Derek S

2018-06-23

Medium-ring natural products exhibit diverse biological activities but such scaffolds are underrepresented in probe and drug discovery efforts due to the limitations of classical macrocyclization reactions. We report herein a tandem oxidative dearomatization-ring-expanding rearoma¬tization (ODRE) reaction that generates benzannulated medium-ring lactams directly from simple bicyclic substrates. The reaction accommodates diverse aryl substrates (haloarenes, aryl ethers, aryl amides, heterocycles) and strategic incorporation of a bridgehead alcohol generates a versatile ketone moiety in the products amenable to downstream modifications. Cheminformatic analysis indicates that these medium rings access regions of chemical space that overlap with related natural products and are distinct from synthetic drugs, setting the stage for their use in discovery screening against novel biological targets. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zinc electrodeposition from flowing alkaline zincate solutions: Role of hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Dundálek, Jan; Šnajdr, Ivo; Libánský, Ondřej; Vrána, Jiří; Pocedič, Jaromír; Mazúr, Petr; Kosek, Juraj

2017-12-01

The hydrogen evolution reaction is known as a parasitic reaction during the zinc electrodeposition from alkaline zincate solutions and is thus responsible for current efficiency losses during the electrolysis. Besides that, the rising hydrogen bubbles may cause an extra convection within a diffusion layer, which leads to an enhanced mass transport of zincate ions to an electrode surface. In this work, the mentioned phenomena were studied experimentally in a flow through electrolyzer and the obtained data were subsequently evaluated by mathematical models. The results prove the indisputable influence of the rising hydrogen bubbles on the additional mixing of the diffusion layer, which partially compensates the drop of the current efficiency of the zinc deposition at higher current flows. Moreover, the results show that the current density ratio (i.e., the ratio of an overall current density to a zinc limiting current density) is not suitable for the description of the zinc deposition, because the hydrogen evolution current density is always involved in the overall current density.

The Pauson-Khand reaction of medium sized trans-cycloalkenes.

PubMed

Lledó, Agustí; Fuster, Aida; Revés, Marc; Verdaguer, Xavier; Riera, Antoni

2013-04-14

Medium sized trans-cycloalkenes are unusually reactive in the intermolecular Pauson-Khand reaction (PKR) with regard to typical monocyclic alkenes. This is due to the ring strain imparted by the E stereochemistry. The PKR of these alkenes offers a modular, regioselective and straightforward entry to trans fused [n.3.0] bicyclic scaffolds (n = 6-8).

Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

USGS Publications Warehouse

Chen, S.G.; Yang, R.T.

1997-01-01

From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

Adverse effects of mineral-alkali reactions in alkaline flooding: Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thornton, S.D.

1988-01-01

Two slim-tube experiments and supporting bottle tests were performed for a study of sandstone-alkali reactions. The two samples of reservoir sandstone used are from oilfields in the People's Republic of China. The first sandstone contains 16 percent clay and is from the Gu-Dao oilfield. The second sandstone contains 12 percent clay and is from the Liao-He oilfield. These two sandstones were allowed to react with alkaline solutions in 6-month bottle tests. Each sandstone consumed the most alkali from 0.5 N NaOH solution, an intermediate amount of alkali from 0.5 N Na/sub 2/SiO/sub 3/ solution, and the least amount of alkalimore » from 0.5 N Na/sub 2/CO/sub 3/ solution. 59 refs., 14 figs., 20 tabs.« less

Interaction of ammonium with birnessite: Evidence of a chemical and structural transformation in alkaline aqueous medium

NASA Astrophysics Data System (ADS)

Boumaiza, Hella; Coustel, Romain; Despas, Christelle; Ruby, Christian; Bergaoui, Latifa

2018-02-01

The ammonium cation interaction with Na-birnessite in aqueous alkaline medium was studied. Solution and solid analysis give evidence that birnessite is not only acting as a cationic exchanger toward NH4+. The surface analysis performed by XPS showed that N1s spectra are characterized by the existence of two different environments: one assignable to an interlayer NH4+ and the second to a chemisorbed N-species. Structural and chemical transformations were observed on birnessite with nitrogen mass balance deficit. The monitoring of NH4+, Na+, Mn2+, NO3- and NO2- and solid changes (average oxidation state of Mn, cation exchange capacity, solid nitrogen content and symmetry evolution identified by XRD and FTIR) indicate unambiguously that NH4+ reacts chemically with the birnessite.

Simultaneous recovery of Zn and Mn from used batteries in acidic and alkaline mediums: A comparative study.

PubMed

Abid Charef, S; Affoune, A M; Caballero, A; Cruz-Yusta, M; Morales, J

2017-10-01

A parallel study of acidic and alkaline leaching for the recovery of Mn and Zn from spent alkaline batteries is outlined. Using H 2 SO 4 as solvent and selecting appropriate conditions of temperature and concentration, all residues were dissolved except carbon. The separation and recovery of the two components were performed by electrodeposition with satisfactory results at pH values above 4 (current efficiency above 70% for Zn and Mn) but rather lower efficiencies as the pH decreased. Most of the Zn was selectively dissolved by alkaline leaching using a 6.5M NaOH solution, and its recovery was examined by means of both electrochemical and chemical processes. The expected formation of pure Zn by electrowinning failed due to the formation of ZnO, the content of which was highly dependent on the electrodeposition time. For short periods, Zn was the main component. For longer periods the electrodeposit consisted of agglomerated microparticles of ZnO with a minor fraction of Zn metal (barely 3% as measured by X-ray diffraction). A chemical reaction of the element with oxygen released at the anode surface might be responsible for its conversion to ZnO. A simple chemical route is described for the first time for the direct conversion of Zn(OH) 4 2- solution to nanostructured ZnO by lowering the pH to values around 12 using 2M HCl solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development of an alkaline/surfactant/polymer compositional reservoir simulator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhuyan, D.

1989-01-01

The mathematical formulation of a generalized three-dimensional compositional reservoir simulator for high-pH chemical flooding processes is presented in this work. The model assumes local thermodynamic equilibrium with respect to both reaction chemistry and phase behavior and calculates equilibrium electrolyte and phase compositions as a function of time and position. The reaction chemistry considers aqueous electrolytic chemistry, precipitation/dissolution of minerals, ion exchange reactions on matrix surface, reaction of acidic components of crude oil with the bases in the aqueous solution and cation exchange reactions with the micelles. The simulator combines this detailed reaction chemistry associated with these processes with the extensivemore » physical and flow property modeling schemes of an existing chemical flood simulator (UTCHEM) to model the multiphase, multidimensional displacement processes. The formulation of the chemical equilibrium model is quite general and is adaptable to simulate a variety of chemical descriptions. In addition to its use in the simulation of high-pH chemical flooding processes, the model will find application in the simulation of other reactive flow problems like the ground water contamination, reinjection of produced water, chemical waste disposal, etc. in one, two or three dimensions and under multiphase flow conditions. In this work, the model is used to simulate several hypothetical cases of high-pH chemical floods, which include cases from a simple alkaline preflush of a micellar/polymer flood to surfactant enhanced alkaline-polymer flooding and the results are analyzed. Finally, a few published alkaline, alkaline-polymer and surfactant-alkaline-polymer corefloods are simulated and compared with the experimental results.« less

In Situ Infrared Spectroscopy of Oligoaniline Intermediates Created under Alkaline Conditions.

PubMed

Šeděnková, Ivana; Stejskal, Jaroslav; Trchová, Miroslava

2014-12-26

The progress of the oxidation of aniline with ammonium peroxydisulfate in an alkaline aqueous medium has been monitored in situ by attenuated total reflection (ATR) Fourier transform infrared spectroscopy. The growth of the microspheres and of the film at the ATR crystal surface, as well as the changes proceeding in the surrounding aqueous medium, are reflected in the spectra. The evolution of the spectra and the changes in the molecular structure occurring during aniline oxidation in alkaline medium are discussed with the help of differential spectra. Several processes connected with the various stages of aniline oxidation were distinguished. The progress of hydrolysis of the aniline in water and further an oxidation of aminophenol to benzoquinone imines in the presence of peroxydisulfate in alkaline medium have been detected in the spectra in real time. The precipitated solid oxidation product was analyzed by mass spectrometry. It is composed of oligomers, mainly trimers to octamers, of various molecular structures incorporating in addition to aniline constitutional units also p-benzoquinone or p-benzoquinoneimine moieties.

Hydration of Hybrid Alkaline Cement Containing a Very Large Proportion of Fly Ash: A Descriptive Model

PubMed Central

Garcia-Lodeiro, Inés; Donatello, Shane; Fernández-Jiménez, Ana; Palomo, Ángel

2016-01-01

In hybrid alkaline fly ash cements, a new generation of binders, hydration, is characterized by features found in both ordinary portland cement (OPC) hydration and the alkali activation of fly ash (AAFA). Hybrid alkaline fly ash cements typically have a high fly ash (70 wt % to 80 wt %) and low clinker (20 wt % to 30 wt %) content. The clinker component favors curing at ambient temperature. A hydration mechanism is proposed based on the authors’ research on these hybrid binders over the last five years. The mechanisms for OPC hydration and FA alkaline activation are summarized by way of reference. In hybrid systems, fly ash activity is visible at very early ages, when two types of gel are formed: C–S–H from the OPC and N–A–S–H from the fly ash. In their mutual presence, these gels tend to evolve, respectively, into C–A–S–H and (N,C)–A–S–H. The use of activators with different degrees of alkalinity has a direct impact on reaction kinetics but does not modify the main final products, a mixture of C–A–S–H and (N,C)–A–S–H gels. The proportion of each gel in the mix does, however, depend on the alkalinity generated in the medium. PMID:28773728

Benchmarking nanoparticulate metal oxide electrocatalysts for the alkaline water oxidation reaction

DOE PAGES

Jung, Suho; McCrory, Charles C. L.; Ferrer, Ivonne M.; ...

2016-11-27

Nanoparticulate metal-oxide catalysts are among the most prevalent systems for alkaline water oxidation. However, comparisons of the electrochemical performance of these materials have been challenging due to the different methods of attachment, catalyst loadings, and electrochemical test conditions reported in the literature. Here in this paper, we have leveraged a conventional drop-casting method that allows for the successful adhesion of a wide range of nanoparticulate catalysts to glassy-carbon electrode surfaces. We have applied this adhesion method to prepare catalyst films from 16 crystalline metal-oxide nanoparticles with a constant loading of 0.8 mg cm -2, and evaluated the resulting nanoparticulate filmsmore » for the oxygen evolution reaction under conditions relevant to an integrated solar fuels device. In general, the activities of the adhered nanoparticulate films are similar to those of thin-film catalysts prepared by electrodeposition or sputtering, achieving 10 mA cm -2 current densities per geometric area at overpotentials of ~0.35–0.5 V.« less

Alkaline earth cation extraction from acid solution

DOEpatents

Dietz, Mark; Horwitz, E. Philip

2003-01-01

An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

Synthesis and characterization of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in Alkaline Exchange Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Hossen, Md Mosaddek; Artyushkova, Kateryna; Atanassov, Plamen; Serov, Alexey

2018-01-01

In this article, three different Fe-N-C oxygen reduction reaction (ORR) catalysts derived from different organic molecules i.e. Fe-NMG, Fe-NMP, Fe-MBZ have been synthesized, characterized by physical-chemical methods and studied in the reaction of oxygen reduction (ORR). It is found that Fe-NMG shows higher ORR performance than Fe-NMP and Fe-MBZ, by both rotating ring disk electrode (RRDE) and fuel cell tests. From characterization and surface analysis, it can be explained that the presence of higher amount of surface oxides and pyridinic nitrogen is the main reason for better performance towards ORR in alkaline media. To achieve the highest performance in alkaline exchange membrane fuel cell (AEMFC), the optimization of catalyst layer composition using various concentrations of ionomer (Tokuyama, AS4) was performed. At the optimum cathode layer configuration utilizing Fe-NMG produces the peak power density of 218 mWcm-2, which is one of the highest values presented in the open literature.

Hydroxide Self-Feeding High-Temperature Alkaline Direct Formate Fuel Cells.

PubMed

Li, Yinshi; Sun, Xianda; Feng, Ying

2017-05-22

Conventionally, both the thermal degradation of the anion-exchange membrane and the requirement of additional hydroxide for fuel oxidation reaction hinder the development of the high-temperature alkaline direct liquid fuel cells. The present work addresses these two issues by reporting a polybenzimidazole-membrane-based direct formate fuel cell (DFFC). Theoretically, the cell voltage of the high-temperature alkaline DFFC can be as high as 1.45 V at 90 °C. It has been demonstrated that a proof-of-concept alkaline DFFC without adding additional hydroxide yields a peak power density of 20.9 mW cm -2 , an order of magnitude higher than both alkaline direct ethanol fuel cells and alkaline direct methanol fuel cells, mainly because the hydrolysis of formate provides enough OH - ions for formate oxidation reaction. It was also found that this hydroxide self-feeding high-temperature alkaline DFFC shows a stable 100 min constant-current discharge at 90 °C, proving the conceptual feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrophilic cobalt sulfide nanosheets as a bifunctional catalyst for oxygen and hydrogen evolution in electrolysis of alkaline aqueous solution.

PubMed

Zhu, Mingchao; Zhang, Zhongyi; Zhang, Hu; Zhang, Hui; Zhang, Xiaodong; Zhang, Lixue; Wang, Shicai

2018-01-01

Hydrophilic medium and precursors were used to synthesize a hydrophilic electro-catalyst for overall water splitting. The cobalt sulfide (Co 3 S 4 ) catalyst exhibits a layered nanosheet structure with a hydrophilic surface, which can facilitate the diffusion of aqueous substrates into the electrode pores and towards the active sites. The Co 3 S 4 catalyst shows excellent bifunctional catalytic activity for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline solution. The assembled water electrolyzer based on Co 3 S 4 exhibits better performance and stability than that of Pt/C-RuO 2 catalyst. Thereforce the hydrophilic Co 3 S 4 is a highly promising bifunctional catalyst for the overall water splitting reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

Zirconia coating stabilized super-iron alkaline cathodes

NASA Astrophysics Data System (ADS)

Yu, Xingwen; Licht, Stuart

A low-level zirconia coating significantly stabilizes high energy alkaline super-iron cathodes, and improves the energy storage capacity of super-iron batteries. Zirconia coating is derived from ZrCl 4 in an organic medium through the conversion of ZrCl 4 to ZrO 2. In alkaline battery system, ZrO 2 provides an intact shield for the cathode materials and the hydroxide shuttle through the coating sustains alkaline cathode redox chemistry. Most super-iron cathodes are solid-state stable, such as K 2FeO 4 and Cs 2FeO 4, but tend to be passivated in alkaline electrolyte due to the formation of Fe(III) over layer. Zirconia coating effectively enhances the stability of these super-iron cathodes. However, for solid-state unstable super-iron cathode (e.g. BaFeO 4), only a little stabilization effect of zirconia coating is observed.

New insights into the formation mechanism of Ag, Au and AgAu nanoparticles in aqueous alkaline media: alkoxides from alcohols, aldehydes and ketones as universal reducing agents.

PubMed

Gomes, Janaina F; Garcia, Amanda C; Ferreira, Eduardo B; Pires, Cleiton; Oliveira, Vanessa L; Tremiliosi-Filho, Germano; Gasparotto, Luiz H S

2015-09-07

In this report we present new insights into the formation mechanism of Ag, Au and AgAu nanoparticles with alcohols, aldehydes and ketones in alkaline medium at room temperature. We selected methanol, ethanol, glycerol, formaldehyde, acetaldehyde and acetone to demonstrate their capability of reducing gold and silver ions under the above-mentioned conditions. We showed that the particles are also formed with potassium tert-butoxide in the absence of hydroxides. Our results strongly suggest that alkoxides, formed from any molecule containing a hydroxyl or a functional group capable of generating them in alkaline medium, are the actual and universal reducing agent of silver and gold ions, in opposition to the currently accepted mechanisms. The universality of the reaction mechanism proposed in this work may impact on the production of noble nanoparticles with simple chemicals normally found in standard laboratories.

Cyanide Degradation under Alkaline Conditions by a Strain of Fusarium solani Isolated from Contaminated Soils

PubMed Central

Dumestre, A.; Chone, T.; Portal, J.; Gerard, M.; Berthelin, J.

1997-01-01

Several cyanide-tolerant microorganisms have been selected from alkaline wastes and soils contaminated with cyanide. Among them, a fungus identified as Fusarium solani IHEM 8026 shows a good potential for cyanide biodegradation under alkaline conditions (pH 9.2 to 10.7). Results of K(sup14)CN biodegradation studies show that fungal metabolism seems to proceed by a two-step hydrolytic mechanism: (i) the first reaction involves the conversion of cyanide to formamide by a cyanide-hydrolyzing enzyme, cyanide hydratase (EC 4.2.1.66); and (ii) the second reaction consists of the conversion of formamide to formate, which is associated with fungal growth. No growth occurred during the first step of cyanide degradation, suggesting that cyanide is toxic to some degree even in cyanide-degrading microorganisms, such as F. solani. The presence of organic nutrients in the medium has a major influence on the occurrence of the second step. Addition of small amounts of yeast extract led to fungal growth, whereas no growth was observed in media containing cyanide as the sole source of carbon and nitrogen. The simple hydrolytic detoxification pathway identified in the present study could be used for the treatment of many industrial alkaline effluents and wastes containing free cyanide without a prior acidification step, thus limiting the risk of cyanhydric acid volatilization; this should be of great interest from an environmental and health point of view. PMID:16535647

Arsanilic acid modified superparamagnetic iron oxide nanoparticles for Purification of alkaline phosphatase from hen's egg yolk.

PubMed

Farzi-Khajeh, Hamed; Safa, Kazem D; Dastmalchi, Siavoush

2017-09-01

Recent studies of magnetic carrier technology have focused on its applications in separation and purification technologies, due to easy separation of the target from the reaction medium by applying an external magnetic field. In the present study, Fe 3 O 4 superparamagnetic nanoparticles were prepared to utilize a chemical co-precipitation method, then the surfaces of the nanoparticles were modified with arsanilic acid derivatives which were used as the specific nanocarriers for the affinity purification of alkaline phosphatase from the hen's egg yolk. The six different types of magnetic nanocarriers with varied lengths of the linkers were obtained. All samples were characterized step by step and validated using FTIR, SEM, EDX, VSM and XRD analysis methods As the results were shown, the use of inflexible tags with long linkers on the surface of the nanocarrier could lead to better results for separation of alkaline phosphatase from the hen's egg yolk with 76.2% recovery and 1361.7-fold purification. The molecular weight of the purified alkaline phosphatase was estimated to be 68kDa by SDS-PAGE. The results of this study showed that the novel magnetic nanocarriers were capable of purifying alkaline phosphatase in a practically time and cost effective way. Copyright © 2017 Elsevier B.V. All rights reserved.

Enhanced alkaline hydrolysis and biodegradability studies of nitrocellulose-bearing missile propellant

NASA Technical Reports Server (NTRS)

Sidhoum, Mohammed; Christodoulatos, Christos; Su, Tsan-Liang; Redis, Mercurios

1995-01-01

Large amounts of energetic materials which have been accumulated over the years in various manufacturing and military installations must be disposed of in an environmentally sound manner. Historically, the method of choice for destruction of obsolete or aging energetic materials has been open burning or open detonation (OB/OD). This destruction approach has become undesirable due to air pollution problems. Therefore, there is a need for new technologies which will effectively and economically deal with the disposal of energetic materials. Along those lines, we have investigated a chemical/biological process for the safe destruction and disposal of a double base solid rocket propellant (AHH), which was used in several 8 inch projectile systems. The solid propellant is made of nitrocellulose and nitroglycerin as energetic components, two lead salts which act as ballistic modifiers, triacetin as a plasticizer and 2-Nitrodiphenylamine (2-NDPA) as a stabilizer. A process train is being developed to convert the organic components of the propellant to biodegradable products and remove the lead from the process stream. The solid propellant is first hydrolyzed through an enhanced alkaline hydrolysis process step. Following lead removal and neutralization, the digested liquor rich in nitrates and nitrites is found to be easily biodegradable. The digestion rate of the intact ground propellant as well as the release of nitrite and nitrate groups were substantially increased when ultrasound were supplied to the alkaline reaction medium compared to the conventional alkaline hydrolysis. The effects of reaction time, temperature, sodium hydroxide concentration and other relevant parameters on the digestion efficiency and biodegradability have been studied. The present work indicates that the AHH propellant can be disposed of safely with a combination of physiochemical and biological processes.

Posttranslational heterogeneity of bone alkaline phosphatase in metabolic bone disease.

PubMed

Langlois, M R; Delanghe, J R; Kaufman, J M; De Buyzere, M L; Van Hoecke, M J; Leroux-Roels, G G

1994-09-01

Bone alkaline phosphatase is a marker of osteoblast activity. In order to study the posttranscriptional modification (glycosylation) of bone alkaline phosphatase in bone disease, we investigated the relationship between mass and catalytic activity of bone alkaline phosphatase in patients with osteoporosis and hyperthyroidism. Serum bone alkaline phosphatase activity was measured after lectin precipitation using the Iso-ALP test kit. Mass concentration of bone alkaline phosphatase was determined with an immunoradiometric assay (Tandem-R Ostase). In general, serum bone alkaline phosphatase mass and activity concentration correlated well. The activity : mass ratio of bone alkaline phosphatase was low in hyperthyroidism. Activation energy of the reaction catalysed by bone alkaline phosphatase was high in osteoporosis and in hyperthyroidism. Experiments with neuraminidase digestion further demonstrated that the thermodynamic heterogeneity of bone alkaline phosphatase can be explained by a different glycosylation of the enzyme.

Influence of a reaction medium on the oxidation of aromatic nitrogen-containing compounds by peroxyacids

NASA Astrophysics Data System (ADS)

Dutka, V. S.; Matsyuk, N. V.; Dutka, Yu. V.

2011-01-01

The influence of different solvents on the oxidation reaction rate of pyridine (Py), quinoline (QN), acridine (AN), α-oxyquinoline (OQN) and α-picolinic acid (APA) by peroxydecanoic acid (PDA) was studied. It was found that the oxidation rate grows in the series Py < QN < AN, and the rate of the oxidation reaction of compounds containing a substituent in the α position from a reactive center is significantly lower than for unsubstituted analogues. The effective energies of activation of the oxidation reaction were found. It was shown that in the first stage, the reaction mechanism includes the rapid formation of an intermediate complex nitrogen-containing compound, peroxyacid, which forms products upon decomposing in the second stage. A kinetic equation that describes the studied process is offered. The constants of equilibrium of the intermediate complex formation ( K eq) and its decomposition constant ( k 2) in acetone and benzene were calculated. It was shown that the nature of the solvent influences the numerical values of both K p and k 2. It was established that introduction of acetic acid (which is able to form compounds with Py) into the reaction medium slows the rate of the oxidation process drastically. Correlation equations linking the polarity, polarizability, electrophilicity, and basicity of solvents with the constant of the PDA oxidation reaction rate for Py were found. It was concluded that the basicity and polarity of the solvent have a decisive influence on the oxidation reaction rate, while the polarizability and electrophilicity of the reaction medium do not influence the oxidation reaction rate.

Ion-atom charge-transfer reactions and a hot intercloud medium. [in interstellar space

NASA Technical Reports Server (NTRS)

Steigman, G.

1975-01-01

An investigation is conducted concerning the ionization equilibrium of carbon in a hot intercloud medium (ICM), taking into account various charge-transfer reactions. Attention is given to problems related to observations of carbon along the lines of sight to several unreddened stars. It is pointed out that the observed underabundance of C III and overabundance of C I can be consistent with the presence of a hot, partially ionized ICM, provided that two of the charge-transfer reactions considered are rapid at thermal energies.

Multi-component Fe–Ni hydroxide nanocatalyst for oxygen evolution and methanol oxidation reactions under alkaline conditions

DOE PAGES

Candelaria, Stephanie L.; Bedford, Nicholas M.; Woehl, Taylor J.; ...

2016-11-29

Here, iron-incorporated nickel-based materials show promise as catalysts for the oxygen evolution reac-tion (OER) half-reaction of water electrolysis. Nickel has also exhibited high catalytic activity for methanol oxidation, particularly when in the form of a bimetallic catalyst. In this work, bimetallic iron-nickel nanoparticles were synthesized using a multi-step procedure in water under ambient conditions. When compared to monometallic iron and nickel nanoparticles, Fe-Ni nanoparticles show enhanced catalytic activity for both OER and methanol oxidation under alkaline conditions. At 1 mA/cm 2, the overpotential for monometallic iron and nickel nanoparticles was 421 mV and 476 mV, respectively, while the bimetallic Fe-Nimore » nanoparticles had a greatly reduced overpotential of 256 mV. At 10 mA/cm 2, bimetallic Fe-Ni nanoparticles had an overpotential of 311 mV. Spec-troscopy characterization suggests that the primary phase of nickel in Fe-Ni nanoparticles is the more disordered alpha phase of nickel hydroxide.« less

Hydrolytic degradation of alkaline lignin in hot-compressed water and ethanol.

PubMed

Yuan, Zhongshun; Cheng, Shuna; Leitch, Mathew; Xu, Chunbao Charles

2010-12-01

Alkaline lignin of a very high molecular weight was successfully degraded into oligomers in a hot-compressed water-ethanol medium with NaOH as the catalyst and phenol as the capping agent at 220-300 degrees C. Under the optimal reaction conditions, i.e., 260 degrees C, 1 h, with the lignin/phenol ratio of 1:1 (w/w), almost complete degradation was achieved, producing <1% solid residue and negligible gas products. The obtained degraded lignin had a number-average molecular weight M(n) and weight-average molecular weight M(w) of 450 and 1000 g/mol respectively, significantly lower than the M(n) and M(w) of 10,000 and 60,000 g/mol of the original lignin. A higher temperature and a longer reaction time favoured phenol combination, but increased the formation of solid residue due to the condensation reactions of the degradation intermediates/products. The degraded lignin products were soluble in organic solvents (such as THF), and were characterized by HPLC/GPC, IR and NMR. A possible mechanism for lignin hydrolytic degradation was also proposed in this study. 2010 Elsevier Ltd. All rights reserved.

Transformation of proanthocyanidin A2 to its isomers under different physiological pH conditions and common cell culture medium.

PubMed

Lu, Wen-Chien; Huang, Wei-Ting; Kumaran, Alaganandam; Ho, Chi-Tang; Hwang, Lucy Sun

2011-06-08

Proanthocyanidins constitute an important class of polyphenols ubiquitously found in plants. They have been extensively studied for their antioxidant capacity and bioactivity in vitro and in animal models. However, their stability under different pH conditions and in cell culture medium has not been well documented. In the present study, it was observed that proanthocyanidin A2 (PA2) was relatively more stable in acidic condition than in weak alkaline condition. PA2 was also quite unstable in basal-Dulbecco's Modified Eagle medium (b-DMEM medium) at 37 °C. The addition of PA2 to the cell culture medium accelerated its epimerization with a half-life of <15 min, and ethylenediaminetetraacetic acid (EDTA) could not stop the reaction. The results also demonstrated that the major isomers transformed in the weak alkaline condition or cell culture medium at 37 °C were identified as epicatechin-(4β→8; 2β→O→7)-ent-catechin (proanthocyanidin A4) and epicatechin-(4β→6; 2β→O→7)-ent-catechin. The rates of transformation were dependent on the pH or the components of the medium. Therefore, the results obtained for PA2 in the cell culture bioassays, which were usually carried out for 24 h, might not represent the true activity of the original PA2. The stability and transformation of PA2 should be considered when the bioactivity of PA2 is evaluated in a given cell culture system.

Syntheses and structures of alkaline earth metal bis(diphenylamides).

PubMed

Gärtner, Martin; Fischer, Reinald; Langer, Jens; Görls, Helmar; Walther, Dirk; Westerhausen, Matthias

2007-06-11

Various preparative procedures are employed in order to synthesize alkaline earth metal bis(diphenylamides) such as (i) metalation of HNPh2 with the alkaline earth metal M, (ii) metalation of HNPh2 with MPh2, (iii) metathesis reaction of MI2 with KNPh2, (iv) metalation of HNPh2 with PhMI in THF, and (v) metathesis reaction of PhMI with KNPh2 followed by a dismutation reaction yielding MPh2 and M(NPh2)2. The magnesium compounds [(diox)MgPh2]infinity (1) and (thf)2Mg(NPh2)2 (2) show tetracoordinate metal atoms, whereas in (dme)2Ca(NPh2)2 (3), (thf)4Sr(NPh2)2 (4), and (thf)4Ba(NPh2)2 (5) the metals are 6-fold coordinated. Additional agostic interactions between an ipso-carbon of one of the phenyl groups of the amide ligand and the alkaline earth metal atom lead to unsymmetric coordination of the NPh2 anions with two strongly different M-N-C angles in 3-5.

Alternative Alkaline Conditioning of Amidoxime Based Adsorbent for Uranium Extraction from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, S.; Liao, W. -P.; Flicker Byers, M.

2016-04-20

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21-30% decrease in the cost of uranium recovery.« less

Reaction Behaviors of Al-Killed Medium-Manganese Steel with Different Refractories

NASA Astrophysics Data System (ADS)

Kong, Lingzhong; Deng, Zhiyin; Zhu, Miaoyong

2018-03-01

In order to understand the reaction mechanism between medium-manganese steel and different refractories, some laboratory experiments were carried out at 1873 K (1600 °C). Three types of refractory plates (Al2O3, MgO, and MgO·Al2O3) were used. The results show that Mn in liquid medium-manganese steel does not react easily with the Al2O3 refractory, but can react with the MgO refractory to generate a (Mn, Mg)O layer at the boundary between the refractory plate and liquid steel. After the formation of (Mn, Mg)O, a layer of (Mn, Mg)O·Al2O3 spinel is also formed at the edge of the MgO refractory. Similar to the MgO refractory, the dissolved Mn can react with the MgO·Al2O3 refractory as well, and a layer of (Mn, Mg)O·Al2O3 was also detected after reaction. It was found that the formation of (Mn, Mg)O·Al2O3 at the edge of the refractory is a source of (Mn, Mg)O·Al2O3 inclusions in liquid steel. The flush-off of the (Mn, Mg)O·Al2O3 layer would result in the formation of (Mn, Mg)O·Al2O3 inclusions.

Reaction Behaviors of Al-Killed Medium-Manganese Steel with Different Refractories

NASA Astrophysics Data System (ADS)

Kong, Lingzhong; Deng, Zhiyin; Zhu, Miaoyong

2018-06-01

In order to understand the reaction mechanism between medium-manganese steel and different refractories, some laboratory experiments were carried out at 1873 K (1600 °C). Three types of refractory plates (Al2O3, MgO, and MgO·Al2O3) were used. The results show that Mn in liquid medium-manganese steel does not react easily with the Al2O3 refractory, but can react with the MgO refractory to generate a (Mn, Mg)O layer at the boundary between the refractory plate and liquid steel. After the formation of (Mn, Mg)O, a layer of (Mn, Mg)O·Al2O3 spinel is also formed at the edge of the MgO refractory. Similar to the MgO refractory, the dissolved Mn can react with the MgO·Al2O3 refractory as well, and a layer of (Mn, Mg)O·Al2O3 was also detected after reaction. It was found that the formation of (Mn, Mg)O·Al2O3 at the edge of the refractory is a source of (Mn, Mg)O·Al2O3 inclusions in liquid steel. The flush-off of the (Mn, Mg)O·Al2O3 layer would result in the formation of (Mn, Mg)O·Al2O3 inclusions.

Online monitoring of electrocatalytic reactions of alcohols at platinum and gold electrodes in acidic, neutral and alkaline media by capillary electrophoresis with contactless conductivity detection (EC-CE-C4 D).

PubMed

Ferreira Santos, Mauro Sérgio; Silva Lopes, Fernando; Gutz, Ivano Gebhardt Rolf

2017-11-01

An EC-CE-C 4 D flow system was applied to the investigation of electrocatalytic processes by monitoring carboxylic acids formed during the electro-oxidation at various potentials of primary alcohols (mixture of 1 mmol/L of ethanol, n-propanol, n-butanol and n-pentanol) in acidic, neutral and alkaline media. The electro-oxidation was carried out on gold and platinum disk electrodes (3 mm of diameter) in a thin-layer electrochemical flow cell. Products were sampled 50 μm apart from the electrode directly into the capillary. All the generated carboxylates were determined in near real time (less than 2 min) by CE-C 4 D in counter-flow mode, with Tris/HCl buffer solution (pH 8.6) as BGE. Long sequences of 5-min experiments were run automatically, exploring the applied potential, electrolysis time and solution composition. Electro-oxidation at 1.5 V (versus Ag/AgCl quasi-reference) during 50 s in acidic medium was found appropriate for both Pt and Au electrodes when the determination of alcohols after derivatization is intended. A noteworthy selectivity effect was observed on the Au electrode. The signal corresponding to pentanoate is similar on both electrodes while the signal of ethanoate (acetate) is four times larger on gold than on platinum. The carboxylate signals were lower in alkaline medium (below the determination limit on Pt) than in acidic and neutral media. On gold, the formation of carboxylates was anticipated (0.85 V in alkaline medium versus 1.40 V in neutral medium). The automatic online monitoring of electrochemical processes by EC-CE-C 4 D holds great potential to investigate ionic/ionizable intermediates/products of new electrocatalysts and/or alternative fuels. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental investigation of the reaction between corundum xenocrysts and alkaline basaltic host magma: Constraints on magma residence times of basalt-hosted sapphires

NASA Astrophysics Data System (ADS)

Baldwin, L. C.; Ballhaus, C.

2018-03-01

Megacrystic sapphires (Fe-Ti-rich corundum) of up to 5 cm in size are well known from alkaline mafic rocks from intra-continental rift-related magmatic fields. There is no doubt that these sapphires represent xenocrysts that were trapped from their original lithology by ascending basaltic magmas carrying them to the Earth's surface. Most studies about basalt-hosted sapphires address the question about the origin of the sapphires, but there is hardly any information available about the time the sapphires resided inside the carrier melt. Sapphires are in reaction relationship with basalt and produce spinel coronas at the sapphire-basalt interface, spatially separating the mutually incompatible phases from one another. Assuming isothermal and isobaric conditions of spinel rim formation, the rim-thickness should be a function of the reaction time with the basaltic melt. In this paper, we report time-series experiments aimed at investigating the kinetics of spinel rim formation due to igneous corrosion of corundum. Therefore, we reacted corundum fragments with alkaline basalt powder at 1250 °C and 1GPa, using a Piston Cylinder Apparatus. The width of the spinel rim was used to estimate a residence time. Extrapolating the experimentally derived reaction rates to the thickness of natural spinel rims as described from the Siebengebirge Volcanic Field, Germany, and from Changle, China, we estimated residence times in the order of a few weeks to months.

Benzene Adsorption - A Significant Inhibitor for the Hydrogen Oxidation Reaction in Alkaline Conditions

DOE PAGES

Gonzales, Ivana; Chung, Hoon Taek; Kim, Yu Seung

2017-09-25

Slow hydrogen oxidation reaction (HOR) kinetics on Pt under alkaline conditions is a significant technical barrier for the development of high-performance hydroxide exchange membrane fuel cells. Here we report that benzene adsorption on Pt is a major factor responsible for the sluggish HOR. Furthermore, we demonstrate that bimetallic catalysts, such as PtMo/C, PtNi/C, and PtRu/C, can reduce the adsorption of benzene and thereby improve HOR activity. In particular, the HOR voltammogram of PtRu/C in 0.1 M benzyl ammonium showed minimal benzene adsorption. Density functional theory calculations indicate that the adsorption of benzyl ammonium on the bimetallic PtRu is endergonic formore » all four possible orientations of the cation, which explains the significantly better HOR activity observed for the bimetallic catalysts. In conclusion, the new HOR inhibition mechanism described here provides insights for the design of future polymer electrolytes and electrocatalysts for better-performing polymer membrane-based fuel cells.« less

Structural, morphological, and physicochemical properties of acetylated high-, medium-, and low-amylose rice starches.

PubMed

Colussi, Rosana; Pinto, Vania Zanella; El Halal, Shanise Lisie Mello; Vanier, Nathan Levien; Villanova, Franciene Almeida; Marques E Silva, Ricardo; da Rosa Zavareze, Elessandra; Dias, Alvaro Renato Guerra

2014-03-15

The high-, medium-, and low-amylose rice starches were isolated by the alkaline method and acetylated by using acetic anhydride for 10, 30, and 90 min of reaction. The degree of substitution (DS), the Fourier-transformed infrared spectroscopy (FTIR), the X-ray diffractograms, the thermal, morphological, and pasting properties, and the swelling power and solubility of native and acetylated starches were evaluated. The DS of the low-amylose rice starch was higher than the DS of the medium- and the high-amylose rice starches. The introduction of acetyl groups was confirmed by FTIR spectroscopy. The acetylation treatment reduced the crystallinity, the viscosity, the swelling power, and the solubility of rice starch; however, there was an increase in the thermal stability of rice starch modified by acetylation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of Human Bone Alkaline Phosphatase in Pichia Pastoris

NASA Technical Reports Server (NTRS)

Malone, Christine C.; Ciszak, Eva; Karr, Laurel J.

1999-01-01

A soluble form of human bone alkaline phosphatase has been expressed in a recombinant strain of the methylotrophic yeast Pichia pastoris. We constructed a plasmid containing cDNA encoding for human bone alkaline phosphatase, with the hydrophobic carboxyl terminal portion deleted. Alkaline phosphatase was secreted into the medium to a level of 32mg/L when cultured in shake flasks, and enzyme activity was 12U/mg, as measured by a spectrophotometric assay. By conversion to a fermentation system, a yield of 880mg/L has been achieved with an enzyme activity of 968U/mg. By gel electrophoresis analysis, it appears that greater than 50% of the total protein in the fermentation media is alkaline phosphatase. Although purification procedures are not yet completely optimized, they are expected to include filtration, ion exchange and affinity chromatography. Our presentation will focus on the purification and crystallization results up to the time of the conference. Structural data should provide additional information on the role of alkaline phosphatase in normal bone mineralization and in certain bone mineralization anomalies.

Hydrolysis of alkaline pretreated banana peel

NASA Astrophysics Data System (ADS)

Fatmawati, A.; Gunawan, K. Y.; Hadiwijaya, F. A.

2017-11-01

Banana peel is one of food wastes that are rich in carbohydrate. This shows its potential as fermentation substrate including bio-ethanol. This paper presented banana peel alkaline pretreatment and enzymatic hydrolysis. The pretreatment was intended to prepare banana peel in order to increase hydrolysis performance. The alkaline pretreatment used 10, 20, and 30% w/v NaOH solution and was done at 60, 70 and 80°C for 1 hour. The hydrolysis reaction was conducted using two commercial cellulose enzymes. The reaction time was varied for 3, 5, and 7 days. The best condition for pretreatment process was one conducted using 30% NaOH solution and at 80°C. This condition resulted in cellulose content of 90.27% and acid insoluble lignin content of 2.88%. Seven-day hydrolysis time had exhibited the highest reducing sugar concentration, which was7.2869 g/L.

Influence of acid and alkaline sources on optical, structural and photovoltaic properties of CdSe nanoparticles precipitated from aqueous solution

NASA Astrophysics Data System (ADS)

Coria-Monroy, C. Selene; Sotelo-Lerma, Mérida; Hu, Hailin

2016-06-01

CdSe is a widely researched material for photovoltaic applications. One of the most important parameters of the synthesis is the pH value, since it determines the kinetics and the mechanism of the reaction and in consequence, the optical and morphological properties of the products. We present the synthesis of CdSe in solution with strict control of pH and the comparison of ammonia and KOH as alkaline sources and diluted HCl as acid medium. CdSe formation was monitored with photoluminescence emission spectra (main peak in 490 nm, bandgap of CdSe nanoparticles). XRD patterns indicated that CdSe nanoparticles are mainly of cubic structure for ammonia and HCl, but the hexagonal planes appear with KOH. Product yield decreases with pH and also decreases with KOH at constant pH value since ammonia has a double function, as complexing agent and alkaline source. Changes in morphology were observed in SEM images as well with the different alkaline source. The effect of alkaline sources on photovoltaic performance of hybrid organic solar cells with CdSe and poly(3-hexylthiophene) as active layers was clearly observed, indicating the importance of synthesis conditions on optoelectronic properties of promising semiconductor nanomaterials for solar cell applications.

High-Efficiency Artificial Photosynthesis Using a Novel Alkaline Membrane Cell

NASA Technical Reports Server (NTRS)

Narayan, Sri; Haines, Brennan; Blosiu, Julian; Marzwell, Neville

2009-01-01

A new cell designed to mimic the photosynthetic processes of plants to convert carbon dioxide into carbonaceous products and oxygen at high efficiency, has an improved configuration using a polymer membrane electrolyte and an alkaline medium. This increases efficiency of the artificial photosynthetic process, achieves high conversion rates, permits the use of inexpensive catalysts, and widens the range of products generated by this type of process. The alkaline membrane electrolyte allows for the continuous generation of sodium formate without the need for any additional separation system. The electrolyte type, pH, electrocatalyst type, and cell voltage were found to have a strong effect on the efficiency of conversion of carbon dioxide to formate. Indium electrodes were found to have higher conversion efficiency compared to lead. Bicarbonate electrolyte offers higher conversion efficiency and higher rates than water solutions saturated with carbon dioxide. pH values between 8 and 9 lead to the maximum values of efficiency. The operating cell voltage of 2.5 V, or higher, ensures conversion of the carbon dioxide to formate, although the hydrogen evolution reaction begins to compete strongly with the formate production reaction at higher cell voltages. Formate is produced at indium and lead electrodes at a conversion efficiency of 48 mg of CO2/kilojoule of energy input. This efficiency is about eight times that of natural photosynthesis in green plants. The electrochemical method of artificial photosynthesis is a promising approach for the conversion, separation and sequestration of carbon dioxide for confined environments as in space habitats, and also for carbon dioxide management in the terrestrial context. The heart of the reactor is a membrane cell fabricated from an alkaline polymer electrolyte membrane and catalyst- coated electrodes. This cell is assembled and held in compression in gold-plated hardware. The cathode side of the cell is supplied with carbon

MERCURIC CHLORIDE CAPTURE BY ALKALINE SORBENTS

EPA Science Inventory

The paper gives results of bench-scale mechanistic studies of mercury/sorbent reactions that showed that mercuric chloride (HgC12) is readily adsorbed by alkaline sorbents, which may offers a less expensive alternative to the use of activated carbons. A laboratory-scale, fixed-b...

Alternative alkaline conditioning of amidoxime based adsorbent for uranium extraction from seawater

DOE PAGES

Das, Sadananda; Liao, Wei -Po; Byers, Maggie Flicker; ...

2015-10-18

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Furthermore, the use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21–30% decrease in the cost of uranium recovery.« less

Alternative alkaline conditioning of amidoxime based adsorbent for uranium extraction from seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Sadananda; Liao, Wei -Po; Byers, Maggie Flicker

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagentmore » for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Furthermore, the use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21–30% decrease in the cost of uranium recovery.« less

Electroconversion of glycerol in alkaline medium: From generation of energy to formation of value-added products

NASA Astrophysics Data System (ADS)

Da Silva, Rodrigo Garcia; Aquino Neto, Sidney; Kokoh, Kouakou Boniface; De Andrade, Adalgisa Rodrigues

2017-05-01

We have investigated the electroconversion of glycerol in alkaline medium using bimetallic M50@Pt50 nanocatalysts (where M = Ru, Sn or Ni) supported on multi-walled carbon nanotubes. The electrocatalysts have been synthesized via an electrostatically oriented co-reduction method in which self-assembly of the positively charged metal species (Sn, Ni and Ru) into the internal catalyst level and of the negatively charged platinum species towards the outer layer afford nanocatalysts with the desired morphology. The physicochemical characterizations have confirmed the atomic ratios, the metal loadings, and the spherical shape of the nanoparticles with average diameter lying between 2 and 3 nm. In terms of electrochemical performance, the Ni@Pt composition displays the highest electrochemically active surface area, the best relation between the peak current and the onset oxidation potential in the presence of glycerol (275 mA mg-1Pt and -492 mV vs. Hg/HgO/OH-), and the most remarkable electrochemical stability in chronoamperometric tests. Long-term experiments to evaluate the oxidation of glycerol and analysis of the products indicate that the different electrocatalysts synthesized herein efficiently perform the electroconversion of glycerol at high rates and generate of value-added products.

Formation of {eta}-mesic nuclei by the ({pi},N) reaction and properties of N*(1535) in medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagahiro, Hideko; Jido, Daisuke; Hirenzaki, Satoru

2009-08-15

We calculate formation spectra of the {eta}-nucleus systems in the ({pi},N) reactions with nuclear targets, which can be performed at existing and/or forthcoming facilities, including the Japan Proton Accelerator Research Complex, to investigate the {eta}-nucleus interaction. Based on the N*(1535) dominance in the {eta}N system, the {eta}-mesic nuclei are suitable systems for the study of in-medium properties of the N*(1535) baryon resonance, such as reduction of the mass difference of N and N* in the nuclear medium, which affects the level structure of the {eta} and N*-hole modes. We find that clear information on the in-medium N*- and {eta}-nucleus interactionsmore » can be obtained through the formation spectra of the {eta}-mesic nuclei. We also discuss the experimental feasibilities by showing several spectra of the ({pi},N) reactions calculated with possible experimental settings. Coincident measurements of the N{pi} pairs from the N* decays in nuclei help us to reduce backgrounds.« less

Ethanol electrooxidation in alkaline medium on electrochemically synthesized Co(OH)2/Au composite

NASA Astrophysics Data System (ADS)

Babu, Sreejith P.; Elumalai, Perumal

2017-01-01

Gold (Au), cobalt hydroxide (Co(OH)2) and different Co(OH)2/Au compositions were electro-deposited onto stainless steel by a potentiodynamic method from the respective metal-ion solutions. The deposits were characterized by x-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transformed infra-red spectroscopy (FT-IR). The XRD and IR data confirmed that the deposits were Au, α-Co(OH)2 or Co(OH)2/Au composites. The SEM observations confirmed that the morphology of the Au was spherical, while the α-Co(OH)2 was flakey with pores. The morphology of the Co(OH)2/Au composites consisted of highly agglomerated Au grains distributed on the Co(OH)2 matrix. The electrocatalytic activity of each of the Au, Co(OH)2 and Co(OH)2/Au-composite electrodes towards ethanol electrooxidation in an alkaline medium was investigated by cyclic voltammetry and chronoamperometry. It turned out that the Co(OH)2/Au-composite electrodes exhibited superior catalytic activity for ethanol electrooxidation compared with the pristine Au or Co(OH)2 electrodes. A peak current density as high as 25 mA cm-2 was exhibited by the Co(OH)2/ Au composite while the Au and Co(OH)2 showed only 0.9 and 13 mA cm-2, respectively. The enhanced conductivity of the Co(OH)2/Au matrix due to the presence of Au, as well as the combined catalytic activity, seemed to be responsible for the superior performance of the Co(OH)2/Au-composite electrodes.

Overexpression of Human Bone Alkaline Phosphatase in Pichia Pastoris

NASA Technical Reports Server (NTRS)

Karr, Laurel; Malone, Christine, C.; Rose, M. Franklin (Technical Monitor)

2000-01-01

The Pichiapastoris expression system was utilized to produce functionally active human bone alkaline phosphatase in gram quantities. Bone alkaline phosphatase is a key enzyme in bone formation and biomineralization, yet important questions about its structural chemistry and interactions with other cellular enzymes in mineralizing tissues remain unanswered. A soluble form of human bone alkaline phosphatase was constructed by deletion of the 25 amino acid hydrophobic C-terminal region of the encoding cDNA and inserted into the X-33 Pichiapastoris strain. An overexpression system was developed in shake flasks and converted to large-scale fermentation. Alkaline phosphatase was secreted into the medium to a level of 32mgAL when cultured in shake flasks. Enzyme activity was 12U/mg measured by a spectrophotometric assay. Fermentation yielded 880mgAL with enzymatic activity of 968U/mg. Gel electrophoresis analysis indicates that greater than 50% of the total protein in the fermentation is alkaline phosphatase. A purification scheme has been developed using ammonium sulfate precipitation followed by hydrophobic interaction chromatography. We are currently screening crystallization conditions of the purified recombinant protein for subsequent X-ray diffraction analyses. Structural data should provide additional information on the role of alkaline phosphatase in normal bone mineralization and in certain bone mineralization anomalies.

Dissociation Energies of the Alkaline Earth Monofluorides

DOE Office of Scientific and Technical Information (OSTI.GOV)

BLUE, GARY D.; GREEN, JOHN W.; EHLERT, THOMAS C.

1963-08-24

New results and theoretical calculations are presented that indicate consistently high dissocintion energies for all the alkaline earth monofluorides. Experimental results were obtained by utilizing a mass spectrometer to analyze the vapors from a heated Ta Knudsen cell containing an alkaline earth fluoride salt with Al present as a reducing agent. Ionization efficiency curves were obtained and temperature dependence investigations were made to determine the molecular precursor of the ions observed. Values of the equilibrium constants at different temperatures were used together with the free-energy functions to calculate the third law heats of reaction at 298 deg K. Data aremore » tabulated for the heats of various reactions for Al--MF2 systems with M = Mg, Ca, Sr, and Ba, and dissociation energies of MF molecules by various methods for Be, Mg, Ca, Sr, and Ba. (C.H.)« less

Nitrogen-doped graphene anchored with mixed growth patterns of CuPt alloy nanoparticles as a highly efficient and durable electrocatalyst for the oxygen reduction reaction in an alkaline medium.

PubMed

Illathvalappil, Rajith; Dhavale, Vishal M; Bhange, Siddheshwar N; Kurungot, Sreekumar

2017-07-06

A highly active and durable CuPt alloy catalyst with trigonal bipyramidal and truncated cube-type mixed morphologies, anchored on the nitrogen-doped graphene (NGr) surface (CuPt-TBTC/NGr), was prepared by a simple and fast method. The obtained CuPt alloy showed improved oxygen reduction reaction (ORR) activity, with a 30 mV positive shift in the half-wave potential value, as compared to the state-of-the-art Pt/C catalyst in a 0.1 M KOH solution. The CuPt alloy with the trigonal bipyramidal morphology possesses porous type inter-connected sides, which help to achieve improved mass transport of oxygen during the ORR. The exposure of the (111) plane of the CuPt alloy further improved the catalytic activity towards the dioxygen reduction in alkaline media. The ORR activity of the NGr-supported CuPt alloy was found to be dependent on the reaction time, and improved activity was obtained on the material derived at a reaction time of 90 min (CuPt-TBTC/NGr-90). The material synthesized at a lower or higher reaction time than 90 min resulted in a partially formed trigonal bipyramidal morphology with more truncated cubes or agglomerated trigonal bipyramidal and truncated cubes with closed type structures, respectively. Along with the high intrinsic ORR activity, CuPt-TBTC/NGr-90 displayed excellent electrochemical stability. Even after repeated 1000 potential cycling in a window ranging from 0.10 to 1.0 V (vs. RHE), the system clearly outperformed the state-of-the-art Pt/C catalyst with 15 and 60 mV positive shifts in the onset and half-wave potentials, respectively. CuPt-TBTC/NGr-90 also exhibited 2.1 times higher mass activity and 2.2 times higher specific activity, compared to Pt/C at 0.90 V (vs. RHE). Finally, a zinc-air battery fabricated with the alloy catalyst as the air electrode displayed a peak power density of 300 mW cm -2 , which is much higher than the peak power density of 253 mW cm -2 obtained for the state-of-the-art Pt/C catalyst as the air electrode.

Cation exchange properties of zeolites in hyper alkaline aqueous media.

PubMed

Van Tendeloo, Leen; de Blochouse, Benny; Dom, Dirk; Vancluysen, Jacqueline; Snellings, Ruben; Martens, Johan A; Kirschhock, Christine E A; Maes, André; Breynaert, Eric

2015-02-03

Construction of multibarrier concrete based waste disposal sites and management of alkaline mine drainage water requires cation exchangers combining excellent sorption properties with a high stability and predictable performance in hyper alkaline media. Though highly selective organic cation exchange resins have been developed for most pollutants, they can serve as a growth medium for bacterial proliferation, impairing their long-term stability and introducing unpredictable parameters into the evolution of the system. Zeolites represent a family of inorganic cation exchangers, which naturally occur in hyper alkaline conditions and cannot serve as an electron donor or carbon source for microbial proliferation. Despite their successful application as industrial cation exchangers under near neutral conditions, their performance in hyper alkaline, saline water remains highly undocumented. Using Cs(+) as a benchmark element, this study aims to assess the long-term cation exchange performance of zeolites in concrete derived aqueous solutions. Comparison of their exchange properties in alkaline media with data obtained in near neutral solutions demonstrated that the cation exchange selectivity remains unaffected by the increased hydroxyl concentration; the cation exchange capacity did however show an unexpected increase in hyper alkaline media.

Efficient acquisition of iron confers greater tolerance to saline-alkaline stress in rice (Oryza sativa L.)

PubMed Central

Li, Qian; Yang, An; Zhang, Wen-Hao

2016-01-01

To elucidate the mechanisms underlying tolerance to saline-alkaline stress in two rice genotypes, Dongdao-4 and Jigeng-88, we exposed them to medium supplemented with 10 mM Na2CO3 and 40 mM NaCl (pH 8.5). Dongdao-4 plants displayed higher biomass, chlorophyll content, and photosynthetic rates, and a larger root system than Jigeng-88 under saline-alkaline conditions. Dongdao-4 had a higher shoot Na+/K+ ratio than Jigeng-88 under both control and saline-alkaline conditions. Dongdao-4 exhibited stronger rhizospheric acidification than Jigeng-88 under saline-alkaline conditions, resulting from greater up-regulation of H+-ATPases at the transcriptional level. Moreover, Fe concentrations in shoots and roots of Dongdao-4 were higher than those in Jigeng-88, and a higher rate of phytosiderophore exudation was detected in Dongdao-4 versus Jigeng-88 under saline-alkaline conditions. The Fe-deficiency-responsive genes OsIRO2, OsIRT1, OsNAS1, OsNAS2, OsYSL2, and OsYSL15 were more strongly up-regulated in Dongdao-4 than Jigeng-88 plants in saline-alkaline medium, implying greater tolerance of Dongdao-4 plants to Fe deficiency. To test this hypothesis, we compared the effects of Fe deficiency on the two genotypes, and found that Dongdao-4 was more tolerant to Fe deficiency. Exposure to Fe-deficient medium led to greater rhizospheric acidification and phytosiderophore exudation in Dongdao-4 than Jigeng-88 plants. Expression levels of OsIRO2, OsIRT1, OsNAS1, OsNAS2, OsYSL2, and OsYSL15 were higher in Dongdao-4 than Jigeng-88 plants under Fe-deficient conditions. These results demonstrate that a highly efficient Fe acquisition system together with a large root system may underpin the greater tolerance of Dongdao-4 plants to saline-alkaline stress. PMID:27811002

Effects of medium-chain triacylglycerols on Maillard reaction in bread baking.

PubMed

Toyosaki, Toshiyuki

2018-06-01

To investigate the relationship between the fatty acid composition of medium-chain triacylglycerols (MCTs) and the Maillard reaction induced during bread baking, a comparison with various fatty acids was conducted. Saturated fatty acids had a remarkable inhibitory effect on the amount of advanced glycation end products (AGEs) generated from the Maillard reaction in bread baking compared to unsaturated fatty acids. The amount of AGEs produced by each fatty acid (mg kg -1 ) was as follows: C18:0, 18.7; C12:0, 35.2; C16:0, 21.4; C18:0, 38.2; C18:1, 68.7; C18:2, 80.1; C20:4, 80.8; C22:4, 89.8. Saturated fatty acids were possibly involved in the Maillard reaction and, as a result, acted to inhibit it. In the case of unsaturated fatty acids, amounts of AGEs during the Maillard reaction in baking tended to increase as the degree of unsaturation increased. In other words, there was a positive correlation between the degree of unsaturation and the amount of AGEs. It was also confirmed that the air pore distribution in baked bread was closely related to AGEs. These results led us to conclude that the fatty acid composition of the added lipids also influences properties that determine the tastiness of bread. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Convection and reaction in a diffusive boundary layer in a porous medium: nonlinear dynamics.

PubMed

Andres, Jeanne Therese H; Cardoso, Silvana S S

2012-09-01

We study numerically the nonlinear interactions between chemical reaction and convective fingering in a diffusive boundary layer in a porous medium. The reaction enhances stability by consuming a solute that is unstably distributed in a gravitational field. We show that chemical reaction profoundly changes the dynamics of the system, by introducing a steady state, shortening the evolution time, and altering the spatial patterns of velocity and concentration of solute. In the presence of weak reaction, finger growth and merger occur effectively, driving strong convective currents in a thick layer of solute. However, as the reaction becomes stronger, finger growth is inhibited, tip-splitting is enhanced and the layer of solute becomes much thinner. Convection enhances the mass flux of solute consumed by reaction in the boundary layer but has a diminishing effect as reaction strength increases. This nonlinear behavior has striking differences to the density fingering of traveling reaction fronts, for which stronger chemical kinetics result in more effective finger merger owing to an increase in the speed of the front. In a boundary layer, a strong stabilizing effect of reaction can maintain a long-term state of convection in isolated fingers of wavelength comparable to that at onset of instability.

Dispersion polymerization of L-lactide utilizing ionic liquids as reaction medium

NASA Astrophysics Data System (ADS)

Fahmiati, Sri; Minami, Hideto; Haryono, Agus; Adilina, Indri B.

2017-11-01

Dispersion polymerization of L-lactide was proceeded in various ionic liquids. Ionic liquids as 1-Hexyl-3-methylimidazolium bis (trifluormethylsulfonyl) imide, [HMIM] [TFSI], 1-Butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, [BMP] [TFSI], and N,N,N-Trimethyl-N-Propylammonium Bis (trifloromethanesulfonyl) imide, [TMPA] [TFSI], were employed as reaction medium that dissolved both of lactide and stabilizer (polyvinylprrolidone). Sn-supported on bentonite was used as a ring opening catalyst of L-lactide. Gel Permeation Chromatography result showed that poly-(L-lactic acid) were formed in ionic liquids [HMIM] [TFSI] and [BMP] [TFSI] with molecular weight as 19390 and 20844, respectively.

Amine-Modulated/Engineered Interfaces of NiMo Electrocatalysts for Improved Hydrogen Evolution Reaction in Alkaline Solutions.

PubMed

Gao, Wei; Gou, Wangyan; Zhou, Xuemei; Ho, Johnny C; Ma, Yuanyuan; Qu, Yongquan

2018-01-17

The interface between electrolytes and electrocatalysts would largely determine their corresponding activity and stability. Herein, modulating the surface characteristics of NiMo nanoparticles by various adsorbed amines gives the tunability on their interfacial properties and subsequently improves their catalytic performance for hydrogen evolution reaction (HER) in alkaline solutions. Diamines can significantly improve their HER activity by decreasing the charge-transfer resistance and modulating the electronic structures of interfacial active sites. Importantly, among various amines, ethylenediamine facilitates the HER activity of NiMo with a remarkable decrease of 268 mV in the overpotential to reach 10 mA cm -2 as compared with that of the unmodified NiMo in 1.0 M KOH. This method provides a novel strategy of regulating the interfacial properties to strengthen the catalytic performance of electrocatalysts.

Osteoblast Differentiation on Collagen Scaffold with Immobilized Alkaline Phosphatase.

PubMed

Jafary, F; Hanachi, P; Gorjipour, K

2017-01-01

In tissue engineering, scaffold characteristics play an important role in the biological interactions between cells and the scaffold. Cell adhesion, proliferation, and activation depend on material properties used for the fabrication of scaffolds. In the present investigation, we used collagen with proper characteristics including mechanically stability, biodegradability and low antigenicity. Optimization of the scaffold was done by immobilization of alkaline phosphatase on the collagen surface via cross-linking method, because this enzyme is one of the most important markers of osteoblast, which increases inorganic phosphate concentration and promote mineralization of bone formation. Alkaline phosphatase was immobilized on a collagen surface by 1-ethyl-3-(dimethylaminopropyl) carbodiimide hydrochloride, as a reagent. Then, rat mesenchymal stem cells were cultured in osteogenic medium in control and treated groups. The osteogenesis-related genes were compared between treatments (differentiated cells with immobilized alkaline phosphatase/collagen scaffold) and control groups (differentiated cells on collagen surface without alkaline phosphatase) on days 3 and 7 by quantitative real-time PCR (QIAGEN software). Several genes, including alkaline phosphatase, collagen type I and osteocalcine associated with calcium binding and mineralization, showed upregulation in expression during the first 3 days, whereas tumor necrosis factor-α, acting as an inhibitor of differentiation, was down-regulated during osteogenesis. Collagen scaffold with immobilized alkaline phosphatase can be utilized as a good candidate for enhancing the differentiation of osteoblasts from mesenchymal stem cells.

Identification of a New Marine Bacterial Strain SD8 and Optimization of Its Culture Conditions for Producing Alkaline Protease

PubMed Central

Cui, Hongxia; Yang, Muyang; Wang, Liping; Xian, Cory J.

2015-01-01

While much attention has been given to marine microorganisms for production of enzymes, which in general are relatively more stable and active compared to those from plants and animals, studies on alkaline protease production from marine microorganisms have been very limited. In the present study, the alkaline protease producing marine bacterial strain SD8 isolated from sea muds in the Geziwo Qinhuangdao sea area of China was characterized and its optimal culture conditions were investigated. Strain SD8 was initially classified to belong to genus Pseudomonas by morphological, physiological and biochemical characterizations, and then through 16S rDNA sequence it was identified to be likely Pseudomonas hibiscicola. In addition, the culture mediums, carbon sources and culture conditions of strain SD8 were optimized for maximum production of alkaline protease. Optimum enzyme production (236U/mL when cultured bacteria being at 0.75 mg dry weight/mL fermentation broth) was obtained when the isolate at a 3% inoculum size was grown in LB medium at 20 mL medium/100mL Erlenmeyer flask for 48h culture at 30°C with an initial of pH 7.5. This was the first report of strain Pseudomonas hibiscicola secreting alkaline protease, and the data for its optimal cultural conditions for alkaline protease production has laid a foundation for future exploration for the potential use of SD8 strain for alkaline protease production. PMID:26716833

One-pot synthesis of nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle as an efficient metal-free catalyst for oxygen reduction reaction in alkaline solution

NASA Astrophysics Data System (ADS)

Han, Ce; Bo, Xiangjie; Zhang, Yufan; Li, Mian; Guo, Liping

2014-12-01

Nitrogen and sulfur co-doped onion-like mesoporous carbon vesicle (NS-MCV) with multilayer lamellar structure is synthesized as a metal-free catalyst through a convenient and economical procedure. The synthesized materials are systematically characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, nitrogen adsorption-desorption, and X-ray photoelectron spectroscopy (XPS). The characterization results demonstrate that N and S atoms can be successfully doped into the framework of MCV with little impact on the morphology and structure. The NS-MCV manifests a remarkably high electrocatalytic activity as a metal-free electrocatalyst for the oxygen reduction reaction (ORR) with mainly a four-electron transfer pathway. Moreover, in contrast to the commercially available Pt/C catalyst, the NS-MCV shows much better long-term stability and tolerance toward methanol crossover in an alkaline medium. Such excellent performances can be mainly attributed to the synergistic effect arising from the addition of N and S heteroatom, optimized S content and high surface area. The NS-MCV with a simple synthesis method may further exploited as potentially efficient and inexpensive metal-free ORR catalyst materials.

Probing the Origin of the Compromised Catalysis of E. coli Alkaline Phosphatase in its Promiscuous Sulfatase Reaction

PubMed Central

Catrina, Irina; O'Brien, Patrick J.; Purcell, Jamie; Nikolic-Hughes, Ivana; Zalatan, Jesse G.; Hengge, Alvan C.; Herschlag, Daniel

2008-01-01

The catalytic promiscuity of E. coli alkaline phosphatase (AP) and many other enzymes provides a unique opportunity to dissect the origin of enzymatic rate enhancements via a comparative approach. Here we use kinetic isotope effects (KIEs) to explore the origin of the 109-fold greater catalytic proficiency by AP for phosphate monoester hydrolysis relative to sulfate monoester hydrolysis. The primary 18O KIEs for the leaving group oxygen atoms in the AP-catalyzed hydrolysis of p-nitrophenyl phosphate (pNPP) and p-nitrophenylsulfate (pNPS) decrease relative to the values observed for nonenzymatic hydrolysis reactions. Prior linear free energy relationship results suggest that the transition states for AP-catalyzed reactions of phosphate and sulfate esters are ‘loose’ and indistinguishable from that in solution, suggesting that the decreased primary KIEs do not reflect a change in the nature of the transition state but rather a strong interaction of the leaving group oxygen atom with an active site Zn2+ ion. Furthermore, the KIEs for the two reactions are identical within error, suggesting that the differential catalysis of these reactions cannot be attributed to differential stabilization of the leaving group. In contrast, AP perturbs the KIE for the nonbridging oxygen atoms in the reaction of pNPP but not pNPS, suggesting a differential interaction with the transferred group in the transition state. These and prior results are consistent with a strong electrostatic interaction between the active site bimetallo Zn2+ cluster and one of the nonbridging oxygen atoms on the transferred group. We suggest that the lower charge density of this oxygen atom on a transferred sulfuryl group accounts for a large fraction of the decreased stabilization of the transition state for its reaction relative to phosphoryl transfer. PMID:17411045

Spectrophotometric determination of triclosan based on diazotization reaction: response surface optimization using Box-Behnken design.

PubMed

Kaur, Inderpreet; Gaba, Sonal; Kaur, Sukhraj; Kumar, Rajeev; Chawla, Jyoti

2018-05-01

A spectrophotometric method based on diazotization of aniline with triclosan has been developed for the determination of triclosan in water samples. The diazotization process involves two steps: (1) reaction of aniline with sodium nitrite in an acidic medium to form diazonium ion and (2) reaction of diazonium ion with triclosan to form a yellowish-orange azo compound in an alkaline medium. The resulting yellowish-orange product has a maximum absorption at 352 nm which allows the determination of triclosan in aqueous solution in the linear concentration range of 0.1-3.0 μM with R 2 = 0.998. The concentration of hydrochloric acid, sodium nitrite, and aniline was optimized for diazotization reaction to achieve good spectrophotometric determination of triclosan. The optimization of experimental conditions for spectrophotometric determination of triclosan in terms of concentration of sodium nitrite, hydrogen chloride and aniline was also carried out by using Box-Behnken design of response surface methodology and results obtained were in agreement with the experimentally optimized values. The proposed method was then successfully applied for analyses of triclosan content in water samples.

Ultrafine and highly disordered Ni 2 Fe 1 nanofoams enabled highly efficient oxygen evolution reaction in alkaline electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Song, Junhua; Zhu, Chengzhou

Nickel iron hydroxides are the most promising non-noble electrocatalysts for oxygen evolution reaction (OER) in alkaline media. By in situ reduction of metal precursors, compositionally controlled three-dimensional (3D) NixFeyB nanofoams (NFs) are synthesized with high surface area and uniformly distributed bimetallic networks. The resultant ultrafine amorphous Ni2Fe1B NFs exhibit extraordinary electrocatalytic performance toward OER and overall water splitting in alkaline media. At a potential as low as 1.42 V (vs. RHE), Ni2Fe1B NFs can deliver a current density of 10 mA/cm2 and show negligible activity loss after 12 hours’ stability test. Even at large current flux of 100 mA/cm2, anmore » ultralow overpotential of 0.27 V is achieved, which is about 0.18 V more negative than benchmark RuO2. Both ex-situ Mӧssbauer spectroscopy and X-ray Absorption Spectroscopy (XAS) reveal a phase separation and transformation for the Ni2Fe1B catalyst during OER process. The evolution of oxidation state and disordered structure of Ni2Fe1B might be a key to the high catalytic performance for OER.« less

Alkaline pH enhances farnesol production by Saccharomyces cerevisiae.

PubMed

Muramatsu, Masayoshi; Ohto, Chikara; Obata, Shusei; Sakuradani, Eiji; Shimizu, Sakayu

2009-07-01

External environments affect prenyl alcohol production by squalene synthetase-deficient mutant Saccharomyces cerevisiae ATCC 64031. Cultivation of the yeast in medium with an initial pH ranging from 7.0 to 8.0 increased the amount of secreted farnesol (FOH). In contrast, acidic medium with a pH below 4.0 increased the intracellular FOH and its isomer nerolidol. These effects of alkaline pH were also observed on constant pH cultivation in a jar fermenter. On cultivation for 133 h, the FOH production reached 102.8 mg/l.

Reduction of nitrobenzene with alkaline ascorbic acid: Kinetics and pathways.

PubMed

Liang, Chenju; Lin, Ya-Ting; Shiu, Jia-Wei

2016-01-25

Alkaline ascorbic acid (AA) exhibits the potential to reductively degrade nitrobenzene (NB), which is the simplest of the nitroaromatic compounds. The nitro group (NO2(-)) of NB has a +III oxidation state of the N atom and tends to gain electrons. The effect of alkaline pH ranging from 9 to 13 was initially assessed and the results demonstrated that the solution pH, when approaching or above the pKa2 of AA (11.79), would increase reductive electron transfer to NB. The rate equation for the reactions between NB and AA at pH 12 can be described as r=((0.89±0.11)×10(-4) mM(1-(a+b))h(-1))×[NB](a=1.35±0.10)[AA](b=0.89±0.01). The GC/MS analytical method identified nitrosobenzene, azoxybenzene, and azobenzene as NB reduction intermediates, and aniline (AN) as a final product. These experimental results indicate that the alkaline AA reduction of NB to AN mainly proceeds via the direct route, consisting of a series of two-electron or four-electron transfers, and the condensation reaction plays a minor route. Preliminary evaluation of the remediation of spiked NB contaminated soils revealed that maintenance of alkaline pH and a higher water to soil ratio are essential for a successful alkaline AA application. Copyright © 2015 Elsevier B.V. All rights reserved.

Efficient acquisition of iron confers greater tolerance to saline-alkaline stress in rice (Oryza sativa L.).

PubMed

Li, Qian; Yang, An; Zhang, Wen-Hao

2016-12-01

To elucidate the mechanisms underlying tolerance to saline-alkaline stress in two rice genotypes, Dongdao-4 and Jigeng-88, we exposed them to medium supplemented with 10 mM Na 2 CO 3 and 40 mM NaCl (pH 8.5). Dongdao-4 plants displayed higher biomass, chlorophyll content, and photosynthetic rates, and a larger root system than Jigeng-88 under saline-alkaline conditions. Dongdao-4 had a higher shoot Na + /K + ratio than Jigeng-88 under both control and saline-alkaline conditions. Dongdao-4 exhibited stronger rhizospheric acidification than Jigeng-88 under saline-alkaline conditions, resulting from greater up-regulation of H + -ATPases at the transcriptional level. Moreover, Fe concentrations in shoots and roots of Dongdao-4 were higher than those in Jigeng-88, and a higher rate of phytosiderophore exudation was detected in Dongdao-4 versus Jigeng-88 under saline-alkaline conditions. The Fe-deficiency-responsive genes OsIRO2, OsIRT1, OsNAS1, OsNAS2, OsYSL2, and OsYSL15 were more strongly up-regulated in Dongdao-4 than Jigeng-88 plants in saline-alkaline medium, implying greater tolerance of Dongdao-4 plants to Fe deficiency. To test this hypothesis, we compared the effects of Fe deficiency on the two genotypes, and found that Dongdao-4 was more tolerant to Fe deficiency. Exposure to Fe-deficient medium led to greater rhizospheric acidification and phytosiderophore exudation in Dongdao-4 than Jigeng-88 plants. Expression levels of OsIRO2, OsIRT1, OsNAS1, OsNAS2, OsYSL2, and OsYSL15 were higher in Dongdao-4 than Jigeng-88 plants under Fe-deficient conditions. These results demonstrate that a highly efficient Fe acquisition system together with a large root system may underpin the greater tolerance of Dongdao-4 plants to saline-alkaline stress. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

DOE PAGES

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; ...

2016-01-14

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

PubMed Central

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

2016-01-01

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

Double layer effects in electrocatalysis: The oxygen reduction reaction and ethanol oxidation reaction on Au(111), Pt(111) and Ir(111) in alkaline media containing Na and Li cations

DOE PAGES

Lopes, Pietro P.; Strmcnik, Dusan; Jirkovsky, Jakub S.; ...

2015-09-28

Oxygen reduction and ethanol oxidation reactions were studied on Au(111), Pt(111) and Ir(111) in alkaline solutions containing sodium and/or lithium cations. By keeping the same (111) surface orientation and exploring oxophilicity trends and non-covalent interactions between OH ad and alkali metal cations (AMC n+), we were able to gain deep insights into the multiple roles that OH ad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OH ad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OH ad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formationmore » of a “true oxide” layer at higher electrode potentials. Although OH ad is a simple spectator for the ORR, it promotes the ethanol oxidation reaction (EOR) at lower potentials and act as spectator at high OHad coverages. By changing the alkali metal cation at the interface (Li +) on more oxophilic surfaces, it was possible to promote the EOR even more, relative to Na +, without changing the product distribution for the reaction. This cation effect suggests that OH ad—Li +(H 2O) x clusters can stabilize the ethoxide adlayer, thus improving the EOR activity. Finally, our results indicate the importance of the entire electrochemical interface in determining the electrocatalytic activity during reaction.« less

Usefulness of organic acid produced by Exiguobacterium sp. 12/1 on neutralization of alkaline wastewater.

PubMed

Kulshreshtha, Niha Mohan; Kumar, Anil; Bisht, Gopal; Pasha, Santosh; Kumar, Rita

2012-01-01

The aim of this study was to investigate the role of organic acids produced by Exiguobacterium sp. strain 12/1 (DSM 21148) in neutralization of alkaline wastewater emanated from beverage industry. This bacterium is known to be able to grow in medium of pH as high as pH 12.0 and to neutralize alkaline industrial wastewater from pH 12.0 to pH 7.5. The initial investigation on the type of functional groups present in medium, carried out using FT-IR spectroscopy, revealed the presence of peaks corresponding to carbonyl group and hydroxyl group, suggesting the release of carboxylic acid or related metabolic product(s). The identification of specific carboxylic group, carried out using RP-HPLC, revealed the presence of a single peak in the culture supernatant with retention time most similar to formic acid. The concentration of acid produced on different carbon sources was studied as a function of time. Although acid was present in same final concentration, the rate of acid production was highest in case of medium supplemented with sucrose followed by fructose and glucose. The knowledge of metabolic products of the bacterium can be considered as a first step towards realization of its potential for large-scale bioremediation of alkaline wastewater from beverage industry.

Usefulness of Organic Acid Produced by Exiguobacterium sp. 12/1 on Neutralization of Alkaline Wastewater

PubMed Central

Kulshreshtha, Niha Mohan; Kumar, Anil; Bisht, Gopal; Pasha, Santosh; Kumar, Rita

2012-01-01

The aim of this study was to investigate the role of organic acids produced by Exiguobacterium sp. strain 12/1 (DSM 21148) in neutralization of alkaline wastewater emanated from beverage industry. This bacterium is known to be able to grow in medium of pH as high as pH 12.0 and to neutralize alkaline industrial wastewater from pH 12.0 to pH 7.5. The initial investigation on the type of functional groups present in medium, carried out using FT-IR spectroscopy, revealed the presence of peaks corresponding to carbonyl group and hydroxyl group, suggesting the release of carboxylic acid or related metabolic product(s). The identification of specific carboxylic group, carried out using RP-HPLC, revealed the presence of a single peak in the culture supernatant with retention time most similar to formic acid. The concentration of acid produced on different carbon sources was studied as a function of time. Although acid was present in same final concentration, the rate of acid production was highest in case of medium supplemented with sucrose followed by fructose and glucose. The knowledge of metabolic products of the bacterium can be considered as a first step towards realization of its potential for large-scale bioremediation of alkaline wastewater from beverage industry. PMID:22666107

Influence of media composition on the production of alkaline α-amylase from Bacillus subtilis CB-18.

PubMed

Ogbonnaya, Nwokoro; Odiase, Anthonia

2012-01-01

Starch, a homopolysaccharide is an important and an abundant food reserve and energy source. Starches are processed to yield different products which find many industrial applications. Alpha-amylases hydrolyze starch by cleaving α-1,4-glucosidic bonds and have been used in food, textile and pharmaceutical industries [Sun et al. 2010]. Enzymatic conversion of starch with amylase presents an economically superior alternative to the conventional method of starch gelatinization. Alkaline α-amylase has an important position in the global enzyme market as a constituent of detergent. In this paper, we screened soil bacteria and an isolate, alkalophilic Bacillus subtilis CB-18 was found to produce an alkaline α-amylase in different media. MATERIAL AND METHODS. Screening of the isolates for amylolytic activity was carried out by growing bacteria isolated from the soil in starch agar plates and subsequently staining the plates with iodine solution to reveal zones of hydrolysis of starch. The selected isolate, Bacillus subtlis CB-18 was grown in different media at alkaline pH to evaluate the influence of media composition on alkaline α-amylase production. Enzyme assay was carried out by growing the culture in a broth medium and obtaining cell - free culture supernatant after centrifugation at 2515 × g for 15 minutes Amylase activity was determined by incubating 0.5 ml of crude enzyme solution in 0.1M Tris/HCl buffer (pH 8.5) with 0.5 ml of 1% soluble starch solution. The reaction was terminated by the addition of DNS reagent and reducing sugar produced from the amylolytic reaction was determined. Bacillus subtilis CB-18 used for this work was selected because it produced 7 mm zone diameter on starch agar plate. This organism was cultured in different alkaline broth media containing 2% soluble starch as inducer carbohydrate for α-amylase production. Among the carbon sources used for enzyme production, sorbitol was the best to stimulate enzyme production with �

Multidrug resistance protein MdtM adds to the repertoire of antiporters involved in alkaline pH homeostasis in Escherichia coli

PubMed Central

2013-01-01

Background In neutralophilic bacteria, monovalent metal cation/H+ antiporters play a key role in pH homeostasis. In Escherichia coli, only four antiporters (NhaA, NhaB, MdfA and ChaA) are identified to function in maintenance of a stable cytoplasmic pH under conditions of alkaline stress. We hypothesised that the multidrug resistance protein MdtM, a recently characterised homologue of MdfA and a member of the major facilitator superfamily, also functions in alkaline pH homeostasis. Results Assays that compared the growth of an E. coli ΔmdtM deletion mutant transformed with a plasmid encoding wild-type MdtM or the dysfunctional MdtM D22A mutant at different external alkaline pH values (ranging from pH 8.5 to 10) revealed a potential contribution by MdtM to alkaline pH tolerance, but only when millimolar concentrations of sodium or potassium was present in the growth medium. Fluorescence-based activity assays using inverted vesicles generated from transformants of antiporter-deficient (ΔnhaA, ΔnhaB, ΔchaA) E. coli TO114 cells defined MdtM as a low-affinity antiporter that catalysed electrogenic exchange of Na+, K+, Rb+ or Li+ for H+. The K+/H+ antiport reaction had a pH optimum at 9.0, whereas the Na+/H+ exchange activity was optimum at pH 9.25. Measurement of internal cellular pH confirmed MdtM as contributing to maintenance of a stable cytoplasmic pH, acid relative to the external pH, under conditions of alkaline stress. Conclusions Taken together, the results support a role for MdtM in alkaline pH tolerance. MdtM can therefore be added to the currently limited list of antiporters known to function in pH homeostasis in the model organism E. coli. PMID:23701827

Multidrug resistance protein MdtM adds to the repertoire of antiporters involved in alkaline pH homeostasis in Escherichia coli.

PubMed

Holdsworth, Scarlett R; Law, Christopher J

2013-05-23

In neutralophilic bacteria, monovalent metal cation/H+ antiporters play a key role in pH homeostasis. In Escherichia coli, only four antiporters (NhaA, NhaB, MdfA and ChaA) are identified to function in maintenance of a stable cytoplasmic pH under conditions of alkaline stress. We hypothesised that the multidrug resistance protein MdtM, a recently characterised homologue of MdfA and a member of the major facilitator superfamily, also functions in alkaline pH homeostasis. Assays that compared the growth of an E. coli ΔmdtM deletion mutant transformed with a plasmid encoding wild-type MdtM or the dysfunctional MdtM D22A mutant at different external alkaline pH values (ranging from pH 8.5 to 10) revealed a potential contribution by MdtM to alkaline pH tolerance, but only when millimolar concentrations of sodium or potassium was present in the growth medium. Fluorescence-based activity assays using inverted vesicles generated from transformants of antiporter-deficient (ΔnhaA, ΔnhaB, ΔchaA) E. coli TO114 cells defined MdtM as a low-affinity antiporter that catalysed electrogenic exchange of Na+, K+, Rb+ or Li+ for H+. The K+/H+ antiport reaction had a pH optimum at 9.0, whereas the Na+/H+ exchange activity was optimum at pH 9.25. Measurement of internal cellular pH confirmed MdtM as contributing to maintenance of a stable cytoplasmic pH, acid relative to the external pH, under conditions of alkaline stress. Taken together, the results support a role for MdtM in alkaline pH tolerance. MdtM can therefore be added to the currently limited list of antiporters known to function in pH homeostasis in the model organism E. coli.

Constructing Solid-Gas-Interfacial Fenton Reaction over Alkalinized-C3N4 Photocatalyst To Achieve Apparent Quantum Yield of 49% at 420 nm.

PubMed

Li, Yunxiang; Ouyang, Shuxin; Xu, Hua; Wang, Xin; Bi, Yingpu; Zhang, Yuanfang; Ye, Jinhua

2016-10-03

Efficient generation of active oxygen-related radicals plays an essential role in boosting advanced oxidation process. To promote photocatalytic oxidation for gaseous pollutant over g-C 3 N 4 , a solid-gas interfacial Fenton reaction is coupled into alkalinized g-C 3 N 4 -based photocatalyst to effectively convert photocatalytic generation of H 2 O 2 into oxygen-related radicals. This system includes light energy as power, alkalinized g-C 3 N 4 -based photocatalyst as an in situ and robust H 2 O 2 generator, and surface-decorated Fe 3+ as a trigger of H 2 O 2 conversion, which attains highly efficient and universal activity for photodegradation of volatile organic compounds (VOCs). Taking the photooxidation of isopropanol as model reaction, this system achieves a photoactivity of 2-3 orders of magnitude higher than that of pristine g-C 3 N 4 , which corresponds to a high apparent quantum yield of 49% at around 420 nm. In-situ electron spin resonance (ESR) spectroscopy and sacrificial-reagent incorporated photocatalytic characterizations indicate that the notable photoactivity promotion could be ascribed to the collaboration between photocarriers (electrons and holes) and Fenton process to produce abundant and reactive oxygen-related radicals. The strategy of coupling solid-gas interfacial Fenton process into semiconductor-based photocatalysis provides a facile and promising solution to the remediation of air pollution via solar energy.

Production of Alkaline Protease by Solvent-Tolerant Alkaliphilic Bacillus circulans MTCC 7942 Isolated from Hydrocarbon Contaminated Habitat: Process Parameters Optimization

PubMed Central

Patil, Ulhas; Chaudhari, Ambalal

2013-01-01

In the present investigation, a newly isolated organic solvent-tolerant and alkaliphilic bacterial strain was reported from a hydrocarbon (gasoline and diesel) contaminated soil collected from the petrol station, Shirpur (India). The strain was identified as Bacillus circulans MTCC 7942, based on phenotype, biochemical, and phylogenetic analysis of 16S rRNA gene sequence. The capability of Bacillus circulans to secrete an extracellular, thermostable, alkaline protease and grow in the presence of organic solvents was explored. Bacillus circulans produced maximum alkaline protease (412 U/mL) in optimized medium (g/L): soybean meal, 15; starch, 10; KH2PO4, 1; MgSO4·7H2O, 0.05; CaCl2, 1; Na2CO3, 8; pH 10.0 at 37°C and 100 rpm. The competence of strain to grow in various organic solvents—n-octane, dodecane, n-decane, N,N-dimethylformamide, n-hexane, and dimethyl sulfoxide, establishes its potential as solvent-stable protease source for the possible applications in nonaqueous reactions and fine chemical synthesis. PMID:25937965

Alkaline Activator Impact on the Geopolymer Binders

NASA Astrophysics Data System (ADS)

Błaszczyński, Tomasz Z.; Król, Maciej R.

2017-10-01

Concrete structures are constantly moving in the direction of improving the durability. Durability depends on many factors, which are the composition of concrete mix, the usage of additives and admixtures and the place, where material will work and carry the load. The introduction of new geopolymer binders for geopolymer structures adds a new aspect that is type of used activator. This substance with strongly alkaline reaction is divided because of the physical state, the alkaline degree and above all the chemical composition. Taking into account, that at present the geopolymer binders are made essentially from waste materials or by-products from the combustion of coal or iron ore smelting, unambiguous determination of the effect of the activator on the properties of the geopolymer material requires a number of trials, researches and observation. This paper shows the influence of the most alkaline activators on the basic parameters of the durability of geopolymer binders. In this study there were used highly alkaline hydroxides, water glasses and granules, which are waste materials in a variety of processes taking place in chemical plants. As the substrate of geopolymer binders there were used fly ash which came from coal and high calcareous ash from the burning of lignite.

TANDEM BIS-ALDOL REACTION OF KETONES: A FACILE ONE-POT SYNTHESIS OF 1,3-DIOXANES IN AQUEOUS MEDIUM

EPA Science Inventory

A novel tandem bis-aldol reaction of ketone with paraformaldehyde catalyzed by polystyrenesulfonic acid in aqueous medium delivers 1,3-dioxanes in high yield. This one pot, operationally simple microwave-assisted synthetic protocol proceeds efficiently in water in the absence of ...

Sensitive and selective determination of fluvoxamine maleate using a sensitive chemiluminescence system based on the alkaline permanganate-Rhodamine B-gold nanoparticles reaction.

PubMed

Hassanzadeh, Javad; Amjadi, Mohammad

2015-06-01

A high-yield chemiluminescence (CL) system based on the alkaline permanganate-Rhodamine B reaction was developed for the sensitive determination of fluvoxamine maleate (Flu). Rhodamine B is oxidized by alkaline KMnO4 and a weak CL emission is produced. It was demonstrated that gold nanoparticles greatly enhance this CL emission due to their interaction with Rhodamine B molecules. It is also observed that sodium dodecyl sulfate, an anionic surfactant, can strongly increase this enhancement. In addition, it was demonstrated that a notable decrease in the CL intensity is observed in the presence of Flu. This may be related to Flu oxidation with KMnO4 . There is a linear relationship between the decrease in CL intensity and the Flu concentration over a range of 2-300 µg/L. A new simple, rapid and sensitive CL method was developed for the determination of Flu with a detection limit (3s) of 1.35 µg/L. The proposed method was used for the determination of Flu in pharmaceutical and urine samples. Copyright © 2014 John Wiley & Sons, Ltd.

Influence of surface properties on the mechanism of H2S removal by alkaline activated carbons.

PubMed

Yan, Rong; Chin, Terence; Ng, Yuen Ling; Duan, Huiqi; Liang, David Tee; Tay, Joo Hwa

2004-01-01

Alkaline activated carbons are widely used as adsorbents of hydrogen sulfide (H2S), one of the major odorous compounds arising from sewage treatment facilities. Although a number of studies have explored the effects of various parameters, mechanisms of H2S adsorption by alkaline carbons are not yet fully understood. The major difficulty seems to lie in the fact that little is known with certainty about the predominant reactions occurring on the carbon surface. In this study, the surface properties of alkaline activated carbons were systematically investigated to further exploit and better understand the mechanisms of H2S adsorption by alkaline activated carbons. Two commercially available alkaline activated carbons and their representative exhausted samples (8 samples collected at different height of the column after H2S breakthrough tests) were studied. The 8 portions of the exhausted carbon were used to represent the H2S/carbon reaction process. The surface properties of both the original and the exhausted carbons were characterized using the sorption of nitrogen (BET test), surface pH, Boehm titration, thermal and FTIR analysis. Porosity and surface area provide detailed information about the pore structure of the exhausted carbons with respect to the reaction extent facilitating the understanding of potential pore blockages. Results of Boehm titration and FTIR both demonstrate the significant effects of surface functional groups, and identification of oxidation products confirmed the different mechanisms involved with the two carbons. From the DTG curves of thermal analysis, two well-defined peaks representing two products of surface reactions (i.e., sulfur and sulfuric acid) were observed from the 8 exhausted portions with gradually changing patterns coinciding with the extent of the reaction. Surface pH values of the exhausted carbons show a clear trend of pH drop along the reaction extent, while pH around 2 was observed for the bottom of the bed indicating

Alkaline flocculation of Phaeodactylum tricornutum induced by brucite and calcite

DOE PAGES

Vandamme, Dries; Pohl, Philip I.; Beuckels, Annelies; ...

2015-08-20

Alkaline flocculation holds great potential as a low-cost harvesting method for marine microalgae biomass production. Alkaline flocculation is induced by an increase in pH and is related to precipitation of calcium and magnesium salts. In this study, we used the diatom Phaeodactylum tricornutum as model organism to study alkaline flocculation of marine microalgae cultured in seawater medium. Flocculation started when pH was increased to 10 and flocculation efficiency reached 90% when pH was 10.5, which was consistent with precipitation modeling for brucite or Mg(OH) 2. Compared to freshwater species, more magnesium is needed to achieve flocculation (>7.5 mM). Zeta potentialmore » measurements suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5 mM, flocculation was also observed at a pH of 10. Furthermore, zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism.« less

Extracellular Ca2(+)-dependent inducible alkaline phosphatase from extremely halophilic archaebacterium Haloarcula marismortui.

PubMed Central

Goldman, S; Hecht, K; Eisenberg, H; Mevarech, M

1990-01-01

When starved of inorganic phosphate, the extremely halophilic archaebacterium Haloarcula marismortui produces the enzyme alkaline phosphatase and secretes it to the medium. This inducible extracellular enzyme is a glycoprotein whose subunit molecular mass is 160 kDa, as estimated by sodium dodecyl sulfate-gel electrophoresis. The native form of the enzyme is heterogeneous and composed of multiple oligomeric forms. The enzymatic activity of the halophilic alkaline phosphatase is maximal at pH 8.5, and the enzyme is inhibited by phosphate. Unlike most alkaline phosphatases, the halobacterial enzyme requires Ca2+ and not Zn2+ ions for its activity. Both calcium ions (in the millimolar range) and NaCl (in the molar range) are required for the stability of the enzyme. Images PMID:2123861

Degradation of cellulose under alkaline conditions: new insights from a 12 years degradation study.

PubMed

Glaus, Martin A; Van Loon, Luc R

2008-04-15

Cellulose degradation under alkaline conditions is of relevance to the mobility of many cations of the transition metal, lanthanide, and actinide series in the geosphere because strong complexants such as isosaccharinic acids, 3-deoxy-2-C-hydroxymethyl-D-erythro-pentonic acid (alpha-ISA) and 3-deoxy-2-C-hydroxymethyl-D-threo-pentonic acid (beta-ISA) may be formed. In the context of the long-term safety of cementitious repositories for low- and intermediate-level radioactive waste, where large amounts of cellulose may be present, the question of the time scales needed for the complete degradation of cellulose is important. The present paper reports the results of a 12 year study of the degradation of four different cellulosic materials (pure cellulose, tissue, cotton, paper) in an artificial cement pore water under anaerobic conditions at approximately 25 degrees C. The observed reaction characteristics can be divided into a fast reaction phase (2-3 years), dominated by the stepwise conversion of terminal glucose monomeric units to alpha-ISA and beta-ISA, and a very slow reaction phase during which the same products were found. The slow rate of the alkaline degradation of cellulose during this second reaction phase shows that previous kinetic models of cellulose degradation did not adequately describe the long-term behavior under alkaline conditions and need to be reassessed. It is postulated that a previously unknown mechanism by which crystalline or inaccessible reducing end groups of the polysaccharide chain become temporarily susceptible to alkaline attack is responsible for the slow rate of cellulose degradation.

Determination of dipyrone in pharmaceutical preparations based on the chemiluminescent reaction of the quinolinic hydrazide-H2O2-vanadium(IV) system and flow-injection analysis.

PubMed

Pradana Pérez, Juan A; Durand Alegría, Jesús S; Hernando, Pilar Fernández; Sierra, Adolfo Narros

2012-01-01

A rapid, economic and sensitive chemiluminescent method involving flow-injection analysis was developed for the determination of dipyrone in pharmaceutical preparations. The method is based on the chemiluminescent reaction between quinolinic hydrazide and hydrogen peroxide in a strongly alkaline medium, in which vanadium(IV) acts as a catalyst. Principal chemical and physical variables involved in the flow-injection system were optimized using a modified simplex method. The variations in the quantum yield observed when dipyrone was present in the reaction medium were used to determine the concentration of this compound. The proposed method requires no preconcentration steps and reliably quantifies dipyrone over the linear range 1-50 µg/mL. In addition, a sample throughput of 85 samples/h is possible. Copyright © 2011 John Wiley & Sons, Ltd.

Methodology of analysis of very weak acids by isotachophoresis with electrospray-ionization mass-spectrometric detection: Anionic electrolyte systems for the medium-alkaline pH range.

PubMed

Malá, Zdena; Gebauer, Petr

2018-01-15

This work describes for the first time a functional electrolyte system setup for anionic isotachophoresis (ITP) with electrospray-ionization mass-spectrometric (ESI-MS) detection in the neutral to medium-alkaline pH range. So far no application was published on the analysis of very weak acids by anionic ITP-MS although there is a broad spectrum of potential analytes with pK a values in the range 5-10, where application of this technique promises interesting gains in both sensitivity and specificity. The problem so far was the lack of anionic ESI-compatible ITP systems in the mentioned pH range as all typical volatile anionic system components are fully ionized at neutral and alkaline pH and thus too fast to suit as terminators. We propose an original solution of the problem based on the combination of two ITP methods: (i) use of the hydroxyl ion as a natural and ESI-compatible terminator, and (ii) use of configurations based on moving-boundary ITP. The former method ensures effective stacking of analytes by an alkaline terminator of sufficiently low mobility and the latter offers increased flexibility for tuning of the separation window and selectivity according to actual needs. A theoretical description of the proposed model is presented and applied to the design of very simple functional electrolyte configurations. The properties of example systems are demonstrated by both computer simulation and experiments with a group of model analytes. Potential effects of carbon dioxide present in the solutions are demonstrated for particular systems. Experimental results confirm that the proposed methodology is well capable of performing sensitive and selective ITP-MS analyses of very weak acidic analytes (e.g. sulfonamides or chlorophenols). Copyright © 2017 Elsevier B.V. All rights reserved.

Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction.

PubMed

Yang, Liu; Cheng, Daojian; Xu, Haoxiang; Zeng, Xiaofei; Wan, Xin; Shui, Jianglan; Xiang, Zhonghua; Cao, Dapeng

2018-06-26

It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm -2 Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

Elucidating Performance Limitations in Alkaline-Exchange- Membrane Fuel Cells

DOE PAGES

Shiau, Huai-Suen; Zenyuk, Iryna V.; Weber, Adam Z.

2017-07-15

Water management is a serious concern for alkaline-exchange-membrane fuel cells (AEMFCs) because water is a reactant in the alkaline oxygen-reduction reaction and hydroxide conduction in alkaline-exchange membranes is highly hydration dependent. Here in this article, we develop and use a multiphysics, multiphase model to explore water management in AEMFCs. We demonstrate that the low performance is mostly caused by extremely non-uniform distribution of water in the ionomer phase. A sensitivity analysis of design parameters including humidification strategies, membrane properties, and water transport resistance was undertaken to explore possible optimization strategies. Furthermore, the strategy and issues of reducing bicarbonate/carbonate buildup inmore » the membrane-electrode assembly with CO 2 from air is demonstrated based on the model prediction. Overall, mathematical modeling is used to explore trends and strategies to overcome performance bottlenecks and help enable AEMFC commercialization.« less

Mechanism of alcohol-enhanced lucigenin chemiluminescence in alkaline solution.

PubMed

Chi, Quan; Chen, Wanying; He, Zhike

2015-11-01

The chemiluminescence (CL) of lucigenin (Luc(2+)) can be enhanced by different alcohols in alkaline solution. The effect of different fatty alcohols on the CL of lucigenin was related to the carbon chain length and the number of hydroxyl groups. Glycerol provides the greatest enhancement. UV/Vis absorption spectra and fluorescence spectra showed that N-methylacridone (NMA) was produced in the CL reaction in the presence of different alcohols. The peak of the CL spectrum was located at 470 nm in all cases, indicating that the luminophore was always the excited-state NMA. The quenching of lucigenin CL by superoxide dismutase (SOD) and the electron spin resonance (ESR) results with the spin trap of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) demonstrated that superoxide anions (O2 (•-)) were generated from dissolved oxygen in the CL reaction and that glycerol and dihydroxyacetone (DHA) can promote O2 (•-) production by the reduction of dissolved oxygen in alkaline solution. It was assumed that the enhancement provided by different alcohols was related to the solvent effect and reducing capacity. Glycerol and DHA can also reduce Luc(2+) into lucigenin cation radicals (Luc(•+) ), which react with O2 (•-) to produce CL, and glycerol can slowly transform into DHA, which is oxidized quickly in alkaline solution. Copyright © 2015 John Wiley & Sons, Ltd.

Electrochemical Oxidation of Resorcinol in Aqueous Medium Using Boron-Doped Diamond Anode: Reaction Kinetics and Process Optimization with Response Surface Methodology

PubMed Central

Körbahti, Bahadır K.; Demirbüken, Pelin

2017-01-01

Electrochemical oxidation of resorcinol in aqueous medium using boron-doped diamond anode (BDD) was investigated in a batch electrochemical reactor in the presence of Na2SO4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100–500 g/L), current density (2–10 mA/cm2), Na2SO4 concentration (0–20 g/L), and reaction temperature (25–45°C) was analyzed on electrochemical oxidation using response surface methodology (RSM). The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm2 current density, 12 g/L Na2SO4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction. PMID:29082225

Coordinate responses to alkaline pH stress in budding yeast

PubMed Central

Serra-Cardona, Albert; Canadell, David; Ariño, Joaquín

2015-01-01

Alkalinization of the medium represents a stress condition for the budding yeast Saccharomyces cerevisiae to which this organism responds with profound remodeling of gene expression. This is the result of the modulation of a substantial number of signaling pathways whose participation in the alkaline response has been elucidated within the last ten years. These regulatory inputs involve not only the conserved Rim101/PacC pathway, but also the calcium-activated phosphatase calcineurin, the Wsc1-Pkc1-Slt2 MAP kinase, the Snf1 and PKA kinases and oxidative stress-response pathways. The uptake of many nutrients is perturbed by alkalinization of the environment and, consequently, an impact on phosphate, iron/copper and glucose homeostatic mechanisms can also be observed. The analysis of available data highlights cases in which diverse signaling pathways are integrated in the gene promoter to shape the appropriate response pattern. Thus, the expression of different genes sharing the same signaling network can be coordinated, allowing functional coupling of their gene products. PMID:28357292

Alkaline nanoparticle coatings improve resin bonding of 10-methacryloyloxydecyldihydrogenphosphate-conditioned zirconia.

PubMed

Qian, Mengke; Lu, Zhicen; Chen, Chen; Zhang, Huaiqin; Xie, Haifeng

Creating an alkaline environment prior to 10-methacryloyloxydecyldihydrogenphosphate (MDP) conditioning improves the resin bonding of zirconia. The present study evaluated the effects of four alkaline coatings with different water solubilities and pH values on resin bonding of MDP-conditioned zirconia. Two alkaline nanoparticle coatings were studied in particular. Thermodynamics calculations were performed to evaluate the strengths of MDP-tetragonal phase zirconia chemical bonds at different pH values. Zirconia surfaces with and without alkaline coatings were characterized by scanning electron microscope (SEM)/energy dispersive spectrometer and Fourier transform infrared spectroscopy; alkaline coatings included NaOH, Ca(OH) 2 , nano-MgO, and nano-Zr(OH) 4 . A shear bond strength (SBS) test was performed to evaluate the effects of the four alkaline coatings on bonding; the alkaline coatings were applied to the surfaces prior to conditioning the zirconia with MDP-containing primers. Gibbs free energies of the MDP-tetragonal zirconia crystal model coordination reaction in different pH environments were -583.892 (NaOH), -569.048 [Ca(OH) 2 ], -547.393 (MgO), and -530.279 kJ/mol [Zr(OH) 4 ]. Thermodynamic calculations indicated that the alkaline coatings improved bonding in the following order: NaOH > Ca(OH) 2 > MgO > Zr(OH) 4 . Statistical analysis of SBS tests showed a different result. SBSs were significantly different in groups that had different alkaline coatings, but it was not influenced by different primers. All four alkaline coatings increased SBS compared to control groups. Of the four coatings, nano-Zr(OH) 4 and -MgO showed higher SBS. Therefore, preparing nano-Zr(OH) 4 or -MgO coatings prior to conditioning with MDP-containing primers may potentially improve resin bonding of zirconia in the clinic.

Alkaline nanoparticle coatings improve resin bonding of 10-methacryloyloxydecyldihydrogenphosphate-conditioned zirconia

PubMed Central

Qian, Mengke; Lu, Zhicen; Chen, Chen; Zhang, Huaiqin; Xie, Haifeng

2016-01-01

Creating an alkaline environment prior to 10-methacryloyloxydecyldihydrogenphosphate (MDP) conditioning improves the resin bonding of zirconia. The present study evaluated the effects of four alkaline coatings with different water solubilities and pH values on resin bonding of MDP-conditioned zirconia. Two alkaline nanoparticle coatings were studied in particular. Thermodynamics calculations were performed to evaluate the strengths of MDP-tetragonal phase zirconia chemical bonds at different pH values. Zirconia surfaces with and without alkaline coatings were characterized by scanning electron microscope (SEM)/energy dispersive spectrometer and Fourier transform infrared spectroscopy; alkaline coatings included NaOH, Ca(OH)2, nano-MgO, and nano-Zr(OH)4. A shear bond strength (SBS) test was performed to evaluate the effects of the four alkaline coatings on bonding; the alkaline coatings were applied to the surfaces prior to conditioning the zirconia with MDP-containing primers. Gibbs free energies of the MDP-tetragonal zirconia crystal model coordination reaction in different pH environments were −583.892 (NaOH), −569.048 [Ca(OH)2], −547.393 (MgO), and −530.279 kJ/mol [Zr(OH)4]. Thermodynamic calculations indicated that the alkaline coatings improved bonding in the following order: NaOH > Ca(OH)2 > MgO > Zr(OH)4. Statistical analysis of SBS tests showed a different result. SBSs were significantly different in groups that had different alkaline coatings, but it was not influenced by different primers. All four alkaline coatings increased SBS compared to control groups. Of the four coatings, nano-Zr(OH)4 and -MgO showed higher SBS. Therefore, preparing nano-Zr(OH)4 or -MgO coatings prior to conditioning with MDP-containing primers may potentially improve resin bonding of zirconia in the clinic. PMID:27785013

Iron carbide encapsulated by porous carbon nitride as bifunctional electrocatalysts for oxygen reduction and evolution reactions

NASA Astrophysics Data System (ADS)

Wei, Liangqin; Sun, Hongdi; Yang, Tiantian; Deng, Shenzhen; Wu, Mingbo; Li, Zhongtao

2018-05-01

Herein, the study reports a facile and scale-up able strategy to synthesize metal organic frameworks (MOFs) Fe-7,7,8,8-Tetracyanoquinodimethane (Fe-TCNQ) as precursors to develop non-precious metal bifunctional electrocatalysts through a one-step hydrothermal route. Then, Fe3C/carbon nitride (Fe3C@CNx) core-shell structure composites are readily available through pyrolyzing Fe-TCNQ at reasonable temperature, during which hierarchical porous structures with multimodal porosity formed. Nitrogen doped porosity carbon layers can facilitate mass access to active sites and accelerate reaction. Consequently, the optimized catalyst exhibits superior oxygen reduction reaction (ORR) electrocatalytic activity and better catalytic activity for oxygen evolution reaction (OER) in alkaline medium than that of Pt/C, which can be attributed to the synergistic effect of strong coupling between Fe3C and nitrogen doped carbon shells, active sites Fe-NX, optimal level of nitrogen doping, and appropriate multimodal porosity.

Evaluation studies on carbon supported catalysts for oxygen reduction in alkaline medium

NASA Technical Reports Server (NTRS)

Srinivasan, Vakula S.; Singer, Joseph

1986-01-01

This paper describes tests designed to predict the performance of fuel cell electrodes, as applied to an alkaline oxygen-fuel cell having specially fabricated porous-carbon electrodes with various amounts of dispersed platinum or gold as active catalysts. The tests are based on information obtained from the techniques of cyclic voltammetry and polarization. The parameters obtained from cyclic voltammetry were of limited use in predicting fuel cell performance of the cathode. On the other hand, half-cell polarization measurements offered close simulation of the oxygen electrode, although a predictor of the electrode life is still lacking. The very low polarization of the Au-10 percent Pt catalytic electrode suggests that single-phase catalysts should be considered.

The Effect of Alkaline Concentration on Coconut Husk Crystallinity and the Yield of Sugars Released

NASA Astrophysics Data System (ADS)

Sangian, H. F.; Widjaja, A.

2018-02-01

This work was to analyze the effect of alkaline concentration on coconut coir husk crystallinity and sugar liberated enzymatically. The data showed that the employing of alkaline on lignocellulose transformed the crystallinity. The XRD peaks increased highly which indicated that cellulose was more opened and exposed. After pretreatment, the chemical compositions (cellulose, hemicellulose, and lignin) were changed significantly. The employing 1% alkaline, the cellulosic content inclined if compared to that of non-pretreatment. When the alkaline concentration was added to 4%, the cellulose was decreased slightly which indicated that a part of cellulose and hemicellulose was dissolved into solution. It was found the alkaline pretreatment influenced by the biochemical reaction of treated substrates in producing the reducing sugars. The amounts of sugar liberated enzymatically of coconut husk treated by 1% and 4% alkaline increased to 0.26, and 0.24 g sugar/g (cellulose+hemicellulose), respectively, compared to that of native solid recorded at 0.18 g sugar/g (cellulose+hemicellulose).

Prophylactic treatment with alkaline phosphatase in cardiac surgery induces endogenous alkaline phosphatase release.

PubMed

Kats, Suzanne; Brands, Ruud; Hamad, Mohamed A Soliman; Seinen, Willem; Scharnhorst, Volkher; Wulkan, Raymond W; Schönberger, Jacques P; Oeveren, Wim van

2012-02-01

Laboratory and clinical data have implicated endotoxin as an important factor in the inflammatory response to cardiopulmonary bypass. We assessed the effects of the administration of bovine intestinal alkaline phosphatase (bIAP), an endotoxin detoxifier, on alkaline phosphatase levels in patients undergoing coronary artery bypass grafting. A total of 63 patients undergoing coronary artery bypass grafting were enrolled and prospectively randomized. Bovine intestinal alkaline phosphatase (n=32) or placebo (n=31) was administered as an intravenous bolus followed by continuous infusion for 36 hours. The primary endpoint was to evaluate alkaline phosphatase levels in both groups and to find out if administration of bIAP to patients undergoing CABG would lead to endogenous alkaline phosphatase release. No significant adverse effects were identified in either group. In all the 32 patients of the bIAP-treated group, we found an initial rise of plasma alkaline phosphatase levels due to bolus administration (464.27±176.17 IU/L). A significant increase of plasma alkaline phosphatase at 4-6 hours postoperatively was observed (354.97±95.00 IU/L) as well. Using LHA inhibition, it was shown that this second peak was caused by the generation of tissue non specific alkaline phosphatase (TNSALP-type alkaline phosphatase). Intravenous bolus administration plus 8 hours continuous infusion of alkaline phosphatase in patients undergoing coronary artery bypass grafting with cardiopulmonary bypass results in endogenous alkaline phosphatase release. This endogenous alkaline phosphatase may play a role in the immune defense system.

Production of Alkaline Cellulase by Fungi Isolated from an Undisturbed Rain Forest of Peru

PubMed Central

Vega, Karin; Villena, Gretty K.; Sarmiento, Victor H.; Ludeña, Yvette; Vera, Nadia; Gutiérrez-Correa, Marcel

2012-01-01

Alkaline cellulase producing fungi were isolated from soils of an undisturbed rain forest of Peru. The soil dilution plate method was used for the enumeration and isolation of fast growing cellulolytic fungi on an enriched selective medium. Eleven out of 50 different morphological colonies were finally selected by using the plate clearing assay with CMC as substrate at different pH values. All 11 strains produced cellulases in liquid culture with activities at alkaline pH values without an apparent decrease of them indicating that they are true alkaline cellulase producers. Aspergillus sp. LM-HP32, Penicillium sp. LM-HP33, and Penicillium sp. LM-HP37 were the best producers of FP cellulase (>3 U mL−1) with higher specific productivities (>30 U g−1 h−1). Three strains have been found suitable for developing processes for alkaline cellulase production. Soils from Amazonian rain forests are good sources of industrial fungi with particular characteristics. The results of the present study are of commercial and biological interest. Alkaline cellulases may be used in the polishing and washing of denim processing of the textile industry. PMID:23213539

Heterologous expression, biochemical characterization, and overproduction of alkaline α-amylase from Bacillus alcalophilus in Bacillus subtilis

PubMed Central

2011-01-01

Background Alkaline α-amylases have potential applications for hydrolyzing starch under high pH conditions in the starch and textile industries and as ingredients in detergents for automatic dishwashers and laundries. While the alkaline α-amylase gains increased industrial interest, the yield of alkaline α-amylases from wild-type microbes is low, and the combination of genetic engineering and process optimization is necessary to achieve the overproduction of alkaline α-amylase. Results The alkaline α-amylase gene from Bacillus alcalophilus JN21 (CCTCC NO. M 2011229) was cloned and expressed in Bacillus subtilis strain WB600 with vector pMA5. The recombinant alkaline α-amylase was stable at pH from 7.0 to 11.0 and temperature below 40°C. The optimum pH and temperature of alkaline α-amylase was 9.0 and 50°C, respectively. Using soluble starch as the substrate, the Km and Vmax of alkaline α-amylase were 9.64 g/L and 0.80 g/(L·min), respectively. The effects of medium compositions (starch, peptone, and soybean meal) and temperature on the recombinant production of alkaline α-amylase in B. subtilis were investigated. Under the optimal conditions (starch concentration 0.6% (w/v), peptone concentration 1.45% (w/v), soybean meal concentration 1.3% (w/v), and temperature 37°C), the highest yield of alkaline α-amylase reached 415 U/mL. The yield of alkaline α-amylase in a 3-L fermentor reached 441 U/mL, which was 79 times that of native alkaline α-amylase from B. alcalophilus JN21. Conclusions This is the first report concerning the heterologous expression of alkaline α-amylase in B. subtilis, and the obtained results make it feasible to achieve the industrial production of alkaline α-amylase with the recombinant B. subtilis. PMID:21978209

Enhanced decomposition of 1,4-dioxane in water by ozonation under alkaline condition.

PubMed

Tian, Gui-Peng; Wu, Qian-Yuan; Li, Ang; Wang, Wen-Long; Hu, Hong-Ying

2014-01-01

1,4-Dioxane is a probable human carcinogenic and refractory substance that is widely detected in aquatic environments. Traditional wastewater treatment processes, including activated sludge, cannot remove 1,4-dioxane. Removing 1,4-dioxane with a reaction kinetic constant of 0.32 L/(mol·s) by using ozone, a strong oxidant, is difficult. However, under alkaline environment, ozone generates a hydroxyl radical (•OH) that exhibits strong oxidative potential. Thus, the ozonation of 1,4-dioxane in water under different pH conditions was investigated in this study. In neutral solution, with an inlet ozone feed rate of 0.19 mmol/(L·min), the removal efficiency of 1,4-dioxane was 7.6% at 0.5 h, whereas that in alkaline solution was higher (16.3-94.5%) within a pH range of 9-12. However, the removal efficiency of dissolved organic carbon was considerably lower than that of 1,4-dioxane. This result indicates that several persistent intermediates were generated during 1,4-dioxane ozonation. The pseudo first-order reaction further depicted the reaction of 1,4-dioxane. The obvious kinetic constants (kobs) at pH 9, 10, 11 and 12 were 0.94, 2.41, 24.88 and 2610 L/(mol·s), respectively. Scavenger experiments on radical species indicated that •OH played a key role in removing 1,4-dioxane during ozonation under alkaline condition.

Free-standing ternary NiWP film for efficient water oxidation reaction

NASA Astrophysics Data System (ADS)

Yang, Yunpeng; Zhou, Kuo; Ma, Lili; Liang, Yanqin; Yang, Xianjin; Cui, Zhenduo; Zhu, Shengli; Li, Zhaoyang

2018-03-01

High-efficient catalysts for oxygen evolution reaction (OER) is of great concern in improving energy efficiency for water splitting. Here we report a high-performance OER electrocatalyst of nickel-tungsten-phosphorus (NiWP) film prepared by template method. This free-standing ternary electrocatalyst exhibits a remarkable electrocatalytic activity of OER in alkaline medium due to the synergetic effect among these elements and the good electrical conductivity. The reported NiWP composite catalyst has an overpotential of as low as 0.4 V (vs. RHE) at 30 mA cm-2, better than that of the commercial RuO2 catalyst. Moreover, a small charge transfer resistance of 4.06 Ω and a Tafel slope of 68 mV dec-1 demonstrate the outstanding catalytic activity.

Influence of culture medium supplementation of tobacco NT1 cell suspension cultures on the N-glycosylation of human secreted alkaline phosphatase.

PubMed

Becerra-Arteaga, Alejandro; Shuler, Michael L

2007-08-15

We report for the first time that culture conditions, specifically culture medium supplementation with nucleotide-sugar precursors, can alter significantly the N-linked glycosylation of a recombinant protein in plant cell culture. Human secreted alkaline phosphatase produced in tobacco NT1 cell suspension cultures was used as a model system. Plant cell cultures were supplemented with ammonia (30 mM), galactose (1 mM) and glucosamine (10 mM) to improve the extent of N-linked glycosylation. The highest levels of cell density and active extracellular SEAP in supplemented cultures were on average 260 g/L and 0.21 U/mL, respectively, compared to 340 g/L and 0.4 U/mL in unsupplemented cultures. The glycosylation profile of SEAP produced in supplemented cultures was determined via electrospray ionization mass spectrometry with precursor ion scanning and compared to that of SEAP produced in unsupplemented cultures. In supplemented and unsupplemented cultures, two biantennary complex-type structures terminated with one or two N-acetylglucosamines and one paucimannosidic glycan structure comprised about 85% of the SEAP glycan pool. These three structures contained plant-specific xylose and fucose residues and their relative abundances were affected by each supplement. High mannose structures (6-9 mannose residues) accounted for the remaining 15% glycans in all cases. The highest proportion (approximately 66%) of a single complex-type biantennary glycan structure terminated in both antennae by N- acetylglucosamine was obtained with glucosamine supplementation versus only 6% in unsupplemented medium. This structure is amenable for in vitro modification to yield a more human-like glycan and could serve as a route to plant cell culture produced therapeutic glycoproteins. (c) 2007 Wiley Periodicals, Inc.

Alkaline Hydrothermal Vents as Electrochemical Reactors Driving an Auto-Trophic Origin of Life

NASA Astrophysics Data System (ADS)

Camprubi, E.; Lane, N.

2017-07-01

We report the reduction of CO2 to formaldehyde under simulated alkaline hydrothermal conditions. Formaldehyde is transformed into relevant sugars via the formose reaction. Acetyl phosphate can also be synthesised and phosphorylates organic molecules.

A real-time polymerase chain reaction-based protocol for low/medium-throughput Y-chromosome microdeletions analysis.

PubMed

Segat, Ludovica; Padovan, Lara; Doc, Darja; Petix, Vincenzo; Morgutti, Marcello; Crovella, Sergio; Ricci, Giuseppe

2012-12-01

We describe a real-time polymerase chain reaction (PCR) protocol based on the fluorescent molecule SYBR Green chemistry, for a low- to medium-throughput analysis of Y-chromosome microdeletions, optimized according to the European guidelines and aimed at making the protocol faster, avoiding post-PCR processing, and simplifying the results interpretation. We screened 156 men from the Assisted Reproduction Unit, Department of Obstetrics and Gynecology, Institute for Maternal and Child Health IRCCS Burlo Garofolo (Trieste, Italy), 150 not presenting Y-chromosome microdeletion, and 6 with microdeletions in different azoospermic factor (AZF) regions. For each sample, the Zinc finger Y-chromosomal protein (ZFY), sex-determining region Y (SRY), sY84, sY86, sY127, sY134, sY254, and sY255 loci were analyzed by performing one reaction for each locus. AZF microdeletions were successfully detected in six individuals, confirming the results obtained with commercial kits. Our real-time PCR protocol proved to be a rapid, safe, and relatively cheap method that was suitable for a low- to medium-throughput diagnosis of Y-chromosome microdeletion, which allows an analysis of approximately 10 samples (with the addition of positive and negative controls) in a 96-well plate format, or approximately 46 samples in a 384-well plate for all markers simultaneously, in less than 2 h without the need of post-PCR manipulation.

Porous boron doped diamonds as metal-free catalysts for the oxygen reduction reaction in alkaline solution

NASA Astrophysics Data System (ADS)

Suo, Ni; Huang, Hao; Wu, Aimin; Cao, Guozhong; Hou, Xiaoduo; Zhang, Guifeng

2018-05-01

Porous boron doped diamonds (BDDs) were obtained on foam nickel substrates with a porosity of 80%, 85%, 90% and 95% respectively by hot filament chemical vapor deposition (HFCVD) technology. Scanning electron microscopy (SEM) reveals that uniform and compact BDDs with a cauliflower-like morphology have covered the overall frame of the foam nickel substrates. Raman spectroscopy shows that the BDDs have a poor crystallinity due to heavily doping boron. X-ray photoelectron spectroscopy (XPS) analysis effectively demonstrates that boron atoms can be successfully incorporated into the crystal lattice of diamonds. Electrochemical measurements indicate that the oxygen reduction potential is unaffected by the specific surface area (SSA), and both the onset potential and the limiting diffusion current density are enhanced with increasing SSA. It is also found that the durability and methanol tolerance of the boron doped diamond catalysts are attenuated as the increasing of SSA. The SSA of the catalyst is directly proportional to the oxygen reduction activity and inversely to the durability and methanol resistance. These results provide a reference to the application of porous boron doped diamonds as potential cathodic catalysts for the oxygen reduction reaction in alkaline solution by adjusting the SSA.

Electrochemical behavior of meso-substituted iron porphyrins in alkaline aqueous media

NASA Astrophysics Data System (ADS)

Berezina, N. M.; Bazanov, M. I.; Maksimova, A. A.; Semeikin, A. S.

2017-12-01

The effect meso-substitution in iron porphyrin complexes has on their redox behavior in alkaline aqueous solutions is studied via cyclic voltammetry. The voltammetric features of the reduction of iron pyridylporphyrins suggest that the sites of electron transfer lie at the ligand, the metal ion, and the pyridyl moieties. The electron transfer reactions between the different forms of these compounds, including the oxygen reduction reaction they mediate, are outlined to show the sequence and potential ranges in which they occur in alkaline aqueous media. Under our experimental conditions, the iron porphyrins exist as μ-oxo dimmers whose activity for the electrocatalytic reduction of oxygen displays a considerable dependence on the nature of the substitutents and nitrogen isomerization (for pyridylporphyrins) and grows in the order (Fe( ms-Ph)4P)2O, (Fe[ ms-(Py-3)Ph3]P)2O, (Fe[ ms-(Py-4)4]P)2O, and (Fe[ ms-(Py-3)4]P)2O.

Effect of medium acidity on the thermodynamics and kinetics of the reaction of pyridoxal 5'-phosphate with isoniazid in an aqueous solution

NASA Astrophysics Data System (ADS)

Gamov, G. A.; Zavalishin, M. N.; Usacheva, T. R.; Sharnin, V. A.

2017-05-01

Thermodynamic characteristics of the formation of the Schiff base between isoniazid and pyridoxal 5'-phosphate in an aqueous solution at different pH values of a medium are determined by means of spectrophotometry and calorimetric titration. The process kinetics is studied spectrophotometrically, and the reaction rate constants for the formation of the imine at different acidities of a medium are determined. Biochemical aspects of the binding of pyridoxal 5'-phosphate into stable compounds are discussed.

pH regulation of recombinant glucoamylase production in Fusarium venenatum JeRS 325, a transformant with a Fusarium oxysporum alkaline (trypsin-like) protease promoter.

PubMed

Wiebe, M G; Robson, G D; Shuster, J R; Trinci, A P

1999-08-05

Fusarium venenatum (formerly Fusarium graminearum) JeRS 325 produces heterologous glucoamylase (GAM) under the regulation of a Fusarium oxysporum alkaline (trypsin-like) protease promoter. The glucoamylase gene was used as a reporter gene to study the effects of ammonium and pH on GAM production under the control of the alkaline protease promoter. Between pH 4.0 and 5.8, GAM production in glucose-limited chemostat cultures of JeRS 325 grown at a dilution rate of 0.10 h-1 (doubling time, 6.9 h) on (NH4)2SO4 medium increased in a linear manner with increase in pH. However, at pH 4.0 and below GAM production was almost completely repressed in glucose-limited chemostat cultures grown on (NH4)2SO4 or NaNO3 medium. Thus GAM production in JeRS 325 is regulated by culture pH, not by the nature of the nitrogen source in the medium. The difficulty of using unbuffered medium when investigating putative ammonium repression is also shown. The study demonstrates the potential for use of the alkaline protease promoter in F. graminearum for the production of recombinant proteins in a pH dependent man ner. Copyright 1999 John Wiley & Sons, Inc.

Nickel/metal hydride secondary batteries using an alkaline solid polymer electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vassal, N.; Salmon, E.; Fauvarque, J.F.

1999-01-01

Sealed alkaline solid polymer electrolyte nickel/metal hydride laboratory cells have been constructed and tested to evaluate their properties. Studies of the cycle life, self-discharge, and behavior of cells at different temperatures were carried out. The first results on the electrochemical behavior of an alkaline solid polymer electrolyte [based on poly(ethylene oxide), potassium hydroxide, and water] medium are presented here and show good reversibility of this all-solid-state system for more than 500 cycles, without significant loss of capacity and with a reasonable average discharge efficiency (close to 80%). The temperature-dependence study allowed the determination of optimum operating conditions between 0 andmore » 40 C. Characteristics of the solid polymer electrolyte based Ni/MH cells are compared to those of several other rechargeable battery systems.« less

High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei

2017-01-18

The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkalinemore » solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.« less

Evaluation of High Solids Alkaline Pretreatment of Rice Straw

PubMed Central

Cheng, Yu-Shen; Zheng, Yi; Yu, Chao Wei; Dooley, Todd M.; Jenkins, Bryan M.

2010-01-01

Fresh-harvested, air-dried rice straw was pretreated at a water content of 5 g H2O/g straw using sodium hydroxide (NaOH) and compared to pretreatment at 10 g H2O/g straw by hydrated lime (Ca(OH)2). Full factorial experiments including parallel wash-only treatments were completed with both sources of alkali. The experiments were designed to measure the effects of alkaline loading and pretreatment time on delignification and sugar yield upon enzymatic hydrolysis. Reaction temperature was held constant at 95°C for lime pretreatment and 55°C for NaOH pretreatment. The range of delignification was 13.1% to 27.0% for lime pretreatments and was 8.6% to 23.1% for NaOH pretreatments. Both alkaline loading and reaction time had significant positive effects (p < 0.001) on delignification under the design conditions, but only alkaline loading had a significant positive effect on enzymatic hydrolysis. Treatment at higher temperature also improved delignification; delignification with water alone ranged from 9.9% to 14.5% for pretreatment at 95°C, but there was little effect observed at 55°C. Post-pretreatment washing of biomass was not necessary for subsequent enzymatic hydrolysis. Maximum glucose yields were 176.3 mg/g dried biomass (48.5% conversion efficiency of total glucose) in lime-pretreated and unwashed biomass and were 142.3 mg/g dried biomass (39.2% conversion efficiency of total glucose) in NaOH-pretreated and unwashed biomass. PMID:20440580

Electrodeposition of Nickel Nanoparticles for the Alkaline Hydrogen Evolution Reaction: Correlating Electrocatalytic Behavior and Chemical Composition.

PubMed

Tao, Shasha; Yang, Florent; Schuch, Jona; Jaegermann, Wolfram; Kaiser, Bernhard

2018-03-09

Ni nanoparticles (NPs) consisting of Ni, NiO, and Ni(OH) 2 were formed on Ti substrates by electrodeposition as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. Additionally, the deposition parameters including the potential range and the scan rate were varied, and the resulting NPs were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. The chemical composition of the NPs changed upon using different conditions, and it was found that the catalytic activity increased with an increase in the amount of NiO. From these data, optimized NPs were synthesized; the best sample showed an onset potential of approximately 0 V and an overpotential of 197 mV at a cathodic current density of 10 mA cm -2 as well as a small Tafel slope of 88 mV dec -1 in 1 m KOH, values that are comparable to those of Pt foil. These NPs consist of approximately 25 % Ni and Ni(OH) 2 each, as well as approximately 50 % NiO. This implies that to obtain a successful HER electrocatalyst, active sites with differing compositions have to be close to each other to promote the different reaction steps. Long-time measurements (30 h) showed almost complete transformation of the highly active catalyst compound consisting of Ni 0 , NiO, and Ni(OH) 2 into the less active Ni(OH) 2 phase. Nevertheless, the here-employed electrodeposition of nonprecious metal/metal-oxide combination compounds represents a promising alternative to Pt-based electrocatalysts for water reduction to hydrogen. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extracting nuclear sizes of medium to heavy nuclei from total reaction cross sections

NASA Astrophysics Data System (ADS)

Horiuchi, W.; Hatakeyama, S.; Ebata, S.; Suzuki, Y.

2016-04-01

Background: Proton and neutron radii are fundamental quantities of atomic nuclei. To study the sizes of short-lived unstable nuclei, there is a need for an alternative to electron scattering. Purpose: The recent paper by Horiuchi et al. [Phys. Rev. C 89, 011601(R) (2014)], 10.1103/PhysRevC.89.011601 proposed a possible way of extracting the matter and neutron-skin thickness of light- to medium-mass nuclei using total reaction cross section, σR. The analysis is extended to medium to heavy nuclei up to lead isotopes with due attention to Coulomb breakup contributions as well as density distributions improved by paring correlation. Methods: We formulate a quantitative calculation of σR based on the Glauber model including the Coulomb breakup. To substantiate the treatment of the Coulomb breakup, we also evaluate the Coulomb breakup cross section due to the electric dipole field in a canonical-basis-time-dependent-Hartree-Fock-Bogoliubov theory in the three-dimensional coordinate space. Results: We analyze σR's of 103 nuclei with Z =20 , 28, 40, 50, 70, and 82 incident on light targets, H,21, 4He, and 12C. Three kinds of Skyrme interactions are tested to generate those wave functions. To discuss possible uncertainty due to the Coulomb breakup, we examine its dependence on the target, the incident energy, and the Skyrme interaction. The proton is a most promising target for extracting the nuclear sizes as the Coulomb excitation can safely be neglected. We find that the so-called reaction radius, aR=√{σR/π } , for the proton target is very well approximated by a linear function of two variables, the matter radius and the skin thickness, in which three constants depend only on the incident energy. We quantify the accuracy of σR measurements needed to extract the nuclear sizes. Conclusions: The proton is the best target because, once the incident energy is set, its aR is very accurately determined by only the matter radius and neutron-skin thickness. If σR's at

Acid and alkaline phosphatase localization in the digestive tract mucosa of the Hemisorubim platyrhynchos.

PubMed

Faccioli, Claudemir Kuhn; Chedid, Renata Alari; Mori, Ricardo Hideo; Amaral, Antônio Carlos do; Franceschini-Vicentini, Irene Bastos; Vicentini, Carlos Alberto

2016-09-01

This cytochemical study investigated the acid and alkaline phosphatase of the digestive tract of Hemisorubim platyrhynchos. Acid phosphatase was detected in the lining epithelium throughout the digestive tract, whereas alkaline phosphatase was only observed in the intestine. In the esophagus, an acid phosphatase reaction occurred in the apical cytoplasm of the epithelial cells and was related to epithelial protection and freeing of superficial cells for sloughing. Similar results were also observed in epithelial cells of gastric epithelium. In the gastric glands, acid phosphatase occurred in lysosomes of the oxynticopeptic cells acting in the macromolecule degradation for use as an energy source, whereas in the vesiculotubular system, its presence could be related to secretion processes. Furthermore, acid phosphatase in the intestine occurred in microvilli and lysosomes of the enterocytes and was correlated to absorption and intracellular digestion. However, no difference was reported among the regions of the intestine. However, alkaline phosphatase reaction revealed a large number of reaction dots in the anterior intestine, with the number decreasing toward the posterior intestine. This enzyme has been related to several functions, highlighting its role in the nutrient absorption primarily in the anterior intestine but also being essential in pH regulation because this is a carnivorous species with many gastric glands with secretions that could damage the intestine. Copyright © 2016 Elsevier GmbH. All rights reserved.

The effect of reaction conditions on formation of wet precipitated calcium phosphates

NASA Astrophysics Data System (ADS)

Huang, Chen; Cao, Peng

2015-03-01

The precipitation process discussed in the present study involves the addition of alkaline solutions to an acidic calcium phosphate suspension. Several parameters (pH, pH buffer reagent, ageing and stirring) were investigated. The synthesized powders were calcined at 1000°C for 1 h in air, in order to study the thermal stability and crystalline phase compositions. X-ray diffraction (XRD) and ESEM analysis were used for sample characterization. It is found that all these processing parameters affect the crystalline phases evolved and resultant microstructures. Phase evolution occurred at an elevated pH level. The pH buffer reagent would affect both the phase composition and microstructure. Ageing was essential for the phase maturation. Stirring accelerated the reaction process by providing a homogeneous medium for precipitation.

Advanced inorganic separators for alkaline batteries

NASA Technical Reports Server (NTRS)

Sheibley, D. W. (Inventor)

1982-01-01

A flexible, porous battery separator comprising a coating applied to a porous, flexible substrate is described. The coating comprises: (1) a thermoplastic rubber-based resin which is insoluble and unreactive in the alkaline electrolyte; (2) a polar organic plasticizer which is reactive with the alkaline electrolyte to produce a reaction product which contains a hydroxyl group and/or a carboxylic acid group; and (3) a mixture of polar particulate filler materials which are unreactive with the electrolyte, the mixture comprising at least one first filler material having a surface area of greater than 25 meters sq/gram, at least one second filler material having a surface area of 10 to 25 sq meters/gram, wherein the volume of the mixture of filler materials is less than 45% of the total volume of the fillers and the binder, the filler surface area per gram of binder is about 20 to 60 sq meters/gram, and the amount of plasticizer is sufficient to coat each filler particle. A method of forming the battery separator is also described.

The Influence of Fe Substitution in Lanthanum Calcium Cobalt Oxide on the Oxygen Evolution Reaction in Alkaline Media

DOE PAGES

Abreu-Sepulveda, Maria A.; Dhital, Chetan; Huq, Ashfia; ...

2016-07-30

The effect due to systematic substitution of cobalt by iron in La 0.6Ca 0.4Co 1-xFe xO 3 towards the oxygen evolution reaction(OER) in alkaline media has been investigated. We synthesized these compounds by a facile glycine-nitrate synthesis and the phase formation was confirmed by X-ray diffraction and Neutron Diffraction elemental analysis. The apparent OER activity was evaluated by quasi steady state current measurements in alkaline media using a traditional three-electrode cell. X-ray photoelectron spectroscopy shows iron substitution causes an increase in the surface concentration of various cobalt oxidation states. Tafel slope in the vicinity of 60 mV/decade and electrochemical reactionmore » order towards OH- near unity were achieved for the unsubstituted La 0.6Ca 0.4CoO 3. Moreover, a decrease in the Tafel slope to 49 mV/decade was observed when iron is substituted in high amounts in the perovskite structure. The area specific current density showed dependence on the Fe fraction, however the relationship of specific current density with Fe fraction is not linear. High Fe substitutions, La 0.6Ca 0.4Co 0.2Fe 0.8O 3 and La 0.6Ca 0.4Co 0.1Fe 0.9O 3 showed higher area specific activity towards OER than La 0.6Ca 0.4CoO 3 or La 0.6Ca 0.4FeO 3. Finally, we believe iron inclusion in the cobalt sites of the perovskite helps decrease the electron transfer barrier and facilitates the formation of cobalt-hydroxide at the surface. Possible OER mechanisms based on the observed kinetic parameters will be discussed.« less

Study of aniline polymerization reactions through the particle size formation in acidic and neutral medium

NASA Astrophysics Data System (ADS)

Aribowo, Slamet; Hafizah, Mas Ayu Elita; Manaf, Azwar; Andreas

2018-04-01

In the present paper, we reported particle size kinetic studies on the conducting polyaniline (PANI) which synthesized through a chemical oxidative polymerization technique from aniline monomer. PANI was prepared using ammonium persulfate (APS) as oxidizing agent which carried out in acidic and neutral medium at various batch temperatures of respectively 20, 30 and 50 °C. From the studies, it was noticed that the complete polymerization reaction progressed within 480 minutes duration time. The pH of the solution during reaction kinetic reached values 0.8 - to 1.2 in acidic media, while in the neutral media the pH value reached values 3.8 - 4.9. The batch temperature controlled the polymerization reaction in which the reaction progressing, which followed by the temperature rise of solution above the batch temperature before settled down to the initial temperature. An increment in the batch temperature gave highest rise in the solution temperature for the two media which cannot be more than 50 °C. The final product of polymerization reaction was PANI confirmed by Fourier Transform Infra-Red (FTIR) spectrophotometer for molecule structure identification. The averages particle size of PANI which carried out in the two different media is evidently similar in the range 30 - 40 μm and insensitive to the batch temperature. However, the particle size of PANI which obtained from the polymerization reaction at a batch temperature of 50 °C under acidic condition reached ˜53.1 μm at the tip of the propagation stage which started in the first 5 minutes. The size is obviously being the largest among the batch temperatures. Whereas, under neutral condition the particle size is much larger which reached the size 135 μm at the batch temperature of 20 °C. It is concluded that the particle size formation during the polymerization reaction being one of the important parameter to determine particle growing of polymer which indicated the reaction kinetics mechanism of synthesize

Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Shizhong; White, Michael G.; Liu, Ping

We reported a detailed mechanistic study of the oxygen reduction reaction (ORR) on the model Ag(111) surface in alkaline solution by using density functional theory (DFT) and Kinetic Monte Carlo (KMC) simulations, in which multiple pathways involving either 2 e - or 4 e - mechanisms were included. The theoretical modelling presented here is able to reproduce the experimentally measured polarization curves in both low and high potential regions. An electrochemical 4 e - network including both a chemisorbed water (*H 2O)-mediated 4 e - associative pathway and the conventional associative pathway was identified to dominate the ORR mechanism. Onmore » the basis of the mechanistic understanding derived from these calculations, the ways to promote the ORR on Ag(111) were provided, including facilitating *OH removal, **O 2 reduction by *H 2O, and suppressing **O 2 desorption. Finally, the origin of the different ORR behaviors of Ag(111) and Pt(111) was also discussed in detail.« less

Oxygen Reduction Reaction on Ag(111) in Alkaline Solution: A Combined Density Functional Theory and Kinetic Monte Carlo Study

DOE PAGES

Liu, Shizhong; White, Michael G.; Liu, Ping

2018-01-25

We reported a detailed mechanistic study of the oxygen reduction reaction (ORR) on the model Ag(111) surface in alkaline solution by using density functional theory (DFT) and Kinetic Monte Carlo (KMC) simulations, in which multiple pathways involving either 2 e - or 4 e - mechanisms were included. The theoretical modelling presented here is able to reproduce the experimentally measured polarization curves in both low and high potential regions. An electrochemical 4 e - network including both a chemisorbed water (*H 2O)-mediated 4 e - associative pathway and the conventional associative pathway was identified to dominate the ORR mechanism. Onmore » the basis of the mechanistic understanding derived from these calculations, the ways to promote the ORR on Ag(111) were provided, including facilitating *OH removal, **O 2 reduction by *H 2O, and suppressing **O 2 desorption. Finally, the origin of the different ORR behaviors of Ag(111) and Pt(111) was also discussed in detail.« less

Silica in alkaline brines

USGS Publications Warehouse

Jones, B.F.; Rettig, S.L.; Eugster, H.P.

1967-01-01

Analysis of sodium carbonate-bicarbonate brines from closed basins in volcanic terranes of Oregon and Kenya reveals silica contents of up to 2700 parts per million at pH's higher than 10. These high concentrations of SiO 2 can be attributed to reaction of waters with silicates, and subsequent evaporative concentration accompanied by a rise in pH. Supersaturation with respect to amorphous silica may occur and persist for brines that are out of contact with silicate muds and undersaturated with respect to trona; correlation of SiO2 with concentration of Na and total CO2 support this interpretation. Addition of moredilute waters to alkaline brines may lower the pH and cause inorganic precipitation of substantial amounts of silica.

Supercritical CO2 as a reaction medium for synthesis of capsaicin analogues by lipase-catalyzed transacylation of capsaicin.

PubMed

Kobata, Kenji; Kobayashi, Mamiko; Kinpara, Sachiyo; Watanabe, Tatsuo

2003-09-01

Capsaicin analogues having different acyl moiety were synthesized by lipase-catalyzed transacylation of capsaicin with a corresponding acyl donor in supercritical CO2 as a reaction medium. Transacylation with methyl tetradecanoate using Novozym 435 as a catalyst gave vanillyl tetradecanamide in a 54% yield at 80 degrees C and 19 MPa over 72 h. Vanillyl (Z)-9-octadecenamide, olvanil, was synthesized from triolein in a 21% yield over 7 d.

Inhibition of Alkaline Flocculation by Algal Organic Matter for Chlorella vulgaris

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vandamme, Dries; Beuckels, Annelies; Vadelius, Eric

2016-01-01

Alkaline flocculation is a promising strategy for the concentration of microalgae for bulk biomass production. However, previous studies have shown that biological changes during the cultivation negatively affect flocculation efficiency. The influence of changes in cell properties and in the quality and composition of algal organic matter (AOM) were studied using Chlorella vulgaris as a model species. In batch cultivation, flocculation was increasingly inhibited over time and mainly influenced by changes in medium composition, rather than biological changes at the cell surface. Total carbohydrate content of the organic matter fraction sized bigger than 3 kDa increased over time and thismore » fraction was shown to be mainly responsible for the inhibition of alkaline flocculation. The monosaccharide identification of this fraction mainly showed the presence of neutral and anionic monosaccharides. An addition of 30–50 mg L -1 alginic acid, as a model for anionic carbohydrate polymers containing uronic acids, resulted in a complete inhibition of flocculation. Furthermore, these results suggest that inhibition of alkaline flocculation was caused by interaction of anionic polysaccharides leading to an increased flocculant demand over time.« less

Role of chemical composition in the enhanced catalytic activity of Pt-based alloyed ultrathin nanowires for the hydrogen oxidation reaction under alkaline conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Megan E. Scofield; Wong, Stanislaus S.; Zhou, Yuchen

2016-05-11

With the increased interest in the development of hydrogen fuel cells as a plausible alternative to internal combustion engines, recent work has focused on creating alkaline fuel cells (AFC), which employ an alkaline environment. Working in alkaline as opposed to acidic media yields a number of tangible benefits, including (i) the ability to use cheaper and plentiful precious-metal-free catalysts, due to their increased stability, (ii) a reduction in the amount of degradation and corrosion of Pt-based catalysts, and (iii) a longer operational lifetime for the overall fuel cell configuration. However, in the absence of Pt, no catalyst has achieved activitiesmore » similar to those of Pt. Herein, we have synthesized a number of crystalline ultrathin PtM alloy nanowires (NWs) (M = Fe, Co, Ru, Cu, Au) in order to replace a portion of the costly Pt metal without compromising on activity while simultaneously adding in metals known to exhibit favorable synergistic ligand and strain effects with respect to the host lattice. In fact, our experiments confirm theoretical insights about a clear and correlative dependence between measured activity and chemical composition. We have conclusively demonstrated that our as-synthesized alloy NW catalysts yield improved hydrogen oxidation reaction (HOR) activities as compared with a commercial Pt standard as well as with our as-synthesized Pt NWs. The Pt 7Ru 3 NW system, in particular, quantitatively achieved an exchange current density of 0.493 mA/cm 2, which is higher than the corresponding data for Pt NWs alone. In addition, the HOR activities follow the same expected trend as their calculated hydrogen binding energy (HBE) values, thereby confirming the critical importance and correlation of HBE with the observed activities.« less

Electro-oxidation of methanol on gold in alkaline media: Adsorption characteristics of reaction intermediates studied using time resolved electro-chemical impedance and surface plasmon resonance techniques

NASA Astrophysics Data System (ADS)

Assiongbon, K. A.; Roy, D.

2005-12-01

Electro-catalytic oxidation of methanol is the anode reaction in direct methanol fuel cells. We have studied the adsorption characteristics of the intermediate reactants of this multistep reaction on a gold film electrode in alkaline solutions by combining surface plasmon resonance (SPR) measurements with Fourier transform electro-chemical impedance spectroscopy (FT-EIS). Methanol oxidation in this system shows no significant effects of "site poisoning" by chemisorbed CO. Our results suggest that OH - chemisorbed onto Au acts as a stabilizing agent for the surface species of electro-active methanol. Double layer charging/discharging and adsorption/desorption of OH - show more pronounced effects than adsorption/oxidation of methanol in controlling the surface charge density of the Au substrate. These effects are manifested in both the EIS and the SPR data, and serve as key indicators of the surface reaction kinetics. The data presented here describe the important role of adsorbed OH - in electro-catalysis of methanol on Au, and demonstrate how SPR and FT-EIS can be combined for quantitative probing of catalytically active metal-solution interfaces.

Rapid Detection of Haptoglobin Gene Deletion in Alkaline-Denatured Blood by Loop-Mediated Isothermal Amplification Reaction

PubMed Central

Soejima, Mikiko; Egashira, Kouichi; Kawano, Hiroyuki; Kawaguchi, Atsushi; Sagawa, Kimitaka; Koda, Yoshiro

2011-01-01

Anhaptoglobinemic patients run the risk of severe anaphylactic transfusion reaction because they produce serum haptoglobin antibodies. Being homozygous for the haptoglobin gene deletion allele (HPdel) is the only known cause of congenital anhaptoglobinemia, and detection of HPdel before transfusion is important to prevent anaphylactic shock. In this study, we developed a loop-mediated isothermal amplification (LAMP)-based screening for HPdel. Optimal primer sets and temperature for LAMP were selected for HPdel and the 5′ region of the HP using genomic DNA as a template. Then, the effects of diluent and boiling on LAMP amplification were examined using whole blood as a template. Blood samples diluted 1:100 with 50 mmol/L NaOH without boiling gave optimal results as well as those diluted 1:2 with water followed by boiling. The results from 100 blood samples were fully concordant with those obtained by real-time PCR methods. Detection of the HPdel allele by LAMP using alkaline-denatured blood samples is rapid, simple, accurate, and cost effective, and is readily applicable in various clinical settings because this method requires only basic instruments. In addition, the simple preparation of blood samples using NaOH saves time and effort for various genetic tests. PMID:21497293

A novel regulatory system in plants involving medium-chain fatty acids.

PubMed

Hunzicker, Gretel Mara

2009-12-01

Polyethylene glycol sorbitan monoacylates (Tween) are detergents of widespread use in plant sciences. However, little is known about the plant response to these compounds. Interestingly, the structure of Tweens' detergents (especially from Tween 20) resembles the lipid A structure from gram-negative bacteria polysaccharides (a backbone with short saturated fatty acids). Thus, different assays (microarray, GC-MS, RT-PCR, Northern blots, alkalinization and mutant analyses) were conducted in order to elucidate physiological changes in the plant response to Tween 20 detergent. Tween 20 causes a rapid and complex change in transcript abundance which bears all characteristics of a pathogenesis-associated molecular pattern (PAMP)/elicitor-induced defense response, and they do so at concentrations which cause no detectable deleterious effects on plant cellular integrity. In the present work, it is shown that the PAMP/elicitor-induced defense responses are caused by medium-chain fatty acids which are efficiently released from the Tween backbone by the plant, notably lauric acid (12:0) and methyl lauric acid. These compounds induce the production of ethylene, medium alkalinization and gene activation in a jasmonate-independent manner. Medium-chain fatty acids are thus novel elicitors/regulators of plant pathogen defense as they have being proved in animals.

Nicotine inhibits collagen synthesis and alkaline phosphatase activity, but stimulates DNA synthesis in osteoblast-like cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramp, W.K.; Lenz, L.G.; Galvin, R.J.

1991-05-01

Use of smokeless tobacco is associated with various oral lesions including periodontal damage and alveolar bone loss. This study was performed to test the effects of nicotine on bone-forming cells at concentrations that occur in the saliva of smokeless tobacco users. Confluent cultures of osteoblast-like cells isolated from chick embryo calvariae were incubated for 2 days with nicotine added to the culture medium (25-600 micrograms/ml). Nicotine inhibited alkaline phosphatase in the cell layer and released to the medium, whereas glycolysis (as indexed by lactate production) was unaffected or slightly elevated. The effects on medium and cell layer alkaline phosphatase weremore » concentration dependent with maximal inhibition occurring at 600 micrograms nicotine/ml. Nicotine essentially did not affect the noncollagenous protein content of the cell layer, but did inhibit collagen synthesis (hydroxylation of ({sup 3}H)proline and collagenase-digestible protein) at 100, 300, and 600 micrograms/ml. Release of ({sup 3}H)hydroxyproline to the medium was also decreased in a dose-dependent manner, as was the collagenase-digestible protein for both the medium and cell layer. In contrast, DNA synthesis (incorporation of ({sup 3}H)thymidine) was more than doubled by the alkaloid, whereas total DNA content was slightly inhibited at 600 micrograms/ml, suggesting stimulated cell turnover. Morphologic changes occurred in nicotine-treated cells including rounding up, detachment, and the occurrence of numerous large vacuoles. These results suggest that steps to reduce the salivary concentration of nicotine in smokeless tobacco users might diminish damaging effects of this product on alveolar bone.« less

Kinetic study of microwave-assisted alkaline hydrolysis of Jatropha curcas oil

NASA Astrophysics Data System (ADS)

Yusuf, Nur'aini Raman; Kamil, Ruzaimah Nik Mohamad; Yusup, Suzana

2016-11-01

The kinetics of hydrolysis of Jatropha curcas oil under microwave irradation in the presence of alkaline solution was studied. The temperature of 50°C, 65°C and 80°C were studied in the range of optimum condition of 1.75 M catalyst, solvent/oil ratio of (1: 68) and 15 minutes reaction time. The rate constants of oil hydrolysis are corresponding to triglyceride disappearance concentration. The rates of reaction for fatty acids production was determined by pseudo first order. The activation energy (Ea) achieved at 30.61 kJ/mol is lower using conventional method. This conclude that the rate of reaction via microwave heating is less temperature sensitive therefore reaction can be obtained at lower temperature.

Production, secretion, and stability of human secreted alkaline phosphatase in tobacco NT1 cell suspension cultures.

PubMed

Becerra-Arteaga, Alejandro; Mason, Hugh S; Shuler, Michael L

2006-01-01

Tobacco NT1 cell suspension cultures secreting active human secreted alkaline phosphatase (SEAP) were generated for the first time as a model system to study recombinant protein production, secretion, and stability in plant cell cultures. The SEAP gene encodes a secreted form of the human placental alkaline phosphatase (PLAP). During batch culture, the highest level of active SEAP in the culture medium (0.4 U/mL, corresponding to approximately 27 mg/L) was observed at the end of the exponential growth phase. Although the level of active SEAP decreased during the stationary phase, the activity loss did not appear to be due to SEAP degradation (based on Western blots) but due to SEAP denaturation. The protein-stabilizing agents polyvinylpirrolidone (PVP) and bacitracin were added extracellularly to test for their ability to reduce the loss of SEAP activity during the stationary phase. Bacitracin (100 mg/L) was the most effective treatment at sustaining activity levels for up to 17 days post-subculture. Commercially available human placental alkaline phosphatase (PLAP) was used to probe the mechanism of SEAP deactivation. Experiments with PLAP in sterile and conditioned medium corroborated the denaturation of SEAP by factors generated by cell growth and not due to simple proteolysis. We also show for the first time that the factors promoting activity loss are heat labile at 95 degrees C but not at 70 degrees C, and they are not inactivated after a 5 day incubation period under normal culture conditions (27 degrees C). In addition, there were no significant changes in pH or redox potential when comparing sterile and cell-free conditioned medium during PLAP incubation, indicating that these factors were unimportant.

Ascorbic acid induces alkaline phosphatase, type X collagen, and calcium deposition in cultured chick chondrocytes.

PubMed

Leboy, P S; Vaias, L; Uschmann, B; Golub, E; Adams, S L; Pacifici, M

1989-10-15

During the process of endochondral bone formation, proliferating chondrocytes give rise to hypertrophic chondrocytes, which then deposit a mineralized matrix to form calcified cartilage. Chondrocyte hypertrophy and matrix mineralization are associated with expression of type X collagen and the induction of high levels of the bone/liver/kidney isozyme of alkaline phosphatase. To determine what role vitamin C plays in these processes, chondrocytes derived from the cephalic portion of 14-day chick embryo sternae were grown in the absence or presence of exogenous ascorbic acid. Control untreated cells displayed low levels of type X collagen and alkaline phosphatase activity throughout the culture period. However, cells grown in the presence of ascorbic acid produced increasing levels of alkaline phosphatase activity and type X collagen mRNA and protein. Both alkaline phosphatase activity and type X collagen mRNA levels began to increase within 24 h of ascorbate treatment; by 9 days, the levels of both alkaline phosphatase activity and type X collagen mRNA were 15-20-fold higher than in non-ascorbate-treated cells. Ascorbate treatment also increased calcium deposition in the cell layer and decreased the levels of types II and IX collagen mRNAs; these effects lagged significantly behind the elevation of alkaline phosphatase and type X collagen. Addition of beta-glycerophosphate to the medium increased calcium deposition in the presence of ascorbate but had no effect on levels of collagen mRNAs or alkaline phosphatase. The results suggest that vitamin C may play an important role in endochondral bone formation by modulating gene expression in hypertrophic chondrocytes.

Reactivity of bacterial and fungal laccases with lignin under alkaline conditions.

PubMed

Moya, Raquel; Saastamoinen, Päivi; Hernández, Manuel; Suurnäkki, Anna; Arias, Enriqueta; Mattinen, Maija-Liisa

2011-11-01

The ability of Streptomyces ipomoea laccase to polymerize secoisolariciresinol lignan and technical lignins was assessed. The reactivity of S. ipomoea laccase was also compared to that of low redox fungal laccase from Melanocarpus albomyces using low molecular mass p-coumaric, ferulic and sinapic acid as well as natural (acetosyringone) and synthetic 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) mediators as substrates. Oxygen consumption measurement, MALDI-TOF MS and SEC were used to follow the enzymatic reactions at pH 7, 8, 9 and 10 at 30°C and 50°C. Polymerization of lignins and lignan by S. ipomoea laccase under alkaline reaction conditions was observed, and was enhanced in the presence of acetosyringone almost to the level obtained with M. albomyces laccase without mediator. Reactivities of the enzymes towards acetosyringone and TEMPO were similar, suggesting exploitation of the compounds and low redox laccase in lignin valorization under alkaline conditions. The results have scientific impact on basic research of laccases. Copyright © 2011 Elsevier Ltd. All rights reserved.

Production of alkaline protease from Cellulosimicrobium cellulans

PubMed Central

Ferracini-Santos, Luciana; Sato, Hélia H

2009-01-01

Cellulosimicrobium cellulans is one of the microorganisms that produces a wide variety of yeast cell wall-degrading enzymes, β-1,3-glucanase, protease and chitinase. Dried cells of Saccharomyces cerevisiae were used as carbon and nitrogen source for cell growth and protease production. The medium components KH2PO4, KOH and dried yeast cells showed a significant effect (p<0.05) on the factorial fractional design. A second design was prepared using two factors: pH and percentage of dried yeast cells. The results showed that the culture medium for the maximum production of protease was 0.2 g/l of MgSO4.7H2O, 2.0 g/l of (NH4)2SO4 and 8% of dried yeast cells in 0.15M phosphate buffer at pH 8.0. The maximum alkaline protease production was 7.0 ± 0.27 U/ml over the center point. Crude protease showed best activity at 50ºC and pH 7.0-8.0, and was stable at 50ºC. PMID:24031317

Electricity generation from banana peels in an alkaline fuel cell with a Cu2O-Cu modified activated carbon cathode.

PubMed

Liu, Peng; Liu, Xianhua; Dong, Feng; Lin, Qingxia; Tong, Yindong; Li, Yang; Zhang, Pingping

2018-08-01

Low-cost and highly active catalyst for oxygen reduction reaction is of great importance in the design of alkaline fuel cells. In this work, Cu 2 O-Cu composite catalyst has been fabricated by a facile laser-irradiation method. The addition of Cu 2 O-Cu composite in activated carbon air-cathode greatly improves the performance of the cathode. Our results indicate the enhanced performance is likely attributed to the synergistic effect of high conductivity of Cu and the catalytic activity of Cu 2 O towards the oxygen reduction reaction. Furthermore, an alkaline fuel cell equipped with the composite air-cathode has been built to turn banana peels into electricity. Peak power density of 16.12Wm -2 is obtained under the condition of 3M KOH and 22.04gL -1 reducing sugar, which is higher than other reported low-temperature direct biomass alkaline fuel cells. HPLC results indicate the main oxidation products in the alkaline fuel cell were small organic acids. Copyright © 2018 Elsevier B.V. All rights reserved.

Composite Ni/NiO-Cr2O3 Catalyst for Alkaline Hydrogen Evolution Reaction

PubMed Central

Bates, Michael K.; Jia, Qingying; Ramaswamy, Nagappan; Allen, Robert J.; Mukerjee, Sanjeev

2015-01-01

We report a Ni–Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary and ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte. The highest HER mass-activity was observed for Ni–Cr materials which exhibit metallic Ni as well as NiOx and Cr2O3 phases as determined by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) analysis. The onset of the HER is significantly improved compared to numerous binary and ternary Ni-alloys, including Ni–Mo materials. It is likely that at adjacent Ni/NiOx sites, the oxide acts as a sink for OHads, while the metallic Ni acts as a sink for the Hads intermediate of the HER, thus minimizing the high activation energy of hydrogen evolution via water reduction. This is confirmed by in situ XAS studies that show that the synergistic HER enhancement is due to NiOx content and that the Cr2O3 appears to stabilize the composite NiOx component under HER conditions (where NiOx would typically be reduced to metallic Ni0). Furthermore, in contrast to Pt, the Ni(Ox)/Cr2O3 catalyst appears resistant to poisoning by the anion exchange ionomer (AEI), a serious consideration when applied to an anionic polymer electrolyte interface. Furthermore, we report a detailed model of the double layer interface which helps explain the observed ensemble effect in the presence of AEI. PMID:26191118

Fluorescent Biosensor for Phosphate Determination Based on Immobilized Polyfluorene-Liposomal Nanoparticles Coupled with Alkaline Phosphatase.

PubMed

Kahveci, Zehra; Martínez-Tomé, Maria José; Mallavia, Ricardo; Mateo, C Reyes

2017-01-11

This work describes the development of a novel fluorescent biosensor based on the inhibition of alkaline phosphatase (ALP). The biosensor is composed of the enzyme ALP and the conjugated cationic polyfluorene HTMA-PFP. The working principle of the biosensor is based on the fluorescence quenching of this polyelectrolyte by p-nitrophenol (PNP), a product of the hydrolysis reaction of p-nitrophenyl phosphate (PNPP) catalyzed by ALP. Because HTMA-PFP forms unstable aggregates in buffer, with low fluorescence efficiency, previous stabilization of the polyelectrolyte was required before the development of the biosensor. HTMA-PFP was stabilized through its interaction with lipid vesicles to obtain stable blue-emitting nanoparticles (NPs). Fluorescent NPs were characterized, and the ability to be quenched by PNP was evaluated. These nanoparticles were coupled to ALP and entrapped in a sol-gel matrix to produce a biosensor that can serve as a screening platform to identify ALP inhibitors. The components of the biosensor were examined before and after sol-gel entrapment, and the biosensor was optimized to allow the determination of phosphate ion in aqueous medium.

The origin of life in alkaline hydrothermal vents

NASA Astrophysics Data System (ADS)

Sojo, V.; Herschy, B.; Whicher, A.; Camprubí, E.; Lane, N.

2016-12-01

The origin of life remains one of Science's greatest unresolved questions. The answer will no doubt involve almost all the basic disciplines, including Physics, Chemistry, Astronomy, Geology, and Biology. Chiefly, it is the link between the latter two that must be elucidated: how geochemistry gave rise to biochemistry. Serpentinizing systems such as alkaline hydrothermal vents offer the most robust combination of conditions to have hosted the origin of life on the early Earth, while bearing many parallels to modern living cells. Stark gradients of concentration, pH, oxidation/reduction, and temperature provided the ability to synthesise and concentrate organic products, drive polymerisation reactions, and develop an autotrophic lifestyle independent of foreign sources of organics. In the oxygen-depleted waters of the Hadean, alkaline vents would have acted as electrochemical flow reactors, in which alkaline fluids saturated in H2 mixed with the relatively acidic CO2-rich waters of the ocean, through interconnected micropores made of thin inorganic walls containing catalytic Fe(Ni)S minerals. Perhaps not coincidentally, the unit cells of these Fe(Ni)S minerals closely resemble the active sites of crucial ancestral bioenergetic enzymes. Meanwhile, differences in pH across the thin barriers produced natural proton gradients similar to those used for carbon fixation in modern archaea and bacteria. At the earliest stages, the problem of the origin of life is the problem of the origin of carbon fixation. I will discuss work over the last decade that suggests several possible hypotheses for how simple one-carbon molecules could have given rise to more complex organics, particularly within a serpentinizing alkaline hydrothermal vent. I will discuss the perplexing differences in carbon and energy metabolism in methanogenic archaea and acetogenic bacteria, thought to be the earliest representatives of each domain, to propose a possible ancestral mechanism of CO2 reduction in

Mineralogical, petrological and geochemical aspects of alkaline and alkaline-carbonatite associations from Brazil

NASA Astrophysics Data System (ADS)

Morbidelli, L.; Gomes, C. B.; Beccaluva, L.; Brotzu, P.; Conte, A. M.; Ruberti, E.; Traversa, G.

1995-12-01

A general description of Mesozoic and Tertiary (Fortaleza) Brazilian alkaline and alkaline-carbonatite districts is presented with reference to mineralogy, petrology, geochemistry and geochronology. It mainly refers to scientific results obtained during the last decade by an Italo-Brazilian research team. Alkaline occurrences are distributed across Brazilian territory from the southern (Piratini, Rio Grande do Sul State) to the northeastern (Fortaleza, Ceará State) regions and are mainly concentrated along the borders of the Paraná Basin generally coinciding with important tectonic lineaments. The most noteworthy characteristics of these alkaline and alkaline-carbonatite suites are: (i) prevalence of intrusive forms; (ii) abundance of cumulate assemblages (minor dunites, frequent clinopyroxenites and members of the ijolite series) and (iii) abundance of evolved rock-types. Many data demonstrate that crystal fractionation was the main process responsible for magma evolution of all Brazilian alkaline rocks. A hypothesis is proposed for the genesis of carbonatite liquids by immiscibility processes. The incidence of REE and trace elements for different major groups of lithotypes, belonging both to carbonatite-bearing and carbonatite-free districts, are documented. Sr and preliminary Nd isotopic data are indicative of a mantle origin for the least evolved magmas of all the studied occurrences. Mantle source material and melting models for the generation of the Brazilian alkaline magma types are also discussed.

Alkaline "Permanent" Paper.

ERIC Educational Resources Information Center

Pacey, Antony

1991-01-01

Discussion of paper manufacturing processes and their effects on library materials focuses on the promotion of alkaline "permanent" paper, with less acid, by Canadian library preservation specialists. Standards for paper acidity are explained; advantages of alkaline paper are described, including decreased manufacturing costs; and…

Stacking and determination of phenazine-1-carboxylic acid with low pKa in soil via moving reaction boundary formed by alkaline and double acidic buffers in capillary electrophoresis.

PubMed

Sun, Chong; Yang, Xiao-Di; Fan, Liu-Yin; Zhang, Wei; Xu, Yu-Quan; Cao, Cheng-Xi

2011-04-01

As shown herein, a normal moving reaction boundary (MRB) formed by an alkaline buffer and a single acidic buffer had poor stacking to the new important plant growth promoter of phenazine-1-carboxylic acid (PCA) in soil due to the leak induced by its low pK(a). To stack the PCA with low pK(a) efficiently, a novel stacking system of MRB was developed, which was formed by an alkaline buffer and double acidic buffers (viz., acidic sample and blank buffers). With the novel system, the PCA leaking into the blank buffer from the sample buffer could be well stacked by the prolonged MRB formed between the alkaline buffer and blank buffer. The relevant mechanism of stacking was discussed briefly. The stacking system, coupled with sample pretreatment, could achieve a 214-fold increase of PCA sensitivity under the optimal conditions (15 mM (pH 11.5) Gly-NaOH as the alkaline buffer, 15 mM (pH 3.0) Gly-HCl-acetonitrile (20%, v/v) as the acidic sample buffer, 15 mM (pH 3.0) Gly-HCl as the blank buffer, 3 min 13 mbar injection of double acidic buffers, benzoic acid as the internal standard, 75 μm i.d. × 53 cm (44 cm effective length) capillary, 25 kV and 248 nm). The limit of detection of PCA in soil was decreased to 17 ng/g, the intra-day and inter-day precision values (expressed as relative standard deviations) were 3.17-4.24% and 4.17-4.87%, respectively, and the recoveries of PCA at three concentration levels changed from 52.20% to 102.61%. The developed method could be used for the detection of PCA in soil at trace level.

Structure and reactivity of thiazolium azo dyes: UV-visible, resonance Raman, NMR, and computational studies of the reaction mechanism in alkaline solution.

PubMed

Abbott, Laurence C; Batchelor, Stephen N; Moore, John N

2013-03-07

UV-visible absorption, resonance Raman, and (1)H NMR spectroscopy, allied with density functional theory (DFT) calculations, have been used to study the structure, bonding, and alkaline hydrolysis mechanism of the cationic thiazloium azo dye, 2-[2-[4-(diethylamino)phenyl]diazenyl]-3-methyl-thiazolium (1a), along with a series of six related dyes with different 4-dialkylamino groups and/or other phenyl ring substituents (2a-c, 3a-c) and the related isothiazolium azo dye, 5-[2-[4-(dimethylamino)phenyl]diazenyl]-2-methyl-isothiazolium (4). These diazahemicyanine dyes are calculated to have a similar low-energy structure that is cis, trans at the (iso)thiazolium-azo group, and for which the calculated Raman spectra provide a good match with the experimental data; the calculations on these structures are used to assign and discuss the transitions giving rise to the experimental spectra, and to consider the bonding and its variation between the dyes. UV-visible, Raman, and NMR spectra recorded from minutes to several weeks after raising the pH of an aqueous solution of 1a to ca. 11.5 show that the dominant initial step in the reaction is loss of diethylamine to produce a quinonimine (ca. hours), with subsequent reactions occurring on longer time scales (ca. days to weeks); kinetic analyses give a rate constant of 2.6 × 10(-2) dm(3) mol(-1) s(-1) for reaction of 1a with OH(-). UV-visible spectra recorded on raising the pH of the other dyes in solution show similar changes that are attributed to the same general reaction mechanism, but with different rate constants for which the dependence on structure is discussed.

Preparation and performance evaluation of novel alkaline stable anion exchange membranes

NASA Astrophysics Data System (ADS)

Irfan, Muhammad; Bakangura, Erigene; Afsar, Noor Ul; Hossain, Md. Masem; Ran, Jin; Xu, Tongwen

2017-07-01

Novel alkaline stable anion exchange membranes are prepared from various amounts of N-methyl dipicolylamine (MDPA) and brominated poly (2,6-dimethyl-1,4-phenylene oxide) (BPPO). The dipicolylamine and MDPA are synthesized through condensation reaction and confirmed by 1H NMR spectroscopy. The morphologies of prepared membranes are investigated by atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), 1H NMR spectroscopy and scanning electron microscopy (SEM). The electrochemical and physical properties of AEMs are tested comprising water uptake (WU), ion exchange capacity (IEC), alkaline stability, linear expansion ratio (LER), thermal stability and mechanical stability. The obtained hydroxide conductivity of MDPA-4 is 66.5 mS/cm at 80 °C. The MDPA-4 membrane shows good alkaline stability, high hydroxide conductivity, low methanol permeability (3.43 × 10-7 cm2/s), higher selectivity (8.26 × 107 mS s/cm3), less water uptake (41.1%) and lower linear expansion (11.1%) despite of high IEC value (1.62 mmol/g). The results prove that MDPA membranes have great potential application in anion exchange membrane fuel cell.

Transient removal of alkaline zones after excitation of Chara cells is associated with inactivation of high conductance in the plasmalemma

PubMed Central

2009-01-01

The action potential (AP) of excitable plant cells is a multifunctional physiological signal. Its generation in characean algae suppresses the pH banding for 15–30 min and enhances the heterogeneity of spatial distribution of photosynthetic activity. This suppression is largely due to the cessation of H+ influx (OH− efflux) in the alkaline cell regions. Measurements of local pH and membrane conductance in individual space-clamped alkaline zones (small cell areas bathed in an isolated pool of external medium) showed that the AP generation is followed by the transient disappearance of alkaline zone in parallel with a large decrease in membrane conductance. These changes, specific to alkaline zones, were only observed under continuous illumination following a relaxation period of at least 15 min after previous excitation. The excitation of dark-adapted cells produced no conductance changes in the post-excitation period. The results indicate that the origin of alkaline zones in characean cells is not due to operation of electroneutral H+/HCO3− symport or OH−/HCO3− antiport. It is concluded that the membrane excitation is associated with inactivation of plasmalemma high conductance in the alkaline cell regions. PMID:19820298

Hexavalent chromium reduction by bacterial consortia and pure strains from an alkaline industrial effluent.

PubMed

Piñón-Castillo, H A; Brito, E M S; Goñi-Urriza, M; Guyoneaud, R; Duran, R; Nevarez-Moorillon, G V; Gutiérrez-Corona, J F; Caretta, C A; Reyna-López, G E

2010-12-01

To characterize the bacterial consortia and isolates selected for their role in hexavalent chromium removal by adsorption and reduction. Bacterial consortia from industrial wastes revealed significant Cr(VI) removal after 15 days when incubated in medium M9 at pH 6·5 and 8·0. The results suggested chromium reduction. The bacterial consortia diversity (T-RFLP based on 16S rRNA gene) indicated a highest number of operational taxonomic units in an alkaline carbonate medium mimicking in situ conditions. However, incubations under such conditions revealed low Cr(VI) removal. Genomic libraries were obtained for the consortia exhibiting optimal Cr(VI) removal (M9 medium at pH 6·5 and 8·0). They revealed the dominance of 16S rRNA gene sequences related to the genera Pseudomonas/Stenotrophomonas or Enterobacter/Halomonas, respectively. Isolates related to Pseudomonas fluorescens and Enterobacter aerogenes were efficient in Cr(VI) reduction and adsorption to the biomass. Cr(VI) reduction was better at neutral pH rather than under in situ conditions (alkaline pH with carbonate). Isolated strains exhibited significant capacity for Cr(VI) reduction and adsorption. Bacterial communities from chromium-contaminated industrial wastes as well as isolates were able to remove Cr(VI). The results suggest a good potential for bioremediation of industrial wastes when optimal conditions are applied. Journal of Applied Microbiology © 2010 The Society for Applied Microbiology. No claim to Mexican Government works.

Does Cholecystectomy Increase the Esophageal Alkaline Reflux? Evaluation by Impedance-pH Technique.

PubMed

Uyanikoglu, Ahmet; Akyuz, Filiz; Ermis, Fatih; Arici, Serpil; Bas, Gurhan; Cakirca, Mustafa; Baran, Bulent; Mungan, Zeynel

2012-04-01

The aim of this study is to investigate the reflux patterns in patients with galbladder stone and the change of reflux patterns after cholecystectomy in such patients. Fourteen patients with cholecystolithiasis and a control group including 10 healthy control subjects were enrolled in this prospective study. Demographical findings, reflux symptom score scale and 24-hour impedance pH values of the 14 cholecystolithiasis cases and the control group were evaluated. The impedance pH study was repeated 3 months after cholecystectomy. Age, gender, and BMI were not different between the two groups. Total and supine weakly alkaline reflux time (%) (1.0 vs 22.5, P = 0.028; 201.85 vs 9.65, P = 0.012), the longest episodes of total, upright and supine weakly alkaline reflux mediums (11 vs 2, P = 0.025; 8.5 vs 1.0, P = 0.035; 3 vs 0, P = 0.027), total and supine weakly alkaline reflux time in minutes (287.35 vs 75.10, P = 0.022; 62.5 vs 1.4, P = 0.017), the number of alkaline reflux episodes (162.5 vs 72.5, P = 0.022) were decreased with statistical significance. No statistically significant difference was found in the comparison of symptoms between the subjects in the control group and the patients with cholecystolithiasis, in preoperative, postoperative and postcholecystectomy status. Significant reflux symptoms did not occur after cholecystectomy. Post cholecystectomy weakly alkaline reflux was decreased, but it was determined that acid reflux increased after cholecystectomy by impedance pH-metry in the study group.

Production and characterization of thermostable alkaline protease of Bacillus subtilis (ATCC 6633) from optimized solid-state fermentation.

PubMed

Chatterjee, Joyee; Giri, Sudipta; Maity, Sujan; Sinha, Ankan; Ranjan, Ashish; Rajshekhar; Gupta, Suvroma

2015-01-01

Proteases are the most important group of enzymes utilized commercially in various arenas of industries, such as food, detergent, leather, dairy, pharmaceutical, diagnostics, and waste management, accounting for nearly 20% of the world enzyme market. Microorganisms of specially Bacillus genera serve as a vast repository of diverse set of industrially important enzymes and utilized for the large-scale enzyme production using a fermentation technology. Approximately 30%-40% of the cost of industrial enzymes originates from the cost of the growth medium. This study is attempted to produce protease from Bacillus subtilis (ATCC 6633) after optimization of various process parameters with the aid of solid-state fermentation using a cheap nutrient source such as wheat bran. B. subtilis (ATCC 6633) produces proteases of molecular weight 36 and 20 kDa, respectively, in the fermented medium as evident from SDS zymogram. Alkaline protease activity has been detected with optimum temperature at 50 °C and is insensitive to ethylenediaminetetraacetic acid. This thermostable alkaline protease exhibits dual pH optimum at 7 and 10 with moderate pH stability at alkaline pH range. It preserves its activity in the presence of detergent such as SDS, Tween 20, and Triton X-100 and may be considered as an effective additive to detergent formulation with some industrial importance. © 2014 International Union of Biochemistry and Molecular Biology, Inc.

Singlet-Oxygen Generation in Alkaline Periodate Solution.

PubMed

Bokare, Alok D; Choi, Wonyong

2015-12-15

A nonphotochemical generation of singlet oxygen ((1)O2) using potassium periodate (KIO4) in alkaline condition (pH > 8) was investigated for selective oxidation of aqueous organic pollutants. The generation of (1)O2 was initiated by the spontaneous reaction between IO4(-) and hydroxyl ions, along with a stoichiometric conversion of IO4(-) to iodate (IO3(-)). The reactivity of in-situ-generated (1)O2 was monitored by using furfuryl alcohol (FFA) as a model substrate. The formation of (1)O2 in the KIO4/KOH system was experimentally confirmed using electron spin resonance (ESR) measurements in corroboration with quenching studies using azide as a selective (1)O2 scavenger. The reaction in the KIO4/KOH solution in both oxic and anoxic conditions initiated the generation of superoxide ion as a precursor of the singlet oxygen (confirmed by using superoxide scavengers), and the presence of molecular oxygen was not required as a precursor of (1)O2. Although hydrogen peroxide had no direct influence on the FFA oxidation process, the presence of natural organic matter, such as humic and fulvic acids, enhanced the oxidation efficiency. Using the oxidation of simple organic diols as model compounds, the enhanced (1)O2 formation is attributed to periodate-mediated oxidation of vicinal hydroxyl groups present in humic and fulvic constituent moieties. The efficient and simple generation of (1)O2 using the KIO4/KOH system without any light irradiation can be employed for the selective oxidation of aqueous organic compounds under neutral and near-alkaline conditions.

Manganese oxide/poly(3,4-ethylenedioxythiophene) hybrid electrocatalysts for the oxygen reduction reaction in alkaline fuel cells

DOE PAGES

Lambert, Timothy N.; Vigil, Julian A.

2016-08-22

Manganese oxide/poly(3,4-ethylene-dioxythiophene) (MnO x/ PEDOT) nanostructured hybrid thin films were prepared using a simple anodic electrodeposition process from aqueous solution, and then tested for oxygen reduction reaction (ORR) activity in alkaline electrolyte using rotating disk electrode and rotating ring disk electrode methods. MnO x/PEDOT provided improvements over MnO x-only and PEDOT-only control films, with > 0.2 V decrease in onset and half-wave overpotentials, and > 1.5 times increase in terminal current density. The MnO x/PEDOT film exhibited only a slightly lower n value (n = 3.86-3.92) than the 20% Pt/C benchmark electrocatalyst (n = 3.98) across all potentials. MnO x/PEDOTmore » also displayed a more positive half-wave potential and superior electrocatalytic selectivity for the ORR upon methanol exposure than 20% Pt/C. Here, the high activity and synergism of MnO x/PEDOT towards the ORR is attributed to effective intermixing/dispersion of the two materials, intimate substrate contact with improved charge transfer processes attained by co-electrodepositing MnO x with PEDOT and due to the increase in Mn 3+ content at the surface of the oxide.« less

Manganese oxide/poly(3,4-ethylenedioxythiophene) hybrid electrocatalysts for the oxygen reduction reaction in alkaline fuel cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lambert, Timothy N.; Vigil, Julian A.

Manganese oxide/poly(3,4-ethylene-dioxythiophene) (MnO x/ PEDOT) nanostructured hybrid thin films were prepared using a simple anodic electrodeposition process from aqueous solution, and then tested for oxygen reduction reaction (ORR) activity in alkaline electrolyte using rotating disk electrode and rotating ring disk electrode methods. MnO x/PEDOT provided improvements over MnO x-only and PEDOT-only control films, with > 0.2 V decrease in onset and half-wave overpotentials, and > 1.5 times increase in terminal current density. The MnO x/PEDOT film exhibited only a slightly lower n value (n = 3.86-3.92) than the 20% Pt/C benchmark electrocatalyst (n = 3.98) across all potentials. MnO x/PEDOTmore » also displayed a more positive half-wave potential and superior electrocatalytic selectivity for the ORR upon methanol exposure than 20% Pt/C. Here, the high activity and synergism of MnO x/PEDOT towards the ORR is attributed to effective intermixing/dispersion of the two materials, intimate substrate contact with improved charge transfer processes attained by co-electrodepositing MnO x with PEDOT and due to the increase in Mn 3+ content at the surface of the oxide.« less

Self-Controlled Synthesis of Hyperbranched Polyetherketones From A3 + B2 Approach Via Different Solubilities of Monomers in the Reaction Medium (Preprint)

DTIC Science & Technology

2006-10-01

higher yields than 1a and 2a after the similar work-up procedure, which involved Soxhlet extraction with water for 2 days and methanol for 2 days to get...the co-monomers. One such reaction medium, optimized PPA/P2O5 mixture, has been established for the electrophilic substitution reaction to yield high... Soxhlet -extracted with water for 2 days, methanol for 2 days, and finally dried under reduced pressure (0.05 mmHg) at 100°C for 150 h to give 3.30 g (76

Duplex-assisted carotid artery stenting without administration of contrast medium for patients with chronic kidney disease or allergic reaction.

PubMed

Mizowaki, Takashi; Fujita, Atsushi; Imahori, Taichiro; Uyama, Atsushi; Inoue, Satoshi; Kohta, Masaaki; Hamaguchi, Hirotoshi; Sasayama, Takashi; Hosoda, Kohkichi; Kohmura, Eiji

2016-07-01

We aimed to investigate the safety and feasibility of duplex-assisted carotid artery stenting (CAS) without administration of contrast medium for the prevention of adverse reactions. Fifteen patients (9 % of all CASs) with severe carotid stenosis (≥70 %) associated with chronic kidney disease (CKD) (stage ≥3) or allergy to contrast medium underwent duplex-assisted CAS without administration of contrast medium over 4 years. The procedural success rate and perioperative complication rates were compared between the duplex-assisted CAS (n = 15) and conventional CAS (n = 153) groups. The technical success rate was 100 % in both groups. Combined stroke or death rates during the post-procedural period did not differ significantly between the duplex-assisted CAS group (0/15, 0 %) and conventional CAS group (4/153, 2.6 %). None of the 14 patients with CKD in the duplex-assisted CAS group experienced further deterioration of renal function. The mean surface radiation dose of participants in the duplex-assisted CAS group (n = 13, 312 ± 131 mGy) was significantly lower than that of the conventional CAS group (n = 31, 1036 ± 571 mGy) (p < 0.001). The mean duration of CAS procedure was not significantly different between the duplex-assisted CAS group (156 ± 39.7 min) and the conventional CAS group (156 ± 37.4 min). Duplex-assisted CAS without administration of contrast medium could be an alternative option in selected patients deemed to be at high risk for renal failure from nephrotoxic contrast medium or who have an allergy to contrast medium.

Palladium and palladium-tin supported on multi wall carbon nanotubes or carbon for alkaline direct ethanol fuel cell

NASA Astrophysics Data System (ADS)

Geraldes, Adriana Napoleão; Furtunato da Silva, Dionisio; Martins da Silva, Júlio César; Antonio de Sá, Osvaldo; Spinacé, Estevam Vitório; Neto, Almir Oliveira; Coelho dos Santos, Mauro

2015-02-01

Pd and PdSn (Pd:Sn atomic ratios of 90:10), supported on Multi Wall Carbon Nanotubes (MWCNT) or Carbon (C), are prepared by an electron beam irradiation reduction method. The obtained materials are characterized by X-Ray diffraction (XRD), Energy dispersive X-ray analysis (EDX), Transmission electron Microscopy (TEM) and Cyclic Voltammetry (CV). The activity for ethanol electro-oxidation is tested in alkaline medium, at room temperature, using Cyclic Voltammetry and Chronoamperometry (CA) and in a single alkaline direct ethanol fuel cell (ADEFC), in the temperature range of 60-90 °C. CV analysis finds that Pd/MWCNT and PdSn/MWCNT presents onset potentials changing to negative values and high current values, compared to Pd/C and PdSn/C electrocatalysts. ATR-FTIR analysis, performed during the CV, identifies acetate and acetaldehyde as principal products formed during the ethanol electro-oxidation, with low conversion to CO2. In single fuel cell tests, at 85 °C, using 2.0 mol L-1 ethanol in 2.0 mol L-1 KOH solutions, the electrocatalysts supported on MWCNT, also, show higher power densities, compared to the materials supported on carbon: PdSn/MWCNT, presents the best result (36 mW cm-2). The results show that the use of MWCNT, instead of carbon, as support, plus the addition of small amounts of Sn to Pd, improves the electrocatalytic activity for Ethanol Oxidation Reaction (EOR).

Comprehensive investigations of kinetics of alkaline hydrolysis of TNT (2,4,6-trinitrotoluene), DNT (2,4-dinitrotoluene), and DNAN (2,4-dinitroanisole).

PubMed

Sviatenko, Liudmyla; Kinney, Chad; Gorb, Leonid; Hill, Frances C; Bednar, Anthony J; Okovytyy, Sergiy; Leszczynski, Jerzy

2014-09-02

Combined experimental and computational techniques were used to analyze multistep chemical reactions in the alkaline hydrolysis of three nitroaromatic compounds: 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), and 2,4-dinitroanisole (DNAN). The study reveals common features and differences in the kinetic behavior of these compounds. The analysis of the predicted pathways includes modeling of the reactions, along with simulation of UV-vis spectra, experimental monitoring of reactions using LC/MS techniques, development of the kinetic model by designing and solving the system of differential equations, and obtaining computationally predicted kinetics for decay and accumulation of reactants and products. Obtained results suggest that DNT and DNAN are more resistant to alkaline hydrolysis than TNT. The direct substitution of a nitro group by a hydroxide represents the most favorable pathway for all considered compounds. The formation of Meisenheimer complexes leads to the kinetic first-step intermediates in the hydrolysis of TNT. Janovsky complexes can also be formed during hydrolysis of TNT and DNT but in small quantities. Methyl group abstraction is one of the suggested pathways of DNAN transformation during alkaline hydrolysis.

Isolation and characterization of two immunochemically distinct alkaline phosphatases from Pseudomonas aeruginosa.

PubMed

Tan, A S; Worobec, E A

1993-02-01

We have isolated two alkaline phosphatases (H-AP and L-AP, for high and low molecular mass, respectively) from Pseudomonas aeruginosa PA01. These two enzymes were found to differ in mobility on sodium dodecyl sulphate polyacrylamide gels (H-AP, M(r) = 51,000 and L-AP, M(r) = 39,500), amino-terminal amino acid sequence and did not cross-react. Both enzymes were active as phosphomonoesterases while only L-AP demonstrated any phosphodiesterase activity. Both enzymes were purified from P. aeruginosa grown in phosphate limiting conditions using the same protocol and were identified in both periplasmic and extracellular locations. A low level of H-AP was produced constitutively whereas L-AP was produced only after induction by reduced phosphate concentration in the growth medium. An L-AP-like enzyme has been previously described, however, this is the first report of a second P. aeruginosa alkaline phosphatase.

Application of alkaline solid residue of electric arc furnace dust for neutralization/purification of electroplating wastewaters.

PubMed

Elez, Loris; Orescanin, Visnja; Sofilic, Tahir; Mikulic, Nenad; Ruk, Damir

2008-10-01

The purpose of this work was development of an appropriate procedure for the neutralization/purification of electroplating wastewater (EWW) with alkaline solid residue (ASR) by-product of the alkaline extraction of zinc and lead from electric arc furnace dust (EAFD). Removal efficiency of ASR at optimum purification conditions (pH 8 and mixing time; 20 minutes) for the elements Pb, Cr (VI), Cr (III), Fe, Ni, Cu and Zn were 94.92%, 97.58%, 99.59%, 99.48%, 97.25% and 99.97%, respectively. The concentrations of all elements in the purified wastewater were significantly lower in relation to the upper permissible limit for wastewaters suitable for discharge into the environment. The remaining waste mud was regenerated in the strong alkaline medium and successfully applied once again for the neutralization/purification of EWW. Removal efficiencies of heavy metals accomplished with regenerated waste mud were comparable to these achieved by original ASR. Elemental concentrations in the leachates of the waste mud were in accordance with regulated values.

Alkaline hydrolysis of dimethyl terephthalate in the presence of [LiAl{sub 2}(OH){sub 6}]Cl.2H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lei Lixu; Zhang Weifeng; Hu Meng

2006-11-15

The alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl{sub 2}(OH){sub 6}]Cl has been investigated to demonstrate a possible application of anion exchange facility of layered double hydroxides (LDHs) to control chemical reactions. The results show that (i) in the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl, most of the interlayer Cl{sup -} of [LiAl{sub 2}(OH){sub 6}]Cl is quickly replaced by OH{sup -} in the alkaline solution because the LDH host favors OH{sup -} more; (ii) the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl is faster than the reaction ofmore » DMT and [LiAl{sub 2}(OH){sub 6}]OH; (iii) The hydrolysis of DMT in a buffer solution of pH{approx}8 takes longer time to reach equilibrium than the alkaline hydrolysis of DMT in the presence of [LiAl{sub 2}(OH){sub 6}]Cl. It is believed that the selective anion exchange chemistry of the LDH plays a key role in storage and controlled release of active reactant, that is, OH{sup -}, thus make the hydrolysis proceeds in a controlled way. - Graphical abstract: XRD patterns of the solid products of the alkaline hydrolysis of dimethyl terephthalate (DMT) in the presence of [LiAl{sub 2}(OH){sub 6}]Cl at 70 deg. C halted at different time, which shows that [LiAl{sub 2}(OH){sub 6}]Cl turns out to be [LiAl{sub 2}(OH){sub 6}]OH, and [LiAl{sub 2}(OH){sub 6}]{sub 2}TP forms gradually. In this reaction, the alkaline hydrolysis of DMT is controlled by replacement of Cl{sup -} in [LiAl{sub 2}(OH){sub 6}]Cl by OH{sup -}, and subsequent replacement of OH{sup -} in [LiAl{sub 2}(OH){sub 6}]OH by terephthalate anion.« less

Bacterial treatment of alkaline cement kiln dust using Bacillus halodurans strain KG1.

PubMed

Kunal; Rajor, Anita; Siddique, Rafat

2016-01-01

This study was conducted to isolate an acid-producing, alkaliphilic bacterium to reduce the alkalinity of cement industry waste (cement kiln dust). Gram-positive isolate KG1 grew well at pH values of 6-12, temperatures of 28-50°C, and NaCl concentrations of 0-16% and thus was further screened for its potential to reduce the pH of an alkaline medium. Phenotypic characteristics of the KG1 isolate were consistent with those of the genus Bacillus, and the highest level of 16S rRNA gene sequence similarity was found with Bacillus halodurans strain DSM 497 (94.7%). On the basis of its phenotypic characteristics and genotypic distinctiveness from other phylogenetic neighbors belonging to alkaliphilic Bacillus species, the isolated strain was designated B. halodurans strain KG1, with GenBank accession number JQ307184 (= NCIM 5439). Isolate KG1 reduced the alkalinity (by 83.64%) and the chloride content (by 86.96%) of cement kiln dust and showed a potential to be used in the cement industry for a variety of applications. Copyright © 2015 Sociedade Brasileira de Microbiologia. Published by Elsevier Editora Ltda. All rights reserved.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Fang; Zhang, Yu; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE PAGES

Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

2017-05-11

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Simultaneous 19F-1H medium resolution NMR spectroscopy for online reaction monitoring

NASA Astrophysics Data System (ADS)

Zientek, Nicolai; Laurain, Clément; Meyer, Klas; Kraume, Matthias; Guthausen, Gisela; Maiwald, Michael

2014-12-01

Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16″ fluorinated ethylene propylene (FEP) tube with an ID of 0.04″ (1.02 mm) was used as a flow cell in combination with a 5 mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a 1H Larmor frequency of 43.32 MHz and 40.68 MHz for 19F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating 19F and 1H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500 MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16″ FEP tube set-up with an ID of 1.02 mm was characterised regarding the limit of detection (LOQ (1H) = 0.335 mol L-1 and LOQ (19F) = 0.130 mol L-1 for trifluoroethanol in

DIRECT SYNTHESIS OF TERTIARY AMINES IN WATER USING MICROWAVES

EPA Science Inventory

A direct synthesis of tertiary amines is presented that proceeds expeditiously via N-alkylation of amines using alkyl halides in alkaline aqueous medium. This environmentally benign reaction is accelerated upon exposure to microwave irradiation resulting in shortened reaction tim...

Novel inorganic materials for polymer electrolyte and alkaline fuel cells

NASA Astrophysics Data System (ADS)

Tadanaga, Kiyoharu

2012-06-01

Inorganic materials with high ionic conductivity must have big advantages for the thermal and long term stability when the materials are used as the electrolyte of fuel cells. In the present paper, novel ionic conductive inorganic materials for polymer electrolyte fuel cells (PEFCs) and all solid state alkaline fuel cells (AFCs) that have been developed by our group have been reviewed. PEFCs which can operate in temperature range from 100 to 200 °C are intensively studied because of some advantages such as reduction of CO poisoning of Pt catalyst and acceleration of electrode reactions. We showed that the fuel cells using the composite membranes prepared from phosphosilicate gel powder and polyimide precursor can operate in the temperature range from 30 to 180 °C. We also found that the inorganic-organic hybrid membranes with acid-base pairs from 3-aminopropyl triethoxy silane and H2SO4 or H3PO4 show high proton conductivity under dry atmosphere, and the membranes are thermally stable at intermediate temperatures. On the other hand, because the use of noble platinum is the serious problem for the commercialization of PEFCs and because oxidation reactions are usually faster than those of acid-type fuel cells, alkaline type fuel cells, in which a nonplatinum catalyst can be used, are attractive. Recently, we have proposed an alkaline-type direct ethanol fuel cell (DEFC) using a natural clay electrolyte with non-platinum catalysts. So-called hydrotalcite clay, Mg-Al layered double hydroxide intercalated with CO32- (Mg-Al CO32- LDH), has been proved to be a hydroxide ion conductor. An alkalinetype DEFC using Mg-Al CO32- LDH as the electrolyte and aqueous solution of ethanol and potassium hydroxide as a source of fuel exhibited excellent electrochemical performance.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkaline pH sensor molecules.

PubMed

Murayama, Takashi; Maruyama, Ichiro N

2015-11-01

Animals can survive only within a narrow pH range. This requires continual monitoring of environmental and body-fluid pH. Although a variety of acidic pH sensor molecules have been reported, alkaline pH sensor function is not well understood. This Review describes neuronal alkaline pH sensors, grouped according to whether they monitor extracellular or intracellular alkaline pH. Extracellular sensors include the receptor-type guanylyl cyclase, the insulin receptor-related receptor, ligand-gated Cl- channels, connexin hemichannels, two-pore-domain K+ channels, and transient receptor potential (TRP) channels. Intracellular sensors include TRP channels and gap junction channels. Identification of molecular mechanisms underlying alkaline pH sensing is crucial for understanding how animals respond to environmental alkaline pH and how body-fluid pH is maintained within a narrow range. © 2015 Wiley Periodicals, Inc.

Alkaline battery operational methodology

DOEpatents

Sholklapper, Tal; Gallaway, Joshua; Steingart, Daniel; Ingale, Nilesh; Nyce, Michael

2016-08-16

Methods of using specific operational charge and discharge parameters to extend the life of alkaline batteries are disclosed. The methods can be used with any commercial primary or secondary alkaline battery, as well as with newer alkaline battery designs, including batteries with flowing electrolyte. The methods include cycling batteries within a narrow operating voltage window, with minimum and maximum cut-off voltages that are set based on battery characteristics and environmental conditions. The narrow voltage window decreases available capacity but allows the batteries to be cycled for hundreds or thousands of times.

Organic syntheses employing supercritical carbon dioxide as a reaction solvent

NASA Technical Reports Server (NTRS)

Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

1993-01-01

Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

Organic syntheses employing supercritical carbon dioxide as a reaction solvent

NASA Technical Reports Server (NTRS)

Barstow, Leon E. (Inventor); Ward, Glen D. (Inventor); Bier, Milan (Inventor)

1991-01-01

Chemical reactions are readily carried out using supercritical carbon dioxide as the reaction medium. Supercritical carbon dioxide is of special value as a reaction medium in reactions for synthesizing polypeptides, for sequencing polypeptides, or for amino acid analysis.

A facile synthesis of highly stable multiblock poly(arylene ether)s based alkaline membranes for fuel cells

NASA Astrophysics Data System (ADS)

Jasti, Amaranadh; Shahi, Vinod K.

2014-12-01

Herein, we are disclosing simple route for the preparation of alkaline membranes (AMs) based on aminated multiblock poly(arylene ether)s (AMPEs) synthesized by nucleophilic substitution-poly condensation followed by quaternization and alkalization reactions. In this procedure, four quaternary ammonium groups are successfully introduced without use of carcinogenic reagents such as chloromethylmethyl ether (CMME). Hydrophilic/hydrophobic phase separation is responsible for their high hydroxide conductivity (∼150 mS cm-1 at 80 °C) due to development of interconnected ion transport pathway. AMs are exhibiting good alkaline stability due to the presence of two vicinal quaternary ammonium groups and avoid degradation such as Sommelet-Hauser rearrangement and Hofmann elimination. Vicinal quaternary ammonium groups also resist nucleophilic (OH-) attack and suppress the Stevens rearrangement as well as SN2 substitution reaction due to stearic hindrance. Optimized AM (AMPE-M20N15 (55% DCM)) exhibits about 0.95 V open circuit voltage (OCV) and 48.8 mW cm-2 power density at 65 °C in alkaline direct methanol fuel cell (ADMFC) operation. These results suggest promising begin for the preparation of stable and conductive AMs for ADMFC applications and useful for developing hydroxide conductive materials.

Porous carbon supported Fe-N-C composite as an efficient electrocatalyst for oxygen reduction reaction in alkaline and acidic media

NASA Astrophysics Data System (ADS)

Liu, Baichen; Huang, Binbin; Lin, Cheng; Ye, Jianshan; Ouyang, Liuzhang

2017-07-01

In recent years, non-precious metal electrocatalysts for oxygen reduction reaction (ORR) have attracted tremendous attention due to their high catalytic activity, long-term stability and excellent methanol tolerance. Herein, the porous carbon supported Fe-N-C catalysts for ORR were synthesized by direct pyrolysis of ferric chloride, 6-Chloropyridazin-3-amine and carbon black. Variation of pyrolysis temperature during the synthesis process leads to the difference in ORR catalytic activity. High pyrolysis temperature is beneficial to the formation of the "N-Fe" active sites and high electrical conductivity, but the excessive temperature will cause the decomposition of nitrogen-containing active sites, which are revealed by Raman, TGA and XPS. A series of synthesis and characterization experiments with/without nitrogen or iron in carbon black indicate that the coordination of iron and nitrogen plays a crucial role in achieving excellent ORR performances. Electrochemical test results show that the catalyst pyrolyzed at 800 °C (Fe-N-C-800) exhibits excellent ORR catalytic activity, better methanol tolerance and higher stability compared with commercial Pt/C catalyst in both alkaline and acidic conditions.

Alkaline thermal sludge hydrolysis.

PubMed

Neyens, E; Baeyens, J; Creemers, C

2003-02-28

The waste activated sludge (WAS) treatment of wastewater produces excess sludge which needs further treatment prior to disposal or incineration. A reduction in the amount of excess sludge produced, and the increased dewaterability of the sludge are, therefore, subject of renewed attention and research. A lot of research covers the nature of the sludge solids and associated water. An improved dewaterability requires the disruption of the sludge cell structure. Previous investigations are reviewed in the paper. Thermal hydrolysis is recognized as having the best potential to meet the objectives and acid thermal hydrolysis is most frequently used, despite its serious drawbacks (corrosion, required post-neutralization, solubilization of heavy metals and phosphates, etc.). Alkaline thermal hydrolysis has been studied to a lesser extent, and is the subject of the detailed laboratory-scale research reported in this paper. After assessing the effect of monovalent/divalent cations (respectively, K(+)/Na(+) and Ca(2+)/Mg(2+)) on the sludge dewaterability, only the use of Ca(2+) appears to offer the best solution. The lesser effects of K(+), Na(+) and Mg(2+) confirm previous experimental findings. As a result of the experimental investigations, it can be concluded that alkaline thermal hydrolysis using Ca(OH)(2) is efficient in reducing the residual sludge amounts and in improving the dewaterability. The objectives are fully met at a temperature of 100 degrees C; at a pH approximately 10 and for a 60-min reaction time, where all pathogens are moreover killed. Under these optimum conditions, the rate of mechanical dewatering increases (the capillary suction time (CST) value is decreased from approximately 34s for the initial untreated sample to approximately 22s for the hydrolyzed sludge sample) and the amount of DS to be dewatered is reduced to approximately 60% of the initial untreated amount. The DS-content of the dewatered cake will be increased from 28 (untreated) to 46

An easy access to nanocrystalline alkaline earth metal fluorides - just by shaking

NASA Astrophysics Data System (ADS)

Dreger, M.; Scholz, G.; Kemnitz, E.

2012-04-01

High energy ball milling as fast, direct and solvent free method allows an easy access to nanocrystalline alkaline earth metal fluorides MF2 (M: Mg, Ca, Sr, Ba). Comparable metal sources (acetates, carbonates, hydroxides, alkoxides) were used for the reaction with NH4F as fluorinating agent. Even very simple manual shaking experiments between NH4F and the corresponding hydroxides in the stoichiometric ratio (M:F = 1:2, M: Ca, Sr, Ba) give phase pure fluorides. Moreover, comparable classical thermal reactions in closed crucibles at higher temperatures provide phase pure crystalline fluorides in nearly all cases as well.

Online assay of bone specific alkaline phosphatase with a flow injection-bead injection system.

PubMed

Hartwell, Supaporn Kradtap; Somprayoon, Duangporn; Kongtawelert, Prachya; Ongchai, Siriwan; Arppornchayanon, Olarn; Ganranoo, Lucksagoon; Lapanantnoppakhun, Somchai; Grudpan, Kate

2007-09-26

Alkaline phosphatase (ALP) has been used as one of the biomarkers for bone resorption and liver diseases. Normally, total alkaline phosphatase is quantified along with other symptoms to determine the releasing source of the alkaline phosphatase. A semi-automated flow injection-bead injection system was proposed to conveniently and selectively assay bone alkaline phosphatase (BALP) based on its specific binding to wheat germ coated beads. Amount of BALP in serum was determined from the intensity of the yellow product produced from bound BALP on the retained beads and its substrate pNPP. The used beads were discarded and the fresh ones were introduced for the next analysis. The reaction cell was designed to be opened and closed using a computer controlled solenoid valve for a precise incubation time. The performance of the proposed system was evaluated by using it to assay BALP in human serum. The results were compared to those obtained by using a commercial ELISA kit. The system is proposed to be an easy and cost effective system for quantification of BALP as an alternative to batch wise wheat germ specific binding technique.

Probable levetiracetam-related serum alkaline phosphatase elevation

PubMed Central

2012-01-01

Background Levetiracetam (LEV) is an antiepileptic drug with a favorable tolerability and safety profile with little or no effect on liver function. Case presentation Here, we reported an epileptic pediatric patient who developed a significant elevation in serum alkaline phosphatase level (ALP) during LEV monotherapy. Moreover, the serum ALP level was surprisingly decreased to normal after LEV discontinuation. The Naranjo Adverse Drug Reaction Probability Scale score was 6, indicating firstly LEV was a probable cause for the increased serum ALP. Conclusions Cautious usage and concerns of the LEV-associated potential ALP elevation should be considered when levetiracetam is prescribed to epilepsy patients, especially pediatric patients. PMID:22994584

Extraction of In-Medium Nucleon-Nucleon Amplitude From Experiment

NASA Technical Reports Server (NTRS)

Tripathi, R. K.; Cucinotta, Francis A.; Wilson, John W.

1998-01-01

The in-medium nucleon-nucleon amplitudes are extracted from the available proton-nucleus total reaction cross sections data. The retrieval of the information from the experiment makes the estimate of reaction cross sections very reliable. Simple expressions are given for the in-medium nucleon-nucleon amplitudes for any system of colliding nuclei as a function of energy. Excellent agreement with experimental observations is demonstrated in the ion-nucleus interactions.

Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

PubMed

Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M

2015-01-01

Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan's upper atmosphere and the interstellar medium

NASA Astrophysics Data System (ADS)

Wang, Zhe-Chen; Bierbaum, Veronica M.

2016-06-01

The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

A newly high alkaline lipase: an ideal choice for application in detergent formulations

PubMed Central

2011-01-01

Background Bacterial lipases received much attention for their substrate specificity and their ability to function in extreme environments (pH, temperature...). Many staphylococci produced lipases which were released into the culture medium. Reports of thermostable lipases from Staphylococcus sp. and active in alkaline conditions are not previously described. Results A newly soil-isolated Staphylococcus sp. strain ESW secretes an induced lipase in the culture medium. The effects of temperature, pH and various components in a detergent on the activity and stability of Staphylococcus sp. lipase (SL1) were studied in a preliminary evaluation for use in detergent formulation solutions. The enzyme was highly active over a wide range of pH from 9.0 to 13.0, with an optimum at pH 12.0. The relative activity at pH 13.0 was about 60% of that obtained at pH 12.0. It exhibited maximal activity at 60°C. This novel lipase, showed extreme stability towards non-ionic and anionic surfactants after pre-incubation for 1 h at 40°C, and relative stability towards oxidizing agents. Additionally, the crude enzyme showed excellent stability and compatibility with various commercial solid and liquid detergents. Conclusions These properties added to the high activity in high alkaline pH make this novel lipase an ideal choice for application in detergent formulations. PMID:22123072

Chronic neutrophilic leukaemia and plasma cell-related neutrophilic leukaemoid reactions.

PubMed

Bain, Barbara J; Ahmad, Shahzaib

2015-11-01

Many cases reported as 'chronic neutrophilic leukaemia' have had an associated plasma cell neoplasm. Recent evidence suggests that the great majority of such cases represent a neutrophilic leukaemoid reaction to the underlying multiple myeloma or monoclonal gammopathy of undetermined significance. We have analysed all accessible reported cases to clarify the likely diagnosis and to ascertain whether toxic granulation, Döhle bodies and an increased neutrophil alkaline phosphatase score were useful in making a distinction between chronic neutrophilic leukaemia and a neutrophilic leukaemoid reaction. We established that all these changes occur in both conditions. Toxic granulation and Döhle bodies are more consistently present in leukaemoid reactions but also occur quite frequently in chronic neutrophilic leukaemia. The neutrophil alkaline phosphatase score is increased in both conditions and is of no value in making a distinction. © 2015 John Wiley & Sons Ltd.

Anodes for alkaline electrolysis

DOEpatents

Soloveichik, Grigorii Lev [Latham, NY

2011-02-01

A method of making an anode for alkaline electrolysis cells includes adsorption of precursor material on a carbonaceous material, conversion of the precursor material to hydroxide form and conversion of precursor material from hydroxide form to oxy-hydroxide form within the alkaline electrolysis cell.

Effect of alkaline microwaving pretreatment on anaerobic digestion and biogas production of swine manure.

PubMed

Yu, Tao; Deng, Yihuan; Liu, Hongyu; Yang, Chunping; Wu, Bingwen; Zeng, Guangming; Lu, Li; Nishimura, Fumitake

2017-05-10

Microwave assisted with alkaline (MW-A) condition was applied in the pretreatment of swine manure, and the effect of the pretreatment on anaerobic treatment and biogas production was evaluated in this study. The two main microwaving (MW) parameters, microwaving power and reaction time, were optimized for the pretreatment. Response surface methodology (RSM) was used to investigate the effect of alkaline microwaving process for manure pretreatment at various values of pH and energy input. Results showed that the manure disintegration degree was maximized of 63.91% at energy input of 54 J/g and pH of 12.0, and variance analysis indicated that pH value played a more important role in the pretreatment than in energy input. Anaerobic digestion results demonstrated that MW-A pretreatment not only significantly increased cumulative biogas production, but also shortened the duration for a stable biogas production rate. Therefore, the alkaline microwaving pretreatment could become an alternative process for effective treatment of swine manure.

A single pH fluorescent probe for biosensing and imaging of extreme acidity and extreme alkalinity.

PubMed

Chao, Jian-Bin; Wang, Hui-Juan; Zhang, Yong-Bin; Li, Zhi-Qing; Liu, Yu-Hong; Huo, Fang-Jun; Yin, Cai-Xia; Shi, Ya-Wei; Wang, Juan-Juan

2017-07-04

A simple tailor-made pH fluorescent probe 2-benzothiazole (N-ethylcarbazole-3-yl) hydrazone (Probe) is facilely synthesized by the condensation reaction of 2-hydrazinobenzothiazole with N-ethylcarbazole-3-formaldehyde, which is a useful fluorescent probe for monitoring extremely acidic and alkaline pH, quantitatively. The pH titrations indicate that Probe displays a remarkable emission enhancement with a pK a of 2.73 and responds linearly to minor pH fluctuations within the extremely acidic range of 2.21-3.30. Interestingly, Probe also exhibits strong pH-dependent characteristics with pK a 11.28 and linear response to extreme-alkalinity range of 10.41-12.43. In addition, Probe shows a large Stokes shift of 84 nm under extremely acidic and alkaline conditions, high selectivity, excellent sensitivity, good water-solubility and fine stability, all of which are favorable for intracellular pH imaging. The probe is further successfully applied to image extremely acidic and alkaline pH values fluctuations in E. coli cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Surfactant-enhanced alkaline flooding: Buffering at intermediate alkaline pH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rudin, J.; Wasan, D.T.

1993-11-01

The alkaline flooding process involves injecting alkaline agents into the reservoir to produce more oil than is produced through conventional waterflooding. The interaction of the alkali in the flood water with the naturally occurring acids in the reservoir oil results in in-situ formation of soaps, which are partially responsible for lowering IFT and improving oil recovery. The extent to which IFT is lowered depends on the specific oil and injection water properties. Numerous investigators have attempted to clarify the relationship between system chemical composition and IFT. An experimental investigation of buffered alkaline flooding system chemistry was undertaken to determine themore » influence of various species present on interfacial tension (IFT) as a function of pH and ionic strength. IFT was found to go through an ultralow minimum in certain pH ranges. This synergism results from simultaneous adsorption of un-ionized and ionized acid species on the interface.« less

Wild soybean roots depend on specific transcription factors and oxidation reduction related genesin response to alkaline stress.

PubMed

DuanMu, Huizi; Wang, Yang; Bai, Xi; Cheng, Shufei; Deyholos, Michael K; Wong, Gane Ka-Shu; Li, Dan; Zhu, Dan; Li, Ran; Yu, Yang; Cao, Lei; Chen, Chao; Zhu, Yanming

2015-11-01

Soil alkalinity is an important environmental problem limiting agricultural productivity. Wild soybean (Glycine soja) shows strong alkaline stress tolerance, so it is an ideal plant candidate for studying the molecular mechanisms of alkaline tolerance and identifying alkaline stress-responsive genes. However, limited information is available about G. soja responses to alkaline stress on a genomic scale. Therefore, in the present study, we used RNA sequencing to compare transcript profiles of G. soja root responses to sodium bicarbonate (NaHCO3) at six time points, and a total of 68,138,478 pairs of clean reads were obtained using the Illumina GAIIX. Expression patterns of 46,404 G. soja genes were profiled in all six samples based on RNA-seq data using Cufflinks software. Then, t12 transcription factors from MYB, WRKY, NAC, bZIP, C2H2, HB, and TIFY families and 12 oxidation reduction related genes were chosen and verified to be induced in response to alkaline stress by using quantitative real-time polymerase chain reaction (qRT-PCR). The GO functional annotation analysis showed that besides "transcriptional regulation" and "oxidation reduction," these genes were involved in a variety of processes, such as "binding" and "response to stress." This is the first comprehensive transcriptome profiling analysis of wild soybean root under alkaline stress by RNA sequencing. Our results highlight changes in the gene expression patterns and identify a set of genes induced by NaHCO3 stress. These findings provide a base for the global analyses of G. soja alkaline stress tolerance mechanisms.

Ionomic and metabolic responses to neutral salt or alkaline salt stresses in maize (Zea mays L.) seedlings.

PubMed

Guo, Rui; Shi, LianXuan; Yan, Changrong; Zhong, Xiuli; Gu, FengXue; Liu, Qi; Xia, Xu; Li, Haoru

2017-02-10

Soil salinity and alkalinity present a serious threat to global agriculture. However, most of the studies have focused on neutral salt stress, and the information on the metabolic responses of plants to alkaline salt stress is limited. This investigation aimed at determining the influence of neutral salt and alkaline salt stresses on the content of metal elements and metabolites in maize plant tissues, by using mixtures of various proportions of NaCl, NaHCO 3 , Na 2 SO 4 , and Na 2 CO 3 . We found that alkaline salt stress suppressed more pronouncedly the photosynthesis and growth of maize plants than salinity stress. Under alkaline salt stress conditions, metal ions formed massive precipitates, which ultimately reduced plant nutrient availability. On the other hand, high neutral salt stress induced metabolic changes in the direction of gluconeogenesis leading to the enhanced formation of sugars as a reaction contributing to the mitigation of osmotic stress. Thus, the active synthesis of sugars in shoots was essential to the development of salt tolerance. However, the alkaline salt stress conditions characterized by elevated pH values suppressed substantially the levels of photosynthesis, N metabolism, glycolysis, and the production of sugars and amino acids. These results indicate the presence of different defensive mechanisms responsible for the plant responses to neutral salt and alkaline salt stresses. In addition, the increased concentration of organic acids and enhanced metabolic energy might be potential major factors that can contribute to the maintenance intracellular ion balance in maize plants and counteract the negative effects of high pH under alkaline salt stress.

A novel IrNi@PdIr/C core-shell electrocatalyst with enhanced activity and durability for the hydrogen oxidation reaction in alkaline anion exchange membrane fuel cells.

PubMed

Qin, Bowen; Yu, Hongmei; Jia, Jia; Jun, Chi; Gao, Xueqiang; Yao, Dewei; Sun, Xinye; Song, Wei; Yi, Baolian; Shao, Zhigang

2018-03-08

Herein, a novel non-platinum core-shell catalyst, namely, IrNi@PdIr/C was prepared via a galvanic replacement reaction; it exhibits enhanced hydrogen oxidation activity and excellent stability under alkaline conditions. Electrochemical experiments demonstrated that the mass and specific activities at 50 mV of IrNi@PdIr/C are 2.1 and 2.2 times that of commercial Pt/C in 0.1 M KOH at 298 K, respectively. Moreover, accelerated degradation tests have shown that the electrochemically active surface area (ECSA) of IrNi@PdIr/C reduces by only 5.1%, which is almost 4 times less than that of commercial Pt/C and the mass activity at 50 mV of IrNi@PdIr/C after 2000 potential cycles is still 1.8 times higher than that of aged Pt/C. XRD and XPS analysis suggest that the enhanced HOR activity is attributed to the weakening of the hydrogen binding to the PdIr overlayers induced by the IrNi core. The better stability to potential cycling can be associated with the PdIr shell, which inhibits oxide formation. These results suggest that IrNi@PdIr/C is a promising non-platinum anode catalyst for alkaline anion exchange membrane fuel cells.

A green method of graphene preparation in an alkaline environment.

PubMed

Štengl, Václav; Henych, Jiří; Bludská, Jana; Ecorchard, Petra; Kormunda, Martin

2015-05-01

We present a new, simple, quick and ecologically friendly method of exfoliating graphite to produce graphene. The method is based on the intercalation of a permanganate M2MnO4 (M=K, Na, Li), which is formed by the reaction of a manganate MMnO4 with an alkali metal hydroxide MOH. The quality of exfoliation and the morphology were determined using X-ray photoelectron spectroscopy, X-ray diffraction and microscopic techniques, including transmission electron microscopy and atomic force microscopy. We observed that a stable graphene suspension could be prepared under strongly alkaline conditions in the presence of permanganate and ultrasound assistance. The use of only an alkaline environment for the direct preparation of graphene from graphite structures has not been previously described or applied. It was found that such a method of preparation leads to surprisingly high yields and a stable product for hydrophilic graphene applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Study of in-medium {\\eta }^{\\prime} properties in the (γ, \\eta ^{\\prime} p) reaction on nuclei

NASA Astrophysics Data System (ADS)

Paryev, E. Ya

2016-01-01

We study the near-threshold photoproduction of {η }\\prime mesons from nuclei in coincidence with forward going protons in the kinematical conditions of the Crystal Barrel/TAPS experiment, recently performed at ELSA. The calculations have been performed within a collision model based on the nuclear spectral function. The model accounts for both the primary γ p\\to η \\prime p process and the two-step intermediate nucleon rescattering processes as well as the effect of the nuclear η \\prime mean-field potential. We calculate the exclusive η \\prime kinetic energy distributions for the 12C(γ, η \\prime p) reaction for different scenarios of η \\prime in-medium modification. We find that the considered two-step rescattering mechanism plays an insignificant role in η \\prime p photoproduction off the carbon target. We also demonstrate that the calculated η \\prime kinetic energy distributions in primary photon-proton η \\prime p production reveal strong sensitivity to the depth of the real η \\prime potential at normal nuclear matter density (or to the η \\prime in-medium mass shift) in the studied incident photon energy regime. Therefore, such observables may be useful to help determine the above η \\prime in-medium renormalization from the comparison of the results of our calculations with the data from the CBELSA/TAPS experiment. In addition, we show that these distributions are also strongly influenced by the momentum-dependent optical potential, which the outgoing participant proton feels inside the carbon nucleus. This potential should be taken into account in the analysis of these data with the aim to obtain information on the η \\prime modification in cold nuclear matter.

Optimization of the Synthesis of Structured Phosphatidylcholine with Medium Chain Fatty Acid.

PubMed

Ochoa-Flores, Angélica A; Hernández-Becerra, Josafat A; Cavazos-Garduño, Adriana; Vernon-Carter, Eduardo J; García, Hugo S

2017-11-01

Structured phosphatidylcholine was successfully produced by acidolysis between phosphatidylcholine and free medium chain fatty acid, using phospholipase A 1 immobilized on Duolite A568. Response surface methodology was applied to optimize the reaction system using three process parameters: molar ratio of substrates (phosphatidylcholine to free medium chain fatty acid), enzyme loading, and reaction temperature. All parameters evaluated showed linear and quadratic significant effects on the production of modified phosphatidylcholine; molar ratio of substrates contributed positively, but temperature influenced negatively. Increased enzyme loading also led to increased production of modified phosphatidylcholine but only during the first 9 hours of the acidolysis reaction. Optimal conditions obtained from the model were a ratio of phosphatidylcholine to free medium chain fatty acid of 1:15, an enzyme loading of 12%, and a temperature of 45°C. Under these conditions a production of modified phosphatidylcholine of 52.98 % were obtained after 24 h of reaction. The prediction was confirmed from the verification experiments; the production of modified phosphatidylcholine was 53.02%, the total yield of phosphatidylcholine 64.28% and the molar incorporation of medium chain fatty acid was 42.31%. The acidolysis reaction was scaled-up in a batch reactor with a similar production of modified phosphatidylcholine, total yield of phosphatidylcholine and molar incorporation of medium chain fatty acid. Purification by column chromatography of the structured phosphatidylcholine yielded 62.53% of phosphatidylcholine enriched with 42.52% of medium chain fatty acid.

Effect of alkaline addition on anaerobic sludge digestion with combined pretreatment of alkaline and high pressure homogenization.

PubMed

Fang, Wei; Zhang, Panyue; Zhang, Guangming; Jin, Shuguang; Li, Dongyi; Zhang, Meixia; Xu, Xiangzhe

2014-09-01

To improve anaerobic digestion efficiency, combination pretreatment of alkaline and high pressure homogenization was applied to pretreat sewage sludge. Effect of alkaline dosage on anaerobic sludge digestion was investigated in detail. SCOD of sludge supernatant significantly increased with the alkaline dosage increase after the combined pretreatment because of sludge disintegration. Organics were significantly degraded after the anaerobic digestion, and the maximal SCOD, TCOD and VS removal was 73.5%, 61.3% and 43.5%, respectively. Cumulative biogas production, methane content in biogas and biogas production rate obviously increased with the alkaline dosage increase. Considering both the biogas production and alkaline dosage, the optimal alkaline dosage was selected as 0.04 mol/L. Relationships between biogas production and sludge disintegration showed that the accumulative biogas was mainly enhanced by the sludge disintegration. The methane yield linearly increased with the DDCOD increase as Methane yield (ml/gVS)=4.66 DDCOD-9.69. Copyright © 2014 Elsevier Ltd. All rights reserved.

New medium for detection of esterase and gelatinase activity.

PubMed

Pácová, Z; Kocur, M

1984-10-01

A new medium was developed for detecting esterase and gelatinase activities in aerobic and facultatively anaerobic bacteria. The new medium was tested with various strains of bacteria and the results showed agreement between the reactions in the new medium and those obtained by conventional techniques. The new medium is more economical and may be used for a rapid differentiation of Serratia, Aeromonas and Vibrio species from biochemically similar bacteria.

Pediatric reference intervals for alkaline phosphatase.

PubMed

Zierk, Jakob; Arzideh, Farhad; Haeckel, Rainer; Cario, Holger; Frühwald, Michael C; Groß, Hans-Jürgen; Gscheidmeier, Thomas; Hoffmann, Reinhard; Krebs, Alexander; Lichtinghagen, Ralf; Neumann, Michael; Ruf, Hans-Georg; Steigerwald, Udo; Streichert, Thomas; Rascher, Wolfgang; Metzler, Markus; Rauh, Manfred

2017-01-01

Interpretation of alkaline phosphatase activity in children is challenging due to extensive changes with growth and puberty leading to distinct sex- and age-specific dynamics. Continuous percentile charts from birth to adulthood allow accurate consideration of these dynamics and seem reasonable for an analyte as closely linked to growth as alkaline phosphatase. However, the ethical and practical challenges unique to pediatric reference intervals have restricted the creation of such percentile charts, resulting in limitations when clinical decisions are based on alkaline phosphatase activity. We applied an indirect method to generate percentile charts for alkaline phosphatase activity using clinical laboratory data collected during the clinical care of patients. A total of 361,405 samples from 124,440 patients from six German tertiary care centers and one German laboratory service provider measured between January 2004 and June 2015 were analyzed. Measurement of alkaline phosphatase activity was performed on Roche Cobas analyzers using the IFCC's photometric method. We created percentile charts for alkaline phosphatase activity in girls and boys from birth to 18 years which can be used as reference intervals. Additionally, data tables of age- and sex-specific percentile values allow the incorporation of these results into laboratory information systems. The percentile charts provided enable the appropriate differential diagnosis of changes in alkaline phosphatase activity due to disease and changes due to physiological development. After local validation, integration of the provided percentile charts into result reporting facilitates precise assessment of alkaline phosphatase dynamics in pediatrics.

The Alkaline Diet: Is There Evidence That an Alkaline pH Diet Benefits Health?

PubMed Central

Schwalfenberg, Gerry K.

2012-01-01

This review looks at the role of an alkaline diet in health. Pubmed was searched looking for articles on pH, potential renal acid loads, bone health, muscle, growth hormone, back pain, vitamin D and chemotherapy. Many books written in the lay literature on the alkaline diet were also reviewed and evaluated in light of the published medical literature. There may be some value in considering an alkaline diet in reducing morbidity and mortality from chronic diseases and further studies are warranted in this area of medicine. PMID:22013455

Pyrophosphate as substrate for alkaline phosphatase activity: A convenient flow-injection chemiluminescence assay.

PubMed

Zhang, Qingfeng; Zhang, Cuiyun; Yang, Meiding; Yu, Donghong; Yu, Cong

2017-11-01

A sensitive and convenient flow-injection chemiluminescence (FI-CL) turn-on assay for alkaline phosphatase (ALP) activity without any label and synthesis is developed. Cu 2+ can catalyze the luminol-H 2 O 2 CL reaction. Pyrophosphate (PPi) can chelate Cu 2+ and therefore the Cu 2+ -mediated luminol-H 2 O 2 CL reaction is inhibited. The addition of ALP can catalyze the hydrolysis of PPi into phosphate ions, Cu 2+ is released and the chemiluminescence recovers. A detection limit of 1 mU/mL ALP is obtained. Copyright © 2017 John Wiley & Sons, Ltd.

Interfacial activity in alkaline flooding enhanced oil recovery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chan, M.K.

1981-01-01

The ionization of long-chained organic acids in the crude oil to form soaps was shown to be primarily responsible for the lowering of oil-water interfacial tension at alkaline pH. These active acids can be concentrated by silica gel chromatography into a minor polar fraction. An equilibrium chemical model was proposed based on 2 competing reactions: the ionization of acids to form active anions, and the formation of undissociated soap between acid anions and sodium ions. It correlates the interfacial activity with the interfacial concentration of active acid anions which is expressed in terms of the concentrations of the chemical speciesmore » in the system. The model successfully predicts the observed oil-alkaline solution interfacial phenomenon, including its dependence on pH, alkali and salt concentrations, type of acid present and type of soap formed. Flooding at different alkali concentrations to activate different acid species present in the crude was shown to give better recovery than flooding at a single high alkali concentration. Treating the crude oil with a dilute solution of mineral acids liberates additional free active acids and yields better interfacial activity during subsequent alkali contact.« less

Characterization and quantification of biochar alkalinity.

PubMed

Fidel, Rivka B; Laird, David A; Thompson, Michael L; Lawrinenko, Michael

2017-01-01

Lack of knowledge regarding the nature of biochar alkalis has hindered understanding of pH-sensitive biochar-soil interactions. Here we investigate the nature of biochar alkalinity and present a cohesive suite of methods for its quantification. Biochars produced from cellulose, corn stover and wood feedstocks had significant low-pK a organic structural (0.03-0.34 meq g -1 ), other organic (0-0.92 meq g -1 ), carbonate (0.02-1.5 meq g -1 ), and other inorganic (0-0.26 meq g -1 ) alkalinities. All four categories of biochar alkalinity contributed to total biochar alkalinity and are therefore relevant to pH-sensitive soil processes. Total biochar alkalinity was strongly correlated with base cation concentration, but biochar alkalinity was not a simple function of elemental composition, soluble ash, fixed carbon, or volatile matter content. More research is needed to characterize soluble biochar alkalis other than carbonates and to establish predictive relationships among biochar production parameters and the composition of biochar alkalis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Millimeter-scale alkalinity measurement in marine sediment using DET probes and colorimetric determination.

PubMed

Metzger, E; Viollier, E; Simonucci, C; Prévot, F; Langlet, D; Jézéquel, D

2013-10-01

Constrained DET (Diffusive Equilibration in Thin films) probes equipped with 75 sampling layers of agarose gel (DGT Research(©)) were used to sample bottom and pore waters in marine sediment with a 2 mm vertical resolution. After retrieval, each piece of hydrogel, corresponding to 25 μL, was introduced into 1 mL of colorimetric reagent (CR) solution consisting of formic acid and bromophenol blue. After the elution/reaction time, absorbance of the latter mixture was read at 590 nm and compared to a calibration curve obtained with the same protocol applied to mini DET probes soaked in sodium hydrogen carbonate standard solutions. This method allows rapid alkalinity determinations for the small volumes of anoxic pore water entrapped into the gel. The method was assessed on organic-rich coastal marine sediments from Thau lagoon (France). Alkalinity values in the overlying waters were in agreement with data obtained by classical sampling techniques. Pore water data showed a progressive increase of alkalinity in the sediment from 2 to 10 mmol kg(-1), corresponding to anaerobic respiration in organic-rich sediments. Moreover, replicates of high-resolution DET profiles showed important lateral heterogeneity at a decimeter scale. This underlines the importance of high-resolution spatial methods for alkalinity profiling in coastal marine systems. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mineral Carbonation Potential of CO2 from Natural and Industrial-based Alkalinity Sources

NASA Astrophysics Data System (ADS)

Wilcox, J.; Kirchofer, A.

2014-12-01

Mineral carbonation is a Carbon Capture and Storage (CSS) technology where gaseous CO2 is reacted with alkaline materials (such as silicate minerals and alkaline industrial wastes) and converted into stable and environmentally benign carbonate minerals (Metz et al., 2005). Here, we present a holistic, transparent life cycle assessment model of aqueous mineral carbonation built using a hybrid process model and economic input-output life cycle assessment approach. We compared the energy efficiency and the net CO2 storage potential of various mineral carbonation processes based on different feedstock material and process schemes on a consistent basis by determining the energy and material balance of each implementation (Kirchofer et al., 2011). In particular, we evaluated the net CO2 storage potential of aqueous mineral carbonation for serpentine, olivine, cement kiln dust, fly ash, and steel slag across a range of reaction conditions and process parameters. A preliminary systematic investigation of the tradeoffs inherent in mineral carbonation processes was conducted and guidelines for the optimization of the life-cycle energy efficiency are provided. The life-cycle assessment of aqueous mineral carbonation suggests that a variety of alkalinity sources and process configurations are capable of net CO2 reductions. The maximum carbonation efficiency, defined as mass percent of CO2 mitigated per CO2 input, was 83% for CKD at ambient temperature and pressure conditions. In order of decreasing efficiency, the maximum carbonation efficiencies for the other alkalinity sources investigated were: olivine, 66%; SS, 64%; FA, 36%; and serpentine, 13%. For natural alkalinity sources, availability is estimated based on U.S. production rates of a) lime (18 Mt/yr) or b) sand and gravel (760 Mt/yr) (USGS, 2011). The low estimate assumes the maximum sequestration efficiency of the alkalinity source obtained in the current work and the high estimate assumes a sequestration efficiency

OPTIMIZATION OF ALKALINE Α-AMYLASE PRODUCTION BY THERMOPHILIC BACILL US SUBTILIS.

PubMed

Al-Johani, Nuha Bakeet; Al-Seeni, Madeha N; Ahmed, Youssri Mohamed

2017-01-01

Starch-degrading amylase enzyme is important in biotechnological applications as food, fermentation, textile, paper and pharmaceutical purposes. The aim of current study to isolate alkaline thermostable α-amylase bacteria and then study the composition of medium and culture conditions to optimize cells growth and a-amylase production. Thermophilic amylase producing bacterium was isolated from local hot water-springs in Gazan city Saudi Arabia. Phylogenetic analysis of 16 S rRNA sequence for the strain revealed that the strain have the same sequence of Bacillus subtilis . Maximum amylase production was observed, when B. subtilis cultured in medium containing starch at concentration 0.5%, and 10 g/L peptones as nitrogen source at pH 8.5 in when it was incubated for 48 h at 45°C. An amylase-producing bacterium were isolated from hot-spring water and was identified as B. subtilis . Amylase produced from B.subtilis had optimum temperature 45°C and pH 8.5 in shaking media.

Copper-zinc electrodeposition in alkaline-sorbitol medium: Electrochemical studies and structural, morphological and chemical composition characterization

NASA Astrophysics Data System (ADS)

de Almeida, M. R. H.; Barbano, E. P.; de Carvalho, M. F.; Tulio, P. C.; Carlos, I. A.

2015-04-01

The galvanostatic technique was used to analyze the electrodeposition of Cu-Zn on to AISI 1010 steel electrode from an alkaline-sorbitol bath with various proportions of the metal ions in the bath: Cu70/Zn30, Cu50/Zn50 and Cu30/Zn70. Coloration of Cu-Zn films were whitish golden, light golden, golden/gray depending on the Cu2+/Zn2+ ratios in the electrodeposition bath, deposition current density (jdep) and charge density (qdep). The highest current efficiency was ∼54.0%, at jdep -1.0 mA cm-2 and qdep 0.40 C cm-2 in the Cu70/Zn30 bath. Energy dispersive spectroscopy indicated that electrodeposits produced from the bath Cu70/Zn30 showed higher Cu content at lower jdep. Also, for same jdep the Cu content increased with qdep. Scanning electron microscopy showed that Cu-Zn electrodeposits of high quality were obtained from the Cu70/Zn30 bath, since the films were fine-grained, except the obtained at jdep -20.0 mA cm-2 and qdep 10.0 C cm-2. Also, these electrodeposits did not present cracks. X-ray analysis of the Cu-Zn electrodeposits obtained at jdep -8.0, -20.0 and -40.0 mA cm-2, in each case, with qdep 2.0 and 10.0 C cm-2, in the Cu70/Zn30 bath, suggested the occurrence of a mixture of the following phases, CuZn, CuZn5 and Cu5Zn8. Galvanostatic electrodeposits of Cu-Zn obtained from sorbitol-alkaline baths exhibited whitish golden color, with good prospects for industrial applications, especially for decorative purposes.

Estrogen and phenol red free medium for osteoblast culture: study of the mineralization ability.

PubMed

de Faria, A N; Zancanela, D C; Ramos, A P; Torqueti, M R; Ciancaglini, P

2016-08-01

To design an estrogen and phenol red free medium for cell culture and check its effectiveness and safety on osteoblast growth it is necessary to maintain the estrogen receptors free for tests. For this purpose, we tested some modifications of the traditional culture media: estrogen depleted fetal bovine serum; estrogen charcoal stripped fetal bovine serum and phenol red free α-MEM. The aim of this work is to examine the effects of its depletion in the proliferation, differentiation, and toxicity of mesenchymal stromal cells differentiated into osteoblasts to obtain an effective interference free culture medium for in vitro studies, focused on non-previously studied estrogen receptors. We performed viability tests using the following techniques: MTT, alkaline phosphatase specific activity, formation of mineralized matrix by Alizarin technique and analysis of SEM/EDX of mineralized nodules. The results showed that the culture media with estrogen free α-MEM + phenol red free α-MEM did not impact viability, alkaline phosphatase activity and mineralization of the osteoblasts culture compared to control. In addition, its nodules possess Ca/P ratio similar to hydroxyapatite nodules on the 14th and 21st day. In conclusion, the modified culture medium with phenol red free α-MEM with estrogen depleted fetal bovine serum can be safely used in experiments where the estrogen receptors need to be free.

Formation of Benzene in the Interstellar Medium

NASA Technical Reports Server (NTRS)

Jones, Brant M.; Zhang, Fangtong; Kaiser, Ralf I.; Jamal, Adeel; Mebel, Alexander M.; Cordiner, Martin A.; Charnley, Steven B.; Crim, F. Fleming (Editor)

2010-01-01

Polycyclic aromatic hydrocarbons and related species have been suggested to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block-the aromatic benzene molecule-has remained elusive for decades. Here we demonstrate in crossed molecular beam experiments combined with electronic structure and statistical calculations that benzene (C6H6) can be synthesized via the barrierless, exoergic reaction of the ethynyl radical and 1,3- butadiene, C2H + H2CCHCHCH2 --> C6H6, + H, under single collision conditions. This reaction portrays the simplest representative of a reaction class in which aromatic molecules with a benzene core can be formed from acyclic precursors via barrierless reactions of ethynyl radicals with substituted 1,3-butadlene molecules. Unique gas-grain astrochemical models imply that this low-temperature route controls the synthesis of the very first aromatic ring from acyclic precursors in cold molecular clouds, such as in the Taurus Molecular Cloud. Rapid, subsequent barrierless reactions of benzene with ethynyl radicals can lead to naphthalene-like structures thus effectively propagating the ethynyl-radical mediated formation of aromatic molecules in the interstellar medium.

Electrodeposition of Ni-Mo alloy coatings for water splitting reaction

NASA Astrophysics Data System (ADS)

Shetty, Akshatha R.; Hegde, Ampar Chitharanjan

2018-04-01

The present study reports the development of Ni-Mo alloy coatings for water splitting applications, using a citrate bath the inducing effect of Mo (reluctant metal) on electrodeposition, its relationship with their electrocatalytic efficiency were studied. The alkaline water splitting efficiency of Ni-Mo alloy coatings, for both hydrogen evolution reaction (HER) and oxygen evolution reaction were tested using cyclic voltammetry (CV) and chronopotentiometry (CP) techniques. Moreover, the practical utility of these electrode materials were evaluated by measuring the amount of H2 and O2 gas evolved. The variation in electrocatalytic activity with composition, structure, and morphology of the coatings were examined using XRD, SEM, and EDS analyses. The experimental results showed that Ni-Mo alloy coating is the best electrode material for alkaline HER and OER reactions, at lower and higher deposition current densities (c. d.'s) respectively. This behavior is attributed by decreased Mo and increased Ni content of the alloy coating and the number of electroactive centers.

Alkaline in situ transesterification of Aurantiochytrium sp. KRS 101 using potassium carbonate.

PubMed

Sung, Mina; Han, Jong-In

2016-04-01

The aims of this work were to evaluate K2CO3 as a potent alkaline catalyst for in situ transesterification of Aurantiochytrium sp. KRS 101, one step process in which oil extraction and conversion take place together. This K2CO3-based in situ transesterification was optimized in terms of recovery yield of fatty acid methyl esters (FAMEs) by way of varying biomass concentration, reaction temperature, reaction time, and catalyst concentration. The optimal condition was achieved at 50g/L of biomass concentration and 1% of K2CO3 in the methanol, 25°C of reaction temperature, and 5min of reaction time, resulting in the FAME recovery yield over 90%. It was found that K2CO3 performed better than any other tested catalysts including acids, supporting the notion that K2CO3 is a promising catalyst, especially for in situ transesterification. Copyright © 2016. Published by Elsevier Ltd.

21 CFR 864.7660 - Leukocyte alkaline phosphatase test.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Leukocyte alkaline phosphatase test. 864.7660... Leukocyte alkaline phosphatase test. (a) Identification. A leukocyte alkaline phosphatase test is a device used to identify the enzyme leukocyte alkaline phosphatase in neutrophilic granulocytes (granular...

21 CFR 864.7660 - Leukocyte alkaline phosphatase test.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Leukocyte alkaline phosphatase test. 864.7660... Leukocyte alkaline phosphatase test. (a) Identification. A leukocyte alkaline phosphatase test is a device used to identify the enzyme leukocyte alkaline phosphatase in neutrophilic granulocytes (granular...

21 CFR 864.7660 - Leukocyte alkaline phosphatase test.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Leukocyte alkaline phosphatase test. 864.7660... Leukocyte alkaline phosphatase test. (a) Identification. A leukocyte alkaline phosphatase test is a device used to identify the enzyme leukocyte alkaline phosphatase in neutrophilic granulocytes (granular...

Microbial communities associated with the anthropogenic, highly alkaline environment of a saline soda lime, Poland.

PubMed

Kalwasińska, Agnieszka; Felföldi, Tamás; Szabó, Attila; Deja-Sikora, Edyta; Kosobucki, Przemysław; Walczak, Maciej

2017-07-01

Soda lime is a by-product of the Solvay soda process for the production of sodium carbonate from limestone and sodium chloride. Due to a high salt concentration and alkaline pH, the lime is considered as a potential habitat of haloalkaliphilic and haloalkalitolerant microbial communities. This artificial and unique environment is nutrient-poor and devoid of vegetation, due in part to semi-arid, saline and alkaline conditions. Samples taken from the surface layer of the lime and from the depth of 2 m (both having pH ~11 and EC e up to 423 dS m -1 ) were investigated using culture-based (culturing on alkaline medium) and culture-independent microbiological approaches (microscopic analyses and pyrosequencing). A surprisingly diverse bacterial community was discovered in this highly saline, alkaline and nutrient-poor environment, with the bacterial phyla Proteobacteria (representing 52.8% of the total bacterial community) and Firmicutes (16.6%) showing dominance. Compared to the surface layer, higher bacterial abundance and diversity values were detected in the deep zone, where more stable environmental conditions may occur. The surface layer was dominated by members of the genera Phenylobacterium, Chelativorans and Skermanella, while in the interior layer the genus Fictibacillus was dominant. The culturable aerobic, haloalkaliphilic bacteria strains isolated in this study belonged mostly to the genus Bacillus and were closely related to the species Bacillus pseudofirmus, B. cereus, B. plakortidis, B. thuringensis and B. pumilus.

Studies on the oxidation reaction of tyrosine (Tyr) with H2O2 catalyzed by horseradish peroxidase (HRP) in alcohol-water medium by spectrofluorimetry and differential spectrophotometry.

PubMed

Tang, Bo; Wang, Yan; Liang, Huiling; Chen, Zhenzhen; He, Xiwen; Shen, Hanxi

2006-03-01

An oxidation reaction of tyrosine (Tyr) with H(2)O(2) catalyzed by horseradish peroxidase (HRP) was studied by spectrofluorimetry and differential spectrophotometry in the alcohol(methanol, ethanol, 1-propanol and isopropanol)-water mutual solubility system. Compared with the enzymatic-catalyzed reaction in the water medium, the fluorescence intensities of the product weakened, even extinguished. Because the addition of alcohols made the conformation of HRP change, the catalytic reaction shifted to the side of polymerization and the polymer (A(n)H(2), n>or=3) exhibited no fluorescence. The four alcohols cannot deactivate HRP. Moreover isopropanol activated HRP remarkably.

Kinetic Release of Alkalinity from Particle-Containing Oil-in-Water Emulsions

NASA Astrophysics Data System (ADS)

Muller, K.; Chapra, S. C.; Ramsburg, A.

2014-12-01

Oil-in-water emulsions are typically employed during remediation to promote biotic reduction of contaminants. Emulsions, however, hold promise for encapsulated delivery of many types of active ingredients required for successful site remediation or long-term site stewardship. Our research is currently focused on using alkalinity-containing particles held within oil-in-water emulsions to sustain control of subsurface pH. Here we describe results from laboratory experiments and mathematical modeling conducted to quantify the kinetics associated with the emulsion delivery and alkalinity release process. Kinetically stable oil-in-water emulsions containing (~60 nmCaCO3 or ~100 nm MgO particles) were previously developed using soybean oil and Gum Arabic as a stabilizing agent. Batch and column experiments were employed to assess the accessibility and release of the alkalinity from the emulsion. Successive additions of HCl were used in batch systems to produce several pH responses (pH rebounds) that were subsequently modeled to elucidate release mechanisms and rates for varying emulsion compositions and particle types. Initial results suggest that a linear-driving-force model is generally able to capture the release behavior in the batch system when the temporally-constant, lumped mass-transfer coefficient is scaled by the fraction of particle mass remaining within the droplets. This result suggests that the rate limiting step in the release process may be the interphase transfer of reactive species at the oil-water interface. 1-d column experiments were also completed in order to quantify the extent and rate of alkalinity release from emulsion droplets retained in a sandy medium. Alkalinity release from the retained droplets treated a pH 4 influent water for 25-60 pore volumes (the duration depended on particle type and mass loading), and the cessation in treatment corresponded to exhaustion of the particle mass held within the oil. Column experiments were simulated

Redistribution of wastewater alkalinity with a microbial fuel cell to support nitrification of reject water.

PubMed

Modin, Oskar; Fukushi, Kensuke; Rabaey, Korneel; Rozendal, René A; Yamamoto, Kazuo

2011-04-01

In wastewater treatment plants, the reject water from the sludge treatment processes typically contains high ammonium concentrations, which constitute a significant internal nitrogen load in the plant. Often, a separate nitrification reactor is used to treat the reject water before it is fed back into the plant. The nitrification reaction consumes alkalinity, which has to be replenished by dosing e.g. NaOH or Ca(OH)(2). In this study, we investigated the use of a two-compartment microbial fuel cell (MFC) to redistribute alkalinity from influent wastewater to support nitrification of reject water. In an MFC, alkalinity is consumed in the anode compartment and produced in the cathode compartment. We use this phenomenon and the fact that the influent wastewater flow is many times larger than the reject water flow to transfer alkalinity from the influent wastewater to the reject water. In a laboratory-scale system, ammonium oxidation of synthetic reject water passed through the cathode chamber of an MFC, increased from 73.8 ± 8.9 mgN/L under open-circuit conditions to 160.1 ± 4.8 mgN/L when a current of 1.96 ± 0.37 mA (15.1 mA/L total MFC liquid volume) was flowing through the MFC. These results demonstrated the positive effect of an MFC on ammonium oxidation of alkalinity-limited reject water. Copyright © 2011 Elsevier Ltd. All rights reserved.

Why and How Life is Driven into Being at Ancient Submarine Alkaline Springs

NASA Astrophysics Data System (ADS)

Russell, Michael

2016-07-01

The disequilibria between volcanic CO2 plus NO dissolved in acidulous oceans, as against the H2 plus CH4 exhaling through hot alkaline springs on the ocean floors of young wet rocky worlds, cannot be relaxed, much less put to useful biological work, through mere geochemical reactions. Instead their dissipation must be coupled to the production of essential thermodynamically 'up-hill' products. A metabolic pathway, involving disequilibria converting nano-engines, is the only way to achieve such tasks as fixing the otherwise intractable CO2. Indeed, hydrogenating CO2 is life's contribution to entropy generation in the Universe. Long-lived alkaline springs could have supplied the low entropy nourishment in the form of H2 as electrons and CH4 as a carbon source, while the CO2, nitrate, photolytic Fe3+ and Mn4+ in the earliest ocean could have accepted the waste electrons, i.e., the 'breathing' [1]. But what of life's first boundaries? These could be generated spontaneously at the vent, where natural precipitates of iron oxyhydroxides and sulfides would have acted as precipitate membranes, separating the reduced alkaline hydrothermal fluid from the acidulous carbonic ocean, thus imposing steep redox and protonic (ambient pmf) gradients with the potential to drive otherwise endergonic reactions such as the reduction of CO2 to formate or CO, and the oxidation of CH4 to methyl and formyl entities. In turn, the CO and the methyl group reacted to form acetate. Acetate was then hydrogenated and carbonated to pyruvate. However, these endergonic reactions could not progress by catalysis or mass action chemistry as often assumed. They would have required natural processors acting as nanoengines to couple the endergonic driven processes to appropriate exergonic driving reactions. This is what the nano-engines do in life. These mechanochemical 'engines' are protein complexes that are each precisely tuned to the specific driving and driven disequilibria pairs being converted. They

Exogenous γ-Aminobutyric Acid Improves the Structure and Function of Photosystem II in Muskmelon Seedlings Exposed to Salinity-Alkalinity Stress

PubMed Central

Xu, Weinan; Zhen, Ai; Zhang, Liang; Hu, Xiaohui

2016-01-01

Gamma-aminobutyric acid (GABA) is important in plant responses to environmental stresses. We wished to clarify the role of GABA in maintenance of photosynthesis in muskmelon seedlings (Cucumis melo L., cv. Yipintianxia) during saline-alkaline stress. To this end, we assessed the effect of GABA on the structure and function of the photosynthetic apparatus in muskmelon seedlings grown under saline-alkaline stress. These stresses in combination reduced net photosynthetic rate, gas-exchange, and inhibited photosystem II (PSII) electron transport as measured by the JIP-test. They also reduced the activity of chloroplast ATPases and disrupted the internal lamellar system of the thylakoids. Exogenous GABA alleviated the stress-induced reduction of net photosynthesis, the activity of chloroplast ATPases, and overcame some of the damaging effects of stress on the chloroplast structure. Based on interpretation of the JIP-test, we conclude that exogenous GABA alleviated stress-related damage on the acceptor side of PSII. It also restored energy distribution, the reaction center status, and enhanced the ability of PSII to repair reaction centers in stressed seedlings. GABA may play a crucial role in protecting the chloroplast structure and function of PSII against the deleterious effects of salinity-alkalinity stress. PMID:27764179

Inhibition of microbiological sulfide oxidation by methanethiol and dimethyl polysulfides at natron-alkaline conditions.

PubMed

van den Bosch, Pim L F; de Graaff, Marco; Fortuny-Picornell, Marc; van Leerdam, Robin C; Janssen, Albert J H

2009-06-01

To avoid problems related to the discharge of sulfidic spent caustics, a biotechnological process is developed for the treatment of gases containing both hydrogen sulfide and methanethiol. The process operates at natron-alkaline conditions (>1 mol L(-1) of sodium- and potassium carbonates and a pH of 8.5-10) to enable the treatment of gases with a high partial CO(2) pressure. In the process, methanethiol reacts with biologically produced sulfur particles to form a complex mixture predominantly consisting of inorganic polysulfides, dimethyl disulfide (DMDS), and dimethyl trisulfide (DMTS). The effect of these organic sulfur compounds on the biological oxidation of sulfide to elemental sulfur was studied with natron-alkaliphilic bacteria belonging to the genus Thioalkalivibrio. Biological oxidation rates were reduced by 50% at 0.05 mM methanethiol, while for DMDS and DMTS, this was estimated to occur at 1.5 and 1.0 mM, respectively. The inhibiting effect of methanethiol on biological sulfide oxidation diminished due to its reaction with biologically produced sulfur particles. This reaction increases the feasibility of biotechnological treatment of gases containing both hydrogen sulfide and methanethiol at natron-alkaline conditions.

The mechanism of hydrolysis of beta-glycerophosphate by kidney alkaline phosphatase.

PubMed Central

Ahlers, J

1975-01-01

1. To identify the functional groups that are involved in the conversion of beta-glycerophosphate by alkaline phosphatase (EC 3.1.3.1) from pig kidney, the kinetics of alkaline phosphatase were investigated in the pH range 6.6-10.3 at substrate concentrations of 3 muM-30 mM. From the plots of log VH+ against pH and log VH+/KH+m against pH one functional group with pK = 7.0 and two functional groups with pK = 9.1 were identified. These groups are involved in substrate binding. Another group with pK = 8.8 was found, which in its unprotonated form catalyses substrate conversion. 2. GSH inhibits the alkaline phosphatase reversibly and non-competitively by attacking the bound Zn(II). 3. The influence of the H+ concentration on the activation by Mg2+ ions of alkaline pig kidney phosphate was investigated between pH 8.4 and 10.0. The binding of substrate and activating Mg2+ ions occurs independently at all pH values between 8.4 and 10.0. The activation mechanism is not affected by the H+ concentration. The Mg2+ ions are bound by a functional group with a pK of 10.15. 4. A scheme is proposed for the reaction between enzyme, substrate, Mg2+ and H+ and the overall rate equation is derived. 5. The mechanism of substrate binding and splitting by the functional groups of the active centre is discussed on the basis of a model. Mg2+ seems to play a role as an autosteric effector. PMID:995

Seeking effective dyes for a mediated glucose-air alkaline battery/fuel cell

NASA Astrophysics Data System (ADS)

Eustis, Ross; Tsang, Tsz Ming; Yang, Brigham; Scott, Daniel; Liaw, Bor Yann

2014-02-01

A significant level of power generation from an abiotic, air breathing, mediated reducing sugar-air alkaline battery/fuel cell has been achieved in our laboratories at room temperature without complicated catalysis or membrane separation in the reaction chamber. Our prior studies suggested that mass transport limitation by the mediator is a limiting factor in power generation. New and effective mediators were sought here to improve charge transfer and power density. Forty-five redox dyes were studied to identify if any can facilitate mass transport in alkaline electrolyte solution; namely, by increasing the solubility and mobility of the dye, and the valence charge carried per molecule. Indigo dyes were studied more closely to understand the complexity involved in mass transport. The viability of water-miscible co-solvents was also explored to understand their effect on solubility and mass transport of the dyes. Using a 2.0 mL solution, 20% methanol by volume, with 100 mM indigo carmine, 1.0 M glucose and 2.5 M sodium hydroxide, the glucose-air alkaline battery/fuel cell attained 8 mA cm-2 at short-circuit and 800 μW cm-2 at the maximum power point. This work shall aid future optimization of mediated charge transfer mechanism in batteries or fuel cells.

Effects of alkaline catalysts on acetone-based organosolv pretreatment of rice straw.

PubMed

Raita, Marisa; Denchokepraguy, Naphatsaya; Champreda, Verawat; Laosiripojana, Navadol

2017-10-01

Organosolv is an effective pretreatment strategy for increasing digestibility of lignocellulosic materials owing to selectivity of solvents on separating biopolymeric constituents of plant biomass. In the present work, a novel low-temperature alkali-catalyzed organosolv pretreatment of rice straw was studied. The effects of alkaline catalysts (i.e., NaOH, ammonia, and tri-ethylamine) and solvent types (i.e., acetone, ethanol, and water) were carried out. Addition of alkalis led to increasing sugar from enzymatic hydrolysis while acetone was found to be superior to ethanol and water on selectivity towards cellulose preservation. The optimal alkaline-catalyzed pretreatment reaction contained 5% (w/v) NaOH in an aqueous-acetone mixture (1:4) at 80 °C for 5 min. A glucose yield of 913 mg/g of pretreated biomass was achieved, equivalent to a maximal glucose recovery of 93.0% from glucan in the native biomass. Scanning electron microscope revealed efficient removal of non-cellulosic components, resulting in exposed cellulose microfibers with a reduced crystallite size as determined by X-ray diffraction. With potential on obtaining high-quality lignin, the work demonstrated potential of the novel low-temperature alkaline-catalyzed acetone-based organosolv process for pretreatment of lignocellulosic materials in biorefineries.

Alkaline hydrothermal liquefaction of swine carcasses to bio-oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Ji-Lu, E-mail: triace@163.com; Zhu, Ming-Qiang; Wu, Hai-tang

Highlights: • Swine carcasses can be converted to bio-oil by alkaline hydrothermal liquefaction. • It seems that the use of the bio-oil for heat or CHP is technically suitable. • Some valuable chemicals were found in the bio-oils. • The bio-oil and the solid residue constituted an energy efficiency of 93.63% for the feedstock. • The solid residue can be used as a soil amendment, to sequester C and for preparing activated carbon. - Abstract: It is imperative that swine carcasses are disposed of safely, practically and economically. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil was performed. Firstly, themore » effects of temperature, reaction time and pH value on the yield of each liquefaction product were determined. Secondly, liquefaction products, including bio-oil and solid residue, were characterized. Finally, the energy recovery ratio (ERR), which was defined as the energy of the resultant products compared to the energy input of the material, was investigated. Our experiment shows that reaction time had certain influence on the yield of liquefaction products, but temperature and pH value had bigger influence on the yield of liquefaction products. Yields of 62.2 wt% bio-oil, having a high heating value of 32.35 MJ/kg and a viscosity of 305cp, and 22 wt% solid residue were realized at a liquefaction temperature of 250 °C, a reaction time of 60 min and a pH value of 9.0. The bio-oil contained up to hundreds of different chemical components that may be classified according to functional groups. Typical compound classes in the bio-oil were hydrocarbons, organic acids, esters, ketones and heterocyclics. The energy recovery ratio (ERR) reached 93.63%. The bio-oil is expected to contribute to fossil fuel replacement in stationary applications, including boilers and furnaces, and upgrading processes for the bio-oil may be used to obtain liquid transport fuels.« less

Ferroelectric fluoride compositions and methods of making and using same

DOEpatents

Halasyamani, P Shiv; Chang, Hong-Young

2015-04-07

A method for synthesis of a ferroelectric material characterized by the general formula A.sub.xB.sub.yF.sub.z where A is an alkaline earth metal, B is transition metal or a main group metal, x and y each range from about 1 to about 5, and z ranges from about 1 to about 20 comprising contacting an alkaline earth metal fluoride, a difluorometal compound and a fluoroorganic acid in a medium to form a reaction mixture; and subjecting the reaction mixture to conditions suitable for hydrothermal crystal growth.

Electrochemical kinetic and mass transfer model for direct ethanol alkaline fuel cell (DEAFC)

NASA Astrophysics Data System (ADS)

Abdullah, S.; Kamarudin, S. K.; Hasran, U. A.; Masdar, M. S.; Daud, W. R. W.

2016-07-01

A mathematical model is developed for a liquid-feed DEAFC incorporating an alkaline anion-exchange membrane. The one-dimensional mass transport of chemical species is modelled using isothermal, single-phase and steady-state assumptions. The anode and cathode electrochemical reactions use the Tafel kinetics approach, with two limiting cases, for the reaction order. The model fully accounts for the mixed potential effects of ethanol oxidation at the cathode due to ethanol crossover via an alkaline anion-exchange membrane. In contrast to a polymer electrolyte membrane model, the current model considers the flux of ethanol at the membrane as the difference between diffusive and electroosmotic effects. The model is used to investigate the effects of the ethanol and alkali inlet feed concentrations at the anode. The model predicts that the cell performance is almost identical for different ethanol concentrations at a low current density. Moreover, the model results show that feeding the DEAFC with 5 M NaOH and 3 M ethanol at specific operating conditions yields a better performance at a higher current density. Furthermore, the model indicates that crossover effects on the DEAFC performance are significant. The cell performance decrease from its theoretical value when a parasitic current is enabled in the model.

Net alkalinity and net acidity 2: Practical considerations

USGS Publications Warehouse

Kirby, C.S.; Cravotta, C.A.

2005-01-01

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples. Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5-4) or near neutral (pH 6-7); ??? 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6. The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze. The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO2 and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= -net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the

Refining cocoon to prepare (N, S, and Fe) ternary-doped porous carbon aerogel as efficient catalyst for the oxygen reduction reaction in alkaline medium

NASA Astrophysics Data System (ADS)

Li, Changqing; Sun, Fengzhan; Lin, Yuqing

2018-04-01

Various advanced sulfur doped Fe-N-C non-noble metal catalysts of oxygen reduction reaction (ORR) have been recently designed and reported with excellent catalytic activity. Herein, we refined cocoon with several steps to form silk fibroin solution, treated with iron salt to prepare an easy available, heteroatom (N, S, and Fe) ternary-doped, porous carbon aerogel (HDCA). Heteroatom existed in organic compounds in silk fibroin endow active site for ORR of the resultant carbon frameworks. Moreover, the amino acids presented in silk fibroin acted as ligands, functioning with Fe ions to form FeNx coordination compounds, which also served as active sites towards ORR. The synthesized HDCA electrocatalysts, especially HDCA-800 (obtained at 800 °C) displayed excellent catalytic activity with onsets, half-wave potential of 0.94 V, 0.79 V and higher limited current density of 3.80 mA cm-2 through a near four-electron reduction pathway with an average electron transferred number of 3.86, making them promising alternatives for state-of-the-art ORR electrocatalysts in fuel cell field. The porous structure with synergistic effect of N and S heteroatom doping has been proposed to play a key role in facilitating the desired ORR reaction.

Formation of benzene in the interstellar medium

PubMed Central

Jones, Brant M.; Zhang, Fangtong; Kaiser, Ralf I.; Jamal, Adeel; Mebel, Alexander M.; Cordiner, Martin A.; Charnley, Steven B.

2011-01-01

Polycyclic aromatic hydrocarbons and related species have been suggested to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block—the aromatic benzene molecule—has remained elusive for decades. Here we demonstrate in crossed molecular beam experiments combined with electronic structure and statistical calculations that benzene (C6H6) can be synthesized via the barrierless, exoergic reaction of the ethynyl radical and 1,3-butadiene, C2H + H2CCHCHCH2 → C6H6 + H, under single collision conditions. This reaction portrays the simplest representative of a reaction class in which aromatic molecules with a benzene core can be formed from acyclic precursors via barrierless reactions of ethynyl radicals with substituted 1,3-butadiene molecules. Unique gas-grain astrochemical models imply that this low-temperature route controls the synthesis of the very first aromatic ring from acyclic precursors in cold molecular clouds, such as in the Taurus Molecular Cloud. Rapid, subsequent barrierless reactions of benzene with ethynyl radicals can lead to naphthalene-like structures thus effectively propagating the ethynyl-radical mediated formation of aromatic molecules in the interstellar medium. PMID:21187430

Evaluation of Alkaline Cleaner Materials

NASA Technical Reports Server (NTRS)

Partz, Earl

1998-01-01

Alkaline cleaners used to process aluminum substrates have contained chromium as the corrosion inhibitor. Chromium is a hazardous substance whose use and control are described by environmental laws. Replacement materials that have the characteristics of chromated alkaline cleaners need to be found that address both the cleaning requirements and environmental impacts. This report will review environmentally friendly candidates evaluated as non-chromium alkaline cleaner replacements and methods used to compare those candidates one versus another. The report will also list characteristics used to select candidates based on their declared contents. It will also describe and evaluate methods used to discriminate among the large number of prospective candidates.

Nickel hydroxide positive electrode for alkaline rechargeable battery

DOEpatents

Young, Kwo; Wang, Lixin; Mays, William; Reichman, Benjamin; Chao-Ian, Hu; Wong, Diana; Nei, Jean

2018-04-03

Certain nickel hydroxide active cathode materials for use in alkaline rechargeable batteries are capable of transferring >1.3 electrons per Ni atom under reversible electrochemical conditions. The specific capacity of the nickel hydroxide active materials is for example .gtoreq.325 mAh/g. The cathode active materials exhibit an additional discharge plateau near 0.8 V vs. a metal hydride (MH) anode. Ni in an oxidation state of less than 2, such as Ni.sup.1+, is able to participate in electrochemical reactions when using the present cathode active materials. It is possible that up to 2.3 electrons, up to 2.5 electrons or more may be transferred per Ni atom under electrochemical conditions.

Nickel hydroxide positive electrode for alkaline rechargeable battery

DOEpatents

Young, Kwo; Wang, Lixin; Mays, William; Reichman, Benjamin; Chao-Ian, Hu; Wong, Diana; Nei, Jean

2018-02-20

Certain nickel hydroxide active cathode materials for use in alkaline rechargeable batteries are capable of transferring >1.3 electrons per Ni atom under reversible electrochemical conditions. The specific capacity of the nickel hydroxide active materials is for example .gtoreq.325 mAh/g. The cathode active materials exhibit an additional discharge plateau near 0.8 V vs. a metal hydride (MH) anode. Ni in an oxidation state of less than 2, such as Ni.sup.1+, is able to participate in electrochemical reactions when using the present cathode active materials. It is possible that up to 2.3 electrons, up to 2.5 electrons or more may be transferred per Ni atom under electrochemical conditions.

Effective alkaline metal-catalyzed oxidative delignification of hybrid poplar

DOE PAGES

Bhalla, Aditya; Bansal, Namita; Stoklosa, Ryan J.; ...

2016-02-09

-batch, two-stage Cu-AHP pretreatment process was effective in pretreating hybrid poplar for its conversion into fermentable sugars. Results showed sugar yields near the theoretical maximum were achieved from enzymatically hydrolyzed hybrid poplar by incorporating an alkaline extraction step prior to pretreatment and by efficiently utilizing H 2O 2 during the Cu-AHP process. Significantly, this study reports high sugar yields from woody biomass treated with an AHP pretreatment under mild reaction conditions.« less

Catalytically active alkaline molten globular enzyme: Effect of pH and temperature on the structural integrity of 5-aminolevulinate synthase*

PubMed Central

Stojanovski, Bosko M.; Breydo, Leonid; Hunter, Gregory A.; Uversky, Vladimir N.; Ferreira, Gloria C.

2014-01-01

5-Aminolevulinate synthase (ALAS), a pyridoxal-5′phosphate (PLP)-dependent enzyme, catalyzes the first step of heme biosynthesis in mammals. Circular dichroism (CD) and fluorescence spectroscopies were used to examine the effects of pH (1.0–3.0 and 7.5–10.5) and temperature (20 and 37 °C) on the structural integrity of ALAS. The secondary structure, as deduced from far-UV CD, is mostly resilient to pH and temperature changes. Partial unfolding was observed at pH 2.0, but further decreasing pH resulted in acid-induced refolding of the secondary structure to nearly native levels. The tertiary structure rigidity, monitored by near-UV CD, is lost under acidic and specific alkaline conditions (pH 10.5 and pH 9.5/37 °C), where ALAS populates a molten globule state. As the enzyme becomes less structured with increased alkalinity, the chiral environment of the internal aldimine is also modified, with a shift from a 420 nm to 330 nm dichroic band. Under acidic conditions, the PLP cofactor dissociates from ALAS. Reaction with 8-anilino-1-naphtalenesulfonic acid corroborates increased exposure of hydrophobic clusters in the alkaline and acidic molten globules, although the reaction is more pronounced with the latter. Furthermore, quenching the intrinsic fluorescence of ALAS with acrylamide at pH 1.0 and 9.5 yielded subtly different dynamic quenching constants. The alkaline molten globule state of ALAS is catalytically active (pH 9.5/37 °C), although the kcat value is significantly decreased. Finally, the binding of 5-aminolevulinate restricts conformational fluctuations in the alkaline molten globule. Overall, our findings prove how the structural plasticity of ALAS contributes to reaching a functional enzyme. PMID:25240868

Catalytically active alkaline molten globular enzyme: Effect of pH and temperature on the structural integrity of 5-aminolevulinate synthase.

PubMed

Stojanovski, Bosko M; Breydo, Leonid; Hunter, Gregory A; Uversky, Vladimir N; Ferreira, Gloria C

2014-12-01

5-Aminolevulinate synthase (ALAS), a pyridoxal-5'phosphate (PLP)-dependent enzyme, catalyzes the first step of heme biosynthesis in mammals. Circular dichroism (CD) and fluorescence spectroscopies were used to examine the effects of pH (1.0-3.0 and 7.5-10.5) and temperature (20 and 37°C) on the structural integrity of ALAS. The secondary structure, as deduced from far-UV CD, is mostly resilient to pH and temperature changes. Partial unfolding was observed at pH2.0, but further decreasing pH resulted in acid-induced refolding of the secondary structure to nearly native levels. The tertiary structure rigidity, monitored by near-UV CD, is lost under acidic and specific alkaline conditions (pH10.5 and pH9.5/37°C), where ALAS populates a molten globule state. As the enzyme becomes less structured with increased alkalinity, the chiral environment of the internal aldimine is also modified, with a shift from a 420nm to 330nm dichroic band. Under acidic conditions, the PLP cofactor dissociates from ALAS. Reaction with 8-anilino-1-naphthalenesulfonic acid corroborates increased exposure of hydrophobic clusters in the alkaline and acidic molten globules, although the reaction is more pronounced with the latter. Furthermore, quenching the intrinsic fluorescence of ALAS with acrylamide at pH1.0 and 9.5 yielded subtly different dynamic quenching constants. The alkaline molten globule state of ALAS is catalytically active (pH9.5/37°C), although the kcat value is significantly decreased. Finally, the binding of 5-aminolevulinate restricts conformational fluctuations in the alkaline molten globule. Overall, our findings prove how the structural plasticity of ALAS contributes to reaching a functional enzyme. Copyright © 2014 Elsevier B.V. All rights reserved.

Advanced inorganic separators for alkaline batteries and method of making the same

NASA Technical Reports Server (NTRS)

Sheibley, D. W. (Inventor)

1983-01-01

A flexible, porous battery separator includes a coating applied to a porous, flexible substrate. The coating comprises: (1) a thermoplastic rubber-based resin which is insoluble and unreactive in the alkaline electrolyte, (2) a polar organic plasticizer which is reactive with the alkaline electrolyte to produce a reaction product which contains a hydroxyl group and/or a carboxylic acid group, and (3) a mixture of polar particulate filler materials which are unreactive with the electrode. The mixture comprises at least one first filler material having a surface area of greater than 25 sq meters/gram, at last one second filler material having a surface area of 10 to 25 sq meters/gram. The volume of the mixture of filler materials is less than 45% of the total volume of the fillers and the binder. The filler surface area per gram of binder is about 20 to 60 sq meters/gram, and the amount of plasticizer is sufficient to coat each filler particle.

Anaerobic digestion of the microalga Spirulina at extreme alkaline conditions: biogas production, metagenome, and metatranscriptome

PubMed Central

Nolla-Ardèvol, Vímac; Strous, Marc; Tegetmeyer, Halina E.

2015-01-01

A haloalkaline anaerobic microbial community obtained from soda lake sediments was used to inoculate anaerobic reactors for the production of methane rich biogas. The microalga Spirulina was successfully digested by the haloalkaline microbial consortium at alkaline conditions (pH 10, 2.0 M Na+). Continuous biogas production was observed and the obtained biogas was rich in methane, up to 96%. Alkaline medium acted as a CO2 scrubber which resulted in low amounts of CO2 and no traces of H2S in the produced biogas. A hydraulic retention time (HRT) of 15 days and 0.25 g Spirulina L−1 day−1 organic loading rate (OLR) were identified as the optimal operational parameters. Metagenomic and metatranscriptomic analysis showed that the hydrolysis of the supplied substrate was mainly carried out by Bacteroidetes of the “ML635J-40 aquatic group” while the hydrogenotrophic pathway was the main producer of methane in a methanogenic community dominated by Methanocalculus. PMID:26157422

Characterization of brush borders purified in iso-osmotic medium and microvillar membranes subfractionated from mouse small intestine.

PubMed Central

Fujita, M; Ohta, H; Uezato, T

1981-01-01

Brush borders free of nuclei were isolated by repeated homogenization and centrifugation in iso-osmotic medium. They showed typical morphology under electron microscopy. The mean recovery and enrichment of alkaline phosphatase activity in the brush-border fraction were 50% and 17.5-fold respectively. gamma-Glutamyl transpeptidase showed a close parallelism with alkaline phosphatase and sucrase in subcellular distribution. Microvillar membranes were purified from isolated brush borders; they showed a further enrichment for alkaline phosphatase and were composed of homogeneous vesicles. Both brush-border and microvillar-membrane preparations were analysed for contamination by basolateral and endoplasmic-reticular membranes. Sodium dodecyl sulphate/polyacrylamide-gel electrophoresis of the microvillar-membrane preparation in six different systems revealed approx. 40 components in the mol.wt. range 15 000-232 000. They were grouped into seven major classes on the basis of molecular weight and electrophoretic patterns. Images PLATE 1 PLATE 2 PMID:7317008

Highly thermostable, thermophilic, alkaline, SDS and chelator resistant amylase from a thermophilic Bacillus sp. isolate A3-15.

PubMed

Arikan, Burhan

2008-05-01

A thermostable alkaline alpha-amylase producing Bacillus sp. A3-15 was isolated from compost samples. There was a slight variation in amylase synthesis within the pH range 6.0 and 12.0 with an optimum pH of 8.5 (8mm zone diameter in agar medium) on starch agar medium. Analyses of the enzyme for molecular mass and amylolytic activity were carried out by starch SDS-PAGE electrophoresis, which revealed two independent bands (86,000 and 60,500 Da). Enzyme synthesis occurred at temperatures between 25 and 65 degrees C with an optimum of 60 degrees C on petri dishes. The partial purification enzyme showed optimum activity at pH 11.0 and 70 degrees C. The enzyme was highly active (95%) in alkaline range of pH (10.0-11.5), and it was almost completely active up to 100 degrees C with 96% of the original activity remaining after heat treatment at 100 degrees C for 30 min. Enzyme activity was enhanced in the presence of 5mM CaCl2 (130%) and inhibition with 5mM by ZnCl2, NaCl, Na-sulphide, EDTA, PMSF (3mM), Urea (8M) and SDS (1%) was obtained 18%, 20%, 36%, 5%, 10%, 80% and 18%, respectively. The enzyme was stable approximately 70% at pH 10.0-11.0 and 60 degrees C for 24h. So our result showed that the enzyme was both, highly thermostable-alkaline, thermophile and chelator resistant. The A3-15 amylase enzyme may be suitable in liquefaction of starch in high temperature, in detergent and textile industries and in other industrial applications.

Platinum Monolayer Shell on Non-Noble Metal Core Electrocatalysts for the Hydrogen Oxidation Reaction

NASA Astrophysics Data System (ADS)

Teeluck, Krishani Malini

According to the United States Environmental Protection Agency, as of 2015, transportation accounted for 32% of the carbon dioxide emissions in the United States (and all carbon dioxide emissions in the U.S. accounted for 82.2% of all greenhouse gases from human activity). A hydrogen fuel cell is a device that efficiently produces electrical energy directly from a chemical reaction, with zero carbon emissions, and therefore holds great promise in alleviating our dependence on harmful use of energy sources. Due to their clean emissions and high efficiencies, there has been focus on the hydrogen fuel cell for vehicle applications using proton exchange membrane and alkaline fuel cells. Although the proton exchange membrane fuel cell is currently being used in vehicles, their high cost limits their feasibility in the market. This has inspired the development of the alkaline fuel cell whose efficiency and simplicity suggest the possibility of manufacturing high power fuel cell vehicles at a low cost, since the electrocatalysts in the alkaline fuel cell can be made from non-noble metals. Although the hydrogen oxidation reaction is one of the fastest electrochemical reactions in acidic media, it is two orders of magnitude slower in alkaline media, which hinders the overall efficiency of the alkaline fuel cell. Pure platinum is currently the best catalyst for the hydrogen oxidation reaction, but platinum’s high cost and rarity yields economic issues, rendering the technology futile if it cannot be commercialized. Furthermore, platinum’s hydrogen binding energy is slightly stronger than the optimal hydrogen binding energy. As the hydrogen oxidation reaction happens only on the surface of the catalyst, there is no need for platinum content beyond the exterior. Since tungsten and nickel are cheap, as well as abundant, they are ideal elements to replace the core of the catalyst with, while leaving a platinum shell surrounding this core. The activity of the hydrogen

Kinetics of the mechanochemical synthesis of alkaline-earth metal amides

NASA Astrophysics Data System (ADS)

Garroni, Sebastiano; Takacs, Laszlo; Leng, Haiyan; Delogu, Francesco

2014-07-01

A phenomenological framework is developed to model the kinetics of the formation of alkaline-earth metal amides by the ball milling induced reaction of their hydrides with gaseous ammonia. It is shown that the exponential character of the kinetic curves is modulated by the increase of the total volume of the powder inside the reactor due to the substantially larger molar volume of the products compared to the reactants. It is claimed that the volume of powder effectively processed during each collision connects the transformation rate to the physical and chemical processes underlying the mechanochemical transformations.

2,3-diaminopyridine functionalized reduced graphene oxide-supported palladium nanoparticles with high activity for electrocatalytic oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon

2017-06-01

The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H2O2 yield.

Effects of tunicamycin, mannosamine, and other inhibitors of glycoprotein processing on skeletal alkaline phosphatase in human osteoblast-like cells.

PubMed

Farley, J R; Magnusson, P

2005-01-01

Skeletal alkaline phosphatase (sALP) is a glycoprotein- approximately 20% carbohydrate by weight, with five presumptive sites for N-linked glycosylation, as well as a carboxy-terminal site for attachment of the glycolipid structure (glycosylphosphatidylinositol, GPI), which anchors sALP to the outer surface of osteoblasts. The current studies were intended to characterize the effects of inhibiting glycosylation and glycosyl-processing on the synthesis, plasma membrane attachment, cellular-extracellular distribution, and reaction kinetics of sALP in human osteosarcoma (SaOS-2) cells. sALP synthesis, glycosylation, and GPI-anchor attachment were assessed as total protein synthesis/immunospecific sALP synthesis, sialic acid content (i.e., wheat germ agglutinin precipitation), and insolubility (i.e., temperature-dependent phase-separation), respectively. sALP reaction kinetics were characterized by analysis of dose-dependent initial velocity data, with a phosphoryl substrate. The results of these studies revealed that the inhibition of either N-linked glycosylation or oligosaccharide synthesis for GPI-anchor addition could affect the synthesis and the distribution of sALP, but not the kinetics of the phosphatase reaction. Tunicamycin-which blocks N-linked glycosylation by inhibiting core oligosaccharide synthesis-decreased cell layer protein and the total amount of sALP in the cells, while increasing the relative level of sALP in the cell-conditioned culture medium (CM, i.e., the amount of sALP released). These effects were attributed to dose- and time-dependent decreases in sALP synthesis and N-linked glycosylation, and an increase in apoptotic cell death (P <0.001 for each). In contrast to the effects of tunicamycin on N-linked glycosylation, the effects of mannosamine, which inhibits GPI-anchor glycosylation/formation, included (1) an increase in cell layer protein; (2) decreases in sALP specific activity, in the cells and in the CM; and (3) increases in the

Oxygen electrodes for rechargeable alkaline fuel cells

NASA Technical Reports Server (NTRS)

Swette, Larry; Giner, Jose

1987-01-01

Electrocatalysts and supports for the positive electrode of moderate temperature single unit rechargeable alkaline fuel cells were investigated and developed. The electrocatalysts are defined as the material with a higher activity for the oxygen electrode reaction than the support. Advanced development will require that the materials be prepared in high surface area forms, and may also entail integration of various candidate materials. Eight candidate support materials and seven electrocatalysts were investigated. Of the 8 support, 3 materials meet the preliminary requirements in terms of electrical conductivity and stability. Emphasis is now on preparing in high surface area form and testing under more severe corrosion stress conditions. Of the 7 electrocatalysts prepared and evaluated, at least 5 materials remain as potential candidates. The major emphasis remains on preparation, physical characterization and electrochemical performance testing.

Phosphatidylinositol anchor of HeLa cell alkaline phosphatase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jemmerson, R.; Low, M.G.

1987-09-08

Alkaline phosphatase from cancer cells, HeLa TCRC-1, was biosynthetically labeled with either /sup 3/H-fatty acids or (/sup 3/H)ethanolamine as analyzed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and fluorography of immunoprecipitated material. Phosphatidylinositol-specific phospholipase C (PI-PLC) released a substantial proportion of the /sup 3/H-fatty acid label from immunoaffinity-purified alkaline phosphatase but had no effect on the radioactivity of (/sup 3/H)ethanolamine-labeled material. PI-PLC also liberated catalytically active alkaline phosphatase from viable cells, and this could be selectively blocked by monoclonal antibodies to alkaline phosphatase. However, the alkaline phosphatase released from /sup 3/H-fatty acid labeled cells by PI-PLC was not radioactive. By contrast,more » treatment with bromelain removed both the /sup 3/H-fatty acid and the (/sup 3/H)ethanolamine label from purified alkaline phosphatase. Subtilisin was also able to remove the (/sup 3/H)ethanolamine label from the purified alkaline phosphatase. The /sup 3/H radioactivity in alkaline phosphatase purified from (/sup 3/H)ethanolamine-labeled cells comigrated with authentic (/sup 3/H)ethanolamine by anion-exchange chromatography after acid hydrolysis. The data suggest that the /sup 3/H-fatty acid and (/sup 3/H)ethanolamine are covalently attached to the carboxyl-terminal segment since bromelain and subtilisin both release alkaline phosphatase from the membrane by cleavage at that end of the polypeptide chain. The data are consistent with findings for other proteins recently shown to be anchored in the membrane through a glycosylphosphatidylinositol structure and indicate that a similar structure contributes to the membrane anchoring of alkaline phosphatase.« less

Dramatic effects of external alkalinity on neuronal calcium recovery following a short-duration glutamate challenge: the role of the plasma membrane Ca2+/H+ pump.

PubMed

Khodorov, B; Pinelis, V; Vergun, O; Storozhevykh, T; Fajuk, D; Vinskaya, N; Arsenjeva, E; Khaspekov, L; Lyzin, A; Isaev, N

1995-09-11

Alkalinization of the external medium has been shown to suppress Ca2+ extrusion from neurons due to inhibition of the plasmalemmal Ca2+/H+ pump. In our experiments on fura-2-loaded rat cerebellar granule cells and mouse hippocampal neurons, an increase in pHo from 7.4 to 8.5 following a 1-min glutamate or NMDA challenge caused a dramatic delay in [Ca2+]i recovery which in some cases was accompanied by an additional increase in [Ca2+]i. Normalization of pHo, or removal of Ca2+ from the alkaline solution allowed [Ca2+]i to decrease rapidly again. External alkalinity did not affect the initial rapid decline in [Ca2+]i following a 25 mMK+ pulse. In cerebellar granule cells, the alkaline pHo considerably increased the 45Ca2+ uptake both at rest and following a 2-min GLU pulse. A comparison of these effects of alkaline pHo with those produced by removal of the external Na+ led us to conclude that the Ca2+/H+ pump plays a dominant role in the mechanism of the fast Ca2+ extrusion from glutamate- or NMDA-treated neurons.

Increased river alkalinization in the Eastern U.S.

PubMed

Kaushal, Sujay S; Likens, Gene E; Utz, Ryan M; Pace, Michael L; Grese, Melissa; Yepsen, Metthea

2013-09-17

The interaction between human activities and watershed geology is accelerating long-term changes in the carbon cycle of rivers. We evaluated changes in bicarbonate alkalinity, a product of chemical weathering, and tested for long-term trends at 97 sites in the eastern United States draining over 260,000 km(2). We observed statistically significant increasing trends in alkalinity at 62 of the 97 sites, while remaining sites exhibited no significant decreasing trends. Over 50% of study sites also had statistically significant increasing trends in concentrations of calcium (another product of chemical weathering) where data were available. River alkalinization rates were significantly related to watershed carbonate lithology, acid deposition, and topography. These three variables explained ~40% of variation in river alkalinization rates. The strongest predictor of river alkalinization rates was carbonate lithology. The most rapid rates of river alkalinization occurred at sites with highest inputs of acid deposition and highest elevation. The rise of alkalinity in many rivers throughout the Eastern U.S. suggests human-accelerated chemical weathering, in addition to previously documented impacts of mining and land use. Increased river alkalinization has major environmental implications including impacts on water hardness and salinization of drinking water, alterations of air-water exchange of CO2, coastal ocean acidification, and the influence of bicarbonate availability on primary production.

Uric acid-derived Fe3C-containing mesoporous Fe/N/C composite with high activity for oxygen reduction reaction in alkaline medium

NASA Astrophysics Data System (ADS)

Ma, Jun; Xiao, Dejian; Chen, Chang Li; Luo, Qiaomei; Yu, Yue; Zhou, Junhao; Guo, Changding; Li, Kai; Ma, Jie; Zheng, Lirong; Zuo, Xia

2018-02-01

In this work, a category of Fe3C-containing Fe/N/C mesoporous material has been fabricated by carbonizing the mixture of uric acid, Iron (Ⅲ) chloride anhydrous and carbon support (XC-72) under different pyrolysis temperature. Of all these samples, pyrolysis temperature (800 °C) becomes the most crucial factor in forming Fe3C active sites which synergizes with high content of graphitic N to catalyze oxygen reduction reaction (ORR). X-ray absorption fine structure spectroscopy (XAFS) is used to exhibit that the space structure around Fe atoms in the catalyst. This kind of catalyst possesses comparable ORR properties with commercial 20% Pt/C (onset potential is 0 V vs. Ag/AgCl in 0.1 M KOH), the average transfer electron number is 3.84 reflecting the 4-electron process. Moreover, superior stability and methanol tolerance deserve to be mentioned.

Removal of metallic Al and Al/Zn alloys in MSWI bottom ash by alkaline treatment.

PubMed

Xuan, Dongxing; Poon, Chi Sun

2018-02-15

In order to reduce the leaching of pollutants and remove the Al and Zn/Al alloy from municipal solid waste incineration bottom ash (MSWIBA), an optimized alkaline pre-treatment procedure was developed in this study. The influences of alkaline conditions on the removal rate of Al and Zn/Al alloy were investigated, including [OH] - concentration, temperature, particle size, liquid/solid ratio and treatment duration. The experimental results showed that the optimized alkaline pre-treatment conditions to efficiently remove the Al and Zn/Al alloy was by using a minimum of 1.0mol/l [OH] - , at 55°C and with a minimal liquid/solid ratio of 5. The removal rate of Al and Zn/Al alloy followed an S-shape curve, in which the slow beginning stage was attributed to the protection of the oxidation layer and the quenched product around the Al and Al/Zn alloy. After 3h of the optimized alkaline pre-treatment, the leaching of Cr, Cu, Pb and Zn of the treated MSWIBA was reduced by more than 90% of that of the original MSWIBA. The alkali-silica reaction test further indicated that the expansion of concrete prepared with the pre-treated MSWIBA was significantly reduced and there was no macro-crack or spalling damage on the surface of the tested specimens. Copyright © 2017 Elsevier B.V. All rights reserved.

[Effect of carbon and nitrogen sources and complex B vitamins on the synthesis of alkaline protease by different strains of Bacillus mesentericus and Bacillus subtilis].

PubMed

Emtseva, T V

1975-01-01

The effect of different sources of carbon, nitrogen, amino acids and vitamins on the synthesis of alkaline proteases by the stock and mutant strains of Bacillus mesentericus and by the natural strain of Bacillus subtilis-12 has been investigated. The maximum synthesis of alkaline protease has been obtained in the media containing starch or its hydrolysates--dextrine and maltose as the carbon source. Ammonium phosphate and casein as the nitrogen source prove to be optimal for Bac. mesentericus and Bac. subtilis, respectively. Complex B vitamins added to the nutrient medium accelerate the enzyme synthesis 2.5-4-fold.

Significantly enhancing recombinant alkaline amylase production in Bacillus subtilis by integration of a novel mutagenesis-screening strategy with systems-level fermentation optimization.

PubMed

Ma, Yingfang; Shen, Wei; Chen, Xianzhong; Liu, Long; Zhou, Zhemin; Xu, Fei; Yang, Haiquan

2016-01-01

Alkaline amylase has significant potential for applications in the textile, paper and detergent industries, however, low yield of which cannot meet the requirement of industrial application. In this work, a novel ARTP mutagenesis-screening method and fermentation optimization strategies were used to significantly improve the expression level of recombinant alkaline amylase in B. subtilis 168. The activity of alkaline amylase in mutant B. subtilis 168 mut-16# strain was 1.34-fold greater than that in the wild-type, and the highest specific production rate was improved from 1.31 U/(mg·h) in the wild-type strain to 1.57 U/(mg·h) in the mutant strain. Meanwhile, the growth of B. subtilis was significantly enhanced by ARTP mutagenesis. When the agitation speed was 550 rpm, the highest activity of recombinant alkaline amylase was 1.16- and 1.25-fold of the activities at 450 and 650 rpm, respectively. When the concentration of soluble starch and soy peptone in the initial fermentation medium was doubled, alkaline amylase activity was increased 1.29-fold. Feeding hydrolyzed starch and soy peptone mixture or glucose significantly improved cell growth, but inhibited the alkaline amylase production in B. subtilis 168 mut-16#. The highest alkaline amylase activity by feeding hydrolyzed starch reached 591.4 U/mL, which was 1.51-fold the activity by feeding hydrolyzed starch and soy peptone mixture. Single pulse feeding-based batch feeding at 10 h favored the production of alkaline amylase in B. subtilis 168 mut-16#. The results indicated that this novel ARTP mutagenesis-screening method could significantly improve the yield of recombinant proteins in B. subtilis . Meanwhile, fermentation optimization strategies efficiently promoted expression of recombinant alkaline amylase in B. subtilis 168 mut-16#. These findings have great potential for facilitating the industrial-scale production of alkaline amylase and other enzymes, using B. subtilis cultures as microbial cell

Colloidal Assemblies Effect on Chemical Reactions

DTIC Science & Technology

1988-12-01

phenoxyacetic acid (2,4,5-T) and 2,4,5-trichlorophenol on TiO led to complete mineralization into CO and HCl. In the degradatior of 2,4,5-T several...for the reasons already given. Of course this effect is much more evident in the acidic medium than in the alkaline me- dium where a very large amount...nearly similar times (see Fig.42). The results of Table 4 also indicate that a HC104 effect exists, and at higher concentrations of this acid the

Coupling alkaline pre-extraction with alkaline-oxidative post-treatment of corn stover to enhance enzymatic hydrolysis and fermentability.

PubMed

Liu, Tongjun; Williams, Daniel L; Pattathil, Sivakumar; Li, Muyang; Hahn, Michael G; Hodge, David B

2014-04-03

A two-stage chemical pretreatment of corn stover is investigated comprising an NaOH pre-extraction followed by an alkaline hydrogen peroxide (AHP) post-treatment. We propose that conventional one-stage AHP pretreatment can be improved using alkaline pre-extraction, which requires significantly less H2O2 and NaOH. To better understand the potential of this approach, this study investigates several components of this process including alkaline pre-extraction, alkaline and alkaline-oxidative post-treatment, fermentation, and the composition of alkali extracts. Mild NaOH pre-extraction of corn stover uses less than 0.1 g NaOH per g corn stover at 80°C. The resulting substrates were highly digestible by cellulolytic enzymes at relatively low enzyme loadings and had a strong susceptibility to drying-induced hydrolysis yield losses. Alkaline pre-extraction was highly selective for lignin removal over xylan removal; xylan removal was relatively minimal (~20%). During alkaline pre-extraction, up to 0.10 g of alkali was consumed per g of corn stover. AHP post-treatment at low oxidant loading (25 mg H2O2 per g pre-extracted biomass) increased glucose hydrolysis yields by 5%, which approached near-theoretical yields. ELISA screening of alkali pre-extraction liquors and the AHP post-treatment liquors demonstrated that xyloglucan and β-glucans likely remained tightly bound in the biomass whereas the majority of the soluble polymeric xylans were glucurono (arabino) xylans and potentially homoxylans. Pectic polysaccharides were depleted in the AHP post-treatment liquor relative to the alkaline pre-extraction liquor. Because the already-low inhibitor content was further decreased in the alkaline pre-extraction, the hydrolysates generated by this two-stage pretreatment were highly fermentable by Saccharomyces cerevisiae strains that were metabolically engineered and evolved for xylose fermentation. This work demonstrates that this two-stage pretreatment process is well suited for

Coupling alkaline pre-extraction with alkaline-oxidative post-treatment of corn stover to enhance enzymatic hydrolysis and fermentability

PubMed Central

2014-01-01

Background A two-stage chemical pretreatment of corn stover is investigated comprising an NaOH pre-extraction followed by an alkaline hydrogen peroxide (AHP) post-treatment. We propose that conventional one-stage AHP pretreatment can be improved using alkaline pre-extraction, which requires significantly less H2O2 and NaOH. To better understand the potential of this approach, this study investigates several components of this process including alkaline pre-extraction, alkaline and alkaline-oxidative post-treatment, fermentation, and the composition of alkali extracts. Results Mild NaOH pre-extraction of corn stover uses less than 0.1 g NaOH per g corn stover at 80°C. The resulting substrates were highly digestible by cellulolytic enzymes at relatively low enzyme loadings and had a strong susceptibility to drying-induced hydrolysis yield losses. Alkaline pre-extraction was highly selective for lignin removal over xylan removal; xylan removal was relatively minimal (~20%). During alkaline pre-extraction, up to 0.10 g of alkali was consumed per g of corn stover. AHP post-treatment at low oxidant loading (25 mg H2O2 per g pre-extracted biomass) increased glucose hydrolysis yields by 5%, which approached near-theoretical yields. ELISA screening of alkali pre-extraction liquors and the AHP post-treatment liquors demonstrated that xyloglucan and β-glucans likely remained tightly bound in the biomass whereas the majority of the soluble polymeric xylans were glucurono (arabino) xylans and potentially homoxylans. Pectic polysaccharides were depleted in the AHP post-treatment liquor relative to the alkaline pre-extraction liquor. Because the already-low inhibitor content was further decreased in the alkaline pre-extraction, the hydrolysates generated by this two-stage pretreatment were highly fermentable by Saccharomyces cerevisiae strains that were metabolically engineered and evolved for xylose fermentation. Conclusions This work demonstrates that this two

Electrochemical incineration of diclofenac in neutral aqueous medium by anodic oxidation using Pt and boron-doped diamond anodes.

PubMed

Brillas, Enric; Garcia-Segura, Sergi; Skoumal, Marcel; Arias, Conchita

2010-04-01

The degradation of diclofenac, a common non-steroidal anti-inflammatory drug, in aqueous medium has been studied by anodic oxidation (AO) using an undivided cell with a Pt or boron-doped diamond (BDD) anode. Operating without pH regulation, AO with Pt acidifies the solution with precipitation of its protonated form, whereas using BDD, the solution becomes alkaline and only attains partial mineralization. Total incineration of low contents of the drug is feasible by AO with BDD in a neutral buffer medium of pH 6.5. Comparative treatment with Pt gives poor decontamination. The diclofenac decay always follows a pseudo first-order reaction. The increase in current for AO with BDD accelerates the degradative process, but decreases its efficiency. 2-Hydroxyphenylacetic acid, 2,5-dihydroxyphenylacetic acid, 2,6-dichloroaniline and 2,6-dichlorohydroquinone have been identified as aromatic intermediates. For AO with Pt, high amounts of malic, succinic, tartaric and oxalic acids are accumulated in the bulk and the N-derivatives produced are rapidly destroyed with loss of NH4+. When BDD is employed, some carboxylic acids are also accumulated in small extent, with a larger persistence of oxalic and oxamic acids. The process involves the formation of different N-derivatives that slowly release NH4+ and NO3(-) ions. Chloride ion is lost in all cases. 2010 Elsevier Ltd. All rights reserved.

Identification and characterization of miRNAs and targets in flax (Linum usitatissimum) under saline, alkaline, and saline-alkaline stresses.

PubMed

Yu, Ying; Wu, Guangwen; Yuan, Hongmei; Cheng, Lili; Zhao, Dongsheng; Huang, Wengong; Zhang, Shuquan; Zhang, Liguo; Chen, Hongyu; Zhang, Jian; Guan, Fengzhi

2016-05-27

MicroRNAs (miRNAs) play a critical role in responses to biotic and abiotic stress and have been characterized in a large number of plant species. Although flax (Linum usitatissimum L.) is one of the most important fiber and oil crops worldwide, no reports have been published describing flax miRNAs (Lus-miRNAs) induced in response to saline, alkaline, and saline-alkaline stresses. In this work, combined small RNA and degradome deep sequencing was used to analyze flax libraries constructed after alkaline-salt stress (AS2), neutral salt stress (NSS), alkaline stress (AS), and the non-stressed control (CK). From the CK, AS, AS2, and NSS libraries, a total of 118, 119, 122, and 120 known Lus-miRNAs and 233, 213, 211, and 212 novel Lus-miRNAs were isolated, respectively. After assessment of differential expression profiles, 17 known Lus-miRNAs and 36 novel Lus-miRNAs were selected and used to predict putative target genes. Gene ontology term enrichment analysis revealed target genes that were involved in responses to stimuli, including signaling and catalytic activity. Eight Lus-miRNAs were selected for analysis using qRT-PCR to confirm the accuracy and reliability of the miRNA-seq results. The qRT-PCR results showed that changes in stress-induced expression profiles of these miRNAs mirrored expression trends observed using miRNA-seq. Degradome sequencing and transcriptome profiling showed that expression of 29 miRNA-target pairs displayed inverse expression patterns under saline, alkaline, and saline-alkaline stresses. From the target prediction analysis, the miR398a-targeted gene codes for a copper/zinc superoxide dismutase, and the miR530 has been shown to explicitly target WRKY family transcription factors, which suggesting that these two micRNAs and their targets may significant involve in the saline, alkaline, and saline-alkaline stress response in flax. Identification and characterization of flax miRNAs, their target genes, functional annotations, and gene

Highly Stable, Anion Conductive, Comb-Shaped Copolymers for Alkaline Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, NW; Leng, YJ; Hickner, MA

2013-07-10

To produce an anion-conductive and durable polymer electrolyte for alkaline fuel cell applications, a series of quaternized poly(2,6-dimethyl phenylene oxide)s containing long alkyl side chains pendant to the nitrogen-centered cation were synthesized using a Menshutkin reaction to form comb-shaped structures. The pendant alkyl chains were responsible for the development of highly conductive ionic domains, as confirmed by small-angle X-ray scattering (SAXS). The comb-shaped polymers having one alkyl side chain showed higher hydroxide conductivities than those with benzyltrimethyl ammonium moieties or structures with more than one alkyl side chain per cationic site. The highest conductivity was observed for comb-shaped polymers withmore » benzyldimethylhexadecyl ammonium cations. The chemical stabilities of the comb-shaped membranes were evaluated under severe, accelerated-aging conditions, and degradation was observed by measuring IEC and ion conductivity changes during aging. The comb-shaped membranes retained their high ion conductivity in 1 M NaOH at 80 degrees C for 2000 h. These cationic polymers were employed as ionomers in catalyst layers for alkaline fuel cells. The results indicated that the C-16 alkyl side chain ionomer had a slightly better initial performance, despite its low IEC value, but very poor durability in the fuel cell. In contrast, 90% of the initial performance was retained for the alkaline fuel cell with electrodes containing the C-6 side chain after 60 h of fuel cell operation.« less

Electrode Reactions in Slowly Relaxing Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matyushov, Dmitry V.; Newton, Marshall D.

Here, standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate preexponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamicallymore » freeze on the reaction time-scale and do not contribute to the activation barrier. In this paper, we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing electrode overpotential speeds electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends of the relaxation spectrum of the medium. The reorganization energy experiences a sudden drop with increasing overpotential for a medium with a Debye relaxation, but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. Finally, this result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.« less

Electrode Reactions in Slowly Relaxing Media

DOE PAGES

Matyushov, Dmitry V.; Newton, Marshall D.

2017-11-17

Here, standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate preexponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamicallymore » freeze on the reaction time-scale and do not contribute to the activation barrier. In this paper, we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing electrode overpotential speeds electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends of the relaxation spectrum of the medium. The reorganization energy experiences a sudden drop with increasing overpotential for a medium with a Debye relaxation, but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. Finally, this result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.« less

Alkaline polymer electrolyte membranes for fuel cell applications.

PubMed

Wang, Yan-Jie; Qiao, Jinli; Baker, Ryan; Zhang, Jiujun

2013-07-07

In this review, we examine the most recent progress and research trends in the area of alkaline polymer electrolyte membrane (PEM) development in terms of material selection, synthesis, characterization, and theoretical approach, as well as their fabrication into alkaline PEM-based membrane electrode assemblies (MEAs) and the corresponding performance/durability in alkaline polymer electrolyte membrane fuel cells (PEMFCs). Respective advantages and challenges are also reviewed. To overcome challenges hindering alkaline PEM technology advancement and commercialization, several research directions are then proposed.

A facile microwave-assisted Diels-Alder reaction of vinylboronates.

PubMed

Sarotti, Ariel M; Pisano, Pablo L; Pellegrinet, Silvina C

2010-11-21

The Diels-Alder reaction of vinylboronates can be easily performed using microwave irradiation giving excellent yields of the cycloadducts. Pinacol vinylboronate was the reagent of choice due to its stability towards hydrolysis, operational simplicity and yields of Diels-Alder products. To the best of our knowledge, this is the first example of microwave-assisted Diels-Alder reaction of boron-substituted dienophiles. Subsequent in situ oxidation of the cycloadducts with alkaline hydrogen peroxide afforded the alcohols efficiently.

The effect of alkaline cations on the Intercalation of Carbon Dioxide in Sepiolite Minerals: a Molecular Dynamics Investigation.

NASA Astrophysics Data System (ADS)

Tavanti, Francesco; Muniz-Miranda, Francesco; Pedone, Alfonso

2018-03-01

The ability of the sepiolite mineral to intercalate CO2 molecules inside its channels in the presence of different alkaline cations (K+, Na+ and Li+) has been studied by classical Molecular Dynamics simulations. Starting from an alkaline-free sepiolite crystalline model we built three models with stoichiometry Mg320Si440Al40O1200(OH)160X+40•480H2O. On these models, we gradually replaced the water molecules present in the channels with carbon dioxide and determined the energy of this exchange reaction as well as the structural organization and dynamics of carbon dioxide in the channels. The adsorption energy shows that the Li-containing sepiolite mineral retains more carbon dioxide with respect to those with sodium and potassium cations in the channels. Moreover, the ordered patterns of CO2 molecules observed in the alkaline-free sepiolite mineral are in part destabilized by the presence of cations decreasing the adsorption capacity of this clay mineral.

Effect of unsteady oscillatory MHD flow through a porous medium in porous vertical channel with chemical reaction and concentration

NASA Astrophysics Data System (ADS)

Chitra, M.; Suhasini, M.

2018-04-01

In this paper, we investigate the effect of chemical reaction on the unsteady oscillatory MHD flow through porous medium in a porous vertical channel in the presence of suction velocity. The flow is assumed to be incompressible electrically conducting and radiating viscoelastic fluid in the presence of uniform magnetic flied applied perpendicular to the plane of the plates of the channel. The closed forms of analytical solution are obtained for the momentum, energy and concentration equation. The effect of various flow parameters like Schmidt number, chemical radiation parameter, Grashof number, solutal Grashof number on velocity profile, temperature, concentration, wall shear stress, and the rate of heat and mass transfer are obtained and their behaviour are discussed graphically.

Reaction of benzene with atomic carbon: pathways to fulvenallene and the fulvenallenyl radical in extraterrestrial atmospheres and the interstellar medium.

PubMed

da Silva, Gabriel

2014-06-05

The reaction of benzene with ground-state atomic carbon, C((3)P), has been investigated using the G3X-K composite quantum chemical method. A suite of novel energetically favorable pathways that lead to previously unconsidered products are identified. Reaction is initiated by barrierless C atom cycloaddition to benzene on the triplet surface, producing a vibrationally excited [C7H6]* adduct that can dissociate to the cycloheptatrienyl radical (+ H) via a relatively loose transition state 4.4 kcal mol(-1) below the reactant energies. This study also identifies that this reaction adduct can isomerize to generate five-membered ring intermediates that can further dissociate to the global C7H5 minima, the fulvenallenyl radical (+ H), or to c-C5H4 and acetylene, with limiting barriers around 20 and 10 kcal mol(-1) below the reactants, respectively. If intersystem crossing to the singlet surface occurs, isomerization pathways that are lower-yet in energy are available leading to the C7H6 minima fulvenallene, with all barriers over 40 kcal mol(-1) below the reactants. From here further barrierless fragmentation to fulvenallenyl + H can proceed at ca. 25 kcal mol(-1) below the reactants. In the reducing atmospheres of planets like Jupiter and satellites like Titan, where benzene and C((3)P) are both expected, it is proposed that fulvenallene and the fulvenallenyl radical would be the dominant products of the C6H6 + C((3)P) reaction. Fulvenallenyl may also be a significant reaction product under collision-free conditions representative of the interstellar medium, although further work is required here to confirm the identity of the C7H5 radical product.

Investigation of Unexpected Reaction Intermediates in the Alkaline Hydrolysis of Methyl 3,5-Dinitrobenzoate

ERIC Educational Resources Information Center

Silva, Clesia C.; Silva, Ricardo O.; Navarro, Daniela M. A. F.; Navarro, Marcelo

2009-01-01

An experimental project aimed at identifying stable reaction intermediates is described. Initially, the studied reaction appears to involve the simple hydrolysis, by aqueous sodium hydroxide, of methyl 3,5-dinitrobenzoate dissolved in dimethyl sulfoxide. On mixing the substrates, however, the reaction mixture unexpectedly turns an intense red in…

HYDROGENATION OF 4-OXOISOPHORONE OVER PD/AL2/O2 CATALYST UNDER SUPERCRITICAL CO2 MEDIUM

EPA Science Inventory

Hydrogenation of 4-oxoisophorone has been studied over 1% Pd/Al2O3 impregnated catalyst in supercritical CO2 medium at different reaction conditions. The effect of temperature, pressure and reaction medium on the conversion and product selectivity is discussed. Phase behavior stu...

Alkaline Hydrolysis/Polymerization of 2,4,6-Trinitrotoluene: Characterization of Products by 13C and 15N NMR

USGS Publications Warehouse

Thorn, K.A.; Thorne, P.G.; Cox, L.G.

2004-01-01

Alkaline hydrolysis has been investigated as a nonbiological procedure for the destruction of 2,4,6-trinitrotoluene (TNT) in explosives contaminated soils and munitions scrap. Nucleophilic substitutions of the nitro and methyl groups of TNT by hydroxide ion are the initial steps in the alkaline degradation of TNT. Potential applications of the technique include both in situ surface liming and ex situ alkaline treatment of contaminated soils. A number of laboratory studies have reported the formation of an uncharacterized polymeric material upon prolonged treatment of TNT in base. As part of an overall assessment of alkaline hydrolysis as a remediation technique, and to gain a better understanding of the chemical reactions underlying the hydrolysis/polymerization process, the soluble and precipitate fractions of polymeric material produced from the calcium hydroxide hydrolysis of unlabeled and 15N-labeled TNT were analyzed by elemental analysis and 13C and 15N nuclear magnetic resonance spectroscopy. Spectra indicated that reactions leading to polymerization included nucleophilic displacement of nitro groups by hydroxide ion, formation of ketone, carboxyl, alcohol, ether, and other aliphatic carbons, conversion of methyl groups to diphenyl methylene carbons, and recondensation of aromatic amines and reduced forms of nitrite, including ammonia and possibly hydroxylamine, into the polymer. Compared to the distribution of carbons in TNT as 14% sp 3- and 86% sp2-hybridized, the precipitate fraction from hydrolysis of unlabeled TNT contained 33% sp3- and 67% sp 2-hybridized carbons. The concentration of nitrogen in the precipitate was 64% of that in TNT. The 15N NMR spectra showed that, in addition to residual nitro groups, forms of nitrogen present in the filtrate and precipitate fractions include aminohydroquinone, primary amide, indole, imine, and azoxy, among others. Unreacted nitrite was recovered in the filtrate fraction. The toxicities and susceptibilities to

Conceptual Model of Uranium in the Vadose Zone for Acidic and Alkaline Wastes Discharged at the Hanford Site Central Plateau

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truex, Michael J.; Szecsody, James E.; Qafoku, Nikolla

2014-09-01

Historically, uranium was disposed in waste solutions of varying waste chemistry at the Hanford Site Central Plateau. The character of how uranium was distributed in the vadose zone during disposal, how it has continued to migrate through the vadose zone, and the magnitude of potential impacts on groundwater are strongly influenced by geochemical reactions in the vadose zone. These geochemical reactions can be significantly influenced by the disposed-waste chemistry near the disposal location. This report provides conceptual models and supporting information to describe uranium fate and transport in the vadose zone for both acidic and alkaline wastes discharged at amore » substantial number of waste sites in the Hanford Site Central Plateau. The conceptual models include consideration of how co-disposed acidic or alkaline fluids influence uranium mobility in terms of induced dissolution/precipitation reactions and changes in uranium sorption with a focus on the conditions near the disposal site. This information, when combined with the extensive information describing uranium fate and transport at near background pH conditions, enables focused characterization to support effective fate and transport estimates for uranium in the subsurface.« less

Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

PubMed Central

Huang, K.; Bi, K.; Liang, C.; Lin, S.; Zhang, R.; Wang, W. J.; Tang, H. L.; Lei, M.

2015-01-01

A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45 nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR activity, including a 75 percent value of the diffusion-limited current density and a 0.11 V smaller value about the onset potential with respect to Pt/C catalyst. Moreover, the excellent methanol-tolerance performance of VN/C has also been verified with 3 M methanol. Combined with the competitive prices, this VN/C nanocomposite can serve as an appropriate non-precious methanol-tolerant ORR catalyst for alkaline fuel cells. PMID:26100367

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jingkun; Ghoshal, Shraboni; Bates, Michael K.

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data,more » which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.« less

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media

DOE PAGES

Li, Jingkun; Ghoshal, Shraboni; Bates, Michael K.; ...

2017-10-16

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data,more » which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.« less

Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

NASA Astrophysics Data System (ADS)

Huang, K.; Bi, K.; Liang, C.; Lin, S.; Zhang, R.; Wang, W. J.; Tang, H. L.; Lei, M.

2015-06-01

A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45 nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR activity, including a 75 percent value of the diffusion-limited current density and a 0.11 V smaller value about the onset potential with respect to Pt/C catalyst. Moreover, the excellent methanol-tolerance performance of VN/C has also been verified with 3 M methanol. Combined with the competitive prices, this VN/C nanocomposite can serve as an appropriate non-precious methanol-tolerant ORR catalyst for alkaline fuel cells.

Net alkalinity and net acidity 1: Theoretical considerations

USGS Publications Warehouse

Kirby, C.S.; Cravotta, C.A.

2005-01-01

Net acidity and net alkalinity are widely used, poorly defined, and commonly misunderstood parameters for the characterization of mine drainage. The authors explain theoretical expressions of 3 types of alkalinity (caustic, phenolphthalein, and total) and acidity (mineral, CO2, and total). Except for rarely-invoked negative alkalinity, theoretically defined total alkalinity is closely analogous to measured alkalinity and presents few practical interpretation problems. Theoretically defined "CO 2-acidity" is closely related to most standard titration methods with an endpoint pH of 8.3 used for determining acidity in mine drainage, but it is unfortunately named because CO2 is intentionally driven off during titration of mine-drainage samples. Using the proton condition/mass- action approach and employing graphs to illustrate speciation with changes in pH, the authors explore the concept of principal components and how to assign acidity contributions to aqueous species commonly present in mine drainage. Acidity is defined in mine drainage based on aqueous speciation at the sample pH and on the capacity of these species to undergo hydrolysis to pH 8.3. Application of this definition shows that the computed acidity in mg L -1 as CaCO3 (based on pH and analytical concentrations of dissolved FeII, FeIII, Mn, and Al in mg L -1):aciditycalculated=50{1000(10-pH)+[2(FeII)+3(FeIII)]/56+2(Mn)/ 55+3(Al)/27}underestimates contributions from HSO4- and H+, but overestimates the acidity due to Fe3+ and Al3+. However, these errors tend to approximately cancel each other. It is demonstrated that "net alkalinity" is a valid mathematical construction based on theoretical definitions of alkalinity and acidity. Further, it is shown that, for most mine-drainage solutions, a useful net alkalinity value can be derived from: (1) alkalinity and acidity values based on aqueous speciation, (2) measured alkalinity minus calculated acidity, or (3) taking the negative of the value obtained in a

Hydroponics gel as a new electrolyte gelling agent for alkaline zinc-air cells

NASA Astrophysics Data System (ADS)

Othman, R.; Basirun, W. J.; Yahaya, A. H.; Arof, A. K.

The viability of hydroponics gel as a new alkaline electrolyte gelling agent is investigated. Zinc-air cells are fabricated employing 12 wt.% KOH electrolyte immobilised with hydroponics gel. The cells are discharged at constant currents of 5, 50 and 100 mA. XRD and SEM analysis of the anode plates after discharge show that the failure mode is due to the formation of zinc oxide insulating layers and not due to any side reactions between the gel and the plate or the electrolyte.

Medium pH in submerged cultivation modulates differences in the intracellular protein profile of Fusarium oxysporum.

PubMed

da Rosa-Garzon, Nathália Gonsales; Laure, Hélen Julie; Souza-Motta, Cristina Maria de; Rosa, José César; Cabral, Hamilton

2017-08-09

Fusarium oxysporum is a filamentous fungus that damages a wide range of plants and thus causes severe crop losses. In fungal pathogens, the genes and proteins involved in virulence are known to be controlled by environmental pH. Here, we report the influence of culture-medium pH (5, 6, 7, and 8) on the production of degradative enzymes involved in the pathogenesis of F. oxysporum URM 7401 and on the 2D-electrophoresis profile of intracellular proteins in this fungus. F. oxysporum URM 7401 was grown in acidic, neutral, and alkaline culture media in a submerged bioprocess. After 96 hr, the crude extract was processed to enzyme activity assays, while the intracellular proteins were obtained from mycelium and analyzed using 2D electrophoresis and mass spectrometry. We note that the diversity of secreted enzymes was changed quantitatively in different culture-medium pH. Also, the highest accumulated biomass and the intracellular protein profile of F. oxysporum URM 7401 indicate an increase in metabolism in neutral-alkaline conditions. The differential profiles of secreted enzymes and intracellular proteins under the evaluated conditions indicate that the global protein content in F. oxysporum URM 7401 is modulated by extracellular pH.

Optical reaction cell and light source for [18F] fluoride radiotracer synthesis

DOEpatents

Ferrieri, R.A.; Schlyer, D.; Becker, R.J.

1998-09-15

An apparatus is disclosed for performing organic synthetic reactions, particularly no-carrier-added nucleophilic radiofluorination reactions for PET radiotracer production. The apparatus includes an optical reaction cell and a source of broadband infrared radiant energy, which permits direct coupling of the emitted radiant energy with the reaction medium to heat the reaction medium. Preferably, the apparatus includes means for focusing the emitted radiant energy into the reaction cell, and the reaction cell itself is preferably configured to reflect transmitted radiant energy back into the reaction medium to further improve the efficiency of the apparatus. The apparatus is well suited to the production of high-yield syntheses of 2-[{sup 18}F]fluoro-2-deoxy-Dglucose. Also provided is a method for performing organic synthetic reactions, including the manufacture of [{sup 18}F]-labeled compounds useful as PET radiotracers, and particularly for the preparation of 2-[{sup 18}F]fluoro-2-deoxy-D-glucose in higher yields than previously possible. 4 figs.

Francisella DnaK Inhibits Tissue-nonspecific Alkaline Phosphatase*

PubMed Central

Arulanandam, Bernard P.; Chetty, Senthilnath Lakshmana; Yu, Jieh-Juen; Leonard, Sean; Klose, Karl; Seshu, Janakiram; Cap, Andrew; Valdes, James J.; Chambers, James P.

2012-01-01

Following pulmonary infection with Francisella tularensis, we observed an unexpected but significant reduction of alkaline phosphatase, an enzyme normally up-regulated following inflammation. However, no reduction was observed in mice infected with a closely related Gram-negative pneumonic organism (Klebsiella pneumoniae) suggesting the inhibition may be Francisella-specific. In similar fashion to in vivo observations, addition of Francisella lysate to exogenous alkaline phosphatase (tissue-nonspecific isozyme) was inhibitory. Partial purification and subsequent proteomic analysis indicated the inhibitory factor to be the heat shock protein DnaK. Incubation with increasing amounts of anti-DnaK antibody reduced the inhibitory effect in a dose-dependent manner. Furthermore, DnaK contains an adenosine triphosphate binding domain at its N terminus, and addition of adenosine triphosphate enhances dissociation of DnaK with its target protein, e.g. alkaline phosphatase. Addition of adenosine triphosphate resulted in decreased DnaK co-immunoprecipitated with alkaline phosphatase as well as reduction of Francisella-mediated alkaline phosphatase inhibition further supporting the binding of Francisella DnaK to alkaline phosphatase. Release of DnaK via secretion and/or bacterial cell lysis into the extracellular milieu and inhibition of plasma alkaline phosphatase could promote an orchestrated, inflammatory response advantageous to Francisella. PMID:22923614

Francisella DnaK inhibits tissue-nonspecific alkaline phosphatase.

PubMed

Arulanandam, Bernard P; Chetty, Senthilnath Lakshmana; Yu, Jieh-Juen; Leonard, Sean; Klose, Karl; Seshu, Janakiram; Cap, Andrew; Valdes, James J; Chambers, James P

2012-10-26

Following pulmonary infection with Francisella tularensis, we observed an unexpected but significant reduction of alkaline phosphatase, an enzyme normally up-regulated following inflammation. However, no reduction was observed in mice infected with a closely related gram-negative pneumonic organism (Klebsiella pneumoniae) suggesting the inhibition may be Francisella-specific. In similar fashion to in vivo observations, addition of Francisella lysate to exogenous alkaline phosphatase (tissue-nonspecific isozyme) was inhibitory. Partial purification and subsequent proteomic analysis indicated the inhibitory factor to be the heat shock protein DnaK. Incubation with increasing amounts of anti-DnaK antibody reduced the inhibitory effect in a dose-dependent manner. Furthermore, DnaK contains an adenosine triphosphate binding domain at its N terminus, and addition of adenosine triphosphate enhances dissociation of DnaK with its target protein, e.g. alkaline phosphatase. Addition of adenosine triphosphate resulted in decreased DnaK co-immunoprecipitated with alkaline phosphatase as well as reduction of Francisella-mediated alkaline phosphatase inhibition further supporting the binding of Francisella DnaK to alkaline phosphatase. Release of DnaK via secretion and/or bacterial cell lysis into the extracellular milieu and inhibition of plasma alkaline phosphatase could promote an orchestrated, inflammatory response advantageous to Francisella.

A differential medium for the enumeration of the spoilage yeast Zygosaccharomyces bailii in wine.

PubMed

Schuller, D; Côrte-Real, M; Leão, C

2000-11-01

A collection of yeasts, isolated mostly from spoiled wines, was used in order to develop a differential medium for Zygosaccharomyces bailii. The 118 selected strains of 21 species differed in their origin and resistance to preservatives and belonged to the genera Pichia, Torulaspora, Dekkera, Debaryomyces, Saccharomycodes, Issatchenkia, Kluyveromyces, Kloeckera, Lodderomyces, Schizosaccharomyces, Rhodotorula, Saccharomyces, and Zygosaccharomyces. The design of the culture medium was based on the different ability of the various yeast species to grow in a mineral medium with glucose and formic acid (mixed-substrate medium) as the only carbon and energy sources and supplemented with an acid-base indicator. By manipulating the concentration of the acid and the sugar it was possible to select conditions where only Z. bailii strains gave rise to alkalinization, associated with a color change of the medium (positive response). The final composition of the mixed medium was adjusted as a compromise between the percentage of recovery and selectivity for Z. bailii. This was accomplished by the use of pure or mixed cultures of the yeast strains and applying the membrane filtration methodology. The microbiological analysis of two samples of contaminated Vinho Verde showed that the new medium can be considered as a differential medium to distinguish Z. bailii from other contaminating yeasts, having potential application in the microbiological control of wines and probably other beverages and foods.

Water miscible mono alcohols' effect on the proteolytic performance of Bacillus clausii serine alkaline protease.

PubMed

Duman, Yonca Avci; Kazan, Dilek; Denizci, Aziz Akin; Erarslan, Altan

2014-01-01

In this study, our investigations showed that the increasing concentrations of all examined mono alcohols caused a decrease in the Vm, kcat and kcat/Km values of Bacillus clausii GMBE 42 serine alkaline protease for casein hydrolysis. However, the Km value of the enzyme remained almost the same, which was an indicator of non-competitive inhibition. Whereas inhibition by methanol was partial non-competitive, inhibition by the rest of the alcohols tested was simple non-competitive. The inhibition constants (KI) were in the range of 1.32-3.10 M, and the order of the inhibitory effect was 1-propanol>2-propanol>methanol>ethanol. The ΔG(≠) and ΔG(≠)E-T values of the enzyme increased at increasing concentrations of all alcohols examined, but the ΔG(≠)ES value of the enzyme remained almost the same. The constant Km and ΔG(≠)ES values in the presence and absence of mono alcohols indicated the existence of different binding sites for mono alcohols and casein on enzyme the molecule. The kcat of the enzyme decreased linearly by increasing log P and decreasing dielectric constant (D) values, but the ΔG(≠) and ΔG(≠)E-T values of the enzyme increased by increasing log P and decreasing D values of the reaction medium containing mono alcohols.

Let's think in alkaline phosphatase at heart function.

PubMed

Martins, Maria João; Azevedo, Isabel

2010-10-08

In their recent paper, Cheung et al [B.M. Cheung, K.L. Ong, L.Y. Wong, Elevated serum alkaline phosphatase and peripheral arterial disease in the United States National Health and Nutrition Examination Survey 1999-2004. Int J Cardiol 2008 (Electronic publication ahead of print)] described a significant association between serum alkaline phosphatase levels and low ankle-brachial blood pressure index, a risk factor for cardiovascular pathology. We had verified that alkaline phosphatase is present at the rat heart, showing a distribution compatible with cardiomyocyte sarcoplasmic reticulum. Moreover, several drugs with cardiac effect were shown to interfere with heart alkaline phosphatase activity. We therefore propose that alkaline phosphatase may be a local regulator at heart function and a putative target for therapeutic interventions. Copyright © 2009 Elsevier Ireland Ltd. All rights reserved.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete.

PubMed

Simescu, Florica; Idrissi, Hassane

2008-12-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 . After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

NASA Astrophysics Data System (ADS)

Simescu, Florica; Idrissi, Hassane

2008-12-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca10(PO4)6(OH)2. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating.

Effect of zinc phosphate chemical conversion coating on corrosion behaviour of mild steel in alkaline medium: protection of rebars in reinforced concrete

PubMed Central

Simescu, Florica; Idrissi, Hassane

2008-01-01

We outline the ability of zinc phosphate coatings, obtained by chemical conversion, to protect mild steel rebars against localized corrosion, generated by chloride ions in alkaline media. The corrosion resistance of coated steel, in comparison with uncoated rebars and coated and uncoated steel rebars embedded in mortar, were evaluated by open-circuit potential, potentiodynamic polarization, cronoamperometry and electrochemical impedance spectroscopy. The coated surfaces were characterized by x-ray diffraction and scanning electron microscopy. First, coated mild steel rebars were studied in an alkaline solution with and without chloride simulating a concrete pore solution. The results showed that the slow dissolution of the coating generates hydroxyapatite Ca10(PO4)6(OH)2. After a long immersion, the coating became dense and provided an effective corrosion resistance compared with the mild steel rebar. Secondly, the coated and uncoated steel rebars embedded in mortar and immersed in chloride solution showed no corrosion or deterioration of the coated steel. Corrosion rate is considerably lowered by this phosphate coating. PMID:27878037

Alkaline phosphatase activity of rumen bacteria.

PubMed

Cheng, K J; Costerton, J W

1977-11-01

Of the 54 strains of rumen bacteria examined for alkaline phosphatase (APase) production, 9 of 33 gram-negative strains and none of 21 gram-positive strains produced the enzyme. The APase of the cells of the three strains of Bacteroides ruminicola that produced significant amounts of the enzyme was located in the periplasmic area of the cell envelope, whereas the enzyme was located in the strains of Selenomonas ruminantium and Succinivibrio dextrinosolvens was associated with the outer membrane. The localization of APase production in the cells of natural populations of rumen bacteria from hay-fed sheep was accomplished by reaction product deposition, and both the proportion of APase-producing bacteria and the location of the enzyme in the cell envelope of the producing cells could be determined. We suggest that this procedure is useful in detecting shifts in the bacterial population and the release of cell-bound APase that accompany feedlot bloat and other sequelae of dietary manipulation in ruminants.

Alkaline phosphatase activity of rumen bacteria.

PubMed Central

Cheng, K J; Costerton, J W

1977-01-01

Of the 54 strains of rumen bacteria examined for alkaline phosphatase (APase) production, 9 of 33 gram-negative strains and none of 21 gram-positive strains produced the enzyme. The APase of the cells of the three strains of Bacteroides ruminicola that produced significant amounts of the enzyme was located in the periplasmic area of the cell envelope, whereas the enzyme was located in the strains of Selenomonas ruminantium and Succinivibrio dextrinosolvens was associated with the outer membrane. The localization of APase production in the cells of natural populations of rumen bacteria from hay-fed sheep was accomplished by reaction product deposition, and both the proportion of APase-producing bacteria and the location of the enzyme in the cell envelope of the producing cells could be determined. We suggest that this procedure is useful in detecting shifts in the bacterial population and the release of cell-bound APase that accompany feedlot bloat and other sequelae of dietary manipulation in ruminants. Images PMID:563216

Alkaline sorbent injection for mercury control

DOEpatents

Madden, Deborah A.; Holmes, Michael J.

2003-01-01

A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

Alkaline sorbent injection for mercury control

DOEpatents

Madden, Deborah A.; Holmes, Michael J.

2002-01-01

A mercury removal system for removing mercury from combustion flue gases is provided in which alkaline sorbents at generally extremely low stoichiometric molar ratios of alkaline earth or an alkali metal to sulfur of less than 1.0 are injected into a power plant system at one or more locations to remove at least between about 40% and 60% of the mercury content from combustion flue gases. Small amounts of alkaline sorbents are injected into the flue gas stream at a relatively low rate. A particulate filter is used to remove mercury-containing particles downstream of each injection point used in the power plant system.

Inorganic-organic separators for alkaline batteries

NASA Technical Reports Server (NTRS)

Sheibley, D. W. (Inventor)

1978-01-01

A flexible separator is reported for use between the electrodes of Ni-Cd and Ni-Zn batteries using alkaline electrolytes. The separator was made by coating a porous substrate with a battery separator composition. The coating material included a rubber-based resin copolymer, a plasticizer and inorganic and organic fillers which comprised 55% by volume or less of the coating as finally dried. One or more of the filler materials, whether organic or inorganic, is preferably active with the alkaline electrolyte to produce pores in the separator coating. The plasticizer was an organic material which is hydrolyzed by the alkaline electrolyte to improve conductivity of the separator coating.

Impact of 6-month frozen storage of cervical specimens in alkaline buffer conditions on human papillomavirus genotyping.

PubMed

LaMere, Brandon J; Howell, Renee; Fetterman, Barbara; Shieh, Jen; Castle, Philip E

2008-08-01

The impact of 6-month storage of cervical specimens under alkaline conditions that occurs as the result of Hybrid Capture 2 testing on human papillomavirus (HPV) genotyping is not well documented. To examine this issue, 143 frozen hc2-positive specimens in specimen transport medium were selected at random from each of the following groups: specimens stored for 6 months, 4 months, and 2.5 months under alkaline pH (pH 12-13) and specimens stored 1 month at neutral pH (pH 6-7) as controls. Specimens were tested in a masked fashion for 20 HPV genotypes (HPV6, 11, 16, 18, 26, 31, 33, 35, 39, 45, 51, 52, 53, 56, 58, 59, 66, 68, 73, and 82) using a prototype, research-use-only GP5+/6+ L1 consensus PCR method and multiplex hybridization using Luminex xMAP for detection of specific HPV genotypes One control specimen had missing test results. There were no statistical differences in the number of HPV genotypes detected, number of carcinogenic HPV genotypes detected, or in the signal strength among HPV-positive results across groups. Six-month frozen storage of cervical specimens at alkaline pH had little impact on testing for HPV genotypes among hc2-positive women using this HPV genotyping method.

Computational design of a pH stable enzyme: understanding molecular mechanism of penicillin acylase's adaptation to alkaline conditions.

PubMed

Suplatov, Dmitry; Panin, Nikolay; Kirilin, Evgeny; Shcherbakova, Tatyana; Kudryavtsev, Pavel; Svedas, Vytas

2014-01-01

Protein stability provides advantageous development of novel properties and can be crucial in affording tolerance to mutations that introduce functionally preferential phenotypes. Consequently, understanding the determining factors for protein stability is important for the study of structure-function relationship and design of novel protein functions. Thermal stability has been extensively studied in connection with practical application of biocatalysts. However, little work has been done to explore the mechanism of pH-dependent inactivation. In this study, bioinformatic analysis of the Ntn-hydrolase superfamily was performed to identify functionally important subfamily-specific positions in protein structures. Furthermore, the involvement of these positions in pH-induced inactivation was studied. The conformational mobility of penicillin acylase in Escherichia coli was analyzed through molecular modeling in neutral and alkaline conditions. Two functionally important subfamily-specific residues, Gluβ482 and Aspβ484, were found. Ionization of these residues at alkaline pH promoted the collapse of a buried network of stabilizing interactions that consequently disrupted the functional protein conformation. The subfamily-specific position Aspβ484 was selected as a hotspot for mutation to engineer enzyme variant tolerant to alkaline medium. The corresponding Dβ484N mutant was produced and showed 9-fold increase in stability at alkaline conditions. Bioinformatic analysis of subfamily-specific positions can be further explored to study mechanisms of protein inactivation and to design more stable variants for the engineering of homologous Ntn-hydrolases with improved catalytic properties.

Computational Design of a pH Stable Enzyme: Understanding Molecular Mechanism of Penicillin Acylase's Adaptation to Alkaline Conditions

PubMed Central

Suplatov, Dmitry; Panin, Nikolay; Kirilin, Evgeny; Shcherbakova, Tatyana; Kudryavtsev, Pavel; Švedas, Vytas

2014-01-01

Protein stability provides advantageous development of novel properties and can be crucial in affording tolerance to mutations that introduce functionally preferential phenotypes. Consequently, understanding the determining factors for protein stability is important for the study of structure-function relationship and design of novel protein functions. Thermal stability has been extensively studied in connection with practical application of biocatalysts. However, little work has been done to explore the mechanism of pH-dependent inactivation. In this study, bioinformatic analysis of the Ntn-hydrolase superfamily was performed to identify functionally important subfamily-specific positions in protein structures. Furthermore, the involvement of these positions in pH-induced inactivation was studied. The conformational mobility of penicillin acylase in Escherichia coli was analyzed through molecular modeling in neutral and alkaline conditions. Two functionally important subfamily-specific residues, Gluβ482 and Aspβ484, were found. Ionization of these residues at alkaline pH promoted the collapse of a buried network of stabilizing interactions that consequently disrupted the functional protein conformation. The subfamily-specific position Aspβ484 was selected as a hotspot for mutation to engineer enzyme variant tolerant to alkaline medium. The corresponding Dβ484N mutant was produced and showed 9-fold increase in stability at alkaline conditions. Bioinformatic analysis of subfamily-specific positions can be further explored to study mechanisms of protein inactivation and to design more stable variants for the engineering of homologous Ntn-hydrolases with improved catalytic properties. PMID:24959852

Chemistry of nitrile anions in the interstellar medium

NASA Astrophysics Data System (ADS)

Carles, S.; Le Garrec, J.-L.; Guillemin, J.-C.; Biennier, L.

2015-12-01

Despite the extreme conditions of temperature (down to 10K) and density (down to 100 molecules/cm3), the giant molecular clouds and the circumstellar envelopes present a rich and complex chemistry. To date, more than 180 molecules have been detected in the InterStellar Medium (ISM) with a large abundance of nitriles (RC≡N). In addition, several anions have been recently observed in this medium: C4H¯, C6H¯, C8H¯, CN¯, C3N¯ and C5N¯. These last species should play a key role in the molecular growth towards complexity. To explore this hypothesis, their reactivity must be studied in the laboratory. The FALP-MS and the CRESU experimental apparatuses of the Rennes University are able to measure absolute rate coefficient of various chemical reactions, including the ion - molecule reactions, in gas phase at low temperature (from 300K for the FALP-MS down to 15K for the CRESU). Therefore, these experimental tools are particularly adapted to the kinetic studies of reactions potentially involved in the Interstellar Medium. One of the difficulties encountered in experiments with anions is their generation. We describe here the formation of the CN¯ and C3N¯ anions by dissociative electron attachment on the molecular precursors BrCN and BrC3N.

Temperature enhances the affinity of soil alkaline phosphatase to Cd.

PubMed

Tan, Xiangping; Machmuller, Megan B; Wang, Ziquan; Li, Xudong; He, Wenxiang; Cotrufo, M Francesca; Shen, Weijun

2018-04-01

Both elevated temperature and heavy metal contamination can have profound effects on microbial function and soil biogeochemical cycling. However, the interactive effects of heavy metal toxicity and temperature on microbial activity have been poorly understood. The aim of this study was to quantify the effect of temperature and cadmium (Cd) toxicity on alkaline phosphatase (ALP) produced by microbes to acquire phosphorus. To determine whether these effects were dependent on soil properties, we utilized 11 soil types from cropland throughout China. We measured ALP activities and kinetics across a temperature (17, 27, 37, and 47 °C) and Cd concentration gradient (0, 0.6, 5, 25, 50, 100, 200, 300, and 500 mg kg -1 ). We found that the half saturation constant (K m ) and the velocity constant (k) of ALP increased nonlinearly with temperature across all soil types. However, the maximum reaction velocity (V max ) increased linearly with temperature. Regardless of soil type and temperature, Cd had a non-competitive inhibitory mechanism. Soil pH, TOC, and clay content were the major factors controlling the affinity of ALP for Cd (K i ). The ecology dose (ED 50 ) for V max and k, and K i were negatively related to temperature, indicating that the toxicity of Cd on ALP is temperature-dependent. Additionally, higher temperatures led to more inhibition of Cd on ALP activity in alkaline soils than that in acidic and neutral soils. Our results suggest that global warming might accelerate the deficiency of available phosphorus in Cd contaminated soils due to higher inhibition of Cd on ALP activity, particularly in alkaline soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

A fluorescence-based alkaline phosphatase-coupled polymerase assay for identification of inhibitors of dengue virus RNA-dependent RNA polymerase.

PubMed

Niyomrattanakit, Pornwaratt; Abas, Siti Nurdiana; Lim, Chin Chin; Beer, David; Shi, Pei-Yong; Chen, Yen-Liang

2011-02-01

The flaviviral RNA-dependent RNA polymerase (RdRp) is an attractive drug target. To discover new inhibitors of dengue virus RdRp, the authors have developed a fluorescence-based alkaline phosphatase-coupled polymerase assay (FAPA) for high-throughput screening (HTS). A modified nucleotide analogue (2'-[2-benzothiazoyl]-6'-hydroxybenzothiazole) conjugated adenosine triphosphate (BBT-ATP) and 3'UTR-U(30) RNA were used as substrates. After the polymerase reaction, treatment with alkaline phosphatase liberates the BBT fluorophore from the polymerase reaction by-product, BBT(PPi), which can be detected at excitation and emission wavelengths of 422 and 566 nm, respectively. The assay was evaluated by examining the time dependency, assay reagent effects, reaction kinetics, and signal stability and was validated with 3'dATP and an adenosine-nucleotide triphosphate inhibitor, giving IC(50) values of 0.13 µM and 0.01 µM, respectively. A pilot screen of a diverse compound library of 40,572 compounds at 20 µM demonstrated good performance with an average Z factor of 0.81. The versatility and robustness of FAPA were evaluated with another substrate system, BBT-GTP paired with 3'UTR-C(30) RNA. The FAPA method presented here can be readily adapted for other nucleotide-dependent enzymes that generate PPi.

Alkaline Phosphatase: MedlinePlus Lab Test Information

MedlinePlus

... Test Information → Alkaline Phosphatase URL of this page: https://medlineplus.gov/labtests/alkalinephosphatase.html Alkaline Phosphatase To ... 2017 Mar 13]; [about 3 screens]. Available from: http://www.liverfoundation.org/abouttheliver/info/liverfunctiontests/ Centers for ...

Production of zinc and manganese oxide particles by pyrolysis of alkaline and Zn-C battery waste.

PubMed

Ebin, Burçak; Petranikova, Martina; Steenari, Britt-Marie; Ekberg, Christian

2016-05-01

Production of zinc and manganese oxide particles from alkaline and zinc-carbon battery black mass was studied by a pyrolysis process at 850-950°C with various residence times under 1L/minN2(g) flow rate conditions without using any additive. The particular and chemical properties of the battery waste were characterized to investigate the possible reactions and effects on the properties of the reaction products. The thermodynamics of the pyrolysis process were studied using the HSC Chemistry 5.11 software. The carbothermic reduction reaction of battery black mass takes place and makes it possible to produce fine zinc particles by a rapid condensation, after the evaporation of zinc from a pyrolysis batch. The amount of zinc that can be separated from the black mass is increased by both pyrolysis temperature and residence time. Zinc recovery of 97% was achieved at 950°C and 1h residence time using the proposed alkaline battery recycling process. The pyrolysis residue is mainly MnO powder with a low amount of zinc, iron and potassium impurities and has an average particle size of 2.9μm. The obtained zinc particles have an average particle size of about 860nm and consist of hexagonal crystals around 110nm in size. The morphology of the zinc particles changes from a hexagonal shape to s spherical morphology by elevating the pyrolysis temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

21 CFR 862.1050 - Alkaline phosphatase or isoenzymes test system.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Alkaline phosphatase or isoenzymes test system... Test Systems § 862.1050 Alkaline phosphatase or isoenzymes test system. (a) Identification. An alkaline phosphatase or isoenzymes test system is a device intended to measure alkaline phosphatase or its isoenzymes...

Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

NASA Astrophysics Data System (ADS)

Khan, Sameera Razi; Ashfaq, Maria; Mubashir; Masood, Summyia

2016-05-01

The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298-318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy ( E a), enthalpy change (Δ H*), free energy change (Δ G*), and entropy change (Δ S*) have also been evaluated.

Introducing catalyst in alkaline membrane for improved performance direct borohydride fuel cells

NASA Astrophysics Data System (ADS)

Qin, Haiying; Lin, Longxia; Chu, Wen; Jiang, Wei; He, Yan; Shi, Qiao; Deng, Yonghong; Ji, Zhenguo; Liu, Jiabin; Tao, Shanwen

2018-01-01

A catalytic material is introduced into the polymer matrix to prepare a novel polymeric alkaline electrolyte membrane (AEM) which simultaneously increases ionic conductivity, reduces the fuel cross-over. In this work, the hydroxide anion exchange membrane is mainly composed of poly(vinylalcohol) and alkaline exchange resin. CoCl2 is added into the poly(vinylalcohol) and alkaline exchange resin gel before casting the membrane to introduce catalytic materials. CoCl2 is converted into CoOOH after the reaction with KOH solution. The crystallinity of the polymer matrix decreases and the ionic conductivity of the composite membrane is notably improved by the introduction of Co-species. A direct borohydride fuel cell using the composite membrane exhibits an open circuit voltage of 1.11 V at 30 °C, which is notably higher than that of cells using other AEMs. The cell using the composite membrane achieves a maximum power density of 283 mW cm-2 at 60 °C while the cell using the membrane without Co-species only reaches 117 mW cm-2 at the same conditions. The outstanding performance of the cell using the composite membrane benefits from impregnation of the catalytic Co-species in the membrane, which not only increases the ionic conductivity but also reduces electrode polarization thus improves the fuel cell performance. This work provides a new approach to develop high-performance fuel cells through adding catalysts in the electrolyte membrane.

Laboratory study on the behaviour of spent AA household alkaline batteries in incineration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Almeida, Manuel F.; Xara, Susana M.; Delgado, Julanda

2009-01-15

was done for most of potential reactions between components in the batteries as well as between them and the surrounding atmosphere and it reasonably agrees the experimental results. The results obtained show the role of alkaline batteries at the acid gases cleaning process, through the neutralization reactions of some of their components. Therefore, LCA of spent AA alkaline batteries at the municipal solid waste (MSW) incineration process must consider this contribution.« less

Prebiotic Peptide (Amide) Bond Synthesis Accelerated by Glycerol and Bicarbonate Under Neutral to Alkaline Dry-Down Conditions

NASA Technical Reports Server (NTRS)

Forsythe, J. G.; Weber, A. L.

2017-01-01

Past studies of prebiotic peptide bond synthesis have generally been carried out in the acidic to neutral pH range [1, 2]. Here we report a new process for peptide bond (amide) synthesis in the neutral to alkaline pH range that involves simple dry-down heating of amino acids in the presence of glycerol and bicarbonate. Glycerol was included in the reaction mixture as a solvent and to provide hydroxyl groups for possible formation of ester intermediates previously implicated in peptide bond synthesis under acidic to neutral conditions [1]. Bicarbonate was added to raise the reaction pH to 8-9.

Mechanisms and kinetics of alkaline hydrolysis of the energetic nitroaromatic compounds 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroanisole (DNAN).

PubMed

Salter-Blanc, Alexandra J; Bylaska, Eric J; Ritchie, Julia J; Tratnyek, Paul G

2013-07-02

The environmental impacts of energetic compounds can be minimized through the design and selection of new energetic materials with favorable fate properties. Building predictive models to inform this process, however, is difficult because of uncertainties and complexities in some major fate-determining transformation reactions such as the alkaline hydrolysis of energetic nitroaromatic compounds (NACs). Prior work on the mechanisms of the reaction between NACs and OH(-) has yielded inconsistent results. In this study, the alkaline hydrolysis of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroanisole (DNAN) was investigated with coordinated experimental kinetic measurements and molecular modeling calculations. For TNT, the results suggest reversible formation of an initial product, which is likely either a Meisenheimer complex or a TNT anion formed by abstraction of a methyl proton by OH(-). For DNAN, the results suggest that a Meisenheimer complex is an intermediate in the formation of 2,4-dinitrophenolate. Despite these advances, the remaining uncertainties in the mechanisms of these reactions-and potential variability between the hydrolysis mechanisms for different NACs-mean that it is not yet possible to generalize the results into predictive models (e.g., quantitative structure-activity relationships, QSARs) for hydrolysis of other NACs.

Alkaline hydrolysis/polymerization of 2,4,6-Trinitrotoluene:  Characterization of products by 13C and 15N NMR

USGS Publications Warehouse

Thorn, Kevin A.; Thorne, Philip G.; Cox, Larry G.

2004-01-01

Alkaline hydrolysis has been investigated as a nonbiological procedure for the destruction of 2,4,6-trinitrotoluene (TNT) in explosives contaminated soils and munitions scrap. Nucleophilic substitutions of the nitro and methyl groups of TNT by hydroxide ion are the initial steps in the alkaline degradation of TNT. Potential applications of the technique include both in situ surface liming and ex situ alkaline treatment of contaminated soils. A number of laboratory studies have reported the formation of an uncharacterized polymeric material upon prolonged treatment of TNT in base. As part of an overall assessment of alkaline hydrolysis as a remediation technique, and to gain a better understanding of the chemical reactions underlying the hydrolysis/polymerization process, the soluble and precipitate fractions of polymeric material produced from the calcium hydroxide hydrolysis of unlabeled and 15N-labeled TNT were analyzed by elemental analysis and 13C and 15N nuclear magnetic resonance spectroscopy. Spectra indicated that reactions leading to polymerization included nucleophilic displacement of nitro groups by hydroxide ion, formation of ketone, carboxyl, alcohol, ether, and other aliphatic carbons, conversion of methyl groups to diphenyl methylene carbons, and recondensation of aromatic amines and reduced forms of nitrite, including ammonia and possibly hydroxylamine, into the polymer. Compared to the distribution of carbons in TNT as 14% sp3- and 86% sp2-hybridized, the precipitate fraction from hydrolysis of unlabeled TNT contained 33% sp3- and 67% sp2-hybridized carbons. The concentration of nitrogen in the precipitate was 64% of that in TNT. The 15N NMR spectra showed that, in addition to residual nitro groups, forms of nitrogen present in the filtrate and precipitate fractions include aminohydroquinone, primary amide, indole, imine, and azoxy, among others. Unreacted nitrite was recovered in the filtrate fraction. The toxicities and susceptibilities to

Alkaline pH induces IRR-mediated phosphorylation of IRS-1 and actin cytoskeleton remodeling in a pancreatic beta cell line.

PubMed

Deyev, Igor E; Popova, Nadezhda V; Serova, Oxana V; Zhenilo, Svetlana V; Regoli, Marì; Bertelli, Eugenio; Petrenko, Alexander G

2017-07-01

Secretion of mildly alkaline (pH 8.0-8.5) juice to intestines is one of the key functions of the pancreas. Recent reports indicate that the pancreatic duct system containing the alkaline juice may adjoin the endocrine cells of pancreatic islets. We have previously identified the insulin receptor-related receptor (IRR) that is expressed in islets as a sensor of mildly alkaline extracellular media. In this study, we show that those islet cells that are in contact with the excretory ducts are also IRR-expressing cells. We further analyzed the effects of alkaline media on pancreatic beta cell line MIN6. Activation of endogenous IRR but not of the insulin receptor was detected that could be inhibited with linsitinib. The IRR autophosphorylation correlated with pH-dependent linsitinib-sensitive activation of insulin receptor substrate 1 (IRS-1), the primary adaptor in the insulin signaling pathway. However, in contrast with insulin stimulation, no protein kinase B (Akt/PKB) phosphorylation was detected as a result of alkali treatment. We observed overexpression of several early response genes (EGR2, IER2, FOSB, EGR1 and NPAS4) upon alkali treatment of MIN6 cells but those were IRR-independent. The alkaline medium but not insulin also triggered actin cytoskeleton remodeling that was blocked by pre-incubation with linsitinib. We propose that the activation of IRR by alkali might be part of a local loop of signaling between the exocrine and endocrine parts of the pancreas where alkalinization of the juice facilitate insulin release that increases the volume of secreted juice to control its pH and bicabonate content. Copyright © 2017 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

Spectroscopic research of Lambda hypernuclei up to medium-heavy mass region with the (e,e'K +) reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gogami, Toshiyuki

In 2009 (August-November), the E05-115 experiment was carried out at JLab to investigate L hypernuclei in the wide mass region up to A = 52 (more » $$7\\atop{Λ}$$He, $$10\\atop{Λ}$$Be, $$12\\atop{Λ}$$B and $$52\\atop{Λ}$$V) with the (e,e'K +) reaction. This is the first attempt to investigate a medium heavy L hypernucleus with the (e,e'K +) reaction. Experimentally, it is difficult to measure heavier L hypernuclei as background rates of particles which originate from electromagnetic processes are roughly in proportion to Z2 (Z: target proton number) in the (e,e'K +) experiment. To perform the experiment, many experimental techniques have been developed and introduced such as optimization of the electron spectrometer configuration (tilt method), clean kaon identification, particle tracking under high multiplicity environment, precise energy scale calibration and so on. In the present thesis, experimental results of the elementary process of p(e,e'K +)L, L hypernuclei of $$7\\atop{Λ}$$He, $$10\\atop{Λ}$$Be, $$12\\atop{Λ}$$B and $$52\\atop{Λ}$$V are shown. Elementary processes of the electroproduction of L and Σ 0, p(e,e'K +)L, Σ 0 were used for the absolute energy scale calibration of our spectrometer systems. A careful Monte Carlo simulation shows that the binding energy can be obtained with a systematic error of 0.11 MeV with our energy scale calibration method. A study of the elementary process of L is important to understand L hypernuclei as it is essential for theoretical calculations of L hypernuclei. The differential cross section of the p(e,e'K +)L reaction at the small K + scattering angle (theta-CM/gamma-K approx. 15.5°), the small Q 2 (approx 0.01 [GeV/c] 2) and the total energy of W = 1.92 GeV, where no experimental data exists was obtained to be 235 ± 13$$+28\\atop{-24}$$ nb/sr. The ground state (1/2 +) binding energy of $$7\\atop{Λ}$$He was already measured in JLab E01-011 (2005). In the present work, the binding energy of 1/2 + state was

Novel nanowire-structured polypyrrole-cobalt composite as efficient catalyst for oxygen reduction reaction

PubMed Central

Yuan, Xianxia; Li, Lin; Ma, Zhong; Yu, Xuebin; Wen, Xiufang; Ma, Zi-Feng; Zhang, Lei; Wilkinson, David P.; Zhang, Jiujun

2016-01-01

A novel nanowire-structured polypyrrole-cobalt composite, PPy-CTAB-Co, is successfully synthesized with a surfactant of cetyltrimethylammounium bromide (CTAB). As an electro-catalyst towards oxygen reduction reaction (ORR) in alkaline media, this PPy-CTAB-Co demonstrates a superior ORR performance when compared to that of granular PPy-Co catalyst and also a much better durability than the commercial 20 wt% Pt/C catalyst. Physiochemical characterization indicates that the enhanced ORR performance of the nanowire PPy-CTAB-Co can be attributed to the high quantity of Co-pyridinic-N groups as ORR active sites and its large specific surface area which allows to expose more active sites for facilitating oxygen reduction reaction. It is expected this PPy-CTAB-Co would be a good candidate for alkaline fuel cell cathode catalyst. PMID:26860889

Acidity and alkalinity in mine drainage: Theoretical considerations

USGS Publications Warehouse

Kirby, Carl S.; Cravotta,, Charles A.

2004-01-01

Acidity, net acidity, and net alkalinity are widely used parameters for the characterization of mine drainage, but these terms are not well defined and are often misunderstood. Incorrect interpretation of acidity, alkalinity, and derivative terms can lead to inadequate treatment design or poor regulatory decisions. We briefly explain derivations of theoretical expressions of three types of alkalinities (caustic, phenolphthalein, and total) and acidities (mineral, CO2, and total). Theoretically defined total alkalinity is closely analogous to measured alkalinity and presents few practical interpretation problems. Theoretically defined “CO2- acidity” is closely related to most standard titration methods used for mine drainage with an endpoint pH of 8.3, but it presents numerous interpretation problems, and it is unfortunately named because CO2 is intentionally driven off during titration of mine-drainage samples. Using the proton condition/massaction approach and employing graphs for visualization, we explore the concept of principal components and how to assign acidity contributions to solution species, including aqueous complexes, commonly found in mine drainage. We define a comprehensive theoretical definition of acidity in mine drainage on the basis of aqueous speciation at the sample pH and the capacity of these species to undergo hydrolysis to pH 8.3. This definition indicates the computed acidity in milligrams per liter (mg L-1 ) as CaCO3 (based on pH and analytical concentrations of dissolved FeIII , FeII , Mn, and Al in mg L-1 ): Aciditycomputed = 50. (10(3-pH) + 3.CFeIII/55.8 + 2.CFeII/55.8 + 2.CMn/54.9 + 3.CAl/27.0) underestimates contributions from HSO4 - and H+ , but overestimates the acidity due to Fe3+. These errors tend to approximately cancel each other. We demonstrate that “net alkalinity” is a valid mathematical construction based on theoretical definitions of alkalinity and acidity. We demonstrate that, for most mine-drainage solutions, a

Facile synthesis of PdSx/C porous nanospheres and their applications for ethanol oxidation reaction

NASA Astrophysics Data System (ADS)

Zhang, Qiang; Zhang, Fuhua; Ma, Xuemei; Zheng, Yiqun; Hou, Shifeng

2016-12-01

We report a facile approach for the synthesis of carbon-supported palladium polysulphide porous nanospheres (PdSx/C) and their applications for ethanol oxidation reaction. Typical synthesis started with generation of palladium/poly (3,4-ethylenedioxythiophene)(Pd/PEDOT) nanospheres, followed by a calcination process at an optimized temperature to form PdSx/C, with an average size of 2.47 ± 0.60 and 50 nm of PdSx nanoparticles and carbon porous nanospheres, respectively. Various techniques, such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electrochemical techniques were performed to characterize their morphologies, compositions and structures. In contrary to most Pd-based electrochemical catalysts that could be easily poised with trace sulfur during the catalytic oxidation process, the as-prepared PdSx/C porous nanospheres exhibited high electrocatalytic activities and stabilities for the electrochemical catalytic oxidation of ethanol in alkaline medium. In particular, the forward peak current intensity achieved 162.1 mA mg-1 and still maintained at 46.7 mA mg-1 even after 1000 cycles. This current work not only offers a novel type of fuel-cell catalyst for ethanol oxidation reaction, but also provides a possible route for solving the sulfur-poisoning problem in catalysis.

Proton-induced knockout reactions with polarized and unpolarized beams

NASA Astrophysics Data System (ADS)

Wakasa, T.; Ogata, K.; Noro, T.

2017-09-01

Proton-induced knockout reactions provide a direct means of studying the single particle or cluster structures of target nuclei. In addition, these knockout reactions are expected to play a unique role in investigations of the effects of the nuclear medium on nucleon-nucleon interactions as well as the properties of nucleons and mesons. However, due to the nature of hadron probes, these reactions can suffer significant disturbances from the nuclear surroundings and the quantitative theoretical treatment of such processes can also be challenging. In this article, we review the experimental and theoretical progress in this field, particularly focusing on the use of these reactions as a spectroscopic tool and as a way to examine the medium modification of nucleon-nucleon interactions. With regard to the former aspect, the review presents a semi-quantitative evaluation of these reactions based on existing experimental data. In terms of the latter point, we introduce a significant body of evidence that suggests, although does not conclusively prove, the existence of medium effects. In addition, this paper also provides information and comments on other related subjects.

Two-Dimensional MoS2 Confined Co(OH)2 Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes.

PubMed

Luo, Yuting; Li, Xu; Cai, Xingke; Zou, Xiaolong; Kang, Feiyu; Cheng, Hui-Ming; Liu, Bilu

2018-05-22

The development of abundant and cheap electrocatalysts for the hydrogen evolution reaction (HER) has attracted increasing attention over recent years. However, to achieve low-cost HER electrocatalysis, especially in alkaline media, is still a big challenge due to the sluggish water dissociation kinetics as well as the poor long-term stability of catalysts. In this paper we report the design and synthesis of a two-dimensional (2D) MoS 2 confined Co(OH) 2 nanoparticle electrocatalyst, which accelerates water dissociation and exhibits good durability in alkaline solutions, leading to significant improvement in HER performance. A two-step method was used to synthesize the electrocatalyst, starting with the lithium intercalation of exfoliated MoS 2 nanosheets followed by Co 2+ exchange in alkaline media to form MoS 2 intercalated with Co(OH) 2 nanoparticles (denoted Co-Ex-MoS 2 ), which was fully characterized by spectroscopic studies. Electrochemical tests indicated that the electrocatalyst exhibits superior HER activity and excellent stability, with an onset overpotential and Tafel slope as low as 15 mV and 53 mV dec -1 , respectively, which are among the best values reported so far for the Pt-free HER in alkaline media. Furthermore, density functional theory calculations show that the cojoint roles of Co(OH) 2 nanoparticles and MoS 2 nanosheets result in the excellent activity of the Co-Ex-MoS 2 electrocatalyst, and the good stability is attributed to the confinement of the Co(OH) 2 nanoparticles. This work provides an imporant strategy for designing HER electrocatalysts in alkaline solutions, and can, in principle, be expanded to other materials besides the Co(OH) 2 and MoS 2 used here.

Carbon Dioxide Removal and Conversion to Ocean Alkalinity: Why and How

NASA Astrophysics Data System (ADS)

Rau, G. H.

2014-12-01

Drastic reduction in anthropogenic CO2 emissions is the most obvious way to stabilize atmospheric CO2. However, there is growing risk that effective emissions reduction policies and technologies will not engage soon enough to avoid significant CO2-induced climate and ocean acidification impacts. This realization has lead to increased interest (e.g., IPCC AR5, 2014; NRC/NAS, 2014) in the possibility of pro-actively increasing CO2 removal (CDR) from the atmosphere above the 55% of our emissions that are already removed from air by natural land and ocean processes. While a variety of biotic, abiotic, and hybrid CDR methods have been proposed, those involving geochemistry have much to recommend them. These methods employ the same geochemical reactions that naturally and effectively remove excess planetary CO2 and neutralize ocean acidity on geologic time scales. These reactions proceed when the hydrosphere, acidified by excess air CO2, contacts and reacts with carbonate and silicate minerals (>90% of the Earth's crust), producing dissolved bicarbonates and carbonates, i.e., ocean alkalinity. This alkalinity is eventually removed and the excess carbon stored via carbonate precipitation. So while the importance and global effectiveness of such reactions are not in question, it remains to be seen if this very slow, natural CDR could be safely and cost-effectively accelerated to help manage air CO2 levels on human rather than geologic time scales. Various terrestrial and marine, geochemistry-based CDR methods will be reviewed including: 1) the addition of minerals to soils and the ocean, 2) removal of CO2 from waste streams, esp. from biomass energy, via wet mineral contacting, and 3) the production and use of mineral derivatives, e.g. oxides or hydroxides, as CDR agents. The additional potential environmental benefits (e.g., reversal of ocean carbonate saturation loss) and impacts (e.g., increased mineral extraction), as well as potential economics will also be discussed.

Field measurement of alkalinity and pH

USGS Publications Warehouse

Barnes, Ivan

1964-01-01

The behavior of electrometric pH equipment under field conditions departs from the behavior predicted from Nernst's law. The response is a linear function of pH, and hence measured pH values may be corrected to true pH if the instrument is calibrated with two reference solutions for each measurement. Alkalinity titrations may also be made in terms of true pH. Standard methods, such as colorimetric titrations, were rejected as unreliable or too cumbersome for rapid field use. The true pH of the end point of the alkalinity titration as a function of temperature, ionic strength, and total alkalinity has been calculated. Total alkalinity in potable waters is the most important factor influencing the end point pH, which varies from 5.38 (0 ? C, 5 ppm (parts per million) HC0a-) to 4.32 (300 ppm HC0a-,35 ? C), for the ranges of variables considered. With proper precautions, the pH may be determined to =i:0.02 pH and the alkalinity to =i:0.6 ppm HCO3- for many naturally occurring bodies of fresh water.

Diclofenac salts. III. Alkaline and earth alkaline salts.

PubMed

Fini, Adamo; Fazio, Giuseppe; Rosetti, Francesca; Angeles Holgado, M; Iruín, Ana; Alvarez-Fuentes, Josefa

2005-11-01

Diclofenac salts containing the alkaline and two earth alkaline cations have been prepared and characterized by scanning electron microscopy (SEM) and EDAX spectroscopy; and by thermal and thermogravimetric analysis (TGA): all of them crystallize as hydrate when precipitated from water. The salts dehydrate at room temperature and more easily on heating, but recovery the hydration, when placed in a humid environment. X-ray diffraction spectra suggest that on dehydration new peaks appear on diffractograms and the lattice of the salts partially looses crystallinity. This phenomenon is readily visible in the case of the calcium and magnesium salts, whose thermograms display a crystallization exotherm, before melting or decomposing at temperatures near or above 200 degrees C; these last salts appear to form solvates, when prepared from methanol. The thermogram of each salt shows a complex endotherm of dehydration about 100 degrees C; the calcium salt displays two endotherms, well separated at about 120 and 160 degrees C, which disappear after prolonged heating. Decomposition exotherms, before or soon after the melting, appear below 300 degrees C. The ammonium salt is thermally unstable and, when heated to start dehydration, dissociates and leaves acidic diclofenac.

Pathways for external alkalinization in intact and in microwounded Chara cells are differentially sensitive to wortmannin

PubMed Central

Bulychev, Alexander A.; Foissner, Ilse

2017-01-01

ABSTRACT Proton flows across the plant cell membranes play a major role in electrogenesis and regulation of photosynthesis and ion balance. The profiles of external pH along the illuminated internodal cells of characean algae consist of alternating high- and low-pH zones that are spatially coordinated with the distribution of photosynthetic activity of chloroplasts underlying these zones. The results based on confocal laser scanning fluorescence microscopy, pH microsensors, and pulse-amplitude-modulated chlorophyll microfluorometry revealed that the coordination of H+ transport and photosynthesis is disrupted by the 2 different environmental cues (low light and wounding) and by a chemical, wortmannin interfering with the inositol phospholipid metabolism. On the one hand, the transition from moderate to low irradiance diminished the peaks in the profiles of photosystem II (PSII) quantum efficiency but did not remove the pH bands. On the other hand, the microwounding of the internode with a glass micropipette, impacting primarily the cell wall, resulted in a rapid local alkalinization of the external medium (by 2–2.5 pH units) near the cell surface, thus mimicking the appearance of natural pH bands. Despite their seeming similarity, the alkaline bands of intact cells were eliminated by wortmannin, whereas the wound-induced alkalinization was insensitive to this drug. Furthermore, the attenuation of natural pH bands in wortmannin-treated cells was accompanied by the enhancement in spatial heterogeneity of PSII efficiency and electron transport rates, which indicates the complexity of chloroplast–plasma membrane interactions. The results suggest that the light- and wound-induced alkaline areas on the cell surface are associated with different ion-transport systems. PMID:28805493

Effects of storage medium and UV photofunctionalization on time-related changes of titanium surface characteristics and biocompatibility.

PubMed

Shen, Jian-Wei; Chen, Yun; Yang, Guo-Li; Wang, Xiao-Xiang; He, Fu-Ming; Wang, Hui-Ming

2016-07-01

Storage in aqueous solution and ultraviolet (UV) photofunctionalization are two applicable methods to overcome the biological aging and increase the bioactivity of titanium. As information regarding the combined effects of storage medium and UV photofunctionalization has never been found in published literatures, this study focused on whether appropriate storage methods and UV photofunctionalization have synergistic effects on the biological properties of aged titanium surfaces. Titanium plates and discs were sandblasted and acid etched and then further prepared in five different modes as using different storage mediums (air or dH2 O) for 4 weeks and then with or without UV treatment. The surface characteristics were evaluated with scanning electron microscopy, contact angle measurements, and X-ray photoelectron spectroscopy. MC3T3-E1 cells were cultured on the surfaces, and cellular morphology, proliferation, alkaline phosphatase activity, and osteocalcin release were evaluated. The results showed that nanostructures were observed on water-stored titanium surfaces with a size of about 15 × 20 nm(2) . UV treatment was effective to remove the hydrocarbon contamination on titanium surfaces stored in either air or water. UV photofunctionalization further enhanced the already increased bioactivity of modSLA on initial cell attachment, proliferation, alkaline phosphatase activity, and osteocalcin release. Overall, UV photofunctionalization was effective in further enhancing the already increased bioactivity by using dH2 O as storage medium, and the effect of UV treatment was much more overwhelming than that of the storage medium. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 932-940, 2016. © 2015 Wiley Periodicals, Inc.

From Geochemistry to Biochemistry: Simulating Prebiotic Chemistry Driven by Geochemical Gradients in Alkaline Hydrothermal Vents

NASA Astrophysics Data System (ADS)

Barge, Laurie

2016-07-01

Planetary water-rock interfaces generate energy in the form of redox, pH, and thermal gradients, and these disequilibria are particularly focused in hydrothermal vent systems where the reducing, heated hydrothermal fluid feeds back into the more oxidizing ocean. Alkaline hydrothermal vents have been proposed as a likely location for the origin of life on the early Earth due to various factors: including the hydrothermal pH / Eh gradients that resemble the ubiquitous electrical / proton gradients in biology, the catalytic hydrothermal precipitates that resemble inorganic catalysts in enzymes, and the presence of electron donors and acceptors in hydrothermal systems (e.g. H2 + CH4 and CO2) that are thought to have been utilized in the earliest metabolisms. Of particular importance for the emergence of metabolism are the mineral "chimneys" that precipitate at the vent fluid / seawater interface. Hydrothermal chimneys are flow-through chemical reactors that form porous and permeable inorganic membranes transecting geochemical gradients; in some ways similar to biological membranes that transect proton / ion gradients and harness these disequilibria to drive metabolism. These emergent chimney structures in the far-from-equilibrium system of the alkaline vent have many properties of interest to the origin of life that can be simulated in the laboratory: for example, they can generate electrical energy and drive redox reactions, and produce catalytic minerals (in particular the metal sulfides and iron oxyhydroxides - "green rust") that can facilitate chemical reactions towards proto-metabolic cycles and biosynthesis. Many of the factors prompting interest in alkaline hydrothermal vents on Earth may also have been present on early Mars, or even presently within icy worlds such as Europa or Enceladus - thus, understanding the disequilibria and resulting prebiotic chemistry in these systems can be of great use in assessing the potential for other environments in the Solar

Structure and ionic diffusion of alkaline-earth ions in mixed cation glasses A 2O–2MO–4SiO 2 with molecular dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konstantinou, Konstantinos; Sushko, Petr; Duffy, Dorothy M.

2015-05-15

A series of mixed cation silicate glasses of the composition A2O – 2MO – 4SiO2, with A=Li,Na,K and M=Ca,Sr,Ba has been investigated by means of molecular dynamics simulations in order to understand the effect of the nature of the cations on the mobility of the alkaline-earth ions within the glass network. The size of the alkaline-earth cation was found to affect the inter-atomic distances, the coordination number distributions and the bond angle distributions , whereas the medium-range order was almost unaffected by the type of the cation. All the alkaline-earth cations contribute to lower vibrational frequencies but it is observedmore » that that there is a shift to smaller frequencies and the vibrational density of states distribution gets narrower as the size of the alkaline-earth increases. The results from our modeling for the ionic diffusion of the alkaline-earth cations are in a qualitative agreement with the experimental observations in that there is a distinct correlation between the activation energy for diffusion of alkaline earth-ions and the cation radii ratio. An asymmetrical linear behavior in the diffusion activation energy with increasing size difference is observed. The results can be described on the basis of a theoretical model that relates the diffusion activation energy to the electrostatic interactions of the cations with the oxygens and the elastic deformation of the silicate network.« less

Medium pH, carbon and nitrogen concentrations modulate the phosphate solubilization efficiency of Penicillium purpurogenum through organic acid production.

PubMed

Scervino, J M; Papinutti, V L; Godoy, M S; Rodriguez, M A; Della Monica, I; Recchi, M; Pettinari, M J; Godeas, A M

2011-05-01

To study phosphate solubilization in Penicillium purpurogenum as function of medium pH, and carbon and nitrogen concentrations. Tricalcium phosphate (CP) solubilization efficiency of P. purpurogenum was evaluated at acid or alkaline pH using different C and N sources. Glucose- and (NH(4) )(2) SO(4) -based media showed the highest P solubilization values followed by fructose. P. purpurogenum solubilizing ability was higher in cultures grown at pH 6·5 than cultures at pH 8·5. Organic acids were detected in both alkaline and neutral media, but the relative percentages of each organic acid differed. Highest P release coincided with the highest organic acids production peak, especially gluconic acid. When P. purpurogenum grew in alkaline media, the nature and concentration of organic acids changed at different N and C concentrations. A factorial categorical experimental design showed that the highest P-solubilizing activity, coinciding with the highest organic acid production, corresponded to the highest C concentration and lowest N concentration. The results described in the present study show that medium pH and carbon and nitrogen concentrations modulate the P solubilization efficiency of P. purpurogenum through the production of organic acids and particularly that of gluconic acid. In the P solubilization optimization studies, glucose and (NH(4) )(2) SO(4) as C and N sources allowed a higher solubilization efficiency at high pH. This organism is a potentially proficient soil inoculant, especially in P-poor alkaline soils where other P solubilizers fail to release soluble P. Further work is necessary to elucidate whether these results can be extrapolated to natural soil ecosystems, where different pH values are present. Penicillium purpurogenum could be used to develop a bioprocess for the manufacture of phosphatic fertilizer with phosphate calcium minerals. © 2011 The Authors. Journal of Applied Microbiology © 2011 The Society for Applied Microbiology.

Temperature Dependence of Mineral Solubility in Water. Part 3. Alkaline and Alkaline Earth Sulfates

NASA Astrophysics Data System (ADS)

Krumgalz, B. S.

2018-06-01

The databases of alkaline and alkaline earth sulfate solubilities in water at various temperatures were created using experimental data from the publications over about the last two centuries. Statistical critical evaluation of the created databases was produced since there were enough independent data sources to justify such evaluation. The reliable experimental data were adequately described by polynomial expressions over various temperature ranges. Using the Pitzer approach for ionic activity and osmotic coefficients, the thermodynamic solubility products for the discussed minerals have been calculated at various temperatures and represented by polynomial expressions.

Temperature Dependence of Mineral Solubility in Water. Part 2. Alkaline and Alkaline Earth Bromides

NASA Astrophysics Data System (ADS)

Krumgalz, B. S.

2018-03-01

Databases of alkaline and alkaline earth bromide solubilities in water at various temperatures were created using experimental data from publications over about the last two centuries. Statistical critical evaluation of the created databases was produced since there were enough independent data sources to justify such evaluation. The reliable experimental data were adequately described by polynomial expressions over various temperature ranges. Using the Pitzer approach for ionic activity and osmotic coefficients, the thermodynamic solubility products for the discussed bromide minerals have been calculated at various temperature intervals and also represented by polynomial expressions.

Stability of a Cu0.7Co2.3O4 electrode during the oxygen evolution reaction for alkaline anion-exchange membrane water electrolysis

NASA Astrophysics Data System (ADS)

Kang, Kyoung Eun; Kim, Chi Ho; Lee, Myung Sup; Jung, Chang Wook; Kim, Yang Do; Lee, Jae Ho

2018-01-01

The electrode materials for oxygen evolution, especially non-platinum group metal oxides, have attracted increasing attention. Among the spinel-type transition metal oxides, Cu0.7Co2.3O4 powders were evaluated as a potential replacement for expensive dimensionally stabilized anode materials. Cu0.7Co2.3O4 powder for use as an electrode material for oxygen evolution in an alkaline anion-exchange membrane water electrolyzer was prepared using a thermal decomposition method. The Cu0.7Co2.3O4 powders heat-treated at 250 °C exhibited the same X-ray diffraction patterns without any secondary phases as the Co3O4 spinel structure did. The Cu0.7Co2.3O4 powders heat-treated at 250 °C for 30 minutes showed the smallest mean particle size of approximately 376 nm with the powders having a homogeneous shape and size distribution. The fine powders with a relatively homogeneous size distribution showed a higher current density during the oxygen evolution reaction. The lifetime of the Cu0.7Co2.3O4 electrode was relatively long at a low current density, but was quickly shortened due to physical detachment of the Cu0.7Co2.3O4 powders as the current density was increased. This study showed that the efficiency and the stability of Cu0.7Co2.3O4 powders during the oxygen evolution reaction were related directly to the active electrode area.

Spectrophotometric determination of cyclotrimethylenetrinitramine (RDX) in explosive mixtures and residues with the Berthelot reaction.

PubMed

Uzer, A; Erçağ, E; Apak, R

2008-03-31

On-site colorimetric methods are a valuable, cost-effective tool to assess the nature and extent of contamination in remediated sites and to enable on-site screening for police criminology laboratories. The existing colorimetric method for cyclotrimethylenetrinitramine (RDX) based on a Griess reaction suffers from the non-quantitative reduction to nitrite and from the unstable character of HNO2 in acidic medium. Thus we propose a novel spectrophotometric RDX assay in explosive mixtures and residues, based on (Zn+HCl) reduction of RDX in a microwave oven, followed by neutralization of the reduction products to ammonia and low molecular-weight amines, and Berthelot reaction of these amine-compounds with phenol and hypochlorite in alkaline medium to give an intensely blue indophenol dye absorbing at 631nm. The molar absorptivity and limit of detection (LOD) for RDX were (1.08+/-0.04)x10(4) L mol(-1) cm(-1) and 0.18 mg L(-1), respectively. Application of the method to synthetic mixture solutions of RDX and trinitrotoluene (TNT) at varying proportions showed that there was minimal interference from TNT (which could be compensated for by dicyclohexylamine colorimetry), since the Berthelot reaction was essentially non-responsive to m-substituted anilines derived from TNT upon (Zn+HCl) reduction. The proposed method was successfully applied to military-purpose explosive mixtures of (RDX+inert matter) such as Comp A5, Comp C4, and Hexal P30, and to (RDX+TNT) mixtures such as Comp B. The molar absorptivity of RDX was much higher than that of either ammonium or nitrate; RDX could be effectively separated from ammonium and nitrate in soil mixtures, based on solubility differences. The Berthelot method for RDX was statistically validated using Comp B mixtures against standard HPLC equipped with a Hypersil C-18 column with (40% MeOH-60% H2O) mobile phase, and against gas chromatography-thermal energy analysis (GC-TEA) system.

Differentiation of Mesenchymal Stem Cells from Human Umbilical Cord Tissue into Odontoblast-Like Cells Using the Conditioned Medium of Tooth Germ Cells In Vitro

PubMed Central

Li, Tian Xia; Yuan, Jie; Chen, Yan; Pan, Li Jie; Song, Chun; Bi, Liang Jia; Jiao, Xiao Hui

2013-01-01

The easily accessible mesenchymal stem cells in the Wharton's jelly of human umbilical cord tissue (hUCMSCs) have excellent proliferation and differentiation potential, but it remains unclear whether hUCMSCs can differentiate into odontoblasts. In this study, mesenchymal stem cells were isolated from the Wharton's jelly of human umbilical cord tissue using the simple method of tissue blocks culture attachment. UCMSC surface marker expression was then evaluated for the isolated cells using flow cytometry. The third-passage hUCMSCs induced by conditioned medium from developing tooth germ cells (TGC-CM) displayed high alkaline phosphatase (ALP) levels (P < 0.001), an enhanced ability to proliferate (P < 0.05), and the presence of mineralized nodules. These effects were not observed in cells treated with regular medium. After induction of hUCMSCs, the results of reverse transcriptional polymerase chain reaction (PCR) indicated that the dentin sialophosphoprotein (DSPP) and dentin matrix protein 1 (DMP1) genes were significantly tested. Additionally, dentin sialoprotein (DSP) and DMP1 demonstrated significant levels of staining in an immunofluorescence analysis. In contrast, the control cells failed to display the characteristics of odontoblasts. Taken together, these results suggest that hUCMSCs can be induced to differentiate into odontoblast-like cells with TGC-CM and provide a novel strategy for tooth regeneration research. PMID:23762828

A Comparative Study: Taxonomic Grouping of Alkaline Protease Producing Bacilli.

PubMed

Tekin, Nilgun; Cihan, Arzu Coleri; Karaca, Basar; Cokmus, Cumhur

2017-03-30

Alkaline proteases have biotechnological importance due to their activity and stability at alkaline pH. 56 bacteria, capable of growing under alkaline conditions were isolated and their alkaline protease activities were carried out at different parameters to determine their optimum alkaline protease production conditions. Seven isolates were showed higher alkaline protease production capacity than the reference strains. The highest alkaline protease producing isolates (103125 U/g), E114 and C265, were identified as Bacillus licheniformis with 99.4% and Bacillus mojavensis 99.8% based on 16S rRNA gene sequence similarities, respectively. Interestingly, the isolates identified as Bacillus safensis were also found to be high alkaline protease producing strains. Genotypic characterizations of the isolates were also determined by using a wide range of molecular techniques (ARDRA, ITS-PCR, (GTG)5-PCR, BOX-PCR). These different techniques allowed us to differentiate the alkaliphilic isolates and the results were in concurrence with phylogenetic analyses of the 16S rRNA genes. While ITS-PCR provided the highest correlation with 16S rRNA groups, (GTG)5-PCR showed the highest differentiation at species and intra-species level. In this study, each of the biotechnologically valuable alkaline protease producing isolates was grouped into their taxonomic positions with multi-genotypic analyses.

Reaction pH of urea-formaldehyde resins as related to strength properties of southern pine particleboard

Treesearch

C. -Y. Hse

1974-01-01

Twelve urea-formaldehyde resins were prepared with factorial combinations of 4 alkaline and 3 acidic reaction phases; i. e., the reaction mixture was adjusted to pH 7, 8, 9, or 10 for the first hour and then made weakly acid to pH 5.8, 4.8, or 3.8.

Acidic and alkaline pretreatments of activated carbon and their effects on the performance of air-cathodes in microbial fuel cells.

PubMed

Wang, Xin; Gao, Ningshengjie; Zhou, Qixing; Dong, Heng; Yu, Hongbing; Feng, Yujie

2013-09-01

Activated carbon (AC) is a high performing and cost effective catalyst for oxygen reduction reactions (ORRs) of air-cathodes in microbial fuel cells (MFCs). Acidic (HNO3) and alkaline (KOH) pretreatments on AC at low temperature (85°C) are conducted to enhance the performance of MFCs. The alkaline pretreatment increased the power density by 16% from 804±70 to 957±31 mW m(-2), possibly due to the decrease of ohmic resistance (from 20.58 to 19.20 Ω) and the increase of ORR activities provided by the adsorbed hydroxide ion and extra micropore area/volume after alkaline pretreatment. However, acidic pretreatment decreased the power output to 537±36 mW m(-2), which can be mainly attributed to the corrosion by adsorbed proton at the interface of AC powder and stainless steel mesh and the decreased pore area. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mineral textures in Serpentine-hosted Alkaline Springs from the Oman ophiolite

NASA Astrophysics Data System (ADS)

Giampouras, Manolis; Garcia-Ruiz, Juan Manuel; Bach, Wolfgang; Garrido, Carlos J.; Los, Karin; Fussmann, Dario; Monien, Monien

2017-04-01

is spatially controlled by the hydrology of the system and is localized around mixing zones between Ca-type with Mg-type waters. Residence time of discharging waters in the ponds before mixing has an impact on fluid chemistry as it influences the equilibration time with the atmosphere. Acicular aragonite is the main textural type in hyper-alkaline Ca-type waters, acting as a substratum for the growth of calcite and brucite crystals. Low crystallinity, dumbbell shaped and double pyramid aragonite dominates in Mix-type water precipitates. Rate of supersaturation is essential for precipitation intensity and textural variation among the mineral assemblages in the different water types. Low S/ S˚ ratios in Mg-type and Ca-type waters (<1) reveal limited precipitation. Chemical reactions that lead to rapid mineral formation are enhanced in cases of Mix-type waters characterized by higher S/ S˚ ratios (>1.2). Detailed investigation of individual spring sites allowed the determination of geochemical and hydrological factors controlling the phases and textures of mineralogical assemblages in active, serpentinization-related, alkaline environments. Funding: We acknowledge funding from the People programme (Marie Curie Actions - ITN) of the European Union FP7 under REA Grant Agreement n˚ 608001.

WATER AS A REACTION MEDIUM FOR CLEAN CHEMICAL PROCESSES.

EPA Science Inventory

Green chemistry is a rapid developing new field that provides us a pro-active avenue for the sustainable development of future science and technologies. When designed properly, clean chemical technology can be developed in water as a reaction media. The technologies generated f...

In Silico Alkaline Hydrolysis of Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine: Density Functional Theory Investigation.

PubMed

Sviatenko, Liudmyla K; Gorb, Leonid; Hill, Frances C; Leszczynska, Danuta; Shukla, Manoj K; Okovytyy, Sergiy I; Hovorun, Dmytro; Leszczynski, Jerzy

2016-09-20

HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), an energetic material used in military applications, may be released to the environment during manufacturing, transportation, storage, training, and disposal. A detailed investigation of a possible mechanism of alkaline hydrolysis, as one of the most promising methods for HMX remediation, was performed by computational study at PCM(Pauling)/M06-2X/6-311++G(d,p) level. Obtained results suggest that HMX hydrolysis at pH 10 represents a highly exothermic multistep process involving initial deprotonation and nitrite elimination, hydroxide attachment accompanied by cycle cleavage, and further decomposition of cycle-opened intermediate to the products caused by a series of C-N bond ruptures, hydroxide attachments, and proton transfers. Computationally predicted products of HMX hydrolysis such as nitrite, 4-nitro-2,4-diazabutanal, formaldehyde, nitrous oxide, formate, and ammonia correspond to experimentally observed species. Based on computed reaction pathways for HMX decomposition by alkaline hydrolysis, the kinetics of the entire process was modeled. Very low efficiency of this reaction at pH 10 was observed. Computations predict significant increases (orders of magnitude) of the hydrolysis rate for hydrolysis reactions undertaken at pH 11, 12, and 13.

Nitrogen-doped carbonaceous catalysts for gas-diffusion cathodes for alkaline aluminum-air batteries

NASA Astrophysics Data System (ADS)

Davydova, E. S.; Atamanyuk, I. N.; Ilyukhin, A. S.; Shkolnikov, E. I.; Zhuk, A. Z.

2016-02-01

Cobalt tetramethoxyphenyl porphyrin and polyacrylonitrile - based catalysts for oxygen reduction reaction were synthesized and characterized by means of SEM, TEM, XPS, BET, limited evaporation method, rotating disc and rotating ring-disc electrode methods. Half-cell and Al-air cell tests were carried out to determine the characteristics of gas-diffusion cathodes. Effect of active layer thickness and its composition on the characteristics of the gas-diffusion cathodes was investigated. Power density of 300 mW cm-2 was achieved for alkaline Al-air cell with an air-breathing polyacrylonitrile-based cathode.

Global Variability and Changes in Ocean Total Alkalinity from Aquarius Satellite

NASA Astrophysics Data System (ADS)

Fine, R. A.; Willey, D. A.; Millero, F. J., Jr.

2016-02-01

To document effects of ocean acidification it is important to have an understanding of the processes and parameters that influence alkalinity. Alkalinity is a gauge on the ability of seawater to neutralize acids. We use Aquarius satellite data, which allow unprecedented global mapping of surface total alkalinity as it correlates strongly with salinity and to a lesser extent with temperature. Spatial variability in total alkalinity and salinity exceed temporal variability, the latter includes seasonal and differences compared to climatological data. The northern hemisphere has more spatial and monthly variability in total alkalinity and salinity, while less variability in Southern Ocean alkalinity is due to less salinity variability and upwelling of waters enriched in alkalinity. Satellite alkalinity data are providing a global baseline that can be used for comparing with future carbon data, and for evaluating spatial and temporal variability and past trends. For the first time it is shown that recent satellite derived total alkalinity in the subtropics have increased as compared with climatological data; this is reflective of large scale changes in the global water cycle. Total alkalinity increases imply increased dissolution of calcareous minerals and difficulty for calcifying organisms to make their shells.

Online Monitoring of Methanol Electro-Oxidation Reactions by Ambient Mass Spectrometry

NASA Astrophysics Data System (ADS)

Cheng, Si; Wu, Qiuhua; Dewald, Howard D.; Chen, Hao

2017-06-01

Online detection of methanol electro-oxidation reaction products [e.g., formaldehyde (HCHO)] by mass spectrometry (MS) is challenging, owing to the high salt content and extreme pH of the electrolyte solution as well as the difficulty in ionizing the reaction products. Herein we present an online ambient mass spectrometric approach for analyzing HCHO generated from methanol electro-oxidation, taking the advantage of high salt tolerance of desorption electrospray ionization mass spectrometry (DESI-MS). It was found that HCHO can be detected as PhNHNH+=CH2 ( m/z 121) by DESI after online derivatization with PhNHNH2. With this approach, the analysis of HCHO from methanol electro-oxidation by MS was carried out not only in acidic condition but also in alkaline media for the first time. Efficiencies of different electrodes for methanol oxidation at different pHs were also evaluated. Our results show that Au electrode produces more HCHO than Pt-based electrodes at alkaline pH, while the latter have higher yields at acidic solution. The presented methodology would be of great value for elucidating fuel cell reaction mechanisms and for screening ideal fuel cell electrode materials. [Figure not available: see fulltext.

Process for extracting technetium from alkaline solutions

DOEpatents

Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.

1995-01-01

A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

Synthesis and electrocatalytic activity of Au/Pt bimetallic nanodendrites for ethanol oxidation in alkaline medium.

PubMed

Han, Xinyi; Wang, Dawei; Liu, Dong; Huang, Jianshe; You, Tianyan

2012-02-01

Gold/Platinum (Au/Pt) bimetallic nanodendrites were successfully synthesized through seeded growth method using preformed Au nanodendrites as seeds and ascorbic acid as reductant. Cyclic voltammograms (CVs) of a series of Au/Pt nanodendrites modified electrodes in 1M KOH solution containing 1M ethanol showed that the electrocatalyst with a molar ratio (Au:Pt) of 3 exhibited the highest peak current density and the lowest onset potential. The peak current density of ethanol electro-oxidation on the Au(3)Pt(1) nanodendrites modified glassy carbon electrode (Au(3)Pt(1) electrode) is about 16, 12.5, and 4.5 times higher than those on the polycrystalline Pt electrode, polycrystalline Au electrode, and Au nanodendrites modified glassy carbon electrode (Au dendrites electrode), respectively. The oxidation peak potential of ethanol electro-oxidation on the Au(3)Pt(1) electrode is about 299 and 276 mV lower than those on the polycrystalline Au electrode and Au dendrites electrode, respectively. These results demonstrated that the Au/Pt bimetallic nanodendrites may find potential application in alkaline direct ethanol fuel cells (ADEFCs). Copyright © 2011 Elsevier Inc. All rights reserved.

Alkaline tolerant dextranase from streptomyces anulatus

DOEpatents

Decker, Stephen R.; Adney, William S.; Vinzant, Todd B.; Himmel, Michael E.

2003-01-01

A process for production of an alkaline tolerant dextranase enzyme comprises culturing a dextran-producing microorganism Streptomyces anulatus having accession no. ATCC PTA-3866 to produce an alkaline tolerant dextranase, Dex 1 wherein the protein in said enzyme is characterized by a MW of 63.3 kDa and Dex 2 wherein its protein is characterized by a MW of 81.8 kDa.

40 CFR 420.110 - Applicability; description of the alkaline cleaning subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... alkaline cleaning subcategory. 420.110 Section 420.110 Protection of Environment ENVIRONMENTAL PROTECTION... Alkaline Cleaning Subcategory § 420.110 Applicability; description of the alkaline cleaning subcategory... alkaline cleaning baths to remove mineral and animal fats or oils from the steel, and those rinsing...

40 CFR 420.110 - Applicability; description of the alkaline cleaning subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... alkaline cleaning subcategory. 420.110 Section 420.110 Protection of Environment ENVIRONMENTAL PROTECTION... Alkaline Cleaning Subcategory § 420.110 Applicability; description of the alkaline cleaning subcategory... alkaline cleaning baths to remove mineral and animal fats or oils from the steel, and those rinsing...

40 CFR 420.110 - Applicability; description of the alkaline cleaning subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... alkaline cleaning subcategory. 420.110 Section 420.110 Protection of Environment ENVIRONMENTAL PROTECTION... Alkaline Cleaning Subcategory § 420.110 Applicability; description of the alkaline cleaning subcategory... alkaline cleaning baths to remove mineral and animal fats or oils from the steel, and those rinsing...

40 CFR 420.110 - Applicability; description of the alkaline cleaning subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... alkaline cleaning subcategory. 420.110 Section 420.110 Protection of Environment ENVIRONMENTAL PROTECTION... Alkaline Cleaning Subcategory § 420.110 Applicability; description of the alkaline cleaning subcategory... alkaline cleaning baths to remove mineral and animal fats or oils from the steel, and those rinsing...

40 CFR 420.110 - Applicability; description of the alkaline cleaning subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... alkaline cleaning subcategory. 420.110 Section 420.110 Protection of Environment ENVIRONMENTAL PROTECTION... Alkaline Cleaning Subcategory § 420.110 Applicability; description of the alkaline cleaning subcategory... alkaline cleaning baths to remove mineral and animal fats or oils from the steel, and those rinsing...

Lectin histochemistry and alkaline phosphatase activity in the pia mater vessels of spontaneously hypertensive rats (SHR).

PubMed

Szumańska, G; Gadamski, R

1992-01-01

Some lectins were used to study the localization of sugar residues on the endothelial cell surface in the pia mater blood vessels of control (WKY) and hypertensive rats (SHR). The lectins tested recognized the following residues: beta-D-galactosyl (Ricinus communis agglutinin 120, RCA-1), alpha-L-fucosyl (Ulex europaeus agglutinin, UEA-1), N-acetylglucosaminyl and sialyl (Wheat germ agglutinin, WGA), N-glycolyl-neuraminic acid (Limax flavus agglutinin, LFA), and N-acetyl-D-galactosaminyl (Helix pomatia agglutinin, HPA). Several differences were revealed in the presence of sugar receptors on the surface of endothelial cells between the control and the hypertensive rats. Our studies showed also differences in the localization of the tested glycoconjugates between pial capillaries, small, medium-size and large pial arteries. The histochemical evaluation of alkaline phosphatase revealed an increased activity of the enzyme in the pial vessels of SHRs as compared with control rats with a similar localization of the enzyme activity. Some differences in the distribution of lectin binding sites and alkaline phosphatase activity could be associated with the different functions of particular segments of the pial vascular network.

Assessing ocean alkalinity for carbon sequestration

NASA Astrophysics Data System (ADS)

Renforth, Phil; Henderson, Gideon

2017-09-01

Over the coming century humanity may need to find reservoirs to store several trillions of tons of carbon dioxide (CO2) emitted from fossil fuel combustion, which would otherwise cause dangerous climate change if it were left in the atmosphere. Carbon storage in the ocean as bicarbonate ions (by increasing ocean alkalinity) has received very little attention. Yet recent work suggests sufficient capacity to sequester copious quantities of CO2. It may be possible to sequester hundreds of billions to trillions of tons of C without surpassing postindustrial average carbonate saturation states in the surface ocean. When globally distributed, the impact of elevated alkalinity is potentially small and may help ameliorate the effects of ocean acidification. However, the local impact around addition sites may be more acute but is specific to the mineral and technology. The alkalinity of the ocean increases naturally because of rock weathering in which >1.5 mol of carbon are removed from the atmosphere for every mole of magnesium or calcium dissolved from silicate minerals (e.g., wollastonite, olivine, and anorthite) and 0.5 mol for carbonate minerals (e.g., calcite and dolomite). These processes are responsible for naturally sequestering 0.5 billion tons of CO2 per year. Alkalinity is reduced in the ocean through carbonate mineral precipitation, which is almost exclusively formed from biological activity. Most of the previous work on the biological response to changes in carbonate chemistry have focused on acidifying conditions. More research is required to understand carbonate precipitation at elevated alkalinity to constrain the longevity of carbon storage. A range of technologies have been proposed to increase ocean alkalinity (accelerated weathering of limestone, enhanced weathering, electrochemical promoted weathering, and ocean liming), the cost of which may be comparable to alternative carbon sequestration proposals (e.g., $20-100 tCO2-1). There are still many

Optical reaction cell and light source for ›18F! fluoride radiotracer synthesis

DOEpatents

Ferrieri, Richard A.; Schlyer, David; Becker, Richard J.

1998-09-15

Apparatus for performing organic synthetic reactions, particularly no-carrier-added nucleophilic radiofluorination reactions for PET radiotracer production. The apparatus includes an optical reaction cell and a source of broadband infrared radiant energy, which permits direct coupling of the emitted radiant energy with the reaction medium to heat the reaction medium. Preferably, the apparatus includes means for focusing the emitted radiant energy into the reaction cell, and the reaction cell itself is preferably configured to reflect transmitted radiant energy back into the reaction medium to further improve the efficiency of the apparatus. The apparatus is well suited to the production of high-yield syntheses of 2-›.sup.18 F!fluoro-2-deoxy-D-glucose. Also provided is a method for performing organic synthetic reactions, including the manufacture of ›.sup.18 F!-labeled compounds useful as PET radiotracers, and particularly for the preparation of 2-›.sup.18 F!fluoro-2-deoxy-D-glucose in higher yields than previously possible.

Chocolate agar, a differential medium for gram-positive cocci.

PubMed Central

Gunn, B A

1984-01-01

Reactions incurred on chocolate agar by gram-positive cocci were correlated with species identity. Darkening and clearing of the medium was usually associated with the species Staphylococcus epidermidis, Staphylococcus aureus, Staphylococcus simulans, and Streptococcus faecalis. Yellowing of chocolate agar was associated with alpha-hemolytic species of Streptococcus. The study demonstrated that reactions occurring on chocolate agar are useful in identifying gram-positive cocci. PMID:6490866

Chemical computing with reaction-diffusion processes.

PubMed

Gorecki, J; Gizynski, K; Guzowski, J; Gorecka, J N; Garstecki, P; Gruenert, G; Dittrich, P

2015-07-28

Chemical reactions are responsible for information processing in living organisms. It is believed that the basic features of biological computing activity are reflected by a reaction-diffusion medium. We illustrate the ideas of chemical information processing considering the Belousov-Zhabotinsky (BZ) reaction and its photosensitive variant. The computational universality of information processing is demonstrated. For different methods of information coding constructions of the simplest signal processing devices are described. The function performed by a particular device is determined by the geometrical structure of oscillatory (or of excitable) and non-excitable regions of the medium. In a living organism, the brain is created as a self-grown structure of interacting nonlinear elements and reaches its functionality as the result of learning. We discuss whether such a strategy can be adopted for generation of chemical information processing devices. Recent studies have shown that lipid-covered droplets containing solution of reagents of BZ reaction can be transported by a flowing oil. Therefore, structures of droplets can be spontaneously formed at specific non-equilibrium conditions, for example forced by flows in a microfluidic reactor. We describe how to introduce information to a droplet structure, track the information flow inside it and optimize medium evolution to achieve the maximum reliability. Applications of droplet structures for classification tasks are discussed. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Biotransformation of tryptophan by liquid medium culture of Psilocybe coprophila (Basidiomycetes).

PubMed

Alarcón, Julio; Foncea, Leyla; Aguila, Sergio; Alderete, Joel B

2006-01-01

Chemical reactions performed by fungi have been used as a modern tool in chemistry. In this work, we show the tryptophan biotransformation with Psilocybe coprophila on liquid culture medium. The results prove once more the versatility of fungi in performing a wide range of industrially attractive chemical reactions.

Intracellular signal propagation in a two-dimensional autocatalytic reaction model.

PubMed

Castiglione, F; Bernaschi, M; Succi, S; Heinrich, R; Kirschner, M W

2002-09-01

We study a simple reaction scheme in a two-dimensional lattice of particles or molecules with a refractory state. We analyze the dynamics of the propagating front as a function of physical-chemical properties of the host medium. The anisotropy of the medium significantly affects the smoothness of the wave front. Similarly, if particles or molecules may diffuse slowly to neighboring sites, then the front wave is more likely to be irregular. Both situations affect the ability of the whole system to relax to the original state, which is a required feature in the biological cells. Attempts to map this simple reaction scheme to reactions involved in the intracellular pathways suggest that, in some cases, signal transduction might take both connotation of a random walk and a propagating wave, depending on the local density of the medium. In particular, a sufficient condition for the appearance of waves in high-density regions of the media, is the existence of at least one autocatalytic reaction in the chain of reactions characterizing the pathway.

Electrodeposition of Sn-Ni Alloy Coatings for Water-Splitting Application from Alkaline Medium

NASA Astrophysics Data System (ADS)

Shetty, Sandhya; Hegde, A. Chitharanjan

2017-02-01

In this work, Sn-Ni alloy coatings were developed onto the surface of copper from a newly formulated electrolytic bath by a simple and cost-effective electrodeposition technique using gelatin as an additive. The electrocatalytic behavior of coatings deposited at different current densities (c.d.'s) for water-splitting applications, in terms of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), has been researched. The experimental results showed that the electrocatalytic activity of Sn-Ni coatings has a close relationship with its composition, surface morphology, and phase structure depending on the c.d. used, supported by scanning electron microscopy (SEM-EDX) and X-ray diffraction (XRD) analyses. Cyclic voltammetry and chronopotentiometry techniques have demonstrated that Sn-Ni alloy deposited at 4.0 A dm-2 (having 37.6 wt pct Ni) and 1.0 A dm-2 (having 19.6 wt pct Ni) exhibit, respectively, the highest electrocatalytic behavior for HER and OER in 1.0-M KOH solution. Sn-Ni alloy coatings were found to be stable under working conditions of electrolysis, confirmed by electrochemical corrosion tests. High electrocatalytic activity of Sn-Ni alloy coatings for both HER and OER is specific to their composition, surface morphology, and active surface area.

Heteromorphic NiCo2S4/Ni3S2/Ni Foam as a Self-Standing Electrode for Hydrogen Evolution Reaction in Alkaline Solution.

PubMed

Liu, Hui; Ma, Xiao; Rao, Yuan; Liu, Yang; Liu, Jialiang; Wang, Luyang; Wu, Mingbo

2018-04-04

Considerable works have been devoted on developing high-efficiency nonplatinum electrocatalysts for hydrogen evolution reaction (HER). Herein, 3D heteromorphic NiCo 2 S 4 /Ni 3 S 2 nanosheets network has been constructed on Ni foam (denoted as NiCo 2 S 4 /Ni 3 S 2 /NF) serving as a self-standing electrocatalyst through directly thermal sulfurization of a single-source NiCo-layered double hydroxide precursor. The resultant NiCo 2 S 4 /Ni 3 S 2 /NF electrode exhibits outstanding electrocatalytic HER performance with an extremely low onset overpotential of 15 mV and long-term durability in alkaline solution. Such enhanced HER performance can be credited to (1) the massive exposed active sites provided by mixed transition metal chalcogenides (NiCo 2 S 4 and Ni 3 S 2 ), (2) the strong interfacial interaction at NiCo 2 S 4 /Ni 3 S 2 heterojunction interfaces with the strengthened H binding, and (3) the porous highly conductive Ni foam substrate with accelerated electron transfer. This work opens up a new direction to fabricate effective and non-noble-metal electrodes for water splitting and hydrogen generation.

Fusion cross sections for reactions involving medium and heavy nucleus-nucleus systems

NASA Astrophysics Data System (ADS)

Atta, Debasis; Basu, D. N.

2014-12-01

Existing data on near-barrier fusion excitation functions of medium and heavy nucleus-nucleus systems have been analyzed by using a simple diffused-barrier formula derived assuming the Gaussian shape of the barrier-height distributions. The fusion cross section is obtained by folding the Gaussian barrier distribution with the classical expression for the fusion cross section for a fixed barrier. The energy dependence of the fusion cross section, thus obtained, provides good description to the existing data on near-barrier fusion and capture excitation functions for medium and heavy nucleus-nucleus systems. The theoretical values for the parameters of the barrier distribution are estimated which can be used for fusion or capture cross-section predictions that are especially important for planning experiments for synthesizing new superheavy elements.

Ultrasensitive electrochemical DNA detection based on dual amplification of circular strand-displacement polymerase reaction and hybridization chain reaction.

PubMed

Wang, Cui; Zhou, Hui; Zhu, Wenping; Li, Hongbo; Jiang, Jianhui; Shen, Guoli; Yu, Ruqin

2013-09-15

We developed a novel electrochemical strategy for ultrasensitive DNA detection using a dual amplification strategy based on the circular strand-displacement polymerase reaction (CSDPR) and the hybridization chain reaction (HCR). In this assay, hybridization of hairpin-shaped capture DNA to target DNA resulted in a conformational change of the capture DNA with a concomitant exposure of its stem. The primer was then hybridized with the exposed stem and triggered a polymerization reaction, allowing a cyclic reaction comprising release of target DNA, hybridization of target with remaining capture DNA, polymerization initiated by the primer. Furthermore, the free part of the primer propagated a chain reaction of hybridization events between two DNA hairpin probes with biotin labels, enabling an electrochemical reading using the streptavidin-alkaline phosphatase. The proposed biosensor showed to have very high sensitivity and selectivity with a dynamic response range through 10fM to 1nM, and the detect limit was as low as 8fM. The proposed strategy could have the potential for molecular diagnostics in complex biological systems. Copyright © 2013 Elsevier B.V. All rights reserved.

The alkaline zinc electrode as a mixed potential system

NASA Technical Reports Server (NTRS)

Fielder, W. L.

1979-01-01

Cathodic and anodic processes for the alkaline zinc electrode in 0.01 molar zincate electrolyte (9 molar hydroxide) were investigated. Cyclic voltammograms and current-voltage curves were obtained by supplying pulses through a potentiostat to a zinc rotating disk electrode. The data are interpreted by treating the system as one with a mixed potential; the processes are termed The zincate and corrosion reactions. The relative proportions of the two processes vary with the supplied potential. For the cathodic region, the cathodic corrosion process predominates at higher potentials while both processes occur simultaneously at a lower potential (i.e., 50 mV). For the anodic region, the anodic zincate process predominates at higher potentials while the anodic corrosion process is dominant at lower potential (i.e., 50 mV) if H2 is present.

Hollow raspberry-like PdAg alloy nanospheres: High electrocatalytic activity for ethanol oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Peng, Cheng; Hu, Yongli; Liu, Mingrui; Zheng, Yixiong

2015-03-01

Palladium-silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs).

Alkaline earth metal complexes of a phosphine-borane-stabilized carbanion: synthesis, structures, and stabilities.

PubMed

Izod, Keith; Wills, Corinne; Clegg, William; Harrington, Ross W

2007-05-14

The reaction between either MgI2 or CaI2 and 2 equiv of [(Me3Si)2{Me2(H3B)P}C]K (2) in toluene gives the corresponding organo-alkaline earth metal compounds [(Me3Si)2{Me2(H3B)P}C]2M in moderate to good yields [M = Mg (3), Ca (4)]. Compound 3 crystallizes solvent-free, whereas X-ray quality crystals of 4 could not be obtained in the absence of coordinating solvents; crystallization of 4 from cold methylcyclohexane/THF gives the solvate [(Me3Si)2{Me2(H3B)P}C]2Ca(THF)4 (4a). The corresponding heavier alkaline earth metal complexes [(Me3Si)2{Me2(H3B)P}C]2M(THF)5 [M = Sr (7), Ba (8)] are obtained from the reaction between MI2 and 2 equiv of 2 in THF, followed by recrystallization from cold methylcyclohexane/THF. Compound 3 degrades over a period of several weeks at room-temperature both in the solid state and in toluene solution to give the free phosphine-borane (Me3Si)2{Me2(H3B)P}CH (5) as the sole phosphorus-containing product. In addition, compounds 3, 4, and 4a react rapidly with THF in toluene solution, yielding 5 as the sole phosphorus-containing product; in contrast, compounds 7 and 8 are stable toward this solvent.

Saponification reaction system: a detailed mass transfer coefficient determination.

PubMed

Pečar, Darja; Goršek, Andreja

2015-01-01

The saponification of an aromatic ester with an aqueous sodium hydroxide was studied within a heterogeneous reaction medium in order to determine the overall kinetics of the selected system. The extended thermo-kinetic model was developed compared to the previously used simple one. The reaction rate within a heterogeneous liquid-liquid system incorporates a chemical kinetics term as well as mass transfer between both phases. Chemical rate constant was obtained from experiments within a homogeneous medium, whilst the mass-transfer coefficient was determined separately. The measured thermal profiles were then the bases for determining the overall reaction-rate. This study presents the development of an extended kinetic model for considering mass transfer regarding the saponification of ethyl benzoate with sodium hydroxide within a heterogeneous reaction medium. The time-dependences are presented for the mass transfer coefficient and the interfacial areas at different heterogeneous stages and temperatures. The results indicated an important role of reliable kinetic model, as significant difference in k(L)a product was obtained with extended and simple approach.

Nitrogen mineralization from sludge in an alkaline, saline coal gasification ash environment.

PubMed

Mbakwe, Ikenna; De Jager, Pieter C; Annandale, John G; Matema, Taurai

2013-01-01

Rehabilitating coal gasification ash dumps by amendment with waste-activated sludge has been shown to improve the physical and chemical properties of ash and to facilitate the establishment of vegetation. However, mineralization of organic N from sludge in such an alkaline and saline medium and the effect that ash weathering has on the process are poorly understood and need to be ascertained to make decisions regarding the suitability of this rehabilitation option. This study investigated the rate and pattern of N mineralization from sludge in a coal gasification ash medium to determine the prevalent inorganic N form in the system and assess the effect of ash weathering on N mineralization. An incubation experiment was performed in which fresh ash, weathered ash, and soil were amended with the equivalent of 90 Mg ha sludge, and N mineralization was evaluated over 63 d. More N (24%) was mineralized in fresh ash than in weathered ash and soil, both of which mineralized 15% of the initial organic N in sludge. More nitrification occurred in soil, and most of the N mineralized in ash was in the form of ammonium, indicating an inhibition of nitrifying organisms in the ash medium and suggesting that, at least initially, plants used for rehabilitation of coal gasification ash dumps will take up N mostly as ammonium. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Alkaline quinone flow battery.

PubMed

Lin, Kaixiang; Chen, Qing; Gerhardt, Michael R; Tong, Liuchuan; Kim, Sang Bok; Eisenach, Louise; Valle, Alvaro W; Hardee, David; Gordon, Roy G; Aziz, Michael J; Marshak, Michael P

2015-09-25

Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy. Copyright © 2015, American Association for the Advancement of Science.

Influence of medium components on the expression of recombinant lipoproteins in Escherichia coli.

PubMed

Tseng, Chi-Ling; Leng, Chih-Hsiang

2012-02-01

Bacterial lipoproteins are crucial antigens for protective immunity against bacterial pathogens. Expression of exogenous lipoproteins in Escherichia coli at high levels is thought to be an extremely difficult endeavor because it frequently results in incomplete or absent lipid modification. Previously, we identified a fusion sequence (D1) from a Neisseria meningitidis lipoprotein that induced a non-lipidated protein, E3 (the domain III of the dengue virus envelope protein), to become lipidated. However, without optimizing the growth conditions, some of the D1-fusion proteins were not lipidated. Here, we report the influence of medium components on the expression of recombinant lipoproteins in E. coli. For high-level expression of mature lipoproteins in the C43 (DE3) strain, M9 medium was better than M63 and the rich medium. Furthermore, we analyzed the influence of other media factors (including nitrogen and carbon sources, phosphate, ferrous ions, calcium, magnesium, and pH) on the levels of lipoprotein expression. The results showed that excess nitrogen sources and phosphate in M9 medium could increase the amount of immature lipoproteins, and glucose was a better carbon source than glycerol for expressing mature lipoproteins. We also found that lipoproteins tended to be completely processed in the alkaline environment, even in the nutrient-rich medium. Additional constructs expressing different immunogens or lipid signal peptides as targets were also utilized, demonstrating that these targets could be expressed as completely mature lipoproteins in the M9 medium but not in the rich medium. Our results provide the useful information for expressing mature exogenous lipoproteins in E. coli.

Technetium recovery from high alkaline solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash, Charles A.

2016-07-12

Disclosed are methods for recovering technetium from a highly alkaline solution. The highly alkaline solution can be a liquid waste solution from a nuclear waste processing system. Methods can include combining the solution with a reductant capable of reducing technetium at the high pH of the solution and adding to or forming in the solution an adsorbent capable of adsorbing the precipitated technetium at the high pH of the solution.

Wnt/β-Catenin Expression Does Not Correlate with Serum Alkaline Phosphatase Concentration in Canine Osteosarcoma Patients

PubMed Central

Piskun, Caroline M.; Muthuswamy, Anantharaman; Huelsmeyer, Michael K.; Thompson, Victoria; Stein, Timothy J.

2011-01-01

Osteosarcoma is an aggressive malignancy of the bone and an increase in serum alkaline phosphatase concentration has clinical prognostic value in both humans and canines. Increased serum alkaline phosphatase concentration at the time of diagnosis has been associated with poorer outcomes for osteosarcoma patients. The biology underlying this negative prognostic factor is poorly understood. Given that activation of the Wnt signaling pathway has been associated with alkaline phosphatase expression in osteoblasts, we hypothesized that the Wnt/β-catenin signaling pathway would be differentially activated in osteosarcoma tissue based on serum ALP status. Archived canine osteosarcoma samples and primary canine osteosarcoma cell lines were used to evaluate the status of Wnt/β-catenin signaling pathway activity through immunohistochemical staining, western immunoblot analyses, quantitative reverse-transcription polymerase chain reaction, and a Wnt-responsive promoter activity assay. We found no significant difference in β-catenin expression or activation between OSA populations differing in serum ALP concentration. Pathway activity was mildly increased in the primary OSA cell line generated from a patient with increased serum ALP compared to the normal serum ALP OSA cell line. Further investigation into the mechanisms underlying differences in serum ALP concentration is necessary to improve our understanding of the biological implications of this negative prognostic indicator. PMID:22022527

Alkaline hydrolysis of ethylene phosphate: an ab initio study by supermolecule model and polarizable continuum approach.

PubMed

Xia, Futing; Zhu, Hua

2011-09-01

The alkaline hydrolysis reaction of ethylene phosphate (EP) has been investigated using a supermolecule model, in which several explicit water molecules are included. The structures and single-point energies for all of the stationary points are calculated in the gas phase and in solution at the B3LYP/6-31++G(df,p) and MP2/6-311++G(df,2p) levels. The effect of water bulk solvent is introduced by the polarizable continuum model (PCM). Water attack and hydroxide attack pathways are taken into account for the alkaline hydrolysis of EP. An associative mechanism is observed for both of the two pathways with a kinetically insignificant intermediate. The water attack pathway involves a water molecule attacking and a proton transfer from the attacking water to the hydroxide in the first step, followed by an endocyclic bond cleavage to the leaving group. While in the first step of the hydroxide attack pathway the nucleophile is the hydroxide anion. The calculated barriers in aqueous solution for the water attack and hydroxide attack pathways are all about 22 kcal/mol. The excellent agreement between the calculated and observed values demonstrates that both of the two pathways are possible for the alkaline hydrolysis of EP. Copyright © 2011 Wiley Periodicals, Inc.

Development of an analytical technique for the detection of alteration minerals formed in bentonite by reaction with alkaline solutions

NASA Astrophysics Data System (ADS)

Sakamoto, H.; Shibata, M.; Owada, H.; Kaneko, M.; Kuno, Y.; Asano, H.

A multibarrier system consisting of cement-based backfill, structures and support materials, and a bentonite-based buffer material has been studied for the TRU waste disposal concept being developed in Japan, the aim being to restrict the migration of radionuclides. Concern regarding bentonite-based materials in this disposal environment relates to long-term alteration under hyper-alkaline conditions due to the presence of cementitious materials. In tests simulating the interaction between bentonite and cement, formation of secondary minerals due to alteration reactions under the conditions expected for geological disposal of TRU waste (equilibrated water with cement at low liquid/solid ratio) has not been observed, although alteration was observed under extremely hyper-alkaline conditions with high temperatures. This was considered to be due to the fact that analysis of C-S-H gel formed at the interface as a secondary mineral was difficult using XRD, because of its low crystallinity and low content. This paper describes an analytical technique for the characterization of C-S-H gel using a heavy liquid separation method which separates C-S-H gel from Kunigel V1 bentonite (bentonite produced in Japan) based on the difference in specific gravity between the crystalline minerals constituting Kunigel V1 and the secondary C-S-H gel. For development of C-S-H gel separation methods, simulated alteration samples were prepared by mixing 990 mg of unaltered Kunigel V1 and 10 mg of C-S-H gel synthesized using pure chemicals at a ratio of Ca/Si = 1.2. The simulated alteration samples were dispersed in bromoform-methanol mixtures with specific gravities ranging from 2.00 to 2.57 g/cm 3 and subjected to centrifuge separation to recover the light density fraction. Subsequent XRD analysis to identify the minerals was complemented by dissolution in 0.6 N hydrochloric acid to measure the Ca and Si contents. The primary peak (2 θ = 29.4°, Cu Kα) and secondary peaks (2 θ = 32.1�

Ethanol production from bamboo using mild alkaline pre-extraction followed by alkaline hydrogen peroxide pretreatment.

PubMed

Yuan, Zhaoyang; Wen, Yangbing; Kapu, Nuwan Sella

2018-01-01

A sequential two-stage pretreatment process comprising alkaline pre-extraction and alkaline hydrogen peroxide pretreatment (AHP) was investigated to convert bamboo carbohydrates into bioethanol. The results showed that mild alkaline pre-extraction using 8% (w/w) sodium hydroxide (NaOH) at 100°C for 180min followed by AHP pretreatment with 4% (w/w) hydrogen peroxide (H 2 O 2 ) was sufficient to generate a substrate that could be efficiently digested with low enzyme loadings. Moreover, alkali pre-extraction enabled the use of lower H 2 O 2 charges in AHP treatment. Two-stage pretreatment followed by enzymatic hydrolysis with only 9FPU/g cellulose led to the recovery of 87% of the original sugars in the raw feedstock. The use of the pentose-hexose fermenting Saccharomyces cerevisiae SR8u strain enabled the utilization of 95.7% sugars in the hydrolysate to reach 4.6%w/v ethanol titer. The overall process also enabled the recovery of 62.9% lignin and 93.8% silica at high levels of purity. Copyright © 2017 Elsevier Ltd. All rights reserved.

High performance nano-Ni/Graphite electrode for electro-oxidation in direct alkaline ethanol fuel cells

NASA Astrophysics Data System (ADS)

Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Ahmed, Mohamed A.; Hassan, Hamdy H.

2016-09-01

Ni/Graphite electrocatalysts (Ni/G) are successfully prepared through electrodeposition of Ni from acidic (pH = 0.8) and feebly acidic (pH = 5.5) aqueous Ni (II) baths. The efficiencies of such electrodes are investigated as anodes for direct alkaline ethanol fuel cells through their ethanol electrooxidation cyclic voltammetric (CV) response in alkaline medium. A direct proportionality between the amount of the electrodeposited Ni and its CV response is found. The amounts of the deposited Ni from the two baths are recorded using the Electrochemical Quartz Crystal Microbalance (eQCM). The Ni/G electrodes prepared from the feebly acidic bath show a higher electrocatalytic response than those prepared from the acidic bath. Surface morphology of the Ni particles electrodeposited from feebly acidic bath appears in a nano-scale dimension. Various electrochemical experiments are conducted to confirm that the Ni/G ethanol electrooxidation CV response greatly depends on the pH rather than nickel ion concentration of the deposition bath. The eQCM technique is used to detect the crystalline phases of nickel as α-Ni(OH)2/γ-NiOOH and β-Ni(OH)2/β-NiOOH and their in-situ inter-transformations during the potentiodynamic polarization.

Calcic amphiboles in calc-alkaline and alkaline magmas: thermobarometric and chemometric empirical equations valid up to 1,130°C and 2.2 GPa

NASA Astrophysics Data System (ADS)

Ridolfi, Filippo; Renzulli, Alberto

2012-05-01

The following article presents constraints of the stability of Mg-rich (Mg/(Mg + Fe2+) > 0.5) calcic amphibole in both calc-alkaline and alkaline magmas, testing of previous thermobarometers, and formulation of new empirical equations that take into consideration a large amount of literature data (e.g. more than one thousand amphibole compositions among experimental and natural crystals). Particular care has been taken in choosing a large number of natural amphiboles and selecting quality experimental data from literature. The final database of experimental data, composed of 61 amphiboles synthesized in the ranges of 800-1,130°C and 130-2,200 MPa, indicates that amphibole crystallization occurs in a horn-like P- T stability field limited by two increasing curves (i.e. the thermal stability and an upper limit), which should start to bend back to higher pressures. Among calcic amphiboles, magnesiohornblendes and tschermakitic pargasites are only found in equilibrium with calc-alkaline melts and crystallize at relatively shallow conditions ( P up to ~1 GPa). Kaersutite and pargasite are species almost exclusively found in alkaline igneous products, while magnesiohastingsite is equally distributed in calc-alkaline and alkaline rocks. The reliability of previous amphibole applications was checked using the selected experimental database. The results of this testing indicate that none of the previous thermobarometers can be successfully used to estimate the P, T and fO2 in a wide range of amphibole crystallization conditions. Multivariate least-square analyses of experimental amphibole compositions and physico-chemical parameters allowed us to achieve a new thermobarometric model that gives reasonably low uncertainties ( T ± 23.5°C, P ± 11.5%, H2Omelt ± 0.78wt%) for calc-alkaline and alkaline magmas in a wide range of P- T conditions (up to 1,130°C and 2,200 MPa) and ΔNNO values (±0.37 log units) up to 500 MPa. The AK-[4]Al relation in amphibole can be readily

Metal Based Synthetic Strategies and the Examination of Structure Determining Factors in Alkaline Earth Metal Compounds

NASA Astrophysics Data System (ADS)

Takahashi, Yuriko

Last decades have witnessed a large expansion of the organometallic heavier alkaline earth metal species. However, continued growth of this promising area of chemistry has been slowed by severe restrictions and limitations in viable synthetic methodologies leading to difficulties in preparing and characterizing the target compounds. There is clearly a need for the further development of synthetic methodologies and detailed structure function analysis that will promote the further advancement of organoalkaline earth metal chemistry in applications as diverse as materials chemistry and catalysis. This thesis work greatly extends the synthetic options currently available towards organoalkaline earth metal species by introducing redox transmetallation protolysis (RTP), a reaction based on the readily available Ph3Bi as a non-toxic transmetallation agent. Based on a straightforward one-pot procedure and work-up, Ph3Bi based RTP presents a powerful synthetic alternative for the facile preparation of a large variety of heavy alkaline earth metal compounds. The second part of the thesis explores the effect of secondary non covalent interactions on the coordination chemistry as well as thermal properties of a series of novel alkali, alkaline earth, rare earth as well as heterobimetallic alkali/alkaline earth fluoroalkoxides. These compounds showcase the significance of non-covalent M···F-C and agostic interactions on metal stabilization and structural features, providing critical input on ligand design for the design of advanced metal organic vapor deposition (MOCVD) precursor materials. This work also showcases the impact of M···F-C interactions over M---co-ligand coordination, a critical precursor design element as well.

High-performance oxygen reduction catalysts in both alkaline and acidic fuel cells based on pre-treating carbon material and iron precursor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Ping; Barkholtz, Heather M.; Wang, Ying

We demonstrate a new and simple method for pre-treating the carbon material and iron precursor to prepare oxygen reduction reaction (ORR) catalysts, which can produce super-high performance and stability in alkaline solution, with high performance in acid solution. This strategy using cheap materials is simply controllable. Moreover, it has achieved smaller uniform nanoparticles to exhibit high stability, and the synergetic effect of Fe and N offered much higher performance in ORR than commercial Pt/C, with high maximum power density in alkaline and acid fuel cell test. So it can make this kind of catalysts be the most promising alternatives ofmore » Pt-based catalysts with best performance/price.« less

Discomfort from an Alkaline Formulation Delivered Subcutaneously in Humans

PubMed Central

Ward, W. Kenneth; Castle, Jessica R.; Branigan, Deborah L.; Massoud, Ryan G.; Youssef, Joseph El

2013-01-01

Background and Objective There is a paucity of data regarding tolerability of alkaline drugs administered subcutaneously. The aim of this study was to assess the tolerability of alkaline preparations of human albumin delivered subcutaneously to healthy humans. Methods We compared the tolerability of neutral versus alkaline (pH 10) formulations of human albumin in ten volunteers. With an intent to minimize the time required to reach physiological pH after injection, the alkaline formulation was buffered with a low concentration of glycine (20 mmol/L). Each formulation was given at two rates: over 5 seconds and over 60 seconds. A six-point scale was used to assess discomfort. Results For slow injections, there was a significant difference between pH 7.4 and pH 10 injections (0.4 ± 0.2 vs 1.1 ± 0.2, mean ± SEM; p = 0.025), though the degree of discomfort at pH 10 injections was only ‘mild or slight’. For fast injections, the difference between neutral and alkaline formulations was of borderline significance. Inflammation and oedema, as judged by a physician, were very minimal for all injections, irrespective of pH. Conclusion For subcutaneous drug administration (especially when delivered slowly), there was more discomfort associated with alkaline versus neutral formulations of albumin, though the discomfort was mild. This study suggests that there is little discomfort and inflammation resulting from subcutaneous administration of protein drugs formulated with weak buffers at alkaline pH. PMID:22568666

Safety of an alkalinizing buffer designed for inhaled medications in humans.

PubMed

Davis, Michael D; Walsh, Brian K; Dwyer, Scott T; Combs, Casey; Vehse, Nico; Paget-Brown, Alix; Pajewski, Thomas; Hunt, John F

2013-07-01

Airway acidification plays a role in disorders of the pulmonary tract. We hypothesized that the inhalation of alkalinized glycine buffer would measurably alkalinize the airways without compromising lung function or causing adverse events. We evaluated the safety of an inhaled alkaline glycine buffer in both healthy subjects and in subjects with stable obstructive airway disease. This work includes 2 open-label safety studies. The healthy controls were part of a phase 1 safety study of multiple inhalations of low-dose alkaline glycine buffer; nebulized saline was used as a comparator in 8 of the healthy controls. Subsequently, a phase 2 study in subjects with stable obstructive airway disease was completed using a single nebulized higher-dose strategy of the alkaline inhalation. We studied 20 non-smoking adults (10 healthy controls and 10 subjects with obstructive airway disease), both at baseline and after inhalation of alkaline buffer. We used spirometry and vital signs as markers of clinical safety. We used changes in fraction of exhaled nitric oxide (NO) and exhaled breath condensate (EBC) pH as surrogate markers of airway pH modification. Alkaline glycine inhalation was tolerated by all subjects in both studies, with no adverse effects on spirometric parameters or vital signs. Airway alkalinization was confirmed by a median increase in EBC pH of 0.235 pH units (IQR 0.56-0.03, P = .03) in subjects after inhalation of the higher-dose alkaline buffer (2.5 mL of 100 mmol/L glycine). Alkalinization of airway lining fluid is accomplished with inhalation of alkaline glycine buffer and causes no adverse effects on pulmonary function or vital signs.

Comparative evaluation of acid and alkaline sulfite pretreatments for enzymatic saccharification of bagasses from three different sugarcane hybrids.

PubMed

Monte, Joseana R; Laurito-Friend, Debora F; Ferraz, André; Milagres, Adriane M F

2018-04-26

Sugarcane bagasses from three experimental sugarcane hybrids and a mill-reference sample were used to compare the efficiency and mode of action of acid and alkaline sulfite pretreatment processes. Varied chemical loads and reaction temperatures were used to prepare samples with distinguished characteristics regarding xylan and lignin removals, as well as sulfonation levels of residual lignins. The pretreatment with low sulfite loads (5%) under acidic conditions (pH 2) provided maximum glucose yield of 70% during enzymatic hydrolysis with cellulases (10 FPU/g) and β-glucosidases (20 UI/g bagasse). In this case, glucan enzymatic conversion from pretreated materials was mostly associated with extensive xylan removal (70-100%) and partial delignification occurred during the pretreatment. The use of low sulfite loads under acidic conditions required pretreatment temperatures of 160°C. In contrast, at a lower pretreatment temperature (120°C), alkaline sulfite process achieved similar glucan digestibility, but required a higher sulfite load (7.5%). Residual xylans from acid pretreated materials were almost completely hydrolysed by commercial enzymes, contrasting with relatively lower xylan to xylose conversions observed in alkaline pretreated samples. Efficient xylan removal during acid sulfite pretreatment and also during enzymatic digestion can be useful to enhance glucan accessibility and digestibility by cellulases. Alkaline sulfite process also provided substrates with high glucan digestibility, mainly associated with delignification and sulfonation of residual lignins. The results demonstrate that temperature, pH and sulfite can be combined for reducing lignocellulose recalcitrance and achieve similar glucan conversion rates in the alkaline and acid sulfite pretreated bagasses. This article is protected by copyright. All rights reserved. © 2018 American Institute of Chemical Engineers.

Peroxidase-type reactions suggest a heterolytic/nucleophilic O–O joining mechanism in the heme-dependent chlorite dismutase†

PubMed Central

Mayfield, Jeffrey A.; Blanc, Béatrice; Rodgers, Kenton R.; Lukat-Rodgers, Gudrun S.; DuBois, Jennifer L.

2015-01-01

Heme-containing chlorite dismutases (Clds) catalyze a highly unusual O–O bond forming reaction. The O–O cleaving reactions of hydrogen peroxide and peracetic acid (PAA) with the Cld from Dechloromonas aromatica (DaCld) were studied to better understand the Cl–O cleavage of the natural substrate and subsequent O–O bond formation. While reactions with H2O2 resulted in slow destruction of the heme, at acidic pH, heterolytic cleavage of the O–O bond of PAA cleanly yielded the ferryl porphyrin cation radical (Compound I). At alkaline pH, the reaction proceeds more rapidly and the first observed intermediate is a ferryl heme. Freezequench EPR confirmed that the latter has an uncoupled protein-based radical, indicating that Compound I is the first intermediate formed at all pH values and that radical migration is faster at alkaline pH. These results suggest by analogy that two-electron Cl–O bond cleavage to yield a ferryl-porphyrin cation radical is the most likely initial step in O–O bond formation from chlorite. PMID:24001266

Enhanced reaction kinetics in biological cells

NASA Astrophysics Data System (ADS)

Loverdo, C.; Bénichou, O.; Moreau, M.; Voituriez, R.

2008-02-01

The cell cytoskeleton is a striking example of an `active' medium driven out-of-equilibrium by ATP hydrolysis. Such activity has been shown to have a spectacular impact on the mechanical and rheological properties of the cellular medium, as well as on its transport properties: a generic tracer particle freely diffuses as in a standard equilibrium medium, but also intermittently binds with random interaction times to motor proteins, which perform active ballistic excursions along cytoskeletal filaments. Here, we propose an analytical model of transport-limited reactions in active media, and show quantitatively how active transport can enhance reactivity for large enough tracers such as vesicles. We derive analytically the average interaction time with motor proteins that optimizes the reaction rate, and reveal remarkable universal features of the optimal configuration. We discuss why active transport may be beneficial in various biological examples: cell cytoskeleton, membranes and lamellipodia, and tubular structures such as axons.

Photonuclear activation of pure isotopic mediums.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grohman, Mark A.; Lukosi, Eric Daniel

2010-06-01

This work simulated the response of idealized isotopic U-235, U-238, Th-232, and Pu-239 mediums to photonuclear activation with various photon energies. These simulations were conducted using MCNPX version 2.6.0. It was found that photon energies between 14-16 MeV produce the highest response with respect to neutron production rates from all photonuclear reactions. In all cases, Pu-239 responds the highest, followed by U-238. Th-232 produces more overall neutrons at lower photon energies then U-235 when material thickness is above 3.943 centimeters. The time it takes each isotopic material to reach stable neutron production rates in time is directly proportional to themore » material thickness and stopping power of the medium, where thicker mediums take longer to reach stable neutron production rates and thinner media display a neutron production plateau effect, due to the lack of significant attenuation of the activating photons in the isotopic mediums. At this time, no neutron sensor system has time resolutions capable of verifying these simulations, but various indirect methods are possible and should be explored for verification of these results.« less

The Epoxidation of 2,5-Di-tert-butyl-1,4-benzoquinone: A Consecutive Reaction for the Physical Chemistry Laboratory.

ERIC Educational Resources Information Center

Hairfield, E. M.; And Others

1985-01-01

Reports a consecutive first-order reaction for which the concentrations of reactant, intermediate, and products can be determined simulataneously. This reaction is the epoxidation of 2,5-di-tert-butyl-1,4-benzoquinone (I) by alkaline hydroperoxidation using tert-butyl hydroperoxide and benzyltrimethylammonium hydroxide (Triton B) catalyst.…

New Spectrophotometric and Fluorimetric Methods for Determination of Fluoxetine in Pharmaceutical Formulations

PubMed Central

Darwish, Ibrahim A.; Amer, Sawsan M.; Abdine, Heba H.; Al-Rayes, Lama I.

2009-01-01

New simple and sensitive spectrophotometric and fluorimetric methods have been developed and validated for the determination of fluoxetine hydrochloride (FLX) in its pharmaceutical formulations. The spectrophotometric method was based on the reaction of FLX with 1,2-naphthoquinone-4-sulphonate (NQS) in an alkaline medium (pH 11) to form an orange-colored product that was measured at 490 nm. The fluorimetric method was based on the reaction of FLX with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) in an alkaline medium (pH 8) to form a highly fluorescent product that was measured at 545 nm after excitation at 490 nm. The variables affecting the reactions of FLX with both NQS and NBD-Cl were carefully studied and optimized. The kinetics of the reactions were investigated, and the reaction mechanisms were presented. Under the optimum reaction conditions, good linear relationships were found between the readings and the concentrations of FLX in the ranges of 0.3–6 and 0.035–0.5 μg mL−1 for the spectrophotometric and fluorimetric methods, respectively. The limits of detection were 0.1 and 0.01 μg mL−1 for the spectrophotometric and fluorimetric methods, respectively. Both methods were successfully applied to the determination of FLX in its pharmaceutical formulations. PMID:20107560

TMC-1 mediates alkaline sensation in C. elegans through nociceptive neurons

PubMed Central

Wang, Xiang; Li, Guang; Liu, Jie; Liu, Jianfeng; Xu, X.Z. Shawn

2016-01-01

Noxious pH triggers pungent taste and nocifensive behavior. While the mechanisms underlying acidic pH sensation has been extensively characterized, little is known about how animals sense alkaline pH in the environment. TMC genes encode a family of evolutionarily conserved membrane proteins, whose functions are largely unknown. Here, we characterize C. elegans TMC-1 which was suggested to form a Na+-sensitive channel mediating salt chemosensation. Interestingly, we find that TMC-1 is required for worms to avoid noxious alkaline environment. Alkaline pH evokes an inward current in nociceptive neurons, which is primarily mediated by TMC-1 and to a lesser extent by the TRP channel OSM-9. However, unlike OSM-9 which is sensitive to both acidic and alkaline pH, TMC-1 is only required for alkali-activated current, revealing a specificity for alkaline sensation. Ectopic expression of TMC-1 confers alkaline sensitivity to alkali-insensitive cells. Our results identify an unexpected role for TMCs in alkaline sensation and nociception. PMID:27321925

Cogeneration of biodiesel and nontoxic rapeseed meal from rapeseed through in-situ alkaline transesterification.

PubMed

Qian, Junfeng; Yang, Qiuhui; Sun, Fuan; He, Mingyang; Chen, Qun; Yun, Zhi; Qin, Lizhen

2013-01-01

In-situ alkaline transesterification of rapeseed oil with methanol for the production of biodiesel and nontoxic rapeseed meal was carried out. Water removal from milled rapeseed by methanol washing was more effective than vacuum drying. The conversion rate of rapeseed oil into FAME was 92%, FAME mass was 8.81 g, glucosinolates content in remaining rapeseed meal was 0.12% by methanol washing, while by vacuum drying the values were 46%, 4.44 g, 0.58%, respectively. In the presence of 0.10 mol/L NaOH in methanol, with methanol/oil molar ratio of 180:1 and a 3h reaction at 40 °C, a conversion rate of 98% was achieved, and the glucosinolates content was reduce to 0.07%, a value which below the GB/T 22514-2008 standard in China. Thus the rapeseed meal can be used as a source of protein in animal feed. The FAME prepared through in-situ alkaline transesterification met the ASTM specifications for biodiesel. Copyright © 2012 Elsevier Ltd. All rights reserved.

Alkaline hydrothermal liquefaction of swine carcasses to bio-oil.

PubMed

Zheng, Ji-Lu; Zhu, Ming-Qiang; Wu, Hai-tang

2015-09-01

It is imperative that swine carcasses are disposed of safely, practically and economically. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil was performed. Firstly, the effects of temperature, reaction time and pH value on the yield of each liquefaction product were determined. Secondly, liquefaction products, including bio-oil and solid residue, were characterized. Finally, the energy recovery ratio (ERR), which was defined as the energy of the resultant products compared to the energy input of the material, was investigated. Our experiment shows that reaction time had certain influence on the yield of liquefaction products, but temperature and pH value had bigger influence on the yield of liquefaction products. Yields of 62.2wt% bio-oil, having a high heating value of 32.35MJ/kg and a viscosity of 305cp, and 22wt% solid residue were realized at a liquefaction temperature of 250°C, a reaction time of 60min and a pH value of 9.0. The bio-oil contained up to hundreds of different chemical components that may be classified according to functional groups. Typical compound classes in the bio-oil were hydrocarbons, organic acids, esters, ketones and heterocyclics. The energy recovery ratio (ERR) reached 93.63%. The bio-oil is expected to contribute to fossil fuel replacement in stationary applications, including boilers and furnaces, and upgrading processes for the bio-oil may be used to obtain liquid transport fuels. Copyright © 2015 Elsevier Ltd. All rights reserved.

40 CFR 721.9680 - Alkaline titania silica gel (generic name).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkaline titania silica gel (generic... Specific Chemical Substances § 721.9680 Alkaline titania silica gel (generic name). (a) Chemical substance... alkaline titania silica gel (PMN P-95-529) is subject to reporting under this section for the significant...

40 CFR 721.9680 - Alkaline titania silica gel (generic name).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkaline titania silica gel (generic... Specific Chemical Substances § 721.9680 Alkaline titania silica gel (generic name). (a) Chemical substance... alkaline titania silica gel (PMN P-95-529) is subject to reporting under this section for the significant...

40 CFR 721.9680 - Alkaline titania silica gel (generic name).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkaline titania silica gel (generic... Specific Chemical Substances § 721.9680 Alkaline titania silica gel (generic name). (a) Chemical substance... alkaline titania silica gel (PMN P-95-529) is subject to reporting under this section for the significant...

40 CFR 721.9680 - Alkaline titania silica gel (generic name).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkaline titania silica gel (generic... Specific Chemical Substances § 721.9680 Alkaline titania silica gel (generic name). (a) Chemical substance... alkaline titania silica gel (PMN P-95-529) is subject to reporting under this section for the significant...

40 CFR 721.9680 - Alkaline titania silica gel (generic name).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkaline titania silica gel (generic... Specific Chemical Substances § 721.9680 Alkaline titania silica gel (generic name). (a) Chemical substance... alkaline titania silica gel (PMN P-95-529) is subject to reporting under this section for the significant...

Dynamic Properties of the Alkaline Vesicle Population at Hippocampal Synapses

PubMed Central

Röther, Mareike; Brauner, Jan M.; Ebert, Katrin; Welzel, Oliver; Jung, Jasmin; Bauereiss, Anna; Kornhuber, Johannes; Groemer, Teja W.

2014-01-01

In compensatory endocytosis, scission of vesicles from the plasma membrane to the cytoplasm is a prerequisite for intravesicular reacidification and accumulation of neurotransmitter molecules. Here, we provide time-resolved measurements of the dynamics of the alkaline vesicle population which appears upon endocytic retrieval. Using fast perfusion pH-cycling in live-cell microscopy, synapto-pHluorin expressing rat hippocampal neurons were electrically stimulated. We found that the relative size of the alkaline vesicle population depended significantly on the electrical stimulus size: With increasing number of action potentials the relative size of the alkaline vesicle population expanded. In contrast to that, increasing the stimulus frequency reduced the relative size of the population of alkaline vesicles. Measurement of the time constant for reacification and calculation of the time constant for endocytosis revealed that both time constants were variable with regard to the stimulus condition. Furthermore, we show that the dynamics of the alkaline vesicle population can be predicted by a simple mathematical model. In conclusion, here a novel methodical approach to analyze dynamic properties of alkaline vesicles is presented and validated as a convenient method for the detection of intracellular events. Using this method we show that the population of alkaline vesicles is highly dynamic and depends both on stimulus strength and frequency. Our results implicate that determination of the alkaline vesicle population size may provide new insights into the kinetics of endocytic retrieval. PMID:25079223

Influence of cobalt and manganese content on the dehydrogenation capacity and kinetics of air-exposed LaNi 5+ x-type alloys in solid gas and electrochemical reactions

NASA Astrophysics Data System (ADS)

Raekelboom, E.; Cuevas, F.; Knosp, B.; Percheron-Guégan, A.

The effect of cobalt and manganese content on the dehydrogenation properties of air-exposed MmB 5+ x-type (Mm = mischmetal; B = Ni, Al, Co and Mn) alloys was investigated both in solid gas and electrochemical reactions. The cobalt and manganese content were varied separately while keeping constant the plateau pressure of the hydrides. The increase of the cobalt content leads to a decrease of the hydrogen capacity whereas the manganese content has no much effect. In solid gas reactions, the kinetics were found to be limited by the hydrogen diffusion through the surface oxidation layer. As for the electrochemistry, the kinetics are limited by a corrosion layer formed in alkaline medium. The desorption rates for both processes increase as the cobalt or manganese content decreases. This is thought to be due to an enhancement of the hydrogen diffusivity through the oxidation layer. As a result, a low cobalt or manganese content in MmB 5+ x alloys is found to be beneficial for the hydrogen desorption kinetics in both processes.

Temperature and base requirements for the alkaline hydrolysis of okadaite's esters.

PubMed

Rodrigues, Susana M; Vale, Paulo

2009-06-01

Portuguese bivalves are recurrently contaminated with okadaic acid (OA) and dinophysistoxin-2 (DTX2), found mainly in esterified forms. Throughout the years different conditions have been reported in the literature for releasing the parent toxins through an alkaline hydrolysis step, in order to simplify their detection by HPLC-FLD or LC-MS. In order to clearly understand toxin stability and reaction end-point the binominous temperature/time course and base concentration were studied using naturally contaminated bivalve samples. The results showed a strong temperature dependence of the reaction. At 60 degrees C and 70 degrees C the hydrolysis was fast, and 40min were sufficient for maximal recovery of OA and DTX2, while at 40 degrees C and 50 degrees C it was only complete after 100min and 60min, respectively. At room temperature the reaction was slow and incomplete even after 2h. Stability of OA and DTX2 in semi-purified bivalve matrix at 70 degrees C for 2h was demonstrated. Concentrations of sodium hydroxide lower than 2.5M, corresponding to a final incubation concentration of 0.23M, resulted in incomplete release of parent toxins, demonstrating that high concentrations are needed when taking into account the dilution in the supernatant extract.

Synthesis and Structure-Conductivity Relationship of Polystyrene-block-Poly(vinyl benzyl trimethylammonium) for Alkaline Anion Exchange Membrane Fuel Cells

DTIC Science & Technology

2012-01-01

Proton exchange membrane fuel cells ( PEMFCs ), which convert chemical energy to electrical energy through redox reactions, have been developed as...platinum)-based electrocata- lysts, the commercialization of PEMFCs is still limited. Addi- tionally, oxygen reduction and fuel (hydrogen or alcohol) oxi...These are serious obstacles to the extensive adoption of PEMFCs as energy devices.4 An alkaline fuel cell (AFC) uses potassium hydroxide as a liq- uid

Synthesis of nonionic-anionic colloidal systems based on alkaline and ammonium β-nonylphenol polyethyleneoxy (n = 3-20) propionates/dodecylbenzenesulfonates with prospects for food hygiene

PubMed Central

2012-01-01

Background The main objective of this work was to obtain a binary system of surface-active components (nonionic soap – alkaline and/or ammonium dodecylbenzenesulfonate) with potential competences in food hygiene, by accessing a scheme of classical reactions (cyanoethylation, total acid hydrolysis and stoichiometric neutralization with inorganic alkaline and/or organic ammonium bases) adapted to heterogeneously polyethoxylated nonylphenols (n = 3-20). In the processing system mentioned, dodecylbenzenesulfonic acid, initially the acid catalyst for the exhaustive hydrolysis of β-nonylphenolpolyethyleneoxy (n = 3-20) propionitriles, becomes together with the nonionic soap formed the second surface-active component of the binary system. Results In the reaction scheme adopted the influence of the main operating (duration, temperature, molar ratio of reagents) and structural parameters (degree of oligomerization of the polyoxyethylene chain) on the processing yields for the synthetic steps was followed. The favorable role of the polyoxyethylene chain size is remarked, through its specific conformation and its alkaline cations sequestration competences on the yields of cyanoethylation, but also the beneficial influence of phase-transfer catalysts in the total acid hydrolysis step. The chemical stability of dodecylbenzenesulfonic acid (DBSH) at the temperature and strongly acidic pH of the reaction environment is confirmed. The controlled change of the amount of DBSH in the final binary system will later confer it potential colloidal competences in food hygiene receipts. Conclusions The preliminary synthetic tests performed confirmed the prospect of obtaining a broad range of useful colloidal competences in various food hygiene scenarios. PMID:22958389

Non-stationary filtration mode during chemical reactions with the gas phase

NASA Astrophysics Data System (ADS)

Zavialov, Ivan; Konyukhov, Andrey; Negodyaev, Sergey

2015-04-01

An experimental and numerical study of filtration accompanied by chemical reactions between displacing fluid and solid skeleton is considered. Glass balls (400-500 μm in diameter) were placed in 1 cm gap between two glass sheets and were used as model porous medium. The baking soda was added to the glass balls. The 70% solution of acetic acid was used as the displacer. The modeling porous medium was saturated with a mineral oil, and then 70% solution of colored acetic acid was pumped through the medium. The glass balls and a mineral oil have a similar refractive index, so the model porous medium was optically transparent. During the filtration, the gas phase was generated by the chemical reactions between the baking soda and acetic acid, and time-dependent displacement of the chemical reaction front was observed. The front of the chemical reaction was associated with the most intensive gas separation. The front moved, stopped, and then moved again to the area where it had been already. We called this process a secondary oxidation wave. To describe this effect, we added to the balance equations a term associated with the formation and disappearance of phases due to chemical reactions. The equations were supplemented by Darcy's law for multiphase filtration. Nonstationarity front propagation of the chemical reaction in the numerical experiment was observed at Damköhler numbers greater than 100. The mathematical modelling was agreed well with the experimental results.

Alkaline β-fructofuranosidases of tuberous roots: Possible physiological function.

PubMed

Ricardo, C P

1974-12-01

Alkaline invertase of roots of carrot (Daucus carota L.) did not hydrolyze raffinose while the acid invertase from the same tissue showed with this sugar ca. 60% of the activity found with sucrose. The activity of the two invertases was inhibited by fructose to a different extent, the K i value being ca. 4×10(-2) M and 3×10(-1)M, respectively, for the alkaline and the acid invertases from the roots of both carrot and turnip (Brassica rapa L.). It is proposed that fructose inhibition of acid invertase is of no physiological significance but that, in contrast, hexoses might regulate the activity of alkaline invertase.Comparing several species and cultivars, it was found that the content of reducing sugars and the activity of alkaline invertase of mature tuberous roots showed a positive correlation. This indicates that alkaline invertase may participate in the regulation of the hexose level of the cell, as was previously suggested for sugar-cane. A scheme is presented which proposes a way of participation of alkaline invertase in such a regulation, assuming that this enzyme is located in the cytoplasm and acid invertase is membrane-bound and mainly located at the cell surface.

Hydrazine-induced post-chemiluminescence phenomenon of permanganate-luminol reaction and its applications.

PubMed

Du, Jianxiu; Lu, Jiuru

2004-01-01

The post-chemiluminescence phenomenon arising from the permanganate-luminol reaction induced by hydrazine and isoniazid was investigated. When hydrazine or isoniazid was injected into the mixture after the end of the reaction of permanganate with alkaline luminol, a new chemiluminescence (CL) reaction was initiated and strong CL signal was detected. A possible CL mechanism is suggested, based upon the studies of the kinetic characteristics of the CL reaction, the UV-visible spectra, the CL spectra and some other experiments. The present reactions allow the determination of 0.1-10.0 mg/L hydrazine and 0.02-1.0 mg/L isoniazid, with detection limits of 0.03 mg/L and 0.006 mg/L, respectively. The method was applied to the determination of isoniazid in pharmaceutical preparations.

Coal char oxidation kinetics in air medium

NASA Astrophysics Data System (ADS)

Slyusarskiy, K. V.; Jankovskiy, S. A.; Korotkikh, A. G.; Sorokin, I. V.

2017-01-01

Research on oxidation in air medium process of three different coal chars with various carbon content was presented. The anthracite, T-grade bituminous coal and 2B-grade lignite char powders with particle size less than 80 µm were studied. The coal char oxidation was studied by isothermal method using coupled TG-DSC analyzer Netzsch STA 449 Jupiter F3 in the temperature range 1000-1200 °C. Experiments were carried out at ambient pressure. Volumetric flow rate of oxidation medium into analyzer chamber was 250 ml/min and consisted of oxygen and argon with volumetric ratio 24:1. Based on experimental data, the average rate of carbon oxidation reaction values were defined at each temperature. Kinetic constants (frequency factor and activation energy) of reaction were defined as well via 1st order Arrhenius equation. Activation energy values are in good agreement with the data presented in the literature. Activation energy values for anthracite char are 1.6-1.7 times higher than those for bituminous coal and lignite chars, respectively.

Efficacy of cuff inflation media to prevent postintubation-related emergence phenomenon: air, saline and alkalinized lignocaine.

PubMed

Shroff, Prerana P; Patil, Vijay

2009-06-01

We wished to examine the efficacy of different media used for inflation of tracheal tube cuffs. In our prospective randomized, controlled study over 3 months, there were 150 patients of either sex undergoing surgery under general anaesthesia with controlled ventilation with nitrous oxide and oxygen. The patients were divided into three equal groups (air, isotonic saline and alkalinized lignocaine as inflation media) using sealed envelope technique. The volume of the inflation medium, intracuff pressure, duration of intubation, volume of the inflation medium withdrawn from the cuff and complications like tube intolerance, coughing on tube, restlessness, hoarseness, sore throat, breathlessness and laryngospasm were analysed. Continuous data are presented as mean +/- SD, whereas categorical data are presented as frequencies and percentages. A [chi]2, analysis of variance and student's t-test were used to analyse the data. A P value less than 0.05 was considered as statistically significant. Age, sex, duration of intubation, intracuff pressure at the time of intubation were comparable. After intubation at all intervals, the intracuff pressure was higher in the air group with statistical significance at 5 min, 30 min, 1 h and just before extubation when air and saline groups were comparable and at all intervals after intubation up to just before extubation when air and lignocaine groups were comparable. The volume of air increased just before extubation in the air group, as compared with a fall in volume in the other groups. Tube intolerance, hoarseness and sore throat were least in the lignocaine group. We found that alkalinized 2% lignocaine and saline are better cuff inflation media, than air.

Contemporaneous eruption of calc-alkaline and alkaline lavas in a continental arc (Eastern Mexican Volcanic Belt): chemically heterogeneous but isotopically homogeneous source

NASA Astrophysics Data System (ADS)

Carrasco-Núñez, Gerardo; Righter, Kevin; Chesley, John; Siebert, Lee; Aranda-Gómez, José Jorge

2005-11-01

Nearly contemporaneous eruption of alkaline and calc-alkaline lavas occurred about 900 years BP from El Volcancillo paired vent, located behind the volcanic front in the Mexican Volcanic Belt (MVB). Emission of hawaiite (Toxtlacuaya) was immediately followed by calc-alkaline basalt (Río Naolinco). Hawaiites contain olivine microphenocrysts (Fo67-72), plagioclase (An56-60) phenocrysts, have 4-5 wt% MgO and 49.6-50.9 wt% SiO2. In contrast, calc-alkaline lavas contain plagioclase (An64-72) and olivine phenocrysts (Fo81-84) with spinel inclusions, and have 8-9 wt% MgO and 48.4-49.4 wt% SiO2. The most primitive lavas in the region (Río Naolinco and Cerro Colorado) are not as primitive as parental melts in other arcs, and could represent either (a) variable degrees of melting of a subduction modified, garnet-bearing depleted mantle source, followed by AFC process, or (b) melting of two distinct mantle sources followed by AFC processes. These two hypotheses are evaluated using REE, HFSE, and Sr, Os and Pb isotopic data. The Toxtlacuaya flow and the Y & I lavas can be generated by combined fractional crystallization and assimilation of gabbroic granulite, starting with a parental liquid similar to the Cerro Colorado basalt. Although calc-alkaline and alkaline magmas commonly occur together in other areas of the MVB, evidence for subduction component in El Volcancillo magmas is minimal and limited to <1%, which is a unique feature in this region further from the trench. El Volcancillo lavas were produced from two different magma batches: we surmise that the injection of calc-alkaline magma into an alkaline magma chamber triggered the eruption of hawaiites. Our results suggest that the subalkaline and hawaiitic lavas were formed by different degrees of partial melting of a similar, largely depleted mantle source, followed by later AFC processes. This model is unusual for arcs, where such diversity is usually explained by melting of heterogeneous (enriched and depleted) and

Intestinal alkaline phosphatase to treat necrotizing enterocolitis.

PubMed

Biesterveld, Ben E; Koehler, Shannon M; Heinzerling, Nathan P; Rentea, Rebecca M; Fredrich, Katherine; Welak, Scott R; Gourlay, David M

2015-06-15

Intestinal alkaline phosphatase (IAP) activity is decreased in necrotizing enterocolitis (NEC), and IAP supplementation prevents NEC development. It is not known if IAP given after NEC onset can reverse the course of the disease. We hypothesized that enteral IAP given after NEC induction would not reverse intestinal injury. NEC was induced in Sprague-Dawley pups by delivery preterm followed by formula feedings with lipopolysaccharide (LPS) and hypoxia exposure and continued up to 4 d. IAP was added to feeds on day 2 until being sacrificed on day 4. NEC severity was scored based on hematoxylin and eosin-stained terminal ileum sections, and AP activity was measured using a colorimetric assay. IAP and interleukin-6 expression were measured using real time polymerase chain reaction. NEC pups' alkaline phosphatase (AP) activity was decreased to 0.18 U/mg compared with controls of 0.57 U/mg (P < 0.01). Discontinuation of LPS and hypoxia after 2 d increased AP activity to 0.36 U/mg (P < 0.01). IAP supplementation in matched groups did not impact total AP activity or expression. Discontinuing LPS and hypoxia after NEC onset improved intestinal injury scores to 1.14 compared with continued stressors, score 2.25 (P < 0.01). IAP supplementation decreased interleukin-6 expression two-fold (P < 0.05), though did not reverse NEC intestinal damage (P = 0.5). This is the first work to demonstrate that removing the source of NEC improves intestinal damage and increases AP activity. When used as a rescue treatment, IAP decreased intestinal inflammation though did not impact injury making it likely that IAP is best used preventatively to those neonates at risk. Copyright © 2015 Elsevier Inc. All rights reserved.

Clastic dikes of the Hatrurim basin (western flank of the Dead Sea) as natural analogues of alkaline concretes: Mineralogy, solution chemistry, and durability

NASA Astrophysics Data System (ADS)

Sokol, E. V.; Gaskova, O. L.; Kozmenko, O. A.; Kokh, S. N.; Vapnik, E. A.; Novikova, S. A.; Nigmatulina, E. N.

2014-11-01

This study shows that the mineral assemblages from clastic dikes in areas adjacent to the Dead Sea graben may be considered as natural analogues of alkaline concretes. The main infilling material of the clastic dikes is composed of well-sorted and well-rounded quartz sand. The cement of these hard rocks contains hydroxylapophyllite, tacharanite, calcium silicate hydrates, opal, calcite, and zeolite-like phases, which is indicative of a similarity of the natural cementation processes and industrial alkaline concrete production from quartz sands and industrial alkaline cements. The quartz grains exhibit a variety of reaction textures reflecting the interaction with alkaline solutions (opal and calcium hydrosilicate overgrowths; full replacement with apophyllite or thomsonite + apophyllite). The physicochemical analysis and reconstruction of the chemical composition of peralkaline Ca, Na, and K solutions that formed these assemblages reveal that the solutions evolved toward a more stable composition of zeolite-like phases, which are more resistant to long-term chemical weathering and atmospheric corrosion. The 40Ar/39Ar age of 6.2 ± 0.7 Ma obtained for apophyllite provides conclusive evidence for the high corrosion resistance of the assemblages consisting of apophyllite and zeolite-like phases.

Association between serum alkaline phosphatase and primary resistance to erythropoiesis stimulating agents in chronic kidney disease: a secondary analysis of the HERO trial.

PubMed

Badve, Sunil V; Zhang, Lei; Coombes, Jeff S; Pascoe, Elaine M; Cass, Alan; Clarke, Philip; Ferrari, Paolo; McDonald, Stephen P; Morrish, Alicia T; Pedagogos, Eugenie; Perkovic, Vlado; Reidlinger, Donna; Scaria, Anish; Walker, Rowan; Vergara, Liza A; Hawley, Carmel M; Johnson, David W

2015-01-01

Erythropoiesis stimulating agent (ESA)-resistant anemia is common in chronic kidney disease (CKD). To evaluate the determinants of severity of ESA resistance in patients with CKD and primary ESA-resistance. Secondary analysis of a randomized controlled trial (the Handling Erythropoietin Resistance with Oxpentifylline, HERO). 53 adult patients with CKD stage 4 or 5 and primary ESA-resistant anemia (hemoglobin ≤120 g/L, ESA resistance index [ERI] ≥1.0 IU/kg/week/gHb for erythropoietin or ≥0.005 μg/kg/week/gHb for darbepoeitin, no cause for ESA-resistance identified). Iron studies, parathyroid hormone, albumin, liver enzymes, phosphate or markers of oxidative stress and inflammation. Participants were divided into tertiles of ERI. Multinomial logistic regression was used to analyse the determinants of ERI tertiles. All patients, except one, were receiving dialysis for end-stage kidney disease. The mean ± SD ERI values in the low (n = 18), medium (n = 18) and high (n = 17) ERI tertiles were 1.4 ± 0.3, 2.3 ± 0.2 and 3.5 ± 0.8 IU/kg/week/gHb, respectively (P < 0.001). There were no significant differences observed in age, gender, ethnicity, cause of kidney disease, diabetes, iron studies, parathyroid hormone, albumin, liver enzymes, phosphate or markers of oxidative stress and inflammation between the ERI tertiles. The median [inter-quartile range] serum alkaline phosphatase concentrations in the low, medium and high ERI tertiles were 89 [64,121], 99 [76,134 and 148 [87,175] U/L, respectively (P = 0.054). There was a weak but statistically significant association between ERI and serum alkaline phosphatase (R(2) = 0.06, P = 0.03). Using multinomial logistic regression, the risk of being in the high ERI tertile relative to the low ERI tertile increased with increasing serum alkaline phosphatase levels (P = 0.02). No other variables were significantly associated with ERI. Small sample size; bone

Design principles for hydrogen evolution reaction catalyst materials

DOE PAGES

Strmcnik, Dusan; Lopes, Pietro Papa; Genorio, Bostjan; ...

2016-04-19

Design and synthesis of active, stable and cost-effective materials for efficient hydrogen production (hydrogen evolution reaction, HER) is of paramount importance for the successful deployment of hydrogen -based alternative energy technologies. The HER, seemingly one of the simplest electrochemical reactions, has served for decades to bridge the gap between fundamental electrocatalysis and practical catalyst design. However, there are still many open questions that need to be answered before it would be possible to claim that design principles of catalyst materials are fully developed for the efficient hydrogen production. Here in this review, by summarizing key results for the HER onmore » well-characterized electrochemical interfaces in acidic and alkaline media, we have broadened our understanding of the HER in the whole range of pH by considering three main parameters: the nature of the proton donor (H 3O + in acid and H 2O in alkaline), the energy of adsorption of H ad and OH ad, and the presence of spectator species. Simply by considering these three parameters we show that great deal has already been learned and new trends are beginning to emerge, giving some predictive ability with respect to the nature of electrochemical interface and electrocatalytic activity of the HER.« less

Ethanol oxidation on Pt single-crystal electrodes: surface-structure effects in alkaline medium.

PubMed

Busó-Rogero, Carlos; Herrero, Enrique; Feliu, Juan M

2014-07-21

Ethanol oxidation in 0.1 M NaOH on single-crystal electrodes has been studied using electrochemical and FTIR techniques. The results show that the activity order is the opposite of that found in acidic solutions. The Pt(111) electrode displays the highest currents and also the highest onset potential of all the electrodes. The onset potential for the oxidation of ethanol is linked to the adsorption of OH on the electrode surface. However, small (or even negligible) amounts of CO(ads) and carbonate are detected by FTIR, which implies that cleavage of the C-C bond is not favored in this medium. The activity of the electrodes diminishes quickly upon cycling. The diminution of the activity is proportional to the measured currents and is linked to the formation and polymerization of acetaldehyde, which adsorbs onto the electrode surface and prevents further oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

When can ocean acidification impacts be detected from decadal alkalinity measurements?

NASA Astrophysics Data System (ADS)

Carter, B. R.; Frölicher, T. L.; Dunne, J. P.; Rodgers, K. B.; Slater, R. D.; Sarmiento, J. L.

2016-04-01

We use a large initial condition suite of simulations (30 runs) with an Earth system model to assess the detectability of biogeochemical impacts of ocean acidification (OA) on the marine alkalinity distribution from decadally repeated hydrographic measurements such as those produced by the Global Ship-Based Hydrographic Investigations Program (GO-SHIP). Detection of these impacts is complicated by alkalinity changes from variability and long-term trends in freshwater and organic matter cycling and ocean circulation. In our ensemble simulation, variability in freshwater cycling generates large changes in alkalinity that obscure the changes of interest and prevent the attribution of observed alkalinity redistribution to OA. These complications from freshwater cycling can be mostly avoided through salinity normalization of alkalinity. With the salinity-normalized alkalinity, modeled OA impacts are broadly detectable in the surface of the subtropical gyres by 2030. Discrepancies between this finding and the finding of an earlier analysis suggest that these estimates are strongly sensitive to the patterns of calcium carbonate export simulated by the model. OA impacts are detectable later in the subpolar and equatorial regions due to slower responses of alkalinity to OA in these regions and greater seasonal equatorial alkalinity variability. OA impacts are detectable later at depth despite lower variability due to smaller rates of change and consistent measurement uncertainty.

Nitrogen-doped graphdiyne as a metal-free catalyst for high-performance oxygen reduction reactions

NASA Astrophysics Data System (ADS)

Liu, Rongji; Liu, Huibiao; Li, Yuliang; Yi, Yuanping; Shang, Xinke; Zhang, Shuangshuang; Yu, Xuelian; Zhang, Suojiang; Cao, Hongbin; Zhang, Guangjin

2014-09-01

Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts.Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts. Electronic supplementary information (ESI) available: Detailed RDE and RRDE experiments, additional tables and figures. See DOI: 10.1039/c4nr03185g

Contemporaneous alkaline and calc-alkaline series in Central Anatolia (Turkey): Spatio-temporal evolution of a post-collisional Quaternary basaltic volcanism

NASA Astrophysics Data System (ADS)

Dogan-Kulahci, Gullu Deniz; Temel, Abidin; Gourgaud, Alain; Varol, Elif; Guillou, Hervé; Deniel, Catherine

2018-05-01

This study focuses on spatio-temporal evolution of basaltic volcanism in the Central Anatolian post-collisional Quaternary magmatic province which developed along a NE-SW orientation in Turkey. This magmatic province consists of the stratovolcanoes Erciyes (ES) and Hasandag (HS), and the basaltic volcanic fields of Obruk-Zengen (OZ) and Karapınar (KA). The investigated samples range between basic to intermediate in composition (48-56 wt% SiO2), and exhibit calc-alkaline affinity at ES whereas HS, OZ and KA are alkaline in composition. Based on new Ksbnd Ar ages and major element data, the oldest basaltic rock of ES is 1700 ± 40 ka old and exhibits alkaline character, whereas the youngest basaltic trachyandesite is 12 ± 5 ka old and calc-alkaline in composition. Most ES basaltic rocks are younger than 350 ka. All samples dated from HS are alkaline basalts, ranging from 543 ± 12 ka to 2 ± 7 ka old. With the exception of one basalt, all HS basalts are 100 ka or younger in age. Ksbnd Ar ages range from 797 ± 20 ka to 66 ± 7 ka from OZ. All the basalt samples are alkaline in character and are older than the HS alkaline basalts, with the exception of the youngest samples. The oldest and youngest basaltic samples from KA are 280 ± 7 ka and 163 ± 10 ka, respectively, and are calc-alkaline in character. Based on thermobarometric estimates samples from OZ exhibit the highest cpx-liqidus temperature and pressure. For all centers the calculated crystallization depths are between 11 and 28 km and increase from NE to SW. Multistage crystallization in magma chamber(s) located at different depths can explain this range in pressure. Harker variation diagrams coupled with least-squares mass balance calculations support fractional crystallization for ES and, to lesser extend for HS, OZ and KA. All basaltic volcanic rocks of this study are enriched in large-ion lithophile elements (LILE) and light rare earth elements (LREE). The lack of negative anomalies for high field

MICROWAVE EFFECTS IN ORGANIC SYNTHESIS: MECHANISTIC AND REACTION MEDIUM CONSIDERATIONS

EPA Science Inventory

The scope of applications of microwave irradiation relates to a wide spectrum of organic syntheses with numerous benefits (reduction in reaction times, improved purity of products and better yields) encompassing advantages of both thermal and (or) specific non-purely thermal effe...

Alkaline Ammonia Electrolysis on Electrodeposited Platinum for Controllable Hydrogen Production.

PubMed

Gwak, Jieun; Choun, Myounghoon; Lee, Jaeyoung

2016-02-19

Ammonia is beginning to attract a great deal of attention as an alternative energy source carrier, because clean hydrogen can be produced through electrolytic processes without the emission of COx . In this study, we deposited various shapes of Pt catalysts under potentiostatic mode; the electrocatalytic oxidation behavior of ammonia using these catalysts was studied in alkaline media. The electrodeposited Pt was characterized by both qualitative and quantitative analysis. To discover the optimal structure and the effect of ammonia concentration, the bulk pH value, reaction temperature, and applied current of ammonia oxidation were investigated using potential sweep and galvanostatic methods. Finally, ammonia electrolysis was conducted using a zero-gap cell, producing highly pure hydrogen with an energy efficiency over 80 %. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave-Assisted Organic Synthesis Using Benign Reaction Medium and Reagents

EPA Science Inventory

Account of chemical reactions expedited by microwave (MW) exposure of neat reactants for the rapid one-pot assembly of heterocyclic compounds from in situ generated reactive intermediates via enamines or using hypervalent iodine reagents will be described that can be adapted for ...

Structural Analysis of Alkaline β-Mannanase from Alkaliphilic Bacillus sp. N16-5: Implications for Adaptation to Alkaline Conditions

PubMed Central

Zhao, Yueju; Zhang, Yunhua; Cao, Yang; Qi, Jianxun; Mao, Liangwei; Xue, Yanfen; Gao, Feng; Peng, Hao; Wang, Xiaowei; Gao, George F.; Ma, Yanhe

2011-01-01

Significant progress has been made in isolating novel alkaline β-mannanases, however, there is a paucity of information concerning the structural basis for alkaline tolerance displayed by these β-mannanases. We report the catalytic domain structure of an industrially important β-mannanase from the alkaliphilic Bacillus sp. N16-5 (BSP165 MAN) at a resolution of 1.6 Å. This enzyme, classified into subfamily 8 in glycosyl hydrolase family 5 (GH5), has a pH optimum of enzymatic activity at pH 9.5 and folds into a classic (β/α)8-barrel. In order to gain insight into molecular features for alkaline adaptation, we compared BSP165 MAN with previously reported GH5 β-mannanases. It was revealed that BSP165 MAN and other subfamily 8 β-mannanases have significantly increased hydrophobic and Arg residues content and decreased polar residues, comparing to β-mannanases of subfamily 7 or 10 in GH5 which display optimum activities at lower pH. Further, extensive structural comparisons show alkaline β-mannanases possess a set of distinctive features. Position and length of some helices, strands and loops of the TIM barrel structures are changed, which contributes, to a certain degree, to the distinctly different shaped (β/α)8-barrels, thus affecting the catalytic environment of these enzymes. The number of negatively charged residues is increased on the molecular surface, and fewer polar residues are exposed to the solvent. Two amino acid substitutions in the vicinity of the acid/base catalyst were proposed to be possibly responsible for the variation in pH optimum of these homologous enzymes in subfamily 8 of GH5, identified by sequence homology analysis and pK a calculations of the active site residues. Mutational analysis has proved that Gln91 and Glu226 are important for BSP165 MAN to function at high pH. These findings are proposed to be possible factors implicated in the alkaline adaptation of GH5 β-mannanases and will help to further understanding of alkaline

VSL#3 probiotic upregulates intestinal mucosal alkaline sphingomyelinase and reduces inflammation.

PubMed

Soo, I; Madsen, K L; Tejpar, Q; Sydora, B C; Sherbaniuk, R; Cinque, B; Di Marzio, L; Cifone, M Grazia; Desimone, C; Fedorak, R N

2008-03-01

Alkaline sphingomyelinase, an enzyme found exclusively in bile and the intestinal brush border, hydrolyzes sphingomyelin into ceramide, sphingosine and sphingosine-1-phosphate, thereby inducing epithelial apoptosis. Reduced levels of alkaline sphingomyelinase have been found in premalignant and malignant intestinal epithelia and in ulcerative colitis tissue. Probiotic bacteria can be a source of sphingomyelinase. To determine the effect of VSL#3 probiotic therapy on mucosal levels of alkaline sphingomyelinase, both in a mouse model of colitis and in patients with ulcerative colitis. Interleukin-10 gene-deficient (IL10KO) and wild type control mice were treated with VSL#3 (10(9) colony-forming units per day) for three weeks, after which alkaline sphingomyelinase activity was measured in ileal and colonic tissue. As well, 15 patients with ulcerative colitis were treated with VSL#3 (900 billion bacteria two times per day for five weeks). Alkaline sphingomyelinase activity was measured through biopsies and comparison of ulcerative colitis disease activity index scores obtained before and after treatment. Lowered alkaline sphingomyelinase levels were seen in the colon (P=0.02) and ileum (P=0.04) of IL10KO mice, as compared with controls. Treatment of these mice with VSL#3 resulted in upregulation of mucosal alkaline sphingomyelinase activity in both the colon (P=0.04) and the ileum (P=0.01). VSL#3 treatment of human patients who had ulcerative colitis decreased mean (+/- SEM) ulcerative colitis disease activity index scores from 5.3+/-1.8946 to 0.70+/-0.34 (P=0.02) and increased mucosal alkaline sphingomyelinase activity. Mucosal alkaline sphingomyelinase activity is reduced in the intestine of IL10KO mice with colitis and in humans with ulcerative colitis. VSL#3 probiotic therapy upregulates mucosal alkaline sphingomyelinase activity.

Membrane contactor assisted extraction/reaction process employing ionic liquids

DOEpatents

Lin, Yupo J [Naperville, IL; Snyder, Seth W [Lincolnwood, IL

2012-02-07

The present invention relates to a functionalized membrane contactor extraction/reaction system and method for extracting target species from multi-phase solutions utilizing ionic liquids. One preferred embodiment of the invented method and system relates to an extraction/reaction system wherein the ionic liquid extraction solutions act as both extraction solutions and reaction mediums, and allow simultaneous separation/reactions not possible with prior art technology.

Low-heat, mild alkaline pretreatment of switchgrass for anaerobic digestion.

PubMed

Jin, Guang; Bierma, Tom; Walker, Paul M

2014-01-01

This study examines the effectiveness of alkaline pretreatment under mild heat conditions (100°C or 212°F) on the anaerobic co-digestion of switchgrass. The effects of alkaline concentration, types of alkaline, heating time and rinsing were evaluated. In addition to batch studies, continuous-feed studies were performed in triplicate to identify potential digester operational problems caused by switchgrass co-digestion while accounting for uncertainty due to digester variability. Few studies have examined anaerobic digestion of switchgrass or the effects of mild heating to enhance alkaline pretreatment prior to biomass digestion. Results indicate that pretreatment can significantly enhance digestion of coarse-ground (≤ 0.78 cm particle size) switchgrass. Energy conversion efficiency as high as 63% was observed, and was comparable or superior to fine-grinding as a pretreatment method. The optimal NaOH concentration was found to be 5.5% (wt/wt alkaline/biomass) with a 91.7% moisture level. No evidence of operational problems such as solids build-up, poor mixing, or floating materials were observed. These results suggest the use of waste heat from a generator could reduce the concentration of alkaline required to adequately pretreat lignocellulosic feedstock prior to anaerobic digestion.

A macro-enzyme cause of an isolated increase of alkaline phosphatase.

PubMed

Cervinski, Mark A; Lee, Hong Kee; Martin, Isabella W; Gavrilov, Dimitar K

2015-02-02

Macroenzyme complexes of serum enzymes and antibody can increase the circulating enzymatic activity and may lead to unnecessary additional testing and procedures. Laboratory physicians and scientists need to be aware of techniques to identify macroenzyme complexes when suspected. To investigate the possibility of a macro-alkaline phosphatase in the serum of a 74 year old male with persistently increased alkaline phosphatase we coupled a protein A/G agarose affinity chromatography technique with isoenzyme electrophoresis to look for the presence of macro-alkaline phosphatase. The majority of the alkaline phosphatase activity in the patient's serum sample was bound to the column and only a minor fraction (25%) of alkaline phosphatase activity was present in the column flow-through. The alkaline phosphatase activity was also found to co-elute with the immunoglobulins in the patient sample. The alkaline phosphatase activity in a control serum sample concurrently treated in the same manner did not bind to the column and was found in the column flow-through. The use of protein A/G agarose affinity chromatography is a rapid and simple method that can be applied to the investigation of other macro-enzyme complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

Alkalinity-salinity relationship in the Chesapeake Bay

NASA Astrophysics Data System (ADS)

Cintrón Del Valle, S. M.; Najjar, R.; Herrmann, M.; Goldberger, S.; Stets, E.

2016-12-01

Estuaries are a significant source of atmospheric CO2, a major greenhouse gas. However, it is not known whether the Chesapeake Bay, the largest estuary in the United States, is a source or sink of CO2. Extensive pH measurements in the Bay offer the possibility of estimating the air-water CO2 flux if robust relationships between alkalinity, the acid neutralizing capacity of a water body, and salinity can be established. Here we conduct a comprehensive analysis of the alkalinity-salinity relationship in the Chesapeake Bay based on more than 18,000 alkalinity measurements made between 1985 and 2015. It was found that seven segments of the Bay could be grouped into three different linear functions, suggesting that alkalinity is conserved in the Bay and has properties that change depending on the freshwater endmember (the riverine source). The highest freshwater endmember was 1.21 mol m-3 for the Potomac River, the lowest one was 0.41 mol m-3 for the York and Rappahannock Rivers, and an intermediate freshwater endmember was 0.79 mol m-3 for the remaining four segments. For some segments, most notably the Potomac River, the scatter of the data increases with decreasing salinity, which is due, in part, to seasonal and interannual variations in the freshwater endmember.

Flow-injection chemiluminescence method for the determination of chloramphenicol based on luminol-sodium periodate order-transform second-chemiluminescence reaction.

PubMed

Zhuang, Ya-Feng; Zhu, Sheng-Nan; Wei, Wei; Li, Jie-Li

2011-01-01

A new chemiluminescence (CL) reaction was observed when chloramphenicol solution was injected into the mixture after the end of the reaction of alkaline luminol and sodium periodate or sodium periodate was injected into the reaction mixture of chloramphenicol and alkaline luminol. This reaction is described as an order-transform second-chemiluminescence (OTSCL) reaction. The OTSCL method combined with a flow-injection technique was applied to the determination of chloramphenicol. The optimum conditions for the order-transform second-chemiluminescence emission were investigated. A mechanism for OTSCL has been proposed on the basis of the chemiluminescence kinetic characteristics, the UV-visible spectra and the chemiluminescent spectra. Under optimal experimental conditions, the CL response is proportional to the concentration of chloramphenicol over the range 5.0 × 10(-7)-5.0 × 10(-5) mol/L with a correlation coefficient of 0.9969 and a detection limit of 6.0 × 10(-8) mol/L (3σ). The relative standard deviation (RSD) for 11 repeated determinations of 5.0 × 10(-6) mol/L chloramphenicol is 1.7%. The method has been applied to the determination of chloramphenicol in pharmaceutical samples with satisfactory results. Copyright © 2011 John Wiley & Sons, Ltd.

Electrode reactions of iron oxide-hydroxide colloids.

PubMed

Mahmoudi, Leila; Kissner, Reinhard

2014-11-07

Small-sized FeO(OH) colloids stabilised by sugars, commercially available for the clinical treatment of iron deficiency, show two waves during cathodic polarographic sweeps, or two current maxima with stationary electrodes, in neutral to slightly alkaline aqueous medium. Similar signals are observed with Fe(III) in alkaline media, pH > 12, containing citrate in excess. Voltammetric and polarographic responses reveal a strong influence of fast adsorption processes on gold and mercury. Visible spontaneous accumulation was also observed on platinum. The voltammetric signal at more positive potential is caused by Fe(III)→Fe(II) reduction, while the one at more negative potential has previously been assigned to Fe(II)→Fe(0) reduction. However, the involvement of adsorption phenomena leads us to the conclusion that the second cathodic current is caused again by Fe(III)→Fe(II), of species deeper inside the particles than those causing the first wave. This is further supported by X-ray photoelectron spectra obtained after FeO(OH) particle adsorption and reduction on a gold electrode surface. The same analysis suggests that sucrose stabilising the colloid is still bound to the adsorbed material, despite dilution and rinsing.

A method for making an alkaline battery electrode plate

NASA Technical Reports Server (NTRS)

Chida, K.; Ezaki, T.

1983-01-01

A method is described for making an alkaline battery electrode plate where the desired active substances are filled into a nickel foam substrate. In this substrate an electrolytic oxidation reduction occurs in an alkaline solution containing lithium hydroxide.

Elevated serum level of human alkaline phosphatase in obesity.

PubMed

Khan, Abdul Rehman; Awan, Fazli Rabbi; Najam, Syeda Sadia; Islam, Mehboob; Siddique, Tehmina; Zain, Maryam

2015-11-01

To investigate a correlation between serum alkaline phosphatase level and body mass index in human subjects. The comparative cross-sectional study was carried out at the National Institute for Biotechnology and Genetic Engineering, Faisalabad, Pakistan, from April 2012 to June 2013. Blood serum alkaline phosphatase levels were estimated and the subjects were divided into three sub-groups on the basis of their body mass. normal weight (<25kg/m2), overweight (25-27kg/m2) and obese (>27kg/m2) subjects. The serum samples were used for the estimation of clinically important biochemical parameters, using commercial kits on clinical chemistry analyser. Of the 197 subjects, 97(49%) were obese and 100(51%) were non-obese. The serum alkaline phosphatase level increased in obese (214±6.4 IU/L) compared to the non-obese subjects (184.5±5 IU/L). Furthermore, a significant linear relationship (r=0.3;p-0.0001) was found between serum alkaline phosphatase and body mass index. Other biochemical variables were not correlated to the body mass index. Over activity and higher amounts of alkaline phosphatase were linked to the development of obesity.

Graphene-cobaltite-Pd hybrid materials for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells.

PubMed

Sharma, Chandra Shekhar; Awasthi, Rahul; Singh, Ravindra Nath; Sinha, Akhoury Sudhir Kumar

2013-12-14

Hybrid materials comprising of Pd, MCo2O4 (where M = Mn, Co or Ni) and graphene have been prepared for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells. Structural and electrochemical characterizations were carried out using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, chronoamperometry and cyclic, CO stripping, and linear sweep voltammetries. The study revealed that all the three hybrid materials are active for both methanol oxidation (MOR) and oxygen reduction (ORR) reactions in 1 M KOH. However, the Pd-MnCo2O4/GNS hybrid electrode exhibited the greatest MOR and ORR activities. This active hybrid electrode has also outstanding stability under both MOR and ORR conditions, while Pt- and other Pd-based catalysts undergo degradation under similar experimental conditions. The Pd-MnCo2O4/GNS hybrid catalyst exhibited superior ORR activity and stability compared to even Pt in alkaline solutions.

Electrochemical oxidation of hydrazine and its derivatives on the surface of metal electrodes in alkaline media

NASA Astrophysics Data System (ADS)

Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa; Taniguchi, Masatoshi; Oguro, Keisuke

Electrochemical oxidation of hydrazine and its derivatives on the surface of various metal electrodes in alkaline media was investigated. A comparison of various polycrystalline metal electrodes (Ni, Co, Fe, Cu, Ag, Au, and Pt) showed that Co and Ni electrodes have a lower onset potential for hydrazine oxidation than the Pt electrode. The onset oxidation potential of APA (aminopolyacrylamide), a hydrazine derivative (-0.127 V vs. reversible hydrogen electrode, RHE), was similar to that of hydrazine hydrate (-0.178 V vs. RHE) in the case of the Co electrode. APA oxidation was possible because of hydrazine desorption that was caused by APA hydrolysis. The hydrolysis reaction was brought about by a heat treatment. This result suggests that the hydrazine hydrolysis reaction of hydrazine derivatives makes it possible to store hydrazine hydrate safely.

Polyvinyl alcohol battery separator containing inert filler. [alkaline batteries

NASA Technical Reports Server (NTRS)

Sheibley, D. W.; Hsu, L. C.; Manzo, M. A. (Inventor)

1981-01-01

A cross-linked polyvinyl alcohol battery separator is disclosed. A particulate filler, inert to alkaline electrolyte of an alkaline battery, is incorporated in the separator in an amount of 1-20% by weight, based on the weight of the polyvinyl alcohol, and is dispersed throughout the product. Incorporation of the filler enhances performance and increases cycle life of alkaline batteries when compared with batteries containing a similar separator not containing filler. Suitable fillers include titanates, silicates, zirconates, aluminates, wood floor, lignin, and titania. Particle size is not greater than about 50 microns.

Reactivity of alkaline lignite fly ashes towards CO{sub 2} in water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin Back; Michael Kuehn; Helge Stanjek

2008-06-15

The reaction kinetics between alkaline lignite fly ashes and CO{sub 2} (pCO{sub 2} = 0.01-0.03 MPa) were studied in a laboratory CO{sub 2} flow-through reactor at 25-75{sup o}C. The reaction is characterized by three phases that can be separated according to the predominating buffering systems and the rates of CO{sub 2} uptake. Phase I (pH > 12, < 30 min) is characterized by the dissolution of lime, the onset of calcite precipitation and a maximum uptake, the rate of which seems to be limited by dissolution of CO{sub 2}. Phase II (pH < 10.5, 10-60 min) is dominated by themore » carbonation reaction. CO{sub 2} uptake in phase III (pH < 8.3) is controlled by the dissolution of periclase (MgO) leading to the formation of dissolved magnesium-bicarbonate. Phase I could be significantly extended by increasing the solid-liquid ratios and temperature, respectively. At 75{sup o}C the rate of calcite precipitation was doubled leading to the neutralization of approximately 0.23 kg CO{sub 2} per kg fly ash within 4.5 h, which corresponds to nearly 90% of the total acid neutralizing capacity. 21 refs., 5 figs., 1 tab.« less

A systematic investigation of the (α, 2nγ) reaction on medium-heavy nuclei

NASA Astrophysics Data System (ADS)

Fields, C. A.; De Boer, F. W. N.; Ristinen, R. A.; Smith, P. A.; Sugarbaker, E.

1982-03-01

Exclusive neutron spectra and angular distributions have been measured for 28-35 MeV (α, 2nγ) reactions on various nuclei in the 80 ≦ A ≦ 210 region. Pre-equilibrium processes dominate the 35 MeV (α, 2nγ) reaction mechanism in much of this region. Analysis of systematic variation in the neutron spectrum parameters shows that the reaction mechanism is strongly correlated with the target neutron excess parameter ( N- Z/ A. Analysis of the γ-decay of the entry states shows that well-defined incident angular momentum windows exist for the pre-etjuilibrium (α, 2nγ) reaction. These features are discussed in terms of various models for the reaction mechanism.

Production of bioethanol and value added compounds from wheat straw through combined alkaline/alkaline-peroxide pretreatment.

PubMed

Yuan, Zhaoyang; Wen, Yangbing; Li, Guodong

2018-07-01

An efficient scheme was developed for the conversion of wheat straw (WS) into bioethanol, silica and lignin. WS was pre-extracted with 0.2 mol/L sodium hydroxide at 30 °C for 5 h to remove about 91% of initial silica. Subsequently, the alkaline-pretreated solids were subjected to alkaline hydrogen peroxide (AHP) pretreatment with 40 mg hydrogen peroxide (H 2 O 2 )/g biomass at 50 °C for 7 h to prepare highly digestible substrate. The results of enzymatic hydrolysis demonstrated that the sequential alkaline-AHP pretreated WS was efficiently hydrolyzed at 10% (w/v) solids loading using an enzyme dosage of 10 mg protein/g glucan. The total sugar conversion of 92.4% was achieved. Simultaneous saccharification and co-fermentation (SSCF) was applied to produce ethanol from the two-stage pretreated substrate using Saccharomyces cerevisiae SR8u strain. Ethanol with concentration of 31.1 g/L was produced. Through the proposed process, about 86.4% and 54.1% of the initial silica and lignin were recovered, respectively. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ultrasound and polar homogeneous reactions.

PubMed

Tuulmets, A

1997-04-01

The effect of ultrasound on the rates of homogeneous heterolytic reactions not switched to a free radical pathway can be explained by the perturbation of the molecular organization of or the solvation in the reacting system. A quantitative analysis of the sonochemical acceleration on the basis of the microreactor concept was carried out. It was found that (1) the Diels-Alder reaction cannot be accelerated by ultrasound except when SET or free radical processes are promoted, (2) the rectified diffusion during cavitation cannot be responsible for the acceleration of reactions, and (3) the sonochemical acceleration of polar homogeneous reactions takes place in the bulk reaction medium. This implies the presence of a 'sound-field' sonochemistry besides the 'hot-spot' sonochemistry. The occurrence of a sonochemical deceleration effect can be predicted.

Acid transformation of bauxite residue: Conversion of its alkaline characteristics.

PubMed

Kong, Xiangfeng; Li, Meng; Xue, Shengguo; Hartley, William; Chen, Chengrong; Wu, Chuan; Li, Xiaofei; Li, Yiwei

2017-02-15

Bauxite residue (BR) is a highly alkaline solid hazardous waste produced from bauxite processing for alumina production. Alkaline transformation appears to reduce the environmental risk of bauxite residue disposal areas (BRDAs) whilst potentially providing opportunities for the sustainable reuse and on-going management of BR. Mineral acids, a novel citric acid and a hybrid combination of acid-gypsum treatments were investigated for their potential to reduce residue pH and total alkalinity and transform the alkaline mineral phase. XRD results revealed that with the exception of andradite, the primary alkaline solid phases of cancrinite, grossular and calcite were transformed into discriminative products based on the transformation used. Supernatants separated from BR and transformed bauxite residue (TBR) displayed distinct changes in soluble Na, Ca and Al, and a reduction in pH and total alkalinity. SEM images suggest that mineral acid transformations promote macro-aggregate formation, and the positive promotion of citric acid, confirming the removal or reduction in soluble and exchangeable Na. NEXAFS analysis of Na K-edge revealed that the chemical speciation of Na in TBRs was consistent with BR. Three acid treatments and gypsum combination had no effect on Na speciation, which affects the distribution of Na revealed by sodium STXM imaging. Copyright © 2016 Elsevier B.V. All rights reserved.

Safety of medium-chain triglycerides used as an intraocular tamponading agent in an experimental vitrectomy model rabbit.

PubMed

Auriol, Sylvain; Mahieu, Laurence; Brousset, Pierre; Malecaze, François; Mathis, Véronique

2013-01-01

To evaluate safety of medium-chain triglycerides used as a possible intraocular tamponading agent. A 20-gauge pars plana vitrectomy was performed in the right eye of 28 rabbits. An ophthalmologic examination was performed every week until rabbits were killed. At days 7, 30, 60, and 90, rabbits were killed and the treated eyes were examined macroscopically and prepared for histologic examination. Principal outcome was retinal toxicity evaluated by light and electron microscopy, and secondary outcomes were the presence of medium-chain triglyceride emulsification, inflammatory reactions, and the development of cataract. Histologic examination did not reveal any retinal toxicity. Two cases of moderate emulsification were observed, but in these cases, emulsification was caused by the perioperative injection of the agent and did not increase during the postoperative period. We noted 13 cases of inflammatory reaction in vitreous cavity and no case of inflammatory reaction in anterior chamber. Two eyes developed cataract as a result of perioperative trauma to the lens with the vitreous cutter and not secondary to the presence of medium-chain triglycerides in the vitreous cavity. Medium-chain triglycerides did not induce morphologic evidence of retinal toxicity. The results suggest that medium-chain triglycerides could be a promising alternative intraocular tamponading agent for the treatment of retinal detachments.

Alkaline electrochemical advanced oxidation process for chromium oxidation at graphitized multi-walled carbon nanotubes.

PubMed

Xue, Yudong; Zheng, Shili; Sun, Zhi; Zhang, Yi; Jin, Wei

2017-09-01

Alkaline electrochemical advanced oxidation processes for chromium oxidation and Cr-contaminated waste disposal were reported in this study. The highly graphitized multi-walled carbon nanotubes g-MWCNTs modified electrode was prepared for the in-situ electrochemical generation of HO 2 - . RRDE test results illustrated that g-MWCNTs exhibited much higher two-electron oxygen reduction activity than other nanocarbon materials with peak current density of 1.24 mA cm -2 , %HO 2 - of 77.0% and onset potential of -0.15 V (vs. Hg/HgO). It was originated from the highly graphitized structure and good electrical conductivity as illustrated from the Raman, XRD and EIS characterizations, respectively. Large amount of reactive oxygen species (HO 2 - and ·OH) were in-situ electro-generated from the two-electron oxygen reduction and chromium-induced alkaline electro-Fenton-like reaction. The oxidation of Cr(III) was efficiently achieved within 90 min and the conversion ratio maintained more than 95% of the original value after stability test, offering an efficient and green approach for the utilization of Cr-containing wastes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Block copolymers for alkaline fuel cell membrane materials

NASA Astrophysics Data System (ADS)

Li, Yifan

Alkaline fuel cells (AFCs) using anion exchange membranes (AEMs) as electrolyte have recently received considerable attention. AFCs offer some advantages over proton exchange membrane fuel cells, including the potential of non-noble metal (e.g. nickel, silver) catalyst on the cathode, which can dramatically lower the fuel cell cost. The main drawback of traditional AFCs is the use of liquid electrolyte (e.g. aqueous potassium hydroxide), which can result in the formation of carbonate precipitates by reaction with carbon dioxide. AEMs with tethered cations can overcome the precipitates formed in traditional AFCs. Our current research focuses on developing different polymer systems (blend, block, grafted, and crosslinked polymers) in order to understand alkaline fuel cell membrane in many aspects and design optimized anion exchange membranes with better alkaline stability, mechanical integrity and ionic conductivity. A number of distinct materials have been produced and characterized. A polymer blend system comprised of poly(vinylbenzyl chloride)-b-polystyrene (PVBC-b-PS) diblock copolymer, prepared by nitroxide mediated polymerization (NMP), with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or brominated PPO was studied for conversion into a blend membrane for AEM. The formation of a miscible blend matrix improved mechanical properties while maintaining high ionic conductivity through formation of phase separated ionic domains. Using anionic polymerization, a polyethylene based block copolymer was designed where the polyethylene-based block copolymer formed bicontinuous morphological structures to enhance the hydroxide conductivity (up to 94 mS/cm at 80 °C) while excellent mechanical properties (strain up to 205%) of the polyethylene block copolymer membrane was observed. A polymer system was designed and characterized with monomethoxy polyethylene glycol (mPEG) as a hydrophilic polymer grafted through substitution of pendent benzyl chloride groups of a PVBC

Alkaline and non-aqueous proton-conducting pouch-cell batteries

DOEpatents

Young, Kwo-hsiung; Nei, Jean; Meng, Tiejun

2018-01-02

Provided are sealed pouch-cell batteries that are alkaline batteries or non-aqueous proton-conducing batteries. A pouch cell includes a flexible housing such as is used for pouch cell construction where the housing is in the form of a pouch, a cathode comprising a cathode active material suitable for use in an alkaline battery, an anode comprising an anode active material suitable for use in an alkaline battery, an electrolyte that is optionally an alkaline or proton-conducting electrolyte, and wherein the pouch does not include or require a safety vent or other gas absorbing or releasing system as the anode active material and the cathode active material do not increase the internal atmospheric pressure any more than 2 psig during cycling. The batteries provided function contrary to the art recognized belief that such battery systems were impossible due to unacceptable gas production during cycling.

MALEIC ANHYDRIDE HYDROGENATION OF PD/AL2O3 CATALYST UNDER SUPERCRITICAL CO2 MEDIUM

EPA Science Inventory

Hydrogenation of maleic anhydride (MA) to either y-butyrolactone of succinic anhydride over simple Pd/Al2O3 impregnated catalyst in supercritical CO2 medium has been studied at different temperatures and pressures. A comparison of the supercritical CO2 medium reaction with the c...

Potassium extrusion by the moderately halophilic and alkaliphilic methanogen methanolobus taylorii GS-16 and homeostasis of cytosolic pH.

PubMed Central

Ni, S; Boone, J E; Boone, D R

1994-01-01

Methanolobus taylorii GS-16, a moderately halophilic and alkaliphilic methanogen, grows over a wide pH range, from 6.8 to 9.0. Cells suspended in medium with a pH above 8.2 reversed their transmembrane pH gradient (delta pH), making their cytosol more acidic than the medium. The decreased energy in the proton motive force due to the reversed delta pH was partly compensated by an increased electric membrane potential (delta psi). The cytosolic acidification by M. taylorii at alkaline pH values was accompanied by K+ extrusion. The cytosolic K+ concentration was 110 mM in cells suspended at pH 8.7, but it was 320 mM in cells suspended at neutral pH values. High external K+ concentrations (210 mM or higher) inhibited the growth of M. taylorii at alkaline pH values, perhaps by preventing K+ extrusion. Cells suspended at pH 8.5 and 300 mM external K+ failed to acidify their cytosol. The key observation indicative of the involvement of K+ transport in cytosolic acidification was that valinomycin (0.8 microM), a K+ uniporter, inhibited the growth of M. taylorii only at alkaline pH values. Experiments with resting cells indicated that at alkaline pH values valinomycin uncoupled catabolic reactions from ATP synthesis. Thus, K+/H+ antiport activity was proposed to account for the K+ extrusion and the uncoupling effect of valinomycin at alkaline pH values. Such antiport activity was demonstrated by the sharp drop in pH of the bulk medium of the cell suspension upon the addition of 0.1 M KCl. The antiporter appeared to be active only at alkaline pH values, which was in accordance with a possible role in pH homeostasis by M. taylorii growing at alkaline pH values. PMID:7961499

Characterization of polyphenol oxidase from the Manzanilla cultivar (Olea europaea pomiformis) and prevention of browning reactions in bruised olive fruits.

PubMed

Segovia-Bravo, Kharla A; Jarén-Galan, Manuel; García-García, Pedro; Garrido-Fernandez, Antonio

2007-08-08

The crude extract of the polyphenol oxidase (PPO) enzyme from the Manzanilla cultivar (Olea europaea pomiformis) was obtained, and its properties were characterized. The browning reaction followed a zero-order kinetic model. Its maximum activity was at pH 6.0. This activity was completely inhibited at a pH below 3.0 regardless of temperature; however, in alkaline conditions, pH inhibition depended on temperature and was observed at values above 9.0 and 11.0 at 8 and 25 degrees C, respectively. The thermodynamic parameters of substrate oxidation depended on pH within the range in which activity was observed. The reaction occurred according to an isokinetic system because pH affected the enzymatic reaction rate but not the energy required to carry out the reaction. In the alkaline pH region, browning was due to a combination of enzymatic and nonenzymatic reactions that occurred in parallel. These results correlated well with the browning behavior observed in intentionally bruised fruits at different temperatures and in different storage solutions. The use of a low temperature ( approximately 8 degrees C) was very effective for preventing browning regardless of the cover solution used.

Mechanism and models for zinc metal morphology in alkaline media

NASA Technical Reports Server (NTRS)

May, C. E.; Kautz, H. E.

1981-01-01

Based on experimental observations, a mechanism is presented to explain existence of the different morphologies of electrodeposited zinc in alkaline solution. The high current density dendrites appear to be due to more rapid growth on the nonbasal crystallographic planes than on the basal plane. The low current density moss apparently results from dissolution from the nonbasal planes at low cathodic voltages. Electrochemical models were sought which would produce such a phenomenon. The fundamental plating mechanism alone accounts only for different rates on different planes, not for zinc dissolution from a plane in the cathodic region. Fourteen models were explored; two models were in accord with the proposed mechanism. One involves rapid disproportionation of the zinc +1 species on the nonbasal planes. The other involves a redox reaction (corrosion) between the zinc-zincate and hydrogen-water systems.

Alkaline decomposition of synthetic jarosite with arsenic

PubMed Central

2013-01-01

The widespread use of jarosite-type compounds to eliminate impurities in the hydrometallurgical industry is due to their capability to incorporate several elements into their structures. Some of these elements are of environmental importance (Pb2+, Cr6+, As5+, Cd2+, Hg2+). For the present paper, AsO43- was incorporated into the lattice of synthetic jarosite in order to carry out a reactivity study. Alkaline decomposition is characterized by removal of sulfate and potassium ions from the lattice and formation of a gel consisting of iron hydroxides with absorbed arsenate. Decomposition curves show an induction period followed by a conversion period. The induction period is independent of particle size and exponentially decreases with temperature. The conversion period is characterized by formation of a hydroxide halo that surrounds an unreacted jarosite core. During the conversion period in NaOH media for [OH-] > 8 × 10-3 mol L-1, the process showed a reaction order of 1.86, and an apparent activation energy of 60.3 kJ mol-1 was obtained. On the other hand, during the conversion period in Ca(OH)2 media for [OH-] > 1.90 × 10-2 mol L-1, the reaction order was 1.15, and an apparent activation energy of 74.4 kJ mol-1 was obtained. The results are consistent with the spherical particle model with decreasing core and chemical control. PMID:23566061

Oxidative transformation of a tunichrome model compound provides new insight into the crosslinking and defense reaction of tunichromes.

PubMed

Abebe, Adal; Kuang, Qun F; Evans, Jason; Robinson, William E; Sugumaran, Manickam

2017-04-01

Tunichromes, small oligopeptides with dehydrodopa units isolated from the blood cells of ascidians, have been implicated in the defense reactions, metal binding, wound repair, or tunic formation. Their instability and high reactivity has severely hampered the assessment of their biological role. Experiments conducted with the model compound, 1,2-dehydro-N-acetyldopamine, indicated that the instability of tunichromes is due to this basic structure. Exposure of this catecholamine derivative to even mild alkaline condition such as pH 7.5 causes rapid nonenzymatic oxidation. High performance liquid chromatography and mass spectrometry studies confirmed the production of dimeric and other oligomeric products in the reaction mixture. The nonenzymatic reaction seemed to proceed through the intermediary formation of semiquinone free radical and superoxide anion. Ultraviolet and visible spectral studies associated with the oxidation of tunichromes isolated from Ascidia nigra by tyrosinase indicated the probable formation of oligomeric tunichrome products. Attempts to monitor the polymerization reaction by mass spectrometry ended in vain. Tunichrome also exhibited instability in mild alkaline conditions generating superoxide anions. Based on these studies, a possible role for oxidative transformation of tunichrome in defense reaction, tunic formation and wound healing is proposed. Copyright © 2017 Elsevier Inc. All rights reserved.

Evaluation of ASR potential of quartz-rich rocks by alkaline etching of polished rock sections

NASA Astrophysics Data System (ADS)

Šachlová, Šárka; Kuchařová, Aneta; Pertold, Zdeněk; Přikryl, Richard

2015-04-01

Damaging effect of alkali-silica reaction (ASR) on concrete structures has been observed in various countries all over the World. Civil engineers and real state owners are demanding reliable methods in the assessment of ASR potential of aggregates before they are used in constructions. Time feasible methods are expected, as well as methods which enable prediction of long-term behaviour of aggregates in concrete. The most frequently employed accelerated mortar bar test (AMBT) quantifies ASR potential of aggregates according to the expansion values of mortar bars measured after fourteen days testing period. Current study aimed to develop a new methodical approach facilitating identification and quantification of ASR potential of aggregates. Polished rock sections of quartz and amorphous SiO2 (coming from orthoquartzite, quartz meta-greywacke, pegmatite, phyllite, chert, and flint) were subjected to experimental leaching in 1M NaOH solution at 80°C. After 14 days of alkaline etching, the rock sections were analyzed employing scanning electron microscope combined with energy dispersive spectrometer. Representative areas were documented in back scattered electron (BSE) images and measured using fully-automatic petrographic image analysis (PIA). Several features connected to alkaline etching were observed on the surface of polished rock sections: deep alkaline etching, partial leach-out of quartz and amorphous particles, alkaline etching connected to quartz grain boundaries, and alkaline etching without any connection to grain boundaries. All features mentioned above had significant influence on grey-scale spectrum of BSE images. A specific part of the grey-scale spectrum (i.e. grey-shade 0-70) was characteristic of areas affected by alkaline etching (ASR area). By measuring such areas we quantified the extent of alkaline etching in studied samples. Very good correlation was found between the ASR area and ASR potential of investigated rocks measured according to the

Microfluidic study of fast gas-liquid reactions.

PubMed

Li, Wei; Liu, Kun; Simms, Ryan; Greener, Jesse; Jagadeesan, Dinesh; Pinto, Sascha; Günther, Axel; Kumacheva, Eugenia

2012-02-15

We present a new concept for studies of the kinetics of fast gas-liquid reactions. The strategy relies on the microfluidic generation of highly monodisperse gas bubbles in the liquid reaction medium and subsequent analysis of time-dependent changes in bubble dimensions. Using reactions of CO(2) with secondary amines as an exemplary system, we demonstrate that the method enables rapid determination of reaction rate constant and conversion, and comparison of various binding agents. The proposed approach addresses two challenges in studies of gas-liquid reactions: a mass-transfer limitation and a poorly defined gas-liquid interface. The proposed strategy offers new possibilities in studies of the fundamental aspects of rapid multiphase reactions, and can be combined with throughput optimization of reaction conditions.

Alkaline modified oil shale fly ash: optimal synthesis conditions and preliminary tests on CO2 adsorption.

PubMed

Reinik, Janek; Heinmaa, Ivo; Kirso, Uuve; Kallaste, Toivo; Ritamäki, Johannes; Boström, Dan; Pongrácz, Eva; Huuhtanen, Mika; Larsson, William; Keiski, Riitta; Kordás, Krisztián; Mikkola, Jyri-Pekka

2011-11-30

Environmentally friendly product, calcium-silica-aluminum hydrate, was synthesized from oil shale fly ash, which is rendered so far partly as an industrial waste. Reaction conditions were: temperature 130 and 160°C, NaOH concentrations 1, 3, 5 and 8M and synthesis time 24h. Optimal conditions were found to be 5M at 130°C at given parameter range. Original and activated ash samples were characterized by XRD, XRF, SEM, EFTEM, (29)Si MAS-NMR, BET and TGA. Semi-quantitative XRD and MAS-NMR showed that mainly tobermorites and katoite are formed during alkaline hydrothermal treatment. Physical adsorption of CO(2) on the surface of the original and activated ash samples was measured with thermo-gravimetric analysis. TGA showed that the physical adsorption of CO(2) on the oil shale fly ash sample increases from 0.06 to 3-4 mass% after alkaline hydrothermal activation with NaOH. The activated product has a potential to be used in industrial processes for physical adsorption of CO(2) emissions. Copyright © 2011 Elsevier B.V. All rights reserved.

Electrocatalytic activity and operational stability of electrodeposited Pd-Co films towards ethanol oxidation in alkaline electrolytes

NASA Astrophysics Data System (ADS)

Tsui, Lok-kun; Zafferoni, Claudio; Lavacchi, Alessandro; Innocenti, Massimo; Vizza, Francesco; Zangari, Giovanni

2015-10-01

Direct alkaline ethanol fuel cells (DEFCs) are usually run with Pd anodic catalysts, but their performance can be improved by utilizing alloys of Pd and Co. The oxyphilic Co serves to supply ample -OH to the ethanol oxidation reaction, accelerating the rate limiting step at low overpotential under alkaline conditions. Pd-Co films with compositions between 20 and 80 at% Co can be prepared by electrodeposition from a NH3 complexing electrolyte. Cyclic voltammetry studies show that the ethanol oxidation peak exhibits increasing current density with increasing Co content, reaching a maximum at 77% Co. In contrast, potentiostatic measurements under conditions closer to fuel cell operating conditions show that a 50 at% Co alloy has the highest performance. Importantly, the Co-Pd film is also found to undergo phase and morphological transformations during ethanol oxidation, resulting in a change from a compact film to high surface area flake-like structures containing Co3O4 and CoOOH; such a transformation instead is not observed when operating at a constant potential of 0.7 VRHE.

Experimental and analytical analysis of polarization and water transport behaviors of hydrogen alkaline membrane fuel cell

NASA Astrophysics Data System (ADS)

Huo, Sen; Zhou, Jiaxun; Wang, Tianyou; Chen, Rui; Jiao, Kui

2018-04-01

Experimental test and analytical modeling are conducted to investigate the operating behavior of an alkaline electrolyte membrane (AEM) fuel cell fed by H2/air (or O2) and explore the effect of various operating pressures on the water transfer mechanism. According to the experimental test, the cell performance is greatly improved through increasing the operating pressure gradient from anode to cathode which leads to significant liquid water permeation through the membrane. The high frequency resistance of the A901 alkaline membrane is observed to be relatively stable as the operating pressure varies based on the electrochemical impedance spectroscopy (EIS) method. Correspondingly, based on the modeling prediction, the averaged water content in the membrane electrode assembly (MEA) does not change too much which leads to the weak variation of membrane ohmic resistance. This reveals that the performance enhancement should give the credit to better electro-chemical reaction kinetics for both the anode and cathode, also prone by the EIS results. The reversion of water back diffusion direction across the membrane is also observed through analytical solution.

A New Insight into the Mechanism of NADH Model Oxidation by Metal Ions in Non-Alkaline Media.

PubMed

Yang, Jin-Dong; Chen, Bao-Long; Zhu, Xiao-Qing

2018-06-11

For a long time, it has been controversial that the three-step (e-H+-e) or two-step (e-H•) mechanism was used for the oxidations of NADH and its models by metal ions in non-alkaline media. The latter mechanism has been accepted by the majority of researchers. In this work, 1-benzyl-1,4-dihydronicotinamide (BNAH) and 1-phenyl-l,4-dihydronicotinamide (PNAH) are used as NADH models, and ferrocenium (Fc+) metal ion as an electron acceptor. The kinetics for oxidations of the NADH models by Fc+ in pure acetonitrile were monitored by using UV-Vis absorption and quadratic relationship between of kobs and the concentrations of NADH models were found for the first time. The rate expression of the reactions developed according to the three-step mechanism is quite consistent with the quadratic curves. The rate constants, thermodynamic driving forces and KIEs of each elementary step for the reactions were estimated. All the results supported the three-step mechanism. The intrinsic kinetic barriers of the proton transfer from BNAH+• to BNAH and the hydrogen atom transfer from BNAH+• to BNAH+• were estimated, the results showed that the former is 11.8 kcal/mol, and the latter is larger than 24.3 kcal/mol. It is the large intrinsic kinetic barrier of the hydrogen atom transfer that makes the reactions choose the three-step rather than two-step mechanism. Further investigation of the factors affecting the intrinsic kinetic barrier of chemical reactions indicated that the large intrinsic kinetic barrier of the hydrogen atom transfer originated from the repulsion of positive charges between BNAH+• and BNAH+•. The greatest contribution of this work is the discovery of the quadratic dependence of kobs on the concentrations of the NADH models, which is inconsistent with the conventional viewpoint of the "two-step mechanism" on the oxidations of NADH and its models by metal ions in the non-alkaline media.

40 CFR 434.40 - Applicability; description of the alkaline mine drainage subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... alkaline mine drainage subcategory. 434.40 Section 434.40 Protection of Environment ENVIRONMENTAL... BPT, BAT, BCT LIMITATIONS AND NEW SOURCE PERFORMANCE STANDARDS Alkaline Mine Drainage § 434.40 Applicability; description of the alkaline mine drainage subcategory. The provisions of this subpart are...

40 CFR 434.40 - Applicability; description of the alkaline mine drainage subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... alkaline mine drainage subcategory. 434.40 Section 434.40 Protection of Environment ENVIRONMENTAL... BPT, BAT, BCT LIMITATIONS AND NEW SOURCE PERFORMANCE STANDARDS Alkaline Mine Drainage § 434.40 Applicability; description of the alkaline mine drainage subcategory. The provisions of this subpart are...

40 CFR 434.40 - Applicability; description of the alkaline mine drainage subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... alkaline mine drainage subcategory. 434.40 Section 434.40 Protection of Environment ENVIRONMENTAL... BPT, BAT, BCT LIMITATIONS AND NEW SOURCE PERFORMANCE STANDARDS Alkaline Mine Drainage § 434.40 Applicability; description of the alkaline mine drainage subcategory. The provisions of this subpart are...

40 CFR 434.40 - Applicability; description of the alkaline mine drainage subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... alkaline mine drainage subcategory. 434.40 Section 434.40 Protection of Environment ENVIRONMENTAL..., BCT LIMITATIONS AND NEW SOURCE PERFORMANCE STANDARDS Alkaline Mine Drainage § 434.40 Applicability; description of the alkaline mine drainage subcategory. The provisions of this subpart are applicable to...

40 CFR 434.40 - Applicability; description of the alkaline mine drainage subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... alkaline mine drainage subcategory. 434.40 Section 434.40 Protection of Environment ENVIRONMENTAL..., BCT LIMITATIONS AND NEW SOURCE PERFORMANCE STANDARDS Alkaline Mine Drainage § 434.40 Applicability; description of the alkaline mine drainage subcategory. The provisions of this subpart are applicable to...

Orogenic potassic mafic magmatism, a product of alkaline-peraluminous mixing ? Variscan 'calc-alkaline' rocks from the Central Iberian and Ossa Morena Zones, Central Spain.