Effect of nucleoside analogue antimetabolites on the structure of PEO–PPO–PEO micelles investigated by SANS

DOE PAGES

Han, Youngkyu; Zhang, Zhe; Smith, Gregory S.; ...

2017-04-19

In this work, the effect of three nucleoside analogue antimetabolites (5-fluorouracil, floxuridine, and gemcitabine) on the structure of Pluronic L62 copolymer micelles was investigated using small-angle neutron scattering. These antimetabolites used for cancer chemotherapy have analogous molecular structures but different molecular sizes and aqueous solubilities. It was found that the addition of the three antimetabolites slightly reduced the micellar size and aggregation number, and the micellar anisotropy. The added antimetabolites also changed the internal molecular distribution of the micelles as measured by the scattering length densities, resulting in enhanced hydration of the hydrophobic core region of the micelle. The strengthmore » of the effect was found to correlate with the molecular properties of the model drugs, i.e. a larger molecular size and a higher aqueous solubility lead to enhanced hydration of the micellar core.« less

Evaporation for Lithium Bromide Aqueous Solution in a Falling Film Heater under Reduced Pressures

NASA Astrophysics Data System (ADS)

Matsuda, Akira; Ide, Tetsuo; Yukino, Keiji

Experiments on evaporation for water and lithium bromide (LiBr) aqueous solution were made in a externally heated wetted-wall column under reduced pressures. For water, evaporation rate increased slightly as feed rate decreased. The heat transfer coefficients of falling film agreed with those for filmwise condensation. For LiBr solution, evaporation rate decreased and outlet temperature of LiBr solution increased as feed rate decreased. The equations of continuity, diffusion and energy which assume that only water moves to the surface and LiBr doesn't move through falling film of LiBr solution were solved numerically. Calculated values of evaporation rate and outlet temperature of solution agreed with experimental results. The results of this work were compared with pool boiling data reported previously, and it was shown that falling film heater is superior to pool boiling heater concerning heat transfer.

Effect of nucleoside analogue antimetabolites on the structure of PEO–PPO–PEO micelles investigated by SANS

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

Han, Youngkyu; Zhang, Zhe; Smith, Gregory S.

2017-01-01

The effect of three nucleoside analogue antimetabolites (5-fluorouracil, floxuridine, and gemcitabine) on the structure of Pluronic L62 copolymer micelles was investigated using small-angle neutron scattering. These antimetabolites used for cancer chemotherapy have analogous molecular structures but different molecular sizes and aqueous solubilities. It was found that the addition of the three antimetabolites slightly reduced the micellar size and aggregation number, and the micellar anisotropy. The added antimetabolites also changed the internal molecular distribution of the micelles as measured by the scattering length densities, resulting in enhanced hydration of the hydrophobic core region of the micelle. The strength of the effectmore » was found to correlate with the molecular properties of the model drugs, i.e. a larger molecular size and a higher aqueous solubility lead to enhanced hydration of the micellar core.« less

Synthesis of peptides from amino acids and ATP with lysine-rich proteinoid

NASA Technical Reports Server (NTRS)

Nakashima, T.; Fox, S. W.

1980-01-01

The paper examines the synthesis of peptides from aminoacids and ATP with a lysine-rich protenoid. The latter in aqueous solution catalyzes the formation of peptides from free amino acids and ATP; this catalytic activity is not found in acidic protenoids, even though the latter contain a basic aminoacid. The pH optimum for the synthesis is about 11, but it is appreciable below 8 and above 13. Temperature data indicate an optimum at 20 C or above, with little increase in rate up to 60 C. Pyrophosphate can be used instead of ATP, but the yields are lower. The ATP-aided syntheses of peptides in aqueous solution occur with several types of proteinous aminoacids.

Efficient solar-assisted O2 reduction by a cofacial iron porphyrin dimer integrated to a p-CuBi2O4 photocathode prepared by a simple novel method.

PubMed

Zahran, Zaki N; Mohamed, Eman A; Naruta, Yoshinori; Haleem, Ashraf

2017-10-04

A cofacial iron porphyrin hetero-dimer, Fe2TPFPP-TMP showed high electro-catalytic activity, selectivity, and stability for the O2 reduction to H2O both in homogeneous non-aqueous and heterogeneous neutral aqueous solutions. Moreover, when it is integrated to FTO/p-CuBi2O4 (FTO = fluorine doped tin oxide) photocathode prepared by a simple novel method, a remarkable efficient solar-assisted O2 reduction is achieved in neutral potassium phosphate (KPi) or basic NaOH solutions saturated with O2. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Great Salt Lake Composition and Rare Earth Speciation Analysis

DOE Data Explorer

Jiao, Yongqin; Lammers, Laura; Brewer, Aaron

2017-04-19

We have conducted aqueous speciation analyses of the Great Salt Lake (GSL) brine sample (Table 1) and a mock geo sample (Table 2) spiked with 1 ppb Tb and 100 ppb Tb. The GSL speciation (Figure 1) aligns with our basic speciation expectations that strong carbonate complexes would form at mid to higher pH's. Although we expected strong aqueous complexes with fluorides at neutral pH and with chlorides, and hydroxides at low pH, we observe that the dominant species in the low to mid pH range to be Tb3+ as a free ion. Still, we do see the presence of fluoride and chloride complexes within the expected low to mid pH range.

Sustainable Carbon/Carbon Supercapacitors Operating Down to -40 °C in Aqueous Electrolyte Made with Cholinium Salt.

PubMed

Abbas, Qamar; Béguin, François

2018-03-09

Cholinium chloride at a concentration of 5 mol kg -1 in water is proposed as a low-cost and environmentally friendly aqueous electrolyte, enabling extension of the operating range of carbon/carbon supercapacitors (SCs) down to -40 °C. This solution has a pH close to neutrality (pH 6.1) and high conductivity of 88 mS cm -1 at 24 °C. The supercapacitors demonstrate a high capacitance of 126 F g -1 (per mass of one electrode) and long life span at voltages up to 1.5 V. At -40 °C, the carbon/carbon SCs display excellent electrochemical characteristics with only slightly reduced capacitance of 106 F g -1 and negligible ohmic losses. As compared to previous works, where antifreezing additives were introduced in traditional neutral electrolytes, the low solubility of the salt and related poor conductivity of the solution is no longer an issue, which makes cholinium salt aqueous solutions very promising for SCs operating at sub-ambient temperature conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Transformation Regularity of Nitrogen in Aqueous Product Derived from Hydrothermal Liquefaction of Sewage Sludge in Subcritical Water].

PubMed

Sun, Yan-qing; Sun, Zhen; Zhang, Jing-lai

2015-06-01

Hydrothermal liquefaction in subcritical water is a potential way to treat sewage sludge as a resource rather than a waste. This study focused on the transformation regularity of nitrogen in aqueous product which was derived from hydrothermal liquefaction of sewage sludge under different operating conditions. Results showed, within the studied temperature scope and time span, the concentration of total nitrogen (TN) fluctuated in the range of 2867.62 mg x L(-1) to 4171.30 mg x L(-1). The two major exiting formation of nitrogen in aqueous product was ammonia nitrogen (NH4+ -N) and organic nitrogen (Org-N). NH4+ -N possessed 54.6%-90.7% of TN, while Org-N possessed 7.4%-44.5%. The concentration of nitrate nitrogen (NO- -N) was far more less than NH4+ -N and Org-N. Temperature had a great influence on the transformation regularity of nitrogen. Both the concentration of TN and Org-N increased accordingly to the increase of reaction temperature. With the reaction time prolonging, the concentration of TN and Org-N increased, while the concentration of NH4+ -N increased first, then became stationary, and then decreased slightly.

Ni-Fe2O4 nanoparticles as contrast agents for magnetic resonance imaging.

PubMed

Ahmad, Tanveer; Rhee, Ilsu; Hong, Sungwook; Chang, Yongmin; Lee, Jaejun

2011-07-01

Reported herein is the synthesis of a dextran coating on nickel ferrite (Ni-Fe2O4) nanoparticles via chemical coprecipitation. The aqueous solution of the synthesized nanoparticles showed good colloidal stability, and no precipitate was observed 20 months after the synthesis. The coated nanoparticles were found to be cylindrical in shape in the TEM images, and showed a uniform size distribution with an average length and diameter of 17 and 4 nm, respectively. The coated particles were evaluated as potential T1 and T2 contrast agents for MRI. The T1 and T2 relaxations of the hydrogen protons in the water molecules in an aqueous solution of dextran-coated Ni-Fe2O4 nanoparticles were studied. It was found that the T1 relaxivity for the aqueous solution of dextran-coated nanoparticles was slightly greater than that of a commercial Gd-DTPA-BMA contrast agent. The T2 relaxivity, however, was almost twice that of the commercial Gd-DTPA-BMA contrast agent. Animal experimentation also demonstrated that the dextran-coated Ni-Fe2O4 nanoparticles are suitable for use as either T1 or T2 contrast agents in MRI.

Efficacy of bait supplements for improving the rate of discovery of bait stations in the field by formosan subterranean termites (Isoptera: Rhinotermitidae).

PubMed

Cornelius, Mary L; Lyn, Margaret; Williams, Kelley S; Lovisa, Mary P; De Lucca, Anthony J; Lax, Alan R

2009-06-01

Field tests of four different bait supplements were conducted in City Park, New Orleans, LA. The four bait supplements tested included two different formulations of decayed material, a sports drink, and the combination of an application of an aqueous solution of Summon Preferred Food Source disks with the disk itself. Although all the bait supplements in this study resulted in a slightly greater number of treated stations discovered compared with control stations, only the application of the aqueous solution combined with the disk caused a significant increase in the number of stations discovered by termites. This treatment resulted in a significantly greater rate of discovery of treated stations versus control stations after only 14 d in the field. Termites were able to discover six times as many treated as control stations after 14 d, 9 times as many after 28 d, and 12 times as many after 42 d. These findings provide evidence that the diffusion of an aqueous solution into the soil underneath monitoring stations significantly decreased the length of time required for termites to infest stations.

Total flavonoids content in the raw material and aqueous extractives from Bauhinia monandra Kurz (Caesalpiniaceae).

PubMed

Fernandes, Ana Josane Dantas; Ferreira, Magda Rhayanny Assunção; Randau, Karina Perrelli; de Souza, Tatiane Pereira; Soares, Luiz Alberto Lira

2012-01-01

The aim of this work was to evaluate the spectrophotometric methodology for determining the total flavonoid content (TFC) in herbal drug and derived products from Bauhinia monandra Kurz. Several analytical parameters from this method grounded on the complex formed between flavonoids and AlCl₃ were evaluated such as herbal amount (0.25 to 1.25 g); solvent composition (ethanol 40 to 80%, v/v); as well as the reaction time and AlCl₃ concentration (2 to 9%, w/v). The method was adjusted to aqueous extractives and its performance studied through precision, linearity and preliminary robustness. The results showed an important dependence of the method response from reaction time, AlCl₃ concentration, sample amount, and solvent mixture. After choosing the optimized condition, the method was applied for the matrixes (herbal material and extractives), showing precision lower than 5% (for both parameters repeatability and intermediate precision), coefficient of determination higher than 0.99, and no important influence could be observed for slight variations from wavelength or AlCl₃ concentration. Thus, it could be concluded that the evaluated analytical procedure was suitable to quantify the total flavonoid content in raw material and aqueous extractives from leaves of B. monandra.

Chemical modification of wood

Treesearch

Roger M. Rowell

2007-01-01

After millions of years of evolution, wood was designed to perform in a wet environment, and nature is programmed to recycle it, in a timely way, back to the basic building blocks of carbon dioxide and water through biological, thermal, aqueous, photochemical, chemical, and mechanical degradation. The properties of wood are, for the most part, a result of the chemistry...

A Visual Aid for Teaching Basic Concepts of Soil-Water Physics.

ERIC Educational Resources Information Center

Eshel, Amram

1997-01-01

Presents a visual aid designed to generate an image of water movement among soil particles using an overhead projector to teach the physical phenomena related to water status and water movement in the soil. Utilizes a base plate of thin transparent plastic, opaque plastic sheets, a plate of glass, and a colored aqueous solution. (AIM)

Substitutions mimicking deimination and phosphorylation of 18.5-kDa myelin basic protein exert local structural effects that subtly influence its global folding.

PubMed

Vassall, Kenrick A; Bamm, Vladimir V; Jenkins, Andrew D; Velte, Caroline J; Kattnig, Daniel R; Boggs, Joan M; Hinderberger, Dariush; Harauz, George

2016-06-01

Intrinsically-disordered proteins (IDPs) present a complex interplay of conformational variability and multifunctionality, modulated by environment and post-translational modifications. The 18.5-kDa myelin basic protein (MBP) is essential to the formation of the myelin sheath of the central nervous system and is exemplary in this regard. We have recently demonstrated that the unmodified MBP-C1 component undergoes co-operative global conformational changes in increasing concentrations of trifluoroethanol, emulating the decreasing dielectric environment that the protein encounters upon adsorption to the oligodendrocyte membrane [K.A. Vassall et al., Journal of Molecular Biology, 427, 1977-1992, 2015]. Here, we extended this study to the pseudo-deiminated MBP-C8 charge component, one found in greater proportion in developing myelin and in multiple sclerosis. A similar tri-conformational distribution as for MBP-C1 was observed with slight differences in Gibbs free energy. A more dramatic difference was observed by cathepsin D digestion of the protein in both aqueous and membrane environments, which showed significantly greater accessibility of the F42-F43 cut site of MBP-C8, indicative of a global conformational change. In contrast, this modification caused little change in the protein's density of packing on myelin-mimetic membranes as ascertained by double electron-electron resonance spectroscopy [D.R. Kattnig et al., Biochimica et Biophysica Acta (Biomembranes), 1818, 2636-2647, 2012], or in its affinity for Ca(2+)-CaM. Site-specific threonyl pseudo-phosphorylation at residues T92 and/or T95 did not appreciably affect any of the thermodynamic mechanisms of conformational transitions, susceptibility to cathepsin D, or affinity for Ca(2+)-CaM, despite previously having been shown to affect local structure and disposition on the membrane surface. Copyright © 2016 Elsevier B.V. All rights reserved.

THE INFLUENCE OF THE CHEMICAL NATURE OF SOLID PARTICLES ON THEIR CATAPHORETIC P.D. IN AQUEOUS SOLUTIONS

PubMed Central

Loeb, Jacques

1923-01-01

1. The effect of eight salts, NaCl, Na2SO4, Na4Fe(CN)6, CaCl2, LaCl3, ThCl4, and basic and acid fuchsin on the cataphoretic P.D. between solid particles and aqueous solutions was measured near the point of neutrality of water (pH 5.8). It was found that without the addition of electrolyte the cataphoretic P.D. between particles and water is very minute near the point of neutrality (pH 5.8), often less than 10 millivolts, if care is taken that the solutions are free from impurities. Particles which in the absence of salts have a positive charge in water near the point of neutrality (pH 5.8) are termed positive colloids and particles which have a negative charge under these conditions are termed negative colloids. 2. If care is taken that the addition of the salt does not change the hydrogen ion concentration of the solution (which in these experiments was generally pH 5.8) it can be said in general, that as long as the concentration of salts is not too high, the anions of the salt have the tendency to make the particles more negative (or less positive) and that cations have the opposite effect; and that both effects increase with the increasing valency of the ions. As soon as a maximal P.D. is reached, which varies for each salt and for each type of particles, a further addition of salt depresses the P.D. again. Aside from this general tendency the effects of salts on the P.D. are typically different for positive and negative colloids. 3. Negative colloids (collodion, mastic, Acheson's graphite, gold, and metal proteinates) are rendered more negative by low concentrations of salts with monovalent cation (e.g. Na) the higher the valency of the anion, though the difference in the maximal P.D. is slight for the monovalent Cl and the tetravalent Fe(CN)6 ions. Low concentrations of CaCl2 also make negative colloids more negative but the maximal P.D. is less than for NaCl; even LaCl3 increases the P.D. of negative particles slightly in low concentrations. ThCl4 and basic fuchsin, however, seem to make the negative particles positive even in very low concentrations. 4. Positive colloids (ferric hydroxide, calcium oxalate, casein chloride—the latter at pH 4.0) are practically not affected by NaCl, are rendered slightly negative by high concentrations of Na2SO4, and are rendered more negative by Na4Fe(CN)6 and acid dyes. Low concentrations of CaCl2 and LaCl3 increase the positive charge of the particles until a maximum is reached after which the addition of more salt depresses the P.D. again. 5. It is shown that alkalies (NaOH) act on the cataphoretic P.D. of both negative and positive particles as Na4Fe(CN)6 does at the point of neutrality. 6. Low concentrations of HCl raise the cataphoretic P.D. of particles of collodion, mastic, graphite, and gold until a maximum is reached, after which the P.D. is depressed by a further increase in the concentration of the acid. No reversal in the sign of charge of the particle occurs in the case of collodion, while if a reversal occurs in the case of mastic, gold, and graphite, the P.D. is never more than a few millivolts. When HCl changes the chemical nature of the colloid, e.g. when HCl is added to particles of amphoteric electrolytes like sodium gelatinate, a marked reversal will occur, on account of the transformation of the metal proteinate into a protein-acid salt. 7. A real reversal in the sign of charge of positive particles occurs, however, at neutrality if Na4Fe(CN)6 or an acid dye is added; and in the case of negative colloids when low concentrations of basic dyes or minute traces of ThCl4 are added. 8. Flocculation of the suspensions by salts occurs when the cataphoretic P.D. reaches a critical value which is about 14 millivolts for particles of graphite, gold, or mastic or denatured egg albumin; while for collodion particles it was about 16 millivolts. A critical P.D. of about 15 millivolts was also observed by Northrop and De Kruif for the flocculation of certain bacteria. PMID:19872064

Geochemical Interaction of Middle Bakken Reservoir Rock and CO2 during CO2-Based Fracturing

NASA Astrophysics Data System (ADS)

Nicot, J. P.; Lu, J.; Mickler, P. J.; Ribeiro, L. H.; Darvari, R.

2015-12-01

This study was conducted to investigate the effects of geochemical interactions when CO2 is used to create the fractures necessary to produce hydrocarbons from low-permeability Middle Bakken sandstone. The primary objectives are to: (1) identify and understand the geochemical reactions related to CO2-based fracturing, and (2) assess potential changes of reservoir property. Three autoclave experiments were conducted at reservoir conditions exposing middle Bakken core fragments to supercritical CO2 (sc-CO2) only and to CO2-saturated synthetic brine. Ion-milled core samples were examined before and after the reaction experiments using scanning electron microscope, which enabled us to image the reaction surface in extreme details and unambiguously identify mineral dissolution and precipitation. The most significant changes in the reacted rock samples exposed to the CO2-saturated brine is dissolution of the carbonate minerals, particularly calcite which displays severely corrosion. Dolomite grains were corroded to a lesser degree. Quartz and feldspars remained intact and some pyrite framboids underwent slight dissolution. Additionally, small amount of calcite precipitation took place as indicated by numerous small calcite crystals formed at the reaction surface and in the pores. The aqueous solution composition changes confirm these petrographic observations with increase in Ca and Mg and associated minor elements and very slight increase in Fe and sulfate. When exposed to sc-CO2 only, changes observed include etching of calcite grain surface and precipitation of salt crystals (halite and anhydrite) due to evaporation of residual pore water into the sc-CO2 phase. Dolomite and feldspars remained intact and pyrite grains were slightly altered. Mercury intrusion capillary pressure tests on reacted and unreacted samples shows an increase in porosity when an aqueous phase is present but no overall porosity change caused by sc-CO2. It also suggests an increase in permeability in the former case and possibly a minor decrease in the latter case.

Hematin crystallization from aqueous and organic solvents

NASA Astrophysics Data System (ADS)

Ketchum, Megan A.; Olafson, Katy N.; Petrova, Elena V.; Rimer, Jeffrey D.; Vekilov, Peter G.

2013-09-01

Hematin crystallization is the main mechanism of detoxification of heme that is released in malaria-infected erythrocytes as a byproduct of the hemoglobin catabolism by the parasite. A controversy exists over whether hematin crystals grow from the aqueous medium of the parasite's digestive vacuole or in the lipid bodies present in the vacuole. To this end, we compare the basic thermodynamic and structural features of hematin crystallization in an aqueous buffer at pH 4.8, as in the digestive vacuole, and in water-saturated octanol that mimics the environment of the lipid nanospheres. We show that in aqueous solutions, hematin aggregation into mesoscopic disordered clusters is insignificant. We determine the solubility of the β-hematin crystals in the pH range 4.8-7.6. We image by atomic force microscopy crystals grown at pH 4.8 and show that their macroscopic and mesoscopic morphology features are incompatible with those reported for biological hemozoin. In contrast, crystals grown in the presence of octanol are very similar to those extracted from parasites. We determine the hematin solubility in water-saturated octanol at three temperatures. These solubilities are four orders of magnitude higher than that at pH 4.8, providing for faster crystallization from organic than from aqueous solvents. These observations further suggest that the lipid bodies play a role in mediating biological hemozoin crystal growth to ensure faster heme detoxification.

Study on the interaction of graphene oxide‑silver nanocomposites with bovine serum albumin and the formation of nanoparticle-protein corona.

PubMed

Xu, Xiangyu; Mao, Xuyan; Wang, Yunfei; Li, Dandan; Du, Zhongyu; Wu, Weihua; Jiang, Liang; Yang, Jie; Li, Jianjun

2018-05-09

The interaction between graphene oxide-sliver nanocomposites (GO-AgNCPs) and bovine serum albumin (BSA) in aqueous buffer solution was investigated by using several spectroscopic and imaging techniques. The visible absorbance intensity of GO-AgNCPs increased with increasing concentrations of BSA, and a slight redshift of the surface plasmon resonance band (SPR) occurred due to the absorption of BSA on the surface of GO-AgNCPs. Fluorescence data revealed a static quenching process of BSA caused by GO-AgNCPs. Thermodynamic parameters of the absorption process, including adsorption equilibrium constants, changes in Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS), were evaluated at different temperatures. Negative values of ΔG showed that this process was spontaneous and the BSA-GO-AgNCPs complex might form in aqueous solution. Negative values of ΔH and ΔS suggested that the binding was mainly an enthalpy-driven process, and van der Waals forces and hydrogen bonding were the major force in the formation of the nanoparticle-protein corona. Analysis of synchronous, three dimensional (3D) fluorescence and circular dichroism (CD) spectra demonstrated that the conformation of BSA was slightly altered in the presence of GO-AgNCPs. The protein corona formed on the surface of GO-AgNCPs was directly observed by scanning probe microscopy (SPM). Copyright © 2018 Elsevier B.V. All rights reserved.

Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.

PubMed Central

Huang, T M; Hung, H C; Chang, T C; Chang, G G

1998-01-01

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles. PMID:9461520

Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.

PubMed

Huang, T M; Hung, H C; Chang, T C; Chang, G G

1998-02-15

Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles.

Aqueous corrosion and corrosion-sensitive embrittlement of Fe{sub 3}Al-based and lean-aluminum iron aluminides

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

Kim, J.G.; Buchanan, R.A.

Aqueous corrosion and corrosion-sensitive embrittlement of iron aluminides were characterized as functions of environment, alloying content, notch sensitivity, and strain rate. Polarization resistance and cyclic anodic polarization evaluations were performed in 3.5 wt % NaCl, 200 ppM Cl{sup {minus}} (pH = 4), and 1 N NaOH solutions. In the mild acid-chloride solution [200 ppM Cl{sup {minus}} (pH = 4)], the pitting-corrosion resistance of the new lean-aluminum iron aluminides (FAP-Y and CM-Mo) was comparable to that of the Fe{sub 3}Al-based FAL-Mo. In the higher-chloride 3.5 wt % NaCl, the resistance of CM-Mo was slightly less but FAP-Y showed quite similar behaviormore » to FAL-Mo. In 1 N NaOH solution, all materials exhibited ideal passive behavior. Under slow-strain-rate test conditions in the mild acid-chloride electrolyte, prior work had shown the ductilities (% elongations) of Fe{sub 3}Al-based materials to be {approximately}7% and {approximately}1% at the freely-corroding and hydrogen-charging potentials, respectively. Present studied on the lean-aluminum materials have shown the ductilities to be {approximately}17% and {approximately}5%, respectively. Thus, the present results indicate that these new materials have reasonably-good aqueous-corrosion properties in chloride environments and significantly-enhanced ductilities under aqueous corrosion conditions. The strain rate and notch sensitivities of high-aluminum iron aluminide (FA-129) were investigated by performing slow-strain-rate tests. The notch sensitivity was independent of strain rate and the notch sensitivity in the aqueous environment was similar to that in air.« less

Numerous Connections.

ERIC Educational Resources Information Center

Western Sydney Inst. of TAFE, Blacktown (Australia).

This resource includes units of work developed by different practitioners that integrate the teaching of literacy with the teaching of numeracy in adult basic education. It is designed to provide models of integration for teachers to develop similar resources on different contexts or themes. The units follow slightly different formats. Unit…

Gastroprotective and ulcer healing effects of Piptadeniastrum Africanum on experimentally induced gastric ulcers in rats.

PubMed

Ateufack, Gilbert; Domgnim Mokam, Elisabeth Carol; Mbiantcha, Marius; Dongmo Feudjio, Rostand Breuil; David, Nana; Kamanyi, Albert

2015-07-08

Gastric peptic ulcer is one of the common disorders of gastrointestinal tract, which occur due to an imbalance between the offensive and defensive factors. It is an illness that affects a considerable number of people worldwide. This study was conducted to evaluate the antiulcerogenic and antiulcer effects and recognize the basic mechanism of action of Piptadeniastrum africanum stem bark extracts. The aqueous and methanol extracts of Piptadeniastrum africanum were administered at the doses 125, 250 and 500 mg/kg to evaluate their effects on gastric ulcer induced by the HCl/ethanol mixture, indomethacin and acetic acid in Wistar strain male adult rats, aged between 12 and 16 weeks and weighing between 180 and 220 g. Ranitidine, Maalox and Misoprostol were used as standard drugs. Histopathological examination and nitric oxide level were performed to evaluate the basic mechanism of action of Piptadeniastrum africanum. Phytochemical screening was carried out to identify known phytochemicals present in these extracts. The aqueous and methanol extracts of stem bark of Piptadeniastrum africanum significantly inhibited (p < 0.01) gastric ulceration induced by HCl/ethanol to the percentages of inhibition of 81.38; 98.75 and 100 % for the aqueous extract and then 75.83, 89.76 and 96.52 % for the methanol extract, and with the Indomethacin-induced ulcers, aqueous and methanol extracts of bark of Piptadeniastrum africanum reduce significantly (p < 0.01) induced gastric lesions in rats, with percentage of cure 35.75; 52.33 and 98.58 % for the aqueous extract, and 33.7; 51.97; and 65.93 to the methanol extract. The results revealed a significant reduction of ulcerated surface in both extracts and increase of nitric oxide (NO) level with methanol extract. When compared to methanol extract, aqueous extract showed more pronounced effects, corresponding to percentages of healing of 59. 92; 84.12 and 59.65 % for the aqueous extract; and 70.43; 55.49 and 57.59 % for the methanol extract in the ulcer induced by acetic acid, all at the respective doses of 125, 250 and 500 mg/kg. Histopathological observations also demonstrated curative effect. As such, both extracts were found to exhibit preventive and curative effects through the release of NO and growth factors. This could also be due to the presence of phytochemicals such as alkaloids, flavonoids, phenols and saponins which act as antisecretory agents. Piptadeniastrum africanum stem bark extracts thus have gastroprotective and ulcer healing effects, which could result from their activities by stimulating important cellular mechanisms such as migration and proliferation of epithelial cells that may have a cytoprotective effect by stimulating the release of prostaglandins. These results are required to confirm the ethnopharmacological use of Piptadeniastrum africanum stem bark in the treatment of ulcer.

Effect of solute nature on the polyamorphic transition in glassy polyol aqueous solutions.

PubMed

Suzuki, Yoshiharu

2017-08-14

I examined the polyamorphic behavior of glassy dilute aqueous solutions of polyols (ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol) under pressure at low temperatures. Although the volume change of the glassy aqueous solution varied continuously against pressure, the rate of the volume change appeared to vary discontinuously at the onset pressure of the gradual polyamorphic transition. It is thought that low-density liquid-like solvent water and high-density liquid-like solvent water coexist during the transition. Moreover, the existence of a solute induces the shift of polyamorphic transition to the lower-pressure side. The effect of a solute on the polyamorphic transition becomes larger in the order ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol. Therefore, the solute can become a variable controlling the polyamorphic state of liquid water. This experimental result suggests that the metastable-equilibrium phase boundary between the low-density and the high-density amorphs for pure water is likely to be located at 0.22-0.23 GPa at about 150 K, which is slightly larger than the previously estimated pressure. Moreover, the solute-nature dependence on the polyamorphic transition seems to connect to that on the homogeneous nucleation temperature of polyol aqueous solution at ambient pressure. The region in which a low-density liquid appears coincides with the region in which the nucleus of ice Ih appears, suggesting that the formation of a low-density liquid is a precursory phenomenon of the nucleation of ice Ih.

Penetration, permeation, and resorption of 8-methoxypsoralen. Comperative in vitro and in vivo studies after topical application of four standard preparations.

PubMed

Kammerau, B; Klebe, U; Zesch, A; Schaefer, H

1976-03-10

The penetration, permeation, and resorption of radioactively labelled 8-Methoxypsoralen was investigated in human skin. Siultaneously, the effects to time and ointment carrier on the penetration kinetics were ascertained. The carriers tested were: vaseline, aqueous wool-wax alcohol ointment, aqueous hydrophilic ointment and polyethylene glycol ointment. The absolute concentrations of 8-Methoxypsoralen were estimated in the horny layer, epidermis and dermis. With the most advantageous carrier, aqueous wool-wax alcohol ointment, 4-6X10(-5) M and 10(-5) M were attained in the epidermis and dermis, respectively. Moreover, it was shown that the substance penetrates rapidly (10 min) into the epidermis and dermis and the high concentrations reached constant over a period of 16 h. Only with a formulation of aqueous wool-wax alcohols is any accumulation at all achieved in the deeper areas of the horny layer. A uniform decrease in drug concentration with increasing depth of the horny layer is found with the other 3 vehicles, whereby slight variations in concentrations pertain from carrier to carrier. 4 h after local application, 8-Methoxypsoralen can be detected in the urine. Regardless of the ointment base employed, 8-Methoxypsoralen is no longer detectable in the urine 40 h after application. In comparison to the oral therapy, the same magnitude of percutaneous resorption into the central compartment is to be derived from the data, if half the body surface is treated locally.

Effect of Hibiscus sabdariffa and its anthocyanins on some reproductive aspects in rats.

PubMed

Ali, Badreldin H; Al-Lawati, Intisar; Beegam, Sumyia; Ziada, Amal; Al Salam, Suhail; Nemmar, Abderrahim; Blunden, Gerald

2012-01-01

An aqueous extract of Hibiscus sabdariffa L. is a common beverage in many parts of the world. Reports on its effect on reproduction are conflicting, with anecdotal evidence that the plant is an aphrodisiac, while others report that it is estrogenic, and adversely affects spermatogenesis in rats. We have studied the effect of different concentrations of aqueous extracts of H. sabdariffa calyces (10%, 15% and 20%) used as drinking water for 10 consecutive weeks, and its anthocyanins (50, 100, 200 mg/kg for 5 days, orally) on the weight and histology of the testis, and on some biochemical constituents in testicular homogenates, in addition to the plasma concentrations of testosterone, luteinizing hormone and estradiol. The possible presence of an estrogenic effect of the extract and anthocyanins on the uteri of immature female rats was also tested. Neither the H. sabdariffa extract nor the anthocyanins significantly altered either testicular weight and histology, or uterus weight. Plasma concentrations of the three hormones studied, the testicular concentrations of protein, reduced glutathione and total cholesterol, and superoxide dismutase activity were all insignificantly affected by either the extract or the anthocyanins, except for a slight, but statistically significant, decrease in testicular protein concentration caused by the 15% aqueous extract when compared with controls. These results suggest that H. sabdariffa exerts no adverse effect on the male reproductive system. Consumption of H. sabdariffa aqueous extract inhibited the growth of the rats compared with the controls.

Effect of solute nature on the polyamorphic transition in glassy polyol aqueous solutions

NASA Astrophysics Data System (ADS)

Suzuki, Yoshiharu

2017-08-01

I examined the polyamorphic behavior of glassy dilute aqueous solutions of polyols (ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol) under pressure at low temperatures. Although the volume change of the glassy aqueous solution varied continuously against pressure, the rate of the volume change appeared to vary discontinuously at the onset pressure of the gradual polyamorphic transition. It is thought that low-density liquid-like solvent water and high-density liquid-like solvent water coexist during the transition. Moreover, the existence of a solute induces the shift of polyamorphic transition to the lower-pressure side. The effect of a solute on the polyamorphic transition becomes larger in the order ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol. Therefore, the solute can become a variable controlling the polyamorphic state of liquid water. This experimental result suggests that the metastable-equilibrium phase boundary between the low-density and the high-density amorphs for pure water is likely to be located at 0.22-0.23 GPa at about 150 K, which is slightly larger than the previously estimated pressure. Moreover, the solute-nature dependence on the polyamorphic transition seems to connect to that on the homogeneous nucleation temperature of polyol aqueous solution at ambient pressure. The region in which a low-density liquid appears coincides with the region in which the nucleus of ice Ih appears, suggesting that the formation of a low-density liquid is a precursory phenomenon of the nucleation of ice Ih.

Extraction and separation of tungsten (VI) from aqueous media with Triton X-100-ammonium sulfate-water aqueous two-phase system without any extractant.

PubMed

Yongqiang Zhang; Tichang Sun; Tieqiang Lu; Chunhuan Yan

2016-11-25

An aqueous two-phase system composed of Triton X-100-(NH 4 ) 2 SO 4 -H 2 O was proposed for extraction and separation of tungsten(VI) from aqueous solution without using any extractant. The effects of aqueous pH, concentration of ammonium sulfate, Triton X-100 and tungsten, extracting temperature on the extraction of tungsten were investigated. The extraction of tungsten has remarkable relationship with aqueous pH and are to above 90% at pH=1.0-3.0 under studied pH range (pH=1.0-7.0) and increases gradually with increasing Triton X-100 concentration, but decreases slightly with increasing ammonium sulfate concentration. The extraction percentage of tungsten is hardly relevant to temperature but its distribution coefficient linearly increases with increasing temperature within 303.15-343.15K. The distribution coefficient of tungsten increases with the increase of initial tungsten concentration (0.1-3%) and temperature (303.15 K-333.15K). The solubilization capacity of tungsten in Triton X-100 micellar phase is independent of temperature. FT-IR analysis reveals that there is no evident interaction between polytungstate anion and ether oxygen unit in Triton X-100, and DLS analysis indicates that zeta potential of Triton X-100 micellar phase have a little change from positive to negative after extracting tungsten. Based on the above-mentioned results, it can be deduced that polytungstate anions are solubilized in hydrophilic outer shell of Triton X-100 micelles by electrostatic attraction depending on its relatively high hydrophobic nature. The stripping of tungsten is mainly influenced by temperature and can be easily achieved to 95% in single stage stripping. The tungsten (VI) is separated out from solution containing Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Al(III), Cr(III) and Mn(II) under the suitable conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Biosorption of Basic Green 4 from aqueous solution by Ananas comosus (pineapple) leaf powder.

PubMed

Chowdhury, Shamik; Chakraborty, Sagnik; Saha, Papita

2011-06-01

Biosorption characteristics of Ananas comosus (pineapple) leaf powder was investigated for decolorization of Basic Green 4 (BG 4), a cationic dye from its aqueous solutions employing a batch experimental set-up. Parameters that influence the sorption process such as pH, biosorbent dosage, contact time, initial dye concentration and temperature were systematically studied. The optimum conditions for removal of BG 4 were found to be pH 9.0, contact time=150 min, biosorbent dosage=5.0 g L(-1), initial dye concentration=50 mg L(-1). The temperature had a strong influence on the biosorption process. Further, the biosorbent was characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and Brunauer, Emmett, Teller (BET) surface area and pore size analysis. Experimental biosorption data were modeled by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The biosorption process followed the Langmuir isotherm model with high coefficients of correlation (R(2)>0.99) at different temperatures. The pseudo second order kinetic model fitted well in correlation to the experimental results. Activation energy of the biosorption process (E(a)) was found to be 45.79 kJ mol(-1) by using the Arrhenius equation, indicating chemisorption nature of BG 4 sorption onto pineapple leaf powder. Thermodynamic parameters suggest that the biosorption process is spontaneous and exothermic in nature. Overall, the present findings suggest that this environmentally friendly, efficient and low-cost biosorbent may be useful for the removal of BG 4 from aqueous media. Copyright © 2011 Elsevier B.V. All rights reserved.

Method for loading lipsomes with ionizable phosphorylated hydrophobic compounds, pharmaceutical preparations and a method for administering the preparations

DOEpatents

Mehlhorn, Rolf Joachim

1998-10-27

A method of entrapping ionizable compounds, preferably phosphorylated hydrophobic compounds, into liposomes having transmembrane gradients is disclosed. The procedures involve forming liposomes in an acidic medium or a basic medium, adding to the acidic medium a cationic compound or to the basic medium an anionic compound and then adding a base to the cationic-containing medium or an acid to the anionic-containing medium, thereby inducing the ionizable compound into the liposomes' internal aqueous phase. The compound-entrapped liposomes prepared in accordance with the disclosed methods may be used as pharmaceutical preparations. Methods of administering such pharmaceutical preparations are also disclosed.

Kinetic Studies and Product Characterization during the Basic Hydrolysis of Glyceryl Nitrate Esters

DTIC Science & Technology

1979-08-01

elaborate instrumentation, which was considered too time consuming and costly to construct for this study. 25 The quantitative estimation of the calcium...0.6 [ l-exp(- Kfc ) 1 Figure 21. Formation of N03~ during hydrolysis of 1-MNG in aqueous Ca(0H)2 solution at 25°C (See Tables 2 and 8) 6 5

Detection of Fe[superscript 3+] and Al[superscript 3+] by Test Paper

ERIC Educational Resources Information Center

Li, Lili; Xiang, Haifeng; Zhou, Xiangge; Li, Menglong; Wu, Di

2012-01-01

A porphyrin-based test paper has been designed and prepared. It can be used to analyze for Al[superscript 3+] and Fe[superscript 3+] in aqueous solution. An experiment employing the test paper can help students understand basic principles of spectrophotometry and how spectrophotometry is used in analyzing for metal ions. (Contains 1 scheme and 1…

Synthesis and Evaluation of Aryl Boronic Acids as Fluorescent Artificial Receptors for Biological Carbohydrates

PubMed Central

Craig, Sandra

2011-01-01

Carbohydrates in various forms play a vital role in numerous critical biological processes. The detection of such saccharides can give insight into the progression of such diseases such as cancer. Boronic acids react with 1,2 and 1,3 diols of saccharides in non-aqueous or basic aqueous media. Herein, we describe the design, synthesis and evaluation of three bisboronic acid fluorescent probes, each having about ten linear steps in its synthesis. Among these compounds that were evaluated, 9b was shown to selectively label HepG2, liver carcinoma cell line within a concentration range of 0.5–10 μM in comparison to COS-7, a normal fibroblast cell line. PMID:22177855

Molecular dynamics test of the Brownian description of Na(+) motion in water

NASA Technical Reports Server (NTRS)

Wilson, M. A.; Pohorille, A.; Pratt, L. R.

1985-01-01

The present paper provides the results of molecular dynamics calculations on a Na(+) ion in aqueous solution. Attention is given to the sodium-oxygen and sodium-hydrogen radial distribution functions, the velocity autocorrelation function for the Na(+) ion, the autocorrelation function of the force on the stationary ion, and the accuracy of Brownian motion assumptions which are basic to hydrodynamic models of ion dyanmics in solution. It is pointed out that the presented calculations provide accurate data for testing theories of ion dynamics in solution. The conducted tests show that it is feasible to calculate Brownian friction constants for ions in aqueous solutions. It is found that for Na(+) under the considered conditions the Brownian mobility is in error by only 60 percent.

A Simple and Selective Spectrophotometric Method for the Determination of Trace Gold in Real, Environmental, Biological, Geological and Soil Samples Using Bis (Salicylaldehyde) Orthophenylenediamine

PubMed Central

Soomro, Rubina; Ahmed, M. Jamaluddin; Memon, Najma; Khan, Humaira

2008-01-01

A simple high sensitive, selective, and rapid spectrophotometric method for the determination of trace gold based on the rapid reaction of gold(III) with bis(salicylaldehyde)orthophenylenediamine (BSOPD) in aqueous and micellar media has been developed. BSOPD reacts with gold(III) in slightly acidic solution to form a 1:1 brownish-yellow complex, which has an maximum absorption peak at 490 nm in both aqueous and micellar media. The most remarkable point of this method is that the molar absorptivities of the gold-BSOPD complex form in the presence of the nonionic TritonX-100 surfactant are almost a 10 times higher than the value observed in the aqueous solution, resulting in an increase in the sensitivity and selectivity of the method. The apparent molar absorptivities were found to be 2.3 × 104 L mol−1 cm−1 and 2.5 × 105 L mol−1 cm−1 in aqueous and micellar media, respectively. The reaction is instantaneous and the maximum absorbance was obtained after 10 min at 490 nm and remains constant for over 24 h at room temperature. The linear calibration graphs were obtained for 0.1–30 mg L−1 and 0.01–30 mg L−1 of gold(III) in aqueous and surfactant media, respectively. The interference from over 50 cations, anions and complexing agents has been studied at 1 mg L−1 of Au(III); most metal ions can be tolerated in considerable amounts in aqueous micellar solutions. The Sandell’s sensitivity, the limit of detection and relative standard deviation (n = 9) were found to be 5 ng cm−2, 1 ng mL−1 and 2%, respectively in aqueous micellar solutions. Its sensitivity and selectivity are remarkably higher than that of other reagents in the literature. The proposed method was successfully used in the determination of gold in several standard reference materials (alloys and steels), environmental water samples (potable and polluted), and biological samples (blood and urine), geological, soil and complex synthetic mixtures. The results obtained agree well with those samples analyzed by atomic absorption spectrophotometry (AAS). PMID:19609392

Carbon dioxide capture using resin-wafer electrodeionization

DOEpatents

Lin, YuPo J.; Snyder, Seth W.; Trachtenberg, Michael S.; Cowan, Robert M.; Datta, Saurav

2015-09-08

The present invention provides a resin-wafer electrodeionization (RW-EDI) apparatus including cathode and anode electrodes separated by a plurality of porous solid ion exchange resin wafers, which when in use are filled with an aqueous fluid. The apparatus includes one or more wafers comprising a basic ion exchange medium, and preferably includes one or more wafers comprising an acidic ion exchange medium. The wafers are separated from one another by ion exchange membranes. The fluid within the acidic and/or basic ion exchange wafers preferably includes, or is in contact with, a carbonic anhydrase (CA) enzyme to facilitate conversion of bicarbonate ion to carbon dioxide within the acidic medium. A pH suitable for exchange of CO.sub.2 is electrochemically maintained within the basic and acidic ion exchange wafers by applying an electric potential across the cathode and anode.

An acute toxicity study of Heliotropium scottae Rendle in mice.

PubMed

Wahome, W M; Muchiri, D J; Mugera, G M

1994-08-01

Twenty-four hour ip median lethal doses (LD50) of freeze-dried aqueous extracts of Heliotropium scottae Rendle leaves and stems in mice were determined and clinical signs noted. The LD50 of the leaf extract was 3.0 g/kg, while that of the stems was 3.5 g/kg. Clinical signs were excitement, prostration, rapid breathing, gasping for breath and death. The signs were the same for both the leaf and stem extracts. It was concluded that both the leaves and stems of H scottae have slight acute toxicity.

Carbon Dioxide: The Other Planetary Fluid

NASA Astrophysics Data System (ADS)

Glaser, S.; Gamez, D.; Shock, E.

2016-12-01

Cometary and interstellar ices have carbon dioxide to water mole ratios of up to 0.3. When melted, such high levels of carbon dioxide cannot all be dissolved in the aqueous phase and instead partition into a CO2-rich (carbonic) fluid. This implies that during the accretion and formation of planetary systems carbonic fluids are not only possible, but common. In fact, they make up the atmosphere of Venus, are found bubbling out of Champagne Vent in the Pacific Ocean, and are documented by metamorphic fluid inclusions. Examination of phase diagrams reveals the conditions where carbonic fluids will exist or predominate. Carbonic fluids are predicted to exist in Earth's subduction zones and under the ice of small ocean worlds. CO2 had previously been shown to completely dissolve into NH­­3­-H­­2O oceans on small icy bodies by forming ammonium carbonate, but the newer measurements of CO2­ abundances indicate that not all of the CO2 can partition into the aqueous fluid as ammonium carbonate. The remaining CO2 would necessarily form a separate carbonic fluid making it likely that liquid CO2 would be a major oceanic component on some small icy bodies. The enhanced solubility of nonpolar and slightly polar organic compounds in carbonic fluids relative to aqueous fluids means that generation, transport, and deposition processes can be greatly enhanced in those cases where carbonic fluids occur. As an example, the solubility of benzoic acid, a polar compound, is about an order of magnitude greater in carbonic than in aqueous fluids, which is surprising given that water is a polar solvent and carbon dioxide is a nonpolar solvent. Anthracene, a nonpolar compound, has an even greater solubility difference between carbonic and aqueous fluids at approximately four orders of magnitude. Highly polar compounds, including most of the building blocks of life, are more soluble in aqueous fluids than in carbonic fluids. The solubility difference of organic molecules in carbonic fluids relative to aqueous fluids determines the distribution of the building blocks of life in planetary systems. Partitioning of organics into a carbonic fluid may be the mechanism of removing biochemically irrelevant molecules from the aqueous phase and enabling the emergence of life.

Creativity and Education: An American Retrospective

ERIC Educational Resources Information Center

Feldman, David Henry; Benjamin, Ann C.

2006-01-01

Although early childhood education in America has always had the creative child at the core of its approach, the field itself has generated little systematic research on the topic. In contrast, the scholarly field of creativity studies, with its focus on basic research and theoretical questions, has impacted education only slightly. Creativity and…

Attention Performance in Young Adults with Learning Disabilities

ERIC Educational Resources Information Center

Sterr, Annette M.

2004-01-01

Attention acts as the mind's "gatekeeper" by regulating and prioritizing the stimuli processed by the central nervous system. It is essential for cognitive performance, memory, and behavior, and we know that even slight deficiencies in attention compromise learning. Basic neuroscience research further indicates that attention consists of (fairly)…

Effect of high pressure homogenization on aqueous phase solvent extraction of lipids from Nannochloris Oculata microalgae

DOE PAGES

Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.

2012-12-01

The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage.more » Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.« less

Studies on self-nanoemulsifying drug delivery system of flurbiprofen employing long, medium and short chain triglycerides.

PubMed

Daar, Junaid; Khan, Ahmad; Khan, Jallat; Khan, Amjad; Khan, Gul Majid

2017-03-01

The aim of the study was to successfully design, formulate and evaluate self-nanoemulsifying drug delivery system (SNEDDS) of poorly aqueous soluble drug viz. flurbiprofen using long (LCT), medium (MCT) and short chain triglycerides (SCT). The SNEDDS are thermodynamically stable lipid based drug delivery systems which consist of mixture of oil, surfactant and co-surfactant. Upon aqueous dilution, this mixture produces nano-emulsion spontaneously on slight agitation. The excipients intended to be used were screened for their potential to dissolve the drug and to form clear dispersion upon aqueous dilution. Labrafil M 1944 CS, capryol-90 and triacetin were selected as long, medium and short chain triglycerides, respectively, as lipids while tween-80 and polyethylene glycol-400 (PEG-400)/ethanol (3:1 ratio) were selected as surfactant and co-surfactant, respectively. The excipients were studied at every possible combination ratios using pseudo-ternary diagram. The LCT, MCT and SCT-SNEDDS were optimized using thermodynamic studies, percentage transmittance value, viscosity, refractive index (RI), electrical conductivity, globule size analysis and in-vitro drug release studies. The drug release profiles of optimized SNEDDS were then compared with market product at different pH mediums. The LCT-SNEDDS was considered to be superior for enhancement of the drug bioavailability when compared with other SNEDDS formulations and market product.

Electrogenerated chemiluminescence of tris(2-phenylpyridine)iridium(III) in water, acetonitrile and trifluorethanol.

PubMed

Robinson, Wesley D; Richter, Mark M

2015-02-01

The spectroscopic, electrochemical and coreactant electrogenerated chemiluminescence (ECL) properties of Ir(ppy)3 (where ppy = 2-phenylpyridine) have been obtained in aqueous buffered (KH2PO4), 50 : 50 (v/v) acetonitrile-aqueous buffered (MeCN-KH2PO4) and 30% trifluoroethanol (TFE) solutions. Tri-n-propylamine was used as the oxidative-reductive ECL coreactant. The photoluminescence (PL) efficiency (ϕem) of Ir(ppy)3 in TFE (ϕem ≈ 0.029) was slightly higher than in 50 : 50 MeCN-KH2PO4 (ϕem ≈ 0.0021) and water (ϕem ≈ 0.00016) compared to a Ru(bpy)32+ standard solution in water (Φem ≈ 0.042). PL and ECL emission spectra were nearly identical in all three solvents, with dual emission maxima at 510 and 530 nm. The similarity between the ECL and PL spectra indicate that the same excited state is probably formed in both experiments. ECL efficiencies (ϕecl) in 30% TFE solution (ϕecl = 0.0098) were higher than aqueous solution (ϕecl = 0.00092) system yet lower than a 50% MeCN-KH2PO4 solution (ϕecl = 0.0091). Copyright © 2014 John Wiley & Sons, Ltd.

A critical evaluation of magnetic activated carbon's potential for the remediation of sediment impacted by polycyclic aromatic hydrocarbons.

PubMed

Han, Zhantao; Sani, Badruddeen; Akkanen, Jarkko; Abel, Sebastian; Nybom, Inna; Karapanagioti, Hrissi K; Werner, David

2015-04-09

Addition of activated carbon (AC) or biochar (BC) to sediment to reduce the chemical and biological availability of organic contaminants is a promising in-situ remediation technology. But concerns about leaving the adsorbed pollutants in place motivate research into sorbent recovery methods. This study explores the use of magnetic sorbents. A coal-based magnetic activated carbon (MAC) was identified as the strongest of four AC and BC derived magnetic sorbents for polycyclic aromatic hydrocarbons (PAHs) remediation. An 8.1% MAC amendment (w/w, equal to 5% AC content) was found to be as effective as 5% (w/w) pristine AC in reducing aqueous PAHs within three months by 98%. MAC recovery from sediment after three months was 77%, and incomplete MAC recovery had both, positive and negative effects. A slight rebound of aqueous PAH concentrations was observed following the MAC recovery, but aqueous PAH concentrations then dropped again after six months, likely due to the presence of the 23% unrecovered MAC. On the other hand, the 77% recovery of the 8.1% MAC dose was insufficient to reduce ecotoxic effects of fine grained AC or MAC amendment on the egestion rate, growth and reproduction of the AC sensitive species Lumbriculus variegatus. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of high pressure homogenization on aqueous phase solvent extraction of lipids from Nannochloris Oculata microalgae

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

Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.

The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage.more » Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.« less

The in vitro biological activity of Lepidium meyenii extracts.

PubMed

Valentová, K; Buckiová, D; Kren, V; Peknicová, J; Ulrichová, J; Simánek, V

2006-03-01

The biological activity of methanolic and aqueous extracts from dehydrated hypocotyls of Lepidium meyenii (Brassicaceae, vernacular name "maca"), was studied on rat hepatocytes and human breast cancer MCF-7 cells. The extracts did not exhibit cytotoxicity in hepatocyte primary cultures up to 10 mg/ml as measured by the MTT viability test, and lactate dehydrogenase (LDH) and aspartate aminotransferase (AST) leakage. Moreover, after 72 h, extracts inhibited LDH and AST leakage from the hepatocytes. When hepatocytes were intoxicated by t-butyl hydroperoxide, neither extract prevented oxidative damage. Both extracts showed weak antioxidant activity in the DPPH radical scavenging test with IC(50) values of 3.46 +/- 0.16 and 0.71 +/- 0.10 mg/ml, for aqueous and methanolic extracts, respectively. Thus, the observed effect on spontaneous enzyme leakage is probably mediated through mechanisms other than antioxidant activity. Both methanolic and aqueous extracts have shown estrogenic activity comparable with that of silymarin in MCF-7 cell line. Maca estrogenicity was exhibited in the range from 100 to 200 mug of extract per ml. The findings in the present study show that maca does not display in vitro hepatotoxicity. In contrast, a slight cytoprotective effect, probably not mediated by antioxidant capacity, was noted. Maca extracts exhibited estrogenic activity comparably to the effect of silymarin in MCF-7 cells.

Optimization of Pumpkin Oil Recovery by Using Aqueous Enzymatic Extraction and Comparison of the Quality of the Obtained Oil with the Quality of Cold-Pressed Oil

PubMed Central

Roszkowska, Beata; Czaplicki, Sylwester; Tańska, Małgorzata

2016-01-01

Summary The study was carried out to optimize pumpkin oil recovery in the process of aqueous extraction preceded by enzymatic maceration of seeds, as well as to compare the quality of the obtained oil to the quality of cold-pressed pumpkin seed oil. Hydrated pulp of hulless pumpkin seeds was macerated using a 2% (by mass) cocktail of commercial pectinolytic, cellulolytic and proteolytic preparations (Rohapect® UF, Rohament® CL and Colorase® 7089). The optimization procedure utilized response surface methodology based on Box- -Behnken plan of experiment. The optimized variables of enzymatic pretreatment were pH, temperature and maceration time. The results showed that the pH value, temperature and maceration time of 4.7, 54 °C and 15.4 h, respectively, were conducive to maximize the oil yield up to 72.64%. Among these variables, the impact of pH was crucial (above 73% of determined variation) for oil recovery results. The oil obtained by aqueous enzymatic extraction was richer in sterols, squalene and tocopherols, and only slightly less abundant in carotenoids than the cold-pressed one. However, it had a lower oxidative stability, with induction period shortened by approx. 30% in relation to the cold-pressed oil. PMID:28115898

Total Flavonoids Content in the Raw Material and Aqueous Extractives from Bauhinia monandra Kurz (Caesalpiniaceae)

PubMed Central

Fernandes, Ana Josane Dantas; Ferreira, Magda Rhayanny Assunção; Randau, Karina Perrelli; de Souza, Tatiane Pereira; Soares, Luiz Alberto Lira

2012-01-01

The aim of this work was to evaluate the spectrophotometric methodology for determining the total flavonoid content (TFC) in herbal drug and derived products from Bauhinia monandra Kurz. Several analytical parameters from this method grounded on the complex formed between flavonoids and AlCl3 were evaluated such as herbal amount (0.25 to 1.25 g); solvent composition (ethanol 40 to 80%, v/v); as well as the reaction time and AlCl3 concentration (2 to 9%, w/v). The method was adjusted to aqueous extractives and its performance studied through precision, linearity and preliminary robustness. The results showed an important dependence of the method response from reaction time, AlCl3 concentration, sample amount, and solvent mixture. After choosing the optimized condition, the method was applied for the matrixes (herbal material and extractives), showing precision lower than 5% (for both parameters repeatability and intermediate precision), coefficient of determination higher than 0.99, and no important influence could be observed for slight variations from wavelength or AlCl3 concentration. Thus, it could be concluded that the evaluated analytical procedure was suitable to quantify the total flavonoid content in raw material and aqueous extractives from leaves of B. monandra. PMID:22701375

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments.

PubMed

Stewart, Brandy D; Mayes, Melanie A; Fendorf, Scott

2010-02-01

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a range of aqueous uranyl species. U(VI) adsorption is directly linked to UO(2)(2+) speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K(d) values decrease from 48 to 17 L kg(-1) for goethite, from 64 to 29 L kg (-1) for Hanford sediments, and from 95 to 51 L kg(-1) for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ( approximately 5) and limited dissolved calcium are optimal for uranium adsorption.

AUTOMATED ANALYSIS OF AQUEOUS SAMPLES CONTAINING PESTICIDES, ACIDIC/BASIC/NEUTRAL SEMIVOLATILES AND VOLATILE ORGANIC COMPOUNDS BY SOLID PHASE EXTRACTION COUPLED IN-LINE TO LARGE VOLUME INJECTION GC/MS

EPA Science Inventory

Data is presented on the development of a new automated system combining solid phase extraction (SPE) with GC/MS spectrometry for the single-run analysis of water samples containing a broad range of organic compounds. The system uses commercially available automated in-line 10-m...

Impact of lysozyme on stability mechanism of nanozirconia aqueous suspension

NASA Astrophysics Data System (ADS)

Szewczuk-Karpisz, Katarzyna; Wiśniewska, Małgorzata

2016-08-01

The effect of lysozyme (LSZ) presence on the zirconium(IV) oxide (ZrO2) aqueous suspension stability was examined. The applied zirconia contains mesopores (with a diameter about 30 nm) and its mean particle size is about 100 nm. To determine the stability mechanism of ZrO2 suspension in the biopolymer presence, the adsorption and electrokinetic (surface charge density and zeta potential) measurements were performed in the pH range 3-10. The lysozyme adsorption on the nanozirconia surface proceeds mainly through electrostatic forces. Under solid-polymer repulsion conditions, there is no adsorption of lysozyme (pH < 6, CNaCl 0.01 mol/dm3). The increase of solution ionic strength to 0.2 mol/dm3 causes screening of unfavourable forces and biopolymer adsorption becomes possible. The LSZ addition to the ZrO2 suspension influences its stability. At pH 3, 4.6 and 7.6, slight improvement of the system stability was obtained. In turn, at pH 9 considerable destabilization of nanozirconia particles covered by polymeric layers occurs.

Evaluation studies of persimmon plant (Diospyros kaki) for physiological benefits and bioaccessibility of antioxidants by in vitro simulated gastrointestinal digestion.

PubMed

Martínez-Las Heras, Ruth; Pinazo, Alicia; Heredia, Ana; Andrés, Ana

2017-01-01

This study aims to analyze the antioxidant benefits from persimmon leaf tea, fruit and fibres taking into account their changes along gastrointestinal digestion. The evolution of polyphenols, flavonoids and antioxidant capacity was studied using the recent harmonized in vitro protocol published by Minekus et al. (2014). The digestion was performed with and without digestive enzymes. Results showed aqueous leaf extract was richer in antioxidants than the fruit or the extracted fibres. Nevertheless, persimmon-leaf antioxidants were more sensitive to the digestive environment. In general, the oral conditions greatly affected the antioxidants, while gastric digestion led to slight additional losses. The intestinal step enhanced polyphenols and flavonoids solubility coming from the fruit and fibres. Additionally, the presence of digestive enzymes positively contributed to antioxidant release throughout digestion. Finally, the bioaccessibility of polyphenols, flavonoids and antioxidant activity of persimmon fruit were 1.4, 1.0 and 3.8 times higher than in aqueous leaf extract. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effective adsorption of phenolic compound from aqueous solutions on activated semi coke

NASA Astrophysics Data System (ADS)

Gao, Xiaoming; Dai, Yuan; Zhang, Yu; Fu, Feng

2017-03-01

Activated Semi coke was prepared by KOH activation and employed as adsorbent to study adsorption function of phenolic compound from aqueous solutions. The adsorption result showed that the adsorption capacity of the activated semi coke for phenolic compound increased with contact time and adsorbent dosage, and slightly affected by temperature. The surface structure property of the activated semi coke was characterized by N2 adsorption, indicating that the activated semi coke was essentially macroporous, and the BET surface area was 347.39 m2 g-1. Scanning electron microscopy indicated that the surface of the activated semi coke had a high developed pore. The adsorption kinetics were investigated according to pseudofirst order, pseudosecond order and intraparticle diffusion, and the kinetics data were fitted by pseudosecond order model, and intraparticle diffusion was not the only rate-controlling step. Adsorption isotherm was studied by Langmuir, Freundlich, Temkin, Redlich-Peterson, Sips and Toth models. The result indicated that adsorption isotherm data could fit well with Langmuir, Redlich-Peterson, Sips and Toth models.

Performance and emissions characteristics of aqueous alcohol fumes in a DI diesel engine

NASA Technical Reports Server (NTRS)

Heisey, J. B.; Lestz, S. S.

1981-01-01

A single cylinder DI Diesel engine was fumigated with ethanol and methanol in amounts up to 55% of the total fuel energy. The effects of aqueous alcohol fumigation on engine thermal efficiency, combustion intensity and gaseous exhaust emissions were determined. Assessment of changes in the biological activity of raw particulate and its soluble organic fraction were also made using the Salmonella typhimurium test. Alcohol fumigation improved thermal efficiency slightly at moderate and heavy loads, but increased ignition delay at all operating conditions. Carbon monoxide and unburned hydrocarbon emission generally increased with alcohol fumigation and showed no dependence on alcohol type or quality. Oxide of nitrogen emission showed a strong dependence on alcohol quality; relative emission levels decreased with increasing water content of the fumigant. Particulate mass loading rates were lower for ethanol fueled conditions. However, the biological activity of both the raw particulate and its soluble organic fraction was enhanced by ethanol fumigation at most operating conditions.

Effects of angiotensin, vasopressin and atrial natriuretic peptide on intraocular pressure in anesthetized rats

NASA Technical Reports Server (NTRS)

Palm, D. E.; Shue, S. G.; Keil, L. C.; Balaban, C. D.; Severs, W. B.

1995-01-01

The effects of atrial natriuretic peptide (ANP), vasopressin (AVP) and angiotensin (ANG) on blood and intraocular pressures of pentobarbital anesthetized rats were evaluated following intravenous, intracerebroventricular or anterior chamber routes of administration. Central injections did not affect intraocular pressure. Equipressor intravenous infusions of ANG raised, whereas AVP decreased, intraocular pressure. Direct infusions of a balanced salt solution (0.175 microliter/min) raised intraocular pressure between 30 and 60 min. Adding ANG or ANP slightly reduced this solvent effect but AVP was markedly inhibitory. An AVP-V1 receptor antagonist reversed the blunting of the solvent-induced rise by the peptide, indicating receptor specificity. Acetazolamide pretreatment lowered intraocular pressure, but the solvent-induced rise in intraocular pressure and inhibition by AVP still occurred without altering the temporal pattern. Thus, these effects appear unrelated to aqueous humor synthesis rate. The data support the possibility of intraocular pressure regulation by peptides acting from the blood and aqueous humor.

Constraints on silicates formation in the Si-Al-Fe system: Application to hard deposits in steam generators of PWR nuclear reactors

NASA Astrophysics Data System (ADS)

Berger, Gilles; Million-Picallion, Lisa; Lefevre, Grégory; Delaunay, Sophie

2015-04-01

Introduction: The hydrothermal crystallization of silicates phases in the Si-Al-Fe system may lead to industrial constraints that can be encountered in the nuclear industry in at least two contexts: the geological repository for nuclear wastes and the formation of hard sludges in the steam generator of the PWR nuclear plants. In the first situation, the chemical reactions between the Fe-canister and the surrounding clays have been extensively studied in laboratory [1-7] and pilot experiments [8]. These studies demonstrated that the high reactivity of metallic iron leads to the formation of Fe-silicates, berthierine like, in a wide range of temperature. By contrast, the formation of deposits in the steam generators of PWR plants, called hard sludges, is a newer and less studied issue which can affect the reactor performance. Experiments: We present here a preliminary set of experiments reproducing the formation of hard sludges under conditions representative of the steam generator of PWR power plant: 275°C, diluted solutions maintained at low potential by hydrazine addition and at alkaline pH by low concentrations of amines and ammoniac. Magnetite, a corrosion by-product of the secondary circuit, is the source of iron while aqueous Si and Al, the major impurities in this system, are supplied either as trace elements in the circulating solution or by addition of amorphous silica and alumina when considering confined zones. The fluid chemistry is monitored by sampling aliquots of the solution. Eh and pH are continuously measured by hydrothermal Cormet© electrodes implanted in a titanium hydrothermal reactor. The transformation, or not, of the solid fraction was examined post-mortem. These experiments evidenced the role of Al colloids as precursor of cements composed of kaolinite and boehmite, and the passivation of amorphous silica (becoming unreactive) likely by sorption of aqueous iron. But no Fe-bearing was formed by contrast to many published studies on the Fe-clay interactions in the nuclear waste storage, and by contrast with basic thermodynamic predictions. Conclusion: The Fe-clays and steam generators contexts imply relatively close aqueous environments: hydrothermal, reduced, diluted, neutral to slightly alkaline. The main difference is the status of iron: ferric/ferrous (magnetite) in the steam generators, metallic in the Fe-clay experiments. The concentration of aqueous iron when supplied by magnetite is low and does not allow its incorporation in secondary phases. By contrast, aqueous ferrous iron released by the corrosion of steel is not limited by the source, rather by the sink, and produces Fe-rich silicates. This example illustrates the discrepancy between complex mineral reactions and oversimplified predictions when sorption/passivation and nucleation/growth constraints are ignored. Reference: [1] Lanson et al. (2012) Amer. Min. 97, 864-871. [2] Lantenois et al. (2005) Clays & Clay Min. 53, 597-612. [3] Mosser-Ruck et al. (2010) Clays & Clay Min. 58, 280-291. [4] Perronnet et al. (2008) App. Clay Sci. 38, 187-202. [5] Osacky et al. (2010) App. Clay Sci. 50, 237-244. [6] Guillaume et al. (2003) Clay Min. 38, 281-302. [7] Rivard et al. (2013) Amer. Mineral. 98, 163-180. [8] Svensson and Hansen (2013) Clays & Clay Min. 61, 566-579.

Interfaces Charged by a Nonionic Surfactant.

PubMed

Lee, Joohyung; Zhou, Zhang-Lin; Behrens, Sven Holger

2018-05-24

Highly hydrophobic, water-insoluble nonionic surfactants are often considered irrelevant to the ionization of interfaces at which they adsorb, despite observations that suggest otherwise. In the present study, we provide unambiguous evidence for the participation of a water-insoluble surfactant in interfacial ionization by conducting electrophoresis experiments for surfactant-stabilized nonpolar oil droplets in aqueous continuous phase. It was found that the surfactant with amine headgroup positively charged the surface of oil suspended in aqueous continuous phase (oil/water interface), which is consistent with its basic nature. In nonpolar oil continuous phase, the same surfactant positively charged the surface of solid silica (solid/oil interface) which is often considered acidic. The latter observation is exactly opposite to what the traditional acid-base mechanism of surface charging would predict, most clearly suggesting the possibility for another charging mechanism.

Phenol-formaldehyde carbon with ordered/disordered bimodal mesoporous structure as high-performance electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Cai, Tingwei; Zhou, Min; Han, Guangshuai; Guan, Shiyou

2013-11-01

A novel phenol-formaldehyde carbon with ordered/disordered bimodal mesoporous structure is synthesized by the facile evaporation induced self-assembly strategy under a basic aqueous condition with SiO2 particles as template. The prepared bimodal mesoporous carbons (BMCs) are composed of ordered mesoporous and disordered mesoporous with diameter of about 3.5 nm and 7.0 nm, respectively. They can be employed as supercapacitor electrodes in H2SO4 aqueous electrolyte after the simple acid-treatment. BMC exhibits an exceptional specific capacitance of 344 F g-1 at the current density of 0.1 A g-1, although it has a relatively low surface area of 722 m2 g-1. And the BMC electrode displays an excellent cycling stability over 10,000 cycles.

Material Removes Heavy Metal Ions From Water

NASA Technical Reports Server (NTRS)

Philipp, Warren H., Jr.; Street, Kenneth W.; Hill, Carol; Savino, Joseph M.

1995-01-01

New high capacity ion-exchange polymer material removes toxic metal cations from contaminated water. Offers several advantages. High sensitivities for such heavy metals as lead, cadmium, and copper and capable of reducing concentrations in aqueous solutions to parts-per-billion range. Removes cations even when calcium present. Material made into variety of forms, such as thin films, coatings, pellets, and fibers. As result, adapted to many applications to purify contaminated water, usually hard wherever found, whether in wastewater-treatment systems, lakes, ponds, industrial plants, or homes. Another important feature that adsorbed metals easily reclaimed by either destructive or nondestructive process. Other tests show ion-exchange polymer made inexpensively; easy to use; strong, flexible, not easily torn; and chemically stable in storage, in aqueous solutions, and in acidic or basic solution.

Method for loading lipsomes with ionizable phosphorylated hydrophobic compounds, pharmaceutical preparations and a method for administering the preparations

DOEpatents

Mehlhorn, R.J.

1998-10-27

A method of entrapping ionizable compounds, preferably phosphorylated hydrophobic compounds, into liposomes having transmembrane gradients is disclosed. The procedures involve forming liposomes in an acidic medium or a basic medium, adding to the acidic medium a cationic compound or to the basic medium an anionic compound and then adding a base to the cationic-containing medium or an acid to the anionic-containing medium, thereby inducing the ionizable compound into the liposomes` internal aqueous phase. The compound-entrapped liposomes prepared in accordance with the disclosed methods may be used as pharmaceutical preparations. Methods of administering such pharmaceutical preparations are also disclosed. 2 figs.

Quantitation of Indoleacetic Acid Conjugates in Bean Seeds by Direct Tissue Hydrolysis 1

PubMed Central

Bialek, Krystyna; Cohen, Jerry D.

1989-01-01

Gas chromatography-selected ion monitoring-mass spectral analysis using [13C6]indole-3-acetic acid (IAA) as an internal standard provides an effective means for quantitation of IAA liberated during direct strong basic hydrolysis of bean (Phaseolus vulgaris L.) seed powder, provided that extra precautions are undertaken to exclude oxygen from the reaction vial. Direct seed powder hydrolysis revealed that the major portion of amide IAA conjugates in bean seeds are not extractable by aqueous acetone, the solvent used commonly for IAA conjugate extraction from seeds and other plant tissues. Strong basic hydrolysis of plant tissue can be used to provide new information on IAA content. Images Figure 1 PMID:16666783

Retardation effect of nitrogen compounds and condensed aromatics on shale oil catalytic cracking processing and their characterization.

PubMed

Li, Nan; Chen, Chen; Wang, Bin; Li, Shaojie; Yang, Chaohe; Chen, Xiaobo

Untreated shale oil, shale oil treated with HCl aqueous solution and shale oil treated with HCl and furfural were used to do comparative experiments in fixed bed reactors. Nitrogen compounds and condensed aromatics extracted by HCl and furfural were characterized by electrospray ionization Fourier transform cyclotron resonance mass spectrometry and gas chromatography and mass spectrometry, respectively. Compared with untreated shale oil, the conversion and yield of liquid products increased considerably after removing basic nitrogen compounds by HCl extraction. Furthermore, after removing nitrogen compounds and condensed aromatics by both HCl and furfural, the conversion and yield of liquid products further increased. In addition, N 1 class species are predominant in both basic and non-basic nitrogen compounds, and they are probably indole, carbazole, cycloalkyl-carbazole, pyridine and cycloalkyl-pyridine. As for the condensed aromatics, most of them possess aromatic rings with two to three rings and zero to four carbon atom.

GEOSURF: a computer program for modeling adsorption on mineral surfaces from aqueous solution

NASA Astrophysics Data System (ADS)

Sahai, Nita; Sverjensky, Dimitri A.

1998-11-01

A new program, GEOSURF, has been developed for calculating aqueous and surface speciation consistent with the triple-layer model of surface complexation. GEOSURF is an extension of the original programs MINEQL, MICROQL and HYDRAQL. We present, here, the basic algorithm of GEOSURF along with a description of the new features implemented. GEOSURF is linked to internally consistent data bases for surface species (SURFK.DAT) and for aqueous species (AQSOL.DAT). SURFK.DAT contains properties of minerals such as site densities, and equilibrium constants for adsorption of aqueous protons and electrolyte ions on a variety of oxides and hydroxides. The Helgeson, Kirkham and Flowers version of the extended Debye-Huckel Equation for 1:1 electrolytes is implemented for calculating aqueous activity coefficients. This permits the calculation of speciation at ionic strengths greater than 0.5 M. The activity of water is computed explicitly from the osmotic coefficient of the solution, and the total amount of electrolyte cation (or anion) is adjusted to satisfy the electroneutrality condition. Finally, the use of standard symbols for chemical species rather than species identification numbers is included to facilitate use of the program. One of the main limitations of GEOSURF is that aqueous and surface speciation can only be calculated at fixed pH and at fixed concentration of total adsorbate. Thus, the program cannot perform reaction-path calculations: it cannot determine whether or not a solution is over- or under-saturated with respect to one or more solid phases. To check the proper running of GEOSURF, we have compared results generated by GEOSURF with those from two other programs, HYDRAQL and EQ3. The Davies equation and the "bdot" equation, respectively, are used in the latter two programs for calculating aqueous activity coefficients. An example of the model fit to experimental data for rutile in 0.001 M-2.0 M NaNO 3 is included.

Community Colleges' Use of the Web to Communicate Their Mission: Slights of Commission and Omission

ERIC Educational Resources Information Center

Hegeman, Diane L.; Davies, Timothy Gray; Banning, James H.

2007-01-01

This basic interpretive qualitative study identified, described, and interpreted community college mission statement messages as they appeared in print and on the web site. The study analyzed each institution's similar, different, unique, and unintended messages. The within-case inductive analysis found emergent mission statement messages in the…

On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

USGS Publications Warehouse

Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

2007-01-01

Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 ?? 0.2 to 1.7 ?? 0.3 in the 0.006m chloride solution and from 0.9 ?? 0.7 to 1.8 ?? 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500????C range. Conversely, the number of H2O ligands of Gd(H2O)??-nCln+3-n complexes decreases steadily from 8.9 ?? 0.4 to 5.8 ?? 0.7 in the 0.006m GdCl3 aqueous solution and from 9.0 ?? 0.5 to 5.3 ?? 1.0 in the 0.1m GdCl3 aqueous solution at temperatures from 25 to 500????C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH2 bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction (??? 0.005??A??/100????C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids. ?? 2006 Elsevier B.V. All rights reserved.

Comparative Evaluation of Firefighting Foam Agents

DTIC Science & Technology

1979-08-01

incorporating these basic concepts under a military specification, are being produced on a world-wide MIL - F - 24385 , Navy (reference 6). basis. The original...Program Office for 24385 (Navy), Fire Extinguishing Aircraft Ground Fire Suppression and Agent, Aqueous- F Ilm-Forming-Foam Rescue, SMF, AGFSkS 71-1...fluoroprotein foams (FPF), and three protein foam (?’ F ) agents. Large-scale fire tests were performed under fixed fire conditions employing air

The effect of excipients on the stability of levothyroxine sodium pentahydrate tablets.

PubMed

Patel, Himanshu; Stalcup, Apryll; Dansereau, Richard; Sakr, Adel

2003-10-02

Levothyroxine tablets, 50 microg, have been marketed for many decades but have had numerous recalls due to degradation and failure to meet potency. These experiments were devised to study the effects of various excipients on the stability of levothyroxine sodium pentahydrate in aqueous slurries and in formulated tablets. The active alone was found to be stable in the solid state for 6 months at 40 degrees C/75% RH whether stored in open or closed containers, and was found to be non-hygroscopic under normal processing conditions (>30% RH). In aqueous slurries with an excipient, the stability of the active improved as the pH of the slurry was increased from pH 3 to 11. Tablets manufactured with lactose anhydrous, starch, or microcrystalline cellulose failed to meet USP assay requirements at 3 months at 40 degrees C/75% RH. Tablets manufactured with dibasic calcium phosphate or mannitol met USP assay requirements at 3, but not 6 months when stored at 40 degrees C/75% RH. Tablets manufactured with dibasic calcium phosphate and a basic pH modifier, such as sodium carbonate, sodium bicarbonate, or magnesium oxide, met the USP assay requirements at both 3 and 6 months. Thus, the use of basic pH modifiers is a potential technique for improving the stability of levothyroxine sodium pentahydrate tablets.

Molecular Modeling of Ammonium, Calcium, Sulfur, and Sodium Lignosulphonates in Acid and Basic Aqueous Environments

NASA Astrophysics Data System (ADS)

Salazar Valencia, P. J.; Bolívar Marinez, L. E.; Pérez Merchancano, S. T.

2015-12-01

Lignosulphonates (LS), also known as lignin sulfonates or sulfite lignin, are lignins in sulfonated forms, obtained from the "sulfite liquors," a residue of the wood pulp extraction process. Their main utility lies in its wide range of properties, they can be used as additives, dispersants, binders, fluxing, binder agents, etc. in fields ranging from food to fertilizer manufacture and even as agents in the preparation of ion exchange membranes. Since they can be manufactured relatively easy and quickly, and that its molecular size can be manipulated to obtain fragments of very low molecular weight, they are used as transport agents in the food industry, cosmetics, pharmaceutical and drug development, and as molecular elements for the treatment of health problems. In this paper, we study the electronic structural and optical characteristics of LS incorporating ammonium, sulfur, calcium, and sodium ions in acidic and basic aqueous media in order to gain a better understanding of their behavior and the very interesting properties exhibit. The studies were performed using the molecular modeling program HyperChem 5 using the semiempirical method PM3 of the NDO Family (neglect of differential overlap), to calculate the structural properties. We calculated the electronic and optical properties using the semiempirical method ZINDO / CI.

State of Supported Nickel Nanoparticles during Catalysis in Aqueous Media

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

Chase, Zizwe; Kasakov, Stanislav; Shi, Hui

2015-11-09

The state of Ni supported on HZSM-5 zeolite, silica, and sulfonated carbon was determined during aqueous phase catalysis of phenol hydrodeoxygenation using in situ extended X-ray absorption fine structure spectroscopy (EXAFS). On sulfonated carbon and HZSM-5 supports, the NiO and Ni(OH)2 were readily reduced to Ni(0) under reaction conditions (~35 bar H2 in aqueous phenol solutions containing up to 0.5 wt. % phosphoric acid at 473 K). On the silica support, less than 70% of the Ni was converted to Ni(0) under reaction conditions, which is attributed to the formation of Ni phyllosilicates. Over a broad range of reaction conditionsmore » there was no leaching of Ni from the supports. In contrast, rapid leaching of the Ni(II) from HZSM-5 was observed, when 15 wt. % aqueous acetic acid was substituted for the aqueous phenol solution. Once the metallic state of Ni was established there was no leaching in 15 wt. % acetic acid at 473 K and 35 bar H2. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences & Biosciences. The STEM was supported under the Laboratory Directed Research and Development Program: Chemical Imaging Initiative at Pacific Northwest National Laboratory (PNNL), a multi-program national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830. STEM was performed at EMSL, a DOE Office of Science user facility sponsored by the Office of Biological and Environmental Research and located at PNNL.« less

Theoretical Evidence for the Stronger Ability of Thymine to Disperse SWCNT than Cytosine and Adenine: self-stacking of DNA bases vs their cross-stacking with SWCNT

PubMed Central

Wang, Yixuan

2008-01-01

Self-stacking of four DNA bases, adenine (A), cytosine (C), guanine (G) and thymine (T), and their cross-stacking with (5,5) as well as (10,0) single walled carbon nanotubes (SWCNTs) were extensively investigated with a novel hybrid DFT method, MPWB1K/cc-pVDZ. The binding energies were further corrected with MP2/6-311++G(d,p) method in both gas phase and aqueous solution, where the solvent effects were included with conductor-like polarized continuum model (CPCM) model and UAHF radii. The strongest self-stacking of G and A takes displaced anti-parallel configuration, but un-displaced or “eclipsed” anti-parallel configuration is the most stable for C and T. In gas phase the self-stacking of nucleobases decreases in the sequence G>A>C>T, while because of quite different solvent effects their self-stacking in aqueous solution exhibits a distinct sequence A>G>T>C. For a given base, cross-stacking is stronger than self-stacking in both gas phase and aqueous solution. Binding energy for cross-stacking in gas phase varies as G>A>T>C for both (10,0) and (5,5) SWCNTs, and the binding of four nucleobases to (10,0) is slightly stronger than to (5,5) SWCNT by a range of 0.1–0.5 kcal/mol. The cross-stacking in aqueous solution varies differently from that gas phase: A>G>T>C for (10,0) SWCNT and G>A>T>C for (5,5) SWCNT. It is suggested that the ability of nucleobases to disperse SWCNT depends on relative strength (ΔΔEbinsol) of self-stacking and cross-stacking with SWCNT in aqueous solution. Of the four investigated nucleobases thymine (T) exhibits the highest (ΔΔEbinsol) which can well explain the experimental finding that T more efficiently functionalizes SWCNT than C and A. PMID:18946514

Experiment and Optimization for Simultaneous Carbonation of Ca2+ and Mg2+ in A Two-phase System of Insoluble Diisobutylamine and Aqueous Solution

NASA Astrophysics Data System (ADS)

Wang, Wenlong; Wang, Man; Liu, Xin; Wang, Peng; Xi, Zhenqian

2015-06-01

An optimized approach of CO2 fixation in Ca2+/Mg2+-rich aqueous solutions using insoluble amine as an enhancing medium was reported. Apparent basicity was verified to be an effective indicator for the selection and optimization of organic amine systems and finally the diisobutylamine + n-octanol system was selected to enhance the carbonation reactions of CO2 in an artificial Ca2+/Mg2+-rich solution. In our experiments, when the volume ratio of insoluble organic phase to aqueous one was 2:1 and the reaction temperature was 28 °C, 92% of Ca2+ and 80% of Mg2+ could be converted to calcium and magnesium carbonate precipitates within 5 min of reaction with the bubbling-in of CO2. The organic amine system could be regenerated by using carbide slag as the regeneration agent and could still show attractive enhancement performances after 7 rounds of carbonation-regeneration experiments. In this way, the CO2 capture and sequestration was realized within one single process, with value-added Ca/Mg carbonates being the byproducts. In view of the vast availability of Ca2+/Mg2+-rich aqueous solutions and the feasible technical coordination with desalination industry, this novel process may have a good application potential in the future.

Magnetite Nanoparticles Coated with Rifampicin and Chlortetracycline for Drug Delivery Applications

NASA Astrophysics Data System (ADS)

Nǎdejde, Claudia; Ciurlicǎ, Ecaterina Foca-nici; Creangǎ, Dorina; Cârlescu, Aurelian; Bǎdescu, Vasile

2010-12-01

Four types of biocompatible magnetic fluids based on superparamagnetic nanoparticles with Fe3O4 cores were functionalized with antibiotics (rifampicin or chlortetracycline) as potential candidates for in vivo biomedical applications, such as magnetically controlled drug delivery. The synthesis consisted in coprecipitation of iron oxide in basic, as well as in acid medium, followed by the dispersion of the resulted magnetite nanoparticles in aqueous solution containing the antibiotic. The chosen method to prepare the magnetite-core/drug-shell systems avoided intermediate organic coating of the magnetic nanoparticles. Comparative analysis of the rheological features of the aqueous magnetic fluid samples was performed. The structural features of the coated magnetic particles were investigated by X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and Vibrating Sample Magnetometry (VSM). Good crystallinity and adequate stability in time were evidenced. Drug delivery curves were spectrophotometrically provided.

Water Interfaces, Solvation, and Spectroscopy

NASA Astrophysics Data System (ADS)

Geissler, Phillip L.

2013-04-01

Liquid water consistently expands our appreciation of the rich statistical mechanics that can emerge from simple molecular constituents. Here I review several interrelated areas of recent work on aqueous systems that aim to explore and explain this richness by revealing molecular arrangements, their thermodynamic origins, and the timescales on which they change. Vibrational spectroscopy of OH stretching features prominently in these discussions, with an emphasis on efforts to establish connections between spectroscopic signals and statistics of intermolecular structure. For bulk solutions, the results of these efforts largely verify and enrich existing physical pictures of hydrogen-bond network connectivity, dynamics, and response. For water at interfaces, such pictures are still emerging. As an important example I discuss the solvation of small ions at the air-water interface, whose surface propensities challenge a basic understanding of how aqueous fluctuations accommodate solutes in heterogeneous environments.

Process for the combined removal of SO.sub.2 and NO.sub.x from flue gas

DOEpatents

Chang, Shih-Ger; Liu, David K.; Griffiths, Elizabeth A.; Littlejohn, David

1988-01-01

The present invention in one aspect relates to a process for the simultaneous removal of NO.sub.x and SO.sub.2 from a fluid stream comprising mixtures thereof and in another aspect relates to the separation, use and/or regeneration of various chemicals contaminated or spent in the process and which includes the steps of: (A) contacting the fluid stream at a temperature of between about 105.degree. and 180.degree. C. with a liquid aqueous slurry or solution comprising an effective amount of an iron chelate of an amino acid moiety having at least one --SH group; (B) separating the fluid stream from the particulates formed in step (A) comprising the chelate of the amino acid moiety and fly ash; (C) washing and separating the particulates of step (B) with an aqueous solution having a pH value of between about 5 to 8; (D) subsequently washing and separating the particulates of step (C) with a strongly acidic aqueous solution having a pH value of between about 1 to 3; (E) washing and separating the particulates of step (D) with an basic aqueous solution having a pH value of between about 9 to 12; (F) optionally adding additional amino acid moiety, iron (II) and alkali to the aqueous liquid from step (D) to produce an aqueous solution or slurry similar to that in step (A) having a pH value of between about 4 to 12; and (G) recycling the aqueous slurry of step (F) to the contacting zone of step (A). Steps (D) and (E) can be carried out in the reverse sequence, however the preferred order is (D) and then (E). In another preferred embodiment the present invention provides a process for the removal of NO.sub.x, SO.sub.2 and particulates from a fluid stream which includes the steps of (A) injecting into a reaction zone an aqueous solution itself comprising (i) an amino acid moiety selected from those described above; (ii) iron (II) ion; and (iii) an alkali, wherein the aqueous solution has a pH of between about 4 and 11; followed by solids separation and washing as is described in steps (B), (C), (D) and (E) above. The overall process is useful to reduce acid rain components from combustion gas sources.

Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics, transformation products, and toxicity evolvement.

PubMed

Dong, Bizhang; Hu, Jiye

2016-10-01

The aqueous photodegradation of fluopyram was investigated under UV light (λ ≥ 200 nm) and simulated sunlight irradiation (λ ≥ 290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO3 (-)), Fe (III) ions, and titanium dioxide (TiO2) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO3 (-), Fe (III), and TiO2 slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L(-1) Fe (III) and 500 mg L(-1) TiO2 were about 7-fold and 13-fold faster than that without Fe (III) and TiO2 under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.

Impact of uranyl-calcium-carbonato complexes on uranium(VI) adsorption to synthetic and natural sediments

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

Stewart, B.D.; Mayes, Melanie; Fendorf, Scott

2010-01-01

Adsorption on soil and sediment solids may decrease aqueous uranium concentrations and limit its propensity for migration in natural and contaminated settings. Uranium adsorption will be controlled in large part by its aqueous speciation, with a particular dependence on the presence of dissolved calcium and carbonate. Here we quantify the impact of uranyl speciation on adsorption to both goethite and sediments from the Hanford Clastic Dike and Oak Ridge Melton Branch Ridgetop formations. Hanford sediments were preconditioned with sodium acetate and acetic acid to remove carbonate grains, and Ca and carbonate were reintroduced at defined levels to provide a rangemore » of aqueous uranyl species. U(VI) adsorption is directly linked to UO{sub 2}{sup 2+} speciation, with the extent of retention decreasing with formation of ternary uranyl-calcium-carbonato species. Adsorption isotherms under the conditions studied are linear, and K{sub d} values decrease from 48 to 17 L kg{sup -1} for goethite, from 64 to 29 L kg{sup -1} for Hanford sediments, and from 95 to 51 L kg{sup -1} for Melton Branch sediments as the Ca concentration increases from 0 to 1 mM at pH 7. Our observations reveal that, in carbonate-bearing waters, neutral to slightly acidic pH values ({approx}5) and limited dissolved calcium are optimal for uranium adsorption.« less

Novel electrode structure in a DBD reactor applied to the degradation of phenol in aqueous solution

NASA Astrophysics Data System (ADS)

Mercado-Cabrera, Antonio; Peña-Eguiluz, Rosendo; López-Callejas, Régulo; Jaramillo-Sierra, Bethsabet; Valencia-Alvarado, Raúl; Rodríguez-Méndez, Benjamín; Muñoz-Castro, Arturo E.

2017-07-01

Phenol degradation experimental results are presented in a similar wastewater aqueous solution using a non-thermal plasma reactor in a coaxial dielectric barrier discharge. The novelty of the work is that one of the electrodes of the reactor has the shape of a hollow screw which shows an enhanced efficiency compared with a traditional smooth structure. The experimentation was carried out with gas mixtures of 90% Ar-10% O2, 80% Ar-20% O2 and 0% Ar-100% O2. After one hour of treatment the removal efficiency was 76%, 92%, and 97%, respectively, assessed with a gas chromatographic mass spectrometry technique. For both reactors used, the ozone concentration was measured. The screw electrode required less energy, for all gas mixtures, than the smooth electrode, to maintain the same ozone concentration. On the other hand, it was also observed that in both electrodes the electrical conductivity of the solution changed slightly from ˜0.0115 S m-1 up to ˜0.0430 S m-1 after one hour of treatment. The advantages of using the hollow screw electrode structure compared with the smooth electrode were: (1) lower typical power consumption, (2) the generation of a uniform plasma throughout the reactor benefiting the phenol degradation, (3) a relatively lower temperature of the aqueous solution during the process, and (4) the plasma generation length is larger.

Polyvinylpyrrolidone/polyvinyl butyral composite as a stable binder for castable supercapacitor electrodes in aqueous electrolytes

NASA Astrophysics Data System (ADS)

Aslan, M.; Weingarth, D.; Herbeck-Engel, P.; Grobelsek, I.; Presser, V.

2015-04-01

Mixtures of polyvinylpyrrolidone/polyvinyl butyral (PVP/PVB) are attractive binders for the preparation of carbon electrodes for aqueous electrolyte supercapacitors. The use of PVP/PVB offers several key advantages: They are soluble in ethanol and can be used to spray coat or drain cast activated carbon (AC) electrodes directly on a current collector. Infrared spectroscopy and contact angle measurements show that the PVP-to-PVB ratio determines the degree of binder hydrophilicity. Within our study, the most favorable performance was obtained for AC electrodes with a composition of AC + 1.5 mass% PVP + 6.0 mass% PVB; such electrodes were mechanically stabile and water resistant with a PVP release of less than 5% of total PVP while PVB itself is water insoluble. Compared to when using PVDF, the specific surface area (SSA) of the assembled electrodes was 10% higher, indicating a reduced pore blocking tendency. A good electrochemical performance was observed in different aqueous electrolytes for composite electrodes with the optimized binder composition: 160 F g-1 at 1 A g-1 for 1 M H2SO4 and 6 M KOH and 120 F g-1 for 1 M NaCl. The capacitance was slightly reduced by 2.5% after cycling to 1.2 V with 1.28 A g-1 in 1 M NaCl for 10,000 times.

Partial compilation and revision of basic data in the WATEQ programs

USGS Publications Warehouse

Nordstrom, D. Kirk; Valentine, S.D.; Ball, J.W.; Plummer, Niel; Jones, B.F.

1984-01-01

Several portions of the basic data in the WATEQ series of computer programs (WATEQ, WATEQF, WATEQ2, WATEQ3, and PHREEQE) are compiled. The density and dielectric constant of water and their temperature dependence are evaluated for the purpose of updating the Debye-Huckel solvent parameters in the activity coefficient equations. The standard state thermodynamic properties of the Fe2+ and Fe3+ aqueous ions are refined. The main portion of this report is a comprehensive listing of aluminum hydrolysis constants, aluminum fluoride, aluminum sulfate, calcium chloride, magnesium chloride, potassium sulfate and sodium sulfate stability constants, solubility product constants for gibbsite and amorphous aluminum hydroxide, and the standard electrode potentials for Fe (s)/Fe2+(aq) and Fe2 +(aq)/Fe3+(aq). (USGS)

Fast and Selective Modification of Thiol Proteins/Peptides by N-(Phenylseleno)phthalimide

NASA Astrophysics Data System (ADS)

Wang, Zhengfang; Zhang, Yun; Zhang, Hao; Harrington, Peter B.; Chen, Hao

2012-03-01

We previously reported that selenamide reagents such as ebselen and N-(phenylseleno)phthalimide (NPSP) can be used to selectively derivatize thiols for mass spectrometric analysis, and the introduced selenium tags are useful as they could survive or removed with collision-induced dissociation (CID). Described herein is the further study of the reactivity of various protein/peptide thiols toward NPSP and its application to derivatize thiol peptides in protein digests. With a modified protocol (i.e., dissolving NPSP in acetonitrile instead of aqueous solvent), we found that quantitative conversion of thiols can be obtained in seconds, using NPSP in a slight excess amount (NPSP:thiol of 1.1-2:1). Further investigation shows that the thiol reactivity toward NPSP reflects its chemical environment and accessibility in proteins/peptides. For instance, adjacent basic amino acid residues increase the thiol reactivity, probably because they could stabilize the thiolate form to facilitate the nucleophilic attack of thiol on NPSP. In the case of creatine phosphokinase, the native protein predominately has one thiol reacted with NPSP while all of four thiol groups of the denatured protein can be derivatized, in accordance with the corresponding protein conformation. In addition, thiol peptides in protein/peptide enzymatic digests can be quickly and effectively tagged by NPSP following tri- n-butylphosphine (TBP) reduction. Notably, all three thiols of the peptide QCCASVCSL in the insulin peptic digest can be modified simultaneously by NPSP. These results suggest a novel and selective method for protecting thiols in the bottom-up approach for protein structure analysis.

Preparation of keratin and chemically modified keratin hydrogels and their evaluation as cell substrate with drug releasing ability.

PubMed

Nakata, Ryo; Osumi, Yu; Miyagawa, Shoko; Tachibana, Akira; Tanabe, Toshizumi

2015-07-01

Keratin was extracted as a reduced form from wool, which was then subjected to acetamidation, carboxymethylation or aminoethylation at abundant free cysteine residues to give acetamidated keratin (AAK), carboxymethylated keratin (CMK) and aminoethylated keratin (AEK). Hydrogels were prepared from intact and three chemically modified keratins simply by concentrating their aqueous solution and subsequent cooling. The lowest concentration to form a hydrogel without fluidity was 110 mg/ml for AAK, 120 mg/ml for AEK, 130 mg/ml for keratin and 180 mg/ml for CMK. Comparing with a hydrogel just prepared (swelling ratio: 600-700), each hydrogel slightly shrank in an acidic solution. While AAK hydrogel little swelled in neutral and basic solutions, other hydrogels became swollen and CMK hydrogel reached to dissolution. Hydrogels of keratin, AAK and AEK were found to support cell proliferation, although cell elongation on AAK and AEK hydrogel was a little suppressed. On the other hand, CMK hydrogel did not seem to be suitable for a cell substrate because of its high swelling in culture medium. Evaluation of the hydrogels as a drug carrier showed that keratin and AAK hydrogels were good sustained drug release carriers, which showed the drug release for more than three days, while the release from AEK and CMK hydrogels completed within one day. Thus, keratin and chemically modified keratin hydrogels, especially keratin and AAK hydrogels, were promising biomaterials as a cell substrate and a sustained drug release carrier. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Modulation of intra- and inter-sheet interactions in short peptide self-assembly by acetonitrile in aqueous solution

NASA Astrophysics Data System (ADS)

Deng, Li; Zhao, Yurong; Zhou, Peng; Xu, Hai; Wang, Yanting

2016-12-01

Not Available Project supported by the National Basic Research Program of China (Grant No. 2013CB932804), the National Natural Science Foundation of China (Grant Nos. 91227115, 11421063, 11504431, and 21503275), the Fundamental Research Funds for Central Universities of China (Grant No. 15CX02025A), and the Application Research Foundation for Post-doctoral Scientists of Qingdao City, China (Grant No. T1404096).

Design of Heterogeneous Hoveyda-Grubbs Second-Generation Catalyst-Lipase Conjugates.

PubMed

Neville, Anthony; Iniesta, Javier; Palomo, Jose M

2016-12-06

Heterogeneous catalysts have been synthesi zed by the conjugation of Hoveyda-Grubbs second-generation catalyst with a lipase. The catalytic properties of the organometallic compound in solution were firstly optimized, evaluating the activity of Ru in the ring-closing metathesis of diethyldiallymalonate at 25 °C at different solvents and in the presence of different additives. The best result was found using tetrahydrofuran as a solvent. Some additives such as phenylboronic acid or polyetheneglycol slightly improved the activity of the Ru catalyst whereas others, such as pyridine or dipeptides affected it negatively. The organometallic compound immobilized on functionalized-surface materials activated with boronic acid or epoxy groups (around 50-60 µg per mg support) and showed 50% conversion at 24 h in the ring-closing metathesis. Cross-linked enzyme aggregates (CLEA's) of the Hoveyda-Grubbs second-generation catalyst with Candida antarctica lipase (CAL-B) were prepared, although low Ru catalyst was found to be translated in low conversion. Therefore, a sol-gel preparation of the Hoveyda-Grubbs second-generation and CAL-B was performed. This catalyst exhibited good activity in the metathesis of diethyldiallymalonate in toluene and in aqueous media. Finally, a new sustainable approach was used by the conjugation lipase-Grubbs in solid phase in aqueous media. Two strategies were used: one using lipase previously covalently immobilized on an epoxy-Sepharose support (hydrophilic matrix) and then conjugated with grubbs; and in the second, the free lipase was incubated with organometallic in aqueous solution and then immobilized on epoxy-Sepharose. The different catalysts showed excellent conversion values in the ring-closing metathesis of diethyldiallymalonate in aqueous media at 25 °C.

Nanoscale Zero-Valent Iron Decorated on Bentonite/Graphene Oxide for Removal of Copper Ions from Aqueous Solution.

PubMed

Shao, Jicheng; Yu, Xiaoniu; Zhou, Min; Cai, Xiaoqing; Yu, Chuang

2018-06-04

The removal efficiency of Cu(II) in aqueous solution by bentonite, graphene oxide (GO), and nanoscale iron decorated on bentonite (B-nZVI) and nanoscale iron decorated on bentonite/graphene oxide (GO-B-nZVI) was investigated. The results indicated that GO-B-nZVI had the best removal efficiency in different experimental environments (with time, pH, concentration of copper ions, and temperature). For 16 hours, the removal efficiency of copper ions was 82% in GO-B-nZVI, however, it was 71% in B-nZVI, 26% in bentonite, and 18% in GO. Bentonite, GO, B-nZVI, and GO-B-nZVI showed an increased removal efficiency of copper ions with the increase of pH under a certain pH range. The removal efficiency of copper ions by GO-B-nZVI first increased and then fluctuated slightly with the increase of temperature, while B-nZVI and bentonite increased and GO decreased slightly with the increase of temperature. Lorentz-Transmission Electron Microscope (TEM) images showed the nZVI particles of GO-B-nZVI dispersed evenly with diameters ranging from 10 to 86.93 nm. Scanning electron microscope (SEM) images indicated that the nanoscale iron particles were dispersed evenly on bentonite and GO with no obvious agglomeration. The q e,cal (73.37 mg·g -1 and 83.89 mg·g -1 ) was closer to the experimental value q e,exp according to the pseudo-second-order kinetic model. The q m of B-nZVI and GO-B-nZVI were 130.7 mg·g -1 and 184.5 mg·g -1 according to the Langmuir model.

Solid-phase extraction element based on epoxy polymer monolith for determination of polar organic compounds in aqueous media.

PubMed

Takahashi, Tadashi; Odagiri, Kayo; Watanabe, Atsushi; Watanabe, Chuichi; Kubo, Takuya; Hosoya, Ken

2011-10-01

A solid-phase extraction element based on epoxy polymer monolith was fabricated for sorptive enrichment of polar compounds from liquid and gaseous samples. After ultrasonication of the element in an aqueous solution for a given period of time, the thermal desorption (TD) using a pyrolyzer with gas chromatography/mass spectrometry (GC/MS), in which TD temperature was programmed from 50 to 250 °C for the analytes absorbed in the element, was used to evaluate the element for basic extraction performance using the aqueous standard mixtures consisting of compounds having varied polarities such as hexanol, isoamyl acetate, linalool, furfural and decanoic acid, in concentrations ranging from 10 μg/L to 1 mg/L. Excellent linear relationships were observed for all compounds in the standard mixture, except decanoic acid. In the extraction of beverages such as red wine, the extraction element showed stronger adsorption characteristics for polar compounds such as alcohols and acids than a non-polar polydimethylsiloxane-based element. This feature is derived from the main polymer structure along with hydroxyl and amino groups present in the epoxy-based monolith polymer matrix. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Uranium removal from aqueous solution by coir pith: equilibrium and kinetic studies.

PubMed

Parab, Harshala; Joshi, Shreeram; Shenoy, Niyoti; Verma, Rakesh; Lali, Arvind; Sudersanan, M

2005-07-01

Basic aspects of uranium adsorption by coir pith have been investigated by batch equilibration. The influence of different experimental parameters such as final solution pH, adsorbent dosage, sorption time, temperature and various concentrations of uranium on uptake were evaluated. Maximum uranium adsorption was observed in the pH range 4.0-6.0. The Freundlich and Langmuir adsorption models were used for the mathematical description of the adsorption equilibrium. The equilibrium data fitted well to both the equilibrium models in the studied concentration range of uranium (200-800 mg/l) and temperatures (305-336 K). The coir pith exhibited the highest uptake capacity for uranium at 317 K, at the final solution pH value of 4.3 and at the initial uranium concentration of 800 mg/l. The kinetics of the adsorption process followed a second-order adsorption. The adsorbent used proved to be suitable for removal of uranium from aqueous solutions. 0.2 N HCl was effective in uranium desorption. The results indicated that the naturally abundant coir pith of otherwise nuisance value exhibited considerable potential for application in removal of uranium from aqueous solution.

Effect of the presence of cationic polyacrylamide on the surface properties of aqueous alumina suspension-stability mechanism

NASA Astrophysics Data System (ADS)

Wiśniewska, Małgorzata; Chibowski, Stanisław; Urban, Teresa

2014-11-01

The effects of solution pH and the content of cationic groups in polyacrylamide (PAM) macromolecules on the stability mechanism of aqueous alumina suspension were investigated. The following experimental techniques were applied: spectrophotometry, potentiometric titration, microelectrophoresis, viscosimetry and turbidimetry. They enable determination of polymer adsorbed amount, surface charge density and zeta potential of solid particles in the presence and absence of PAM, as well as thickness of polymer adsorption layer, size of macromolecules in the solution and stability of the Al2O3-polymer systems, respectively. The obtained results indicate that adsorption of PAM increases with the increasing pH, whereas the thickness of polymeric adsorption layer decreases. Additionally, the greater the number of cationic groups in the PAM chains is, the higher adsorption was found. The polymer presence influences on the alumina suspension stability. At pH 3 and 6 the slight deterioration of stability conditions of solid particle covered with polyacrylamide was observed. At pH 9 the systems containing polymer are unstable, similarly to the suspension without PAM, but the mechanism of their destabilization is different.

Carbonate substitution in lead hydroxyapatite Pb5(PO4)3OH

NASA Astrophysics Data System (ADS)

Kwaśniak-Kominek, M.; Manecki, M.; Matusik, J.; Lempart, M.

2017-11-01

Synthetic carbonate lead hydroxyapatite Pb5(PO4,CO3)3(OH,CO3) was precipitated from aqueous solution and characterized. The maximum content of CO32- ion in lead apatites does not exceed 2.25 wt%. For precipitation from aqueous solutions this is even lower and controlled by the solubility of cerussite PbCO3. Carbonate substitution occurs simultaneously in two structural positions: at OH- sites (A-type substitution) and at PO43- sites (B-type substitution). This is the most pronounced in FTIR (Fourier Transform Infrared Spectroscopy) spectra at 865 cm-1 and within the range of 1300-1500 cm-1. The substitution results in slight increase of the unit cell parameter a from 9.874 to 9.904 A. The presence of CO32- in two structural positions results in two stages of the release of CO2 upon heating: at 300-350 °C and at 400 °C. The presence of carbonates has little effect on thermal decomposition of lead hydroxyapatite which starts at about 450 °C resulting in the formation of lead pyrophosphate.

Facile solution-processed aqueous MoOx for feasible application in organic light-emitting diode

NASA Astrophysics Data System (ADS)

Zheng, Qinghong; Qu, Disui; Zhang, Yan; Li, Wanshu; Xiong, Jian; Cai, Ping; Xue, Xiaogang; Liu, Liming; Wang, Honghang; Zhang, Xiaowen

2018-05-01

Solution-processed techniques attract increasing attentions in organic electronics for their low-cost and scalable manufacturing. We demonstrate the favorite hole injection material of solution-processed aqueous MoOx (s-MoOx) with facile fabrication process and cast successful application to constructing efficient organic light-emitting diodes (OLEDs). Atomic force microscopy and X-ray photoelectron spectroscopy analysis show that s-MoOx behaves superior film morphology and non-stoichiometry with slight oxygen deficiency. With tris(8-hydroxy-quinolinato)aluminium as emitting layer, s-MoOx based OLED shows maximum luminous efficiency of 7.9 cd/A and power efficiency of 5.9 lm/W, which have been enhanced by 43.6% and 73.5%, respectively, in comparison with the counterpart using conventional vacuum thermal evaporation MoOx. Current-voltage, impedance-voltage, phase-voltage and capacitance-voltage characteristics of hole-only devices indicate that s-MoOx with two processes of "spin-coating/annealing" shows mostly enhanced hole injection capacity and thus promoting device performance. Our experiments provide an alternative approach for constructing efficient OLED with solution process.

Rhenium-osmium isotope systematics of carbonaceous chondrites

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.

1989-01-01

Rhenium and osmium concentrations and Os isotopic compositions of eight carbonaceous chondrites, one LL3 ordinary chondrite, and two iron meteorites were determined by resonance ionization mass spectrometry. Iron meteorite 187Re/186Os and 187OS/186Os ratios plot on the previously determined iron meteorite isochron, but most chondrite data plot 1 to 2 percent above this meteorite isochron. This suggests either that irons have significantly younger Re-Os closure ages than chondrites or that chondrites were formed from precursor materials with different chemical histories from the precursors of irons. Some samples of Semarkona (LL3) and Murray (C2M) meteorites plot 4 to 6 percent above the iron meteorite isochron, well above the field delineated by other chondrites. Murray may have lost Re by aqueous leaching during its preterrestrial history. Semarkona could have experienced a similar loss of Re, but only slight aqueous alteration is evident in the meteorite. Therefore, the isotopic composition of Semarkona could reflect assembly of isotopically heterogeneous components subsequent to 4.55 billion years ago or Os isotopic heterogeneities in the primordial solar nebula.

Ultrathin nanofibrous films prepared from cadmium hydroxide nanostrands and anionic surfactants.

PubMed

Peng, Xinsheng; Karan, Santanu; Ichinose, Izumi

2009-08-04

We developed a simple fabrication method of ultrathin nanofibrous films from the dispersion of cadmium hydroxide nanostrands and anionic surfactants. The nanostrands were prepared in a dilute aqueous solution of cadmium chloride by using 2-aminoethanol. They were highly positively charged and gave bundlelike fibers upon mixing an aqueous solution of anionic surfactant. The nanostrand/surfactant composite fibers were filtered on an inorganic membrane filter. The resultant nanofibrous film was very uniform in the area of a few centimeters square when the thickness was not less than 60 nm. The films obtained with sodium tetradecyl sulfate (STS) had a composition close to the electroneutral complex, [Cd37(OH)68(H2O)n] x 6(STS), as confirmed by energy dispersive X-ray analysis. They were water-repellent with a contact angle of 117 degrees, and the value slightly decreased with the alkyl chain length of anionic surfactants. Ultrathin nanofibrous films were stable enough to be used for ultrafiltration at pressure difference of 90 kPa. We could effectively separate Au nanoparticles of 40 nm at an extremely high filtration rate of 14000 L/(h m2 bar).

Using Central Composite Experimental Design to Optimize the Degradation of Tylosin from Aqueous Solution by Photo-Fenton Reaction

PubMed Central

Sarrai, Abd Elaziz; Hanini, Salah; Merzouk, Nachida Kasbadji; Tassalit, Djilali; Szabó, Tibor; Hernádi, Klára; Nagy, László

2016-01-01

The feasibility of the application of the Photo-Fenton process in the treatment of aqueous solution contaminated by Tylosin antibiotic was evaluated. The Response Surface Methodology (RSM) based on Central Composite Design (CCD) was used to evaluate and optimize the effect of hydrogen peroxide, ferrous ion concentration and initial pH as independent variables on the total organic carbon (TOC) removal as the response function. The interaction effects and optimal parameters were obtained by using MODDE software. The significance of the independent variables and their interactions was tested by means of analysis of variance (ANOVA) with a 95% confidence level. Results show that the concentration of the ferrous ion and pH were the main parameters affecting TOC removal, while peroxide concentration had a slight effect on the reaction. The optimum operating conditions to achieve maximum TOC removal were determined. The model prediction for maximum TOC removal was compared to the experimental result at optimal operating conditions. A good agreement between the model prediction and experimental results confirms the soundness of the developed model. PMID:28773551

Influence of polymeric excipient properties on crystal hydrate formation kinetics of caffeine in aqueous slurries.

PubMed

Gift, Alan D; Southard, Leslie A; Riesberg, Amanda L

2012-05-01

The influence of polymeric excipients on the hydrate transformation of caffeine (CAF) was studied. Anhydrous CAF was added to aqueous solutions containing different additives and the transformation to the hydrate form was monitored using in-line Raman spectroscopy. Various properties of two known inhibitors of CAF hydrate formation, polyacrylic acid (PAA) and polyvinyl alcohol (PVA), were investigated. For inhibition by PAA, a pH dependence was observed: at low pH, the inhibition was greatest, whereas no inhibitory effects were observed at pH above 6.5. For PVA, grades with high percent hydrolysis were the most effective at inhibiting the transformation. In addition, PVA with higher molecular weight showed slightly more inhibition than the shorter chain PVA polymers. A variety of other hydroxyl containing compounds were examined but none inhibited the CAF anhydrate-to-hydrate transformation. The observed inhibitory effects of PAA and PVA are attributed to the large number of closely spaced hydrogen bond donating groups of the polymer molecule, which can interact with the CAF hydrate crystal. Copyright © 2012 Wiley Periodicals, Inc.

Effect of solubilizing agents on mupirocin loading into and release from PEGylated nanoliposomes.

PubMed

Cern, Ahuva; Nativ-Roth, Einat; Goldblum, Amiram; Barenholz, Yechezkel

2014-07-01

Mupirocin was identified by quantitative structure property relationship models as a good candidate for remote liposomal loading. Mupirocin is an antibiotic that is currently restricted to topical administration because of rapid hydrolysis in vivo to its inactive metabolite. Formulating mupirocin in PEGylated nanoliposomes may potentially expand its use to parenteral administration by protecting it from degradation in the circulation and target it (by the enhanced permeability effect) to the infected tissue. Mupirocin is slightly soluble in aqueous medium and its solubility can be increased using solubilizing agents. The effect of the solubilizing agents on mupirocin remote loading was studied when the solubilizing agents were added to the drug loading solution. Propylene glycol was found to increase mupirocin loading, whereas polyethylene glycol 400 showed no effect. Hydroxypropyl-β-cyclodextrin (HPCD) showed a concentration-dependent effect on mupirocin loading; using the optimal HPCD concentration increased loading, but higher concentrations inhibited it. The inclusion of HPCD in the liposome aqueous phase while forming the liposomes resulted in increased drug loading and substantially inhibited drug release in serum. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

An Experiment in Basic Airborne Electronics Training. Part 5: Evaluation of the Revised Courses.

ERIC Educational Resources Information Center

Baldwin, Robert O.; Johnson, Kirk A.

This is the fifth in a series on shortened versions of the Avionics Fundamentals and Aviation Electronics Technician R (Radar) Courses. The first four studies indicated that the initial revisions of the courses led to substantial savings in training time, but that the graduates from the revised courses were slightly inferior to graduates from the…

Basic Language Comprehension and Production in Greater than 100,000 Young Children from Sixteen Developing Nations

ERIC Educational Resources Information Center

Bornstein, Marc H.; Hendricks, Charlene

2012-01-01

Using the Multiple Indicator Cluster Survey, language comprehension and production were compared in a sample of 101,250 children aged 2 ; 00 to 9 ; 11 and a focus subsample of 38,845 children aged 2 ; 00 to 4 ; 11 from sixteen under-researched developing nations. In the whole sample, comprehension slightly exceeded production; correlations between…

Correlation between substratum roughness and wettability, cell adhesion, and cell migration.

PubMed

Lampin, M; Warocquier-Clérout; Legris, C; Degrange, M; Sigot-Luizard, M F

1997-07-01

Cell adhesion and spreading of chick embryo vascular and corneal explants grown on rough and smooth poly (methyl methacrylate) (PMMA) were analyzed to test the cell response specificity to substratum surface properties. Different degrees of roughness were obtained by sand-blasting PMMA with alumina grains. Hydrophilic and hydrophobic components of the surface free energy (SFE) were calculated according to Good-van Oss's model. Contact angles were determined using a computerized angle meter. The apolar component of the SFE gamma s(LW), increased with a slight roughness whereas the basic component, gamma s-, decreased. The acido-basic properties disappeared as roughness increased. Incubation of PMMA in culture medium, performed to test the influence if the biological environment, allowed surface adsorption of medium proteins which annihilated roughness effect and restored hydrophilic properties. An organotypic culture assay was carried out in an attempt to relate the biocompatibility to substratum surface state. Cell migration was calculated from the area of cell layer. Cellular adhesion was determined by measuring the kinetic of release of enzymatically dissociated cells. A slight roughness raised the migration are to an upper extent no matter which cell type. Enhancement of the cell adhesion potential was related to the degree of roughness and the hydrophobicity.

Photocatalytic degradation of Maxilon C.I. basic dye using CS/CoFe2O4/GONCs as a heterogeneous photo-Fenton catalyst prepared by gamma irradiation.

PubMed

Al-Kahtani, Abdullah A; Abou Taleb, Manal F

2016-05-15

CS/CF/GONCs were synthesized via gamma irradiation cross-linking method with the aid of sonication. The nanocomposites exhibited a photo-Fenton catalytic feature for the degradation of Maxilon C.I. basic dye in aqueous medium using sunlight. The effects of pH, H2O2 concentration, and dosage of the catalyst, on the degradation rates of the dyes were examined. The optimal degradation rate was reached with 10mM H2O2 at pH 9.5. It was verified that the Maxilon C.I. basic dye degradation rate fits a pseudo-first-order kinetics for different initial concentrations of Maxilon C.I. dye. Fourth cyclic tests for Maxilon C.I. degradation showed that the magnetic catalyst was very stable, recoverable, highly active, and easy to separate using an external magnet. Hence, this magnetic catalyst has potential use in organic pollutant removal. Copyright © 2016 Elsevier B.V. All rights reserved.

Flavylium network of chemical reactions in confined media: modulation of 3',4',7-trihydroxyflavilium reactions by host-guest interactions with cucurbit[7]uril.

PubMed

Basílio, Nuno; Pina, Fernando

2014-08-04

In moderately acidic aqueous solutions, flavylium compounds undergo a pH-, and in some cases, light-dependent array of reversible chemical reactions. This network can be described as a single acid-base reaction involving a flavylium cation (acidic form) and a mixture of basic forms (quinoidal base, hemiketal and cis and trans chalcones). The apparent pK'a of the system and the relative mole fractions of the basic forms can be modulated by the interaction with cucurbit[7]uril. The system is studied by using (1) H NMR spectroscopy, UV/Vis spectroscopy, flash photolysis, and steady-state irradiation. Of all the network species, the flavylium cation possesses the highest affinity for cucurbit[7]uril. The rate of interconversion between flavylium cation and the basic species (where trans-chalcone is dominant) is approximately nine times lower inside the cucurbit[7]uril. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Building Damage Extraction Triggered by Earthquake Using the Uav Imagery

NASA Astrophysics Data System (ADS)

Li, S.; Tang, H.

2018-04-01

When extracting building damage information, we can only determine whether the building is collapsed using the post-earthquake satellite images. Even the satellite images have the sub-meter resolution, the identification of slightly damaged buildings is still a challenge. As the complementary data to satellite images, the UAV images have unique advantages, such as stronger flexibility and higher resolution. In this paper, according to the spectral feature of UAV images and the morphological feature of the reconstructed point clouds, the building damage was classified into four levels: basically intact buildings, slightly damaged buildings, partially collapsed buildings and totally collapsed buildings, and give the rules of damage grades. In particular, the slightly damaged buildings are determined using the detected roof-holes. In order to verify the approach, we conduct experimental simulations in the cases of Wenchuan and Ya'an earthquakes. By analyzing the post-earthquake UAV images of the two earthquakes, the building damage was classified into four levels, and the quantitative statistics of the damaged buildings is given in the experiments.

The stability of 6-mercaptopurine riboside in neutral and basic medium.

PubMed

Jelińska, A; Magdziarz, M

2000-01-01

The kinetics of hydrolysis of 6-mercaptopurine riboside (R-6-MP) was studied in aqueous solutions over the pH range of 6.11-12.13 at 353 K. The decomposition was investigated by HPLC method. At the pH range from 6.11 to 12.13 hydrolysis of 6-mercaptopurine riboside includes: spontaeous hydrolysis of non-protonated R-6-MP molecules mono- and di-anions R-6-MP molecules under the effect of water.

Polyglutaraldehyde - A new reagent for coupling proteins to microspheres and for labeling cell-surface receptors

NASA Technical Reports Server (NTRS)

Rembaum, A.; Levy, J.; Margel, S.

1978-01-01

Glutaraldehyde polymerized in basic aqueous solutions was found to react with low molecular weight amines, immunoglobulins and hemoglobin. The polyglutaraldehyde was covalently bound to hydrophilic microspheres. The rate of addition of proteins to the polyglutaraldehyde-derivatized microspheres was investigated spectrophotometrically as a function of pH and temperature. The reaction of polyglutaraldehyde was found to be faster than that of the monomer. The findings led to successful labeling of human lymphocyte subpopulations.

Regeneration of carboxylic acid-laden basic sorbents by leaching with a volatile base in an organic solvent

DOEpatents

King, C. Judson; Husson, Scott M.

1999-01-01

Carboxylic acids are sorbed from aqueous feedstocks onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with an organic solution of alkylamine thus forming an alkylamine/carboxylic acid complex which is decomposed with improved efficiency to the desired carboxylic acid and the alkylamine. Carbon dioxide addition can be used to improve the adsorption or the carboxylic acids by the solid phase sorbent.

Docking and molecular dynamics simulations of the Fyn-SH3 domain with free and phospholipid bilayer-associated 18.5-kDa myelin basic protein (MBP)-Insights into a noncanonical and fuzzy interaction.

PubMed

Bessonov, Kyrylo; Vassall, Kenrick A; Harauz, George

2017-07-01

The molecular details of the association between the human Fyn-SH3 domain, and the fragment of 18.5-kDa myelin basic protein (MBP) spanning residues S38-S107 (denoted as xα2-peptide, murine sequence numbering), were studied in silico via docking and molecular dynamics over 50-ns trajectories. The results show that interaction between the two proteins is energetically favorable and heavily dependent on the MBP proline-rich region (P93-P98) in both aqueous and membrane environments. In aqueous conditions, the xα2-peptide/Fyn-SH3 complex adopts a "sandwich"-like structure. In the membrane context, the xα2-peptide interacts with the Fyn-SH3 domain via the proline-rich region and the β-sheets of Fyn-SH3, with the latter wrapping around the proline-rich region in a form of a clip. Moreover, the simulations corroborate prior experimental evidence of the importance of upstream segments beyond the canonical SH3-ligand. This study thus provides a more-detailed glimpse into the context-dependent interaction dynamics and importance of the β-sheets in Fyn-SH3 and proline-rich region of MBP. Proteins 2017; 85:1336-1350. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Description and Evaluation of Chiral Interactive Sites on Bonded Cyclodextrin Stationary Phases for Liquid Chromatography

NASA Astrophysics Data System (ADS)

Beesley, Thomas E.

Development of chiral separations has been essential to the drug discovery and development process. The solubility requirements for a number of methods and/or the mobile phase requirements for application of certain detection systems have opened up many opportunities for cyclodextrin-based CSPs for liquid chromatography. Even though a few chiral stationary phases cover a wide area of enantioselectivity, they do not meet the entire needs of the industry. Cyclodextrin phases offer some unique mechanisms and opportunities to resolve chiral separation problems especially in the aqueous reversed-phase and non-aqueous polar organic modes. This chapter addresses the need to understand the chiral stationary phase structure, the mechanisms at work, and the role mobile phase composition plays in driving those mechanisms to produce enantioselectivity. In addition, the development of certain derivatives has played an essential part in expanding that basic role for certain chiral separations. What these derivatives contribute in concert with the basic structure is a critical part of the understanding to the effective use of these phases. During this study it was determined that the role of steric hindrance has been vastly underestimated, both to the extent that it has occurred and to its effectiveness for obtaining enantioselectivity. References to the entire 20-year history of the cyclodextrin phase development and application literature up to this current date have been reviewed and incorporated.

Solubility of Gliclazide and Ion-Molecular Interactions with Aminopropanol in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Hamdan, Imad I.; El-Sabawi, Dina; Abu-Dahab, Rana

2018-01-01

A new salt of gliclazide (GZD) was prepared and was shown to have a significantly higher aqueous solubility at physiological pH together with superior dissolution profiles in comparison to GZD employing an organic amino-alcohol base. Characterization by NMR, IR, DSC, conductometry and HPLC techniques concluded that an ion pair salt is formed between acidic GZD and basic aminopropanol (AMP). In addition to the presence of about 5% tightly bound water, hydrogen bonds appeared to form extensively between GZD, AMP and water molecules. Unlike many of solubility enhancing approaches, the salt did not hamper the permeability of GZD as shown by transport through Caco-2 cells model. In vivo studies on rats confirmed that the blood glucose lowering effect of GZD-AMP was significantly higher and more rapid compared to parent GZD indicating an enhanced overall performance of the prepared salt.

Hydration of nonelectrolytes in binary aqueous solutions

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.

2010-10-01

Literature data on the thermodynamic properties of binary aqueous solutions of nonelectrolytes that show negative deviations from Raoult's law due largely to the contribution of the hydration of the solute are briefly surveyed. Attention is focused on simulating the thermodynamic properties of solutions using equations of the cluster model. It is shown that the model is based on the assumption that there exists a distribution of stoichiometric hydrates over hydration numbers. In terms of the theory of ideal associated solutions, the equations for activity coefficients, osmotic coefficients, vapor pressure, and excess thermodynamic functions (volume, Gibbs energy, enthalpy, entropy) are obtained in analytical form. Basic parameters in the equations are the hydration numbers of the nonelectrolyte (the mathematical expectation of the distribution of hydrates) and the dispersions of the distribution. It is concluded that the model equations adequately describe the thermodynamic properties of a wide range of nonelectrolytes partly or completely soluble in water.

New fluorescent symmetrically substituted perylene-3,4,9,10-dianhydride-azohybrid dyes: Synthesis and spectroscopic studies

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Shabir, Ghulam

2014-12-01

Five phenolic azo-dyes (3a-e) were synthesized by diazo coupling of the suitably substituted anilines (1a-e) with phenol at low temperature in alkaline medium. The resulting dyes have low solubility in aqueous medium due to lack of carboxylic or sulfonic solubilizing functionalities. The hybridization of perylene dianhydride with phenolic azo-dyes was achieved by the nucleophilic aromatic substitution (SNAr) reaction of perylene-3,4,9,10-dianhydride 4 with phenolic azo-dyes 3a-e in basic medium. The hybrid dyes exhibit absorption maxima λmax in the range 440-460 nm in aqueous medium due to presence of azo linkage and highly conjugated system of π bonds. Fluorescence spectra of these dyes in water show sharp emission peaks with small band widths. The structures of perylene-azo dyes were confirmed by FTIR and NMR spectroscopy.

Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

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

Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran

A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

DOE PAGES

Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; ...

2014-12-02

A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

Intercalation Pseudocapacitance of Exfoliated Molybdenum Disulfide for Ultrafast Energy Storage

DOE PAGES

Yoo, Hyun Deog; Li, Yifei; Liang, Yanliang; ...

2016-05-23

In this study, we report intercalation pseudocapacitance of 250 F g -1 for exfoliated molybdenum disulfide (MoS 2) in non-aqueous electrolytes that contain lithium ions. The exfoliated MoS 2 shows surface-limited reaction kinetics with high rate capability up to 3 min of charge or discharge. The intercalation pseudocapacitance originates from the extremely fast kinetics due to the enhanced ionic and electronic transport enabled by the slightly expanded layer structure as well as the metallic 1T-phase. The exfoliated MoS 2 could be also used in a Li-Mg-ion hybrid capacitor, which shows full cell specific capacitance of 240 F g -1.

Ion-pairing in aqueous CaCl 2 and RbBr solutions. Simultaneous structural refinement of XAFS and XRD data

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

Pham, Thai V.; Fulton, John L.

2013-01-22

We present a new methodology involving the simultaneous refinement of both x-ray absorption and x-ray diffraction spectra (X-ray Absorption/Diffraction Structural Refinement,XADSR), to study hydration and ion pair structure of CaCl 2 and RbBr salts in concentrated aqueous solutions. The XADSR analysis includes the XAFS spectra analysis of both the cation and anion as a probe of their short-range structure with an XRD spectral analysis as a probe of the global structural. Together they deliver a comprehensive picture of the cation and anion hydration, the contact ion pair (CIP) structure and the solvent-separated ion pair (SSIP) structure. XADSR analysis of 6.0more » m aqueous CaCl 2 reveals that there are an insignificant number of Ca 2+-Cl- CIP’s, but there are approximately 3.4 SSIP’s separated by about 4.99 Å. In contrast XADSR analysis of aqueous RbBr yields about 0.7 pair CIP at a bond length 3.51 Å. The present work demonstrates a new approach for a direct co-refinement of XRD and XAFS spectra in a simple and reliable fashion, opening new opportunities for analysis in various disordered and crystalline systems. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is operated for the U.S. Department of Energy by Battelle.« less

Metal Sulfide Cluster Complexes and their Biogeochemical Importance in the Environment

NASA Astrophysics Data System (ADS)

Luther, George W.; Rickard, David T.

2005-10-01

Aqueous clusters of FeS, ZnS and CuS constitute a major fraction of the dissolved metal load in anoxic oceanic, sedimentary, freshwater and deep ocean vent environments. Their ubiquity explains how metals are transported in anoxic environmental systems. Thermodynamic and kinetic considerations show that they have high stability in oxic aqueous environments, and are also a significant fraction of the total metal load in oxic river waters. Molecular modeling indicates that the clusters are very similar to the basic structural elements of the first condensed phase forming from aqueous solutions in the Fe-S, Zn-S and Cu-S systems. The structure of the first condensed phase is determined by the structure of the cluster in solution. This provides an alternative explanation of Ostwald's Rule, where the most soluble, metastable phases form before the stable phases. For example, in the case of FeS, we showed that the first condensed phase is nanoparticulate, metastable mackinawite with a particle size of 2 nm consisting of about 150 FeS subunits, representing the end of a continuum between aqueous FeS clusters and condensed material. These metal sulfide clusters and nanoparticles are significant in biogeochemistry. Metal sulfide clusters reduce sulfide and metal toxicity and help drive ecology. FeS cluster formation drives vent ecology and AgS cluster formation detoxifies Ag in Daphnia magna neonates. We also note a new reaction between FeS and DNA and discuss the potential role of FeS clusters in denaturing DNA.

Stability and activity of lysozyme in stoichiometric and non-stoichiometric protic ionic liquid (PIL)-water systems

NASA Astrophysics Data System (ADS)

Wijaya, Emmy C.; Separovic, Frances; Drummond, Calum J.; Greaves, Tamar L.

2018-05-01

There has been a substantial increase in enzyme applications within the biochemical and pharmaceutical industries, for example, as industrial biocatalysts. However, enzymes have narrow marginal stability which makes them prone to become inactive and/or denature with a slight change in the solvent environment. Typically industrial applications require harsher solvent environments than enzyme native environments, and hence there is a need to understand solvent-protein interactions in order to develop strategies to maintain, or enhance, the enzymatic activity under industrially relevant solvent conditions. Previously we have shown that protic ionic liquids (PILs) with water can have a stabilising effect on lysozyme, with a large variation dependent on which PIL ions are present, and the water concentration [E. C. Wijaya et al., Phys. Chem. Chem. Phys. 18(37), 25926-25936 (2016)]. Here we extend on this work using non-stoichiometric aqueous PIL solvents to investigate, and isolate, the role of pH and ionicity on enzymes. We have used the PILs ethylammonium nitrate (EAN) and ethanolammonium formate (EOAF) since our previous work has identified these as good solvents for lysozyme. Solvent libraries were made from these two PILs with an additional precursor acid or base to modify the acidity/basicity of the neutral stoichiometric PIL, and with water added, to have solutions with 4-17 mol. % of the PIL ions in water. Molar ratios of base:acid were varied between 1:1.05 and 2:1 for EAN and 1:1.25 and 2:1 for EOAF, which enabled from highly basic to highly acidic solutions to be obtained. This was to modify the acidity/basicity of the neutral stoichiometric PILs, without the addition of buffers. The structure and stability of hen egg white lysozyme (HEWL) were explored under these solvent conditions using synchrotron small angle X-ray scattering (SAXS), Fourier transform infrared (FTIR), and activity assays. The radius of gyration and Kratky plots obtained from the SAXS data showed little change with varying ionicity or acid:base ratio. FTIR showed that α-helix was maintained in all, except for the most acidic solvent conditions. The activity data show that HEWL was active between pH 0 and 11 for the EA:N-water system and pH 4.4 and 11 for the EOA:F-water system. This work indicates that ionic liquids have the potential to enable enzymes to maintain activity across a broader range of solvent conditions.

Converting baker's waste into alcohol. Revised final progress report

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

Halsey, R.; Wilson, P.B.

All types of baker's waste (including waste from candy manufacturers) can be converted into alcohol to be used as a fuel. All types of waste at any stage in process can be converted, such as: basic ingredients (including floor sweepings); dry mixes (including floor sweepings); dough at any stage; partially or fully cooked products; and day old returned products. The basic steps are the same, only the initial preparation will vary slightly. The variation will be: amount of water to be added and amount and type of nutrients (if any) to be added. The basic steps are: slurrying, liquefying tomore » put starch into liquid state, saccharifying to convert starch into fermentable sugars, fermentation to convert sugars into alcohol, and distillation to separate the alcohol from the mash. Each step is discussed in detail along with problems that may arise. Directions are given and materials (enzymes, yeast, etc.) and equipment are descibed briefly.« less

"Miswak" Based Green Synthesis of Silver Nanoparticles: Evaluation and Comparison of Their Microbicidal Activities with the Chemical Synthesis.

PubMed

Shaik, Mohammed Rafi; Albalawi, Ghadeer H; Khan, Shams Tabrez; Khan, Merajuddin; Adil, Syed Farooq; Kuniyil, Mufsir; Al-Warthan, Abdulrahman; Siddiqui, Mohammed Rafiq H; Alkhathlan, Hamad Z; Khan, Mujeeb

2016-11-06

Microbicidal potential of silver nanoparticles (Ag-NPs) can be drastically improved by improving their solubility or wettability in the aqueous medium. In the present study, we report the synthesis of both green and chemical synthesis of Ag-NPs, and evaluate the effect of the dispersion qualities of as-prepared Ag-NPs from both methods on their antimicrobial activities. The green synthesis of Ag-NPs is carried out by using an aqueous solution of readily available Salvadora persica L. root extract (RE) as a bioreductant. The formation of highly crystalline Ag-NPs was established by various analytical and microscopic techniques. The rich phenolic contents of S. persica L. RE (Miswak) not only promoted the reduction and formation of NPs but they also facilitated the stabilization of the Ag-NPs, which was established by Fourier transform infrared spectroscopy (FT-IR) analysis. Furthermore, the influence of the volume of the RE on the size and the dispersion qualities of the NPs was also evaluated. It was revealed that with increasing the volume of RE the size of the NPs was deteriorated, whereas at lower concentrations of RE smaller size and less aggregated NPs were obtained. During this study, the antimicrobial activities of both chemically and green synthesized Ag-NPs, along with the aqueous RE of S. persica L., were evaluated against various microorganisms. It was observed that the green synthesized Ag-NPs exhibit comparable or slightly higher antibacterial activities than the chemically obtained Ag-NPs.

Influence of ultrasound pretreatment on wood physiochemical structure.

PubMed

He, Zhengbin; Wang, Zhenyu; Zhao, Zijian; Yi, Songlin; Mu, Jun; Wang, Xiaoxu

2017-01-01

As an initial step to increase the use of renewable biomass resources, this study was aimed at investigating the effects of ultrasound pretreatment on structural changes of wood. Samples were pretreated by ultrasound with the power of 300W and frequency of 28kHz in aqueous soda solution, aqueous acetic acid, or distilled water, then pretreated and control samples were characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The results shown that ultrasound pretreatment is indeed effective in modifying the physiochemical structure of eucalyptus wood; the pretreatment decreased the quantity of alkali metals (e.g., potassium, calcium and magnesium) in the resulting material. Compared to the control group, the residual char content of samples pretreated in aqueous soda solution increased by 10.08%-20.12% and the reaction temperature decreased from 361°C to 341°C, however, in samples pretreated by ultrasound in acetic solution or distilled water, the residual char content decreased by 12.40%-21.45% and there were no significant differences in reactivity apart from a slightly higher maximum reaction rate. Ultrasound pretreatment increased the samples' crystallinity up to 35.5% and successfully removed cellulose, hemicellulose, and lignin from the samples; the pretreatment also increased the exposure of the sample to the treatment solutions, broke down sample pits, and generated collapses and microchannels on sample pits, and removed attachments in the samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

NASA Technical Reports Server (NTRS)

Iraci, L. T.; Essin, A. M.; Golden, D. M.; Hipskind, R. Stephen (Technical Monitor)

2001-01-01

The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

Antidiabetic and antihyperlipidemic effects of Thespesia populnea fruit pulp extracts on alloxan-induced diabetic rats

PubMed Central

Belhekar, S. N.; Chaudhari, P. D.; Saryawanshi, J. S.; Mali, K. K.; Pandhare, R. B.

2013-01-01

Present study was carried to find out the antihyperglycemic and antihyperlipidemic activity of ethanol and aqueous extract of Thespesia populnea fruit pulp on alloxan-induced diabetic rats. Diabetes was induced in rats by administration of alloxan (150 mg/kg, i.p.). After the successful induction of experimental diabetes, the rats were divided into five groups each comprising a minimum of six rats. Phytochemical analysis and acute toxicity study of extracts was also done. The effects of extracts and metformin on fasting blood glucose and plasma lipid were examined for 28 days. Statistical analysis was carried out by using analysis of variance followed by Dunnet's multiple comparison test and paired t-test were done as the test of significance using GraphPad Prism. P≤0.05 was considered as the minimal level of statistical significance. Therapeutic dose of extract was found to be 200 mg/kg on the basis of acute toxicity study. Aqueous and alcoholic extract showed a significant reduction in blood glucose levels as well as a lipid profile of diabetic rats at the end of 28th day of treatment. However, in groups treated with plant extract the reduction in the blood glucose and improvement in lipid profile was slightly less than that achieved with the standard group (metformin). From this study, it can be concluded that ethanol and aqueous extract of Thespesia populnea exhibited significant antihyperglycemic and antihyperlipidemic effects on alloxan-induced diabetic rats. PMID:24019572

Photocatalytic Oxidation of Isoprene on Hydrated Atmospheric Mineral Dusts

NASA Astrophysics Data System (ADS)

Hoffmann, M. R.; Kameel, F. R.; Colussi, A. J.

2011-12-01

Mineral dust aerosols, an important fraction in the tropospheric aerosol budget, contain transition metal-based semiconductor particles that absorb light and may support diverse chemical transformations. Dust aerosol is primary, mostly originates from deserts, but includes fly ash emitted by power plants, and can be carried over long distances. We propose that such semiconductor particles may produce secondary organic aerosol (SOA) via surface-activated photochemical processes in aqueous media. Isoprene, the most abundant anthropogenic VOC is deemed to be incorporated into SOA by various mechanisms that remain to be fully characterized. We suggest that condensed-phase chemistry, in addition to gas-phase transformations, plays an important role in SOA formation. Isoprene is only slightly soluble in water, but it would react at diffusionally-controlled rates with photochemically generated OH-radicals in aqueous phase to produce more complex, polar compounds via oxidation and polymerization processes. We have found that the similar products are formed in the photolysis of aqueous hydrogen peroxide solutions or titanium dioxide suspensions in the presence of dissolved isoprene, as revealed by HPLC analysis with online high-resolution positive ion electrospray ionization mass spectrometric detection, and 1H and 13C nuclear magnetic resonance spectrometry. In contrast, hematite suspensions display negligible photocatalytic activity toward isoprene oxidation. These results suggest that atmospheric heterogeneous semiconductor photocatalysis of isoprene may play a significant role in global secondary organic aerosol formation under overly dusty conditions. Full product characterization is underway that aims at identifying species that may have adverse health/respiratory effects.

Synthesis and characterization of cadmium-calcium hydroxyapatite solid solutions

NASA Astrophysics Data System (ADS)

Zhao, Xin; Zhu, Yi-nian; Dai, Liu-qin

2014-06-01

A series of cadmium-calcium hydroxyapatite solid solutions was prepared by an aqueous precipitation method. By various means, the characterizations confirmed the formation of continuous solid solutions over all ranges of Cd/(Cd+Ca) atomic ratio. In the results, both lattice parameters a and c display slight deviations from Vegard's rule when the Cd/(Cd+Ca) atomic ratio is greater than 0.6. The particles change from smaller acicular to larger hexagonal columnar crystals as the Cd/(Cd+Ca) atomic ratio increases from 0-0.60 to 0.60-1.00. The area of the phosphate peak for symmetric P-O stretching decreases with the increase in Cd/(Cd+Ca) atomic ratio, and the peak disappears when the Cd/(Cd+Ca) atomic ratio is greater than 0.6; the two phosphate peaks of P-O stretching gradually merge together for the Cd/(Cd+Ca) atomic ratio near 0.60. These variations can be explained by a slight tendency of larger Cd ions to occupy M(2) sites and smaller Ca ions to prefer M(1) sites in the structure.

Ten-Year Change in the Scientific Literacy of Primary Science Teachers in China: Reflections on Training Programs and Personnel Policies

ERIC Educational Resources Information Center

Zhang, Hongshia; Shamsi, Imran Haider; Batool, Iffat; Wan, Dongsheng; Yu, Bo

2016-01-01

Using two rounds in 2003 and 2013 of large sample longitudinal surveys of science teachers in primary schools from 21 provinces and autonomous regions of China, results suggest that Chinese teachers' basic scientific literacy was still low with only a slight increase in the procedural knowledge of science. The evidence also suggests little…

Frequency Diverse Array Receiver Architectures

DTIC Science & Technology

2015-06-29

completely associated with FDA, the Hybrid MIMO phased array (HMPAR) concept presented in [18] developed the basic beam patern synthesis theory for an...20], that analyzed beam paterns of chirp waveforms with slightly 6 different starting frequencies. In [21] and [11] they investigated using FDA for...forward-looking radar GMTI benefits. This research showed the ability of the range-dependent energy distribution characteristics of the FDA beam patern

Magnetic particles

NASA Technical Reports Server (NTRS)

Chang, Manchium (Inventor); Colvin, Michael S. (Inventor)

1989-01-01

Magnetic polymer particles are formed by swelling porous, polymer particles and impregnating the particles with an aqueous solution of precursor magnetic metal salt such as an equimolar mixture of ferrous chloride and ferric chloride. On addition of a basic reagent such as dilute sodium hydroxide, the metal salts are converted to crystals of magnetite which are uniformly contained througout the pores of the polymer particle. The magnetite content can be increased and neutral buoyancy achieved by repetition of the impregnaton and neutralization steps to adjust the magnetite content to a desired level.

A Fundamental Electrochemical Investigation of Bromoaluminate and Mixed Chloro-Bromoaluminate Room Temperature Molten Salt Systems

DTIC Science & Technology

1989-03-01

Non-Aqueous Bromide Research In the late 1950s, Alexander I. Popov and David H. Geske , published a series of papers dealing with the electrochemistry... Geske has also helped to illuminate the electrochemistry occurring in the Zinc-Bromine battery systems. In 1987 Adanuvor et al. studied the effects of the...oxidation waves present in the basic bromide melt system are due to some form of the bromide anion. While Popov and Geske 7 have attributed the first of

Luminescence Probe Studies of Ionomers. I. Steady-State Measurements from Nafion Membrane.

DTIC Science & Technology

1985-02-03

Bu4N+ was monitored by titrating the released protons with NaOH. Bu4N+ uptake by Na+ membranes was assumed to be the same as uptake by acidic form...spaced excited states (21). Because of their solvent sensitivity, 1,5-DNS derivatives may also be used as polarity probes (20). The acid -base... acid . The basic (unprotonated) form of the DNS derivative used here (DA+ ) shows *absorption maxima at ca. 325 and 245 nm (aqueous solution, pH 6.8

Acceleration of Apoptosis by Extracellular Basic pH in a 3D Human Skin Equivalent System.

PubMed

Park, Gunhyuk; Oh, Dal-Seok; Kim, Yong-Ung; Park, Moon Ki

2017-01-01

Previously, we have shown that extracellular basic pH plays a significant role in both the direct and indirect regulation of cellular processes in a wound; this in turn affects the wound-healing process. Several studies have demonstrated the importance of apoptosis modulation in the wound-healing process, especially in removing inflammatory cells and in inhibiting scar formation. However, the effects of extracellular basic pH on wound healing-related skin damage are yet to be examined. Therefore, we investigated the induction of accelerated apoptosis by extracellular basic pH in skin. Apoptosis-related protein levels were measured using an array kit, target protein expression levels were detected by immunostaining, lactate dehydrogenase was analyzed spectrophotometrically, and Annexin V levels were measured by fluorescence staining. Basic pH (8.40) strongly upregulated extrinsic apoptosis proteins (Fas, high temperature requirement A, and p21) and slightly upregulated intrinsic apoptosis proteins (cytochrome c, B-cell lymphoma 2 [Bcl-2], Bcl-2-associated death promoter, and Bcl-2-like protein 4) in a 3D human skin equivalent system. Moreover, basic pH (8.40) induced heat shock protein (HSP) 60 and 70. In addition, basic pH-exposed Fas- and HSP60-knockdown cells showed significantly decreased levels of apoptosis. Taken together, these results indicate that extracellular basic pH increases early-stage apoptosis through Fas/FasL via modulation of HSP60 and HSP70. © 2017 S. Karger AG, Basel.

Aqueous Alteration of Endeavour Crater Rim Apron Rocks

NASA Technical Reports Server (NTRS)

Mittlefehldt, David W.; Ming, Douglas W.; Gellert, Ralf; Clark, Benton C.; Morris, Richard V.; Yen, Albert S.; Arvidson, Raymond E.; Crumpler, Larry S.; Farrand, William H.; Grant, John A.;

Aqueous Alteration of Endeavour Crater Rim Apron Rocks

NASA Astrophysics Data System (ADS)

Ming, D. W.; Mittlefehldt, D. W.; Gellert, R.; Clark, B. C.; Morris, R. V.; Yen, A. S.; Arvidson, R. E.; Crumpler, L. S.; Farrand, W. H.; Grant, J. A., III; Jolliff, B. L.; Parker, T. J.; Peretyazhko, T.

2014-12-01

Mars Exploration Rover Opportunity is exploring Noachian age rocks of the rim of 22 km diameter Endeavour crater. Overlying the pre-impact lithologies and rim breccias is a thin apron of fine-grained sediments, the Grasberg fm, forming annuli on the lower slopes of rim segments. Hesperian Burns fm sandstones overly the Grasberg fm. Grasberg rocks have major element compositions that are distinct from Burns fm sandstones, especially when comparing interior compositions exposed by the Rock Abrasion Tool. Grasberg rocks are also different from Endeavour rim breccias, but have general compositional similarities to them. Grasberg sediments are plausibly fine-grained materials derived from the impact breccias. Veins of CaSO4 transect Grasberg fm rocks demonstrating post-formation aqueous alteration. Minor/trace elements show variations consistent with mobilization by aqueous fluids. Grasberg fm rocks have low Mn and high Fe/Mn ratios compared to the other lithologies. Manganese likely was mobilized and removed from the Grasberg host rock by redox reactions. We posit that Fe2+ from acidic solutions associated with formation of the Burns sulfate-rich sandstones acted as an electron donor to reduce more oxidized Mn to Mn2+. The Fe contents of Grasberg rocks are slightly higher than in other rocks suggesting precipitation of Fe phases in Grasberg materials. Pancam spectra show that Grasberg rocks have a higher fraction of ferric oxide minerals than other Endeavour rim rocks. Solutions transported Mn2+ into the Endeavour rim materials and oxidized and/or precipitated it in them. Grasberg has higher contents of the mobile elements K, Zn, Cl, and Br compared to the rim materials. Similar enrichments of mobile elements were measured by the Spirit APXS on West Spur and around Home Plate in Gusev crater. Enhancements in these elements are attributed to interactions of hydrothermal acidic fluids with the host rocks. Interactions of fluids with the Grasberg fm postdate the genesis of the Endeavour rim phyllosilicates. The aqueous alteration history of Endeavour rim rocks is complicated by different styles of alteration that have spanned the Noachian and Hesperian. Late stage acidic aqueous alteration of Grasberg fm materials is likely penecontemporaneous with the diagenesis of the sulfate-rich sediments of Meridiani Planum.

Human Cytochrome P450 Enzyme Modulation by Gymnema sylvestre: A Predictive Safety Evaluation by LC-MS/MS.

PubMed

Rammohan, Bera; Samit, Karmakar; Chinmoy, Das; Arup, Saha; Amit, Kundu; Ratul, Sarkar; Sanmoy, Karmakar; Dipan, Adhikari; Tuhinadri, Sen

2016-07-01

Traditionally GS is used to treat diabetes mellitus. Drug-herb interaction of GS via cytochrome P450 enzyme system by substrate cocktail method using HLM has not been reported. To evaluate the in-vitro modulatory effects of GS extracts (aqueous, methanol, ethyl acetate, chloroform and n -hexane) and deacylgymnemic acid (DGA) on human CYP1A2, 2C8, 2C9, 2D6 and 3A4 activities in HLM. Probe substrate-based LCMS/MS method was established for all CYPs. The metabolite formations were examined after incubation of probe substrates with HLM in the presence or absence of extracts and DGA. The inhibitory effects of GS extracts and DGA were characterized with kinetic parameters IC50 and Ki values. GS extracts showed differential effect on CYP activities in the following order of inhibitory potency: ethyl acetate > Chloroform > methanol > n -hexane > aqueous > DGA. This differential effect was observed against CYP1A2, 2C9 and less on CYP3A4 and 2C8 but all CYPs were unaffected by aqueous extract and DGA. The ethyl acetate and chloroform extract exhibited moderate inhibition towards CYP1A2 and 3A4. The aqueous extract and DGA however showed negligible inhibition towards all five major human CYPs with very high IC50 values (>90μg/ml). The results of our study revealed that phytoconstituents contained in GS, particularly in ethyl acetate and chloroform extracts, were able to inhibit CYP1A2, 3A4 and 2C9. The presence of relatively small, lipophillic yet slightly polar compounds within the GS extracts may be attributed for inhibition activities. These suggest that the herb or its extracts should be examined for potential pharmacokinetic drug interactions in vivo . Abbreviations used: GS: Gymnema sylvestre , GSE: Gymnema sylvestre extract, DGA: deacyl gymnemic acid, CYP: cytochrome P450, DMSO: dimethylsulphoxide, HLM: human liver microsomes, LC-MS/MS: liquid chromatography tandem mass spectroscopy, NADPH: reduced nicotinamide adeninedinucleotide phosphate, NRS: nicotinamide adeninedinucleotide phosphate regenerating system, CHE: chloroform extract, EAE: ethyl acetate extract, NHE- n -hexane extract, AE: aqueous extract, ME: methanol extract.

A molecular rotor based ratiometric sensor for basic amino acids

NASA Astrophysics Data System (ADS)

Pettiwala, Aafrin M.; Singh, Prabhat K.

2018-01-01

The inevitable importance of basic amino acids, arginine and lysine, in human health and metabolism demands construction of efficient sensor systems for them. However, there are only limited reports on the 'ratiometric' detection of basic amino acids which is further restricted by the use of chemically complex sensor molecules, which impedes their prospect for practical applications. Herein, we report a ratiometric sensor system build on simple mechanism of disassociation of novel emissive Thioflavin-T H-aggregates from heparin surface, when subjected to interaction with basic amino acids. The strong and selective electrostatic and hydrogen bonding interaction of basic amino acids with heparin leads to large alteration in photophysical attributes of heparin bound Thioflavin-T, which forms a highly sensitive sensor platform for detection of basic amino acids in aqueous solution. These selective interactions between basic amino acids and heparin allow our sensor system to discriminate arginine and lysine from other amino acids. This unique mechanism of dissociation of Thioflavin-T aggregates from heparin surface provides ratiometric response on both fluorimetric and colorimetric outputs for detection of arginine and lysine, and thus it holds a significant advantage over other developed sensor systems which are restricted to single wavelength detection. Apart from the sensitivity and selectivity, our system also provides the advantage of simplicity, dual mode of sensing, and more importantly, it employs an inexpensive commercially available probe molecule, which is a significant advantage over other developed sensor systems that uses tedious synthesis protocol for the employed probe in the detection scheme, an impediment for practical applications. Additionally, our sensor system also shows response in complex biological media of serum samples.

The binding of manganese(II) and zinc(II) to the synthetic oligonucleotide d(C-G-C-G-A-A-T-T-C-G-C-G)2. A 1H NMR study.

PubMed

Frøystein, N A; Sletten, E

1991-03-01

The interaction of the synthetic oligonucleotide d(C-G-C-G-A-A-T-T-C-G-C-G)2 with two different transition-metal ions has been investigated in aqueous solution by means of 1H NMR spectroscopy. The effects on the DNA due to the presence of manganese(II) or zinc(II) have been monitored by observing the paramagnetic broadening and diamagnetic shifts of the non-exchangeable proton resonance lines, respectively. The 1H NMR spectra acquired during the course of the manganese(II) titration show very distinct broadening effects on certain DNA resonance lines. Primarily, the H8 resonance of G4 is affected, but also the H5 and H6 resonances of C3 are clearly affected by the metal. The results imply that the binding of manganese(II) to DNA is sequence specific. The 1H spectra obtained during the zinc(II) titration reveal diamagnetic shift effects which largely conform with the paramagnetic broadening effects due to the presence of manganese(II), although this picture is somewhat more complex. The H8 resonance of G4 displays a clearly visible high-field shift, while for the other guanosine H8 protons this effect is absent. The H1' and H2' protons of C3 show an effect of similar strength, although in the opposite direction, while H5 and H6 of C3 are only slightly affected. Local differences in the structure of the DNA and the basicities of potential binding sites on different base steps in the sequence might account for the observed sequence selectivity.

Lanthanum(III)-catalyzed disproportionation of hydrogen peroxide: a heterogeneous generator of singlet molecular oxygen-1O2 (1Deltag)-in near-neutral aqueous and organic media for peroxidation of electron-rich substrates.

PubMed

Nardello, Véronique; Barbillat, Jacques; Marko, Jean; Witte, Peter T; Alsters, Paul L; Aubry, Jean-Marie

2003-01-20

The decomposition of hydrogen peroxide into singlet molecular oxygen-(1)O(2) ((1)Delta(g))-in the presence of lanthanum(iii) salts was studied by monitoring its characteristic IR luminescence at 1270 nm. The process was found to be heterogeneously catalyzed by La(III), provided that the heterogeneous catalyst is generated in situ. The yield of (1)O(2) generation was assessed as 45+/-5 % both in water and in methanol. The pH-dependence on the rate of (1)O(2) generation corresponds to a bell-shaped curve from pH 4.5 to 13 with a maximum around pH 8. The study of the influence of H(2)O(2) showed that the formation of (1)O(2) begins as soon as one equivalent of H(2)O(2) is introduced. It then increases drastically up to two equivalents and more smoothly above. Unlike all other metal salt catalyst systems known to date for H(2)O(2) disproportionation, this chemical source of (1)O(2) is able to generate (1)O(2) not only in basic media, but also under neutral and slightly acidic conditions. In addition, this La-based catalyst system has a very low tendency to induce unwanted oxygenating side reactions, such as epoxidation of alkenes. These two characteristics of the heterogeneous lanthanum catalyst system allow non-photochemical (i.e., "dark") singlet oxygenation of substrate classes that cannot be peroxidized successfully with conventional molybdate catalysts, such as allylic alcohols and alkenyl amines.

Spectroscopic interaction study of human serum albumin and human hemoglobin with Mersilea quadrifolia leaves extract mediated silver nanoparticles having antibacterial and anticancer activity

NASA Astrophysics Data System (ADS)

Maji, Anukul; Beg, Maidul; Mandal, Amit Kumar; Das, Somnath; Jha, Pradeep K.; Kumar, Anoop; Sarwar, Shamila; Hossain, Maidul; Chakrabarti, Pinak

2017-08-01

This study looks into a safe, proficient and low-cost way for the preparation of novel silver nanoparticles by using 5% aqueous leaves extract of a medicinal plant, Marsilea quadrifolia (family: Marsileaceae) without using any external reducing and stabilizing agents. The synthesized AgNPs showed maximum UV-Vis absorbance at 435 nm due to surface plasmon resonance (SPR). The average diameter (∼22.5 nm) of AgNPs was measured from TEM analysis and was also supported by FE-SEM. The existence of a silver signal in EDX spectra supported the AgNPs formation and negative zeta potential value (-18.7 mV) which suggested its stability. FT-IR spectroscopic analysis showed that the functional groups like sbnd Osbnd H, sbnd Nsbnd H and sbnd Cdbnd O were responsible for the synthesis of AgNPs. The antibacterial activity of the AgNPs was tested against E. coli ATCC 25922. The anticancer potential of AgNPs was also assessed using two different cell lines, such as MCF-7 and HeLa. The interaction study of AgNPs with human serum albumin (HSA) and human hemoglobin (Hb) was performed by means of UV-Vis, fluorescence spectroscopy, Circular dichroism (CD) and zeta potential measurement. More negative zeta potential values of AgNPs-HSA/Hb (-21.1/-19.5 mV) complexes than AgNPs (-18.7 mV) indicated corresponding stability of bio-conjugates. The basic structure of HSA/Hb remained unchanged and its secondary structure was slightly changed upon interaction with the AgNPs concluded from Circular dichroism. So, it can be predicted that this AgNPs may be applied in the medical field.

Health effects research in direct coal liquefaction. Studies of H-coal distillates: Phase I. PDU samples - the effects of hydrotreatment

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

Epler, J.L.; Fry, R.J.M.; Larimer, F.W.

1981-11-01

A multi-divisional effort aimed at the integrated assessment of the health and environmental effects of various coal conversion and shale oil technologies is being carried out. The feasibility of using health effects bioassays to predict the potential biohazard of various H-Coal derived test materials is examined in a coupled chemical and biological approach. The primary focus of the research is the use of preliminary chemical characterizations and preparation for bioassay, followed by testing in short-term assays in order to rapidly ascertain the potential biohazard. Mammalian toxicological assays parallel the testing. Raw and hydrotreated product liquids from process development units ofmore » H-Coal and the pilot plant solvent refined coal process were examined for acute toxicity monitored as population growth impairment of Tetrahymena exposed to aqueous extracts and for mutagenic activity monitored as revertants of Salmonella exposed to metabolically activated chemical class fractions. Medium to high severity hydrotreatment appears to be an effective means of reducing biological activity, presumably by reducing the aromaticity and heteroatom content. Five basic mammalian, acute toxicity tests have been conducted with selected H-coal samples and shale oil derivatives. The data show that H-Coal samples are moderately toxic whereas the toxicity of shale oil derived products is slight and comparable to samples obtained from naturally occurring petroleums. No overt skin or eye toxicity was found. The present data reveal that coal-derived distillates generated by the H-coal process are highly carcinogenic to mouse skin. An extreme form of neurotoxicity associated with dermal exposure to one of the lighter, minimally carcinogenic, materials was noted. (DMC)« less

Polysaccharide-thickened aqueous fluoride solutions for rapid destruction of the nerve agent VX. Introducing the opportunity for extensive decontamination scenarios.

PubMed

Elias, Shlomi; Saphier, Sigal; Columbus, Ishay; Zafrani, Yossi

2014-01-01

Among the chemical warfare agents, the extremely toxic nerve agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) is a target of high importance in the development of decontamination methods, due to its indefinite persistence on common environmental surfaces. Liquid decontaminants are mostly characterized by high corrosivity, usually offer poor coverage, and tend to flow and accumulate in low areas. Therefore, the development of a noncorrosive decontaminant, sufficiently viscous to resist dripping from the contaminated surface, is necessary. In the present paper we studied different polysaccharides-thickened fluoride aqueous solutions as noncorrosive decontaminants for rapid and efficient VX degradation to the nontoxic product EMPA (ethyl methylphosphonic acid). Polysaccharides are environmentally benign, natural, and inexpensive. Other known decontaminants cannot be thickened by polysaccharides, due to the sensitivity of the latter toward basic or oxidizing agents. We found that the efficiency of VX degradation in these viscous solutions in terms of kinetics and product identity is similar to that of KF aqueous solutions. Guar gum (1.5 wt %) with 4 wt % KF was chosen for further evaluation. The benign nature, rheological properties, adhering capabilities to different surfaces, and decontamination from a porous matrix were examined. This formulation showed promising properties for implementation as a spray decontaminant for common and sensitive environmental surfaces.

Emission spectra of a pulse needle-to-plane corona-like discharge in conductive aqueous solutions

NASA Astrophysics Data System (ADS)

Šimek, Milan; Člupek, Martin; Babický, Václav; Lukeš, Petr; Šunka, Pavel

2012-10-01

We explored basic optical and electrical characteristics of a positive corona-like discharge produced in conductive aqueous solutions by periodic high-voltage pulses. Emission spectra of the discharge were acquired in a needle-to-plate electrode geometry and analysed in the UV-vis-NIR spectral range with nanosecond time resolution for the solution conductivity of 100 and 500 µS cm-1. The most important emission features are due to electronic excitation of HI, OI, OII and OH species. We found evidence of significant time-dependent line-shape broadening of selected HI and OI transitions. The observed broadening is attributed to the dynamic Stark and pressure broadening mechanisms and significantly increases with the aqueous solution conductivity. Electron densities were estimated by fitting a single Voigt peak function to the observed Hα profiles, and can reach as much as ne ≅ 4 × 1018 cm-3 (tD = 300 ns at 100 µS cm-1 solution conductivity) and ne ≅ 5 × 1018 cm-3 (tD = 1 µs at 500 µS cm-1). Temporal evolution of the partially resolved rotational structure of the OH emission reaches a maximum during the discharge decay, with the onset significantly delayed with respect to the streamer ignition.

Graft polymerization of acrylic acid onto chitin nanofiber to improve dispersibility in basic water.

PubMed

Ifuku, Shinsuke; Iwasaki, Masayoshi; Morimoto, Minoru; Saimoto, Hiroyuki

2012-09-01

Graft copolymerization of acrylic acid (AA) on chitin nanofibers was carried out with potassium persulfate as a free radical initiator in an aqueous medium. The molar ratio of grafted AA increased with the AA concentration. The grafted chitin nanofibers were characterized by FT-IR, FE-SEM, UV-vis, XRD, and TGA. After polymerization, the characteristic morphology of chitin nanofibers was maintained. Chitin nanofibers grafted with AA were efficiently dissociated and dispersed homogeneously in basic water because of the electrostatic repulsion effect between nanofibers. AA was grafted on the surface and amorphous part of chitin nanofibers, and the original crystalline structure of α-chitin was maintained. At 330 °C, the weight residue of the graft copolymer increased with the grafted AA content. Copyright © 2012 Elsevier Ltd. All rights reserved.

Understanding The Interfacial Structure Of Aqueous Phospholipid Monolayer Films Via External Reflection FT-IR Spectroscopy.

NASA Astrophysics Data System (ADS)

Mitchell, Melody L.; Dluhy, Richard A.

1989-12-01

Monolayer films of dimyristoyl-phosphatidic-acid (DMPA) at neutral and basic pH exhibit first-order phase transitions in their pressure-area curves. In situ external reflection FT-IR studies in the CH, stretching bands over this phase transition region exhibit a --6 cm-1 shift similar to that observed in previous studies of dipalmitoyl-phosphotidylcholine (DPPC)1. The acid form of DMPA at pH 3.0 does not exhibit the first order phase transition, but a ~1cm-1 frequency shift is observed in the liquid condensed phase and is also present in the neutral pH form. A solid-solid phase transition is proposed. Examination of the polar headgroup region (1300-960 cm-1)for acidic, neutral, and basic forms of DMPA give characteristic bands of each protonation state of PO3.

The antimalarial activity of Ru–chloroquine complexes against resistant Plasmodium falciparum is related to lipophilicity, basicity, and heme aggregation inhibition ability near water/n-octanol interfaces

PubMed Central

Martínez, Alberto; Rajapakse, Chandima S. K.; Jalloh, Dalanda; Dautriche, Cula

2012-01-01

We have measured water/n-octanol partition coefficients, pKa values, heme binding constants, and heme aggregation inhibition activity of a series of ruthenium–πarene–chloroquine (CQ) complexes recently reported to be active against CQ-resistant strains of Plasmodium falciparum. Measurements of heme aggregation inhibition activity of the metal complexes near water/n-octanol interfaces qualitatively predict their superior antiplasmodial action against resistant parasites, in relation to CQ; we conclude that this modified method may be a better predictor of antimalarial potency than standard tests in aqueous acidic buffer. Some interesting tendencies emerge from our data, indicating that the antiplasmodial activity is related to a balance of effects associated with the lipophilicity, basicity, and structural details of the compounds studied. PMID:19343380

The antimalarial activity of Ru-chloroquine complexes against resistant Plasmodium falciparum is related to lipophilicity, basicity, and heme aggregation inhibition ability near water/n-octanol interfaces.

PubMed

Martínez, Alberto; Rajapakse, Chandima S K; Jalloh, Dalanda; Dautriche, Cula; Sánchez-Delgado, Roberto A

2009-08-01

We have measured water/n-octanol partition coefficients, pK(a) values, heme binding constants, and heme aggregation inhibition activity of a series of ruthenium-pi-arene-chloroquine (CQ) complexes recently reported to be active against CQ-resistant strains of Plasmodium falciparum. Measurements of heme aggregation inhibition activity of the metal complexes near water/n-octanol interfaces qualitatively predict their superior antiplasmodial action against resistant parasites, in relation to CQ; we conclude that this modified method may be a better predictor of antimalarial potency than standard tests in aqueous acidic buffer. Some interesting tendencies emerge from our data, indicating that the antiplasmodial activity is related to a balance of effects associated with the lipophilicity, basicity, and structural details of the compounds studied.

Functional properties of protein isolates extracted from stabilized rice bran by microwave, dry heat, and parboiling.

PubMed

Khan, Saima Hafeez; Butt, Masood Sadiq; Sharif, Mian Kamran; Sameen, Ayesha; Mumtaz, Semee; Sultan, Muhammad Tauseef

2011-03-23

Protein isolates extracted from differently stabilized rice bran were analyzed to work out the food use potential. Bulk density remained higher for isolates obtained from heat stabilized bran, the treatments were found to have positive impact on the oil absorption properties, while the water absorption was slightly impaired owing to some possible configurational changes. Surface hydrophobicity and emulsion properties were improved with bran stabilization. Isolates exhibited better foaming properties owing to the flexible nature of protein molecules, with less intensive disulfide bonding, that were slightly affected by the stabilization treatment. Nitrogen solubility index followed a curved pattern with the least value near isoelectric point that showed an increasing trend toward basic pH, and parboiled protein isolates exhibited better gelling properties among the isolates.

Determination of the n-octanol/water partition coefficients of weakly ionizable basic compounds by reversed-phase high-performance liquid chromatography with neutral model compounds.

PubMed

Liang, Chao; Han, Shu-ying; Qiao, Jun-qin; Lian, Hong-zhen; Ge, Xin

2014-11-01

A strategy to utilize neutral model compounds for lipophilicity measurement of ionizable basic compounds by reversed-phase high-performance liquid chromatography is proposed in this paper. The applicability of the novel protocol was justified by theoretical derivation. Meanwhile, the linear relationships between logarithm of apparent n-octanol/water partition coefficients (logKow '') and logarithm of retention factors corresponding to the 100% aqueous fraction of mobile phase (logkw ) were established for a basic training set, a neutral training set and a mixed training set of these two. As proved in theory, the good linearity and external validation results indicated that the logKow ''-logkw relationships obtained from a neutral model training set were always reliable regardless of mobile phase pH. Afterwards, the above relationships were adopted to determine the logKow of harmaline, a weakly dissociable alkaloid. As far as we know, this is the first report on experimental logKow data for harmaline (logKow = 2.28 ± 0.08). Introducing neutral compounds into a basic model training set or using neutral model compounds alone is recommended to measure the lipophilicity of weakly ionizable basic compounds especially those with high hydrophobicity for the advantages of more suitable model compound choices and convenient mobile phase pH control. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Extended Huckel Theory as a Platform to Introduce Jahn-Teller Distortion: The Spontaneous Distortion of 1,3,5,7-Cyclooctatetraene from a Perfect Octagon

ERIC Educational Resources Information Center

Sohlberg, Karl; Liu, Xiang

2013-01-01

Herein, a slightly enhanced version of extended Huckel molecular orbital theory is applied to demonstrate the spontaneous distortion of 1,3,5,7-cyclooctatetraene from a perfect octagon, a consequence of the Jahn-Teller effect. The exercise is accessible to students who have been introduced to basic quantum mechanics and extended Huckel molecular…

Comparison of pharmacy students' perceived and actual knowledge using the Pharmacy Curricular Outcomes Assessment.

PubMed

Naughton, Cynthia A; Friesner, Daniel L

2012-05-10

To determine whether a correlation exists between third-year PharmD students' perceived pharmacy knowledge and actual pharmacy knowledge as assessed by the Pharmacy Curricular Outcomes Assessment (PCOA). In 2010 and 2011, the PCOA was administered in a low-stakes environment to third-year pharmacy students at North Dakota State University College of Pharmacy, Nursing, and Allied Sciences (COPNAS). A survey instrument was also administered on which students self-assessed their perceived competencies in each of the core areas covered by the PCOA examination. The pharmacy students rated their competencies slightly higher than average. Performance on the PCOA was similar to but slightly higher than national averages. Correlations between each of the 4 content areas (basic biomedical sciences, pharmaceutical sciences, social/administrative sciences, and clinical sciences) mirrored those reported nationally by the National Association of Boards of Pharmacy (NABP). Student performance on the basic biomedical sciences portion of the PCOA was significantly correlated with students' perceived competencies in the biomedical sciences. No other correlations between actual and perceived competencies were significant. A lack of correlation exists between what students perceive they know and what they actually know in the areas of pharmaceutical science; social, behavioral, and administrative science; and clinical science. Therefore, additional standardized measures are needed to assess curricular effectiveness and provide comparisons among pharmacy programs.

URANIUM RECOVERY FROM COMPOSITE UF$sub 4$ REDUCTION BOMB WASTES

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

Johnson, E R; Doyle, R L; Coleman, J R

1954-01-28

A number of techniques have been investigated on a laboratory-scale for separating uranium from fluorides during the recovery of uranium from UF4 reduction bomb wastes (C-oxide) by an HCl leach - NH4OH precipitation process. Among these are included adsorption of fluorides from filtered leach liquors, fractional precipitation of fluorides and uranium, complexing of fluorides into forms soluble in slightly acid solutions, and fluoride volatilization from the uranium concentrate. Solubility studies of CaF2 and MgF2 in aqueous hydrochloric acid at various acidities and temperatures were also conducted. A description of the production-scale processing of C-oxide in the FMPC scrap plant hasmore » been included.« less

Zingiber officinale Roscoe prevents acetaminophen-induced acute hepatotoxicity by enhancing hepatic antioxidant status.

PubMed

Ajith, T A; Hema, U; Aswathy, M S

2007-11-01

A large number of xenobiotics are reported to be potentially hepatotoxic. Free radicals generated from the xenobiotic metabolism can induce lesions of the liver and react with the basic cellular constituents - proteins, lipids, RNA and DNA. Hepatoprotective activity of aqueous ethanol extract of Zingiber officinale was evaluated against single dose of acetaminophen-induced (3g/kg, p.o.) acute hepatotoxicity in rat. Aqueous extract of Z. officinale significantly protected the hepatotoxicity as evident from the activities of serum transaminase and alkaline phosphatase (ALP). Serum glutamate pyruvate transaminase (SGPT), serum glutamate oxaloacetate transaminase (SGOT) and ALP activities were significantly (p<0.01) elevated in the acetaminophen alone treated animals. Antioxidant status in liver such as activities of superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase and glutathione-S-transferase (GST), a phase II enzyme, and levels of reduced glutathione (GSH) were declined significantly (p<0.01) in the acetaminophen alone treated animals (control group). Hepatic lipid peroxidation was enhanced significantly (p<0.01) in the control group. Administration of single dose of aqueous extract of Z. officinale (200 and 400mg/kg, p.o.) prior to acetaminophen significantly declines the activities of serum transaminases and ALP. Further the hepatic antioxidant status was enhanced in the Z. officinale plus acetaminophen treated group than the control group. The results of the present study concluded that the hepatoprotective effect of aqueous ethanol extract of Z. officinale against acetaminophen-induced acute toxicity is mediated either by preventing the decline of hepatic antioxidant status or due to its direct radical scavenging capacity.

Adsorptive potential of cationic Basic Yellow 2 (BY2) dye onto natural untreated clay (NUC) from aqueous phase: Mass transfer analysis, kinetic and equilibrium profile

NASA Astrophysics Data System (ADS)

Öztürk, A.; Malkoc, E.

2014-04-01

In this work, natural untreated clay (NUC) was studied for the removal of Basic Yellow 2 (BY2) from aqueous solution in batch system. The effects of initial BY2 concentration, contact time, solution temperature and solution pH on BY2 adsorption were investigated. Nitrogen sorption measurements were employed to investigate the variation in surface and pore properties after dye adsorption. The adsorbent was characterized by means of FTIR, PSD, TEM, XRD and BET analysis. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin and Scatchard isotherm models. The maximum monolayer adsorption capacity was found to be 833.33 mg/g at 25 °C (at room temperature). The pseudo-second-order kinetic model provided the best fit to the experimental datas compared with pseudo-first-order kinetic adsorption models. To explain mass transfer mechanism of BY2 adsorption, obtained experimental datas were applied Weber and Morris model, Body and Frusawa and Smith models. The results show that the adsorption process is controlled by film diffusion. The thermodynamic parameters such as, Gibbs free energy changes (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) were determined. Adsorption of BY2 on NUC is exothermic and spontaneous in nature. The calculated activation energy of adsorption was found to be 5.24 kJ/mol for BY2. This value indicates that the adsorption process is a physisorption.

Application of polyacrylamide gel as a new membrane in electromembrane extraction for the quantification of basic drugs in breast milk and wastewater samples.

PubMed

Asadi, Sakine; Tabani, Hadi; Nojavan, Saeed

2018-03-20

Introducing new membranes with green chemistry approach seems to be a great challenge for the development of a practical method in separation science. In this regard, for the first time, polyacrylamide gel as a new membrane in electromembrane extraction (EME) was used for the extraction of three model basic drugs (pseudoephedrine (PSE), lidocaine (LID), and propranolol (PRO)), followed by HPLC-UV. In comparison with conventional EME, in this method neither organic solvent nor carrier agents were used for extraction of mentioned drugs. Different variables for fabrication of polyacrylamide gel and extraction process were evaluated. Polyacrylamide gel (containing 12% (w/v) acrylamide, and 3.0% (w/w) bisacrylamide) with 2 mm thickness at pH = 1.5 was fabricated as membrane. The drugs were extracted from aqueous samples, through a polyacrylamide gel membrane, to an aqueous acceptor phase on membrane. Under the optimized extraction conditions (Voltage: 85 V, extraction time: 28 min, acceptor phase's pH: 4.0, and donor phase's pH: 7.0) limits of quantification and detection were in the ranges of 1.0-20.0 ng mL -1 and 0.3-6.0 ng mL -1 , respectively. Applying the proposed method to determine and quantify intended drugs in breast milk, and wastewater samples have revealed acceptable results. Copyright © 2018 Elsevier B.V. All rights reserved.

The effect of pH and concentration upon aggregation transitions in aqueous solutions of poloxamine T701.

PubMed

Armstrong, J K; Chowdhry, B Z; Snowden, M J; Dong, J; Leharne, S A

2001-10-23

Thermally induced aggregation transitions have been investigated for aqueous solutions of the poloxamine block copolymer T701-(OE(4)OP(13))(2)NCH(2)CH(2)N(OP(13)OE(4))(2)-using differential scanning calorimetry. The calorimetric signals obtained were fitted to a mass action model description of aggregation using a previously reported analytical procedure (Patterson et al., Langmuir 13 (1997) 2219). The presence of a central ethylene diamine moiety in the molecular structure renders the T701 molecule basic; this was confirmed and measured by acid/base titration. Basicity is shown to have an important impact upon aggregation. At low pH (2.5), the poloxamine exists in its protonated form and the bulk solution proton concentration is sufficient to suppress de-protonation, aggregation-as a consequence-is shifted to a higher temperature range. Any increase in pH reduces the temperature range over which aggregation occurs. The derived experimental calorimetric parameters, obtained from model fitting procedures, can be used to compute the fraction of poloxamine existing in an aggregated form, at any particular temperature. The data sets obtained were interpolated to show that at human body temperature (310.6 K) the fraction of poloxamine found in its aggregated form is zero at a pH of 2.5. However at a pH of 6.8, the percentage aggregation increases to about 85%. These aggregation characteristics of T701 have important implications for the design of drug delivery systems, which incorporate poloxamines.

Investigation on localized corrosion of 304 stainless steel joints brazed using Sn-plated Ag alloy filler in NaCl aqueous solution

NASA Astrophysics Data System (ADS)

Wang, Xingxing; Li, Shuai; Peng, Jin

2018-03-01

Novel AgCuZnSn filler metal with high Sn contents was prepared from BAg50CuZn filler metal by a process of electroplating and thermal diffusion, and the prepared filler metal was applied to induction brazing of 304 stainless steel. The corrosion behavior of the brazed joints was evaluated based on localized corrosion analysis, the morphology of the joints were analyzed by SEM after immersion in a 3.5 vol% NaCl aqueous solution. The results indicated that corrosion groove occurred near the interface between the stainless steel base metal and the brazing seam. A wide range of defects such as holes and cracks appeared on the surface of the base metal, while the brazing seam zone almost no corrosion defects occur. With the increase of corrosion time, the corrosion rates of both the brazing seam and the base metal first exhibited an increasing trend, followed by a decreasing trend, and the corrosion rate of the base metal was slightly greater than that of the brazing seam. The corrosion potential of the brazing seam and 304 stainless steel were -0.7758 V and -0.7863 V, respectively.

Removal of NO from flue gas by aqueous chlorine-dioxide scrubbing solution in a lab-scale bubbling reactor.

PubMed

Deshwal, Bal Raj; Jin, Dong Seop; Lee, Si Hyun; Moon, Seung Hyun; Jung, Jong Hyeon; Lee, Hyung Keun

2008-02-11

The present study attempts to clean up nitric oxide from the simulated flue gas using aqueous chlorine-dioxide solution in the bubbling reactor. Chlorine-dioxide is generated by chloride-chlorate process. Experiments are carried out to examine the effect of various operating variables like input NO concentration, presence of SO(2), pH of the solution and NaCl feeding rate on the NO(x) removal efficiency at 45 degrees C. Complete oxidation of nitric oxide into nitrogen dioxide occurred on passing sufficient ClO(2) gas into the scrubbing solution. NO is finally converted into nitrate and ClO(2) is reduced into chloride ions. A plausible reaction mechanism concerning NO(x) removal by ClO(2) is suggested. DeNO(x) efficiency increased slightly with the increasing input NO concentration. The presence of SO(2) improved the NO(2) absorption but pH of solution showed marginal effect on NO(2) absorption. NO(x) removal mechanism changed when medium of solution changed from acidic to alkaline. A constant NO(x) removal efficiency of about 60% has been achieved in the wide pH range of 3-11 under optimized conditions.

Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

USGS Publications Warehouse

Moses, Carl O.; Nordstrom, D. Kirk; Herman, Janet S.; Mills, Aaron L.

1987-01-01

Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.

Rapid removal of bisphenol A on highly ordered mesoporous carbon.

PubMed

Sui, Qian; Huang, Jun; Liu, Yousong; Chang, Xiaofeng; Ji, Guangbin; Deng, Shubo; Xie, Tao; Yu, Gang

2011-01-01

Bisphenol A (BPA) is of global concern due to its disruption of endocrine systems and ubiquity in the aquatic environment. It is important, therefore, that efforts are made to remove it from the aqueous phase. A novel adsorbent, mesoporous carbon CMK-3, prepared from hexagonal SBA-15 mesoporous silica was studied for BPA removal from aqueous phase, and compared with conventional powdered activated carbon (PAC). Characterization of CMK-3 by transmission electron microscopy (TEM), X-ray diffraction, and nitrogen adsorption indicated that prepared CMK-3 had an ordered mesoporous structure with a high specific surface area of 920 m2/g and a pore-size of about 4.9 nm. The adsorption of BPA on CMK-3 followed a pseudo second-order kinetic model. The kinetic constant was 0.00049 g/(mg x min), much higher than the adsorption of BPA on PAC. The adsorption isotherm fitted slightly better with the Freundlich model than the Langmuir model, and adsorption capacity decreased as temperature increased from 10 to 40 degrees C. No significant influence of pH on adsorption was observed at pH 3 to 9; however, adsorption capacity decreased dramatically from pH 9 to 13.

Degradation of trichloroethene with a noval ball milled Fe-C nanocomposite

DOE PAGES

Gao, Jie; Wang, Wei; Rondinone, Adam Justin; ...

2015-07-18

Nanoscale zero-valent iron (NZVI) is effective in reductively degrading dense non-aqueous phase liquids (DNAPLs), such as trichloroethene (TCE), in groundwater (i.e., dechlorination) although the NZVI technology itself still suffers from high material costs and inability to target hydrophobic contaminants in source zones. To address these problems, we developed a novel, inexpensive iron-carbon (Fe-C) nanocomposite material by simultaneously milling micron-size iron and activated carbon powder. Microscopic and X-ray diffraction (XRD) characterization of the composite material revealed that nanoparticles of Fe were dispersed in activated carbon and a new iron carbide phase was formed. Bench-scale studies showed that this material instantaneously sorbedmore » >90% of TCE from aqueous solutions and subsequently decomposed TCE into non-chlorinated products. Compared to milled Fe, Fe-C nanocomposite dechlorinated TCE at a slightly slower rate and favored the production of ethene over other TCE degradation products such as C 3-C 6 compounds. When placed in hexane-water mixture, the Fe-C nanocomposite materials are preferentially partitioned into the organic phase, indicating the ability of the composite materials to target DNAPL during remediation.« less

Studies on aerosols. I. Reduction of dust deposition in lungs of rabbits by aqueous aerosols

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

Dautrebande, L.; Highman, B.; Alford, W.C.

1948-01-01

Rabbits were exposed to air containing 0.01 to 0.04 mg/liter zinc silicate dust with a mean diameter of 0.9 ..mu..m. Irregular breathing with some cyanosis after 2 hr was observed. Pulmonary changes after 4.5 to 5 hr included bronchitis, patchy atelectasis, emphysema, interstitial pneumonitis (thickening of septa, moderate congestion, infiltration of mononuclear cells and polymorphonuclear leukocytes). After 1, 7, or 14 days recovery there were no or only slight pulmonary problems. There was localization of particles at surfaces facing, deflecting or slowing air currents, particularly near pleura and hilus and less in central portion of lobes. Rabbits exposed to abovemore » dust plus aqueous wetting agent aerosol averaging 0.5 ..mu..m in diameter showed no cyanosis or marked respiratory difficulty. Rabbits showed less of above pulmonary changes and lesser amount of dust in lungs, particularly in alveoli and alveolar ducts. Most particles were cleared in 1 day in both groups, especially aerosol group, and essentially were all gone after 7 days. Differences were primarily due to coating of particles with liquid (increased size) and aggregation.« less

Detectors based on Pd-doped and PdO-functionalized ZnO nanostructures

NASA Astrophysics Data System (ADS)

Postica, V.; Lupan, O.; Ababii, N.; Hoppe, M.; Adelung, R.; Chow, L.; Sontea, V.; Aschehoug, P.; Viana, V.; Pauporté, Th.

2018-02-01

In this work, zinc oxide (ZnO) nanostructured films were grown using a simple synthesis from chemical solutions (SCS) approach from aqueous baths at relatively low temperatures (< 95 °C). The samples were doped with Pd (0.17 at% Pd) and functionalized with PdO nanoparticles (NPs) using the PdCl2 aqueous solution and subsequent thermal annealing at 650 °C for 30 min. The morphological, micro-Raman and optical properties of Pd modified samples were investigated in detail and were demonstrated to have high crystallinity. Gas sensing studies unveiled that compared to pure ZnO films, the Pd-doped ZnO (ZnO:Pd) nanostructured films showed a decrease in ethanol vapor response and slight increase in H2 response with low selectivity. However, the PdO-functionalized samples showed excellent H2 gas sensing properties with possibility to detect H2 gas even at room temperature (gas response of 2). Up to 200 °C operating temperature the samples are highly selective to H2 gas, with highest response of 12 at 150 °C. This study demonstrates that surface functionalization of n-ZnO nanostructured films with p-type oxides is very important for improvement of gas sensing properties.

Integration of pyrolysis and anaerobic digestion--use of aqueous liquor from digestate pyrolysis for biogas production.

PubMed

Hübner, Tobias; Mumme, Jan

2015-05-01

Anaerobic digestion of aqueous pyrolysis liquor derived from pyrolysis of solid digestate was tested in batch mode using an un-adapted inoculum. Three pyrolysis liquors produced at 330°C, 430°C and 530°C in four COD-based concentrations of 3, 6, 12 and 30 g L(-1) were investigated. The three lower concentrations showed considerable biogas production, whereas the 30 g L(-1) dosage caused process inhibition. The highest methane yield of 199.1±18.5 mL g(COD)(-1) (COD removal: 56.9±5.3%) was observed for the 330°C pyrolysis liquor, followed by the 430°C sample with only slightly lower values. The 530°C sample dropped to a yield of 129.3±19.7 mL g(COD)(-1) (COD removal: 36.9±5.6%). Most VOCs contained in the pyrolysis liquor (i.e. furfural, phenol, catechol, guaiacol, and levoglucosan) were reduced below detection limit (cresol by 10-60%). Consequently, integrated pyrolysis and anaerobic digestion in addition to thermochemical conversion of digestate also promises bioconversion of pyrolysis liquors. Copyright © 2015 Elsevier Ltd. All rights reserved.

New pathway to prepare gold nanoparticles and their applications in catalysis and surface-enhanced Raman scattering.

PubMed

Chang, Chun-Chao; Yang, Kuang-Hsuan; Liu, Yu-Chuan; Hsu, Ting-Chu

2012-05-01

As shown in the literature, additional energies are necessary for the reduction of positively charged noble metal ions to prepare metal nanoparticles (NPs). In this work, we report a new green pathway to prepare Au NPs in neutral 0.1M NaCl aqueous solutions from bulk Au substrates without addition of any stabilizer and reductant just via aid of natural chitosan (Ch) at room temperature. Au- and Ch-containing complexes in aqueous solution were electrochemically prepared. The role of Ch is just an intermediate to perform electron transfer with Au NPs. The stability of these prepared Au NPs is well maintained by Au NPs themselves with slightly positively charged Au remained on the surface of Au NPs. The particle size of prepared spherical Au (111) NPs is ca. 15 nm in diameter. Moreover, increasing the pH of preparation solutions can be contributive to preparing concentrated Au NPs in solutions. The prepared Au NPs are surface-enhanced Raman scattering (SERS)-active for probe molecules of Rhodamine 6G. They also demonstrate significantly catalytic activity for decomposition of acetaldehyde in rice wine. Copyright © 2012 Elsevier B.V. All rights reserved.

Galvanic Tongue Stimulation Inhibits Five Basic Tastes Induced by Aqueous Electrolyte Solutions.

PubMed

Aoyama, Kazuma; Sakurai, Kenta; Sakurai, Satoru; Mizukami, Makoto; Maeda, Taro; Ando, Hideyuki

2017-01-01

Galvanic tongue stimulation (GTS) modulates taste sensation. However, the effect of GTS is contingent on the electrode polarity in the proximity of the tongue. If an anodal electrode is attached in the proximity of the tongue, an electrical or metallic taste is elicited. On the other hand, if only cathodal electrode is attached in the proximity of the tongue, the salty taste, which is induced by electrolyte materials, is inhibited. The mechanism of this taste inhibition is not adequately understood. In this study, we aim to demonstrate that the inhibition is cause by ions, which elicit taste and which migrate from the taste sensors on the tongue by GTS. We verified the inhibitory effect of GTS on all five basic tastes induced by electrolyte materials. This technology is effective for virtual reality systems and interfaces to support dietary restrictions. Our findings demonstrate that cathodal-GTS inhibits all the five basic tastes. The results also support our hypothesis that the effects of cathodal-GTS are caused by migrating tasting ions in the mouth.

Concentrated aqueous sodium chloride solution in clays at thermodynamic conditions of hydraulic fracturing: Insight from molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Svoboda, Martin; Lísal, Martin

2018-06-01

To address a high salinity of flow-back water during hydraulic fracturing, we use molecular dynamics (MD) simulations and study the thermodynamics, structure, and diffusion of concentrated aqueous salt solution in clay nanopores. The concentrated solution results from the dissolution of a cubic NaCl nanocrystal, immersed in an aqueous NaCl solution of varying salt concentration and confined in clay pores of a width comparable to the crystal size. The size of the nanocrystal equals to about 18 Å which is above a critical nucleus size. We consider a typical shale gas reservoir condition of 365 K and 275 bar, and we represent the clay pores as pyrophyllite and Na-montmorillonite (Na-MMT) slits. We employ the Extended Simple Point Charge (SPC/E) model for water, Joung-Cheatham model for ions, and CLAYFF for the slit walls. We impose the pressure in the normal direction and the resulting slit width varies from about 20 to 25 Å when the salt concentration in the surrounding solution increased from zero to an oversaturated value. By varying the salt concentration, we observe two scenarios. First, the crystal dissolves and its dissolution time increases with increasing salt concentration. We describe the dissolution process in terms of the number of ions in the crystal, and the crystal size and shape. Second, when the salt concentration reaches a system solubility limit, the crystal grows and attains a new equilibrium size; the crystal comes into equilibrium with the surrounding saturated solution. After crystal dissolution, we carry out canonical MD simulations for the concentrated solution. We evaluate the hydration energy, density profiles, orientation distributions, hydrogen-bond network, radial distribution functions, and in-plane diffusion of water and ions to provide insight into the microscopic behaviour of the concentrated aqueous sodium chloride solution in interlayer galleries of the slightly hydrophobic pyrophyllite and hydrophilic Na-MMT pores.

Crystallization pathways of sulfate-nitrate-ammonium aerosol particles.

PubMed

Schlenker, Julie C; Martin, Scot T

2005-11-10

Crystallization experiments are conducted for aerosol particles composed of aqueous mixtures of (NH(4))(2)SO(4)(aq) and NH(4)NO(3)(aq), (NH(4))(2)SO(4)(aq) and NH(4)HSO(4)(aq), and NH(4)NO(3)(aq) and NH(4)HSO(4)(aq). Depending on the aqueous composition, crystals of (NH(4))(2)SO(4)(s), (NH(4))(3)H(SO(4))(2)(s), NH(4)HSO(4)(s), NH(4)NO(3)(s), 2NH(4)NO(3) x (NH(4))(2)SO(4)(s), and 3NH(4)NO(3) x (NH(4))(2)SO(4)(s) are formed. Although particles of NH(4)NO(3)(aq) and NH(4)HSO(4)(aq) do not crystallize even at 1% relative humidity, additions of 0.05 mol fraction SO(4)(2-)(aq) or NO(3)(-)(aq) ions promote crystallization, respectively. 2NH(4)NO(3) x (NH(4))(2)SO(4)(s) and (NH(4))(3)H(SO(4))(2)(s) appear to serve as good heterogeneous nuclei for NH(4)NO(3)(s) and NH(4)HSO(4)(s), respectively. 2NH(4)NO(3) x (NH(4))(2)SO(4)(s) crystallizes over a greater range of aqueous compositions than 3NH(4)NO(3) x (NH(4))(2)SO(4)(s). An infrared aerosol spectrum is provided for each solid based upon a linear decomposition analysis of the recorded spectra. Small nonzero residuals occur in the analysis because aerosol spectra depend on particle morphology, which changes slightly across the range of compositions studied. In addition, several of the mixed compositions crystallize with residual aqueous water of up to 5% particle mass. We attribute this water content to enclosed water pockets. The results provide further insights into the nonlinear crystallization pathways of sulfate-nitrate-ammonium aerosol particles.

Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

2017-10-01

Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

Concentrated aqueous sodium chloride solution in clays at thermodynamic conditions of hydraulic fracturing: Insight from molecular dynamics simulations.

PubMed

Svoboda, Martin; Lísal, Martin

2018-06-14

To address a high salinity of flow-back water during hydraulic fracturing, we use molecular dynamics (MD) simulations and study the thermodynamics, structure, and diffusion of concentrated aqueous salt solution in clay nanopores. The concentrated solution results from the dissolution of a cubic NaCl nanocrystal, immersed in an aqueous NaCl solution of varying salt concentration and confined in clay pores of a width comparable to the crystal size. The size of the nanocrystal equals to about 18 Å which is above a critical nucleus size. We consider a typical shale gas reservoir condition of 365 K and 275 bar, and we represent the clay pores as pyrophyllite and Na-montmorillonite (Na-MMT) slits. We employ the Extended Simple Point Charge (SPC/E) model for water, Joung-Cheatham model for ions, and CLAYFF for the slit walls. We impose the pressure in the normal direction and the resulting slit width varies from about 20 to 25 Å when the salt concentration in the surrounding solution increased from zero to an oversaturated value. By varying the salt concentration, we observe two scenarios. First, the crystal dissolves and its dissolution time increases with increasing salt concentration. We describe the dissolution process in terms of the number of ions in the crystal, and the crystal size and shape. Second, when the salt concentration reaches a system solubility limit, the crystal grows and attains a new equilibrium size; the crystal comes into equilibrium with the surrounding saturated solution. After crystal dissolution, we carry out canonical MD simulations for the concentrated solution. We evaluate the hydration energy, density profiles, orientation distributions, hydrogen-bond network, radial distribution functions, and in-plane diffusion of water and ions to provide insight into the microscopic behaviour of the concentrated aqueous sodium chloride solution in interlayer galleries of the slightly hydrophobic pyrophyllite and hydrophilic Na-MMT pores.

Insights into Supramolecular Sites Responsible for Complete Separation of Biomass-Derived Phenolics and Glucose in Metal-Organic Framework NU-1000.

PubMed

Yabushita, Mizuho; Li, Peng; Durkin, Kathleen A; Kobayashi, Hirokazu; Fukuoka, Atsushi; Farha, Omar K; Katz, Alexander

2017-05-02

The molecular origins of adsorption of lignin-derived phenolics to metal-organic framework NU-1000 are investigated from aqueous solution as well as in competitive mode with glucose present in the same aqueous mixture. A comparison of adsorption equilibrium constants (K ads ) for phenolics functionalized with either carboxylic acid or aldehyde substituents demonstrated only a slight increase (less than a factor of 6) for the former according to both experiments and calculations. This small difference in K ads between aldehyde and carboxylic-acid substituted adsorbates is consistent with the pyrene unit of NU-1000 as the adsorption site, rather than the zirconia nodes, while at saturation coverage, the adsorption capacity suggests multiple guests per pyrene. Experimental standard free energies of adsorption directly correlated with the molecular size and electronic structure calculations confirmed this direct relationship, with the pyrene units as adsorption site. The underlying origins of this relationship are grounded in noncovalent π-π interactions as being responsible for adsorption, the same interactions present in the condensed phase of the phenolics, which to a large extent govern their heat of vaporization. Thus, NU-1000 acts as a preformed aromatic cavity for driving aromatic guest adsorption from aqueous solution and does so specifically without causing detectable glucose adsorption from aqueous solution, thereby achieving complete glucose-phenolics separations. The reusability of NU-1000 during an adsorption/desorption cycle was good, even with some of the phenolic compounds with greatest affinity not easiliy removed with water and ethanol washes at room temperature. A competitive adsorption experiment gave an upper bound for K ads for glucose of at most 0.18 M -1 , which can be compared with K ads for the phenolics investigated here, which fell in the range of 443-42 639 M -1 . The actual value of K ads for glucose may be much closer to zero given the lack of observed glucose uptake with NU-1000 as adsorbent.

Hydrogen storage and evolution catalysed by metal hydride complexes.

PubMed

Fukuzumi, Shunichi; Suenobu, Tomoyoshi

2013-01-07

The storage and evolution of hydrogen are catalysed by appropriate metal hydride complexes. Hydrogenation of carbon dioxide by hydrogen is catalysed by a [C,N] cyclometalated organoiridium complex, [Ir(III)(Cp*)(4-(1H-pyrazol-1-yl-κN(2))benzoic acid-κC(3))(OH(2))](2)SO(4) [Ir-OH(2)](2)SO(4), under atmospheric pressure of H(2) and CO(2) in weakly basic water (pH 7.5) at room temperature. The reverse reaction, i.e., hydrogen evolution from formate, is also catalysed by [Ir-OH(2)](+) in acidic water (pH 2.8) at room temperature. Thus, interconversion between hydrogen and formic acid in water at ambient temperature and pressure has been achieved by using [Ir-OH(2)](+) as an efficient catalyst in both directions depending on pH. The Ir complex [Ir-OH(2)](+) also catalyses regioselective hydrogenation of the oxidised form of β-nicotinamide adenine dinucleotide (NAD(+)) to produce the 1,4-reduced form (NADH) under atmospheric pressure of H(2) at room temperature in weakly basic water. In weakly acidic water, the complex [Ir-OH(2)](+) also catalyses the reverse reaction, i.e., hydrogen evolution from NADH to produce NAD(+) at room temperature. Thus, interconversion between NADH (and H(+)) and NAD(+) (and H(2)) has also been achieved by using [Ir-OH(2)](+) as an efficient catalyst and by changing pH. The iridium hydride complex formed by the reduction of [Ir-OH(2)](+) by H(2) and NADH is responsible for the hydrogen evolution. Photoirradiation (λ > 330 nm) of an aqueous solution of the Ir-hydride complex produced by the reduction of [Ir-OH(2)](+) with alcohols resulted in the quantitative conversion to a unique [C,C] cyclometalated Ir-hydride complex, which can catalyse hydrogen evolution from alcohols in a basic aqueous solution (pH 11.9). The catalytic mechanisms of the hydrogen storage and evolution are discussed by focusing on the reactivity of Ir-hydride complexes.

A process for the preparation of cysteine from cystine

DOEpatents

Chang, Shih-Ger; Liu, David K.; Griffiths, Elizabeth A.; Littlejohn, David

1989-01-01

The present invention in one aspect relates to a process for the simultaneous removal of NO.sub.x and SO.sub.2 from a fluid stream comprising mixtures thereof and in another aspect relates to the separation, use and/or regeneration of various chemicals contaminated or spent in the process and which includes the steps of: (A) contacting the fluid stream at a temperature of between about 105.degree. and 180.degree. C. with a liquid aqueous slurry or solution comprising an effective amount of an iron chelate of an amino acid moiety having at least one --SH group; (B) separating the fluid stream from the particulates formed in step (A) comprising the chelate of the amino acid moiety and fly ash; (C) washing and separating the particulates of step (B) with an aqeous solution having a pH value of between about 5 to 8; (D) subsequently washing and separating the particulates of step (C) with a strongly acidic aqueous solution having a pH value of between about 1 to 3; (E) washing and separating the particulates of step (D) with an basic aqueous solution having a pH value of between about 9 to 12; (F) optionally adding additional amino acid moiety, iron (II) and alkali to the aqueous liquid from step (D) to produce an aqueous solution or slurry similar to that in step (A) having a pH value of between about 4 to 12; and (G) recycling the aqueous slurry of step (F) to the contacting zone of step (A). Steps (D) and (E) can be carried out in the reverse sequence, however the preferred order is (D) and then (E). In a preferred embodiment the present invention provides an improved process for the preparation (regeneration) of cysteine from cystine, which includes reacting an aqueous solution of cystine at a pH of between about 9 to 13 with a reducing agent selected from hydrogen sulfide or alkali metal sulfides, sulfur dioxide, an alkali metal sulfite or mixtures thereof for a time and at a temperature effective to cleave and reduce the cystine to cysteine with subsequent recovery of the cysteine. In another preferred embodiment the present invention provides a process for the removal of NO.sub.x, SO.sub.2 and particulates from a fluid stream which includes the steps of (A) injecting into a reaction zone an aqueous solution itself comprising (i) an amino acid moiety selected from those described above; (ii) iron (II) ion; and (iii) an alkali, wherein the aqueous solution has a pH of between about 4 and 11; followed by solids separation and washing as is described in steps (B), (C), (D) and (E) above. The overall process is useful to reduce acid rain components from combustion gas sources.

Effect of Partially Fluorinated N-Alkyl-Substituted Piperidine-2-carboxamides on Pharmacologically Relevant Properties.

PubMed

Vorberg, Raffael; Trapp, Nils; Zimmerli, Daniel; Wagner, Björn; Fischer, Holger; Kratochwil, Nicole A; Kansy, Manfred; Carreira, Erick M; Müller, Klaus

2016-10-06

The modulation of pharmacologically relevant properties of N-alkyl-piperidine-2-carboxamides was studied by selective introduction of 1-3 fluorine atoms into the n-propyl and n-butyl side chains of the local anesthetics ropivacaine and levobupivacaine. The basicity modulation by nearby fluorine substituents is essentially additive and exhibits an exponential attenuation as a function of topological distance between fluorine and the basic center. The intrinsic lipophilicity of the neutral piperidine derivatives displays the characteristic response noted for partially fluorinated alkyl groups attached to neutral heteroaryl systems. However, basicity decrease by nearby fluorine substituents affects lipophilicities at neutral pH, so that all partially fluorinated derivatives are of similar or higher lipophilicity than their non-fluorinated parents. Aqueous solubilities were found to correlate inversely with lipophilicity with a significant contribution from crystal packing energies, as indicated by variations in melting point temperatures. All fluorinated derivatives were found to be somewhat more readily oxidized in human liver microsomes, the rates of degradation correlating with increasing lipophilicity. Because the piperidine-2-carboxamide core is chiral, pairs with enantiomeric N-alkyl groups are diastereomeric. While little response to such stereoisomerism was observed for basicity or lipophilicity, more pronounced variations were observed for melting point temperatures and oxidative degradation. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Uptake of Cr3+ from aqueous solution by lignite-based humic acids.

PubMed

Arslan, G; Pehlivan, E

2008-11-01

Humic acid (HA) produced from brown coal, a relatively abundant and inexpensive material is currently being investigated as an adsorbent to remove toxic metals from aqueous solution. The influence of five parameters (contact time, solution pH, initial metal concentration, temperature and amount of adsorbent) on the removal at 20+/-1 degrees C was studied. HAs were prepared from lignites by using alkaline extraction, sedimentation and acidic precipitation. Adsorption equilibrium was achieved in about 60 min for Cr3+ ion. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The maximum adsorption capacity of 0.17 mmol for Ilgin (HA1), 0.29 mmol for Beysehir (HA2) and 0.18 mmol Ermenek (HA3) and 0.17 mmol of Cr3+/g for activated carbon (AC) was achieved, respectively at pH of 4.1. More than 84% of Cr3+ was removed by HA2, 54% by HA3 and 51% by HA1 and 50% by AC from aqueous solution. The adsorption was strongly dependent on pH but independent of ionic strength and metal ions. The adsorption of Cr3+ was higher between pH 4.1 and 5.1 for all HAs and maximum sorption was observed at pH 4.1. The rise in temperature caused a slight decrease in the value of the equilibrium constant (Kc) for the sorption of Cr3+ ion. Complex mechanisms including ion exchange, complexation and adsorption and size exclusion are possible for sorption of Cr3+ ion on HAs.

Origins of protein denatured state compactness and hydrophobic clustering in aqueous urea: inferences from nonpolar potentials of mean force.

PubMed

Shimizu, Seishi; Chan, Hue Sun

2002-12-01

Free energies of pairwise hydrophobic association are simulated in aqueous solutions of urea at concentrations ranging from 0-8 M. Consistent with the expectation that hydrophobic interactions are weakened by urea, the association of relatively large nonpolar solutes is destabilized by urea. However, the association of two small methane-sized nonpolar solutes in water has the opposite tendency of being slightly strengthened by the addition of urea. Such size effects and the dependence of urea-induced stability changes on the configuration of nonpolar solutes are not predicted by solvent accessible surface area approaches based on energetic parameters derived from bulk-phase solubilities of model compounds. Thus, to understand hydrophobic interactions in proteins, it is not sufficient to rely solely on transfer experiment data that effectively characterize a single nonpolar solute in an aqueous environment but not the solvent-mediated interactions among two or more nonpolar solutes. We find that the m-values for the rate of change of two-methane association free energy with respect to urea concentration is a dramatically nonmonotonic function of the spatial separation between the two methanes, with a distance-dependent profile similar to the corresponding two-methane heat capacity of association in pure water. Our results rationalize the persistence of residual hydrophobic contacts in some proteins at high urea concentrations and explain why the heat capacity signature (DeltaC(P)) of a compact denatured state can be similar to DeltaC(P) values calculated by assuming an open random-coil-like unfolded state. Copyright 2002 Wiley-Liss, Inc.

Critical transport issues for improving the performance of aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zhao, T. S.; An, L.; Zeng, Y. K.; Wei, L.

2017-01-01

As the fraction of electricity generated from intermittent renewable sources (such as solar and wind) grows, developing reliable energy storage technologies to store electrical energy in large scale is of increasing importance. Redox flow batteries are now enjoying a renaissance and regarded as a leading technology in providing a well-balanced solution for current daunting challenges. In this article, state-of-the-art studies of the complex multicomponent transport phenomena in aqueous redox flow batteries, with a special emphasis on all-vanadium redox flow batteries, are reviewed and summarized. Rather than elaborating on the details of previous experimental and numerical investigations, this article highlights: i) the key transport issues in each battery's component that need to be tackled so that the rate capability and cycling stability of flow batteries can be significantly improved, ii) the basic mechanisms that control the active species/ion/electron transport behaviors in each battery's component, and iii) the key experimental and numerical findings regarding the correlations between the multicomponent transport processes and battery performance.

Efficient Hydrogen Storage and Production Using a Catalyst with an Imidazoline-Based, Proton-Responsive Ligand.

PubMed

Wang, Lin; Onishi, Naoya; Murata, Kazuhisa; Hirose, Takuji; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

2017-03-22

A series of new imidazoline-based iridium complexes has been developed for hydrogenation of CO 2 and dehydrogenation of formic acid. One of the proton-responsive complexes bearing two -OH groups at ortho and para positions on a coordinating pyridine ring (3 b) can catalyze efficiently the chemical fixation of CO 2 and release H 2 under mild conditions in aqueous media without using organic additives/solvents. Notably, hydrogenation of CO 2 can be efficiently carried out under CO 2 and H 2 at atmospheric pressure in basic water by 3 b, achieving a turnover frequency of 106 h -1 and a turnover number of 7280 at 25 °C, which are higher than ever reported. Moreover, highly efficient CO-free hydrogen production from formic acid in aqueous solution employing the same catalyst under mild conditions has been achieved, thus providing a promising potential H 2 -storage system in water. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen bond basicity of ionic liquids and molar entropy of hydration of salts as major descriptors in the formation of aqueous biphasic systems.

PubMed

Passos, Helena; Dinis, Teresa B V; Cláudio, Ana Filipa M; Freire, Mara G; Coutinho, João A P

2018-05-23

Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and conventional salts have been largely investigated and successfully used in separation processes, for which the determination of the corresponding ternary phase diagrams is a prerequisite. However, due the large number of ILs that can be prepared and their high structural versatility, it is impossible to experimentally cover and characterize all possible combinations of ILs and salts that may form ABS. The development of tools for the prediction and design of IL-based ABS is thus a crucial requirement. Based on a large compilation of experimental data, a correlation describing the formation of IL-based ABS is shown here, based on the hydrogen-bonding interaction energies of ILs (EHB) obtained by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) and the molar entropy of hydration of the salt ions. The ability of the proposed model to predict the formation of novel IL-based ABS is further ascertained.

Production and physicochemical assessment of new stevia amino acid sweeteners from the natural stevioside.

PubMed

Khattab, Sherine N; Massoud, Mona I; Jad, Yahya El-Sayed; Bekhit, Adnan A; El-Faham, Ayman

2015-04-15

New stevia amino acid sweeteners, stevia glycine ethyl ester (ST-GL) and stevia l-alanine methyl ester (ST-GL), were synthesised and characterised by IR, NMR ((1)H NMR and (13)C NMR) and elemental analysis. The purity of the new sweeteners was determined by HPLC and their sensory properties were evaluated relative to sucrose in an aqueous system. Furthermore, the stevia derivatives (ST-GL and ST-AL) were evaluated for their acute toxicity, melting point, solubility and heat stability. The novel sweeteners were stable in acidic, neutral or basic aqueous solutions maintained at 100 °C for 2 h. The sweetness intensity rate of the novel sweeteners was higher than sucrose. Stevia amino acid (ST-GL and ST-AL) solutions had a clean sweetness taste without bitterness when compared to stevioside. The novel sweeteners can be utilised as non-caloric sweeteners in the production of low-calorie food. Copyright © 2014 Elsevier Ltd. All rights reserved.

Using Basic Principles To Understand Complex Science: Nicotine Smoke Chemistry and Literature Analogies

NASA Astrophysics Data System (ADS)

Seeman, Jeffrey I.

2005-10-01

The Henderson Hasselbalch equation calculates the equilibrium distribution of 50:50 for nicotine in its nonprotonated (free base form), relative to its monoprotonated form, at pH of 8 in dilute aqueous solution. This ratio has then been used in the literature to predict the effect of ammonia compounds in tobacco and in smoke on nicotine pyrolysis and smoke chemistry. Experiments demonstrate that neither the thermal chemistry of tobacco alkaloids nor the transfer of nicotine from tobacco to smoke can be explained by the position of the nonprotonated versus monoprotonated form equilibrium in aqueous extracts of tobacco. The high thermal stability of nicotine in air allows nicotine salts to be converted to nonprotonated nicotine and volatilize during heating prior to any substantial decomposition of the nicotine moiety. In contrast, cocaine hydrochloride is thermally unstable and will rapidly decompose upon heating; cocaine hydrochloride must first be converted to its nonprotonated form prior to heating and volatilization.

Silica adsorbent prepared from spent diatomaceous earth and its application to removal of dye from aqueous solution.

PubMed

Tsai, W T; Hsien, K J; Yang, J M

2004-07-15

The objective of this work is to study the activation regeneration of spent diatomaceous earth (SDE) for the preparation of silica adsorbents using thermal regeneration and acid/alkaline activation methods. Under the experimental conditions investigated, it was found that the alkaline activation method carried out by sodium hydroxide under controlled conditions is significantly superior to other heat and activation methods. The porosities of solids thus obtained are over 0.2, indicating that they are basically mesoporous. The optimal porous material thus prepared was used as a mineral adsorbent for methylene blue at 25 degrees C. The adsorption equilibrium revealed that the silica adsorbent can take up over 50 mg/g at relatively low concentrations in aqueous medium from the fittings of Langmuir and Freundlich isotherms with high correlations. On the other hand, the adsorption kinetic of methylene blue under various adsorbent dosages can be well described with a pseudo-second-order reaction model. Copyright 2004 Elsevier Inc.

A general nuclear magnetic resonance analysis of hetero-association of aromatic molecules in aqueous solution

NASA Astrophysics Data System (ADS)

Veselkov, Alexei N.; Evstigneev, Maxim P.; Veselkov, Dennis A.; Davies, David B.

2001-08-01

A general nuclear magnetic resonance analysis of a statistical-thermodynamical model of hetero-association of aromatic molecules in solution has been developed to take "edge effects" into consideration, i.e., the dependence of proton chemical shifts on the position of the molecule situated inside or at the edge of the aggregate. This generalized approach is compared with a previously published model, where an average contribution to proton shielding is considered irrespective of the position of the molecule in the stack. Association parameters have been determined from experimental concentration and temperature dependences of 500 MHz proton chemical shifts of the hetero-association of the acridine dye, proflavine, and the phenanthridinium dye, ethidium bromide, in aqueous solution. Differences in the parameters in the range 10%-30% calculated using the basic and generalized approaches have been found to depend substantially on the magnitude of the equilibrium hetero-association constant Khet—the larger the value of Khet, the higher the discrepancy between the two methods.

Factors influencing the mechanism of surfactant catalyzed reaction of vitamin C-ferric chloride hexahydrate system

NASA Astrophysics Data System (ADS)

Farrukh, Muhammad Akhyar; Kauser, Robina; Adnan, Rohana

2013-09-01

The kinetics of vitamin C by ferric chloride hexahydrate has been investigated in the aqueous ethanol solution of basic surfactant viz. octadecylamine (ODA) under pseudo-first order conditions. The critical micelle concentration (CMC) of surfactant was determined by surface tension measurement. The effect of pH (2.5-4.5) and temperature (15-35°C) in the presence and absence of surfactant were investigated. Activation parameters, Δ E a, Δ H #, Δ S #, Δ G ≠, for the reaction were calculated by using Arrhenius and Eyring plot. Surface excess concentration (Γmax), minimum area per surfactant molecule ( A min), average area occupied by each molecule of surfactant ( a), surface pressure at the CMC (Πmax), Gibb's energy of micellization (Δ G M°), Gibb's energy of adsorption (Δ G ad°), were calculated. It was found that the reaction in the presence of surfactant showed faster oxidation rate than the aqueous ethanol solution. Reaction mechanism has been deduced in the presence and absence of surfactant.

Facile synthesis of "green" gold nanocrystals using cynarin in an aqueous solution

NASA Astrophysics Data System (ADS)

Katircioğlu, Zeynep; Şakalak, Hüseyin; Ulaşan, Mehmet; Gören, Ahmet Ceyhan; Yavuz, Mustafa Selman

2014-11-01

Herein we describe a water-based protocol that generates Au nanoparticles (AuNPs) by mixing aqueous solutions of HAuCl4 and cynarin (a natural product extract from artichoke leaf). Based on the observations from 1H NMR spectrum of AuNPs, a polyol oxidation mechanism by metal ions which eventually results in AuNPs formation, is proposed. Basically, the aromatic alcohol groups (1,2-benzenediol) of cynarin are oxidized to α-hydroxy ketone intermediate product, and then further oxidized to the vicinal diketone final product while the Au3+ ions are reduced to its atomic form (Au0) which leads the generation of Au nanoparticles. This new protocol has also been employed to prepare multiply twinned Pd nanoparticles and Ag cubical aggregates. Due to exclusion of organic solvent, surfactant, or stabilizer for all these synthesis, this protocol may provide a simple, versatile, and environmentally benign route to fabricate noble-metal nanoparticles having various compositions and morphologies.

Solvent Properties of Water in Aqueous Solutions of Elastin-Like Polypeptide

PubMed Central

Ferreira, Luisa A.; Cole, James T.; Reichardt, Christian; Holland, Nolan B.; Uversky, Vladimir N.; Zaslavsky, Boris Y.

2015-01-01

The phase-transition temperatures of an elastin-like polypeptide (ELP) with the (GVGVP)40 sequence and solvent dipolarity/polarizability, hydrogen-bond donor acidity, and hydrogen-bond acceptor basicity in its aqueous solutions were quantified in the absence and presence of different salts (Na2SO4, NaCl, NaClO4, and NaSCN) and various osmolytes (sucrose, sorbitol, trehalose, and trimethylamine N-oxide (TMAO)). All osmolytes decreased the ELP phase-transition temperature, whereas NaCl and Na2SO4 decreased, and NaSCN and NaClO4 increased it. The determined phase-transition temperatures may be described as a linear combination of the solvent’s dipolarity/polarizability and hydrogen-bond donor acidity. The linear relationship established for the phase-transition temperature in the presence of salts differs quantitatively from that in the presence of osmolytes, in agreement with different (direct and indirect) mechanisms of the influence of salts and osmolytes on the ELP phase-transition temperature. PMID:26075870

Efficient hydrogen storage and production using a catalyst with an imidazoline-based, proton-responsive ligand

DOE PAGES

Wang, Lin; Onishi, Naoya; Murata, Kazuhisa; ...

2016-12-28

A series of new imidazoline-based iridium complexes has been developed for hydrogenation of CO 2 and dehydrogenation of formic acid. One of the proton-responsive complexes bearing two –OH groups at ortho and para positions on a coordinating pyridine ring (3 b) can catalyze efficiently the chemical fixation of CO 2 and release H 2 under mild conditions in aqueous media without using organic additives/solvents. Notably, hydrogenation of CO 2 can be efficiently carried out under CO 2 and H 2 at atmospheric pressure in basic water by 3 b, achieving a turnover frequency of 106 h –1 and a turnovermore » number of 7280 at 25 °C, which are higher than ever reported. Furthermore, highly efficient CO-free hydrogen production from formic acid in aqueous solution employing the same catalyst under mild conditions has been achieved, thus providing a promising potential H 2-storage system in water.« less

Biosorption of metal ions from aqueous solutions

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

Chen, Jiaping; Yiacoumi, Sotira

1997-01-01

Copper biosorption from aqueous solutions by calcium alginate is reported in this paper. The experimental section includes potentiometric titrations of biosorbents, batch equilibrium and kinetic studies of copper biosorption, as well as fixed-bed biosorption experiments. The potentiometric titration results show that the surface charge increases with decreasing pH. The biosorption of copper strongly depends on solution pH; the metal ion binding increases from 0 to 90 percent in pH ranging from 1.5 to 5.0. In addition, a decrease in ionic strength results in an increase of copper ion removal. Kinetic studies indicate that mass transfer plays an important role inmore » the biosorption rate. Furthermore, a fixed-bed biosorption experiment shows that calcium alginate has a significant capacity for copper ion removal. The two-pK Basic Stem model successfully represents the surface charge and equilibrium biosorption experimental data. The calculation results demonstrate that the copper removal may result from the binding of free copper and its hydroxide with surface functional groups of the biosorbents.« less

Degradation of Active Brilliant Red X-3B by a microwave discharge electrodeless lamp in the presence of activated carbon.

PubMed

Fu, Jie; Wen, Teng; Wang, Qing; Zhang, Xue-Wei; Zeng, Qing-Fu; An, Shu-Qing; Zhu, Hai-Liang

2010-06-01

Degradation of Active Brilliant Red X-3B (X-3B) in aqueous solution by a microwave discharge electrodeless lamp (MDEL) in the presence of activated carbon was investigated. The preliminary results proved this method could effectively degrade X-3B in aqueous solution. The removal percentages of colour and chemical oxygen demand were up to approximately 99% and 66%, respectively, at the conditions of 0.8 g/L dye concentration, 20 g/L activated carbon, pH 7.0 and 8 min microwave irradiation time. The degradation basically belonged to first-order reaction kinetics and its rate constant was 0.42 min(-1). No aromatic organics were detected in the final treated solution, indicating that the mineralization was relatively complete. By studying the change in solution properties, it could be concluded that MDEL-assisted oxidation was the dominant reaction mechanism. In addition, the influence of operational parameters and reuse of activated carbon were also discussed.

Interaction of Atmospheric-Pressure Air Microplasmas with Amino Acids as Fundamental Processes in Aqueous Solution

PubMed Central

Zhou, Renwu; Zhou, Rusen; Zhuang, Jinxing; Zong, Zichao; Zhang, Xianhui; Liu, Dongping; Bazaka, Kateryna; Ostrikov, Kostya

2016-01-01

Plasma medicine is a relatively new field that investigates potential applications of cold atmospheric-pressure plasmas in bioengineering, such as for bacterial inactivation and degradation of organic molecules in water. In order to enunciate mechanisms of bacterial inactivation at molecular or atomic levels, we investigated the interaction of atmospheric-pressure air microplasmas with amino acids in aqueous solution by using high-resolution mass spectrometry (HRMS). Results show that the oxidation effect of plasma-induced species on the side chains of the amino acids can be categorized into four types, namely hydroxylation, nitration, dehydrogenation and dimerization. In addition, relative activities of amino acids resulting from plasma treatment come in descending order as follows: sulfur-containing carbon-chain amino acids > aromatic amino acids > five-membered ring amino acids > basic carbon-chain amino acids. Since amino acids are building blocks of proteins vital to the growth and reproduction of bacteria, these results provide an insight into the mechanism of bacterial inactivation by plasma. PMID:27183129

Equilibrium and kinetic adsorption study of Basic Yellow 28 and Basic Red 46 by a boron industry waste.

PubMed

Olgun, Asim; Atar, Necip

2009-01-15

In this study, the adsorption characteristics of Basic Yellow 28 (BY 28) and Basic Red 46 (BR 46) onto boron waste (BW), a waste produced from boron processing plant were investigated. The equilibrium adsorption isotherms and kinetics were investigated. The adsorption equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that adsorption behavior of two dyes could be described reasonably well by a generalized isotherm. Kinetic studies indicated that the kinetics of the adsorption of BY 28 and BR 46 onto BW follows a pseudo-second-order model. The result showed that the BW exhibited high-adsorption capacity for basic dyes and the capacity slightly decreased with increasing temperature. The maximum adsorption capacities of BY 28 and BR 46 are reported at 75.00 and 74.73mgg(-1), respectively. The dye adsorption depended on the initial pH of the solution with maximum uptake occurring at about pH 9 and electrokinetic behavior of BW. Activation energy of 15.23kJ/mol for BY 28 and 18.15kJ/mol for BR 46 were determined confirming the nature of the physisorption onto BW. These results indicate that BW could be employed as low-cost material for the removal of the textile dyes from effluents.

A molecular rotor based ratiometric sensor for basic amino acids.

PubMed

Pettiwala, Aafrin M; Singh, Prabhat K

2018-01-05

The inevitable importance of basic amino acids, arginine and lysine, in human health and metabolism demands construction of efficient sensor systems for them. However, there are only limited reports on the 'ratiometric' detection of basic amino acids which is further restricted by the use of chemically complex sensor molecules, which impedes their prospect for practical applications. Herein, we report a ratiometric sensor system build on simple mechanism of disassociation of novel emissive Thioflavin-T H-aggregates from heparin surface, when subjected to interaction with basic amino acids. The strong and selective electrostatic and hydrogen bonding interaction of basic amino acids with heparin leads to large alteration in photophysical attributes of heparin bound Thioflavin-T, which forms a highly sensitive sensor platform for detection of basic amino acids in aqueous solution. These selective interactions between basic amino acids and heparin allow our sensor system to discriminate arginine and lysine from other amino acids. This unique mechanism of dissociation of Thioflavin-T aggregates from heparin surface provides ratiometric response on both fluorimetric and colorimetric outputs for detection of arginine and lysine, and thus it holds a significant advantage over other developed sensor systems which are restricted to single wavelength detection. Apart from the sensitivity and selectivity, our system also provides the advantage of simplicity, dual mode of sensing, and more importantly, it employs an inexpensive commercially available probe molecule, which is a significant advantage over other developed sensor systems that uses tedious synthesis protocol for the employed probe in the detection scheme, an impediment for practical applications. Additionally, our sensor system also shows response in complex biological media of serum samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Fluid inclusions in jadeitite and jadeite-rich rock from serpentinite mélanges in northern Hispaniola: Trapped ambient fluids in a cold subduction channel

NASA Astrophysics Data System (ADS)

Kawamoto, Tatsuhiko; Hertwig, Andreas; Schertl, Hans-Peter; Maresch, Walter V.

2018-05-01

Freezing-point depression was measured in aqueous fluid inclusions to determine salinities in six samples of jadeitite and jadeite-rich rock from the Jagua Clara serpentinite mélange of the Rio San Juan Complex, Dominican Republic. The mélange represents a fossil subduction-zone channel from a cold, mature subduction zone with a geothermal gradient of 6 °C/km. One hundred and twenty-five determinations of salinity in primary inclusions hosted in jadeite, quartz, apatite and lawsonite range between extremes of 1.2 and 8.7, but yield a well-defined mean of 4.5 ± 1.1 wt% (±1 s.d.) NaCl equiv, slightly higher than mean seawater (3.5 wt%). In one sample, eight additional fluid inclusions in quartz aligned along grain boundaries yield slightly lower values of 2.7 ± 1.3 wt% NaCl equiv. Homogenization temperatures were also measured for 47 fluid inclusions in two samples, but primary entrapment densities are not preserved. It is significant that the suite includes two types of samples: those precipitated directly from an aqueous fluid as well as examples of metasomatic replacement of a pre-existing magmatic rock. Nevertheless, the results indicate identical salinity for both types and suggest a much stronger genetic link between the two types of jadeitite and jadeite-rich rock than has previously been assumed. Based on the results of conductivity measurements in modern subduction zones, we envision a pervasive fluid in the subduction channel that evolved from salinity levels lower than those in sea-water up to the measured values due to on-going but largely completed serpentinization in the subduction channel. The present data represent a reference marker for the subduction channel of the Rio San Juan intra-oceanic subduction zone at 30-50 km depth and after 50-60 Myr of operation.

Catalytic wet peroxide oxidation of aniline in wastewater using copper modified SBA-15 as catalyst.

PubMed

Kong, Liming; Zhou, Xiang; Yao, Yuan; Jian, Panming; Diao, Guowang

2016-01-01

SBA-15 mesoporous molecular sieves modified with copper (Cu-SBA-15) were prepared by pH-adjusting hydrothermal method and characterized by X-ray diffraction, BET, transmission electron microscopy, UV-Vis and (29)Si MAS NMR. The pH of the synthesis gel has a significant effect on the amount and the dispersion of copper on SBA-15. The Cu-SBA-15(4.5) (where 4.5 denotes the pH value of the synthesis gel) modified with highly dispersed copper was used as catalyst for the oxidation of aniline by H2O2. The Cu-SBA-15(4.5) shows a higher catalytic activity compared to CuO on the surface of SBA-15. The influences of reaction conditions, such as initial pH of the aqueous solutions, temperature, as well as the dosages of H2O2 and catalyst were investigated. Under weakly alkaline aqueous solution conditions, the aniline conversion, the H2O2 decomposition and the total organic carbon (TOC) removal could be increased significantly compared to the acid conditions. The percentage of leaching Cu(2+) could be decreased from 45.0% to 3.66% when the initial pH of solution was increased from 5 to 10. The TOC removal could be enhanced with the increases of temperature, H2O2 and catalyst dosage, but the aniline conversion and H2O2 decomposition change slightly with further increasing dosage of catalyst and H2O2. At 343 K and pH 8.0, 100% aniline conversion and 66.9% TOC removal can be achieved under the conditions of 1.0 g/L catalyst and 0.05 mol/L H2O2 after 180 min. Although copper might be slightly leached from catalyst, the homogeneous Cu(2+) contribution to the whole catalytic activity is unimportant, and the highly dispersed copper on SBA-15 plays a dominant role.

Positive electrode processing for Hughes NiH2 cells

NASA Technical Reports Server (NTRS)

Bleser, C. A.

1982-01-01

The basic procedures were developed for the manufacture of nickel cadmium batteries. An electrochemical impregnation in an aqueous ethanol solution is used in this process. Several additional controls were instituted for production of flight electrodes, including a Hughes controlled MCD, a solution reserved exclusively for the impregnation of Hughes positive electrodes a system of complete traceability for individual electrodes, an electrical characterization test to provide information on weight and capacity at the plaque level, and a stress test to provide data on capacity, weight, and physical parameters at the electrode level.

Study of dynamics of glucose-glucose oxidase-ferricyanide reaction

NASA Astrophysics Data System (ADS)

Nováková, A.; Schreiberová, L.; Schreiber, I.

2011-12-01

This work is focused on dynamics of the glucose-glucose oxidase-ferricyanide enzymatic reaction with or without sodium hydroxide in a continuous-flow stirred tank reactor (CSTR) and in a batch reactor. This reaction exhibits pH-variations having autocatalytic character and is reported to provide nonlinear dynamic behavior (bistability, excitability). The dynamical behavior of the reaction was examined within a wide range of inlet parameters. The main inlet parameters were the ratio of concentrations of sodium hydroxide and ferricyanide and the flow rate. In a batch reactor we observed an autocatalytic drop of pH from slightly basic to medium acidic values. In a CSTR our aim was to find bistability in the presence of sodium hydroxide. However, only a basic steady state was found. In order to reach an acidic steady state, we investigated the system in the absence of sodium hydroxide. Under these conditions the transition from the basic to the acidic steady state was observed when inlet glucose concentration was increased.

A Base-Resistant Metalloporphyrin Metal–Organic Framework for C–H Bond Halogenation

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

Lv, Xiu-Liang; Wang, Kecheng; Wang, Bin

A base-resistant porphyrin metal–organic framework (MOF), namely PCN-602 has been constructed with 12-connected [Ni 8(OH) 4(H 2O) 2Pz 12] (Pz = pyrazolate) cluster and a newly designed pyrazolate-based porphyrin ligand, 5,10,15,20-tetrakis(4-(pyrazolate-4-yl)phenyl)porphyrin under the guidance of the reticular synthesis strategy. Besides its robustness in hydroxide solution, PCN-602 also shows excellent stability in aqueous solutions of F –, CO 3 2–, and PO 4 3– ions. Interestingly, the Mn 3+-porphyrinic PCN-602, as a recyclable MOF catalyst, presents high catalytic activity for the C–H bond halogenation reaction in a basic system, significantly outperforming its homogeneous counterpart. For the first time, a porphyrinic MOFmore » was thus used as an efficient catalyst in a basic solution with coordinating anions, to the best of our knowledge.« less

Structure and coarsening at the surface of a dry three-dimensional aqueous foam.

PubMed

Roth, A E; Chen, B G; Durian, D J

2013-12-01

We utilize total-internal reflection to isolate the two-dimensional surface foam formed at the planar boundary of a three-dimensional sample. The resulting images of surface Plateau borders are consistent with Plateau's laws for a truly two-dimensional foam. Samples are allowed to coarsen into a self-similar scaling state where statistical distributions appear independent of time, except for an overall scale factor. There we find that statistical measures of side number distributions, size-topology correlations, and bubble shapes are all very similar to those for two-dimensional foams. However, the size number distribution is slightly broader, and the shapes are slightly more elongated. A more obvious difference is that T2 processes now include the creation of surface bubbles, due to rearrangement in the bulk, and von Neumann's law is dramatically violated for individual bubbles. But nevertheless, our most striking finding is that von Neumann's law appears to holds on average, namely, the average rate of area change for surface bubbles appears to be proportional to the number of sides minus six, but with individual bubbles showing a wide distribution of deviations from this average behavior.

Generation of basic centers in high-silica zeolites and their application in gas-phase upgrading of bio-oil.

PubMed

Keller, Tobias C; Rodrigues, Elodie G; Pérez-Ramírez, Javier

2014-06-01

High-silica zeolites have been reported recently as efficient catalysts for liquid- and gas-phase condensation reactions because of the presence of a complementary source of basicity compared to Al-rich basic zeolites. Herein, we describe the controlled generation of these active sites on silica-rich FAU, BEA, and MFI zeolites. Through the application of a mild base treatment in aqueous Na2CO3, alkali-metal-coordinating defects are generated within the zeolite whereas the porous properties are fully preserved. The resulting catalysts were applied in the gas-phase condensation of propanal at 673 K as a model reaction for the catalytic upgrading of pyrolysis oil, for which an up to 20-fold increased activity compared to the unmodified zeolites was attained. The moderate basicity of these new sites leads to a coke resistance superior to traditional base catalysts such as CsX and MgO, and comparable activity and excellent selectivity is achieved for the condensation pathways. Through strategic acid and base treatments and the use of magic-angle spinning NMR spectroscopy, the nature of the active sites was investigated, which supports the theory of siloxy sites as basic centers. This contribution represents a key step in the understanding and design of high-silica base catalysts for the intermediate deoxygenation of crude bio-oil prior to the hydrotreating step for the production of second-generation biofuels. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Differences in Aqueous Concentrations of Cytokines in Macular Edema Secondary to Branch and Central Retinal Vein Occlusion

PubMed Central

Feng, Jing; Zhao, Tong; Zhang, Yan; Ma, Yan; Jiang, Yanrong

2013-01-01

Purpose This study investigates the differential aqueous concentrations of interleukin 6, 8, 1β (IL-6, IL-8, IL-1β, respectively), serum amyloid A (SAA), transforming growth factor (TGF)-β, basic fibroblast growth factor (bFGF), and vascular endothelial growth factor (VEGF) in eyes with macular edema as a result of a branch retinal vein occlusion (BRVO) or central retinal vein occlusion (CRVO). Principal Findings Significantly higher concentrations of IL-6, IL-8, IL-1β, TGF-β, bFGF, SAA, and VEGF were found in the aqueous humor of CRVO and BRVO patients than in the aqueous humor of control patients. A significant correlation was observed between the concentration of bFGF and the inner central macular thickness (CMT) of BRVO patients (r = 0.688; P = 0.02). A significant correlation was observed between the concentration of SAA and both the full and outer CMT of the ischemic group (r = 0.545 and 0.683, respectively; P = 0.04 and 0.01, respectively). In the non-ischemic group, the level of IL-6 was significantly associated with inner CMT (r = 0.560; P = 0.03). The full and outer CMT was significantly reduced in CRVO patients when compared with BRVO patients (P = 0.02 and 0.02, respectively) after injection of intravitreal bevacizumab (IVB) at 4 weeks. Significance Serum amyloid A as a major protein involved in the acute and chronic stages of inflammation, and IL-6 and bFGF were significantly associated with the extent of macular edema in patients with RVO. Besides VEGF, other inflammatory cytokines and angiogenesic factors may be associated with RVO. This finding may have implications for the medical treatment of RVO. PMID:23861862

High Energy Density Aqueous Electrochemical Capacitors with a KI-KOH Electrolyte.

PubMed

Wang, Xingfeng; Chandrabose, Raghu S; Chun, Sang-Eun; Zhang, Tianqi; Evanko, Brian; Jian, Zelang; Boettcher, Shannon W; Stucky, Galen D; Ji, Xiulei

2015-09-16

We report a new electrochemical capacitor with an aqueous KI-KOH electrolyte that exhibits a higher specific energy and power than the state-of-the-art nonaqueous electrochemical capacitors. In addition to electrical double layer capacitance, redox reactions in this device contribute to charge storage at both positive and negative electrodes via a catholyte of IOx-/I- couple and a redox couple of H2O/Had, respectively. Here, we, for the first time, report utilizing IOx-/I- redox couple for the positive electrode, which pins the positive electrode potential to be 0.4-0.5 V vs Ag/AgCl. With the positive electrode potential pinned, we can polarize the cell to 1.6 V without breaking down the aqueous electrolyte so that the negative electrode potential could reach -1.1 V vs Ag/AgCl in the basic electrolyte, greatly enhancing energy storage. Both mass spectroscopy and Raman spectrometry confirm the formation of IO3- ions (+5) from I- (-1) after charging. Based on the total mass of electrodes and electrolyte in a practically relevant cell configuration, the device exhibits a maximum specific energy of 7.1 Wh/kg, operates between -20 and 50 °C, provides a maximum specific power of 6222 W/kg, and has a stable cycling life with 93% retention of the peak specific energy after 14,000 cycles.

Combined ab initio/empirical approach for optimization of Lennard-Jones parameters for polar-neutral compounds.

PubMed

Chen, I Jen; Yin, Daxu; MacKerell, Alexander D

2002-01-30

The study of small functionalized organic molecules in aqueous solution is a useful step toward gaining a basic understanding of the behavior of biomolecular systems in their native aqueous environment. Interest in studying amines and fluorine-substituted compounds has risen from their intrinsic physicochemical properties and their prevalence in biological and pharmaceutical compounds. In the present study, a previously developed approach which optimizes Lennard-Jones (LJ) parameters via the use of rare gas atoms combined with the reproduction of experimental condensed phase properties was extended to polar-neutral compounds. Compounds studied included four amines (ammonia, methylamine, dimethylamine, and trimethylamine) and three fluoroethanes (1-fluoroethane, 1,1-difluoroethane, and 1,1,1-trifluoroethane). The resulting force field yielded heats of vaporization and molecular volumes in excellent agreement with the experiment, with average differences less than 1%. The current amine CHARMM parameters successfully reproduced experimental aqueous solvation data where methylamine is more hydrophilic than ammonia, with hydrophobicity increasing with additional methylation on the nitrogen. For both the amines and fluoroethanes the parabolic relationship of the extent of methylation or fluorination, respectively, to the heats of vaporization were reproduced by the new parameters. The present results are also discussed with respect to the impact of parameterization approach to molecular details obtained from computer simulations and to the unique biological properties of fluorine in pharmaceutical compounds.

Studies of obtaining and stability in aqueous medium of new complex compounds of Ti(IV) and Zr(IV) used in ecological leather tanning

NASA Astrophysics Data System (ADS)

Crudu, Marian; Sibiescu, Doina; Rosca, Ioan; Sutiman, Daniel; Vizitiu, Mihaela

2009-01-01

In this paper, the study of obtaining new coordination compounds of Ti(IV) and Zr(IV) using as ligand: D,L-β-iso-butyric acid, is presented. Also, the stability of these compounds in aqueous medium is studied. The studies of obtaining and of stability of the new compounds were accomplished in aqueous solutions using methods characteristic for coordination compounds: conductance and pH measurements. The combination ratios and the stability were determined with methods characteristic for studies in solutions. From experimental data resulted that the combination ratio of central metallic atoms with the ligand derived from D,L-β-iso-butyric acid was 1:2. From experimental data resulted that in strong acid and strong basic mediums, the coordination compounds could not be obtained. The optimal stability of the studied compounds is limited between 3-6, pH - values. This fact is in accordance with the conditions of using these compounds in ecological leather tanning. Of great importance is that these compounds were used with very good results in tanning processes of different types of leather. This fact evidenced that the ecological alternative of tanning is better than non-ecological tanning using chrome compounds. The importance of this paper consists in obtaining new coordination compounds that can be used in ecological leather tanning.

Synthesis of layered double hydroxide nanosheets by coprecipitation using a T-type microchannel reactor

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

Pang, Xiujiang; Sun, Meiyu; Ma, Xiuming

The synthesis of Mg{sub 2}Al–NO{sub 3} layered double hydroxide (LDH) nanosheets by coprecipitation using a T-type microchannel reactor is reported. Aqueous LDH nanosheet dispersions were obtained. The LDH nanosheets were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy and particle size analysis, and the transmittance and viscosity of LDH nanosheet dispersions were examined. The two-dimensional LDH nanosheets consisted of 1–2 brucite-like layers and were stable for ca. 16 h at room temperature. In addition, the co-assembly between LDH nanosheets and dodecyl sulfate (DS) anions was carried out, and a DS intercalated LDH nanohybrid was obtained. To the bestmore » of our knowledge, this is the first report of LDH nanosheets being directly prepared in bulk aqueous solution. This simple, cheap method can provide naked LDH nanosheets in high quantities, which can be used as building blocks for functional materials. - Graphical abstract: Layered double hydroxide (LDH) nanosheets were synthesized by coprecipitation using a T-type microchannel reactor, and could be used as basic building blocks for LDH-based functional materials. Display Omitted - Highlights: • LDH nanosheets were synthesized by coprecipitation using a T-type microchannel reactor. • Naked LDH nanosheets were dispersed in aqueous media. • LDH nanosheets can be used as building blocks for functional materials.« less

Applications of Brazilian pine-fruit shell in natural and carbonized forms as adsorbents to removal of methylene blue from aqueous solutions--kinetic and equilibrium study.

PubMed

Royer, Betina; Cardoso, Natali F; Lima, Eder C; Vaghetti, Julio C P; Simon, Nathalia M; Calvete, Tatiana; Veses, Renato Cataluña

2009-05-30

The Brazilian pine-fruit shell (Araucaria angustifolia) is a food residue, which was used in natural and carbonized forms, as low-cost adsorbents for the removal of methylene blue (MB) from aqueous solutions. Chemical treatment of Brazilian pine-fruit shell (PW), with sulfuric acid produced a non-activated carbonaceous material (C-PW). Both PW and C-PW were tested as low-cost adsorbents for the removal of MB from aqueous effluents. It was observed that C-PW leaded to a remarkable increase in the specific surface area, average porous volume, and average porous diameter of the adsorbent when compared to PW. The effects of shaking time, adsorbent dosage and pH on adsorption capacity were studied. In basic pH region (pH 8.5) the adsorption of MB was favorable. The contact time required to obtain the equilibrium was 6 and 4h at 25 degrees C, using PW and C-PW as adsorbents, respectively. Based on error function values (F(error)) the kinetic data were better fitted to fractionary-order kinetic model when compared to pseudo-first order, pseudo-second order, and chemisorption kinetic models. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. For MB dye the equilibrium data were better fitted to the Sips isotherm model using PW and C-PW as adsorbents.

Effects of aqueous extract of Hibiscus sabdariffa on the renin-angiotensin-aldosterone system of Nigerians with mild to moderate essential hypertension: A comparative study with lisinopril.

PubMed

Nwachukwu, Daniel Chukwu; Aneke, Eddy Ikemefuna; Obika, Leonard Fidelis; Nwachukwu, Nkiru Zuada

2015-01-01

The present study investigated the effects of aqueous extract of Hibiscus sabdariffa (HS) on the three basic components of renin-angiotensin-aldosterone system: Plasma renin, serum angiotensin-converting enzyme (ACE), and plasma aldosterone (PA) in mild to moderate essential hypertensive Nigerians and compared with that of lisinopril, an ACE inhibitor. A double-blind controlled randomized clinical study was used. Seventy-eight newly diagnosed but untreated mild to moderate hypertensive subjects attending Medical Outpatients Clinic of Enugu State University Teaching Hospital, Enugu were recruited for the study. Those in Group A received placebo (150 mg/kg/day), Group B were given lisinopril (10 mg once daily) while those in Group C received aqueous extract of HS (150 mg/kg/day). After 4 weeks of treatment, the levels of plasma renin, serum ACE, and PA were determined. HS and lisinopril significantly (P < 0.001) reduced PA compared to placebo by 32.06% and 30.01%, respectively. Their effects on serum ACE and plasma renin activity (PRA) were not significant compared to placebo; they reduced ACE by 6.63% and 5.67% but increased plasma PRA by 2.77% and 5.36%, respectively. HS reduced serum ACE and PA in mild to moderate hypertensive Nigerians with equal efficacy as lisinopril. These actions are possibly due to the presence of anthocyanins in the extract.

Acidic ammonothermal growth of gallium nitride in a liner-free molybdenum alloy autoclave

NASA Astrophysics Data System (ADS)

Malkowski, Thomas F.; Pimputkar, Siddha; Speck, James S.; DenBaars, Steven P.; Nakamura, Shuji

2016-12-01

This paper discusses promising materials for use as internal, non-load bearing components as well as molybdenum-based alloys for autoclave structural components for an ammonothermal autoclave. An autoclave was constructed from the commercial titanium-zirconium-molybdenum (TZM) alloy and was found to be chemically inert and mechanically stable under acidic ammonothermal conditions. Preliminary seeded growth of GaN was demonstrated with negligible incorporation of transition metals (including molybdenum) into the grown material (<1017 cm-3). Molybdenum and TZM were exposed to a basic ammonothermal environment, leading to slight degradation through formation of molybdenum nitride powders on their surface at elevated temperatures (T>560 °C). The possibility of a 'universal', inexpensive, liner-free ammonothermal autoclave capable of exposure to basic and acidic chemistry is demonstrated.

Effect of irradiation on the patulin content and chemical composition of apple juice concentrate.

PubMed

Zegota, H; Zegota, A; Bachman, S

1988-09-01

The influence of ionizing radiation on the patulin content of apple juice concentrate was investigated. The results indicated that patulin, at an initial concentration of about 2 mg/kg, disappeared after irradiation of the concentrate with doses as low as 2.5 kGy. For lower doses, the extent of patulin degradation was proportional to the absorbed dose. Irradiation of the concentrate with doses sufficient for patulin disappearance did not change the titratable acidity, the content of reducing sugars and carbonyl compounds or the amino acid composition. The content of ascorbic acid slightly decreased and the colour of the concentrate brightened. The intensity of the patulin absorption spectra after irradiation of mycotoxin in aqueous solutions decreased.

Allelopathic effects of water extracts ofArtemisia princeps var.orientalis on selected plant species.

PubMed

Kil, B S; Yun, K W

1992-01-01

The allelopathic effects of wormwood plants (Artemisia princeps var.orientalis) and their possible phytotoxicity on receptor species were investigated. The aqueous extracts of mature leaf, stem, and root of wormwood plants caused significant inhibition in germination and decreased seedling elongation of receptor plants, whereas germination of some species was not inhibited by extracts of stems and roots. Dry weight growth was slightly increased at lower concentrations of the extract, whereas it was proportionally inhibited at higher concentrations. The calorie value of the organic matter in receptor plants measured by bomb calorimeter was reduced proportionally to the extract concentration. However, results with extracts of juvenile leaf did not correlate with inhibition or promotion of elongation and dry weight.

Degradable polymeric nanoparticles by aggregation of thermoresponsive polymers and ``click'' chemistry

NASA Astrophysics Data System (ADS)

Dworak, Andrzej; Lipowska, Daria; Szweda, Dawid; Suwinski, Jerzy; Trzebicka, Barbara; Szweda, Roza

2015-10-01

This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent stabilization of aggregated chains was performed by a ``click'' reaction between the azide and alkyne groups. Due to the presence of a carbamate bond the nanoparticles undergo pH dependent degradation under mild basic conditions. The proposed procedure opens a route to new carriers for the controlled release of active species.This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent stabilization of aggregated chains was performed by a ``click'' reaction between the azide and alkyne groups. Due to the presence of a carbamate bond the nanoparticles undergo pH dependent degradation under mild basic conditions. The proposed procedure opens a route to new carriers for the controlled release of active species. Electronic supplementary information (ESI) available: GPC-MALLS chromatograms for P(D-co-A)_1 and P(D-co-A)_2 copolymers, absorbance spectra of P(D-co-A)_1, P(D-co-A)_2, P(D-co-A_Pr) and P(D-co-A_Az) after reaction with ninhydrine. See DOI: 10.1039/c5nr04448k

Comparison of Pharmacy Students’ Perceived and Actual Knowledge Using the Pharmacy Curricular Outcomes Assessment

PubMed Central

Friesner, Daniel L.

2012-01-01

Objective. To determine whether a correlation exists between third-year PharmD students’ perceived pharmacy knowledge and actual pharmacy knowledge as assessed by the Pharmacy Curricular Outcomes Assessment (PCOA). Methods. In 2010 and 2011, the PCOA was administered in a low-stakes environment to third-year pharmacy students at North Dakota State University College of Pharmacy, Nursing, and Allied Sciences (COPNAS). A survey instrument was also administered on which students self-assessed their perceived competencies in each of the core areas covered by the PCOA examination. Results. The pharmacy students rated their competencies slightly higher than average. Performance on the PCOA was similar to but slightly higher than national averages. Correlations between each of the 4 content areas (basic biomedical sciences, pharmaceutical sciences, social/administrative sciences, and clinical sciences) mirrored those reported nationally by the National Association of Boards of Pharmacy (NABP). Student performance on the basic biomedical sciences portion of the PCOA was significantly correlated with students’ perceived competencies in the biomedical sciences. No other correlations between actual and perceived competencies were significant. Conclusion. A lack of correlation exists between what students perceive they know and what they actually know in the areas of pharmaceutical science; social, behavioral, and administrative science; and clinical science. Therefore, additional standardized measures are needed to assess curricular effectiveness and provide comparisons among pharmacy programs. PMID:22611272

Cultural similarities and differences in perceiving and recognizing facial expressions of basic emotions.

PubMed

Yan, Xiaoqian; Andrews, Timothy J; Young, Andrew W

2016-03-01

The ability to recognize facial expressions of basic emotions is often considered a universal human ability. However, recent studies have suggested that this commonality has been overestimated and that people from different cultures use different facial signals to represent expressions (Jack, Blais, Scheepers, Schyns, & Caldara, 2009; Jack, Caldara, & Schyns, 2012). We investigated this possibility by examining similarities and differences in the perception and categorization of facial expressions between Chinese and white British participants using whole-face and partial-face images. Our results showed no cultural difference in the patterns of perceptual similarity of expressions from whole-face images. When categorizing the same expressions, however, both British and Chinese participants were slightly more accurate with whole-face images of their own ethnic group. To further investigate potential strategy differences, we repeated the perceptual similarity and categorization tasks with presentation of only the upper or lower half of each face. Again, the perceptual similarity of facial expressions was similar between Chinese and British participants for both the upper and lower face regions. However, participants were slightly better at categorizing facial expressions of their own ethnic group for the lower face regions, indicating that the way in which culture shapes the categorization of facial expressions is largely driven by differences in information decoding from this part of the face. (c) 2016 APA, all rights reserved).

An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters

NASA Astrophysics Data System (ADS)

Babic, Steven; Schreiner, L. John

2006-09-01

In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters.

PubMed

Babic, Steven; Schreiner, L John

2006-09-07

In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

Binding of basic amphipathic peptides to neutral phospholipid membranes: a thermodynamic study applied to dansyl-labeled melittin and substance P analogues.

PubMed

Pérez-Payá, E; Porcar, I; Gómez, C M; Pedrós, J; Campos, A; Abad, C

1997-08-01

A thermodynamic approach is proposed to quantitatively analyze the binding isotherms of peptides to model membranes as a function of one adjustable parameter, the actual peptide charge in solution z(p)+. The main features of this approach are a theoretical expression for the partition coefficient calculated from the molar free energies of the peptide in the aqueous and lipid phases, an equation proposed by S. Stankowski [(1991) Biophysical Journal, Vol. 60, p. 341] to evaluate the activity coefficient of the peptide in the lipid phase, and the Debye-Hückel equation that quantifies the activity coefficient of the peptide in the aqueous phase. To assess the validity of this approach we have studied, by means of steady-state fluorescence spectroscopy, the interaction of basic amphipathic peptides such as melittin and its dansylcadaverine analogue (DNC-melittin), as well as a new fluorescent analogue of substance P, SP (DNC-SP) with neutral phospholipid membranes. A consistent quantitative analysis of each binding curve was achieved. The z(p)+ values obtained were always found to be lower than the physical charge of the peptide. These z(p)+ values can be rationalized by considering that the peptide charged groups are strongly associated with counterions in buffer solution at a given ionic strength. The partition coefficients theoretically derived using the z(p)+ values were in agreement with those deduced from the Gouy-Chapman formalism. Ultimately, from the z(p)+ values the molar free energies for the free and lipid-bound states of the peptides have been calculated.

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

NASA Astrophysics Data System (ADS)

Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.; Berkemeier, Thomas; Shiraiwa, Manabu; Zuend, Andreas; Nin Chan, Man

2017-12-01

Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5) hydroxyl functionalization product (C5H8O5) and a C4 fragmentation product (C4H6O3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon-carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.

Human Cytochrome P450 Enzyme Modulation by Gymnema sylvestre: A Predictive Safety Evaluation by LC-MS/MS

PubMed Central

Rammohan, Bera; Samit, Karmakar; Chinmoy, Das; Arup, Saha; Amit, Kundu; Ratul, Sarkar; Sanmoy, Karmakar; Dipan, Adhikari; Tuhinadri, Sen

2016-01-01

Background: Traditionally GS is used to treat diabetes mellitus. Drug-herb interaction of GS via cytochrome P450 enzyme system by substrate cocktail method using HLM has not been reported. Objective: To evaluate the in-vitro modulatory effects of GS extracts (aqueous, methanol, ethyl acetate, chloroform and n-hexane) and deacylgymnemic acid (DGA) on human CYP1A2, 2C8, 2C9, 2D6 and 3A4 activities in HLM. Material and Methods: Probe substrate-based LCMS/MS method was established for all CYPs. The metabolite formations were examined after incubation of probe substrates with HLM in the presence or absence of extracts and DGA. The inhibitory effects of GS extracts and DGA were characterized with kinetic parameters IC50 and Ki values. Results: GS extracts showed differential effect on CYP activities in the following order of inhibitory potency: ethyl acetate > Chloroform > methanol > n-hexane > aqueous > DGA. This differential effect was observed against CYP1A2, 2C9 and less on CYP3A4 and 2C8 but all CYPs were unaffected by aqueous extract and DGA. The ethyl acetate and chloroform extract exhibited moderate inhibition towards CYP1A2 and 3A4. The aqueous extract and DGA however showed negligible inhibition towards all five major human CYPs with very high IC50 values (>90μg/ml). Conclusion: The results of our study revealed that phytoconstituents contained in GS, particularly in ethyl acetate and chloroform extracts, were able to inhibit CYP1A2, 3A4 and 2C9. The presence of relatively small, lipophillic yet slightly polar compounds within the GS extracts may be attributed for inhibition activities. These suggest that the herb or its extracts should be examined for potential pharmacokinetic drug interactions in vivo. Abbreviations used: GS: Gymnema sylvestre, GSE: Gymnema sylvestre extract, DGA: deacyl gymnemic acid, CYP: cytochrome P450, DMSO: dimethylsulphoxide, HLM: human liver microsomes, LC-MS/MS: liquid chromatography tandem mass spectroscopy, NADPH: reduced nicotinamide adeninedinucleotide phosphate, NRS: nicotinamide adeninedinucleotide phosphate regenerating system, CHE: chloroform extract, EAE: ethyl acetate extract, NHE- n-hexane extract, AE: aqueous extract, ME: methanol extract PMID:27761064

Reactivity and operational stability of N-tailed TAMLs through kinetic studies of the catalyzed oxidation of orange II by H2 O2 : synthesis and X-ray structure of an N-phenyl TAML.

PubMed

Warner, Genoa R; Mills, Matthew R; Enslin, Clarissa; Pattanayak, Shantanu; Panda, Chakadola; Panda, Tamas Kumar; Gupta, Sayam Sen; Ryabov, Alexander D; Collins, Terrence J

2015-04-13

The catalytic activity of the N-tailed ("biuret") TAML (tetraamido macrocyclic ligand) activators [Fe{4-XC6 H3 -1,2-(NCOCMe2 NCO)2 NR}Cl](2-) (3; N atoms in boldface are coordinated to the central iron atom; the same nomenclature is used in for compounds 1 and 2 below), [X, R=H, Me (a); NO2 , Me (b); H, Ph (c)] in the oxidative bleaching of Orange II dye by H2 O2 in aqueous solution is mechanistically compared with the previously investigated activator [Fe{4-XC6 H3 -1,2-(NCOCMe2 NCO)2 CMe2 }OH2 ](-) (1) and the more aggressive analogue [Fe(Me2 C{CON(1,2-C6 H3 -4-X)NCO}2 )OH2 ](-) (2). Catalysis by 3 of the reaction between H2 O2 and Orange II (S) occurs according to the rate law found generally for TAML activators (v=kI kII [Fe(III) ][S][H2 O2 ]/(kI [H2 O2 ]+kII [S]) and the rate constants kI and kII at pH 7 both decrease within the series 3 b>3 a>3 c. The pH dependency of kI and kII was investigated for 3 a. As with all TAML activators studied to-date, bell-shaped profiles were found for both rate constants. For kI , the maximal activity was found at pH 10.7 marking it as having similar reactivity to 1 a. For kII , the broad bell pH profile exhibits a maximum at pH about 10.5. The condition kI ≪kII holds across the entire pH range studied. Activator 3 b exhibits pronounced activity in neutral to slightly basic aqueous solutions making it worthy of consideration on a technical performance basis for water treatment. The rate constants ki for suicidal inactivation of the active forms of complexes 3 a-c were calculated using the general formula ln([S0 ]/[S∞ ])=(kII /ki )[Fe(III) ]; here [Fe(III) ], [S0 ], and [S∞ ] are the total catalyst concentration and substrate concentration at time zero and infinity, respectively. The synthesis and X-ray characterization of 3 c are also described. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic Analysis of Soil Erosion in Songhua River Watershed

NASA Astrophysics Data System (ADS)

Zhang, Yujuan; Li, Xiuhai; Wang, Qiang; Liu, Jiang; Liang, Xin; Li, Dan; Ni, Chundi; Liu, Yan

2018-01-01

In this paper, based on RS and GIS technology and Revised Universal Soil Loss Equation (RUSLE), the soil erosion dynamic changes during the two periods of 1990 and 2010 in Bin County was analyzed by using the Landsat TM data of the two periods, so as to reveal the soil erosion spatial distribution pattern and spatial and temporal dynamic evolution rule in the region. The results showed that: the overall patterns of soil erosion were basically the same in both periods, mainly featuring slight erosion and mild erosion, with the area proportions of 80.68% and 74.71% respectively. The slight and extremely intensive erosion changing rates showed a narrowing trend; mild, moderate and intensive erosion was increasing, with a trend of increased soil erosion; mild and intensive erosion were developing towards moderate erosion and moderate and extremely intensive erosion were progressing towards intensive erosion.

Hypericum grandifolium Choisy: a species native to Macaronesian Region with antidepressant effect.

PubMed

Sánchez-Mateo, C C; Bonkanka, C X; Rabanal, R M

2009-01-21

Various species of Hypericum genus have been used in the Canary Islands as sedative, diuretic, vermifuge, wound healing, antihysteric and antidepressant agent. Studies have shown that methanol extract of Hypericum grandifolium Choisy is active in tetrabenazine-induced ptosis and forced swimming tests. In the current study, the aqueous, butanol and chloroform fractions obtained from the methanol extract as well as three sub-fractions derived from the chloroform fraction were evaluated for their central nervous effects in mice, particularly their antidepressant activity. The central nervous effect of different fractions and sub-fractions of Hypericum grandifolium was evaluated in mice using various behavioural models including locomotor and muscle relaxant activity, forced swimming test, effect on normal body temperature, barbiturate-induced sleep, tetrabenazine-induced syndrome and 5-hydroxytryptohan-induced head twitches and syndrome. We found that the butanol and chloroform fractions and all sub-fractions showed an antidepressant effect in the forced swimming test, the chloroform fraction being the most active. They produced no effects or only a slight depression of locomotor activity. Chloroform fraction significantly increased the pentobarbital-induced sleeping time, produced a slight but significant hypothermia and antagonized tetrabenazine-induced ptosis, whereas the butanol fraction produced a slight potentiation of 5-HTP-induced head twitches and syndrome. The present results, together with previous pharmacological and phytochemical data, indicated that Hypericum grandifolium possess antidepressant-like effects in mice and that different constituents, such as the flavonoids and the benzophenone derivatives, could be responsible at least in part for the antidepressant effects observed for this species.

Metabolic profiling studies on the toxicological effects of realgar in rats by {sup 1}H NMR spectroscopy

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

Wei Lai; Liao Peiqiu; Wu Huifeng

2009-02-01

The toxicological effects of realgar after intragastrical administration (1 g/kg body weight) were investigated over a 21 day period in male Wistar rats using metabonomic analysis of {sup 1}H NMR spectra of urine, serum and liver tissue aqueous extracts. Liver and kidney histopathology examination and serum clinical chemistry analyses were also performed. {sup 1}H NMR spectra and pattern recognition analyses from realgar treated animals showed increased excretion of urinary Kreb's cycle intermediates, increased levels of ketone bodies in urine and serum, and decreased levels of hepatic glucose and glycogen, as well as hypoglycemia and hyperlipoidemia, suggesting the perturbation of energymore » metabolism. Elevated levels of choline containing metabolites and betaine in serum and liver tissue aqueous extracts and increased serum creatine indicated altered transmethylation. Decreased urinary levels of trimethylamine-N-oxide, phenylacetylglycine and hippurate suggested the effects on the gut microflora environment by realgar. Signs of impairment of amino acid metabolism were supported by increased hepatic glutamate levels, increased methionine and decreased alanine levels in serum, and hypertaurinuria. The observed increase in glutathione in liver tissue aqueous extracts could be a biomarker of realgar induced oxidative injury. Serum clinical chemistry analyses showed increased levels of lactate dehydrogenase, aspartate aminotransferase, and alkaline phosphatase as well as increased levels of blood urea nitrogen and creatinine, indicating slight liver and kidney injury. The time-dependent biochemical variations induced by realgar were achieved using pattern recognition methods. This work illustrated the high reliability of NMR-based metabonomic approach on the study of the biochemical effects induced by traditional Chinese medicine.« less

Changes in total phenol, flavonoid contents and anti-Lactobacillus activity of Callisia fragrans due to extraction solvent

NASA Astrophysics Data System (ADS)

Le, Thom; Cao, Diem Kieu; Pham, Thanh Vy; Huynh, Tan Dat; Ta, Nhat Thuy Anh; Nguyen, Ngoc Thao Linh; Nguyen, Huu Thanh; Le, Hue Huong; Bui, Anh Vo; Truong, Dieu-Hien

2018-04-01

Callisia fragrans is a wonder herb with many medicinal properties such as burn, dental diseases, cancer diseases and arthritis in folk medicine. It is noted that the phytochemical constituents and antimicrobial activity of traditional plants depend on not only the extracting method but also the solvent used for extraction. In this study, the effect of five extraction solvents (i.e., distilled water, 80% methanol, 80% ethanol, 80% ethyl acetate, and 80% chloroform) on yield, total phenolic content (TPC) and total flavonoid content (TFC) of Callisia leaves was determined. Besides, changes in anti-Lactobacillus fermentum activity of C. fragrans freeze-dried extract was also evaluated using disk-diffusion method. The recovery percentage of extractable yield of fresh leaves are ranged from 11.93% w/w for distilled water extract to 16.60% w/w for aqueous ethanol extracts. The yield of 80% aqueous methanol extract (16.27% w/w) is only slightly less than that of the ethanol extract. Significant differences were observed among TPC and TFC obtaining by 80% methanol (0.0522% and 0.0335% w/w, respectively) compared to other solvents (p < 0.05). TPC and TFC of C. fragrans extracts increase in the following order: distilled water < 80% chloroform < 80% ethyl acetate < 80% ethanol < 80% methanol. The results revealed that 80% aqueous methanol Calissia extracts has moderate inhibition (9.0 mm of inhibition zone for 1.5 mg/mL of extracts) of L. fermentum compared to standard antibacterial agent. Based on the study results, it can be concluded that the yield, TPC and TFC of C. frgrans extract varied with the extracting solvent. It also showed that Callisia extracts can prevent dental caries by inhibiting the growth of L. fermentum, towards new insights for treatment of dental caries.

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study.

PubMed

Eklund, Lars; Hofer, Thomas S; Pribil, Andreas B; Rode, Bernd M; Persson, Ingmar

2012-05-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) Å by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.

Experimental uveitis can be maintained in rabbits for a period of six weeks after a safe sensitization method.

PubMed

Eperon, S; Balaskas, K; Vaudaux, J; Guex-Crosier, Y

2013-03-01

New treatments against long-lasting uveitis need to be tested. Our aim was to develop a six-week model of uveitis in rabbits. Rabbits were presensitized with an s.c. injection of Mycobacterium tuberculosis H37RA emulsified with TiterMax Gold adjuvant. Uveitis was induced at day 28 and 50, by intravitreal challenges of antigen suspension. Ocular inflammation was assessed till euthanasia at day 71 after s.c. injection of M. tuberculosis H37RA by: (a) the number of inflammatory cells in aqueous humor (AH); (b) the protein concentration in AH; (c) the clinical score (mean of conjunctival hyperaemia, conjunctival chemosis, oedema and secretion); (d) the microscopical score (mean presence of fibrin and synechiae, aqueous cell density and aqueous flare grade, as scored by slit lamp). At the sites of presensitization injection, rabbits presented flat nodules which progressively vanished. The first challenge induced a significant increase in the four parameters (p < 0.05 the Wilcoxon/Kruskal-Wallis test). The AH contained 764 ± 82 cells/µl and 32 ± 0.77 mg protein/ml. During the following days, inflammatory parameters decreased slightly. The second intravitreal challenge increased inflammation (3564 ± 228 cells/µl AH and 31 ± 1 mg protein/ml), which remained at a high level for a longer period of time. We developed a model of long-term uveitis, which could be maintained in rabbits for at least six weeks. Such a model could be used to test the efficacy of either new drugs or various drug delivery systems intended to deliver active agents during a few months.

[Pollution prevention and control of aqueous extract of astragali radix processed with ZrO2 inorganic ceramic membrane micro-filtration].

PubMed

Pan, Lin-Men; Huang, Min-Yan; Guo, Li-Wei

2012-11-01

To study the measures for preventing and controlling the pollution of aqueous extract of Astragali Radix proceeded with inorganic ceramic membrane micro-filtration, in order to find effective measures for preventing and controlling the membrane pollution. The resistance distribution, polymer removal and changes in physical and chemical parameters of the zirconium oxide film of different pore diameters were determined to analyze the state or location of pollutants as well as the regularity of formation. Meanwhile, recoil and ultrasonic physical measures were adopted to strengthen the membrane process, in order to explore the methods for preventing and controlling the membrane pollution. When 0.2 microm of ZrO2 micro-filtrated aqueous extract of Astragali Radix, the rate of pollution was as high as 44.9%. The hole blocking resistance and the concentration polarization resistance were the main filtration resistances, while the surface deposit resistance decreased with the increase in the membrane's hold diameter; after micro-filtration, the liquid turbidity significantly reduced, with slight changes in both pH and viscosity. The 0.2 microm ZrO2 micro-filtration membrane performed better than the 0.05 microm pore size membrane in terms of conductivity. The 0. 2 microm and 0.05 microm pore diameter membranes showed better performance in the removal of pectin. The ultrasonic measure to strengthen membranes is more suitable to this system, with a flux rate up by 41.7%. The membrane optimization process adopts appropriate measures for preventing and controlling the membrane pollution, in order to reduce the membrane pollution, recover membrane performance and increase filtration efficiency.

Corrosion behavior of binary titanium aluminide intermetallics

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

Saffarian, H.M.; Gan, Q.; Hadkar, R.

1996-08-01

The corrosion behavior of arc-melted binary titanium aluminide intermetallics TiAl, Ti{sub 2}Al, and TiAl{sub 3} in aqueous sodium sulfate and sodium chloride solutions was measured and compared to that of pure Ti and Al. Effects of electrolyte composition (e.g., sulfate [0.25 M SO{sub 4}{sup 2}{sup {minus}}], chloride [0.1 to 1.0 M Cl{sup {minus}}], and pH [3 to 10]) were examined. Anodic polarization of titanium aluminides in aqueous SO{sub 4}{sup 2}{sup {minus}} solutions was similar (showing passive behavior), but no pitting or pitting potential (E{sub pit}) was observed. In aqueous NaCl, however, titanium aluminides were susceptible to pitting, and E{sub pit}more » decreased with increasing Al content (i.e., Ti{sub 3}Al had the highest E{sub pit} and, therefore, a greater resistance to pitting, followed by TiAl and TiAl{sub 3}). For TiAl, E{sub pit} was slightly dependent upon pH or Cl{sup {minus}} concentration. Pit morphology and E{sub pit} values were quite different for TiAl compared to Ti{sub 3}Al. TiAl showed numerous small pits, whereas Ti{sub 3}Al exhibited fewer but larger and deeper pits. The larger pit density for TiAl was associated with Al-rich interdendrite regions. One interesting feature of the anodic polarization curves for Ti{sub 3}Al was a small anodic peak frequently observed at {approximately}1.4 V{sub SCE} to 1.8 V{sub SCE}. Results suggested this peak was associated with pit initiation, since pitting initiated concurrently with the peak or immediately afterward.« less

Cryopreservation of Proteins Using Ionic Liquids: A Case Study of Cytochrome c.

PubMed

Takekiyo, Takahiro; Ishikawa, Yuka; Yoshimura, Yukihiro

2017-08-17

Aqueous ionic liquid (IL) solutions form a glassy state at 77 K over a wide concentration of ILs. They have potential as novel cryopreservation/refolding solvents for proteins. However, even if proteins in glass-forming concentrations of ILs are preserved at 77 K, the recovery of activity and the structure of the proteins after cryopreservation are still unclear. To achieve high recovery of protein activity and structure by removal of ILs after cryopreservation at 77 K, we studied the recovery of activity and structural stability after cryopreservation of bovine heart cytochrome c in aqueous solutions with ILs, including ethylammonium nitrate (EAN) and 1-butyl-3-methylimidazolium thiocyanate ([bmim][SCN]) over wide IL concentrations using UV-vis, Fourier transform infrared (FTIR), and circular dichroism (CD) spectroscopy. On the whole, although the addition of both ILs induced a decrease of activity and unfolding of the secondary structure of cytochrome c before and after cooling to 77 K, EAN, a weak denaturant, showed a reduction in protein damage (decrease of activity and unfolding of secondary structure) during the reheating process from 77 K (protection ability). In contrast, [bmim][SCN], a strong denaturant, did not have this protective ability. A remarkable result is that although the addition of both ILs caused cytochrome c denaturation, > 90% of activity and structure after cryopreservation (X > 10 mol %IL) was recovered after the removal of both ILs by dialysis. These recoveries after the removal of ILs are slightly higher than the results for dimethyl disulfide (DMSO), another cryoprotectant. The present results indicate that concentrated aqueous IL solutions have potential as one-pot (i.e., solubilization/preservation/refolding) solvents for proteins, which easily aggregate after purification, with comparable results to DMSO.

Structure of aqueous proline via parallel tempering molecular dynamics and neutron diffraction.

PubMed

Troitzsch, R Z; Martyna, G J; McLain, S E; Soper, A K; Crain, J

2007-07-19

The structure of aqueous L-proline amino acid has been the subject of much debate centering on the validity of various proposed models, differing widely in the extent to which local and long-range correlations are present. Here, aqueous proline is investigated by atomistic, replica exchange molecular dynamics simulations, and the results are compared to neutron diffraction and small angle neutron scattering (SANS) data, which have been reported recently (McLain, S.; Soper, A.; Terry, A.; Watts, A. J. Phys. Chem. B 2007, 111, 4568). Comparisons between neutron experiments and simulation are made via the static structure factor S(Q) which is measured and computed from several systems with different H/D isotopic compositions at a concentration of 1:20 molar ratio. Several different empirical water models (TIP3P, TIP4P, and SPC/E) in conjunction with the CHARMM22 force field are investigated. Agreement between experiment and simulation is reasonably good across the entire Q range although there are significant model-dependent variations in some cases. In general, agreement is improved slightly upon application of approximate quantum corrections obtained from gas-phase path integral simulations. Dimers and short oligomeric chains formed by hydrogen bonds (frequently bifurcated) coexist with apolar (hydrophobic) contacts. These emerge as the dominant local motifs in the mixture. Evidence for long-range association is more equivocal: No long-range structures form spontaneously in the MD simulations, and no obvious low-Q signature is seen in the SANS data. Moreover, associations introduced artificially to replicate a long-standing proposed mesoscale structure for proline correlations as an initial condition are annealed out by parallel tempering MD simulations. However, some small residual aggregates do remain, implying a greater degree of long-range order than is apparent in the SANS data.

A comparative study of the nanoscale and macroscale tribological attributes of alumina and stainless steel surfaces immersed in aqueous suspensions of positively or negatively charged nanodiamonds

PubMed Central

Curtis, Colin K; Marek, Antonin; Smirnov, Alex I

2017-01-01

This article reports a comparative study of the nanoscale and macroscale tribological attributes of alumina and stainless steel surfaces immersed in aqueous suspensions of positively (hydroxylated) or negatively (carboxylated) charged nanodiamonds (ND). Immersion in −ND suspensions resulted in a decrease in the macroscopic friction coefficients to values in the range 0.05–0.1 for both stainless steel and alumina, while +ND suspensions yielded an increase in friction for stainless steel contacts but little to no increase for alumina contacts. Quartz crystal microbalance (QCM), atomic force microscopy (AFM) and scanning electron microscopy (SEM) measurements were employed to assess nanoparticle uptake, surface polishing, and resistance to solid–liquid interfacial shear motion. The QCM studies revealed abrupt changes to the surfaces of both alumina and stainless steel upon injection of –ND into the surrounding water environment that are consistent with strong attachment of NDs and/or chemical changes to the surfaces. AFM images of the surfaces indicated slight increases in the surface roughness upon an exposure to both +ND and −ND suspensions. A suggested mechanism for these observations is that carboxylated −NDs from aqueous suspensions are forming robust lubricious deposits on stainless and alumina surfaces that enable gliding of the surfaces through the −ND suspensions with relatively low resistance to shear. In contrast, +ND suspensions are failing to improve tribological performance for either of the surfaces and may have abraded existing protective boundary layers in the case of stainless steel contacts. This study therefore reveals atomic scale details associated with systems that exhibit starkly different macroscale tribological properties, enabling future efforts to predict and design complex lubricant interfaces. PMID:29046852

A bio-inspired molecular water oxidation catalyst for renewable hydrogen generation: an examination of salt effects

NASA Astrophysics Data System (ADS)

Brimblecombe, Robin; Rotstein, Miriam; Koo, Annette; Dismukes, G. Charles; Swiegers, Gerhard F.; Spiccia, Leone

2009-08-01

Most transport fuels are derived from fossil fuels, generate greenhouse gases, and consume significant amounts of water in the extraction, purification, and/or burning processes. The generation of hydrogen using solar energy to split water, ideally from abundant water sources such as sea water or other non-potable sources, could potentially provide an unlimited, clean fuel for the future. Solar, electrochemical water splitting typically combines a photoanode at which water oxidation occurs, with a cathode for proton reduction to hydrogen. In recent work, we have found that a bioinspired tetra-manganese cluster catalyzes water oxidation at relatively low overpotentials (0.38 V) when doped into a Nafion proton conduction membrane deposited on a suitable electrode surface, and illuminated with visible light. We report here that this assembly is active in aqueous and organic electrolyte solutions containing a range of different salts in varying concentrations. Similar photocurrents were obtained using electrolytes containing 0.0 - 0.5 M sodium sulfate, sodium perchlorate or sodium chloride. A slight decline in photocurrent was observed for sodium perchlorate but only at and above 5.0 M concentration. In acetonitrile and acetone solutions containing 10% water, increasing the electrolyte concentration was found to result in leaching of the catalytic species from the membrane and a decrease in photocurrent. Leaching was not observed when the system was tested in an ionic liquid containing water, however, a lower photocurrent was generated than observed in aqueous electrolyte. We conclude that immersion of the membrane in an aqueous solution containing an electrolyte concentration of 0.05 - 0.5M represent good conditions for operation for the cubium/Nafion catalytic system.

A framework for expanding aqueous chemistry in the Community Multiscale Air Quality (CMAQ) model version 5.1

NASA Astrophysics Data System (ADS)

Fahey, Kathleen M.; Carlton, Annmarie G.; Pye, Havala O. T.; Baek, Jaemeen; Hutzell, William T.; Stanier, Charles O.; Baker, Kirk R.; Wyat Appel, K.; Jaoui, Mohammed; Offenberg, John H.

2017-04-01

This paper describes the development and implementation of an extendable aqueous-phase chemistry option (AQCHEM - KMT(I)) for the Community Multiscale Air Quality (CMAQ) modeling system, version 5.1. Here, the Kinetic PreProcessor (KPP), version 2.2.3, is used to generate a Rosenbrock solver (Rodas3) to integrate the stiff system of ordinary differential equations (ODEs) that describe the mass transfer, chemical kinetics, and scavenging processes of CMAQ clouds. CMAQ's standard cloud chemistry module (AQCHEM) is structurally limited to the treatment of a simple chemical mechanism. This work advances our ability to test and implement more sophisticated aqueous chemical mechanisms in CMAQ and further investigate the impacts of microphysical parameters on cloud chemistry. Box model cloud chemistry simulations were performed to choose efficient solver and tolerance settings, evaluate the implementation of the KPP solver, and assess the direct impacts of alternative solver and kinetic mass transfer on predicted concentrations for a range of scenarios. Month-long CMAQ simulations for winter and summer periods over the US reveal the changes in model predictions due to these cloud module updates within the full chemical transport model. While monthly average CMAQ predictions are not drastically altered between AQCHEM and AQCHEM - KMT, hourly concentration differences can be significant. With added in-cloud secondary organic aerosol (SOA) formation from biogenic epoxides (AQCHEM - KMTI), normalized mean error and bias statistics are slightly improved for 2-methyltetrols and 2-methylglyceric acid at the Research Triangle Park measurement site in North Carolina during the Southern Oxidant and Aerosol Study (SOAS) period. The added in-cloud chemistry leads to a monthly average increase of 11-18 % in cloud SOA at the surface in the eastern United States for June 2013.

Occurrence of select perfluoroalkyl substances at U.S. Air Force aqueous film-forming foam release sites other than fire-training areas: Field-validation of critical fate and transport properties.

PubMed

Anderson, R Hunter; Long, G Cornell; Porter, Ronald C; Anderson, Janet K

2016-05-01

The use of aqueous film-forming foam (AFFF) to extinguish hydrocarbon-based fires is recognized as a significant source of environmental poly- and perfluoroalkyl substances (PFASs). Although the occurrence of select PFASs in soil and groundwater at former fire-training areas (FTAs) at military installations operable since 1970 has been consistently confirmed, studies reporting the occurrence of PFASs at other AFFF-impacted sites (e.g. emergency response locations, AFFF lagoons, hangar-related AFFF storage tanks and pipelines, and fire station testing and maintenance areas) are largely missing from the literature. Further, studies have mostly focused on a single site (i.e., FTAs at military installations) and, thus, lack a comparison of sites with diverse AFFF release history. Therefore, the purpose of this investigation was to evaluate select PFAS occurrence at non-FTA sites on active U.S. Air Force installations with historic AFFF use of varying magnitude. Concentrations of fifteen perfluoroalkyl acids (PFAAs) and perfluorooctane sulfonamide (PFOSA), an important PFOS precursor, were measured from several hundred samples among multiple media (i.e., surface soil, subsurface soil, sediment, surface water, and groundwater) collected from forty AFFF-impacted sites across ten installations between March and September 2014, representing one of the most comprehensive datasets on environmental PFAS occurrence to date. Differences in detection frequencies and observed concentrations due to AFFF release volume are presented along with rigorous data analyses that quantitatively demonstrate phase-dependent (i.e., solid-phase vs aqueous-phase) differences in the chemical signature as a function of carbon chain-length and in situ PFOS (and to a slightly lesser extent PFHxS) formation, presumably due to precursor biotransformation. Published by Elsevier Ltd.

Examining the impacts of ethanol (E85) versus gasoline photochemical production of smog in a fog using near-explicit gas- and aqueous-chemistry mechanisms

NASA Astrophysics Data System (ADS)

Ginnebaugh, Diana L.; Jacobson, Mark Z.

2012-12-01

This study investigates the air quality impacts of using a high-blend ethanol fuel (E85) instead of gasoline in vehicles in an urban setting when a morning fog is present under summer and winter conditions. The model couples the near-explicit gas-phase Master Chemical Mechanism (MCM v. 3.1) with the extensive aqueous-phase Chemical Aqueous Phase Radical Mechanism (CAPRAM 3.0i) in SMVGEAR II, a fast and accurate ordinary differential equation solver. Summer and winter scenarios are investigated during a two day period in the South Coast Air Basin (SCAB) with all gasoline vehicles replaced by flex-fuel vehicles running on E85 in 2020. We find that E85 slightly increases ozone compared with gasoline in the presence or absence of a fog under summer conditions but increases ozone significantly relative to gasoline during winter conditions, although winter ozone is always lower than summer ozone. A new finding here is that a fog during summer may increase ozone after the fog disappears, due to chemistry alone. Temperatures were high enough in the summer to increase peroxy radical (RO2) production with the morning fog, which led to the higher ozone after fog dissipation. A fog on a winter day decreases ozone after the fog. Within a fog, ozone is always lower than if no fog occurs. The sensitivity of the results to fog parameters like droplet size, liquid water content, fog duration and photolysis are investigated and discussed. The results support previous work suggesting that E85 and gasoline both enhance pollution with E85 enhancing pollution significantly more at low temperatures. Thus, neither E85 nor gasoline is a ‘clean-burning’ fuel.

Influence of Basicity on High-Chromium Vanadium-Titanium Magnetite Sinter Properties, Productivity, and Mineralogy

NASA Astrophysics Data System (ADS)

Zhou, Mi; Yang, Songtao; Jiang, Tao; Xue, Xiangxin

2015-05-01

The effect of basicity on high-chromium vanadium-titanium magnetite (V-Ti-Cr) sintering was studied via sintering pot tests. The sinter rate, yield, and productivity were calculated before determining sinter strength (TI) and reduction degradation index (RDI). Furthermore, the effect of basicity on V-Ti-Cr sinter mineralogy was clarified using metallographic microscopy, x-ray diffraction, and scanning electron microscopy-energy-dispersive x-ray spectroscopy. The results indicate that increasing basicity quickly increases the sintering rate from 25.4 mm min-1 to 28.9 mm min-1, yield from 75.3% to 87.2%, TI from 55.4% to 64.8%, and productivity from 1.83 t (m2 h)-1 to 1.94 t (m2 h)-1 before experiencing a slight drop. The V-Ti-Cr sinter shows complex mineral composition, with main mineral phases such as magnetite, hematite, silicate (dicalcium silicate, Ca-Fe olivine, glass), calcium and aluminum silico-ferrite (SFCA/SFCAI) and perovskite. Perovskite is notable because it lowers the V-Ti sinter strength and RDI. The well intergrowths between magnetite and SFCA/SFCAI, and the decrease in perovskite and secondary skeletal hematite are the key for improving TI and RDI. Finally, a comprehensive index was calculated, and the optimal V-Ti-Cr sinter basicity also for industrial application was 2.55.

RP-HPLC ANALYSIS OF ACIDIC AND BASIC DRUGS IN SYSTEMS WITH DIETHYLAMINE AS ELUENTS ADDITIVE.

PubMed

Petruczynik, Anna; Wroblewski, Karol; Strozek, Szymon; Waksmundzka-Hajnos, Monika

2016-11-01

The chromatographic behavior of some basic and acidic drugs was studied on Cl 8, Phenyl-Hexyl and Polar RP columns with methanol or acetonitrile as organic modifiers of aqueous mobile phases containing addition of diethylamine. Diethylamine plays a double function of silanol blocker reagent in analysis of basic drugs and ion-pair reagent in analysis of acidic drugs. Most symmetrical peaks and highest system efficiency were obtained on Phenyl-Hexyl and Polar RP columns in tested mobile phase systems compared to results obtained on C18 column. A new rapid, simple, specific and accurate reverse phase liquid chromatographic method was developed for the simultaneous determination of atorvastatin - antihyperlipidemic drug and amlodipine - calcium channel blocker in one pharmaceutical formulation. Atorvastatin is an acidic compounds while amlodipine is a basic substance. The chromatographic separation was carried out on Phenyl-Hexyl column by gradient elution mode with acetonitrile as organic modifier, acetate buffer at pH 3.5 and Q.025 M/L diethylamine. The proposed method was validated for specificity, precision, accuracy, linearity, and robustness. The linearity range of atorvastatin and amlodipine for 5 - 100 μg/mL was obtained with limits of-detection (LOD) 3.2750 gg/mL and 3.2102 μg/mL, respectively. The proposed method made use of DAD as a tool for peak identity and purity confirmation.

Inorganic–organic hybrids presenting high basic center content: SBA-15 incorporation, toxic metals sorption and energetic behavior

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

Oliveira, Fernando J.V.E.; Melo, Maurício A.; Airoldi, Claudio, E-mail: airoldi@iqm.unicamp.br

2013-03-15

Highlights: ► Mesoporous SBA-15 silicas were organofunctionalized with new silylant agents. ► Thiocarbamate was used to enhance the silylating agent chains and basic centers. ► The synthesized pendant chains contain nitrogen and sulfur basic centers. ► The new hybrids sorb toxic cations from aqueous solutions with high efficiency. ► The thermodynamic data demonstrated favorable cation/basic center interactions. - Abstract: Mesoporous SBA-15 samples were organofunctionalized with mono, di- and tri-aminosilanes that previously reacted with thiocarbamide to enhance the organic chains and attach nitrogen and sulfur basic centers to the surface of the solids. These new organosilanes were synthesized through a non-solventmore » approach to reduce both cost and hazardous wastes. The high affinities for both hard and soft Lewis acids due to the combination of nitrogen and sulfur atoms attached to the same pendant chain enabled favorable sorption capacities for Cu{sup 2+}, Cd{sup 2+} and Pb{sup 2+} cations, with maximum capacities of 1.90, 3.48 and 5.30 mmol g{sup −1}, respectively, for the most efficient mesoporous silica. Microcalorimetric investigations allowed the calculation of the thermodynamic data at the solid/liquid interface. All Gibbs energy are negative as expected for spontaneous cation/basic center interactions and the positive entropic values from 49 ± 3 to 108 ± 5 J K{sup −1} mol{sup −1}, also reinforced this favorable interactive process in heterogeneous system. The designed organosilanes covalently bonded to the inorganic siliceous skeleton can be suggested as new materials for toxic metal removal from a wastewater with high efficiency.« less

Electromembrane extraction using two separate cells: A new design for simultaneous extraction of acidic and basic compounds.

PubMed

Nojavan, Saeed; Asadi, Sakine

2016-02-01

Simultaneous extraction of acidic and basic analytes from a sample is seen to be a challenging task. In this work, a novel and efficient electromembrane extraction (EME) method based on two separate cells was applied to simultaneously extract and preconcentrate two acidic drugs (naproxen and ibuprofen) along with a basic drug (ketamine). Once both cells were filled with the sample solution, basic drug was extracted from one cell with the other cell used to extract acidic drugs. The employed supported liquid membranes for the extraction of acidic and basic drugs were 2-ethyl hexanol and 1-octanol, respectively. Under an applied potential of 250 V in the course of the extraction process, acidic, and basic drugs were extracted from a 3.0 mL aqueous sample solution into 25 μL acceptor solutions. The pH values of the donor and acceptor solutions in the cathodic cell were 5.0 and 1.5, respectively, the corresponding values in the anodic cell were, however, 8.0 and 12.5, respectively. The rates of recovery obtained within 20 min of extraction time at a stirring rate of 750 rpm ranged from 45 to 54%. With correlation coefficients ranging from 0.990 to 0.996, the proposed EME technique provided good linearity over a concentration range of 20-1000 ng/mL. The LOD for all drugs was found to be 6.7 ng/mL, while reproducibility ranged from 7 to 12% (n = 5). Finally, applying the proposed method to determine and quantify the drugs in urine and wastewater samples, satisfactory results were achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inhibition effect of sugar-based amphiphiles on eutectic formation in the freezing-thawing process of aqueous NaCl solution.

PubMed

Ogawa, Shigesaburo; Osanai, Shuichi

2007-04-01

DSC and simultaneous XRD-DSC measurements were carried out to clarify the interaction among the ingredients in a ternary aqueous solution composed of NaCl, a sugar-based amphiphile or free sugar, and water. Two aspects of the inhibition of eutectic formation were suggested through the addition of the sugar amphiphile. One was the retention of the glass state of the eutectic phase, and the other was the trapping of NaCl hydrate into the sugar moiety of the amphiphilic aggregate. The difference between the free sugar and the amphiphilic one in terms of the trapping of NaCl hydrate was attributable to their dissimilarity in the dissolution state. The results indicated that the free sugars in water could interact with NaCl hydrate on the basis of their various hydroxyl groups. On the other hand, the sugar-based amphiphiles generated a self-assembly aggregate in the system, and interacted with NaCl hydrate by a salting-in effect with their sugar moiety in the freezing-thawing process. It was confirmed that the number of sugar units played an important role in trapping NaCl hydrate in the system. The effects of the structural isomerism in the sugars were slight with regard to the inhibition of eutectic formation.

Characterization of the composition of the aqueous humor and the vitreous body of the eye of the frog Rana temporaria L.

PubMed

Panova, Ina G; Sharova, Natalia P; Dmitrieva, Svetlana B; Levin, Peter P; Tatikolov, Alexander S

2008-12-01

This study aimed to analyze the aqueous humor (AH) and the vitreous body (VB) of the eye of the adult frog Rana temporaria L. as a representative species of amphibians, which lead a semi-terrestrial life. The presence of collagen, albumin, uric acid and electron donors was shown in both media; however, there are slight differences in their concentrations. To determine collagen, a spectral-fluorescent probe, cyanine dye, was used. The presence of collagen in AH of the frog was found at the first time. The total content of electron donors (ascorbic and uric acids, tryptophan, and tyrosine) in VB and HA was roughly estimated at approximately 1.5x10(-4) mol/L. Both VB and AH absorb light in similar UV regions. The total protein and albumin contents in AH were found to be somewhat higher than those in VB. The uric acid content was at an equally low level in both intraocular media. It is supposed that the similarity of VB and AH compositions shown in this work is due to some exchange between VB and AH contents in the course of accommodation. The role of intraocular fluids in physiological functions of the eye and in protecting the retina against UV light is discussed.

The solubility of ethane in aqueous solutions of sodium 1-pentanesulfonate, sodium 1-hexanesulfonate, sodium 1-heptanesulfonate, and sodium 1-octanesulfonate at 25 degrees C.

PubMed

Calhoun, A R; King, A D

2007-05-15

Measurements have been made to determine the solubility of ethane, C2H6, in aqueous solutions of four different surfactants of the linear alkanesulfonate class at 25 degrees C. The surfactants, sodium 1-pentanesulfonate, sodium 1-hexanesulfonate, sodium 1-heptanesulfonate, and sodium 1-octanesulfonate, all share a common head group (-SO-3) and counter ion (Na+), and differ only in the length of the alkyl chain attached to the head group. The solubility of ethane has been determined as a function of surfactant concentration for each surfactant. At surfactant concentrations below the critical micelle concentration (CMC), the solubility of ethane is quite low and differs only slightly from the solubility of ethane in pure water. At concentrations greater than the CMC, the solubility of ethane exhibits a gradual increase with surfactant concentration. At high surfactant concentrations, well in excess of the CMC, the solubility of ethane is found to increase as a linear function of surfactant concentration. From this data it becomes possible to determine the fractional population of the surfactant in the free and micellized states. The solubility data measured for ethane is interpreted in terms of the mass-action model for micelle formation.

Simultaneous adsorption of Cd²⁺ and BPA on amphoteric surfactant activated montmorillonite.

PubMed

Liu, Chongmin; Wu, Pingxiao; Zhu, Yajie; Tran, Lytuong

2016-02-01

The study mainly investigated the simultaneous adsorption of bisphenol A (BPA) and Cd(2+) from aqueous solution on octadecane-betaine modified montmorillonite (BS-Mt). The characteristics of the obtained materials were analyzed by X-ray diffraction (XRD), Fourier-transform infrared (FTIR), Specific surface area (BET) and Scanning electron microscopy/Energy disperse spectroscopy (SEM/EDS), confirming that BS-18 was successfully introduced into Mt. Also, factors including initial solution pH, initial Cd(2+)/BPA concentration, contact time and adsorbent dosage on the adsorption processes were shown to be crucial for Cd(2+) adsorption, whereas had negligible effects on BPA adsorption. In this study, we found that pseudo-second-order model fitted well with the adsorption kinetic studies for both Cd(2+) and BPA with an equilibrium time of 24 h. The Cd(2+) and BPA adsorption isotherm could be well described by Freundlich model and Langmuir model, respectively. On the basis of kinetic models, the maximum adsorption capacity of Cd(2+) in aqueous solution was slightly enhanced after modification, indicating that Cd(2+) adsorption on BS-Mt was mainly attributed to direct electrostatic attraction and the chelate reaction, while the dramatic enhancement of maximum adsorption capacity for BPA was due to the hydrophobic interaction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Characterization, antibacterial, and neurotoxic effect of Green synthesized nanosilver using Ziziphus spina Christi aqueous leaf extract collected from Riyadh, Saudi Arabia

NASA Astrophysics Data System (ADS)

El-Ansary, Afaf; Warsy, Arjumand; Daghestani, Maha; Merghani, Nada M.; Al-Dbass, Abeer; Bukhari, Wadha; Al-Ojayan, Badryah; Ibrahim, Eiman M.; Al-Qahtani, Asma M.; Shafi Bhat, Ramesa

2018-02-01

The current study aims to synthesize silver nanoparticles using Ziziphus spina Christi (ZSC) or (Sidr) aqueous leaf extract collected from Riyadh, Saudi Arabia. The green synthesis of silver nanoparticles using sidr leaves extract was successful. Production of silver nanoparticles was confirmed through UV-vis Spectrophotometer, particles size and zeta potential analysis, Infra-red spectroscopy, Scanning, and Transmission Electron Microscope (SEM and TEM). The UV-visible spectra showed that the absorption peak existed at 400 nm. SEM analysis showed that the synthesized AgNPs were spherical but in slightly aggregated form. TEM demonstrated different size range of 4-33 nm with an average size of 13. The element analysis profile showed silver signal together with oxygen, calcium, and potassium peaks which might be related to the plant structure. Biological effects of the synthesized AgNPs exhibit satisfactory inhibitory effect against ten tested microorganisms. It inhibited the growth of 5 gram-positive and five gram-negative bacteria. Moreover, AgNPs demonstrated a synergistic effect on the neurotoxicity induced in rat pups with orally administered methyl mercury (MeHg). The present study showed that AgNPs prepared from ZSC might be a promising antimicrobial agent for successful treatment of bacterial infection in intensive care units (ICU) especially in case of antibiotic resistance.

Genotoxicity testing of Persicariae Rhizoma (Persicaria tinctoria H. Gross) aqueous extracts

PubMed Central

LEE, WON HO; CHOI, SEONG HUN; KANG, SU JIN; SONG, CHANG HYUN; PARK, SOO JIN; LEE, YOUNG JOON; KU, SAE KWANG

2016-01-01

Persicariae Rhizoma (PR) has been used as an anti-inflammatory and detoxification agent in Korea, and contains the biologically active dyes purple indirubin and blue indigo. Despite synthetic indigo showing genotoxic potential, thorough studies have not been carried out on the genotoxicity of PR. The potential genotoxicity of an aqueous extract of PR containing indigo (0.043%) and indirubin (0.009%) was evaluated using a standard battery of tests for safety assessment. The PR extract did not induce any genotoxic effects under the conditions of this study. The results of a reverse mutation assay in four Salmonella typhimurium strains and one Escherichia coli strain indicated that PR extract did not increase the frequency of revertant colonies in any strain, regardless of whether S9 mix was present or not. The PR extract also did not increase chromosomal aberrations in the presence or absence of S9 mix. Although slight signs of diarrhea were restrictedly detected in the mice treated with 2,000 mg/kg PR extract, no noteworthy changes in the frequency of micronucleated polychromatic erythrocytes were observed at doses ≤2,000 mg/kg in a bone marrow micronucleus test. These results indicate the potential safety of the PR extract, particularly if it is consumed in small amounts compared with the quantities used in the genotoxicity tests. PMID:27347027

On the abnormal "forced hydration" behavior of P(MEA-co-OEGA) aqueous solutions during phase transition from infrared spectroscopic insights.

PubMed

Hou, Lei; Wu, Peiyi

2016-06-21

Turbidity, DLS and FTIR measurements in combination with the perturbation correlation moving window (PCMW) technique and 2D correlation spectroscopy (2Dcos) analysis have been utilized to investigate the LCST-type transition of a oligo ethylene glycol acrylate-based copolymer (POEGA) in aqueous solutions in this work. As demonstrated in turbidity and DLS curves, the macroscopic phase separation was sharp and slightly concentration dependent. Moreover, individual chemical groups along polymer chains also display abrupt changes in temperature-variable IR spectra. However, according to conventional IR analysis, the C-H groups present obvious dehydration, whereas C[double bond, length as m-dash]O and C-O-C groups exhibit anomalous "forced hydration" during the steep phase transition. From these analyses together with the PCMW and 2Dcos results, it has been confirmed that the hydrophobic interaction among polymer chains drove the chain collapse and dominated the phase transition. In addition, the unexpected enhanced hydration behavior of C[double bond, length as m-dash]O and C-O-C groups was induced by forced hydrogen bonding between polar groups along polymer chains and entrapped water molecules in the aggregates, which originated from the special chemical structure of POEGA.

Stability of cefozopran hydrochloride in aqueous solutions.

PubMed

Zalewski, Przemysław; Skibiński, Robert; Paczkowska, Magdalena; Garbacki, Piotr; Talaczyńska, Alicja; Cielecka-Piontek, Judyta; Jelińska, Anna

2016-01-01

The influence of pH on the stability of cefozopran hydrochloride (CZH) was investigated in the pH range of 0.44-13.00. Six degradation products were identified with a hybrid ESI-Q-TOF mass spectrometer. The degradation of CZH as a result of hydrolysis was a pseudo-first-order reaction. As general acid-base hydrolysis of CZH was not occurred in the solutions of hydrochloric acid, sodium hydroxide, acetate, borate and phosphate buffers, kobs = kpH because specific acid-base catalysis was observed. Specific acid-base catalysis of CZH consisted of the following reactions: hydrolysis of CZH catalyzed by hydrogen ions (kH+), hydrolysis of dications (k1H2O), monocations (k2H2O) and zwitter ions (k3H2O) and hydrolysis of zwitter ions (k1OH-) and monoanions (k2OH-) of CZH catalyzed by hydroxide ions. The total rate of the reaction was equal to the sum of partial reactions: [Formula: see text]. CZH similarly like other fourth generation cephalosporin was most stable at slightly acidic and neutral pH and less stable in alkaline pH. The cleavage of the β-lactam ring resulting from a nucleophilic attack on the carbonyl carbon in the β-lactam moiety is the preferred degradation pathway of β-lactam antibiotics in aqueous solutions.

PVC biodeterioration and DEHP leaching by DEHP-degrading bacteria

PubMed Central

Latorre, Isomar; Hwang, Sangchul; Sevillano, Maria; Montalvo-Rodriguez, Rafael

2012-01-01

Newly isolated, not previously reported, di-(2-ethylhexyl) phthalate (DEHP)-degraders were augmented to assess their role in polyvinyl chloride (PVC) shower curtain deterioration and DEHP leaching. The biofilms that developed on the surfaces of the bioaugmented shower curtains with Gram-positive strains LHM1 and LHM2 were thicker than those of the biostimulated and Gram-negative strain LHM3-augmented shower curtains. The first derivative thermogravimetric (DTG) peaks of the bioaugmented shower curtains with the Gram-positive bacteria were observed at ~287°C, whereas the control and Gram-negative strain LHM3-augmented shower curtains were detected at ~283°C. This slight delay in the first DTG peak temperature is indicative of lower plasticizer concentrations in the shower curtains that were bioaugmented with Gram positive bacteria. Despite bioaugmentation with DEHP-degraders, aqueous solutions of the bioaugmentation reactors were not DEHP-free due probably to the presence of co-solutes that must have supported microbial growth. Generally, the bioaugmented reactors with the Gram-positive strains LHM1 and LHM2 had greater aqueous DEHP concentrations in the first-half (<3 wk) of the biodeterioration experiment than the biostimulated and strain LHM3-augmented reactors. Therefore, strains LHM1 and LHM2 may play an important role in DEHP leaching to the environment and PVC biodeterioration. PMID:22736894

Thermal Stability of Oil Palm Empty Fruit Bunch (OPEFB) Nanocrystalline Cellulose: Effects of post-treatment of oven drying and solvent exchange techniques

NASA Astrophysics Data System (ADS)

Indarti, E.; Marwan; Wanrosli, W. D.

2015-06-01

Nanocrystallinecellulose (NCC) from biomass is a promising material with huge potentials in various applications. A big challenge in its utilization is the agglomeration of the NCC's during processing due to hydrogen bonding among the cellulose chains when in close proximity to each other. Obtaining NCC's in a non-agglomerated and non-aqueous condition is challenging. In the present work NCC's was isolated from oil palm empty fruit bunch (OPEFB) using TEMPO-oxidation reaction method. To obtain non-agglomerated and non-aqueous products, the NCC's underwent post-treatment using oven drying (OD) and solvent exchanged (SE) techniques. The thermal stability of all samples was determined from TGA and DTG profiles whilst FTIR was used to analyzethe chemical modifications that occurred under these conditions. NCC-SE has better thermal stability than the NCC-OD and its on-set degradation temperature and residue are also higher. FTIR analysis shows that NCC-SE has a slightly different chemical composition whereby the absorption band at 1300 cm-1 (due to C-O symmetric stretching) is absent as compared to NCC-OD indicating that in NCC-SE the carboxylate group is in acid form which contribute to its thermal stability

Effect of Vaccinium bracteatum Thunb. leaves extract on blood glucose and plasma lipid levels in streptozotocin-induced diabetic mice.

PubMed

Wang, Li; Zhang, Xue Tong; Zhang, Hai Yan; Yao, Hui Yuan; Zhang, Hui

2010-08-09

To investigate the hypoglycemic effects of Vaccinium bracteatum Thunb. leaves (VBTL) extract in streptozotocin-induced diabetic mice. After administration of VBTL extract for 4 weeks, the body weight, organ weight, blood glucose (BG), insulin and plasma lipid levels of streptozotocin-induced diabetic mice were measured. Body weights of diabetic mice treated with VBTL extract were partly recovered. The BG levels of AEG (diabetic mice treated with VBTL aqueous extract) were reduced to 91.52 and 85.82% at week 2 and week 4, respectively (P<0.05), while those of EEG (diabetic mice treated with VBTL ethanolic extract) were reduced slightly (P>0.05). The insulin levels of AEG and EEG were obviously higher (P<0.05) than those of MC (diabetic mice in model control group). Comparing with MC, AEG and EEG had significantly lower (P<0.05) TC or TG levels and similar HDL-cholesterol or LDL-cholesterol levels. In comparison with non-diabetic control mice, AEG had similar plasma lipid levels except higher LDL-cholesterol level, while EEG had higher TC, TG and LDL-cholesterol levels and lower HDL-cholesterol levels. Both aqueous and ethanolic extract of VBTL possess a potential hypoglycemic effect in streptozotocin-induced diabetic mice. Copyright 2010 Elsevier Ireland Ltd. All rights reserved.

Production of Omega-3 Fatty Acid Ethyl Esters from Menhaden Oil Using Proteus vulgaris Lipase-Mediated One-Step Transesterification and Urea Complexation.

PubMed

Kim, Soo-Jin; Kim, Hyung Kwoun

2016-05-01

An organic solvent-stable lipase from Proteus vulgaris K80 was used to produce the omega-3 polyunsaturated fatty acid ethyl esters (ω-3 PUFA EEs). First, the lyophilized recombinant lipase K80 (LyoK80) was used to perform the transesterification reaction of menhaden oil and ethanol. LyoK80 produced the ω-3 PUFA EEs with a conversion yield of 82 % in the presence of 20 % water content via a three-step ethanol-feeding process; however, in a non-aqueous condition, LyoK80 produced only a slight amount of the ω-3 PUFA EEs. To enhance its reaction properties, the lipase K80 was immobilized on a hydrophobic bead to derive ImmK80; the biochemical properties and substrate specificity of ImmK80 are similar to those of LyoK80. ImmK80 was then used to produce ω-3 PUFA EEs in accordance with the same transesterification reaction. Unlike LyoK80, ImmK80 achieved a high ω-3 PUFA EE conversion yield of 86 % under a non-aqueous system via a one-step ethanol-feeding reaction. The ω-3 PUFA EEs were purified up to 92 % using a urea complexation method.

Transdermal iontophoresis of ranitidine: an opportunity in paediatric drug therapy.

PubMed

Djabri, Asma; Guy, Richard H; Delgado-Charro, M Begoña

2012-10-01

The objective of this study was to examine the use of transdermal iontophoresis for the delivery of ranitidine hydrochloride in children. Constant, direct current, anodal iontophoresis of ranitidine was performed in vitro across dermatomed pig skin. The effect of donor vehicle, current intensity, and drug concentration were first examined using aqueous solutions. It was found that drug delivery was higher at pH 7 (donor: 5mM Tris) than pH 5.6 (donor: water). In the presence of low levels of competing background electrolyte, ranitidine delivery increased linearly with applied current but was independent of the donor drug concentration. The second part of the study evaluated two Pluronic(®) F-127 gels as potential vehicles for ranitidine delivery. The formulations were characterised in terms of apparent viscosity, conductivity and passive permeation measurements. Iontophoretic delivery of ranitidine was only slightly affected when delivered from the gels relative to aqueous solutions. Overall the results demonstrated that therapeutic paediatric doses of ranitidine (neonates: 0.09-0.17 μmol/kg h; 1 month to 12 years: 0.36-0.71 μmol/kg h) could be easily achieved by transdermal iontophoresis with simple gel patches of practical surface area (0.2-1.5 cm(2)/kg). Copyright © 2012 Elsevier B.V. All rights reserved.

Hydrogen and Sulfur from Hydrogen Sulfide. 5. Anodic Oxidation of Sulfur on Activated Glassy Carbon

DTIC Science & Technology

1988-12-05

electrolyses of H S can probably be carried out at high rates with modest cell voltages in the range 1-1.5 V. The variation in anode current densities...of H2S from solutions of NaSH in aqueous NaOH was achieved using suitably ac- tivated glassy carbon anodes. Thus electrolyses of H2S can probably be...passivation by using a basic solvent at 850C. Using an H2S-saturated 6M NaOH solution, they conducted electrolyses for extended periods at current densities

Simultaneous extraction and quantitation of several bioactive amines in cheese and chocolate.

PubMed

Baker, G B; Wong, J T; Coutts, R T; Pasutto, F M

1987-04-17

A method is described for simultaneous extraction and quantitation of the amines 2-phenylethylamine, tele-methylhistamine, histamine, tryptamine, m- and p-tyramine, 3-methoxytyramine, 5-hydroxytryptamine, cadaverine, putrescine, spermidine and spermine. This method is based on extractive derivatization of the amines with a perfluoroacylating agent, pentafluorobenzoyl chloride, under basic aqueous conditions. Analysis was done on a gas chromatograph equipped with an electron-capture detector and a capillary column system. The procedure is relatively rapid and provides derivatives with good chromatographic properties. Its application to analysis of the above amines in cheese and chocolate products is described.

Chemistry Division annual progress report for period ending April 30, 1993

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

Poutsma, M.L.; Ferris, L.M.; Mesmer, R.E.

1993-08-01

The Chemistry Division conducts basic and applied chemical research on projects important to DOE`s missions in sciences, energy technologies, advanced materials, and waste management/environmental restoration; it also conducts complementary research for other sponsors. The research are arranged according to: coal chemistry, aqueous chemistry at high temperatures and pressures, geochemistry, chemistry of advanced inorganic materials, structure and dynamics of advanced polymeric materials, chemistry of transuranium elements and compounds, chemical and structural principles in solvent extraction, surface science related to heterogeneous catalysis, photolytic transformations of hazardous organics, DNA sequencing and mapping, and special topics.

Thermally stable booster explosive and process for manufacture

DOEpatents

Quinlin, William T [Amarillo, TX; Thorpe, Raymond [Amarillo, TX; Lightfoot, James M [Amarillo, TX

2006-03-21

A thermally stable booster explosive and process for the manufacture of the explosive. The product explosive is 2,4,7,9-tetranitro-10H-benzo[4,5]furo[3,2-b]indole (TNBFI). A reactant/solvent such as n-methylpyrrolidone (NMP) or dimethyl formamide (DMF) is made slightly basic. The solution is heated to reduce the water content. The solution is cooled and hexanitrostilbene is added. The solution is heated to a predetermined temperature for a specific time period, cooled, and the product is collected by filtration.

JPRS Report, China

DTIC Science & Technology

1993-02-16

regions (including the model regions) are now mostly inclined to have "one boy , one girl" in terms of child-bearing. It is proper to argue that if the...survey questions are slightly modified, the real inclination can be found to be having "two children, one boy " (to want to have two children and to...have at least one boy ). 3. The model regions have basically reached the targets set in the policy in terms of fertility levels. 4. Models of the

VKI Activities in Support of AFOSR Basic Research Interests: Steady State Pyrolysis and Ablation Investigation

DTIC Science & Technology

2008-03-31

flux with and without chocking flows above 0.04 g/ s, the heat flux becomes more constant, only slightly de- creasing with increased transpiration...the flowfield species and the injected species. For air, the initial species are N2 and 02. As the flow passes through the shock wave surrounding the...fiber. The captured light is then sent to an Ocean Optics HR4000CG-UV-NIR spectrometer for dispersion and recording of the spectra. The main

Application of Brazilian kaolinite clay as adsorbent to removal of U(VI) from aqueous solution: Kinetic and thermodynamic of cation-basic interactions

NASA Astrophysics Data System (ADS)

Guerra, Denis L.; Leidens, Victor L.; Viana, Rúbia R.; Airoldi, Claudio

2010-05-01

The compound N 1-[3-(trimethoxysilyl)propyl]diethylenetriamine was anchored onto Amazon kaolinite surface by heterogeneous route. The modified and natural kaolinite samples were characterized by transmission electron microscopy, scanning electron microscopic, X-ray diffraction, and nuclear magnetic nuclei of 29Si and 13C. The well-defined peaks obtained in the 13C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0. The kinetic parameters analyzed by the Lagergren and Elovich models gave a good fit for a pseudo-second order reaction with k2 values 16.0 and 25.1 mmol g -1 min -1 ranges for natural and modified kaolinite clays, respectively. The energetic effects caused by metal ion adsorption were determined through calorimetric titrations.

The Biophysics and Cell Biology of Lipid Droplets

PubMed Central

Thiam, A. Rachid; Farese, Robert V.; Walther, Tobias C.

2015-01-01

Lipid droplets (LDs) are intracellular organelles that are found in most cells, where they have fundamental and dynamic roles in metabolism. Recent investigations showed the importance of basic biophysical principles of emulsions for LD biology. At their essence, LDs are the dispersed phase of an oil-in-water emulsion in the aqueous cytosol of cells. They function prominently in storing oil-based reserves of metabolic energy and components of membrane lipids. Because of their unique architecture, with an interface between the dispersed oil phase and the aqueous cytosol, LDs require specialized mechanisms for their formation, growth, and shrinkage. Such mechanisms enable cells to use emulsified oil in a controlled manner (e.g., when demands for metabolic energy or membrane synthesis increase). Regulation of the composition of the phospholipid surfactants at the LD surface is crucial for LD growth and catabolism and also modifies protein targeting to LD surfaces. Here, we review new insights into the cell biology of LDs, with an emphasis on concepts of emulsion science and biophysics that apply to this organelle. PMID:24220094

Utilization of activated carbon produced from fruit juice industry solid waste for the adsorption of Yellow 18 from aqueous solutions.

PubMed

Angin, Dilek

2014-09-01

The use of activated carbon obtained from sour cherry (Prunus cerasus L.) stones for the removal of a basic textile dye, which is Yellow 18, from aqueous solutions at different contact times, pH values and solution temperatures was investigated. The surface area and micropore volume of chemically modified activated carbon were 1704 m(2) g(-1) and 0.984 cm(3) g(-1), respectively. The experimental data indicated that the adsorption isotherms were well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity was 75.76 mg g(-1) at 318 K. The adsorption kinetic of Yellow 18 obeys the pseudo-second-order kinetic model. The thermodynamic parameters were calculated to estimate the nature of adsorption. The activation energy of the system was calculated as 0.71-2.36 kJ/mol. According to these results, prepared activated carbon could be used as a low-cost adsorbent to compare with the commercial activated carbon for the removal of Yellow 18 from wastewater. Copyright © 2014 Elsevier Ltd. All rights reserved.

Treatment of a non-azo dye aqueous solution by CWAO in continuous reactor using a Ni catalyst derived from hydrotalcite-like precursor.

PubMed

Vallet, Ana; Besson, Michèle; Ovejero, Gabriel; García, Juan

2012-08-15

Catalytic wet air oxidation (CWAO) of a Basic Yellow 11 (BY11) aqueous solution, chosen as a model of a hardly biodegradable non-azo dye was carried out in a continuous-flow trickle-bed reactor, using nickel supported over hydrotalcite precursor calcined at 550°C. An increase in the reaction temperature (120-180°C), and a decrease in dye concentration (1000-3000 ppm) or liquid flow rate (0.1-0.7 mL min(-1)) enhanced the CWAO performance in a 30 and 19% for the variation of the temperature and concentration respectively. After a small leaching observed within the first hours, the catalyst proved to be very stable during the 65-day reaction. The CWAO process was found to be very efficient, achieving BY11 conversion up to 95% and TOC conversion up to 85% at 0.1 mL min(-1) and 180°C under 5 MPa air. Copyright © 2012 Elsevier B.V. All rights reserved.

The effect of pH and triethanolamine on sulfisoxazole complexation with hydroxypropyl-beta-cyclodextrin.

PubMed

Gladys, Granero; Claudia, Garnero; Marcela, Longhi

2003-11-01

A novel complexation of sulfisoxazole with hydroxypropyl-beta-cyclodextrin (HP-beta-CD) was studied. Two systems were used: binary complexes prepared with HP-beta-CD and multicomponent system (HP-beta-CD and the basic compound triethanolamine (TEA)). Inclusion complex formation in aqueous solutions and in solid state were investigated by the solubility method, thermal analysis (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)), Fourier-transform infrared spectroscopy (FT-IR) and dissolution studies. The solid complexes of sulfisoxazole were prepared by freeze-drying the homogeneous concentrated aqueous solutions in molar ratios of sulfisoxazole:HP-beta-CD 1:1 and 1:2, and sulfisoxazole:TEA:HP-beta-CD 1:1:2. FT-IR and thermal analysis showed differences among sulfisoxazole:HP-beta-CD and sulfisoxazole:TEA:HP-beta-CD and their corresponding physical mixtures and individual components. The HP-beta-CD solubilization of sulfisoxazole could be improved by ionization of the drug molecule through pH adjustments. However, larger improvements of the HP-beta-CD solubilization are obtained when multicomponent systems are used, allowing to reduce the amount of CD necessary to prepare the target formulation.

Characterization of Chitin and Chitosan Molecular Structure in Aqueous Solution

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

Franca, Eduardo D.; Lins, Roberto D.; Freitas, Luiz C.

Molecular dynamics simulations have been used to characterize the structure of chitin and chitosan fibers in aqueous solutions. Chitin fibers, whether isolated or in the form of a β-chitin nanoparticle, adopt the so-called 2-fold helix with Φ and φ values similar to its crystalline state. In solution, the intramolecular hydrogen bond HO3(n)•••O5(n+1) responsible for the 2-fold helical motif is stabilized by hydrogen bonds with water molecules in a well-defined orientation. On the other hand, chitosan can adopt five distinct helical motifs and its conformational equilibrium is highly dependent on pH. The hydrogen bond pattern and solvation around the O3 atommore » of insoluble chitosan (basic pH) are nearly identical to these quantities in chitin. Our findings suggest that the solubility and conformation of these polysaccharides are related to the stability of the intrachain HO3(n)•••O5(n+1) hydrogen bond, which is affect by the water exchange around the O3-HO3 hydroxyl group.« less

Determining the relative extent of alteration in CM chondrites

NASA Technical Reports Server (NTRS)

Browning, Lauren B.; Mcsween, Harry Y., Jr.; Zolensky, Michael

1993-01-01

The aqueous alteration of CM chondrites provides a record of the processes attending the earliest stages of parent body evolution. However, resolving the alteration pathways of chondritic evolution requires a means for distinguishing the relative extent of alteration that individual samples have experienced. Three new indices for gauging the relative degree of alteration in CM chondrites based on modal and compositional analyses of 7 CM falls were proposed. The proposed alteration parameters are consistent with the basic tenets of several previous models and correlate with additional indices to produce an integrated method for determining the relative extent of alteration. The model predicts the following order of progressive alteration: Murchison (MC) is less than or equal to Bells (BL) is less than Murray (MY) is less than Cochabamba (CC) is less than Mighei (MI) is less than Nogoya (NG) is less than or equal to Cold Bokkeveld (CB). The broad range of CM phyllosilicate compositions observed within individual meteorites is fundamental to the characterization of the aqueous alteration process. Chemical analyses of CM phyllosilicates suggest that these phases became systematically enriched in Mg and depleted in Fe with increasing alteration.

A thermosensitive hydrogel based on biodegradable amphiphilic poly(ethylene glycol) polycaprolactone poly(ethylene glycol) block copolymers

NASA Astrophysics Data System (ADS)

Gong, Chang Yang; Qian, Zhi Yong; Liu, Cai Bing; Juan Huang, Mei; Gu, Ying Chun; Wen, Yan Jun; Kan, Bing; Wang, Ke; Dai, Mei; Li, Xing Yi; Gou, Ma Ling; Tu, Ming Jing; Wei, Yu Quan

2007-06-01

A series of low molecular weight poly(ethylene glycol)-polycaprolactone-poly(ethylene glycol) (PEG-PCL-PEG) biodegradable block copolymers were successfully synthesized using isophorone diisocyanate (IPDI) as the coupling agent, and were characterized using 1H NMR and Fourier transform infrared spectroscopy. The aqueous solutions of the PEG-PCL-PEG copolymers displayed a special thermosensitive gel-sol transition when the concentration was above the corresponding critical gel concentration. Gel-sol phase diagrams were recorded using the test-tube-inversion method; they depended on the hydrophilic/hydrophobic balance in the macromolecular structure, as well as some other factors, including the heating history, volume, and the ageing time of the copolymer aqueous solutions and dissolution temperature of the copolymers. As a result, the gel-sol transition temperature range could be altered, which might be very useful for application in injectable drug delivery systems. This work was financially supported by the Chinese Key Basic Research Program (2004CB518800 and 2004CB518807), and the Sichuan Key Project of Science and Technology (06(05SG022-021-02)).

A Generalized Model for Transport of Contaminants in Soil by Electric Fields

PubMed Central

Paz-Garcia, Juan M.; Baek, Kitae; Alshawabkeh, Iyad D.; Alshawabkeh, Akram N.

2012-01-01

A generalized model applicable to soils contaminated with multiple species under enhanced boundary conditions during treatment by electric fields is presented. The partial differential equations describing species transport are developed by applying the law of mass conservation to their fluxes. Transport, due to migration, advection and diffusion, of each aqueous component and complex species are combined to produce one partial differential equation hat describes transport of the total analytical concentrations of component species which are the primary dependent variables. This transport couples with geochemical reactions such as aqueous equilibrium, sorption, precipitation and dissolution. The enhanced model is used to simulate electrokinetic cleanup of lead and copper contaminants at an Army Firing Range. Acid enhancement is achieved by the use of adipic acid to neutralize the basic front produced for the cathode electrochemical reaction. The model is able to simulate enhanced application of the process by modifying the boundary conditions. The model showed that kinetics of geochemical reactions, such as metals dissolution/leaching and redox reactions might be significant for realistic prediction of enhanced electrokinetic extraction of metals in real world applications. PMID:22242884

Solid phase extraction--non-aqueous capillary electrophoresis for determination of metformin, phenformin and glyburide in human plasma.

PubMed

Lai, Edward P C; Feng, Sherry Y

2006-10-20

Solid phase extraction (SPE) was coupled at line to capillary electrophoresis (CE) for the determination of three basic and neutral diabetic drugs (metformin, phenformin and glyburide) in human plasma. The SPE procedure employed a C(18) cartridge to remove most of the water and proteins from the plasma sample. Analyte detectability was increased due to trace enrichment during the SPE process. Elution of metformin, phenformin and glyburide was achieved with methanol+3% acetic acid. CE analysis was performed using a non-aqueous buffer, acetonitrile+5mM ammonium acetate+5% acetic acid, which afforded rapid separation of metformin from phenformin within 3 min. Glyburide, with a migration time longer than 6 min, did not cause any interference. The present SPE-CE method, with an electrokinetic injection time of 6s and UV detection at 240 nm, was useful for monitoring down to 1 microg/mL of metformin and phenformin in human plasma. When the electrokinetic injection time was increased to 36s, the detection limits were improved to 12 ng/mL for metformin and 6 ng/mL for phenformin.

[Genealogy of the Books of Practica medicinae in Europe before the End of 18th Century: From the Origin to the Disappearance].

PubMed

Sakai, Tatsuo

2015-09-01

The Practica medicinae represented the books written in Europe before the end of 18th century that dealt with individual deseases. In total, 100 Practica books, written by 95 authors, were collected and divided into four periods from the early 11th to the end of 18th century. The first Practica book was written at the Salernitan medical school on the basis of ancient medical books in the basic style, dealing with regional deseases arranged in "a capite ad calcem" manner, as well as with the fevers. The basic style comprised a majority in the first period and decreased gradually, becoming a minority in the 3rd and 4th periods. Sennert's practica was the largest and it elaborated with precise construction. The additional categories, such as female, children, and surgical deseases increased in the later periods. Those written in non-basic style based on pathogenesis or in alphabetical order also increased in the later periods. The practica books changed slightly and gradually, indicating the essential consistency of the concepts of diseases in these periods.

Synthesis, spectroscopy, and binding constants of ketocatechol-containing iminodiacetic acid and its Fe(III), Cu(II), and Zn(II) complexes and reaction of Cu(II) complex with H₂O₂ in aqueous solution.

PubMed

Gao, Jiaojiao; Xing, Feifei; Bai, Yueling; Zhu, Shourong

2014-06-07

A new neuromelanin-like ketocatechol-containing iminodiacetic acid ligand, (N-(3,4-dihydroxyl)phenacylimino)diacetic acid (H4L), which is also quite similar to compounds found in insect cuticle, has been synthesized and characterized. The X-ray crystal structure of H4L has been successfully determined. Proton binding and coordination with Fe(III), Cu(II), and Zn(II) have been studied by potentiometric titrations and UV-vis spectrophotometry in aqueous solution. UV spectra of H4L in the absence and presence of different metal ions indicate complexes formed with the catechol moiety of H4L in aqueous solution. Visible spectra and NMR reveal that H4L with Fe(III), Cu(II), and Zn(II) can all give stable mono-(ML) and dinuclear complexes [M(ML)]. Fe(III) can also form {Fe(FeL)2} and {Fe(FeL)3} species with sufficient base. The process is accompanied by a drastic color change from light blue to deep-blue to wine-red. The Fe(III)-Cu(II) heteronuclear complex also exists in aqueous solution whose spectra are similar to the homonuclear Fe(III) complex. However, the spectra of {Fe(CuL)} shifted to a longer wavelength and {Fe(CuL)2} and {Fe(CuL)3} shifted to a shorter wavelength. Keto-enol tautomerism was observed in weak basic aqueous solution as indicated by (1)H NMR spectra. The reaction products of Cu(II) complex with H2O2 depend on the H2O2 concentration and pH value. Low concentrations of H2O2 oxidize H4L to a series of semiquinone and quinone compounds with absorption maxima at 314-400 nm, while a high concentration of H2O2 oxidizes H4L to colorless muconic acid derivatives. NaIO4 gives different oxidase products, but no 2,4,5-trihydroxyphenylalanine quinone (TPQ)-like hydroxyquinone can be found.

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

Wang, Guohui; Qafoku, Nikolla; Lawter, Amanda R.

A series of batch and column experiments combined with solid phase characterization studies (i.e., quantitative x-ray diffraction and wet chemical extractions) were conducted to address a variety of scientific issues and evaluate the impacts of the potential leakage of carbon dioxide (CO2) from deep subsurface storage reservoirs. The main objective was to gain an understanding of how CO2 gas influences: 1) the aqueous phase pH; and 2) mobilization of major, minor, and trace elements from minerals present in an aquifer overlying potential CO2 sequestration subsurface repositories. Rocks and slightly weathered rocks representative of an unconfined, oxidizing carbonate aquifer within themore » continental US, i.e., the Edwards aquifer in Texas, were used in these studies. These materials were exposed to a CO2 gas stream or were leached with a CO2-saturated influent solution to simulate different CO2 gas leakage scenarios, and changes in aqueous phase pH and chemical composition were measured in the liquid samples collected at pre-determined experimental times (batch experiments) or continuously (column experiments). The results from the strong acid extraction tests confirmed that in addition to the usual elements present in most soils, rocks, and sediments, the Edward aquifer samples contain As, Cd, Pb, Cu, and occasionally Zn, which may potentially be mobilized from the solid to the aqueous phase during or after exposure to CO2. The results from the batch and column experiments confirmed the release of major chemical elements into the contacting aqueous phase (such as Ca, Mg, Ba, Sr, Si, Na, and K); the mobilization and possible rapid immobilization of minor elements (such as Fe, Al, and Mn), which are able to form highly reactive secondary phases; and sporadic mobilization of only low concentrations of trace elements (such as As, Cd, Pb, Cu, Zn, Mo, etc.). The results from this experimental research effort will help in developing a systematic understanding of how CO2 leakage is likely to influence pertinent geochemical processes (e.g., dissolution/precipitation, sorption/desorption) in the aquifer sediments and will support site selection, risk assessment, policy-making, and public education efforts associated with geologic carbon sequestration.« less

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

NASA Astrophysics Data System (ADS)

Suchomel, Eric J.; Ramsburg, C. Andrew; Pennell, Kurt D.

2007-12-01

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween® 80) and sodium dihexyl sulfosuccinate (Aerosol® MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl 2 yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (> 30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR = 1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (< 5%) occurring when the total trapping number exceeded 2 × 10 - 5 . These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.

Impact of fog processing on water soluble organic aerosols.

NASA Astrophysics Data System (ADS)

Tripathi, S. N.; Chakraborty, A.; Gupta, T.

2017-12-01

Fog is a natural meteorological phenomenon that occurs all around the world, and contains a substantial quantity of liquid water. Fog is generally seen as a natural cleansing agent but can also form secondary organic aerosols (SOA) via aqueous processing of ambient organics. Few field studies have reported elevated O/C ratio and SOA mass during or after fog events. However, mechanism behind aqueous SOA formation and its contribution to total organic aerosols (OA) still remains unclear. In this study we have tried to explore the impact of fog/aqueous processing on the characteristics of water soluble organic aerosols (WSOC), which to our knowledge has not been studied before. To assess this, both online (using HR-ToF-AMS) and offline (using a medium volume PM2.5 sampler and quartz filter) aerosol sampling were carried out at Kanpur, India from 15 December 2014 - 10 February 2015. Further, offline analysis of the aqueous extracts of the collected filters were carried out by AMS to characterize the water soluble OA (WSOA). Several (17) fog events occurred during the campaign and high concentrations of OA (151 ± 68 µg/m3) and WSOA (47 ± 19 µg/m3) were observed. WSOA/OA ratios were similar during fog (0.36 ± 0.14) and nofog (0.34 ± 0.15) periods. WSOA concentrations were also similar (slightly higher) during foggy (49 ± 18 µg/m3) and non-foggy periods (46 ± 20 µg/m3), in spite of fog scavenging. However, WSOA was more oxidized during foggy period (average O/C = 0.81) than non foggy periods (average O/C = 0.70). Like WSOA, OA was also more oxidized during foggy periods (average O/C = 0.64) than non foggy periods (average O/C = 0.53). During fog, WSOA to WIOA (water insoluble OA) ratios were higher (0.65 ± 0.16) compared to non foggy periods (0.56 ± 0.15). These observations clearly showed that WSOA become more dominant and processed during fog events, possibly due to the presence of fog droplets. This study highlights that fog processing of soluble organics can affect the overall chemical characteristics of the entire aerosol population.

Aqueous Lubrication, Structure and Rheological Properties of Whey Protein Microgel Particles.

PubMed

Sarkar, Anwesha; Kanti, Farah; Gulotta, Alessandro; Murray, Brent S; Zhang, Shuying

2017-12-26

Aqueous lubrication has emerged as an active research area in recent years due to its prevalence in nature in biotribological contacts and its enormous technological soft-matter applications. In this study, we designed aqueous dispersions of biocompatible whey-protein microgel particles (WPM) (10-80 vol %) cross-linked via disulfide bonding and focused on understanding their rheological, structural and biotribological properties (smooth polydimethylsiloxane (PDMS) contacts, R a < 50 nm, ball-on-disk set up). The WPM particles (D h = 380 nm) displayed shear-thinning behavior and good lubricating performance in the plateau boundary as well as the mixed lubrication regimes. The WPM particles facilitated lubrication between bare hydrophobic PDMS surfaces (water contact angle 108°), leading to a 10-fold reduction in boundary friction force with increased volume fraction (ϕ ≥ 65%), largely attributed to the close packing-mediated layer of particles between the asperity contacts acting as "true surface-separators", hydrophobic moieties of WPM binding to the nonpolar surfaces, and particles employing a rolling mechanism analogous to "ball bearings", the latter supported by negligible change in size and microstructure of the WPM particles after tribology. An ultralow boundary friction coefficient, μ ≤ 0.03 was achieved using WPM between O 2 plasma-treated hydrophilic PDMS contacts coated with bovine submaxillary mucin (water contact angle 47°), and electron micrographs revealed that the WPM particles spread effectively as a layer of particles even at low ϕ∼ 10%, forming a lubricating load-bearing film that prevented the two surfaces from true adhesive contact. However, above an optimum volume fraction, μ increased in HL+BSM surfaces due to the interpenetration of particles that possibly impeded effective rolling, explaining the slight increase in friction. These effects are reflected in the highly shear thinning nature of the WPM dispersions themselves plus the tendency for the apparent viscosity to fall as dispersions are forced to very high volume fractions. The present work demonstrates a novel approach for providing ultralow friction in soft polymeric surfaces using proteinaceous microgel particles that satisfy both load bearing and kinematic requirements. These findings hold great potential for designing biocompatible particles for aqueous lubrication in numerous soft matter applications.

Synthesis and antitumor activity of seleno- and thio-purines complexed with cis-diamminoplatinum (II).

PubMed

Maeda, M; Abiko, N; Sasaki, T

1982-02-01

cis-Diamminoplatinum (II) complexes with selenoguanine, thioguanine, 6-thioxanthine, or 6-mercaptopurine were synthesized by the reaction of stoichiometric amounts of selenopurine or thiopurine with aquated cis-dichlorodimmineplatinum (II) in slightly acidic medium, and their antitumor activity was studied against L1210 cells in mice. These compounds exhibited a medium antitumor activity with very low toxicity. The antitumor activity was dependent on the nature of the purine ligand. These complexes were very stable in various aqueous solvents at 37 degrees C for 10 d but not in the presence of mouse serum. The mechanism of the action effected by the complex is not clear. However, the slow release of an antitumor active purine from the complex, SeG-Pt (NH3)2, was observed.

Adsorption of Methyl Red by water-hyacinth (Eichornia crassipes) biomass.

PubMed

Tarawou, Temi; Horsfall, Michael; Vicente, José L

2007-09-01

The surface characteristics and adsorbent properties of biomass, obtained from low-cost and environmentally problematic water hyacinth, were determined. Optimum conditions for the elimination of the industrial dye Methyl Red (1) from aqueous solution were established by means of a batch adsorption technique. The ultimate adsorption capacity of water-hyacinth biomass in terms of the elimination of 1 was calculated from a Langmuir-type isotherm as 8.85x10(-2) mol g(-1) at 30 degrees and at an optimum solution pH of 8.0. Dye elimination was found to be associated with strong electrostatic forces (physisorption), the overall process being slightly endergonic (deltaG>0). Our study shows that water hyacinth has a great potential of removing color from wastewater and other dye-polluted aquatic systems.

Amphiphilic Polysaccharide Block Copolymers for pH-Responsive Micellar Nanoparticles.

PubMed

Breitenbach, Benjamin B; Schmid, Ira; Wich, Peter R

2017-09-11

A full polysaccharide amphiphilic block copolymer was prepared from end group-functionalized dextrans using copper-mediated azide-alkyne click chemistry. Sufficient modification of the reducing end in both blocks was achieved by microwave-enhanced reductive amination in a borate-buffer/methanol solvent system. The combination of a hydrophilic dextran block with a hydrophobic acetalated dextran block results in an amphiphilic structure that turns water-soluble upon acid treatment. The material has a low critical micelle concentration and self-assembles in water to spherical micellar nanoparticles. The formed nanoparticles have a narrow size distribution below 70 nm in diameter and disassemble in slightly acidic conditions. The amphiphilic polysaccharide system shows low toxicity and can stabilize the hydrophobic model drug curcumin in aqueous solutions over extended time periods.

Surface plasmon resonance sensing in gaseous media with optical fiber gratings.

PubMed

González-Vila, Álvaro; Ioannou, Andreas; Loyez, Médéric; Debliquy, Marc; Lahem, Driss; Caucheteur, Christophe

2018-05-15

Surface plasmon resonance excitation with optical fiber gratings has been typically studied in aqueous solutions. This work describes the procedure to excite a plasmon wave in gaseous media and perform refractive index measurements in these environments. Grating photo-inscription with 193 nm excimer laser radiation allows us to obtain slightly tilted fiber Bragg gratings exhibiting a cladding mode resonance comb along several hundreds of nanometers. Their refractive index sensitive range extends from gases to liquids, so operation in both media is compared. We demonstrate that the thickness of the metal coating required for surface plasmon excitation in gases is roughly one third of the one usually used for liquids. The developed platforms exhibit a temperature insensitive response of 78 nm/RIU when tested with different gases.

Translational and rotational dynamics of monosaccharide solutions.

PubMed

Lelong, Gérald; Howells, W Spencer; Brady, John W; Talón, César; Price, David L; Saboungi, Marie-Louise

2009-10-01

Molecular dynamics computer simulations have been carried out on aqueous solutions of glucose at concentrations bracketing those previously measured with quasi-elastic neutron scattering (QENS), in order to investigate the motions and interactions of the sugar and water molecules. In addition, QENS measurements have been carried out on fructose solutions to determine whether the effects previously observed for glucose apply to monosaccharide solutions. The simulations indicate a dynamical analogy between higher solute concentration and lower temperature that could provide a key explanation of the bioprotective phenomena observed in many living organisms. The experimental results on fructose solutions show qualitatively similar behavior to the glucose solutions. The dynamics of the water molecules are essentially the same, while the translational diffusion of the sugar molecules is slightly faster in the fructose solutions.

Crystal structure of iron(III) perchlorate nona­hydrate

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

Since the discovery of perchlorate salts on Mars and the known occurrence of ferric salts in the regolith, there is a distinct possibility that the title compound could form on the surface of Mars. [Fe(H2O)6](ClO4)3·3H2O was crystallized from aqueous solutions at low temperatures according to the solid–liquid phase diagram. It consists of Fe(H2O)6 octa­hedra (point group symmetry -3.) and perchlorate anions (point group symmetry .2) as well as non-coordinating water mol­ecules, as part of a second hydrogen-bonded coordination sphere around the cation. The perchlorate appears to be slightly disordered, with major–minor component occupancies of 0.773 (9):0.227 (9). PMID:25552970

Inhibition of Photocatalytic Activity of Basic Blue-41 by ZnO Modified Surface with Amino Silane

NASA Astrophysics Data System (ADS)

Limsapapkasiphon, S.; Sirisaksoontorn, W.; Songsasen, A.

2018-03-01

The reduction of the photo catalytic efficiency of ZnO can be achieved by modifying its surface with amino silane, which synthesized through condensation reaction under basic condition. The pH of solution was varied from 8 to 14 during the synthesis and was found that pH 12 was the most suitable pH for the preparation. All of ZMAS were characterized by Elemental Analysis which showed the highest percentage of nitrogen at 3.1064% and IR technique which indicated the Si-O-Zn bond at about 1000 cm-1. The photodegradation property of ZMAS prepared at pH 8-12 toward basic blue 41 was retarded when compared with the unmodified ZnO. Effect of mole ratio of ZnO:APTES (1:0.1, 1:0.5, 1:1, and 1:2) in the preparation of ZMAS was investigated. The photodegration activity of ZMAS prepared at mole ratio of ZnO:APTES as 1:0.5 to 1:2 toward basic blue 41 was retarded when compared with the unmodified ZnO. The coating of amino silane on ZnO surface did not have much effect on the band gap energy of modified ZnO. The absorption edge of ZMAS was only slightly shifted from 392 to 397 nm.

Role of the P-F bond in fluoride-promoted aqueous VX hydrolysis: an experimental and theoretical study.

PubMed

Marciano, Daniele; Columbus, Ishay; Elias, Shlomi; Goldvaser, Michael; Shoshanim, Ofir; Ashkenazi, Nissan; Zafrani, Yossi

2012-11-16

Following our ongoing studies on the reactivity of the fluoride ion toward organophosphorus compounds, we established that the extremely toxic and environmentally persistent chemical warfare agent VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate) is exclusively and rapidly degraded to the nontoxic product EMPA (ethyl methylphosphonic acid) even in dilute aqueous solutions of fluoride. The unique role of the P-F bond formation in the reaction mechanism was explored using both experimental and computational mechanistic studies. In most cases, the "G-analogue" (O-ethyl methylphosphonofluoridate, Et-G) was observed as an intermediate. Noteworthy and of practical importance is the fact that the toxic side product desethyl-VX, which is formed in substantial quantities during the slow degradation of VX in unbuffered water, is completely avoided in the presence of fluoride. A computational study on a VX-model, O,S-diethyl methylphosphonothioate (1), clarifies the distinctive tendency of aqueous fluoride ions to react with such organophosphorus compounds. The facility of the degradation process even in dilute fluoride solutions is due to the increased reactivity of fluoride, which is caused by the significant low activation barrier for the P-F bond formation. In addition, the unique nucleophilicity of fluoride versus hydroxide toward VX, in contrast to their relative basicity, is discussed. Although the reaction outcomes were similar, much slower reaction rates were observed experimentally for the VX-model (1) in comparison to VX.

Protecting health.

PubMed

Armour, Margaret-Ann; Linetsky, Asya; Ashick, Donna

2008-10-01

Water-soluble heavy metal salts injure health when they leach into water supplies. It is important that students who may later be employed in industries generating aqueous solutions of such salts are aware of the methods that can be used to recover the metal salt or transform it to non-health threatening products. The research was in the management of small quantities of hazardous wastes, such as are generated in school, college, and university teaching laboratories; in research laboratories; in industrial quality control and testing laboratories; and in small industries. Methods for the recovery of silver, nickel, and cobalt salts from relatively small volumes of aqueous solutions of their soluble salts were developed and tested. Where it was not practical to recover the metal salt, the practice has been to convert it to a water-insoluble salt, often the sulfide. This requires the use of highly toxic reagents. It was found that a number of heavy metal salts can be precipitated as the silicates, returning them to the form in which they are found in the natural ore. These salts show similar solubility properties to the sulfides in neutral, acidic, and basic aqueous solutions. The work has determined the conditions, quantities, and solution acidity that result in the most effective precipitation of the heavy metal salt. The concentration of the metal ions remaining in solution was measured by AA and ICP spectrometry. Specific methods have been developed for the conversion of salts of mercury and chromium to nonsoluble products.

Simultaneous measurement of lipid and aqueous layers of tear film using optical coherence tomography and statistical decision theory

NASA Astrophysics Data System (ADS)

Huang, Jinxin; Clarkson, Eric; Kupinski, Matthew; Rolland, Jannick P.

2014-03-01

The prevalence of Dry Eye Disease (DED) in the USA is approximately 40 million in aging adults with about $3.8 billion economic burden. However, a comprehensive understanding of tear film dynamics, which is the prerequisite to advance the management of DED, is yet to be realized. To extend our understanding of tear film dynamics, we investigate the simultaneous estimation of the lipid and aqueous layers thicknesses with the combination of optical coherence tomography (OCT) and statistical decision theory. In specific, we develop a mathematical model for Fourier-domain OCT where we take into account the different statistical processes associated with the imaging chain. We formulate the first-order and second-order statistical quantities of the output of the OCT system, which can generate some simulated OCT spectra. A tear film model, which includes a lipid and aqueous layer on top of a rough corneal surface, is the object being imaged. Then we further implement a Maximum-likelihood (ML) estimator to interpret the simulated OCT data to estimate the thicknesses of both layers of the tear film. Results show that an axial resolution of 1 μm allows estimates down to nanometers scale. We use the root mean square error of the estimates as a metric to evaluate the system parameters, such as the tradeoff between the imaging speed and the precision of estimation. This framework further provides the theoretical basics to optimize the imaging setup for a specific thickness estimation task.

Removal of heavy metal ions from aqueous solution using Fe3O4-SiO2-poly(1,2-diaminobenzene) core-shell sub-micron particles.

PubMed

Zhang, Fan; Lan, Jing; Zhao, Zongshan; Yang, Ye; Tan, Ruiqin; Song, Weijie

2012-12-01

In this work, Fe(3)O(4)-SiO(2)-poly(1,2-diaminobenzene) sub-micron particles (FSPs) with high saturated magnetization of ∼60-70 emu/g were developed and utilized for the removal of As(III), Cu(II), and Cr(III) ions from aqueous solution. The isothermal results fitted well with the Freundlich model and the kinetic results fitted well with the two-site pseudo-second-order model, which indicated that multilayer adsorption of As(III), Cu(II), and Cr(III) ions on FSPs occurred at two sites with different energy of adsorption. The maximum adsorption capacities followed the order of As(III) (84±5 mg/g, pH=6.0)>Cr(III) (77±3 mg/g, pH=5.3)>Cu(II) (65±3 mg/g, pH=6.0). And the chelating interaction was considered as the main adsorption mechanism. The as-prepared materials were chemically stable with low leaching of Fe (≤1.7 wt.%) and poly(1,2-diaminobenzene) (≤4.9 wt.%) in tap water, sea water, and acidic/basic solutions. These metal-loaded FSPs could be easily recovered from aqueous solutions using a permanent magnet within 20s. They could also be easily regenerated with acid. The present work indicates that the FSPs are promising for removal of heavy metal ions in field application. Copyright © 2012 Elsevier Inc. All rights reserved.

Computing gas solubility in reservoir waters for environmental chemistry applications: the role of satellite observations

NASA Astrophysics Data System (ADS)

Rosa, R.; Lima, I.; Ramos, F.; Bambace, L.; Assireu, A.; Stech, J.; Novo, E.; Lorenzeti, L.

Atmospheric greenhouse gases concentration has increased during the past centuries basically due to biogenic and pyrogenic anthopogenic emissions Recent investigations have shown that gas emission methane as an important example from tropical hydroelectric reservoirs may comprise a considerable fraction of the total anthropogenic bulk In order to evaluate the concentration of gases of potential importance in environmental chemistry the solubility of such gases have been collected and converted into a uniform format using the Henry s law which states that the solubility of a gas in a liquid is directly proportional to its partial pressure However the Henry s law can be derived as a function of temperature density molar mixing ratio in the aqueous phase and molar mass of water In this paper we show that due to the complex temperature variation and water composition measured in brazilian tropical reservoirs as Serra da Mesa and Manso expressive secular variation on the traditional solubility constants concentration of a species in the aqueous phase by the partial pressure of that species in the gas phase can change in a rate of approximately 30 in 6 decades This estimation comes from a computational analysis of temperature variation measured during 6 months in Serra da Mesa and Manso reservoirs taking into account a simulated density and molar mass variation of the aqueous composition in these environments As an important global change issue from this preliminary analysis we discuss its role in the current estimations on the concentration emission rates

Evaluating belinjau (Gnetum gnemon L.) seed flour quality as a base for development of novel food products and food formulations.

PubMed

Bhat, Rajeev; binti Yahya, Nabilah

2014-08-01

Belinjau (Gnetum gnemon L.) seed flour was evaluated for nutritional composition, antioxidant activity and functional properties. Seed flour was found to be rich in protein (19.0g/100g), crude fibre (8.66g/100g), carbohydrates (64.1%), total dietary fibre (14.5%) and encompassed adequate amounts of essential amino acids, fatty acids and minerals. Antioxidant compounds such as total phenols (15.1 and 12.6mgGAE/100g), tannins (35.6 and 16.1mgCE/100g) and flavonoids (709 and 81.6mgCEQ/100g) were higher in ethanolic extracts over aqueous extracts, respectively. Inhibition of DPPH was high in ethanol extracts (48.9%) compared to aqueous extracts (19.7%), whereas aqueous extracts showed a higher FRAP value compared to ethanol extracts (0.98 and 0.61mmolFe(II)/100g, respectively). Results on functional properties revealed acceptable water and oil absorption capacities (5.51 and 1.98g/g, respectively), emulsion capacity and stability (15.3% and 6.90%, respectively), and foaming capacity (5.78%). FTIR spectral analysis showed seed flour to encompass major functional groups such as: amines, amides, amino acids, polysaccharides, carboxylic acids, esters and lipids. As belinjau seed flour possesses a rich nutraceutical value, it has high potential to be used as a basic raw material to develop new low cost nutritious functional foods. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of aqueous extract of Hibiscus sabdariffa on the renin-angiotensin-aldosterone system of Nigerians with mild to moderate essential hypertension: A comparative study with lisinopril

PubMed Central

Nwachukwu, Daniel Chukwu; Aneke, Eddy Ikemefuna; Obika, Leonard Fidelis; Nwachukwu, Nkiru Zuada

2015-01-01

Objectives: The present study investigated the effects of aqueous extract of Hibiscus sabdariffa (HS) on the three basic components of renin-angiotensin-aldosterone system: Plasma renin, serum angiotensin-converting enzyme (ACE), and plasma aldosterone (PA) in mild to moderate essential hypertensive Nigerians and compared with that of lisinopril, an ACE inhibitor. Materials and Methods: A double-blind controlled randomized clinical study was used. Seventy-eight newly diagnosed but untreated mild to moderate hypertensive subjects attending Medical Outpatients Clinic of Enugu State University Teaching Hospital, Enugu were recruited for the study. Those in Group A received placebo (150 mg/kg/day), Group B were given lisinopril (10 mg once daily) while those in Group C received aqueous extract of HS (150 mg/kg/day). After 4 weeks of treatment, the levels of plasma renin, serum ACE, and PA were determined. Results: HS and lisinopril significantly (P < 0.001) reduced PA compared to placebo by 32.06% and 30.01%, respectively. Their effects on serum ACE and plasma renin activity (PRA) were not significant compared to placebo; they reduced ACE by 6.63% and 5.67% but increased plasma PRA by 2.77% and 5.36%, respectively. Conclusion: HS reduced serum ACE and PA in mild to moderate hypertensive Nigerians with equal efficacy as lisinopril. These actions are possibly due to the presence of anthocyanins in the extract. PMID:26600645

pH-Dependence of Binding Constants and Desorption Rates of Phosphonate- and Hydroxamate-Anchored [Ru(bpy)3]2+ on TiO2 and WO3.

PubMed

Esarey, Samuel L; Bartlett, Bart M

2018-04-17

The binding constants and rate constants for desorption of the modified molecular dye [Ru(bpy) 3 ] 2+ anchored by either phosphonate or hydroxamate on the bipyridine ligand to anatase TiO 2 and WO 3 have been measured. In aqueous media at pH 1-10, repulsive electrostatic interactions between the negatively charged anchor and the negatively charged surface govern phosphonate desorption under neutral and basic conditions for TiO 2 anatase due to the high acidity of phosphonic acid (p K a,4 = 5.1). In contrast, the lower acidity of hydroxamate (p K a,1 = 6.5, p K a,2 = 9.1) leads to little change in adsorption/desorption properties as a function of pH from 1 to 7. The binding constant for hydroxamate is 10 3 in water, independent of pH in this range. These results are true for WO 3 as well, but are not reported at pH > 4 due to its Arrhenius acidity. Kinetics for desorption as a function of pH are reported, with a proposed mechanism for phosphonate desorption at high pH being the electrostatic repulsion of negative charges between the surface and the anionic anchor. Further, the hydroxamic acid anchor itself is likely the site of quasi-reversible redox activity in [Ru(bpy) 2 (2,2'-bpy-4,4'-(C(O)N(OH)) 2 )] 2+ , which does not lead to any measurable deterioration of the complex within 2 h of dark cyclic voltammogram scans in aqueous media. These results posit phosphonate as the preferred anchoring group under acidic conditions and hydroxamate for neutral/basic conditions.

The Secondary Structure of Human Hageman Factor (Factor XII) and its Alteration by Activating Agents

PubMed Central

McMillin, Carl R.; Saito, Hidehiko; Ratnoff, Oscar D.; Walton, Alan G.

1974-01-01

Hageman factor (factor XII) is activated by exposure to surfaces such as glass or by solutions of certain compounds, notably ellagic acid. Changes in the structure of Hageman factor accompanying activation have been examined in this study by circular dichroism spectroscopy. The spectrum of unactivated Hageman factor in aqueous solutions suggests that its conformation is mainly aperiodic. Various perturbants altered the conformation of Hageman factor in differing ways, demonstrating the sensitivity of Hageman factor to its environment. After activation of Hageman factor with solutions of ellagic acid, a negative trough appeared in the region of the circular dichroism spectrum commonly assigned to tyrosine residues, along with other minor changes in the peptide spectral region. Some of these changes are similar to changes that occurred upon partial neutralization of the basic residues at alkali pH. Activation of Hageman factor by adsorption to quartz surfaces (in an aqueous environment) also produced changes similar to those in the ellagic acid-activated Hageman factor, including the negative ellipticity in the tyrosine region. These observations suggest that the activation process may be related to a change in status of some of the basic amino acid residues, coupled with a specific change in the environment of some tyrosine residues. The importance of these changes during the activation process remains to be determined. The sensitivity of Hageman factor to its environment is consistent with the view that the initiation of clotting by exposure of plasma to appropriate agents is brought about by alterations in the conformation of Hageman factor that occur in the apparent absence of Fletcher factor or other recognized clotting factors. Images PMID:4373492

Mechanistic and Kinetic Study of Singlet O2 Oxidation of Methionine by On-Line Electrospray Ionization Mass Spectrometry.

PubMed

Liu, Fangwei; Lu, Wenchao; Yin, Xunlong; Liu, Jianbo

2016-01-01

We report a reaction apparatus developed to monitor singlet oxygen ((1)O2) reactions in solution using on-line ESI mass spectrometry and spectroscopy measurements. (1)O2 was generated in the gas phase by the reaction of H2O2 with Cl2, detected by its emission at 1270 nm, and bubbled into aqueous solution continuously. (1)O2 concentrations in solution were linearly related to the emission intensities of airborne (1)O2, and their absolute scales were established based on a calibration using 9,10-anthracene dipropionate dianion as an (1)O2 trapping agent. Products from (1)O2 oxidation were monitored by UV-Vis absorption and positive/negative ESI mass spectra, and product structures were elucidated using collision-induced dissociation-tandem mass spectrometry. To suppress electrical discharge in negative ESI of aqueous solution, methanol was added to electrospray via in-spray solution mixing using theta-glass ESI emitters. Capitalizing on this apparatus, the reaction of (1)O2 with methionine was investigated. We have identified methionine oxidation intermediates and products at different pH, and measured reaction rate constants. (1)O2 oxidation of methionine is mediated by persulfoxide in both acidic and basic solutions. Persulfoxide continues to react with another methionine, yielding methionine sulfoxide as end-product albeit with a much lower reaction rate in basic solution. Density functional theory was used to explore reaction potential energy surfaces and establish kinetic models, with solvation effects simulated using the polarized continuum model. Combined with our previous study of gas-phase methionine ions with (1)O2, evolution of methionine oxidation pathways at different ionization states and in different media is described.

SEPARATION OF RADIOACTIVE COLUMBIUM TRACER

DOEpatents

Glendenin, L.E.; Gest, H.

1958-08-26

A process is presented for the recovery of radioactive columbium from solutions containing such columbium together with radioactive tellurium. The columbium and tellurium values are separated from such solutions by means of an inorganic oxide carrier precipitate, such as MnO/sub 2/. This oxide carrier precipitate and its associated columbium and telluriuan values are then dissolved in an aqueous acidic solution and nonradioactive tellurium, in an ionic form, is then introduced into such solution, for example in the form of H/sub 2/TeO/sub 3/. The tellurium present in the solution is then reduced to the elemental state and precipitates, and is then separated from the supernataat solution. A basic acetate precipitate is formed in the supernatant and carries the remaining columblum values therefrom. After separation, this basic ferric acetate precipitate is dissolved, and the ferric ions are removed by means of an organic solvent extraction process utilizing ether. The remaining solution contains carrier-free columbium as its only metal ion.

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

Ertem, Mehmed Zahid; Suna, Yuki; Himeda, Yuichiro

Pentamethylcyclopentadienyl iridium (Cp*Ir) complexes with bidentate ligands consisting of a pyridine ring and an electron-rich diazole ring were prepared. Their catalytic activity towards CO 2 hydrogenation in 2.0 M KHCO 3 aqueous solutions (pH 8.5) at 50 °C, under 1.0 MPa CO 2/H 2 (1:1) have been reported as an alternative to photo- and electrochemical CO 2 reduction. Bidentate ligands incorporating an electron-rich diazole ring improved the catalytic performance of the Ir complexes compared to the bipyridine ligand. Complexes 2, 4 and 6, possessing both a hydroxy group and an uncoordinated NH group, which are proton-responsive and capable of generatingmore » pendent-bases in basic media, recorded high initial TOF values of 1300 h -1, 1550 h -1 and 2000 h -1, respectively. Here, spectroscopic and computational investigations revealed that the reversible deprotonation changes the electronic properties of the complexes and causes interactions between pendent base and substrate and/or solvent water molecules, resulting in the high catalytic performance in basic media.« less

Effect of synthesis parameters on polymethacrylic acid xerogel structures and equilibrium swelling

NASA Astrophysics Data System (ADS)

Panić, V.; Jovanović, J.; Adnadjević, B.; Velicković, S.

2009-09-01

Hydrogels based on crosslinked polymethacrylic acid were synthesized via free-radical polymerization in aqueous solution, using N,N'-methylene bisacrylamide as a crosslinking agent and 2,2'-azobis-[2-(2-imidazolin-2-yl)propane] dihydrochloride as an initiator. The influence of the reaction parameters (the neutralization degree of methacrylic acid and the initial monomer concentration) on the equilibrium swelling degree, the swelling kinetic parameters and the basic structural properties of xerogels was investigated. The change of synthesis parameters leads to the change of the basic structural parameters of xerogel, as well as the equilibrium swelling degree and the initial swelling rate of the hydrogels. It is found that there are power form relationships between the equilibrium swelling degree, the initial swelling rate and the structural xerogel’s properties and the change of the neutralization degree of monomer, i.e. the monomer concentration. The examined correlations proved that the crosslinking density is the crucial parameter which determines all the other investigated structural and swelling parameters.

Pozzolanic filtration/solidification of radionuclides in nuclear reactor cooling water

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

Englehardt, J.D.; Peng, C.

1995-12-31

Laboratory studies to investigate the feasibility of one- and two-step processes for precipitation/coprecipitating radionuclides from nuclear reactor cooling water, filtering with pozzolanic filter aid, and solidifying, are reported in this paper. In the one-step process, ferrocyanide salt and excess lime are added ahead of the filter, and the resulting filter cake solidifies by a pozzolanic reaction. The two-step process involves addition of solidifying agents subsequent to filtration. It was found that high surface area diatomaceous synthetic calcium silicate powders, sold commercially as functional fillers and carriers, adsorb nickel isotopes from solution at neutral and slightly basic pH. Addition of themore » silicates to cooling water allowed removal of the tested metal isotopes (nickel, iron, manganese, cobalt, and cesium) simultaneously at neutral to slightly basic pH. Lime to diatomite ratio was the most influential characteristic of composition on final strength tested, with higher lime ratios giving higher strength. Diatomaceous earth filter aids manufactured without sodium fluxes exhibited higher pozzolanic activity. Pozzolanic filter cake solidified with sodium silicate and a ratio of 0.45 parts lime to 1 part diatomite had compressive strength ranging from 470 to 595 psi at a 90% confidence level. Leachability indices of all tested metals in the solidified waste were acceptable. In light of the typical requirement of removing iron and desirability of control over process pH, a two-step process involving addition of Portland cement to the filter cake may be most generally applicable.« less

Degradation Investigation of Selected Taste and Odor Compounds by a UV/Chlorine Advanced Oxidation Process

PubMed Central

Fang, Jingyun; Liu, Jiajian; Shang, Chii; Fan, Chihhao

2018-01-01

Taste- and odor-causing (T&O) compounds are a major concern in drinking water treatment plants due to their negative impacts on the safety and palatability of water supply. This study explored the degradation kinetics and radical chemistry of four often-detected T&O compounds, geosmin (GSM), 2-methylisoborneol (MIB), benzothiazole (BT), and 2-isobutyl-3-methoxypyrazine (IBMP), in the ultraviolet/chlorine (UV/chlorine) advanced oxidation process. All experiments were carried out in a 700 mL photoreactor and the process effectively degraded the investigated T&O compounds in a slightly acidic environment. The degradation of T&O decreased with increasing pH but slightly with decreasing chlorine dosage. When the pH increased from 6 to 8, the pseudo-first-order rate constants of GSM, MIB, BT, and IBMP dropped from 2.84 × 10−3, 2.29 × 10−3, 3.64 × 10−3, and 2.76 × 10−3 s−1 to 3.77 × 10−4, 2.64 × 10−4, 6.48 × 10−4, and 6.40 × 10−4 s−1, respectively. Increasing the chlorine dosage slightly accelerated the degradation of the investigated T&O compounds, but excessive hypochlorous acid and hypochlorite scavenged the HO• radicals and reactive chlorine species (RCS). Generally, HO• primarily contributed to the degradation of all of the investigated T&O compounds as compared to RCS. The degradation by RCS was found to be structurally selective. RCS could not degrade GSM, but contributed to the degradation of MIB, BT, and IBMP. The results confirmed that the proposed oxidation process effectively degraded typical T&O compounds in aqueous phase. PMID:29414884

Classifying organic materials by oxygen-to-carbon elemental ratio to predict the activation regime of cloud condensation nuclei (CCN)

NASA Astrophysics Data System (ADS)

Kuwata, M.; Shao, W.; Lebouteiller, R.; Martin, S. T.

2012-12-01

The governing highly soluble, slightly soluble, or insoluble activation regime of organic compounds as cloud condensation nuclei (CCN) was examined as a function of oxygen-to-carbon elemental ratio (O : C). New data were collected for adipic, pimelic, suberic, azelaic and pinonic acids. Secondary organic materials (SOMs) produced by α-pinene ozonolysis and isoprene photo-oxidation were also included in the analysis. The saturation concentrations C of the organic compounds in aqueous solutions served as the key parameter for delineating regimes of CCN activation, and the values of C were tightly correlated to the O : C ratios. The highly soluble, slightly soluble, and insoluble regimes of CCN activation were found to correspond to ranges of [O : C] > 0.6, 0.2 < [O : C] < 0.6, and [O : C] < 0.2, respectively. These classifications were evaluated against CCN activation data of isoprene-derived SOM (O : C = 0.69-0.72) and α-pinene-derived SOM (O : C = 0.38-0.48). Isoprene-derived SOM had highly soluble activation behavior, consistent with its high O : C ratio. For α-pinene-derived SOM, although CCN activation can be modeled as a highly soluble mechanism, this behavior was not predicted by the O : C ratio, for which a slightly soluble mechanism was anticipated. Complexity in chemical composition, resulting in continuous water uptake and the absence of a deliquescence transition that can thermodynamically limit CCN activation, might explain the differences of α-pinene-derived SOM compared to the behavior of pure organic compounds. The present results suggest that atmospheric particles dominated by hydrocarbon-like organic components do not activate (i.e. insoluble regime) whereas those dominated by oxygenated organic components activate (i.e. highly soluble regime).

Classifying organic materials by oxygen-to-carbon elemental ratio to predict the activation regime of Cloud Condensation Nuclei (CCN)

NASA Astrophysics Data System (ADS)

Kuwata, M.; Shao, W.; Lebouteiller, R.; Martin, S. T.

2013-05-01

The governing highly soluble, slightly soluble, or insoluble activation regime of organic compounds as cloud condensation nuclei (CCN) was examined as a function of oxygen-to-carbon elemental ratio (O : C). New data were collected for adipic, pimelic, suberic, azelaic, and pinonic acids. Secondary organic materials (SOMs) produced by α-pinene ozonolysis and isoprene photo-oxidation were also included in the analysis. The saturation concentrations C of the organic compounds in aqueous solutions served as the key parameter for delineating regimes of CCN activation, and the values of C were tightly correlated to the O : C ratios. The highly soluble, slightly soluble, and insoluble regimes of CCN activation were found to correspond to ranges of [O : C] > 0.6, 0.2 < [O : C] < 0.6, and [O : C] < 0.2, respectively. These classifications were evaluated against CCN activation data of isoprene-derived SOM (O : C = 0.69-0.72) and α-pinene-derived SOM (O : C = 0.38-0.48). Isoprene-derived SOM had highly soluble activation behavior, consistent with its high O : C ratio. For α-pinene-derived SOM, although CCN activation can be modeled as a highly soluble mechanism, this behavior was not predicted by the O : C ratio, for which a slightly soluble mechanism was anticipated. Complexity in chemical composition, resulting in continuous water uptake and the absence of a deliquescence transition that can thermodynamically limit CCN activation, might explain the difference in the behavior of α-pinene-derived SOM compared to that of pure organic compounds. The present results suggest that atmospheric particles dominated by hydrocarbon-like organic components do not activate (i.e., insoluble regime) whereas those dominated by oxygenated organic components activate (i.e., highly soluble regime) for typical atmospheric cloud life cycles.

Ground-water movement and effects of coal strip mining on water quality of high-wall lakes and aquifers in the Macon-Huntsville area, north- central Missouri

USGS Publications Warehouse

Hall, D.C.; Davis, R.E.

1986-01-01

Glacial drift and Pennsylvanian bedrock were mixed together forming spoil during pre-reclamation strip mining for coal in north-central Missouri. This restructuring of the land increases the porosity of the material, and increases aqueous concentrations of many dissolved constituents. Median sodium and bicarbonate concentrations were slightly greater, calcium 5 times greater, magnesium 6 times greater, manganese 15 times greater, iron 19 times greater, and sulfate 24 times greater in water from spoil than in water from glacial drift. Median potassium concentrations were slightly greater, and chloride concentrations were two times greater in water from glacial drift than in water from spoil. Water types in glacial drift and bedrock were mostly sodium bicarbonate and calcium bicarbonate; in spoil and lakes in the spoil, the water types were mostly calcium sulfate. Median pH values in water from spoil were 6.6, as compared to 7.4 in water from glacial drift and 9.0 in water from bedrock. Neutralization of acid by carbonate rocks causes the moderate pH values in water from spoil; a carbonate system closed to the atmosphere may result in alkaline pH values in bedrock. Transmissivities generally are greatest for spoil, and decrease in the following order: alluvium, glacial drift, and bedrock. Recharge to spoil is from precipitation, lateral flow from glacial drift, and lateral and vertical flow from bedrock. The rate of recharge to the aquifers is unknown, but probably is small. Groundwater discharge from the glacial drift, bedrock, and spoil is to alluvium. The direction of flow generally was from high-wall lakes in the spoil toward East Fork Little Chariton River or South Fork Claybank Creek. Significant differences (95% confidence level) in values and concentrations of aqueous constituents between spoil areas mined at different times (1940, 1952, and 1968) were obtained for pH, calcium, magnesium, manganese, sulfate, chloride, and dissolved solids, but not for iron. These differences are attributed to local variations in the geohydrologic system rather than spoil age. (Lantz-PTT)

Photo-degradation of basic green 1 and basic red 46 dyes in their binary solution by La2O3-Al2O3nanocomposite using first-order derivative spectra and experimental design methodology.

PubMed

Fahimirad, Bahareh; Asghari, Alireza; Rajabi, Maryam

2017-05-15

In this work, the lanthanum oxide-aluminum oxide (La 2 O 3 -Al 2 O 3 ) nanocomposite is introduced as an efficient photocatalyst for the photo-degradation of the dyes basic green 1 (BG1) and basic red 46 (BR46) in their binary aqueous solution under the UV light irradiation. The properties of this catalyst are determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), and UV-visible spectrophotometry. The first-order derivative spectra are used for the simultaneous analysis of the dyes in their binary solution. The screening investigations indicate that five parameters including the catalyst dosage, concentration of the dyes, irradiation time, and solution pH have significant effects on the photo-degradation of the dyes. The effects of these variables together with their interactions in the photo-degradation of the dyes are studied using the Box-Behnken design (BBD). Under the optimum experimental conditions, obtained via the desirability function, the photo-catalytic activities of La 2 O 3 -Al 2 O 3 and pure Al 2 O 3 are also investigated. The results obtained show an enhancement in the photo-catalytic activity when La 2 O 3 nanoparticles are loaded on the surface of Al 2 O 3 nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

Sensitivity of predicted scaling and permeability in Enhanced Geothermal Systems to Thermodynamic Data and Activity Models

NASA Astrophysics Data System (ADS)

Hingerl, Ferdinand F.; Wagner, Thomas; Kulik, Dmitrii A.; Kosakowski, Georg; Driesner, Thomas; Thomsen, Kaj

2010-05-01

A consortium of research groups from ETH Zurich, EPF Lausanne, the Paul Scherrer Institut and the University of Bonn collaborates in a comprehensive program of basic research on key aspects of the Enhanced Geothermal Systems (EGSs). As part of this GEOTHERM project (www.geotherm.ethz.ch), we concentrate on the fundamental investigation of thermodynamic models suitable for describing fluid-rock interactions at geothermal conditions. Predictions of the fluid-rock interaction in EGS still face several major challenges. Slight variations in the input thermodynamic and kinetic parameters may result in significant differences in the predicted mineral solubilities and stable assemblage. Realistic modeling of mineral precipitation in turn has implications onto our understanding of the permeability evolution of the geothermal reservoir, as well as the scaling in technical installations. In order to reasonably model an EGS, thermodynamic databases and activity models must be tailored to geothermal conditions. We therefore implemented in GEMS code the Pitzer formalism, which is the standard model used for computing thermodynamic excess properties of brines at elevated temperatures and pressures. This model, however, depends on a vast amount of interaction parameters, which are to a substantial extend unknown. Furthermore, a high order polynomial temperature interpolation makes extrapolation unreliable if not impossible. As an alternative we additionally implemented the EUNIQUAC activity model. EUNIQUAC requires fewer empirical fit parameters (only binary interaction parameters needed) and uses simpler and more stable temperature and pressure extrapolations. This results in an increase in computation speed, which is of crucial importance when performing coupled long term simulations of geothermal reservoirs. To achieve better performance under geothermal conditions, we are currently partly reformulating EUNIQUAC and refitting the existing parameter set. First results of the Pitzer-EUNIQUAC benchmark applied to relevant aqueous solutions at elevated temperature, pressure and ionic strength will be presented.

Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC-ICP-MS.

PubMed

Ščančar, Janez; Berlinger, Balázs; Thomassen, Yngvar; Milačič, Radmila

2015-09-01

A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Linear gradient elution from 100% water to 100% 0.7 M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO4(2-) species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO4(2-), MoO4(2-) and WO4(2-) are present and were eluted in sharp chromatographic peaks, while VO4(3-) species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420 s, 320 to 370 s, 300 to 350 s and 240 to 360 s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02 ng Cr mL(-1)), molybdate (0.1 ng Mo mL(-1)), tungstate (0.1 ng W mL(-1)) and vanadate (0.2 ng V mL(-1)). The accuracy of analytical procedure for the determination of chromate was checked by analysis of CRM 545, Cr(VI) in welding dust loaded on a filter. Good agreement between determined and reported certified values was obtained. For molybdate, tungstate and vanadate the assessment of accuracy was performed by spiking welding fume filters. Good recoveries for all investigated species (98-101%) confirmed the accuracy of the analytical procedure. Copyright © 2015 Elsevier B.V. All rights reserved.

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

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

Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.

Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C 5Hmore » 8O 4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C 5) hydroxyl functionalization product (C 5H 8O 5) and a C 4 fragmentation product (C 4H 6O 3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.« less

Examination of the Behavior of Bismuth in Shallow-Level Hydrothermal Ore Systems: Constraints Based on Hydrothermal Experiments at 800°C and 100 MPa

NASA Astrophysics Data System (ADS)

Wilmot, M. S.; Candela, P. A.; Piccoli, P. M.; Simon, A. C.; McDonough, W. F.

2006-05-01

The partitioning of ore metals between melt and crystals affects the concentrations of these metals in an evolving ore fluid, and therefore the efficiency of their removal from the magma by hydrothermal processes. Some porphyry-type W-Mo deposits contain recoverable amounts of Bi, whereas others contain only trace amounts. In order to determine the magmatic controls on the ratio of Bi to other commodities in these and other deposits, we examined the partitioning behavior of bismuth between melt, minerals and aqueous phases. Hydrothermal experiments were performed by using externally heated cold seal vessels and employing a double capsule technique. Experiments contained 40 mg of Bishop Tuff glass (SiO2 = 74% ) and 40 mg of either magnetite or pyrrhotite. Bi was added as elemental Bi (< 1 mg). Two different aqueous solutions were used. Initially, the added aqueous phase comprised the solutes HCl, KCl and NaCl in a molar1:1:1 ratio, with a bulk salinity of 10 wt % NaCl eq. The aqueous phase for later experiments contained only the solutes KCl and NaCl in a 1:1 molar ratio. Pre-fractured quartz was added to the experiments to trap fluid inclusions at run PTX conditions. Experiments were performed in Au or Pt capsules held inside Rene 41 cold-seal vessels at 800°C and 100 MPa for durations of up to 36 hours. Analytical data have been collected from the run product solids by using an electron probe microanalyzer (major and trace elements) and laser ablation inductively coupled plasma mass spectrometry (trace elements). Bi in Mt is found in concentrations up to 100 ppm, with higher concentrations in runs where Po decomposed to form magnetite. The Bi concentration in the glass ranges up to 100 ppm. In the Po-bearing runs, data were only collected from Po grains in the experiments containing the HCl-free aqueous solution (the Po grains in the other experiments were too small to analyze). Pyrrhotite contained 10-20 ppm Bi, whereas the glass contained 5-10 ppm. Preliminary Nernst- type partition coefficients for Bi between Mt and melt and Po and melt are approximately 5 and 2, respectively. These data reveal that Bi is only slightly compatible in Mt and Po, and that the Po/melt partition coefficient for Bi is much lower than for Cu, Ag and Au, and is comparable to Mn and Zn. Additional experiments are in progress to more compare the partitioning of Bi with that of W and Mo.

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

DOE PAGES

Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.; ...

2017-12-05

Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C 5Hmore » 8O 4) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C 5) hydroxyl functionalization product (C 5H 8O 5) and a C 4 fragmentation product (C 4H 6O 3). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.« less

Removal of basic dye (methylene blue) from wastewaters utilizing beer brewery waste.

PubMed

Tsai, Wen-Tien; Hsu, Hsin-Chieh; Su, Ting-Yi; Lin, Keng-Yu; Lin, Chien-Ming

2008-06-15

In the work, the beer brewery waste has been shown to be a low-cost adsorbent for the removal of basic dye from the aqueous solution as compared to its precursor (i.e., diatomite) based on its physical and chemical characterizations including surface area, pore volume, scanning electron microscopy (SEM), and non-mineral elemental analyses. The pore properties of this waste were significantly larger than those of its raw material, reflecting that the trapped organic matrices contained in the waste probably provided additional adsorption sites and/or adsorption area. The results of preliminary adsorption kinetics showed that the diatomite waste could be directly used as a potential adsorbent for removal of methylene blue on the basis of its adsorption-biosorption mechanisms. The adsorption parameters thus obtained from the pseudo-second-order model were in accordance with their pore properties. From the results of adsorption isotherm at 298 K and the applicability examinations in treating industrial wastewater containing basic dye, it was further found that the adsorption capacities of diatomite waste were superior to those of diatomite, which were also in good agreement with their corresponding physical properties. From the results mentioned above, it is feasible to utilize the food-processing waste for removing dye from the industrial dying wastewater.

Depolarization of an Ultrashort Pulse in a Disordered Ensemble of Mie Particles

NASA Astrophysics Data System (ADS)

Gorodnichev, E. E.; Ivliev, S. V.; Kuzovlev, A. I.; Rogozkin, D. B.

2017-12-01

We study propagation of an ultrashort pulse of polarized light through a turbid medium with the Reynolds-McCormick phase function. Within the basic mode approach to the vector radiative transfer equation, the temporal profile of the degree of polarization is calculated analytically with the use of the small-angle approximation. The degree of polarization is shown to be described by the self-similar dependence on some combination of the transport scattering coefficient, the temporal delay and the sample thickness. Our results are in excellent agreement with the data of numerical simulations carried out previously for aqueous suspension of polystyrene microspheres.

Colorimetric Detection of Thiophenol Based on a Phenolphthalein Derivative and Its Application as a Molecular Logic Gate.

PubMed

Kim, Hyunsu; Swamy, K M K; Kwon, Nahyun; Kim, Yonghee; Park, Sungsu; Yoon, Juyoung

2017-07-05

A phenolphthalein-based colorimetric probe bearing a dinitrobenzene group is reported as a thiophenol (PhSH)-selective chemodosimeter. PhSH can react with chemodosimeter 1 to afford phenolphthalein. The addition of PhSH to the aqueous solution of 1 followed by a change in pH of the resulting solution to basic induces a selective color change from colorless to pink. Furthermore, using PhSH and base as inputs and color change of 1 by naked eye as an output, leads to the construction of an AND logic gate. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

TREATMENT FOR IMPROVING THE OPERATION OF STRONG BASE ANION EXCHANGE RESINS

DOEpatents

Stevenson, P.C.

1960-11-29

A process is offered for improving quaternary ammonium type strongly basic anion exchange resins so that centain zinc and cadmium residues, which normally stick to and "poison" this type of resin, can be removed by elution. Specifically, the resin as obtained commercially is treated with an aqueous solution of sodium hydroxide of about 1 to 4 M concentration by heating therein and periodically adding small amounts of oxidizing agent selected from hydrogen peroxide, sodium peroxide and hypochlorite. Zinc and cadmium values may then be adsorbed onto the resin from a 0.1 to 3 M HCl and thereafter eluted therefrom with very dilute HCl solutions.

Photolithography of Dithiocarbamate-Anchored Monolayers and Polymers on Gold

PubMed Central

Leonov, Alexei P.; Wei, Alexander

2011-01-01

Dithiocarbamate (DTC)-anchored monolayers and polymers were investigated as positive resists for UV photolithography on planar and roughened Au surfaces. DTCs were formed in situ by the condensation of CS2 with monovalent or polyvalent amines such as linear polyethyleneimine (PEI) under mildly basic aqueous conditions, just prior to surface passivation. The robust adsorption of the polyvalent PEI-DTC to Au surfaces supported high levels of resistance to photoablation, providing opportunities to generate thin films with gradient functionality. Treatment of photopatterned substrates with alkanethiols produced binary coatings, enabling a direct visual comparison of DTC- and thiol-passivated surfaces against chemically induced corrosion using confocal microscopy. PMID:21894240

Design and optimization of disintegrating pellets of MCC by non-aqueous extrusion process using statistical tools.

PubMed

Gurram, Rajesh Kumar; Gandra, Suchithra; Shastri, Nalini R

2016-03-10

The objective of the study was to design and optimize a disintegrating pellet formulation of microcrystalline cellulose by non-aqueous extrusion process for a water sensitive drug using various statistical tools. Aspirin was used as a model drug. Disintegrating matrix pellets of aspirin using propylene glycol as a non-aqueous granulation liquid and croscarmellose as a disintegrant was developed. Plackett-Burman design was initially conducted to screen and identify the significant factors. Final optimization of formula was performed by response surface methodology using a central composite design. The critical attributes of the pellet dosage forms (dependent variables); disintegration time, sphericity and yield were predicted with adequate accuracy based on the regression model. Pareto charts and contour charts were studied to understand the influence of factors and predict the responses. A design space was constructed to meet the desirable targets of the responses in terms of disintegration time <5min, maximum yield, sphericity >0.95 and friability <1.7%. The optimized matrix pellets were enteric coated using Eudragit L 100. The drug release from the enteric coated pellets after 30min in the basic media was ~93% when compared to ~77% from the marketed pellets. The delayed release pellets stored at 25°C/60% RH were stable for a period of 10mo. In conclusion, it can be stated that the developed process for disintegrating pellets using non-aqueous granulating agents can be used as an alternative technique for various water sensitive drugs, circumventing the application of volatile organic solvents in conventional drug layering on inert cores. The scope of this study can be further extended to hydrophobic drugs, which may benefit from the rapid disintegration property and the use of various hydrophilic excipients used in the optimized pellet formulation to enhance dissolution and in turn improve bioavailability. Copyright © 2016 Elsevier B.V. All rights reserved.

Aqueous Cation-Amide Binding: Free Energies and IR Spectral Signatures by Ab Initio Molecular Dynamics

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

Pluharova, Eva; Baer, Marcel D.; Mundy, Christopher J.

2014-07-03

Understanding specific ion effects on proteins remains a considerable challenge. N-methylacetamide serves as a useful proxy for the protein backbone that can be well characterized both experimentally and theoretically. The spectroscopic signatures in the amide I band reflecting the strength of the interaction of alkali cations and alkali earth dications with the carbonyl group remain difficult to assign and controversial to interpret. Herein, we directly compute the IR shifts corresponding to the binding of either sodium or calcium to aqueous N-methylacetamide using ab initio molecular dynamics simulations. We show that the two cations interact with aqueous N-methylacetamide with different affinitiesmore » and in different geometries. Since sodium exhibits a weak interaction with the carbonyl group, the resulting amide I band is similar to an unperturbed carbonyl group undergoing aqueous solvation. In contrast, the stronger calcium binding results in a clear IR shift with respect to N-methylacetamide in pure water. Support from the Czech Ministry of Education (grant LH12001) is gratefully acknowledged. EP thanks the International Max-Planck Research School for support and the Alternative Sponsored Fellowship program at Pacific Northwest National Laboratory (PNNL). PJ acknowledges the Praemium Academie award from the Academy of Sciences. Calculations of the free energy profiles were made possible through generous allocation of computer time from the North-German Supercomputing Alliance (HLRN). Calculations of vibrational spectra were performed in part using the computational resources in the National Energy Research Supercomputing Center (NERSC) at Lawrence Berkeley National Laboratory. This work was supported by National Science Foundation grant CHE-0431312. CJM is supported by the U.S. Department of Energy`s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. PNNL is operated for the Department of Energy by Battelle. MDB is grateful for the support of the Linus Pauling Distinguished Postdoctoral Fellowship Program at PNNL.« less

An experimental measurement of galactic cosmic radiation dose in conventional aircraft between San Francisco and London compared to theoretical values for conventional and supersonic aircraft

NASA Technical Reports Server (NTRS)

Wallace, R.; Boyer, M. F.

1972-01-01

These direct measurements are in fair agreement with computations made using a program which considers both basic cosmic ray atmospheric physics and the focusing effect of the earth's magnetic field. These measurements also agree with those made at supersonic jet aircraft altitudes in Rb-57 aircraft. It is concluded that experiments and theory show that the doses received at conventional jet aircraft altitudes are slightly higher than those encountered in supersonic flights at much higher altitudes.

Most science spared big budget bite

NASA Astrophysics Data System (ADS)

Richman, Barbara T.

Most science budgets emerged unscathed from President Ronald Reagan's fiscal 1983 budget proposal. Total funding for research and development came out slightly ahead of inflation, as did funding for basic research (Eos, February 16, p. 162). The National Science Foundation (NSF) edged past the projected 7.3% inflation rate for 1982, and the National Aeronautics and Space Administration (NASA) budget is to be increased by 10.6%. However, the U.S. Geological Survey (USGS) is budgeted for a 4.2% increase in funding, and the National Oceanic and Atmospheric Administration (NOAA) will take an 8.3% cut.

The development of science during this century

NASA Astrophysics Data System (ADS)

Weisskopf, V. F.

1993-12-01

This is a slightly revised version of a talk delivered at the meeting of the American Association for the Advancement of Science, in Boston, on 14 February 1993, and at a CERN Colloquium, on 5 August 1993, entitled 'Science -yesterday, today and tomorrow'. It describes the tremendous growth of scientific knowledge and insights acquired since the beginning of this century. The changes in the character, sociology and support, of science are discussed, including the growing predominance of American science and the recent trend away from basic science towards applied research.

Influence of ionic strength, anions, cations, and natural organic matter on the adsorption of pharmaceuticals to silica.

PubMed

Bui, Tung Xuan; Choi, Heechul

2010-08-01

The adsorption of four wide-use pharmaceuticals (carbamazepine, diclofenac, ibuprofen, and ketoprofen) onto a porous silica was investigated under varied ionic strengths, different anions, divalent cations (Ca(2+) and Mg(2+)), trivalent cations (Al(3+) and Fe(3+)), and natural organic matter (NOM). The experiments demonstrated that at a given pH the adsorption was most affected by ionic strength, trivalent cations, and properties of pharmaceuticals. The increase of ionic strength resulted in an increase in the adsorption of ketoprofen, but a decrease in the adsorption of carbamazepine. Trivalent metal cations made intense increases in the adsorption of three acidic pharmaceuticals, which could be due to the formation of inner-sphere complex of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the adsorption of carbamazepine was not affected by divalent and trivalent cations, whereas the adsorption of diclofenac was solely impacted by the presence of Al(3+). Moreover, divalent cations at low concentration could slightly enhance the adsorption of ibuprofen and ketoprofen, whereas NOM caused a reduction in the adsorption of the tested pharmaceuticals except for diclofenac. These results suggest that ionic strength, divalent cations, trivalent cations, and NOM are notable factors affecting the adsorption of pharmaceuticals and thus the ultimate fate of pharmaceuticals in the aqueous environment. Copyright 2010 Elsevier Ltd. All rights reserved.

Stability of carbon electrodes for aqueous lithium-air secondary batteries

NASA Astrophysics Data System (ADS)

Ohkuma, Hirokazu; Uechi, Ichiro; Matsui, Masaki; Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki

2014-01-01

The air electrode performance of various carbon materials, such as Ketjen black (KB), acetylene black (AB and AB-S), Vulcan XC-72R (VX), and vapor grown carbon fiber (VGCF) with and without La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) catalyst were examined in an aqueous solution of saturated LiOH with 10 M LiCl in the current density range 0.2-2.0 mA cm-2. The best performance for oxygen reduction and evolution reactions was observed for the KB electrode, which has the highest surface area among the carbon materials examined. A steady over-potential of 0.2 V was obtained for the oxygen reduction reaction using the KB electrode without the catalyst, while the over-potential was 0.15 V for KB with the LSCF catalyst at 2.0 mA cm-2. The over-potentials for the oxygen evolution reaction were slightly higher than those for the oxygen reduction reaction, and gradually increased with the polarization period. Analysis of the gas in the cell after polarization above 0.4 V revealed the evolution of a small amount of CO during the oxygen evolution reaction by the decomposition of carbon in the electrode. The amount of CO evolved was significantly decreased by the addition of LSCF to the carbon electrode.

Effects of single pulse energy on the properties of ceramic coating prepared by micro-arc oxidation on Ti alloy

NASA Astrophysics Data System (ADS)

Wang, Jun-Hua; Wang, Jin; Lu, Yan; Du, Mao-Hua; Han, Fu-Zhu

2015-01-01

The effects of single pulse energy on the properties of ceramic coating fabricated on a Ti-6Al-4V alloy via micro-arc oxidation (MAO) in aqueous solutions containing aluminate, phosphate, and some additives are investigated. The thickness, micro-hardness, surface and cross-sectional morphology, surface roughness, and compositions of the ceramic coating are studied using eddy current thickness meter, micro-hardness tester, JB-4C Precision Surface roughness meter, scanning electron microscopy (SEM) and X-ray diffraction (XRD). Single pulse energy remarkably influences the ceramic coating properties. The accumulative time of impulse width is an important parameter in the scientific and rational measurement of the film forming law of ceramic coating. The ceramic coating thickness approximately linearly increases with the cumulative time of impulse width. Larger impulse width resulted in higher single pulse energy, film forming rates and thicker ceramic coating thickness. The sizes of oxide particles, micro-pores and micro-cracks slightly increase with impulse width and single pulse energy. The main surface conversion products generated during MAO process in aqueous solutions containing aluminate are rutile TiO2, anatase TiO2, and a large amount of Al2TiO5. The effects of single pulse energy on the micro-hardness and phase composition of ceramic coating are not as evident as those of frequency and duty cycle.

Municipal wastewater spiramycin removal by conventional treatments and heterogeneous photocatalysis.

PubMed

Lofrano, G; Libralato, G; Casaburi, A; Siciliano, A; Iannece, P; Guida, M; Pucci, L; Dentice, E F; Carotenuto, M

2018-05-15

This study assessed the effects and removal options of the macrolide spiramycin, currently used for both in human and veterinary medicine- with a special focus on advanced oxidation processes based on heterogeneous TiO 2 _ assisted photocatalysis. Spiramycin real concentrations were investigated on a seasonal basis in a municipal wastewater treatment plant (up to 35μgL -1 ), while its removal kinetics were studied considering both aqueous solutions and real wastewater samples, including by-products toxicity assessment. High variability of spiramycin removal by activated sludge treatments (from 9% (wintertime) to >99.9% (summertime)) was observed on a seasonal basis. Preliminary results showed that a total spiramycin removal (>99.9%) is achieved with 0.1gL -1 of TiO 2 in aqueous solution after 80min. Integrated toxicity showed residual slight acute effects in the photocatalytic treated solutions, independently from the amount of TiO 2 used, and could be linked to the presence of intermediate compounds. Photolysis of wastewater samples collected after activated sludge treatment during summer season (SPY 5μgL -1 ) allowed a full SPY removal after 80min. When photocatalysis with 0.1gL -1 of TiO 2 was carried out in wastewater samples collected in winter season (SPY 30μgL -1 ) after AS treatment, SPY removal was up to 91% after 80min. Copyright © 2017 Elsevier B.V. All rights reserved.

Magnesite Step Growth Rates as a Function of the Aqueous Magnesium:Carbonate Ratio

DOE PAGES

Bracco, Jacquelyn N.; Stack, Andrew G.; Higgins, Steven R.

2014-10-01

Step velocities of monolayer-height steps on the (101 ⁻4) magnesite surface have been measured as functions of the aqueous magnesium-to-carbonate ratio and saturation index (SI) using a hydrothermal atomic force microscope (HAFM). At SI ≤ 1.9 and 80-90 °C, step velocities were found to be invariant with changes in the magnesium-to-carbonate ratio, an observation in contrast with standard models for growth and dissolution of ionically-bonded, multi-component crystals. However, at high saturation indices (SI = 2.15), step velocities displayed a ratio dependence, maximized at magnesium-to-carbonate ratios slightly greater than 1:1. Traditional affinity-based models were unable to describe growth rates at themore » higher saturation index. Step velocities also could not be modeled solely through nucleation of kink sites, in contrast to other minerals whose bonding between constituent ions is also dominantly ionic in nature, such as calcite and barite. Instead, they could be described only by a model that incorporates both kink nucleation and propagation. Based on observed step morphological changes at these higher saturation indices, the step velocity maximum at SI = 2.15 is likely due to the rate of attachment to propagating kink sites overcoming the rate of detachment from kink sites as the latter becomes less significant under far from equilibrium conditions.« less

Rapid degradation, mineralization and detoxification of pharmaceutically active compounds in aqueous solution during pulsed corona discharge treatment.

PubMed

Singh, Raj Kamal; Philip, Ligy; Ramanujam, Sarathi

2017-09-15

In the present study, plasma generated by pulsed corona discharge was used for the degradation of diclofenac, carbamazepine and ciprofloxacin. Pollutants in aqueous solution were plasma treated under two categories: single and mixed pollutant condition. Mixed pollutant condition showed an antagonistic behaviour and thus the degradation time was higher for mixed condition compared to the single condition. At different voltage and frequencies, degradation efficiency followed the trend, diclofenac>carbamazepine>ciprofloxacin. Acidic pH slightly favoured the degradation process whereas in presence of radical scavengers (HCO 3 - , CO 3 2- and humic acid) the degradation yield was significantly decreased. With an input power of 101.5 W, complete degradation was achieved within 4-16 min of plasma treatment for pharmaceutical's concentrations of 1-10 mg/L. As the pollutant concentration increased from 1 to 10 mg/L, the pseudo first order rate constant decreased, while yield increased. Complete degradation pathway of diclofenac, carbamazepine and ciprofloxacin in plasma treatment process are proposed by identifying the intermediates using LC-MS analysis. TOC analysis confirmed 80% mineralization within 10 min of plasma treatment for higher pharmaceutical's concentrations of 10 mg/L. The microalgae ecotoxicity study and disc diffusion test confirmed the complete detoxification of PACs that took place after 6 min of plasma treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessing the growth of Escherichia coli O157:H7 and Salmonella in spinach, lettuce, parsley and chard extracts at different storage temperatures.

PubMed

Posada-Izquierdo, G; Del Rosal, S; Valero, A; Zurera, G; Sant'Ana, A S; Alvarenga, V O; Pérez-Rodríguez, F

2016-06-01

The objective of this work was to study the growth potential of Escherichia coli O157:H7 and Salmonella spp. in leafy vegetable extracts at different temperature conditions. Cocktails of five strains of E. coli O157:H7 and of Salmonella enterica were used. Inoculated aqueous vegetable extracts were incubated at 8, 10, 16 and 20°C during 21 days. Microbial growth was monitored using Bioscreen C(®) . In spinach extract, results showed that for E. coli O157:H7 and Salmonella significant differences (P < 0·05) for μabs (maximum absorbance rate) were obtained. For both pathogens, growth in chard was slightly lower. In contrast, iceberg lettuce and parsley showed the lowest values of μabs , below 0·008 h(-1) . The coefficients of variance (CoV) calculated for the different replicates evidenced that at low temperature (8°C) a more variable behaviour of both pathogens is expected (CoV > 180%). This study provides evidence that aqueous extracts from vegetable tissues can result in distinct growth niche producing different response in various types of vegetables. Finally, these results can be used as basis to establish risk rankings of pathogens and leafy vegetable matrices with relation to their potential growth. © 2016 The Society for Applied Microbiology.

Carbonates in the Martian meteorite Allan Hills 84001 formed at 18 ± 4 °C in a near-surface aqueous environment

PubMed Central

Halevy, Itay; Fischer, Woodward W.; Eiler, John M.

2011-01-01

Despite evidence for liquid water at the surface of Mars during the Noachian epoch, the temperature of early aqueous environments has been impossible to establish, raising questions of whether the surface of Mars was ever warmer than today. We address this problem by determining the precipitation temperature of secondary carbonate minerals preserved in the oldest known sample of Mars’ crust—the approximately 4.1 billion-year-old meteorite Allan Hills 84001 (ALH84001). The formation environment of these carbonates, which are constrained to be slightly younger than the crystallization age of the rock (i.e., 3.9 to 4.0 billion years), has been poorly understood, hindering insight into the hydrologic and carbon cycles of earliest Mars. Using “clumped” isotope thermometry we find that the carbonates in ALH84001 precipitated at a temperature of approximately 18 °C, with water and carbon dioxide derived from the ancient Martian atmosphere. Furthermore, covarying carbonate carbon and oxygen isotope ratios are constrained to have formed at constant, low temperatures, pointing to deposition from a gradually evaporating, subsurface water body—likely a shallow aquifer (meters to tens of meters below the surface). Despite the mild temperatures, the apparently ephemeral nature of water in this environment leaves open the question of its habitability. PMID:21969543

Performance of mesophilic anaerobic granules for removal of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from aqueous solution.

PubMed

An, Chun-jiang; He, Yan-ling; Huang, Guo-he; Liu, Yong-hong

2010-07-15

The performance of mesophilic anaerobic granules to degrade octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) was investigated under various conditions. The results of batch experiments showed that anaerobic granules were capable of removing HMX from aqueous solution with high efficiency. Both biotic and abiotic mechanisms contributed to the removal of HMX by anaerobic granules under mesophilic conditions. Adsorption appeared to play a significant role in the abiotic process. Furthermore, HMX could be biodegraded by anaerobic granules as the sole substrate. After 16 days of incubation, 99.04% and 96.42% of total HMX could be removed by 1g VSS/L acclimated and unacclimated granules, respectively. Vancomycin, an inhibitor of acetogenic bacteria, caused a significant inhibition of HMX biotransformation, while 2-bromoethanesulfonic acid, an inhibitor of methanogenic bacteria, only resulted in a slight decrease of metabolic activity. The presence of the glucose, as a suitable electron donor and carbon source, was found to enhance the degradation of HMX by anaerobic granules. Our study showed that sulfate had little adverse effects on biotransformation of HMX by anaerobic granules. However, nitrate had significant inhibitory effect on the extent of HMX removal especially in the initial period. This study offered good prospects of using high-rate anaerobic technology in the treatment of munition wastewater. 2010 Elsevier B.V. All rights reserved.

Preparation and Characterization of WS2@SiO2 and WS2@PANI Core-Shell Nanocomposites

PubMed Central

Sade, Hagit

2018-01-01

Two tungsten disulfide (WS2)-based core-shell nanocomposites were fabricated using readily available reagents and simple procedures. The surface was pre-treated with a surfactant couple in a layer-by-layer approach, enabling good dispersion of the WS2 nanostructures in aqueous media and providing a template for the polymerization of a silica (SiO2) shell. After a Stöber-like reaction, a conformal silica coating was achieved. Inspired by the resulting nanocomposite, a second one was prepared by reacting the surfactant-modified WS2 nanostructures with aniline and an oxidizing agent in an aqueous medium. Here too, a conformal coating of polyaniline (PANI) was obtained, giving a WS2@PANI nanocomposite. Both nanocomposites were analyzed by electron microscopy, energy dispersive X-ray spectroscopy (EDS) and FTIR, verifying the core-shell structure and the character of shells. The silica shell was amorphous and mesoporous and the surface area of the composite increases with shell thickness. Polyaniline shells slightly differ in their morphologies dependent on the acid used in the polymerization process and are amorphous like the silica shell. Electron paramagnetic resonance (EPR) spectroscopy of the WS2@PANI nanocomposite showed variation between bulk PANI and the PANI shell. These two nanocomposites have great potential to expand the use of transition metals dichalcogenides (TMDCs) for new applications in different fields. PMID:29534426

Numerical study of canister filters with alternatives filter cap configurations

NASA Astrophysics Data System (ADS)

Mohammed, A. N.; Daud, A. R.; Abdullah, K.; Seri, S. M.; Razali, M. A.; Hushim, M. F.; Khalid, A.

2017-09-01

Air filtration system and filter play an important role in getting a good quality air into turbo machinery such as gas turbine. The filtration system and filter has improved the quality of air and protect the gas turbine part from contaminants which could bring damage. During separation of contaminants from the air, pressure drop cannot be avoided but it can be minimized thus helps to reduce the intake losses of the engine [1]. This study is focused on the configuration of the filter in order to obtain the minimal pressure drop along the filter. The configuration used is the basic filter geometry provided by Salutary Avenue Manufacturing Sdn Bhd. and two modified canister filter cap which is designed based on the basic filter model. The geometries of the filter are generated by using SOLIDWORKS software and Computational Fluid Dynamics (CFD) software is used to analyse and simulates the flow through the filter. In this study, the parameters of the inlet velocity are 0.032 m/s, 0.063 m/s, 0.094 m/s and 0.126 m/s. The total pressure drop produce by basic, modified filter 1 and 2 is 292.3 Pa, 251.11 Pa and 274.7 Pa. The pressure drop reduction for the modified filter 1 is 41.19 Pa and 14.1% lower compared to basic filter and the pressure drop reduction for modified filter 2 is 17.6 Pa and 6.02% lower compared to the basic filter. The pressure drops for the basic filter are slightly different with the Salutary Avenue filter due to limited data and experiment details. CFD software are very reliable in running a simulation rather than produces the prototypes and conduct the experiment thus reducing overall time and cost in this study.

Development of Next Generation Stevia Sweetener: Rebaudioside M.

PubMed

Prakash, Indra; Markosyan, Avetik; Bunders, Cynthia

2014-02-27

This work aims to review and showcase the unique properties of rebaudioside M as a natural non-caloric potential sweetener in food and beverage products. To determine the potential of rebaudioside M, isolated from Stevia rebaudiana Bertoni, as a high potency sweetener, we examined it with the Beidler Model. This model estimated that rebaudioside M is 200-350 times more potent than sucrose. Numerous sensory evaluations of rebaudioside M's taste attributes illustrated that this steviol glycoside possesses a clean, sweet taste with a slightly bitter or licorice aftertaste. The major reaction pathways in aqueous solutions (pH 2-8) for rebaudioside M are similar to rebaudioside A. Herein we demonstrate that rebaudioside M could be of great interest to the global food industry because it is well-suited for blending and is functional in a wide variety of food and beverage products.

Structural characterization of an acetylated glucomannan with antiinflammatory activity and gastroprotective property from Cyrtopodium andersonii.

PubMed

Parente, José P; Adão, Camila R; da Silva, Bernadete P; Tinoco, Luzineide W

2014-06-04

A polysaccharide with an estimated weight-average molar mass of 5.35×10(5) was obtained from an aqueous extract of pseudobulbs of Cyrtopodium andersonii R. Br. It was composed of d-glucose and d-mannose in 1:3 molar ratio. Chemical and spectroscopic analyses revealed a linear structure of the polymer with a backbone composed of (1→4)-linked β-d-glucopyranosyl and mannopyranosyl units slightly branched at C-2, C-3, and C-6 by side chains, as terminal non reducing residues of d-mannopyranose and d-glucopyranose. It was found to contain 14.6% of acetyl groups substituted at C-2 of (1→4)-linked β-d-mannopyranosyl units. The acetylated glucomannan demonstrated antiinflammatory and antiulcerogenic activities. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of sugar functional groups, hydrophobicity, and fluorination on carbohydrate-DNA stacking interactions in water.

PubMed

Lucas, Ricardo; Peñalver, Pablo; Gómez-Pinto, Irene; Vengut-Climent, Empar; Mtashobya, Lewis; Cousin, Jonathan; Maldonado, Olivia S; Perez, Violaine; Reynes, Virginie; Aviñó, Anna; Eritja, Ramón; González, Carlos; Linclau, Bruno; Morales, Juan C

2014-03-21

Carbohydrate-aromatic interactions are highly relevant for many biological processes. Nevertheless, experimental data in aqueous solution relating structure and energetics for sugar-arene stacking interactions are very scarce. Here, we evaluate how structural variations in a monosaccharide including carboxyl, N-acetyl, fluorine, and methyl groups affect stacking interactions with aromatic DNA bases. We find small differences on stacking interaction among the natural carbohydrates examined. The presence of fluorine atoms within the pyranose ring slightly increases the interaction with the C-G DNA base pair. Carbohydrate hydrophobicity is the most determinant factor. However, gradual increase in hydrophobicity of the carbohydrate does not translate directly into a steady growth in stacking interaction. The energetics correlates better with the amount of apolar surface buried upon sugar stacking on top of the aromatic DNA base pair.

Titan aerosol analogues: analysis of the nonvolatile tholins.

PubMed

Sarker, Niladri; Somogyi, Arpad; Lunine, Jonathan I; Smith, Mark A

2003-01-01

Laboratory experiments that produced tholins in a simulated Titan atmosphere were conducted. We report the first systematic analyses of these compounds using Fourier-transform ion cyclotron resonance mass spectrometry. The findings suggest surprising simplicity and nonrandomness in the mass distribution and regularity in species clusters. The degree of unsaturation generally increased with increasing molecular weight in a predictable fashion, and nitrogen is proposed as the dominant carrier of unsaturation. In detected compounds with a general formula of C(x)H(y)N(z), the carbon to nitrogen ratio (x/z) varied only slightly within a narrow limit, and decreased with increasing molecular weights. These compounds are of potential prebiotic interest since they sediment to the surface of Titan, and would dissolve readily in transient aqueous pools that might be generated from time to time by impacts and volcanic

Extractive separation of uranium and zirconium sulfates by amines

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

Schroetterova, D.; Nekovar, P.; Mrnka, M.

1992-04-01

This paper describes an amine extraction process for zirconium and uranium separation. The behaviour of an extraction system containing uranium (VI) sulfate, zirconium (IV) sulfate, 0.2 and 0.5 M sulfuric acid (as the original aqueous phase), tertiary amine tri-n-lauryl- amine or primary amine Primene JMT in benzene (as the original organic phase) is discussed on the basis of equilibrium data. The measured dependences show that the degree of extraction of zirconium at the sulfuric acid concentration of 0.5 M and above is only slightly affected by a presence of uranium in solution. From this surprising behaviour it follows that zirconiummore » may be employed for the displacement of uranium from the organic phase. This effect is more pronounced with the primary amine Primene JMT than with TLA. 29 refs., 4 figs., 1 tab.« less

Identification and Characterization of Visible Absorption Components in Aqueous Methylglyoxal-Ammonium Sulfate Mixtures

NASA Astrophysics Data System (ADS)

McGivern, W. S.; Allison, T. C.; Radney, J. G.; Zangmeister, C. D.

2014-12-01

The aqueous reaction of methylglyoxal (MG) with ammonium sulfate has been suggested as a source of atmospheric ``brown carbon.'' We have utilized high-performance liquid chromatography coupled to ultraviolet-visible spectroscopy and tandem mass spectrometry to study the products of this reaction at high concentrations. The overall product spectrum shows a large number of distinct components; however, the visible absorption from this mixture is derived a very small number of components. The largest contributor is an imine-substituted (C=N-H) product of aldol condensation/facile dehydration reaction between the parent MG and a hydrated product of the MG + ammonia reaction. The asymmetric nature of this compound relative to the aldol condensation of two MG results in a sufficiently large redshift of the UV absorption spectrum that absorption of visible radiation can occur in the long-wavelength tail. The simplicity of the imine products is a result of a strong bias toward ketimine products due to the extensive hydration of the aldehydic moiety in the parent in aqueous solution. In addition, a strong pH dependence of the absorption cross section was observed with significantly greater absorption under more basic conditions. We have performed time-dependent density functional theory calculations to evaluate the absorption spectra of all of the possible condensation products and their respective ions, and the results are consistent with the experimental observations. We have also observed smaller concentrations of other condensation products of the imine-substituted parent species that do not contribute significantly to the visible absorption but have not been previously discussed.

Pharmacokinetics and bioavailability of denaverine hydrochloride in healthy subjects following intravenous, oral and rectal single doses.

PubMed

Staab, Alexander; Schug, Barbara S; Larsimont, Véronique; Elze, Martina; Thümmler, Daniela; Mutschler, Ernst; Blume, Henning

2003-02-01

The neurotropic-musculotropic spasmolytic agent denaverine hydrochloride is used mainly in the treatment of smooth muscle spasms of the gastrointestinal and urogenital tract. Despite its commercial availability as a solution for intravenous or intramuscular administration (ampoule) and as a suppository formulation, no pharmacokinetic data in man was available to date. Therefore, the objectives of this clinical trial were to determine the basic pharmacokinetic parameters of denaverine after intravenous administration, to assess the feasibility of using the oral route of administration and to characterise the bioavailability of the suppository formulation. To achieve this, healthy subjects received 50 mg denaverine hydrochloride intravenously, orally and rectally in aqueous solutions and rectally as suppository in an open, randomised crossover design. Total body clearance, volume of distribution at steady-state and half-life of denaverine are 5.7 ml/min per kg, 7.1 l/kg and 33.8 h, respectively. The absolute bioavailability after oral administration of an aqueous solution is 37%. First-pass metabolism leading to the formation of N-monodemethyl denaverine was found to be one reason for the incomplete bioavailability after oral administration. Rectal administration of an aqueous solution of denaverine hydrochloride resulted in a decreased rate (median of C(max) ratios: 26%, difference in median t(max) values: 1.9 h) and extent (31%) of bioavailability compared to oral administration. Using the suppository formulation led to a further reduction in rate (median of C(max) ratios: 30%, difference in median t(max) values: 3 h) and extent (42%) of bioavailability compared to the rectal solution.

Mechanistic insights into aqueous phase propanol dehydration in H-ZSM-5 zeolite

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

Mei, Donghai; Lercher, Johannes A.

Aqueous phase dehydration of 1-propanol over H-ZSM-5 zeolite was investigated using density functional theory (DFT) calculations. The water molecules in the zeolite pores prefer to aggregate via the hydrogen bonding network and be protonated at the Brønsted acidic sites (BAS). Two typical configurations, i.e., dispersed and clustered, of water molecules were identified by ab initio molecular dynamics simulation of the mimicking aqueous phase H-ZSM-5 zeolite unit cell with 20 water molecules per unit cell. DFT calculated Gibbs free energies suggest that the dimeric propanol-propanol, the propanol-water complex, and the trimeric propanol-propanol-water are formed at high propanol concentrations, which provide amore » kinetically feasible dehydration reaction channel of 1-propanol to propene. However, calculation results also indicate that the propanol dehydration via the unimolecular mechanism becomes kinetically discouraged due to the enhanced stability of the protonated dimeric propanol and the protonated water cluster acting as the BAS site for alcohol dehydration reaction. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.« less

Micellar versus hydro-organic mobile phases for retention-hydrophobicity relationship studies with ionizable diuretics and an anionic surfactant.

PubMed

Ruiz-Angel, M J; Carda-Broch, S; García-Alvarez-Coque, M C; Berthod, A

2004-03-19

Logarithm of retention factors (log k) of a group of 14 ionizable diuretics were correlated with the molecular (log P o/w) and apparent (log P(app)) octanol-water partition coefficients. The compounds were chromatographed using aqueous-organic (reversed-phase liquid chromatography, RPLC) and micellar-organic mobile phases (micellar liquid chromatography, MLC) with the anionic surfactant sodium dodecyl sulfate (SDS), in the pH range 3-7, and a conventional octadecylsilane column. Acetonitrile was used as the organic modifier in both modes. The quality of the correlations obtained for log P(app) at varying ionization degree confirms that this correction is required in the aqueous-organic mixtures. The correlation is less improved with SDS micellar media because the acid-base equilibriums are shifted towards higher pH values for acidic compounds. In micellar chromatography, an electrostatic interaction with charged solutes is added to hydrophobic forces; consequently, different correlations should be established for neutral and acidic compounds, and for basic compounds. Correlations between log k and the isocratic descriptors log k(w), log k(wm) (extrapolated retention to pure water in the aqueous-organic and micellar-organic systems, respectively), and psi0 (extrapolated mobile phase composition giving a k = 1 retention factor or twice the dead time), and between these descriptors and log P(app) were also satisfactory, although poorer than those between log k and log P(app) due to the extrapolation. The study shows that, in the particular case of the ionizable diuretics studied, classical RPLC gives better results than MLC with SDS in the retention hydrophobicity correlations.

Impacts on Emergency Department Visits from Personal Responsibility Provisions: Evidence from West Virginia's Medicaid Redesign.

PubMed

Gurley-Calvez, Tami; Kenney, Genevieve M; Simon, Kosali I; Wissoker, Douglas

2016-08-01

To examine the impact of a 2007 redesign of West Virginia's Medicaid program, which included an incentive and "nudging" scheme intended to encourage better health care behaviors and reduce Emergency Department (ED) visits. West Virginia Medicaid enrollment and claims data from 2005 to 2010. We utilized a "differences in differences" technique with individual and time fixed effects to assess the impact of redesign on ED visits. Starting in 2007, categorically eligible Medicaid beneficiaries were moved from traditional Medicaid to the new Mountain Health Choices (MHC) Program on a rolling basis, approximating a natural experiment. Members chose between a Basic plan, which was less generous than traditional Medicaid, or an Enhanced plan, which was more generous but required additional enrollment steps. Data were obtained from the West Virginia Bureau for Medical Services. We found that contrary to intentions, the MHC program increased ED visits. Those who selected or defaulted into the Basic plan experienced increased overall and preventable ED visits, while those who selected the Enhanced plan experienced a slight reduction in preventable ED visits; the net effect was an increase in ED visits, as most individuals enrolled in the Basic plan. © Health Research and Educational Trust.

Isolation of levoglucosan from lignocellulosic pyrolysis oil derived from wood or waste newsprint

DOEpatents

Moens, Luc

1995-01-01

A method is provided for preparing high purity levoglucosan from lignocellulosic pyrolysis oils derived from wood or waste newsprint. The method includes reducing wood or newsprint to fine particle sizes, treating the particles with a hot mineral acid for a predetermined period of time, and filtering off and drying resulting solid wood or newsprint material; pyrolyzing the dried solid wood or newsprint material at temperatures between about 350.degree. and 375.degree. C. to produce pyrolysis oils; treating the oils to liquid-liquid extraction with methyl isobutyl ketone to remove heavy tar materials from the oils, and to provide an aqueous fraction mixture of the oils containing primarily levoglucosan; treating the aqueous fraction mixtures with a basic metal salt in an amount sufficient to elevate pH values to a range of about 12 to about 12.5 and adding an amount of the salt in excess of the amount needed to obtain the pH range to remove colored materials of impurities from the oil and form a slurry, and freeze-drying the resulting slurry to produce a dry solid residue; and extracting the levoglucosan from the residue using ethyl acetate solvent to produce a purified crystalline levoglucosan.

Isolation of levoglucosan from lignocellulosic pyrolysis oil derived from wood or waste newsprint

DOEpatents

Moens, L.

1995-07-11

A method is provided for preparing high purity levoglucosan from lignocellulosic pyrolysis oils derived from wood or waste newsprint. The method includes reducing wood or newsprint to fine particle sizes, treating the particles with a hot mineral acid for a predetermined period of time, and filtering off and drying resulting solid wood or newsprint material; pyrolyzing the dried solid wood or newsprint material at temperatures between about 350 and 375 C to produce pyrolysis oils; treating the oils to liquid-liquid extraction with methyl isobutyl ketone to remove heavy tar materials from the oils, and to provide an aqueous fraction mixture of the oils containing primarily levoglucosan; treating the aqueous fraction mixtures with a basic metal salt in an amount sufficient to elevate pH values to a range of about 12 to about 12.5 and adding an amount of the salt in excess of the amount needed to obtain the pH range to remove colored materials of impurities from the oil and form a slurry, and freeze-drying the resulting slurry to produce a dry solid residue; and extracting the levoglucosan from the residue using ethyl acetate solvent to produce a purified crystalline levoglucosan. 2 figs.

Anodic electrodeposition of NiTSPP from aqueous basic media.

PubMed

Pérez-Morales, Marta; Muñoz, Eulogia; Martín-Romero, María T; Camacho, Luis

2005-06-07

The oxidative electrodeposition of NiTSPP (tetrakis(4-sulfonatophenyl) Ni porphyrin) on ITO electrode from 0.1 M NaOH aqueous solution has been studied, and UV-visible and reflection FTIR spectroscopies have been used to analyze the composition of such film. By use of UV-vis spectroscopy, small absorbance of the film and an almost nulling effect on the Soret band of the porphyrin along the Ni(III)/Ni(II) redox process were observed. The reflection FTIR spectroscopy detected the presence of Ni-OH groups in the reduced film and as well the state of the porphyrin molecules as radical cation. Moreover, the porphyrin has been quantified by means of the area of the vibration bands assigned to the sulfonate groups by using as reference a Langmuir-Blodgett film containing a known surface concentration of NiTSPP. These results lead us propose the formation of a conductor salt by electrocrystallization, with stoichiometries TSPP/Ni(II)(OH)2 and TSPP/Ni(III)OOH, for its reduced and oxidized forms, respectively. In these two forms, the porphyrin rings will be present as radical cation, which may be stabilized through its dimerization or polymerization.

Design and engineering of water-soluble light-harvesting protein maquettes

DOE PAGES

Kodali, Goutham; Mancini, Joshua A.; Solomon, Lee A.; ...

2017-01-01

Natural selection in photosynthesis has engineered tetrapyrrole based, nanometer scale, light harvesting and energy capture in light-induced charge separation. By designing and creating nanometer scale artificial light harvesting and charge separating proteins, we have the opportunity to reengineer and overcome the limitations of natural selection to extend energy capture to new wavelengths and to tailor efficient systems that better meet human as opposed to cellular energetic needs. While tetrapyrrole cofactor incorporation in natural proteins is complex and often assisted by accessory proteins for cofactor transport and insertion, artificial protein functionalization relies on a practical understanding of the basic physical chemistrymore » of protein and cofactors that drive nanometer scale self-assembly. Patterning and balancing of hydrophobic and hydrophilic tetrapyrrole substituents is critical to avoid natural or synthetic porphyrin and chlorin aggregation in aqueous media and speed cofactor partitioning into the non-polar core of a man-made water soluble protein designed according to elementary first principles of protein folding. In conclusion, this partitioning is followed by site-specific anchoring of tetrapyrroles to histidine ligands strategically placed for design control of rates and efficiencies of light energy and electron transfer while orienting at least one polar group towards the aqueous phase.« less

Pacific island ‘Awa (Kava) extracts, but not isolated kavalactones, promote pro-inflammatory responses in model mast cells

PubMed Central

Shimoda, Lori M.N.; Park, Christy; Stokes, Alexander J.; Gomes, Henry Halenani; Turner, Helen

2013-01-01

Kava (‘Awa) is a traditional water-based beverage in Pacific island communities, prepared from the ground root and stems of Piper methysticum. Kava use is associated with an ichthyotic dermatitis and delayed type hypersensitivity reactions. In the current study we collated preparative methodologies from cultural practitioners and recreational kava users in various Pacific communities. We standardized culturally-informed aqueous extraction methods and prepared extracts that were subjected to basic physicochemical analysis. Mast cells exposed to these extracts displayed robust intracellular free calcium responses, and concomitant release of pro-inflammatory mediators. In contrast, mast cells were refractory to single or combinatorial stimulation with kavalactones including methysticin, dihydromethysticin and kavain. Moreover, we reproduced a traditional modification of the kava preparation methodology, pre-mixing with the mucilage of Hibiscus taliaceus, and observed its potentiating effect on the activity of aqueous extracts in mast cells. Taken together, these data indicate that water extractable active ingredients may play a role in the physiological and pathophysiological effects of kava, and suggests that mast cell activation may be a mechanistic component of kava-related skin inflammations. PMID:22473598

An efficient buffer-mediated control between free radical substitution and proton-coupled electron transfer: dehalogenation of iodoethane by the α-hydroxyethyl radical in aqueous solution.

PubMed

Ljubić, Ivan; Matasović, Brunislav; Bonifačić, Marija

2013-11-07

A remarkable buffer-mediated control between free-radical substitution (FRS) and proton-coupled electron transfer (PCET) is demonstrated for the reaction between iodoethane and the α-hydroxyethyl radical in neutral aqueous solution in the presence of bicarbonate or phosphate buffer. The reaction is initiated by the γ-radiolysis of the water solvent, and the products, either the iodine atom (FRS) or anion (PCET), are analysed using ion chromatographic and spectrophotometric techniques. A detailed insight into the mechanism is gained by employing density functional theory (M06-2X), Møller-Plesset perturbation treatment to the second order (MP2), and multireference methods (CASSCF/CASPT2). Addition of a basic buffer anion is indispensable for the reaction to occur and the competition between the two channels depends subtly on its proton accepting affinity, with FRS being the dominant channel in the phosphate and PCET in the bicarbonate containing solutions. Unlike the former, the latter channel sustains a chain-like process which significantly enhances the dehalogenation. The present systems furnish an example of the novel PCET/FRS dichotomy, as well as insights into possibilities of its efficient control.

Adsorption isotherms and kinetics of activated carbons produced from coals of different ranks.

PubMed

Purevsuren, B; Lin, Chin-Jung; Davaajav, Y; Ariunaa, A; Batbileg, S; Avid, B; Jargalmaa, S; Huang, Yu; Liou, Sofia Ya-Hsuan

2015-01-01

Activated carbons (ACs) from six coals, ranging from low-rank lignite brown coal to high-rank stone coal, were utilized as adsorbents to remove basic methylene blue (MB) from an aqueous solution. The surface properties of the obtained ACs were characterized via thermal analysis, N2 isothermal sorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and Boehm titration. As coal rank decreased, an increase in the heterogeneity of the pore structures and abundance of oxygen-containing functional groups increased MB coverage on its surface. The equilibrium data fitted well with the Langmuir model, and adsorption capacity of MB ranged from 51.8 to 344.8 mg g⁻¹. Good correlation coefficients were obtained using the intra-particle diffusion model, indicating that the adsorption of MB onto ACs is diffusion controlled. The values of the effective diffusion coefficient ranged from 0.61 × 10⁻¹⁰ to 7.1 × 10⁻¹⁰ m² s⁻¹, indicating that ACs from lower-rank coals have higher effective diffusivities. Among all the ACs obtained from selected coals, the AC from low-rank lignite brown coal was the most effective in removing MB from an aqueous solution.

A dip-and-read test strip for the determination of mercury(II) ion in aqueous samples based on urease activity inhibition.

PubMed

Shi, Guo-Qing; Jiang, Guibin

2002-11-01

A sensitive dip-and-read test strip for the determination of mercury in aqueous samples based on the inhibition of urease reaction by the ion has been developed. The strip has a circular sensing zone that containing two layers: the top layer is a cellulose acetate membrane where urease is immobilized on it; the bottom layer is a pH indicator wafer that is impregnated with urea. The principle of the measurement is based on the disappearance of a yellow spot on the pH indicator wafer. The elapsing time until the disappearance of the spot which depends on the concentration of mercury(II) ion is measured with a stopwatch. Under the experimental conditions, as low as 0.2 ng/ml mercury can be observed with the detection range from 0.2 to 200 ng/ml in water. Organomercury compounds give essentially the same response as inorganic mercury. Heavy-metal ions such as Ag(I), Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) as well as other sample matrixes basically do not interfere with the mercury measurement.

Flocculation of both anionic and cationic dyes in aqueous solutions by the amphoteric grafting flocculant carboxymethyl chitosan-graft-polyacrylamide.

PubMed

Yang, Zhen; Yang, Hu; Jiang, Ziwen; Cai, Tao; Li, Haijiang; Li, Haibo; Li, Aimin; Cheng, Rongshi

2013-06-15

In the current work, a series of amphoteric grafting chitosan-based flocculants (carboxymethyl chitosan-graft-polyacrylamide, denoted as CMC-g-PAM) was designed and prepared successfully. The flocculants were applied to eliminate various dyes from aqueous solutions. Among different graft copolymers, CMC-g-PAM11 with a PAM grafting ratio of 74% demonstrated the most efficient performance for removal of both the anionic dye (Methyl Orange, MO) and the cationic dye (Basic Bright Yellow, 7GL) under the corresponding favored conditions (80 mg/L of the flocculant at pH 4.0, and 160 mg/L at pH 11.0). In comparison with its precursors, chitosan and carboxymethyl chitosan, CMC-g-PAM11 showed higher removal efficiencies and wider flocculation windows. More importantly, the graft copolymer produced notably more compacted flocs based on image analysis in combination with fractal theory, which was of great significance in practical water treatment. Furthermore, the flocculation mechanism was discussed in detail. The grafted polyacrylamide chains were found to contribute much to the improved bridging and sweeping flocculation effects, but reduced charge neutralization flocculation for the effect of charge screening. Copyright © 2013 Elsevier B.V. All rights reserved.

pH titration monitored by quantum cascade laser-based vibrational circular dichroism.

PubMed

Rüther, Anja; Pfeifer, Marcel; Lórenz-Fonfría, Víctor A; Lüdeke, Steffen

2014-04-10

Vibrational circular dichroism (VCD) spectra of aqueous solutions of proline were recorded in the course of titrations from basic to acidic pH using a spectrometer equipped with a quantum cascade laser (QCL) as an infrared light source in the spectral range from 1320 to 1220 cm(-1). The pH-dependent spectra were analyzed by singular value decomposition and global fitting of a two-pK Henderson-Hasselbalch model. The analysis delivered relative fractions of the three different protonation species. Their agreement with the relative fractions obtained from performing the same analysis on pH-dependent Fourier transform infrared (FT-IR) and QCL-IR spectra validates the quantitative results from QCL-VCD. Global fitting of the pH-dependent VCD spectra of L-proline allowed for extraction of pure spectra corresponding to anionic, zwitterionic, and cationic L-proline. From a static experiment, only pure spectra of the zwitterion would be accessible in a straightforward way. A comparison to VCD spectra calculated for all three species led to assignment of vibrational modes that are characteristic for the respective protonation states. The study demonstrates the applicability of QCL-VCD both for quantitative evaluation and for qualitative interpretation of dynamic processes in aqueous solutions.

Optimization of Biosorptive Removal of Dye from Aqueous System by Cone Shell of Calabrian Pine

PubMed Central

Deniz, Fatih

2014-01-01

The biosorption performance of raw cone shell of Calabrian pine for C.I. Basic Red 46 as a model azo dye from aqueous system was optimized using Taguchi experimental design methodology. L9 (33) orthogonal array was used to optimize the dye biosorption by the pine cone shell. The selected factors and their levels were biosorbent particle size, dye concentration, and contact time. The predicted dye biosorption capacity for the pine cone shell from Taguchi design was obtained as 71.770 mg g−1 under optimized biosorption conditions. This experimental design provided reasonable predictive performance of dye biosorption by the biosorbent (R 2: 0.9961). Langmuir model fitted better to the biosorption equilibrium data than Freundlich model. This displayed the monolayer coverage of dye molecules on the biosorbent surface. Dubinin-Radushkevich model and the standard Gibbs free energy change proposed physical biosorption for predominant mechanism. The logistic function presented the best fit to the data of biosorption kinetics. The kinetic parameters reflecting biosorption performance were also evaluated. The optimization study revealed that the pine cone shell can be an effective and economically feasible biosorbent for the removal of dye. PMID:25405213

Design and engineering of water-soluble light-harvesting protein maquettes

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

Kodali, Goutham; Mancini, Joshua A.; Solomon, Lee A.

Natural selection in photosynthesis has engineered tetrapyrrole based, nanometer scale, light harvesting and energy capture in light-induced charge separation. By designing and creating nanometer scale artificial light harvesting and charge separating proteins, we have the opportunity to reengineer and overcome the limitations of natural selection to extend energy capture to new wavelengths and to tailor efficient systems that better meet human as opposed to cellular energetic needs. While tetrapyrrole cofactor incorporation in natural proteins is complex and often assisted by accessory proteins for cofactor transport and insertion, artificial protein functionalization relies on a practical understanding of the basic physical chemistrymore » of protein and cofactors that drive nanometer scale self-assembly. Patterning and balancing of hydrophobic and hydrophilic tetrapyrrole substituents is critical to avoid natural or synthetic porphyrin and chlorin aggregation in aqueous media and speed cofactor partitioning into the non-polar core of a man-made water soluble protein designed according to elementary first principles of protein folding. In conclusion, this partitioning is followed by site-specific anchoring of tetrapyrroles to histidine ligands strategically placed for design control of rates and efficiencies of light energy and electron transfer while orienting at least one polar group towards the aqueous phase.« less

Dispersion of Nanomaterials in Aqueous Media: Towards Protocol Optimization.

PubMed

Kaur, Inder; Ellis, Laura-Jayne; Romer, Isabella; Tantra, Ratna; Carriere, Marie; Allard, Soline; Mayne-L'Hermite, Martine; Minelli, Caterina; Unger, Wolfgang; Potthoff, Annegret; Rades, Steffi; Valsami-Jones, Eugenia

2017-12-25

The sonication process is commonly used for de-agglomerating and dispersing nanomaterials in aqueous based media, necessary to improve homogeneity and stability of the suspension. In this study, a systematic step-wise approach is carried out to identify optimal sonication conditions in order to achieve a stable dispersion. This approach has been adopted and shown to be suitable for several nanomaterials (cerium oxide, zinc oxide, and carbon nanotubes) dispersed in deionized (DI) water. However, with any change in either the nanomaterial type or dispersing medium, there needs to be optimization of the basic protocol by adjusting various factors such as sonication time, power, and sonicator type as well as temperature rise during the process. The approach records the dispersion process in detail. This is necessary to identify the time points as well as other above-mentioned conditions during the sonication process in which there may be undesirable changes, such as damage to the particle surface thus affecting surface properties. Our goal is to offer a harmonized approach that can control the quality of the final, produced dispersion. Such a guideline is instrumental in ensuring dispersion quality repeatability in the nanoscience community, particularly in the field of nanotoxicology.

Dispersion of Nanomaterials in Aqueous Media: Towards Protocol Optimization

PubMed Central

Kaur, Inder; Ellis, Laura-Jayne; Romer, Isabella; Tantra, Ratna; Carriere, Marie; Allard, Soline; Mayne-L'Hermite, Martine; Minelli, Caterina; Unger, Wolfgang; Potthoff, Annegret; Rades, Steffi; Valsami-Jones, Eugenia

2017-01-01

The sonication process is commonly used for de-agglomerating and dispersing nanomaterials in aqueous based media, necessary to improve homogeneity and stability of the suspension. In this study, a systematic step-wise approach is carried out to identify optimal sonication conditions in order to achieve a stable dispersion. This approach has been adopted and shown to be suitable for several nanomaterials (cerium oxide, zinc oxide, and carbon nanotubes) dispersed in deionized (DI) water. However, with any change in either the nanomaterial type or dispersing medium, there needs to be optimization of the basic protocol by adjusting various factors such as sonication time, power, and sonicator type as well as temperature rise during the process. The approach records the dispersion process in detail. This is necessary to identify the time points as well as other above-mentioned conditions during the sonication process in which there may be undesirable changes, such as damage to the particle surface thus affecting surface properties. Our goal is to offer a harmonized approach that can control the quality of the final, produced dispersion. Such a guideline is instrumental in ensuring dispersion quality repeatability in the nanoscience community, particularly in the field of nanotoxicology. PMID:29364209

Neutron diffraction study of aqueous Laponite suspensions at the NIMROD diffractometer.

PubMed

Tudisca, V; Bruni, F; Scoppola, E; Angelini, R; Ruzicka, B; Zulian, L; Soper, A K; Ricci, M A

2014-09-01

The process of dynamical arrest, leading to formation of different arrested states such as glasses and gels, along with the closely related process of aging, is central for both basic research and technology. Here we report on a study of the time-dependent structural evolution of two aqueous Laponite clay suspensions at different weight concentrations. Neutron diffraction experiments have been performed with the near and intermediate range order diffractometer (NIMROD) that allows studies of the structure of liquids and disordered materials over a continuous length scale ranging from 1 to 300 Å, i.e., from the atomistic to the mesoscopic scales. NIMROD is presently a unique diffractometer, bridging the length scales traditionally investigated by small angle neutron scattering or small angle x-ray scattering with that accessible by traditional diffractometers for liquids. Interestingly, we have unveiled a signature of aging of both suspensions in the length scale region of NIMROD. This phenomenon, ascribed to sporadic contacts between Laponite platelets at long times, has been observed with the sample arrested as gel or as repulsive glass. Moreover, water molecules within the layers closest to Laponite platelets surface show orientational and translational order, which maps into the crystalline structure of Laponite.

Influence of pH on Drug Absorption from the Gastrointestinal Tract: A Simple Chemical Model

NASA Astrophysics Data System (ADS)

Hickman, Raymond J. S.; Neill, Jane

1997-07-01

A simple model of the gastrointestinal tract is obtained by placing ethyl acetate in contact with water at pH 2 and pH 8 in separate test tubes. The ethyl acetate corresponds to the lipid material lining the tract while the water corresponds to the aqueous contents of the stomach (pH 2) and intestine (pH 8). The compounds aspirin, paracetamol and 3-aminophenol are used as exemplars of acidic, neutral and basic drugs respectively to illustrate the influence which pH has on the distribution of each class of drug between the aqueous and organic phases of the model. The relative concentration of drug in the ethyl acetate is judged by applying microlitre-sized samples of ethyl acetate to a layer of fluorescent silica which, after evaporation of the ethyl acetate, is viewed under an ultraviolet lamp. Each of the three drugs, if present in the ethyl acetate, becomes visible as a dark spot on the silica layer. The observations made in the model system correspond well to the patterns of drug absorption from the gastrointestinal tract described in pharmacology texts and these observations are convincingly explained in terms of simple acid-base chemistry.

Direct organogenesis of Mandevilla illustris (Vell) Woodson and effects of its aqueous extract on the enzymatic and toxic activities of Crotalus durissus terrificus snake venom.

PubMed

Biondo, R; Soares, A M; Bertoni, B W; França, S C; Pereira, A M S

2004-03-01

In order to produce explants of Mandevilla illustris (Vell) Woodson for the "Cerrado in vitro", the Germplasm Bank of UNAERP, we carried out a micropropagation protocol using MS or MS/3 medium supplemented with different concentrations of 6-benzyladeninepurine (BA), Zeatin or 2-isopentenyladenine for nodal segment growth, and alpha-naphthaleneacetic acid, indole-3-butyric acid (IBA) or 1,4 dithiothreitol for rooting. For nodal segments, all the cytokinins tested yielded similar results. However, 2.22 micro M BA is more economical to use. MS/3 medium supplemented with 0.49 micro M IBA was the most appropriate medium for rooting, resulting in 29% rooted explants. The crude aqueous extract from the subterranean system (SS) of M. illustris was assayed for its inhibitory action on the enzymatic activity of Crotalus durissus terrificus snake venom, isolated basic phospholipase A2 (CB) and crotoxin. It totally inhibited the phospholipase activity of crude Cdt venom and CB toxin and inhibited the phospholipase activity of crotoxin by 49%. The toxic action of both the crude venom and crotoxin was partially inhibited-there was a prolonged survival time and a 40.0% decrease in lethality.

Experimental investigation of sulphur isotope partitioning during outgassing of hydrogen sulphide from diluted aqueous solutions and seawater.

PubMed

Baune, Claudia; Bottcher, Michael E

2010-12-01

The diffusion of hydrogen sulphide across the sediment-water interface and subsequent liberation to the atmosphere may occur in iron-deficient coastal marine environments with enhanced microbial activity in surface sediments and corresponding accumulation of dissolved H2S in near-surface pore waters. The involvement of analogue processes in periods of global mass extinctions during Earth's history (e.g. at the Permian-Triassic boundary) is currently in discussion [L.R. Kump, A. Pavlov, and M. Arthur,Massive Release of Hydrogen Sulfide to the Surface Ocean and Atmosphere During Intervals of Oceanic Anoxia, Geology 33, 397 (2005)]. The outgassing of H₂S is associated with a fractionation of the stable sulphur isotopes, which has so far only been investigated experimentally at selected acidic and neutral pH values, and no experiments with seawater had been carried out. In this communication, we report on sulphur isotope fractionation that takes place during the experimental degassing of H₂S from aqueous solution by an inert gas (N₂) at 21 °C. Experiments were conducted in the pH range between 2.6 and 10.8, corresponding to the dominance fields of dissolved hydrogen sulphide (H₂S(aq)), bisulphide (HS-(aq)), and mixtures of both sulphide species. Overall isotope enrichment factors between -1.6 and +3.0‰ were observed, with the residual dissolved sulphide being enriched or depleted in ³⁴S compared to the liberated H₂S at low and high pH values, respectively. The difference in the low and high pH isotope fractionation effects can be explained by isotope exchange between H₂S(aq) and HS-(aq) [B. Fry, H. Gest, and J.M. Hayes, Sulfur Isotope Effects Associated with Protonation of HS- and Volatilization of H₂S, Chem. Geol. (Isot. Geosci. Sec.) 58, 253 (1986); R. Geßler and K. von Gehlen, Investigation of Sulfur Isotope Fractionation Between H2S Gas and Aqueous Solutions, Fresenius J. Anal. Chem. 324, 130 (1986)] followed by the subsequent transfer of H₂S(aq) to the gaseous phase. The assumption of pure physical outgassing of H₂S(aq) at low pH values leads to an isotope enrichment factor of -0.9 ± 0.4‰ (n = 14) which is caused by the combined differences in dehydration and diffusion coefficients of H₂³²S(aq) and H₂³⁴S(aq). In the pH range of natural surface and shallow pore waters, ³⁴S will be equal to or enriched in the gaseous phase compared to the aqueous solution, therefore creating no or a slight enrichment of ³²S in the aqueous solution. Experiments in seawater solution showed no significant influence of increased ionic strength and changed corresponding aqueous speciation on sulphur isotope effects.

Plasma Electrolyte Distributions in Humans-Normal or Skewed?

PubMed

Feldman, Mark; Dickson, Beverly

2017-11-01

It is widely believed that plasma electrolyte levels are normally distributed. Statistical tests and calculations using plasma electrolyte data are often reported based on this assumption of normality. Examples include t tests, analysis of variance, correlations and confidence intervals. The purpose of our study was to determine whether plasma sodium (Na + ), potassium (K + ), chloride (Cl - ) and bicarbonate [Formula: see text] distributions are indeed normally distributed. We analyzed plasma electrolyte data from 237 consecutive adults (137 women and 100 men) who had normal results on a standard basic metabolic panel which included plasma electrolyte measurements. The skewness of each distribution (as a measure of its asymmetry) was compared to the zero skewness of a normal (Gaussian) distribution. The plasma Na + distribution was skewed slightly to the right, but the skew was not significantly different from zero skew. The plasma Cl - distribution was skewed slightly to the left, but again the skew was not significantly different from zero skew. On the contrary, both the plasma K + and [Formula: see text] distributions were significantly skewed to the right (P < 0.01 zero skew). There was also a suggestion from examining frequency distribution curves that K + and [Formula: see text] distributions were bimodal. In adults with a normal basic metabolic panel, plasma potassium and bicarbonate levels are not normally distributed and may be bimodal. Thus, statistical methods to evaluate these 2 plasma electrolytes should be nonparametric tests and not parametric ones that require a normal distribution. Copyright © 2017 Southern Society for Clinical Investigation. Published by Elsevier Inc. All rights reserved.

Electronic and chemical state of aluminum from the single- (K) and double-electron excitation (KL II&III, KL I) x-ray absorption near-edge spectra of α-alumina, sodium aluminate, aqueous Al³⁺•(H₂O)₆, and aqueous Al(OH)₄⁻

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

Fulton, John L.; Govind, Niranjan; Huthwelker, Thomas

2015-07-02

We probe, at high energy resolution, the double electron excitation (KL II&II) x-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of α-alumina and sodium aluminate. The two solid standards, α-alumina (octahedral) and sodium aluminate (tetrahedral) are compared to aqueous species that have the same Al coordination symmetries, Al³⁺•6H₂O (octahedral) and Al(OH)₄⁻ (tetrahedral). For the octahedral species, the edge height of the KL II&III-edge is approximately 10% of the main K-edge however the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the α-alumina and aqueous Al³⁺•6H₂Omore » the KL II&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KL II&III-edge feature interferes with an important region of the extended-XAFS region of the spectra for the K-edge of the crystalline and aqueous standards. The K-edge spectra and K-edge positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge XANES spectra reproduce the observed transitions in the experimental spectra of the four Al species. The KL II&III and KL I onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (ΔSCF) method. Research by JLF, NG, EJB, AV, TDS was supported by U.S. Department of Energy’s (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. NG thanks Amity Andersen for help with the α-Al₂O₃ and tetrahedral sodium aluminate (NaAlO₂) clusters. All the calculations were performed using the Molecular Science Computing Capability at EMSL, a national scientific user facility sponsored by the U.S. Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle under Contract # AC05-76RL01830.« less

Evaluation of DNA damage and mutagenicity induced by lead in tobacco plants.

PubMed

Gichner, Tomás; Znidar, Irena; Száková, Jirina

2008-04-30

Tobacco (Nicotiana tabacum L. var. xanthi) seedlings were treated with aqueous solutions of lead nitrate (Pb2+) at concentrations ranging from 0.4 mM to 2.4 mM for 24 h and from 25 microM to 200 microM for 7 days. The DNA damage measured by the comet assay was high in the root nuclei, but in the leaf nuclei a slight but significant increase in DNA damage could be demonstrated only after a 7-day treatment with 200 microM Pb2+. In tobacco plants growing for 6 weeks in soil polluted with Pb2+ severe toxic effects, expressed by the decrease in leaf area, and a slight but significant increase in DNA damage were observed. The tobacco plants with increased levels of DNA damage were severely injured and showed stunted growth, distorted leaves and brown root tips. The frequency of somatic mutations in tobacco plants growing in the Pb2+-polluted soil did not significantly increase. Analytical studies by inductively coupled plasma optical emission spectrometry demonstrate that after a 24-h treatment of tobacco with 2.4 mM Pb2+, the accumulation of the heavy metal is 40-fold higher in the roots than in the above-ground biomass. Low Pb2+ accumulation in the above-ground parts may explain the lower levels or the absence of Pb2+-induced DNA damage in leaves.

Aqueous solubility of diclofenac diethylamine in the presence of pharmaceutical additives: a comparative study with diclofenac sodium.

PubMed

Khalil, E; Najjar, S; Sallam, A

2000-04-01

Aqueous solubility of diclofenac diethylamine (DDEA), a nonsteroidal anti-inflammatory drug currently formulated as a topical emulgel, was studied in the presence of pharmaceutical additives and compared with diclofenac sodium (DS). Electrolytes at low concentrations exhibited a salting-in effect on DDEA with peak solubility that was attributed to the association of DDEA into micelles, followed by a salting-out effect at higher concentrations, by which structure formation by DDEA molecules increased and precipitation occurred. For DS, which is not capable of forming micelles, the salting-out effect was dominant due to the common ion effect. Cosolvents displayed significant enhancement in solubility of both salts except glycerol, which showed a slight increase in solubility of DDEA and a decrease in solubility of DS due to transformation into the less soluble hydrate form. Ethanol and polyethylene glycol (PEG) 400 cosolvent systems at all concentrations showed positive deviations from the log-linear solubility equation. In the case of propylene glycol (PG) cosolvent systems, negative deviations were observed at low volume fractions of cosolvent, while positive deviations were observed at high volume fractions of cosolvent for DS and DDEA. The parent drug, being less ionizable and highly nonpolar, showed negative deviations up to 90% PG content. Thus, the positive deviations for DS and DDEA could be attributed to the more ionizable carboxylic group and its higher ability for hydrogen bonding at higher fractions of cosolvent. Polyvinylpyrrolidone (PVP) and PEG4000 or PEG6000 enhanced the solubility of DS and DDEA, with PVP exerting higher solubilizing efficiency and DS showing better solubility than DDEA. Solubilities of DS in Tween 80 (T80) and Pluronic F-127 (PF127) aqueous solutions were almost similar, while the solubility of DDEA in the presence of T80 was higher than the solubility in the presence of PF127. DS appeared to be located more in the polyoxyethylene mantle of the micelles, while DDEA was located more in the core of the micelles.

Jarosite dissolution rates in perchlorate brine

NASA Astrophysics Data System (ADS)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures <250 K, and may exist as metastable or stable liquids for extended time periods, even under current Mars surface conditions. Therefore, jarosite-bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

Viewpoint 9--molecular structure of aqueous interfaces

NASA Technical Reports Server (NTRS)

Pohorille, A.; Wilson, M. A.

1993-01-01

In this review we summarize recent progress in our understanding of the structure of aqueous interfaces emerging from molecular level computer simulations. It is emphasized that the presence of the interface induces specific structural effects which, in turn, influence a wide variety of phenomena occurring near the phase boundaries. At the liquid-vapor interface, the most probable orientations of a water molecule is such that its dipole moment lies parallel to the interface, one O-H bond points toward the vapor and the other O-H bond is directed toward the liquid. The orientational distributions are broad and slightly asymmetric, resulting in an excess dipole moment pointing toward the liquid. These structural preferences persist at interfaces between water and nonpolar liquids, indicating that the interactions between the two liquids in contact are weak. It was found that liquid-liquid interfaces are locally sharp but broadened by capillary waves. One consequence of anisotropic orientations of interfacial water molecules is asymmetric interactions, with respect to the sign of the charge, of ions with the water surface. It was found that even very close to the surface ions retain their hydration shells. New features of aqueous interfaces have been revealed in studies of water-membrane and water-monolayer systems. In particular, water molecules are strongly oriented by the polar head groups of the amphiphilic phase, and they penetrate the hydrophilic head-group region, but not the hydrophobic core. At infinite dilution near interfaces, amphiphilic molecules exhibit behavior different from that in the gas phase or in bulk water. This result sheds new light on the nature of hydrophobic effect in the interfacial regions. The presence of interfaces was also shown to affect both equilibrium and dynamic components of rates of chemical reactions. Applications of continuum models to interfacial problems have been, so far, unsuccessful. This, again, underscores the importance of molecular-level information about interfaces.

Zr/ZrO2 sensors for in situ measurement of pH in high-temperature and -pressure aqueous solutions.

PubMed

Zhang, R H; Zhang, X T; Hu, S M

2008-04-15

The aim of this study is to develop new pH sensors that can be used to test and monitor hydrogen ion activity in hydrothermal conditions. A Zr/ZrO2 oxidation electrode is fabricated for in situ pH measurement of high-temperature aqueous solutions. This sensor responds rapidly and precisely to pH over a wide range of temperature and pressure. The Zr/ZrO2 electrode was made by oxidizing zirconium metal wire with Na2CO3 melt, which produced a thin film of ZrO2 on its surface. Thus, an oxidation-reduction electrode was produced. The Zr/ZrO2 electrode has a good electrochemical stability over a wide range of pH in high-temperature aqueous solutions when used with a Ag/AgCl reference electrode. Measurements of the Zr/ZrO2 sensor potential against a Ag/AgCl reference electrode is shown to vary linearly with pH between temperatures 20 and 200 degrees C. The slope of the potential versus pH at high temperature is slightly below the theoretical value indicated by the Nernst equation; such deviation is attributed to the fact that the sensor is not strictly at equilibrium with the solution to be tested in a short period of time. The Zr/ZrO2 sensor can be calibrated over the conditions that exist in the natural deep-seawater. Our studies showed that the Zr/ZrO2 electrode is a suitable pH sensor for the hydrothermal systems at midocean ridge or other geothermal systems with the high-temperature environment. Yttria-stabilized zirconia sensors have also been used to investigate the pH of hydrothermal fluids in hot springs vents at midocean ridge. These sensors, however, are not sensitive below 200 degrees C. Zr/ZrO2 sensors have wider temperature range and can be severed as good alternative sensors for measuring the pH of hydrothermal fluids.

The mechanism of antimalarial action of the ruthenium(II)-chloroquine complex [RuCl(2)(CQ)] (2).

PubMed

Martínez, Alberto; Rajapakse, Chandima S K; Naoulou, Becky; Kopkalli, Yasemin; Davenport, Lesley; Sánchez-Delgado, Roberto A

2008-06-01

The mechanism of antimalarial action of the ruthenium-chloroquine complex [RuCl(2)(CQ)](2) (1), previously shown by us to be active in vitro against CQ-resistant strains of Plasmodium falciparum and in vivo against P. berghei, has been investigated. The complex is rapidly hydrolyzed in aqueous solution to [RuCl(OH(2))(3)(CQ)](2)[Cl](2), which is probably the active species. This compound binds to hematin in solution and inhibits aggregation to beta-hematin at pH approximately 5 to a slightly lower extent than chloroquine diphosphate; more importantly, the heme aggregation inhibition activity of complex 1 is significantly higher than that of CQ when measured at the interface of n-octanol-aqueous acetate buffer mixtures under acidic conditions modeling the food vacuole of the parasite. Partition coefficient measurements confirmed that complex 1 is considerably more lipophilic than CQ in n-octanol-water mixtures at pH approximately 5. This suggests that the principal target of complex 1 is the heme aggregation process, which has recently been reported to be fast and spontaneous at or near water-lipid interfaces. The enhanced antimalarial activity of complex 1 is thus probably due to a higher effective concentration of the drug at or near the interface compared with that of CQ, which accumulates strongly in the aqueous regions of the vacuole under those conditions. Furthermore, the activity of complex 1 against CQ-resistant strains of P. falciparum is probably related to its greater lipophilicity, in line with previous reports indicating a lowered ability of the mutated transmembrane transporter PfCRT to promote the efflux of highly lipophilic drugs. The metal complex also interacts with DNA by intercalation, to a comparable extent and in a similar manner to uncomplexed CQ and therefore DNA binding does not appear to be an important part of the mechanism of antimalarial action in this case.

The mechanism of antimalarial action of the ruthenium (II)-chloroquine complex [RuCl2(CQ)]2

PubMed Central

Martínez, Alberto; Rajapakse, Chandima S. K.; Naoulou, Becky; Kopkalli, Yasemin; Davenport, Lesley; Sánchez-Delgado, Roberto A.

2008-01-01

The mechanism of antimalarial action of the ruthenium-chloroquine complex [RuCl2(CQ)]2 (1), previously shown by us to be active in vitro against CQ-resistant strains of Plasmodium falciparum and in vivo against P. berghei, has been investigated. The complex is rapidly hydrolyzed in aqueous solution to [RuCl(OH2)3(CQ)]2 [Cl]2, which is probably the active species. This compound binds to hematin in solution and inhibits aggregation to β-hematin at pH ∼ 5 to a slightly lower extent than chloroquine diphosphate; more importantly, the heme aggregation inhibition activity of complex 1 is significantly higher than that of CQ when measured at the interface of n-octanol-aqueous acetate buffer mixtures under acidic conditions modeling the food vacuole of the parasite. Partition coefficient measurements confirmed that complex 1 is considerably more lipophilic than CQ in n-octanol-water mixtures at pH ∼ 5. This suggests that the principal target of complex 1 is the heme aggregation process, which has recently been reported to be fast and spontaneous at or near water-lipid interfaces. The enhanced antimalarial activity of complex 1 is thus probably due to a higher effective concentration of the drug at or near the interface compared with that of CQ, which accumulates strongly in the aqueous regions of the vacuole under those conditions. Furthermore, the activity of complex 1 against CQ-resistant strains of P. falciparum is probably related to its greater lipophilicity, in line with previous reports indicating a lowered ability of the mutated transmembrane transporter PfCRT to promote the efflux of highly lipophilic drugs. The metal complex also interacts with DNA by intercalation, to a comparable extent and in a similar manner to uncomplexed CQ and therefore DNA binding does not appear to be an important part of the mechanism of antimalarial action in this case. PMID:18305967

Magnetic copper-based metal organic framework as an effective and recyclable adsorbent for removal of two fluoroquinolone antibiotics from aqueous solutions.

PubMed

Wu, Gege; Ma, Jiping; Li, Shuang; Guan, Jing; Jiang, Bo; Wang, Liyan; Li, Jinhua; Wang, Xiaoyan; Chen, Lingxin

2018-05-30

Fe 3 O 4 /HKUST-1 magnetic copper based metal-organic frameworks (MOF) were synthesized by a simple and facile method and applied as an effective and recyclable adsorbent for the adsorptive removal of two widely used ciprofloxacin (CIP) and norfloxacin (NOR) fluoroquinolone antibiotics (FQAs) from aqueous solutions. Fe 3 O 4 /HKUST-1 was thoroughly characterized, and the major influence factors including solution pH, adsorbent amount and salt concentration were investigated. Compared to the reported adsorbents, Fe 3 O 4 /HKUST-1 has a very high adsorption rate, and it is found that CIP and NOR could be removed within 30 min. Moreover, the maximum adsorption capacities of the magnetic composites toward CIP and NOR reached as high as 538 mg g -1 and 513 mg g -1 , respectively, much higher than those of most of the reported adsorbents for these two FQAs. The saturation magnetization value of Fe 3 O 4 /HKUST-1 was 44 emu g -1 , which was sufficient for the separation of the Fe 3 O 4 /HKUST-1adsorbent from the aqueous solution by the application of an external magnetic field. Additionally, this magnetic material showed a good reusability with the adsorption capability decreasing only slightly after reuse for ten cycles. These results indicated that the magnetic composites Fe 3 O 4 /HKUST-1 may be a promising adsorbent in the decontamination of FQAs from wastewater due to its high adsorption capability, fast kinetics, easy separation from water, and excellent recyclability. The adsorption mechanism was proposed based on the effects of pH on adsorption and on the zeta potential of the adsorbent. For the adsorption of CIP and NOR by Fe 3 O 4 /HKUST-1, both electrostatic and π-π interactions may be important. Copyright © 2018 Elsevier Inc. All rights reserved.

Removal of Arsenic (III, V) from aqueous solution by nanoscale zero-valent iron stabilized with starch and carboxymethyl cellulose

PubMed Central

2014-01-01

In this work, synthetic nanoscale zerovalent iron (NZVI) stabilized with two polymers, Starch and Carboxymethyl cellulose (CMC) were examined and compared for their ability in removing As (III) and As (V) from aqueous solutions as the most promising iron nanoparticles form for arsenic removal. Batch operations were conducted with different process parameters such as contact time, nanoparticles concentration, initial arsenic concentration and pH. Results revealed that starch stabilized particles (S-nZVI) presented an outstanding ability to remove both arsenate and arsenite and displayed ~ 36.5% greater removal for As (V) and 30% for As (III) in comparison with CMC-stabilized nanoparticles (C-nZVI). However, from the particle stabilization viewpoint, there is a clear trade off to choosing the best stabilized nanoparticles form. Removal efficiency was enhanced with increasing the contact time and iron loading but reduced with increasing initial As (III, V) concentrations and pH. Almost complete removal of arsenic (up to 500 μg/L) was achieved in just 5 min when the S-nZVI mass concentration was 0.3 g/L and initial solution pH of 7 ± 0.1. The maximum removal efficiency of both arsenic species was obtained at pH = 5 ± 0.1 and starched nanoparticles was effective in slightly acidic and natural pH values. The adsorption kinetics fitted well with pseudo-second-order model and the adsorption data obeyed the Langmuir equation with a maximum adsorption capacity of 14 mg/g for arsenic (V), and 12.2 mg/g for arsenic (III). It could be concluded that starch stabilized Fe0 nanoparticles showed remarkable potential for As (III, V) removal from aqueous solution e.g. contaminated water. PMID:24860660

Do brain lesions in stroke affect basic emotions and attachment?

PubMed

Farinelli, Marina; Panksepp, Jaak; Gestieri, Laura; Maffei, Monica; Agati, Raffaele; Cevolani, Daniela; Pedone, Vincenzo; Northoff, Georg

2015-01-01

The aim of the current study was to investigate basic emotions and attachment in a sample of 86 stroke patients. We included a control group of 115 orthopedic patients (matched for age and cognitive status) without brain lesions to control for unspecific general illness effects of a traumatic recent event on basic emotions and attachment. In order to measure basic emotions and attachment style we applied the Affective Neuroscience Personality Scale (ANPS) and the Attachment Style Questionnaire (ASQ). The stroke patients showed significantly different scores in the SEEKING, SADNESS, and ANGER subscales of the ANPS as well as in the Relationship as Secondary Attachment dimension of the ASQ when compared to the control group. These differences show a pattern influenced by lesion location mainly as concerns basic emotions. Anterior, medial, left, and subcortical patients provide scores significantly lower in ANPS-SEEKING than the control group; ANPS-SADNESS scores in anterior, right, medial, and subcortical patients were significantly higher than those of the control group. ANPS-ANGER scores in posterior, right, and lateral patients were significantly higher than those in the control group; finally, the ANPS-FEAR showed slightly lower scores in posterior patients than in the control group. Minor effects on brain lesions were also individuated in the attachment style. Anterior lesion patients showed a significantly higher average score in the ASQ-Need for Approval subscale than the control group. ASQ-Confidence subscale scores differed significantly in stroke patients with lesions in medial brain regions when compared to control subjects. Scores at ANPS and ASQ subscales appear significantly more correlated in stroke patients than in the control group. Such finding of abnormalities, especially concerning basic emotions in stroke brain-lesioned patients, indicates that the effect of brain lesions may enhance the interrelation between basic emotions and attachment with respect to the control group.

Sorption Behavior of Dye Compounds onto Natural Sediment of Qinghe River.

PubMed

Liu, Ruixia; Liu, Xingmin; Tang, Hongxiao; Su, Yongbo

2001-07-15

The objective of this study is to assess the adsorption behavior of C.I. Basic Yellow X-5GL, C.I. Basic Red 13, C.I. Direct Blue 86, C.I. Vat Yellow 2, and C.I. Mordant Black 11 on natural sediment and to identify sediment characteristics that play a predominant role in the adsorption of the dyes. The potentiometric titration experiment is used to investigate acid-base properties of the sediment surface with a constant capacitance surface complexation model. The parameters controlling the sorption such as solution pH and ion strength, as well as the influence of organic carbon and Ca(2+) ion on the adsorption, are evaluated. It is shown that the titration data can be successfully described by the surface protonation and deprotonation model with the least-squares FITEQL program 2.0. The sorption isotherm data are fitted to the Freundlich equation in a nonlinear form (1/n=0.3-0.9) for all tested dyes. With increasing pH value, the sorption of C.I. Mordant Black 11 and C.I. Direct Blue 86 on the sediment decreases, while for C.I. Basic Yellow X-5GL and C.I. Basic Red 13, the extent of sorption slightly increases. In addition, ion strength also exhibits a considerably different effect on the sorption behavior of these dye compounds. The addition of Ca(2+) can greatly reduce the sorption of C.I. Basic Red 13 on the sediment surface, while it enhances the sorption of C.I. Direct Blue 6. The removal of organic carbon decreases the sorption of C.I. Mordant Black 11 and C.I. Direct Blue 86. In contrast, the sorption of C.I. Basic Red 13 and C.I. Basic Yellow X-5GL is obviously enhanced after the removal of organic carbon. The differences in adsorption behavior are mainly attributed to the physicochemical properties of these dye compounds. Copyright 2001 Academic Press.

An experimental study on the preparation of tochilinite-originated intercalation compounds comprised of Fe 1-xS host layers and various kinds of guest layers

NASA Astrophysics Data System (ADS)

Peng, Yiya; Xi, Guangcheng; Zhong, Chang; Wang, Linping; Lu, Jun; Sun, Ximeng; Zhu, Lu; Han, Qikun; Chen, Lin; Shi, Lei; Sun, Mei; Li, Qianrong; Yu, Min; Yin, Mingwen

2009-08-01

Tochilinite represents a mineral group of ordered mixed-layer structures containing alternating Fe 1-xS layers with mackinawite-like structure and metal hydroxide layers with Mg(OH) 2-like structure. In this article, we report the preparation of a series of tochilinite-originated (or Fe 1-xS-based) intercalation compounds (ICs). According to their preparation procedures, these ICs can be divided into four kinds. The first kind of IC was sodium tochilinite (Na-tochilinite), which was prepared by the hydrothermal reaction of metallic Fe particles with concentrated Na 2S·9H 2O aqueous solutions. The hydroxide layer of the Na-tochilinite was a mixed hydroxide of Na + ions along with a certain amount of Fe 2+ ions. When the hydroxide layer of the Na-tochilinite completely dissolved in aqueous solutions, a Fe-deficient mackinawite-like phase Fe 1-xS was obtained, which was probably an electron-deficient p-type conductor. The second kind of ICs was prepared by 'low-temperature direct intercalation in aqueous solutions, using Na-tochilinite as a parental precursor. When the Na-tochilinite was ultrasonicated in aqueous solutions containing Lewis basic complexing agents (like NH 3, N 2H 4, 2,2'-bipyridine (bipy), and 1,10-phenanthroline (phen)), the Na + ions of the Na-tochilinite were removed and the Lewis basic complexing agents entered the hydroxide layer of the Na-tochilinite and became coordinated with the Fe 2+ ions, and the second kind of ICs was thus produced. The second kind of ICs includes NH 3 IC, N 2H 4 IC, N 2H 4-NH 3 IC, [Fe(bipy) 3] 2+-containing IC and [Fe(phen) 3] 2+-containing IC. The third kind of ICs, which includes NH 3 IC, N 2H 4-NH 3 IC and N 2H 4-LiOH (NaOH) IC, was prepared by the hydrothermal reaction of metallic Fe particles with (NH 4) 2S aqueous solution, S (elemental) + N 2H 4·H 2O aqueous solution, and S + N 2H 4·H 2O + LiOH (NaOH) aqueous solution, respectively. The third kind of ICs has a close relationship with the second kind of ICs both in composition and structure. The fourth kind of ICs was prepared by the oxidation and reduction of some of the N 2H 4-containing ICs mentioned above, which include N 2H 2 (diazene or diimide) IC, N 2 (dinitrogen) IC and NH 3 IC. The N 2H 2 IC was prepared by mild air oxidation of the N 2H 4-LiOH IC. The N 2 IC was prepared by strong air oxidation of the N 2H 4-LiOH IC, however, we have not been able to separate the pure phase N 2 IC. Hydrothermal reduction of the N 2H 4 IC made by the direct intercalation method in strong reducing environment by H 2S + Fe (metal) led to the production of the NH 3 IC of the fourth kind of ICs. The NH 3 ICs prepared by the three methods had similar compositions and structures. As almost all the ICs reported in this paper were extremely sensitive both to air and to the electron beam, they were mainly characterized by XRD. The properties and interrelationships (or mutual transformations) of the Fe 1-xS-based ICs revealed novel chemistry occurring in the sub-nanoscopic space between the micrometer- to nanometer-sized electron-deficient Fe 1-xS layers. An important finding of this novel chemistry was that the Fe 1-xS-based ICs tended to oxidize or reduce the intercalated species when the redox state of their environments varied. The results of our experiments potentially have many cosmochemical implications. The most important implication is that our experimental results, along with previous studies, strongly suggested that some of the ammonium salts, ammonia and carbonates existing in the matrix of the CM carbonaceous chondrites may have been formed by abiotic reactions employing molecular nitrogen as the nitrogen source and carbon monoxide as the carbon source and iron sulfide and/or iron hydroxide as catalysts.