Science.gov

Sample records for acidic aqueous environments

  1. Self-assembly of folic acid: a chiral-aligning medium for enantiodiscrimination of organic molecules in an aqueous environment.

    PubMed

    Lokesh; Suryaprakash, N

    2012-09-10

    Weak orienting medium: Self-assembly of alkaline salt of folic acid yielded a weak liquid-crystalline phase in an aqueous environment. This medium has the ability to discriminate enantiomers. The mesophase exists over a broad range and has the physical parameter dependent tunability of degree of alignment (see scheme).

  2. MIPs in Aqueous Environments.

    PubMed

    Wan, Ying-chun; Ma, Hui-ting; Lu, Bin

    2015-01-01

    When organic solvent-compatible molecularly imprinted polymers (MIPs) are used in aqueous environment, how to reduce nonspecific binding is a major challenge. By modifying the binding solvents and introducing appropriate washing and elution steps, even relatively hydrophobic MIPs can gain optimal rebinding selectivity in aqueous conditions. Furthermore, water-compatible MIPs that can be used to treat aqueous samples directly have been prepared. The use of hydrophilic co-monomers, the controlled surface modification through controlled radical polymerization, and the new interfacial molecular imprinting methods are different strategies to prepare water-compatible MIPs. By combining MIPs with other techniques, both organic solvent-compatible and water-compatible MIPs can display better functional performances in aqueous conditions. Intensive studies on MIPs in aqueous conditions can provide new MIPs with much-improved compatibilities that will lead to more interesting applications in biomedicine and biotechnology.

  3. Oleoylethanolamide-based lyotropic liquid crystals as vehicles for delivery of amino acids in aqueous environment.

    PubMed

    Mohammady, Sayed Z; Pouzot, Matthieu; Mezzenga, Raffaele

    2009-02-18

    ideal vehicles for the delivery of functional hydrophilic active molecules in aqueous environment.

  4. Photochemistry of aqueous pyruvic acid.

    PubMed

    Griffith, Elizabeth C; Carpenter, Barry K; Shoemaker, Richard K; Vaida, Veronica

    2013-07-16

    The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH3COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH3CHOHCOCH3), lactic acid (CH3CHOHCOOH), acetic acid (CH3COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols.

  5. 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.

  6. Structural evolution of molybdenum carbides in hot aqueous environments and impact on low-temperature hydroprocessing of acetic acid

    DOE PAGES

    Choi, Jae -Soon; Schwartz, Viviane; Santillan-Jimenez, Eduardo; ...

    2015-03-13

    In this paper, we investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating themore » possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. Finally, the results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.« less

  7. Structural evolution of molybdenum carbides in hot aqueous environments and impact on low-temperature hydroprocessing of acetic acid

    SciTech Connect

    Choi, Jae -Soon; Schwartz, Viviane; Santillan-Jimenez, Eduardo; Crocker, Mark; Lewis, Sr., Samuel A.; Lance, Michael J.; Meyer, III, Harry M.; More, Karren L.

    2015-03-13

    In this paper, we investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating the possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. Finally, the results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.

  8. Ancient aqueous environments at Endeavour crater, Mars

    USGS Publications Warehouse

    Arvidson, R. E.; Squyres, S. W.; Bell, J.F.; Catalano, J.G.; Clark, B. C.; Crumpler, L.S.; de Souza, P.A.; Fairén, A.G.; Farrand, W. H.; Fox, V.K.; Gellert, Ralf; Ghosh, A.; Golombeck, M.P.; Grotzinger, J.P.; Guinness, E.A.; Herkenhoff, Kenneth E.; Jolliff, B.L.; Knoll, A.H.; Li, R.; McLennan, S.M.; Ming, D. W.; Mittlefehldt, D. W.; Moore, Johnnie N.; Morris, R.V.; Murchie, S.L.; Parker, T.J.; Paulsen, G.; Rice, J.W.; Ruff, S.W.; Smith, M.D.; Wolff, M.J.

    2014-01-01

    Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe+3-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

  9. Ancient aqueous environments at Endeavour crater, Mars.

    PubMed

    Arvidson, R E; Squyres, S W; Bell, J F; Catalano, J G; Clark, B C; Crumpler, L S; de Souza, P A; Fairén, A G; Farrand, W H; Fox, V K; Gellert, R; Ghosh, A; Golombek, M P; Grotzinger, J P; Guinness, E A; Herkenhoff, K E; Jolliff, B L; Knoll, A H; Li, R; McLennan, S M; Ming, D W; Mittlefehldt, D W; Moore, J M; Morris, R V; Murchie, S L; Parker, T J; Paulsen, G; Rice, J W; Ruff, S W; Smith, M D; Wolff, M J

    2014-01-24

    Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe(+3)-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

  10. Ancient Aqueous Environments at Endeavour Crater, Mars

    NASA Technical Reports Server (NTRS)

    Arvidson, R. E.; Squyres, S. W.; Bell, J. F.; Catalano, J. G.; Clark, B. C.; Crumpler, L. S.; de Souza, P. A.; Fairen, A. G.; Farrand, W. H.; Fox, V. K.; Gellert, R.; Ghosh, A.; Golombek, M. P.; Grotzinger, J. P.; Guinness, E. A.; Herkenhoff, K. E.; Jolliff, B. L.; Knoll, A. H.; Li, R.; McLennan, S. M.; Ming, D. W.; Mittlefehldt, D. W.; Moore, J. M.; Morris, R. V.; Murchie, S. L.; Parker, T. J.; Paulsen, G.; Rice, J. W.; Ruff, S. W.; Smith, M. D.; Wolff, M. J.

    2014-01-01

    Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe(+3)-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

  11. Ancient Aqueous Environments at Endeavour Crater, Mars

    NASA Astrophysics Data System (ADS)

    Arvidson, R. E.; Squyres, S. W.; Bell, J. F.; Catalano, J. G.; Clark, B. C.; Crumpler, L. S.; de Souza, P. A.; Fairén, A. G.; Farrand, W. H.; Fox, V. K.; Gellert, R.; Ghosh, A.; Golombek, M. P.; Grotzinger, J. P.; Guinness, E. A.; Herkenhoff, K. E.; Jolliff, B. L.; Knoll, A. H.; Li, R.; McLennan, S. M.; Ming, D. W.; Mittlefehldt, D. W.; Moore, J. M.; Morris, R. V.; Murchie, S. L.; Parker, T. J.; Paulsen, G.; Rice, J. W.; Ruff, S. W.; Smith, M. D.; Wolff, M. J.

    2014-01-01

    Opportunity has investigated in detail rocks on the rim of the Noachian age Endeavour crater, where orbital spectral reflectance signatures indicate the presence of Fe+3-rich smectites. The signatures are associated with fine-grained, layered rocks containing spherules of diagenetic or impact origin. The layered rocks are overlain by breccias, and both units are cut by calcium sulfate veins precipitated from fluids that circulated after the Endeavour impact. Compositional data for fractures in the layered rocks suggest formation of Al-rich smectites by aqueous leaching. Evidence is thus preserved for water-rock interactions before and after the impact, with aqueous environments of slightly acidic to circum-neutral pH that would have been more favorable for prebiotic chemistry and microorganisms than those recorded by younger sulfate-rich rocks at Meridiani Planum.

  12. Heat-initiated prebiotic formation of peptides from glycine/aspartic acid and glycine/valine in aqueous environment and clay suspension

    NASA Astrophysics Data System (ADS)

    Pant, Chandra Kala; Lata, Hem; Pathak, Hari Datt; Mehata, Mohan Singh

    2009-04-01

    The effect of heat on the reaction system of glycine/aspartic acid and glycine/valine in the aqueous environment as well as in montmorillonite clay suspension with or without divalent cations (Ca2+, Mg2+ and Ni2+) has been investigated at 85°C±5°C for varying periods under prebiotic drying and wetting conditions. The resulting products were analysed and characterized by chromatographic and spectroscopic methods. Peptide formation appears to depend on the duration of heat effect, nature of reactant amino acids and, to some extent, on montmorillonite clay incorporated with divalent cations. In the glycine/aspartic acid system, oligomerization of glycine was limited up to trimer level (Gly)3 along with the formation of glycyl-aspartic acid, while linear and cyclic peptides of aspartic acid were not formed, whereas the glycine/valine system preferentially elongated homo-oligopeptide of glycine up to pentamer level (Gly)5 along with formation of hetero-peptides (Gly-Val and Val-Gly). These studies are relevant in the context of the prebiotic origin of proteins and the role of clay and metal ions in condensation and oligomerization of amino acids. The length of the bio-oligomer chain depends upon the reaction conditions. However, condensation into even a small length seems significant, as the same process would have taken millions of years in the primitive era of the Earth, leading to the first proteins.

  13. Plasmon-driven sequential chemical reactions in an aqueous environment

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

    2014-06-01

    Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H+ in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

  14. Plasmon-driven sequential chemical reactions in an aqueous environment.

    PubMed

    Zhang, Xin; Wang, Peijie; Zhang, Zhenglong; Fang, Yurui; Sun, Mengtao

    2014-06-24

    Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H(+) in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.

  15. Corrosion of Si 3N 4-MoSi 2 ceramic composite in acid- and basic-aqueous environments: surface modification and properties degradation

    NASA Astrophysics Data System (ADS)

    Winterhalter, F.; Medri, V.; Ruffini, A.; Bellosi, A.

    2004-03-01

    The corrosion behaviour of an electroconductive Si 3N 4-35 vol.% MoSi 2 composite, hot pressed with the addition of Al 2O 3 and Y 2O 3 as sintering aids, was studied in 1.8 M sulphuric acid and 4 M sodium hydroxide aqueous solutions at room temperature, 40 and 70 °C up to 400 h. In acidic environment, the corrosion follows linear kinetics involving the progressive chemical dissolution of glassy grain boundary phases, in the system Al-Y-Si-O-N up to 40 °C. At 70 °C, the dissolution mechanism is hampered by the formation of a barrier that limits the transport of the aggressive cations towards the sites of chemical attack. In basic environment, the rate controlling step for corrosion of this ceramic composite is the chemical dissolution of MoSi 2. Si 3N 4 phase is less affected by the selected corrosive environments. The effect of the corrosion on electrical resistivity and flexural strength were investigated. The electrical resistivity rises after long term corrosion in line with the progressive chemical dissolution of grain boundary phase and of the electroconductive MoSi 2 particles. The flexural strength values are about 21 and 13% lower than the as-sintered ones, after a permanence of 400 °C at 70 °C in H 2SO 4 and in NaOH solutions, respectively.

  16. Oligonucleofide Imprinting in Aqueous Environment

    DTIC Science & Technology

    2002-04-05

    imprint molecule for various organic and aqueous polymerization formulations (Table I). The polymer ...interactions (Table 1). Table 1. Polymer formulations used to imprint adenosine dimer 1. Molecularly imprinted polymer ( MIP ) using 1% dimer 1 as template ( MIP ... MIP P3 is compared to its rebinding with non- imprinted polymer P30. Cb is the amount of dimer rebound to the polymer . Cf is the

  17. Analysis of the Raman spectra of Ca(2+)-dipicolinic acid alone and in the bacterial spore core in both aqueous and dehydrated environments.

    PubMed

    Kong, Lingbo; Setlow, Peter; Li, Yong-qing

    2012-08-21

    The core of dormant bacterial spores suspended in water contains a large depot of dipicolinic acid (DPA) chelated with divalent cations, predominantly Ca(2+) (CaDPA), and surrounded by water molecules. Since the intensities of the vibration bands of CaDPA molecules depend significantly on the water content in the CaDPA's environment, the Raman spectra of CaDPA in spores may allow the determination of the spore core's hydration state. We have measured Raman spectra of single spores of three Bacillus species in different hydration states including the spores suspended in water, air-dried and vacuum-dried. As a comparison, we also measured the Raman spectra of CaDPA and DPA in different forms including in aqueous solution, and as amorphous powder and crystalline form. We also monitored changes in Raman spectra of an individual spore during dehydration under vacuum. The results indicated that (1) the state of CaDPA in the core of a spore suspended in water is close to an amorphous solid or a glassy state, but still mixed with water molecules; (2) the ratio of intensities of Raman bands at 1575 and 1017 cm(-1) (I(1575)/I(1017)) is sensitive to the water content in the CaDPA's environment; (3) variations in I(1575)/I(1017) are small (∼4%) in a population of dormant Bacillus spores suspended in water; and (4) the I(1575)/I(1017) ratio increases significantly during dehydration under vacuum. Consequently, measurement of the I(1575)/I(1017) ratio of CaDPA in spores may allow a qualitative estimation of the degree of hydration of the bacterial spore's core.

  18. Aqueous thermal degradation of gallic acid

    SciTech Connect

    Boles, J.S.; Crerar, D.A.; Grissom, G.; Key, T.C.

    1988-02-01

    Aqueous thermal degradation experiments show gallic acid, a naturally occurring aromatic carboxylic compound, decomposes rapidly at temperatures between 105/sup 0/ and 150/sup 0/C, with an activation energy of 22.9 or 27.8 kcal/mole, depending on pH of the starting solution. Pyrogallol is the primary product identified, indicating degradation via decarboxylation and a carbanion transition state. Relatively rapid degradation of vanillic, phthalic, ellagic and tannic acids has also been observed,suggesting that these and perhaps other aromatic acids could be short-lived in deep formation waters.

  19. Aqueous thermal degradation of gallic acid

    NASA Astrophysics Data System (ADS)

    Snow Boles, Jennifer; Crerar, David A.; Grissom, Grady; Key, Tonalee C.

    1988-02-01

    Aqueous thermal degradation experiments show gallic acid, a naturally occurring aromatic carboxylic compound, decomposes rapidly at temperatures between 105° and 150°C, with an activation energy of 22.9 or 27.8 kcal/ mole, depending on pH of the starting solution. Pyrogallol is the primary product identified, indicating degradation via decarboxylation and a carbanion transition state. Relatively rapid degradation of vanillic, phthalic, ellagic and tannic acids has also been observed, suggesting that these and perhaps other aromatic acids could be short-lived in deep formation waters.

  20. NIR spectroscopic properties of aqueous acids solutions.

    PubMed

    Omar, Ahmad Fairuz; Atan, Hanafi; Matjafri, Mohd Zubir

    2012-06-15

    Acid content is one of the important quality attributes in determining the maturity index of agricultural product, particularly fruits. Despite the fact that much research on the measurement of acidity in fruits through non-destructive spectroscopy analysis at NIR wavelengths between 700 to 1,000 nm has been conducted, the same response towards individual acids is not well known. This paper presents NIR spectroscopy analysis on aqueous citric, tartaric, malic and oxalic solutions through quantitative analysis by selecting a set of wavelengths that can best be used to measure the pH of the solutions. The aquaphotomics study of the acid solutions has generated R² above 0.9 for the measurement of all acids. The most important wavelengths for pH are located at 918-925 nm and 990-996 nm, while at 975 nm for water.

  1. Unusual mercury isotopic compositions in aqueous environment

    NASA Astrophysics Data System (ADS)

    Chen, J.; Hintelmann, H.; Zheng, W.; Feng, X.; Cai, H.; Wang, Z.; Yuan, S.

    2014-12-01

    Preliminary studies have demonstrated both mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes in natural samples. Laboratory experiments showed that photochemical reduction of inorganic mercury (iHg) and methylmercury (MMHg) and liquid-vapour evaporation could produce MIF of odd Hg isotopes. This was thought to cause the MIF actually observed in aquatic organisms. Although isotopic measurements of Hg in aqueous environment would give direct evidence, little data was reported for surface water samples. Recent work reported, unexpectedly, positive MIF of odd Hg isotopes in both precipitation and ambient air, in contrast with the prediction of laboratory experiments and measurements of Hg accumulated in lichens . Intriguingly, MIF of even-mass Hg isotope (200Hg) was also recently determined in the atmosphere. In contrast with the now mainstream observation of odd Hg isotope anomaly that has several theoretical explanations, the hitherto mysterious even Hg isotope anomalies were neither reported in laboratory experiments, nor predicted by isotope fractionation mechanisms, highlighting the importance of further study on Hg isotopes in variable systems. Our measurements of lichens and lake water samples from different countries show for the first time significant Δ200Hg in surface terrestrial reservoirs, realizing a direct connection of even Hg isotope anomaly in the terrestrial reservoirs to the atmospheric deposition, and fulfilling the gap of Δ200Hg between the atmosphere and the terrestrial receptors. The specific odd Hg isotope compositions determined in lake waters also support the atmosphere contribution, and may be directly linked to the high Δ199Hg values largely determined and manifested on the top of aqueous food web. Our data show that the watershed Hg input is another contributing source, rather than the in-lake processes, to explain the lacustrine Hg isotope anomalies. Interestingly, lake sediments are isotopically

  2. Molecular dynamics simulations of organic crystal dissolution: The lifetime and stability of the polymorphic forms of para-amino benzoic acid in aqueous environment

    NASA Astrophysics Data System (ADS)

    Toroz, D.; Hammond, R. B.; Roberts, K. J.; Harris, S.; Ridley, T.

    2014-09-01

    Para-amino benzoic acid (PABA) manifests crystalline solid-state properties that are typical of a class of chemical compounds with important industrial applications. Hence, it is particularly worthwhile to investigate the lifetime and stability of representative molecular-clusters of two polymorphic forms of PABA in aqueous solution using molecular dynamics simulations. Simulations of 5 ns duration in the isothermal-isobaric ensemble (constant particle number, pressure and temperature (NPT) ensemble) were performed for the two polymorphic forms at three different temperatures 0 °C, 50 °C and 100 °C. The simulations revealed that at 0 °C the representative molecular-clusters of the two polymorphic forms remain ordered while at 50 °C the molecular packing within the clusters becomes partially disordered for both polymorphic forms and at 100 °C the clusters lose long-range order rapidly and come to resemble liquid drops. Care should be taken when assessing the relative stability of polymorphic forms, as a function of temperature, from such computational experiments which explore the dissolution of nano-scale crystals. The long range order of the clusters of the α-form at 50 °C and 100 °C was, respectively, partially and completely lost after 5 ns which merits further investigation given that the α-form is the high-temperature stable polymorph. Importantly, the initial shape of clusters, as well as the number of solute molecules they contained, affected the extent to which order was lost and how rapidly the loss occurred. Given that the classical nucleation theory predicts a finite probability that clusters significantly larger than the critical size, in terms of number of molecules, may dissolve, building clusters containing a greater number of molecules could improve the simulated stability of the α polymorph at 50 °C and 100 °C. Furthermore, the simulations revealed that the selection of a suitable electrostatic potential is very important for the

  3. Speciation in aqueous solutions of nitric acid.

    PubMed

    Hlushak, S; Simonin, J P; De Sio, S; Bernard, O; Ruas, A; Pochon, P; Jan, S; Moisy, P

    2013-02-28

    In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an extension of the binding mean spherical approximation (BiMSA), or associative MSA (AMSA), in which the size and the charge of the ions in the chemical pair may differ from those of the free ions. A simultaneous fit of the osmotic coefficient and of the proportion of free ions (obtained from Raman spectroscopy experiments) led to an estimation of the speciation in nitric acid solutions. The result obtained using this procedure was compared with the estimation obtained from the Raman experiments.

  4. Uranyl fluoride luminescence in acidic aqueous solutions

    SciTech Connect

    Beitz, J.V.; Williams, C.W.

    1996-08-01

    Luminescence emission spectra and decay rates are reported for uranyl species in acidic aqueous solutions containing HF or added NaF. The longest luminescence lifetime, 0.269 {+-} 0.006 ms, was observed from uranyl in 1 M HF + 1 M HClO{sub 4} at 296 K and decreased with increasing temperature. Based on a luminescence dynamics model that assumes equilibrium among electronically excited uranyl fluoride species and free fluoride ion, this long lived uranyl luminescence in aqueous solution is attributed primarily to UO{sub 2}F{sub 2}. Studies on the effect of added LiNO{sub 3} or Na{sub 2}WO{sub 4}{center_dot}2H{sub 2}O showed relatively weak quenching of uranyl fluoride luminescence which suggests that high sensitivity determination of the UF{sub 6} content of WF{sub 6} gas should be feasible via uranyl luminescence analysis of hydrolyzed gas samples of impure WF{sub 6}.

  5. Acidities of Water and Methanol in Aqueous Solution and DMSO

    ERIC Educational Resources Information Center

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  6. Proton defect solvation and dynamics in aqueous acid and base.

    PubMed

    Kale, Seyit; Herzfeld, Judith

    2012-10-29

    Easy come, easy go: LEWIS, a new model of reactive and polarizable water that enables the simulation of a statistically reliable number of proton hopping events in aqueous acid and base at concentrations of practical interest, is used to evaluate proton transfer intermediates in aqueous acid and base (picture, left and right, respectively).

  7. Photophysics of (CdSe)ZnS Colloidal Quantum Dots in an Aqueous Environment Stabilized with Amino Acids and Genetically-Modified Proteins

    SciTech Connect

    Ai, X.; Xu, Q.; Jones, M.; Song, Q.; Ding, S.-Y.; Ellingson, R. J.; Himmel, M.; Rumbles, G.

    2007-01-01

    Using a combination of two amino acids, histidine and N-acetyl-cysteine, to replace the original organic capping groups of (CdSe)ZnS quantum dots, water-soluble and highly luminescent (CdSe)ZnS quantum dots have been successfully prepared at pH 8. Characterization by steady-state and time-resolved photoluminescence spectroscopy, and transient absorption spectroscopy, demonstrate that the electronic properties of these quantum dots exceed those of the original as-synthesized samples dissolved in a more-conventional organic solvent. Furthermore, these amino acid-stabilized quantum dots have been assembled onto a cellulose substrate via cellulose binding proteins that specifically bind to cellulose and was genetically engineered to harbor dual hexahistidine tags at the N- and C-termini to confer binding with the zinc(II) on the quantum dot surface. The spectroscopic measurements show that the protein-bound quantum dots continue to retain their desirable electronic properties when bound on the substrate. Meanwhile, the specific and very selective binding properties of the proteins have remained effective. (1)Select optimal greenhouse gas (GHG) and petroleum reduction strategies for each fleet location, (2)Meet or exceed Federal fleet GHG and petroleum reduction requirements outlined in the Guidance, (3)Acquire vehicles to support these strategies while minimizing fleet size and vehicle miles traveled (VMT), (4)Refine strategies based on agency performance.

  8. Minimizing Unintentional Strain and Doping of Single-Layer Graphene on SiO2 in Aqueous Environments by Acid Treatments.

    PubMed

    Masuda, Katsuya; Sano, Masahito

    2015-05-05

    The effects of treating SiO2/Si with either acidic or alkaline solutions on single-layer graphene were investigated using Raman microscopy. It is well-known that in air graphene on SiO2 is unintentionally strained and hole-doped to different degrees, varying widely by sample. It is also known that various amine compounds act as electron donors to graphitic materials. In this study, a SiO2/Si substrate was simply dipped in either a concentrated HCl solution or pH 9.0 NaOH solution and then rinsed, prior to transferring graphene on it. The G and 2D peaks were followed at a fixed position on a single-layer graphene flake in water and various concentrations of pH 7.4 tris(hydroxymethyl)aminomethane (Tris) buffer. The results demonstrate that these treatments reduce the sample variation, improve the stability against Tris, and even bring some graphene samples close to a freestanding state. The Raman analysis reveals that the main effect of dipping is to relieve strain. The undoping effect on some samples is explained by the HCl solution becoming trapped between the graphene and SiO2 surface.

  9. Techniques for sensing methanol concentration in aqueous environments

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Valdez, Thomas I. (Inventor)

    2001-01-01

    An analyte concentration sensor that is capable of fast and reliable sensing of analyte concentration in aqueous environments with high concentrations of the analyte. Preferably, the present invention is a methanol concentration sensor device coupled to a fuel metering control system for use in a liquid direct-feed fuel cell.

  10. Aqueous-phase source of formic acid in clouds

    NASA Technical Reports Server (NTRS)

    Chameides, W. L.; Davis, D. D.

    1983-01-01

    The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

  11. Sonophotocatalytic mineralization of Norflurazon in aqueous environment.

    PubMed

    Sathishkumar, Panneerselvam; Mangalaraja, Ramalinga Viswanathan; Rozas, Oscar; Vergara, Carola; Mansilla, Héctor D; Gracia-Pinilla, M A; Anandan, Sambandam

    2016-03-01

    Norflurazon (4-chloro-5-(methylamino)-2-[3-(trifluoromethyl)phenyl]pyridazin-3(2H)-one; C12H9ClF3N3O) is an excellent weed controlling agent being practiced in the agricultural lands. The excessive addition or the undissolved Norflurazon (maximum solubility 28 mg/L at 25 °C) enters into the aquatic environment and causes the adverse effects associated with its high concentration. To avoid the perilous effects, visible light assisted photocatalysis set-up coupled with the 42 kHz ultrasound producing bath type sonicator is used to completely mineralize the Norflurazon. TiO2, ZnO and gold loaded zinc oxide nanocatalysts were utilized to study the mineralization of Norflurazon. Au-ZnO shows the greater efficiency for the sonophotocatalytic removal of Norflurazon among the various nanocatalysts employed to study the mineralization. The order of Norflurazon mineralization was sonophotocatalysis > sonocatalysis > photocatalysis. The additive effect was achieved for the sonophotocatalytic degradation. The high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometric (LCMS) analyses were employed to identify the various intermediates produced during the mineralization. The identification of four pseudo molecular ions and various intermediates using the LCMS analysis evidently suggests the sonophotocatalytic degradation was preceded in various decay pathways. A suitable mechanism has been proposed for the sonophotocatalytic mineralization of Norflurazon.

  12. Minimizing Frustration by Folding in an Aqueous Environment

    PubMed Central

    Mattos, Carla; Clark, A. Clay

    2010-01-01

    Although life as we know it evolved in an aqueous medium, the properties of water are not completely understood. In this review, we focus on the role of water in guiding protein folding and stability. Specifically, we discuss the mechanisms of protein folding in an aqueous environment, the effects of water on the folding energy landscape as well as the transition state ensemble, and interactions of water with the folded state. We show that water cannot be viewed as a passive solvent, but rather, plays a very active role in the life of a protein. PMID:17719000

  13. Peptide environment specifies conformation. Helicity of hydrophobic segments compared in aqueous, organic, and membrane environments.

    PubMed

    Li, S C; Deber, C M

    1993-11-05

    Transmembrane segments in integral membrane proteins exist characteristically as helices in lipid bilayers, yet are often rich in residues considered helix-destabilizing (Val, Ile, Gly) in soluble proteins. We propose that helicity of a transmembrane segment is likely to be affected by factors other than the "intrinsic" helical propensities of its component amino acids. This hypothesis is tested by comparing the conformation(s) in aqueous, organic, membrane-mimetic (micellar), and membrane (bilayer) environments of designed model peptides with systematically altered helical propensity and/or segmental hydrophobicity. Peptides of prototypic sequence NH2-(Ser-Lys)2-Ala5-Leu6-Ala7-Ala8-Leu9-Ala10-++ +Trp11-Ala12-Leu13-Ala14- (Lys-Ser)3-OH were synthesized, which incorporate a hydrophobic core "guest" segment (residues 5-14) into a water-soluble hydrophilic host matrix. Related peptides featured substitution of Leu6,9,13-->Gly, Leu6,9,13-->Ala, and Ala7,10,14-->Gly. Circular dichroism spectra revealed that algorithms for soluble proteins correctly predicted peptide helical proclivities in aqueous solutions, but peptide helicity in organic (trifluoroethanol) solvents, membrane-mimetic SDS micelles, and negatively charged lipid bilayer vesicles, was found to be governed almost exclusively by the segmental hydrophobicity of the peptide mid-hydrophobic core segment. In related Trp fluorescence studies, peptide-membrane association was similarly correlated with extent of hydrophobic interaction.

  14. Aqueous infrared carboxylate absorbances: Aliphatic di-acids

    USGS Publications Warehouse

    Cabaniss, S.E.; Leenheer, J.A.; McVey, I.F.

    1998-01-01

    Aqueous attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of 18 aliphatic di-carboxylic acids are reported as a function of pH. The spectra show isosbestic points and intensity changes which indicate that Beer's law is obeyed, and peak frequencies lie within previously reported ranges for aqueous carboxylates and pure carboxylic acids. Intensity sharing from the symmetric carboxylate stretch is evident in many cases, so that bands which are nominally due to alkyl groups show increased intensity at higher pH. The asymmetric stretch of the HA- species is linearly related to the microscopic acidity constant of the H2A species, with ??pK 2 intervening atoms). The results suggest that aqueous ATR-FTIR may be able to estimate 'intrinsic' pKa values of carboxylic acids, in addition to providing quantitative estimates of ionization. ?? 1998 Elsevier Science B.V. All rights reserved.

  15. Perfluoroalkyl acids in aqueous samples from Germany and Kenya.

    PubMed

    Shafique, Umer; Schulze, Stefanie; Slawik, Christian; Böhme, Alexander; Paschke, Albrecht; Schüürmann, Gerrit

    2016-06-22

    Continuous monitoring of chemicals in the environment is important to control their fate and to protect human health, flora, and fauna. Perfluoroalkyl acids (PFAAs) have been detected frequently in different environmental compartments during the last 15 years and have drawn much attention because of their environmental persistence, omnipresence, and bioaccumulation potential. Water is an important source of their transport. In the present study, distributions of PFAAs in river water, wastewater treatment plant (WWTP) effluent, and tap water from eastern part of Germany and western part of Kenya were investigated. Eleven perfluorocarboxylic acids (PFCAs) and five perfluorosulfonic acids (PFSAs) were analyzed using liquid chromatography/tandem mass spectrometry. Sum of mean concentrations of eight PFAAs detected in drinking tap water from Leipzig was 11.5 ng L(-1), dominated by perfluorooctanoic acid (PFOA, 6.2 ng L(-1)). Sums of mean riverine concentrations of PFAAs detected in Pleiße/White Elster, Saale, and Elbe (Germany) were 24.8, 54.3, and 26.8 ng L(-1), respectively. Annual flux of PFAAs from River Saale was estimated to be 164 ± 23 kg a(-1). The effluent of WWTP in Halle was found to contain four times higher levels of PFAAs than river water and was dominated by perfluorobutane sulfonate (PFBS) with 32 times higher concentration than the riverine level. It advocates that WWTPs are the point source of contaminating water bodies with PFAAs, and short-chain PFAAs are substituting long-chain homologues. Sums of mean riverine concentrations of PFAAs in Sosiani (Kenya) in samples from sparsely populated and densely populated areas were 58.8 and 109.4 ng L(-1), respectively, indicating that population directly affected the emissions of PFAAs to surface waters. The discussion includes thorough review and comparison of recently published literature reporting occurrence of PFAAs in aqueous matrices. Graphical abstract Perfluoroalkyl acids in aqueous

  16. Esterified sago waste for engine oil removal in aqueous environment.

    PubMed

    Ngaini, Zainab; Noh, Farid; Wahi, Rafeah

    2014-01-01

    Agro-waste from the bark of Metroxylon sagu (sago) was studied as a low cost and effective oil sorbent in dry and aqueous environments. Sorption study was conducted using untreated sago bark (SB) and esterified sago bark (ESB) in used engine oil. Characterization study showed that esterification has successfully improved the hydrophobicity, buoyancy, surface roughness and oil sorption capacity of ESB. Sorption study revealed that water uptake of SB is higher (30 min static: 2.46 g/g, dynamic: 2.67 g/g) compared with ESB (30 min static: 0.18 g/g, dynamic: 0.14 g/g). ESB, however, showed higher oil sorption capacity in aqueous environment (30 min static: 2.30 g/g, dynamic: 2.14) compared with SB (30 min static: 0 g/g, dynamic: 0 g/g). ESB has shown great poTENTial as effective oil sorbent in aqueous environment due to its high oil sorption capacity, low water uptake and high buoyancy.

  17. Decomposition Studies of Triphenylboron, Diphenylborinic Acid and Phenylboric Acid in Aqueous Alkaline Solutions Containing Copper

    SciTech Connect

    Crawford, C.L.; Peterson, R. A.

    1997-02-11

    This report documents the copper-catalyzed chemical kinetics of triphenylboron, diphenylborinic acid and phenylboric acid (3PB, 2PB and PBA) in aqueous alkaline solution contained in carbon-steel vessels between 40 and 70 degrees C.

  18. A Toolkit to Enable Hydrocarbon Conversion in Aqueous Environments

    PubMed Central

    Brinkman, Eva K.; Schipper, Kira; Bongaerts, Nadine; Voges, Mathias J.; Abate, Alessandro; Wahl, S. Aljoscha

    2012-01-01

    This work puts forward a toolkit that enables the conversion of alkanes by Escherichia coli and presents a proof of principle of its applicability. The toolkit consists of multiple standard interchangeable parts (BioBricks)9 addressing the conversion of alkanes, regulation of gene expression and survival in toxic hydrocarbon-rich environments. A three-step pathway for alkane degradation was implemented in E. coli to enable the conversion of medium- and long-chain alkanes to their respective alkanols, alkanals and ultimately alkanoic-acids. The latter were metabolized via the native β-oxidation pathway. To facilitate the oxidation of medium-chain alkanes (C5-C13) and cycloalkanes (C5-C8), four genes (alkB2, rubA3, rubA4and rubB) of the alkane hydroxylase system from Gordonia sp. TF68,21 were transformed into E. coli. For the conversion of long-chain alkanes (C15-C36), theladA gene from Geobacillus thermodenitrificans was implemented. For the required further steps of the degradation process, ADH and ALDH (originating from G. thermodenitrificans) were introduced10,11. The activity was measured by resting cell assays. For each oxidative step, enzyme activity was observed. To optimize the process efficiency, the expression was only induced under low glucose conditions: a substrate-regulated promoter, pCaiF, was used. pCaiF is present in E. coli K12 and regulates the expression of the genes involved in the degradation of non-glucose carbon sources. The last part of the toolkit - targeting survival - was implemented using solvent tolerance genes, PhPFDα and β, both from Pyrococcus horikoshii OT3. Organic solvents can induce cell stress and decreased survivability by negatively affecting protein folding. As chaperones, PhPFDα and β improve the protein folding process e.g. under the presence of alkanes. The expression of these genes led to an improved hydrocarbon tolerance shown by an increased growth rate (up to 50%) in the presences of 10% n-hexane in the culture

  19. Biodegradability of organic nanoparticles in the aqueous environment.

    PubMed

    Kümmerer, Klaus; Menz, Jakob; Schubert, Thomas; Thielemans, Wim

    2011-03-01

    Synthetic nanoparticles have already been detected in the aquatic environment. Therefore, knowledge on their biodegradability is of utmost importance for risk assessment but such information is currently not available. Therefore, the biodegradability of fullerenes, single, double, multi-walled as well as COOH functionalized carbon nanotubes and cellulose and starch nanocrystals in aqueous environment has been investigated according to OECD standards. The biodegradability of starch and cellulose nanoparticles was also compared with the biodegradability of their macroscopic counterparts. Fullerenes and all carbon nanotubes did not biodegrade at all, while starch and cellulose nanoparticles biodegrade to similar levels as their macroscopic counterparts. However, neither comfortably met the criterion for ready biodegradability (60% after 28 days). The cellulose and starch nanoparticles were also found to degrade faster than their macroscopic counterparts due to their higher surface area. These findings are the first report of biodegradability of organic nanoparticles in the aquatic environment, an important accumulation environment for manmade compounds.

  20. Formation of droplet networks that function in aqueous environments

    NASA Astrophysics Data System (ADS)

    Villar, Gabriel; Heron, Andrew J.; Bayley, Hagan

    2011-12-01

    Aqueous droplets in oil that are coated with lipid monolayers and joined through interface bilayers are useful for biophysical measurements on membrane proteins. Functional networks of droplets that can act as light sensors, batteries and electrical components can also be made by incorporating pumps, channels and pores into the bilayers. These networks of droplets mimic simple tissues, but so far have not been used in physiological environments because they have been constrained to a bulk oil phase. Here, we form structures called multisomes in which networks of aqueous droplets with defined compositions are encapsulated within small drops of oil in water. The encapsulated droplets adhere to one another and to the surface of the oil drop to form interface bilayers that allow them to communicate with each other and with the surrounding aqueous environment through membrane pores. The contents in the droplets can be released by changing the pH or temperature of the surrounding solution. The multicompartment framework of multisomes mimics a tissue and has potential applications in synthetic biology and medicine.

  1. Polymerization of beta-amino acids in aqueous solution

    NASA Technical Reports Server (NTRS)

    Liu, R.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    1998-01-01

    We have compared carbonyl diimidazole (CDI) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as activating agents for the oligomerization of negatively-charged alpha- and beta-amino acids in homogeneous aqueous solution. alpha-Amino acids can be oligomerized efficiently using CDI, but not by EDAC. beta-Amino acids can be oligomerized efficiently using EDAC, but not by CDI. Aspartic acid, an alpha- and beta-dicarboxylic acid is oligomerized efficiently by both reagents. These results are explained in terms of the mechanisms of the reactions, and their relevance to prebiotic chemistry is discussed.

  2. Persistent ion pairing in aqueous hydrochloric acid.

    PubMed

    Baer, Marcel D; Fulton, John L; Balasubramanian, Mahalingam; Schenter, Gregory K; Mundy, Christopher J

    2014-07-03

    For strong acids, like hydrochloric acid, the complete dissociation into an excess proton and conjugated base as well as the formation of independent solvated charged fragments is assumed. The existence of chloride-hydronium (Cl(-)···H3O(+)) contact ion pairs even in moderate concentration hydrochloric acid (2.5 m) demonstrates that the counterions do not behave merely as spectators. Through comparison of recent extended X-ray absorption fine structure (EXAFS) measurements to state-of-the-art density functional theory (DFT) simulations, we are able to obtain a unique view into the molecular structure of medium-to-high concentrated electrolytes. Here we report that the Cl(-)···H3O(+) contact ion pair structure persists throughout the entire concentration range studied and that these structures differ significantly from moieties studied in microsolvated hydrochloric acid gas phase clusters. Characterizing distinct populations of these ion pairs gives rise to a novel molecular level description of how to view the reaction network for acid dissociation and how it relates to our picture of acid-base equilibria.

  3. Molecularly imprinted polymers for histamine recognition in aqueous environment.

    PubMed

    Trikka, Foteini A; Yoshimatsu, Keiichi; Ye, Lei; Kyriakidis, Dimitrios A

    2012-11-01

    Molecularly imprinted polymers (MIP) for histamine using methacrylic acid were developed and recognition mechanisms were thoroughly characterized for the first time in this study. The binding affinity of imprinted polymer with structurally related compounds was studied in organic and aqueous media, at various conditions. In organic media, MIP was found to bind histamine two and six times more than ranitidine and fluoxetine, respectively, whereas higher selectivity was observed in the case of dimentidene or disodium cromoglycate. The specific binding sites of MIP recognized histamine over L-histidine in aqueous conditions, while higher affinity for histamine compared to ranitidine, disodium cromoglycate, putrescine and to a putrescine analogue was observed. A combination of NMR and UV spectroscopy analyses for investigation of imprinting and recognition properties revealed that strong specific interactions between the functional monomer and histamine in the prepolymerization and in the aqueous solutions were probably responsible for histamine recognition. The preparation of histamine MIPs and elucidation of imprinting and recognition mechanism may serve as useful insight for future application of MIPs.

  4. Aqueous Trifluoromethane Sulfonic Acid Fuel Cells.

    DTIC Science & Technology

    1981-02-01

    Development of Low Tempera- ture Acid Electrolytes," National Fuel Cell Seminar, Bethesda, MD, June 1979. 8 George, M. and Januszkiewicz , S., "New Materials...Department 2- K US Department of Energy (1) LaVerne, CA 91750 ATTN: Mr. Gary Voelker 20 Massachusetts Avenue, NW Union Carbide Corporation (1) Washington, DC

  5. Persistent Ion Pairing in Aqueous Hydrochloric Acid

    SciTech Connect

    Baer, Marcel D.; Fulton, John L.; Balasubramanian, Mahalingam; Schenter, Gregory K.; Mundy, Christopher J.

    2014-07-03

    For strong acids, like hydrochloric acid, the complete dissociation into an excess proton and conjugated base as well as the formation of independent solvated charged fragments is assumed. The existence of a chloride-Hyronium (Cl-H3O+) contact ion pairs even in moderate concentration hydrochloric acid (2.5 m) demonstrates that the counter ions do not behave merely as spectators. Through the use of modern extended X-ray absorption fine structure (EXAFS) measurements in conjunction with state-of-the-art density functional theory (DFT) simulations, we are able to obtain an unprecedented view into the molecular structure of medium to high concentrated electrolytes. Here we report that the Cl-H3O+ contact ion pair structure persists throughout the entire concentration range studied and that these structures differ significantly from moieties studied in micro-solvated hydrochloric acid clusters. Characterizing distinct populations of these ion pairs gives rise to a novel molecular level description of how to think about the activity of the proton that impacts our picture of the pH scale. Funding for CJM, GKS, and JLF was provided by DOE Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences. Funding for MDB was provided throught the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory. MB was funded through Argonne National Laboratory.

  6. The effect of body coverings on the formation of adipocere in an aqueous environment.

    PubMed

    Notter, Stephanie J; Stuart, Barbara H

    2012-01-01

    Adipocere is a postmortem decomposition product that consists of a mixture of fatty acids. The rate of formation of adipocere from pig adipose tissue in an aqueous environment has been monitored. The effect of various clothing and carpet material types on the process was investigated. The fatty acid composition of the adipocere was determined at regular intervals using gas chromatography-mass spectrometry. Examination of the changes to fatty acid concentrations allowed the degree of adipocere formation in the different environments to be estimated. The study demonstrated that the rate at which adipocere forms is particularly accelerated by the presence of coverings produced from natural materials. Elemental analysis by inductively coupled plasma-mass spectrometry revealed, for the most part, little change to the cations present in the adipocere formed. However, an increase in Ca concentration was observed for tissue wrapped in acrylic carpet, which was associated with a CaCO(3) additive used in the carpet manufacture.

  7. Atmospheric Implications of Aqueous Solvation on the Photochemistry of Pyruvic Acid

    NASA Astrophysics Data System (ADS)

    Reed Harris, A. E.; Ervens, B.; Shoemaker, R.; Kroll, J. A.; Rapf, R.; Griffith, E. C.; Monod, A.; Vaida, V.

    2014-12-01

    Formation of aerosol from organic compounds is under investigation in order to better predict the overall radiative forcing from atmospheric aerosols and their influence on global climate. One possible formation pathway for secondary organic aerosol (SOA), which is now becoming more widely accepted, is from bulk aqueous photoreactions in atmospheric particles that create low volatility compounds. These products may remain particulate upon droplet evaporation, increasing SOA mass in the atmosphere. SOA formed in this manner may account for some of the discrepancy between measured and predicted amounts of SOA. This presentation will describe the photochemistry of pyruvic acid, an α-keto acid found in the atmosphere, in aqueous solutions representative of solutes in fogs, clouds, and wet aerosols. Solvation of pyruvic acid in water changes the photodissociation mechanism and products from that of the gas phase. The photoproducts from the aqueous phase are higher in molecular weight and therefore possible SOA precursors. Further, these polymers partition to the surface of water and are expected to modify the the surface properties of atmospheric aerosols that determine the kinetics of water uptake. The reaction mechanism of pyruvic acid as a function of its environment and concentration will be presented along with the kinetics obtained for the photochemistry in aqueous solution. These results are used as input in an atmospheric model to evaluate the atmospheric consequences of solvation of pyruvic acid on its atmospheric reactivity and its role as a global sink.

  8. Nanotribological characterization of human head hair by friction force microscopy in dry atmosphere and aqueous environment.

    PubMed

    Nikogeorgos, Nikos; Fletcher, Ian W; Boardman, Christopher; Doyle, Peter; Ortuoste, Nerea; Leggett, Graham J

    2010-06-01

    Friction force microscopy was employed for the tribological investigation of human head hair in two different environments: a dry atmosphere and de-ionized water. The fibers were immobilized by embedding them in indium. The effects of bleaching, conditioning, and immersion in methanolic KOH were quantified in terms of the relative coefficient of friction (μ). The virgin fibers were clearly distinguished in terms of friction coefficient from the chemically damaged ones in both environments, while all categories of hair exhibited higher friction coefficients in the aqueous environment. Secondary ion mass spectroscopy was used as a complementary technique to examine the presence of fatty acids on the cuticular surface of the different categories of hair as well as the conditioner distribution. Neither bleaching nor 30 min treatment in methanolic KOH was found adequate to completely remove the fatty acids from the fibers' surface. Conditioner species were detected along the whole cuticular surface.

  9. Amino-acid contamination of aqueous hydrochloric acid.

    NASA Technical Reports Server (NTRS)

    Wolman, Y.; Miller, S. L.

    1971-01-01

    Considerable amino-acid contamination in commercially available analytical grade hydrochloric acid (37% HCl) was found. One bottle contained 8,300 nmol of amino-acids per liter. A bottle from another supplier contained 6,700 nmol per liter. The contaminants were mostly protein amino-acids and several unknowns. Data on the volatility of the amino-acids during HCl distillation were also obtained.

  10. Simply enhancing throughput of free-flow electrophoresis via organic-aqueous environment for purification of weak polarity solute of phenazine-1-carboxylic acid in fermentation of Pseudomonas sp. M18.

    PubMed

    Yang, Jing-Hua; Shao, Jing; Wang, Hou-Yu; Dong, Jing-Yu; Fan, Liu-Yin; Cao, Cheng-Xi; Xu, Yu-Quan

    2012-09-01

    Herein, a simple novel free-flow electrophoresis (FFE) method was developed via introduction of organic solvent into the electrolyte system, increasing the solute solubility and throughput of the sample. As a proof of concept, phenazine-1-carboxylic acid (PCA) from Pseudomonas sp. M18 was selected as a model solute for the demonstration on feasibility of novel FFE method on account of its faint solubility in aqueous circumstance. In the developed method, the organic solvent was added into not only the sample buffer to improve the solubility of the solute, but also the background buffer to construct a uniform aqueous-organic circumstance. These factors of organic solvent percentage and types as well as pH value of background buffer were investigated for the purification of PCA in the FFE device via CE. The experiments revealed that the percentage and the types of organic solvent exerted major influence on the purification of PCA. Under the optimized conditions (30 mM phosphate buffer in 60:40 (v/v) water-methanol at an apparent pH 7.0, 3.26 mL/min background flux, 10-min residence time of injected sample, and 400 V), PCA could be continuously purified from its impurities. The flux of sample injection was 10.05 μL/min, and the recovery was up to 93.7%. An 11.9-fold improvement of throughput was found with a carrier buffer containing 40% (v/v) methanol, compared with the pure aqueous phase. The developed procedure is of evident significance for the purification of weak polarity solute via FFE.

  11. γ-Irradiation of malic acid in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Negron-Mendoza, Alicia; Graff, Rebecca L.; Ponnamperuma, Cyril

    1980-12-01

    The γ-irradiation of malic acid in aqueous solutions was studied under initially oxygenated and oxygen-free conditions in an attempt to determine the possible interconversion of malic acid into other carboxylic acids, specifically those associated with Krebs cycle. The effect of dose on product formation of the system was investigated. Gas-liquid chromatography combined with mass spectrometry was used as the principal means of identification of the non-volatile products. Thin layer chromotography and direct probe mass spectroscopy were also employed. The findings show that a variety of carboxylic acids are formed, with malonic and succinic acids in greatest abundance. These products have all been identified as being formed in the γ-irradiation of acetic acid, suggesting a common intermediary. Since these molecules fit into a metabolic cycle, it is strongly suggestive that prebiotic pathways provided the basis for biological systems.

  12. Investigation of acyl migration in mono- and dicaffeoylquinic acids under aqueous basic, aqueous acidic, and dry roasting conditions.

    PubMed

    Deshpande, Sagar; Jaiswal, Rakesh; Matei, Marius Febi; Kuhnert, Nikolai

    2014-09-17

    Acyl migration in chlorogenic acids describes the process of migration of cinnamoyl moieties from one quinic acid alcohol group to another, thus interconverting chlorogenic acid regioisomers. It therefore constitutes a special case of transesterification reaction. Acyl migration constitutes an important reaction pathway in both coffee roasting and brewing, altering the structure of chlorogenic acid initially present in the green coffee bean. In this contribution we describe detailed and comprehensive mechanistic studies comparing inter- and intramolecular acyl migration involving the seven most common chlorogenic acids in coffee. We employe aqueous acidic and basic conditions mimicking the brewing of coffee along with dry roasting conditions. We show that under aqueous basic conditions intramolecular acyl migration is fully reversible with basic hydrolysis competing with acyl migration. 3-Caffeoylquinic acid was shown to be most labile to basic hydrolysis. We additionally show that the acyl migration process is strongly pH dependent with increased transesterification taking place at basic pH. Under dry roasting conditions acyl migration competes with dehydration to form lactones. We argue that acyl migration precedes lactonization, with 3-caffeoylquinic acid lactone being the predominant product.

  13. Near infrared photochemistry of pyruvic acid in aqueous solution.

    PubMed

    Larsen, Molly C; Vaida, Veronica

    2012-06-21

    Recent experimental and theoretical results have suggested that organic acids such as pyruvic acid, can be photolyzed in the ground electronic state by the excitation of the OH stretch vibrational overtone. These overtones absorb in the near-infrared and visible regions of the spectrum where the solar photons are plentiful and could provide a reaction pathway for the organic acids and alcohols that are abundant in the earth's atmosphere. In this paper the overtone initiated photochemistry of aqueous pyruvic acid is investigated by monitoring the evolution of carbon dioxide. In these experiments CO(2) is being produced by excitation in the near-infrared, between 850 nm and ∼1150 nm (11,765-8696 cm(-1)), where the second OH vibrational overtone (Δν = 3) of pyruvic acid is expected to absorb. These findings show not only that the overtone initiated photochemical decarboxylation reaction occurs but also that in the aqueous phase it occurs at a lower energy than was predicted for the overtone initiated reaction of pyruvic acid in the gas phase (13,380 cm(-1)). A quantum yield of (3.5 ± 1.0) × 10(-4) is estimated, suggesting that although this process does occur, it does so with a very low efficiency.

  14. Biocompatible coatings for CMUTs in a harsh, aqueous environment

    NASA Astrophysics Data System (ADS)

    Zhuang, X.; Nikoozadeh, A.; Beasley, M. A.; Yaralioglu, G. G.; Khuri-Yakub, B. T.; Pruitt, B. L.

    2007-05-01

    The results of coating capacitive micromachined ultrasonic transducer (CMUT) arrays with two different biocompatible materials, parylene-c and polydimethylsiloxane (PDMS), are reported. These materials were characterized for use with CMUTs to enable direct contact transcutaneous and in vivo imaging. A passivation coating is required to provide electrical isolation to the active areas of the device and to protect it from a corrosive environment. It must also provide good mechanical characteristics to void imaging artifacts. The coated devices were compared side by side with uncoated devices for testing in air. The resonant frequency, collapse voltage and crosstalk were sampled. Parylene coated CMUTs were also tested underwater using pulse excitation. The parylene coating provided electrical insulation to the aqueous solution for 14 days. Both coatings showed a decrease in device resonant frequency and an increase in collapse voltage, as expected from the proposed theory.

  15. A critique of homogeneous freezing measurements of aqueous sulfuric acid

    NASA Astrophysics Data System (ADS)

    Alofs, Darryl J.; Vandike, John L.

    2000-08-01

    Two laboratory measurements of homogeneous freezing of aqueous sulfuric acid particles are critiqued: The first by Bertram et al., 1996, J. Phys. Chem., vol. 100, pp. 2376-2383: the second by Koop et al., 1998, J. Phys. Chem. A, vol. 102, pp. 8924-8931. Calculations for a proposed experimental artifact are inconclusive for Bertram et al. A proposed artifact for Koop et al. is shown to be insignificant.

  16. Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, 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 may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

  17. 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.

  18. Proton NMR studies of functionalized nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Tataurova, Yulia Nikolaevna

    Nanoscience is an emerging field that can provide potential routes towards addressing critical issues such as clean and sustainable energy, environmental remediation and human health. Specifically, porous nanomaterials, such as zeolites and mesoporous silica, are found in a wide range of applications including catalysis, drug delivery, imaging, environmental protection, and sensing. The characterization of the physical and chemical properties of nanocrystalline materials is essential to the realization of these innovative applications. The great advantage of porous nanocrystals is their increased external surface area that can control their biological, chemical and catalytic activities. Specific functional groups synthesized on the surface of nanoparticles are able to absorb heavy metals from the solution or target disease cells, such as cancer cells. In these studies, three main issues related to functionalized nanomaterials will be addressed through the application of nuclear magnetic resonance (NMR) techniques including: 1) surface composition and structure of functionalized nanocrystalline particles; 2) chemical properties of the guest molecules on the surface of nanomaterials, and 3) adsorption and reactivity of surface bound functional groups. Nuclear magnetic resonance (NMR) is one of the major spectroscopic techniques available for the characterization of molecular structure and conformational dynamics with atomic level detail. This thesis deals with the application of 1H solution state NMR to porous nanomaterial in an aqueous environment. Understanding the aqueous phase behavior of functionalized nanomaterials is a key factor in the design and development of safe nanomaterials because their interactions with living systems are always mediated through the aqueous phase. This is often due to a lack of fundamental knowledge in interfacial chemical and physical phenomena that occur on the surface of nanoparticles. The use of solution NMR spectroscopy results

  19. Dephosphorization of Steelmaking Slag by Leaching with Acidic Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Qiao, Yong; Diao, Jiang; Liu, Xuan; Li, Xiaosa; Zhang, Tao; Xie, Bing

    2016-09-01

    In the present paper, dephosphorization of steelmaking slag by leaching with acidic aqueous solution composed of citric acid, sodium hydroxide, hydrochloric acid and ion-exchanged water was investigated. The buffer solution of C6H8O7-NaOH-HCl system prevented changes in the pH values. Kinetic parameters including leaching temperature, slag particle size and pH values of the solution were optimized. The results showed that temperature has no obvious effect on the dissolution ratio of phosphorus. However, it has a significant effect on the dissolution ratio of iron. The dephosphorization rate increases with the decrease of slag particle size and the pH value of the solution. Over 90% of the phosphorus can be dissolved in the solution while the corresponding leaching ratio of iron was only 30% below the optimal condition. Leaching kinetics of dephosphorization follow the unreacted shrinking core model with a rate controlled step by the solid diffusion layer, the corresponding apparent activation energy being 1.233 kJ mol-1. A semiempirical kinetic equation was established. After leaching, most of the nC2S-C3P solid solution in the steelmaking slag was selectively dissolved in the aqueous solution and the iron content in the solid residue was correspondingly enriched.

  20. Removal of fluoride from aqueous environment by modified Amberlite resin.

    PubMed

    Solangi, Imam Bakhsh; Memon, Shahabuddin; Bhanger, M I

    2009-11-15

    Fluoride in drinking water above permissible level is responsible for human being affected by skeletal fluorosis. In this study, Amberlite XAD-4 has been modified by introducing amino group onto the aromatic ring for its application in fluoride remediation. Characterization of the modified resin was made by, FT-IR and elemental analysis (CHNS) techniques. The pH 9 was optimum value for quantitative sorption of fluoride in both batch and column experiments. The desorption of fluoride was achieved by using 10% HCl. The batch and column sorption studies of fluoride with modified resin were carried out to evaluate sorption isotherms too. Thus equation isotherms such as Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) were successfully used to model the experimental data. The sorption capacity of modified Amberlite XAD-4 resin was found as 5.04 x 10(-3) mol g(-1). From the D-R isotherm parameters, it has been evaluated that the uptake of fluoride by modified resin occurs through ion exchange adsorption mechanism. The study will contribute toward the removal of fluoride from the aqueous environment as well as in the field of analytical and environmental chemistry.

  1. Protonation Dynamics and Hydrogen Bonding in Aqueous Sulfuric Acid.

    PubMed

    Niskanen, Johannes; Sahle, Christoph J; Juurinen, Iina; Koskelo, Jaakko; Lehtola, Susi; Verbeni, Roberto; Müller, Harald; Hakala, Mikko; Huotari, Simo

    2015-09-03

    Hydration of sulfuric acid plays a key role in new-particle formation in the atmosphere. It has been recently proposed that proton dynamics is crucial in the stabilization of these clusters. One key question is how water molecules mediate proton transfer from sulfuric acid, and hence how the deprotonation state of the acid molecule behaves as a function concentration. We address the proton transfer in aqueous sulfuric acid with O K edge and S L edge core-excitation spectra recorded using inelastic X-ray scattering and with ab initio molecular dynamics simulations in the concentration range of 0-18.0 M. Throughout this range, we quantify the acid-water interaction with atomic resolution. Our simulations show that the number of donated hydrogen bonds per Owater increases from 1.9 to 2.5 when concentration increases from 0 to 18.0 M, in agreement with a rapid disappearance of the pre-edge feature in the O K edge spectrum. The simulations also suggest that for 1.5 M sulfuric acid SO4(2-) is most abundant and that its concentration falls monotonously with increasing concentration. Moreover, the fraction of HSO4(-) peaks at ∼12 M.

  2. Fermentation of aqueous plant seed extracts by lactic acid bacteria

    SciTech Connect

    Schafner, D.W.; Beuchat, R.L.

    1986-05-01

    The effects of lactic acid bacterial fermentation on chemical and physical changes in aqueous extracts of cowpea (Vigna unguiculata), peanut (Arachis hypogea), soybean (Glycine max), and sorghum (Sorghum vulgare) were studied. The bacteria investigated were Lactobacillus helveticus, L. delbrueckii, L. casei, L. bulgaricus, L. acidophilus, and Streptococcus thermophilus. Organisms were inoculated individually into all of the seed extracts; L. bulgaricus and S. thermophilus were also evaluated together as inocula for fermenting the legume extracts. During fermentation, bacterial population and changes in titratable acidity, pH, viscosity, and color were measured over a 72 h period at 37 degrees C. Maximum bacterial populations, titratable acidity, pH, and viscosity varied depending upon the type of extract and bacterial strain. The maximum population of each organism was influenced by fermentable carbohydrates, which, in turn, influenced acid production and change in pH. Change in viscosity was correlated with the amount of protein and titratable acidity of products. Color was affected by pasteurization treatment and fermentation as well as the source of extract. In the extracts inoculated simultaneously with L. bulgaricus and S. thermophilus, a synergistic effect resulted in increased bacterial populations, titratable acidity, and viscosity, and decreased pH in all the legume extracts when compared to the extracts fermented with either of these organisms individually. Fermented extracts offer potential as substitutes for cultured dairy products. 24 references.

  3. Robust magnetic/polymer hybrid nanoparticles designed for crude oil entrapment and recovery in aqueous environments.

    PubMed

    Pavía-Sanders, Adriana; Zhang, Shiyi; Flores, Jeniree A; Sanders, Jonathan E; Raymond, Jeffery E; Wooley, Karen L

    2013-09-24

    Well-defined, magnetic shell cross-linked knedel-like nanoparticles (MSCKs) with hydrodynamic diameters ca. 70 nm were constructed through the co-assembly of amphiphilic block copolymers of PAA20-b-PS280 and oleic acid-stabilized magnetic iron oxide nanoparticles using tetrahydrofuran, N,N-dimethylformamide, and water, ultimately transitioning to a fully aqueous system. These hybrid nanomaterials were designed for application as sequestering agents for hydrocarbons present in crude oil, based upon their combination of amphiphilic organic domains, for aqueous solution dispersibility and capture of hydrophobic guest molecules, with inorganic core particles for magnetic responsivity. The employment of these MSCKs in a contaminated aqueous environment resulted in the successful removal of the hydrophobic contaminants at a ratio of 10 mg of oil per 1 mg of MSCK. Once loaded, the crude oil-sorbed nanoparticles were easily isolated via the introduction of an external magnetic field. The recovery and reusability of these MSCKs were also investigated. These results suggest that deployment of hybrid nanocomposites, such as these, could aid in environmental remediation efforts, including at oil spill sites, in particular, following the bulk recovery phase.

  4. Volatility of organic aerosol: evaporation of ammonium sulfate/succinic acid aqueous solution droplets.

    PubMed

    Yli-Juuti, Taina; Zardini, Alessandro A; Eriksson, Axel C; Hansen, Anne Maria K; Pagels, Joakim H; Swietlicki, Erik; Svenningsson, Birgitta; Glasius, Marianne; Worsnop, Douglas R; Riipinen, Ilona; Bilde, Merete

    2013-01-01

    Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol.

  5. Polymerization of Pu(IV) in aqueous nitric acid solutions

    SciTech Connect

    Toth, L.M.; Friedman, H.A.; Osborne, M.M.

    1980-10-01

    The polymerization of Pu(IV) in aqueous nitric acid solutions has been studied spectrophotometrically both to establish the influence of large UO{sub 2}(NO{sub 3}){sub 2} concentrations on the polymerization rates and, more generally, to review the influence of the major parameters on the polymer reaction. Typically, experiments have been performed at 50{sup 0}C and with 0.05 M Pu in nitric acid solutions that vary in acidity from 0.07 to 0.4 M. An induction period usually precedes the polymer growth stage during which time nucleation of primary hydrolysis products occurs. Uranyl nitrate retards the polymerization reaction by approximately 35% in spite of the counteracting influence of the nitrate ions associated with this solute. The rate of polymer formation, expressed as d(percent polymer)/dt, has been shown to depend on the total plutonium concentration in reactions where the Pu(IV) concentration remained constant; and it is therefore suggested that the polymer reaction rate is not first order with respect to the concentration of plutonium as was previously thought. It has been shown further that accurate acid determinations on stock reagents are essential in order to obtain reliable polymerization experiments. Satisfactory procedures for these analyses did not exist, so appropriate modifications to the iodate precipitation methods were developed. The most ideal plutonium reagent material has been shown to be crystalline Pu(IV) nitrate because it can be added directly to acid solutions without the occurrence of unintentional hydrolysis reactions.

  6. Modeling and 3-D Simulation of Biofilm Dynamics in Aqueous Environment

    NASA Astrophysics Data System (ADS)

    Wang, Qi

    2011-11-01

    We present a complex fluid model for biofilms growing in an aqueous environment. The modeling approach represents a new paradigm to develop models for biofilm-environment interaction that can be used to systematically incorporate refined chemical and physiological mechanisms. Special solutions of the model are presented and analyzed. 3-D numerical simulations in aqueous environment with emphasis on biofilm- ambient fluid interaction will be discussed in detail.

  7. Sunlight-initiated Chemistry of Aqueous Pyruvic Acid: Building Complexity in the Origin of Life

    NASA Astrophysics Data System (ADS)

    Griffith, Elizabeth C.; Shoemaker, Richard K.; Vaida, Veronica

    2013-10-01

    Coupling chemical reactions to an energy source is a necessary step in the origin of life. Here, we utilize UV photons provided by a simulated sun to activate aqueous pyruvic acid and subsequently prompt chemical reactions mimicking some of the functions of modern metabolism. Pyruvic acid is interesting in a prebiotic context due to its prevalence in modern metabolism and its abiotic availability on early Earth. Here, pyruvic acid (CH3COCOOH, a C3 molecule) photochemically reacts to produce more complex molecules containing four or more carbon atoms. Acetoin (CH3CHOHCOCH3), a C4 molecule and a modern bacterial metabolite, is produced in this chemistry as well as lactic acid (CH3CHOHCOOH), a molecule which, when coupled with other abiotic chemical reaction pathways, can provide a regeneration pathway for pyruvic acid. This chemistry is discussed in the context of plausible environments on early Earth such as near the ocean surface and atmospheric aerosol particles. These environments allow for combination and exchange of reactants and products of other reaction environments (such as shallow hydrothermal vents). The result could be a contribution to the steady increase in chemical complexity requisite in the origin of life.

  8. Conformation of poly(γ-glutamic acid) in aqueous solution.

    PubMed

    Muroga, Yoshio; Nakaya, Asami; Inoue, Atsuki; Itoh, Daiki; Abiru, Masaya; Wada, Kaori; Takada, Masako; Ikake, Hiroki; Shimizu, Shigeru

    2016-04-01

    Local conformation and overall conformation of poly(γ-DL-glutamic acid) (PγDLGA) and poly(γ-L-glutamic acid) (PγLGA) in aqueous solution was studied as a function of degree of ionization ε by (1) H-NMR, circular dichroism, and potentiometric titration. It was clarified that their local conformation is represented by random coil over an entire ε range and their overall conformation is represented by expanded random-coil in a range of ε > ε(*) , where ε(*) is about 0.3, 0.35, 0.45, and 0.5 for added-salt concentration of 0.02M, 0.05M, 0.1M, and 0.2M, respectively. In a range of ε < ε(*) , however, ε dependence of their overall conformation is significantly differentiated from each other. PγDLGA tends to aggregate intramolecularly and/or intermolecularly with decreasing ε, but PγLGA still behaves as expanded random-coil. It is speculated that spatial arrangement of adjacent carboxyl groups along the backbone chain essentially affects the overall conformation of PγGA in acidic media.

  9. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid

    NASA Astrophysics Data System (ADS)

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

    2014-10-01

    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (Ep, 1.10 ≤ Ep ≤ 1.50 V), polarization time (tp, 100 ≤ tp ≤ 104 s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (dox). Because X1 > dox for the entire range of Ep, tp, and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Ptδ+-Oδ- surface dipole (μPtO), and the potential drop (Vox) and electric field (Eox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

  10. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment

    SciTech Connect

    Kroning, Annika; Furchner, Andreas; Aulich, Dennis; Bittrich, Eva; Rauch, Sebastian; Uhlmann, Petra; Eichhorn, Klaus-Jochen; Seeber, Michael; Luzinov, Igor; Kilbey, S. Michael; Lokitz, Bradley S.; Minko, Sergiy; Hinrichs, Karsten

    2015-02-10

    The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes with high potential for biosensing and biomedical applications are studied by in-situ infrared-spectroscopic ellipsometry (IRSE). IRSE as a highly sensitive non-destructive technique allows us to investigate protein adsorption on polymer brushes in aqueous environment in dependence of external stimuli like temperature and pH. These stimuli are, for instance, relevant in switchable mixed brushes containing poly(N-isopropyl acrylamide) and poly(acrylic acid), respectively. We use such brushes as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. IRSE can distinguish between polymer-specific vibrational bands, which yield insights into the hydration state of the brushes, and changes in the protein-specific amide bands, which are related to changes of the protein secondary structure.

  11. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment

    DOE PAGES

    Kroning, Annika; Furchner, Andreas; Aulich, Dennis; ...

    2015-02-10

    The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes with high potential for biosensing and biomedical applications are studied by in-situ infrared-spectroscopic ellipsometry (IRSE). IRSE as a highly sensitive non-destructive technique allows us to investigate protein adsorption on polymer brushes in aqueous environment in dependence of external stimuli like temperature and pH. These stimuli are, for instance, relevant in switchable mixed brushes containing poly(N-isopropyl acrylamide) and poly(acrylic acid), respectively. We use such brushes as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. IRSE can distinguish between polymer-specific vibrational bands, which yield insights intomore » the hydration state of the brushes, and changes in the protein-specific amide bands, which are related to changes of the protein secondary structure.« less

  12. Determination of aqueous acid-dissociation constants of aspartic acid using PCM/DFT method

    NASA Astrophysics Data System (ADS)

    Sang-Aroon, Wichien; Ruangpornvisuti, Vithaya

    Determination of acid-dissociation constants, pKa, of aspartic acid in aqueous solution, using density functional theory calculations combined with the conductor-like polarizable continuum model (CPCM) and with integral-equation-formalism polarizable continuum model (IEFPCM) based on the UAKS and UAHF radii, was carried out. The computed pKa values derived from the CPCM and IEFPCM with UAKS cavity model of bare structures of the B3LYP/6-31+G(d,p)-optimized tetrahydrated structures of aspartic acid species are mostly close to the experimental pKa values.0

  13. (Acidic deposition and the environment)

    SciTech Connect

    Garten, C.T.; Lindberg, S.E.; Van Miegroet, H.

    1990-10-24

    The travelers presented several papers at the Fourth International Conference on Acidic Deposition. These covered the following topics: atmospheric chemistry and deposition of airborne nitrogen compounds, soil solution chemistry in high-elevation spruce forests, and forest throughfall measurements for estimating total sulfur deposition to ecosystems. In addition, S. E. Lindberg was invited to organize and chair a conference session on Throughfall and Stemflow Experiments, and to present an invited lecture on Atmospheric Deposition and Canopy Interactions of Metals and Nitrogen in Forest Ecosystems: The Influence of Global Change'' at the 110th Anniversary Celebration of the Free University of Amsterdam.

  14. Theoretical calculations of the thermodynamic stability of ionic substitutions in hydroxyapatite under an aqueous solution environment.

    PubMed

    Matsunaga, Katsuyuki; Murata, Hidenobu; Shitara, Kazuki

    2010-09-29

    Defect formation energies in materials generally depend on chemical potentials determined by a chemical equilibrium condition. In particular, an aqueous solution environment is important for biomaterials such as hydroxyapatite studied here. Therefore, a methodology to obtain ionic chemical potentials under chemical equilibrium between solid and aqueous solution was introduced, and was applied to substitutional divalent cations formed via ion exchange with Ca(2+) in hydroxyapatite. The calculated ranking of the stability of substitutional cations in HAp was in good agreement with the experimentally observed trend. The present theoretical approach would be useful to explore the thermodynamic stability of defects in materials subjected to an aqueous solution environment.

  15. Effects of aqueous environment on long-term durability of phosphate-bonded ceramic waste forms

    SciTech Connect

    Singh, D.; Wagh, A.S.; Jeong, S.Y.

    1996-03-01

    Over the last few years, Argonne National Laboratory has been developing room-temperature-setting chemically-bonded phosphate ceramics for solidifying and stabilizing low-level mixed wastes. This technology is crucial for stabilizing waste streams that contain volatile species and off-gas secondary waste streams generated by high-temperature treatment of such wastes. Magnesium phosphate ceramic has been developed to treat mixed wastes such as ash, salts, and cement sludges. Waste forms of surrogate waste streams were fabricated by acid-base reactions between the mixtures of magnesium oxide powders and the wastes, and phosphoric acid or acid phosphate solutions. Dense and hard ceramic waste forms are produced in this process. The principal advantage of this technology is that the contaminants are immobilized by both chemical stabilization and subsequent microencapsulation of the reaction products. This paper reports the results of durability studies conducted on waste forms made with ash waste streams spiked with hazardous and radioactive surrogates. Standard leaching tests such as ANS 16.1 and TCLP were conducted on the final waste forms. Fates of the contaminants in the final waste forms were established by electron microscopy. In addition, stability of the waste forms in aqueous environments was evaluated with long-term water-immersion tests.

  16. Optical techniques for nanoscale probing and chemical detection in aqueous environments

    NASA Astrophysics Data System (ADS)

    Pristinski, Denis

    We present an investigation of charge-dependent physical properties of water-soluble synthetic polymers and polymer-based layered structures, using optical detection methods in a visible range. We apply in situ nanoscale optical techniques to study response of polymer systems to changes in pH, polymer concentration, and concentration and type of counterions. This work describes three optical techniques and custom built instrumental setups for nanoscale polymer characterization in aqueous environment. Phase-modulated ellipsometry was applied to determine the refraction coefficient and the thickness of a hydrogel-like polymer layer on a substrate. The present study describes the sensitivity of the phase modulated ellipsometry to errors of measurement and determines conditions for decoupling film thickness and refraction index. It is shown that, for a certain range of film thickness, both the thickness and the refractive index can be determined from a single measurement with high precision. This optimal range of the film thickness is calculated for organic thin films, and the analysis is tested on crosslinked poly(methacrylic acid) polymer films in air and in water. Fluorescent correlation spectroscopy was used to investigate diffusion of a synthetic polyelectrolyte in aqueous solutions. Translational diffusion of Alexa-labeled poly(methacrylic acid) chains was studied in very dilute, 10-4 mg/ml, solutions as a function of polymer charge density and counterion concentration. The results illustrate the utility of the technique for studying hydrodynamic sizes of polyelectrolyte coils in response to variation in solution pH or concentration of salt and polyelectrolytes. We apply surface-enhanced Raman scattering (SERS) for studying of enhancement capabilities of individual silver nanoparticles attached to glass and silicon substrates. Nanoparticles were electrostatically bound to a self-assembled polyallylamine hydrochloride (PAH) monolayer, which was deposited on

  17. Uptake of methacrolein into aqueous solutions of sulfuric acid and hydrogen peroxide.

    PubMed

    Liu, Ze; Wu, Ling-Yan; Wang, Tian-He; Ge, Mao-Fa; Wang, Wei-Gang

    2012-01-12

    Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol (SOA) formation from isoprene and its gas-phase oxidation products, but the kinetics and chemical mechanism remain largely uncertain. Here we report the first measurement of uptake of methacrolein into aqueous solutions of sulfuric acid and hydrogen peroxide in the temperature range of 253-293 K. The steady-state uptake coefficients were acquired and increased quickly with increasing sulfuric acid concentration and decreasing temperature. Propyne, acetone, and 2,3-dihydroxymethacrylic acid were suggested as the products. The chemical mechanism is proposed to be the oxidation of carbonyl group and C═C double bonds by peroxide hydrogen in acidic environment, which could explain the large content of polyhydroxyl compounds in atmospheric fine particles. These results indicate that multiphase acid-catalyzed oxidation of methacrolein by hydrogen peroxide can contribute to SOA mass in the atmosphere, especially in the upper troposphere.

  18. Optical properties of chitosan in aqueous solution of L- and D-ascorbic acids

    NASA Astrophysics Data System (ADS)

    Malinkina, Olga N.; Shipovskaya, Anna B.; Kazmicheva, Olga F.

    2016-04-01

    The optical properties of aqueous chitosan solutions in L- and D-ascorbic acids were studied by optical rotatory dispersion and spectrophotometry. The specific optical rotation [α] of all chitosan solutions tested was positive, in contrast to aqueous solutions of the ascorbic acid enantiomers, which exhibit an inverse relationship of [α] values. Significant differences in the absolute values of [α] of the chitosan solutions at polymer-acid ratios exceeding the equimolar one were found.

  19. Fatigue of tooth-colored restoratives in aqueous environment.

    PubMed

    Kawakami, Yoshiko; Takeshige, Fumio; Hayashi, Mikako; Ebisu, Shigeyuki

    2007-01-01

    The purpose of this study was to investigate the interaction between mechanical and chemical fatigue in resin composites and dental ceramics, and the effects thereof on fatigue resistance of tooth-colored restoratives. To this end, the fatigue fracture resistance of restoratives under dry and aqueous conditions were analyzed by a dynamic fatigue crack propagation test using beam-shaped specimens with a precrack. Fatigue crack propagation characteristics were expressed by the correlation between fatigue crack growth rate (da/dN) and stress intensity factor range (deltaK). In addition, fatigue crack growth threshold (deltaKth) was calculated. Following the fatigue test, a fractographic examination was performed using scanning electron microscopy. Fatigue crack initiation was retarded in resin composites under aqueous condition, but dental ceramics were susceptible to slow crack growth after crack initiation. SEM images of the fatigue facture surfaces reflected inorganic and organic filler particles of different sizes in composites and the bonding at crystal-glass interface in ceramics. It was concluded that water exerted different effects on the fatigue resistance of composites and ceramics.

  20. Multiple glass transitions and freezing events of aqueous citric acid.

    PubMed

    Bogdan, Anatoli; Molina, Mario J; Tenhu, Heikki; Loerting, Thomas

    2015-05-14

    Calorimetric and optical cryo-microscope measurements of 10-64 wt % citric acid (CA) solutions subjected to moderate (3 K/min) and slow (0.5 and 0.1 K/min) cooling/warming rates and also to quenching/moderate warming between 320 and 133 K are presented. Depending on solution concentration and cooling rate, the obtained thermograms show one freezing event and from one to three liquid-glass transitions upon cooling and from one to six liquid-glass and reverse glass-liquid transitions, one or two freezing events, and one melting event upon warming of frozen/glassy CA/H2O. The multiple freezing events and glass transitions pertain to the mother CA/H2O solution itself and two freeze-concentrated solution regions, FCS1 and FCS2, of different concentrations. The FCS1 and FCS2 (or FCS22) are formed during the freezing of CA/H2O upon cooling and/or during the freezing upon warming of partly glassy or entirely glassy mother CA/H2O. The formation of two FCS1 and FCS22 regions during the freezing upon warming to our best knowledge has never been reported before. Using an optical cryo-microscope, we are able to observe the formation of a continuous ice framework (IF) and its morphology and reciprocal distribution of IF/(FCS1 + FCS2). Our results provide a new look at the freezing and glass transition behavior of aqueous solutions and can be used for the optimization of lyophilization and freezing of foods and biopharmaceutical formulations, among many other applications where freezing plays a crucial role.

  1. Thermodynamics of the complexation of arabinogalactan with salicylic and p-aminobenzoic acids in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Mudarisova, R. Kh.; Badykova, L. A.

    2016-03-01

    The thermodynamics of complexation of arabinogalactan with salicylic and p-aminobenzoic acids in aqueous solutions is studied by means spectroscopy. The standard thermodynamic characteristics (Δ H°; Δ G°; Δ S°) of complexation are calculated.

  2. Geochemistry of Carbonates on Mars: Implications for Climate History and Nature of Aqueous Environments

    NASA Astrophysics Data System (ADS)

    Niles, Paul B.; Catling, David C.; Berger, Gilles; Chassefière, Eric; Ehlmann, Bethany L.; Michalski, Joseph R.; Morris, Richard; Ruff, Steven W.; Sutter, Brad

    2013-01-01

    Ongoing research on martian meteorites and a new set of observations of carbonate minerals provided by an unprecedented series of robotic missions to Mars in the past 15 years help define new constraints on the history of martian climate with important crosscutting themes including: the CO2 budget of Mars, the role of Mg-, Fe-rich fluids on Mars, and the interplay between carbonate formation and acidity. Carbonate minerals have now been identified in a wide range of localities on Mars as well as in several martian meteorites. The martian meteorites contain carbonates in low abundances (<1 vol.%) and with a wide range of chemistries. Carbonates have also been identified by remote sensing instruments on orbiting spacecraft in several surface locations as well as in low concentrations (2-5 wt.%) in the martian dust. The Spirit rover also identified an outcrop with 16 to 34 wt.% carbonate material in the Columbia Hills of Gusev Crater that strongly resembled the composition of carbonate found in martian meteorite ALH 84001. Finally, the Phoenix lander identified concentrations of 3-6 wt.% carbonate in the soils of the northern plains. The carbonates discovered to date do not clearly indicate the past presence of a dense Noachian atmosphere, but instead suggest localized hydrothermal aqueous environments with limited water availability that existed primarily in the early to mid-Noachian followed by low levels of carbonate formation from thin films of transient water from the late Noachian to the present. The prevalence of carbonate along with evidence for active carbonate precipitation suggests that a global acidic chemistry is unlikely and a more complex relationship between acidity and carbonate formation is present.

  3. The solvent effect on the acidities of haloacetic acids in aqueous solution. A RISM-SCF study

    NASA Astrophysics Data System (ADS)

    Kawata, Masaaki; Ten-no, Seiichiro; Kato, Shigeki; Hirata, Fumio

    1995-06-01

    The acidities of acetic, fluoracetic and chloroacetic acids in aqueous solution are calculated by means of the ab initio method combined with the reference interaction site method in the statistical mechanics of molecular liquids (the RISM-SCF method). The inversion in the order of acidities experimentally observed when a series of haloacetic acids is immersed into aqueous solution is reproduced. It is shown that the inversion is caused by competition between substitution and solvation effects. The solvation effect is discussed in molecular detail in terms of the charge distribution of the solute and the solute-solvent radial distribution functions.

  4. Uptake of Hypobromous Acid (HOBr) by Aqueous Sulfuric Acid Solutions: Low-Temperature Solubility and Reaction

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Michelsen, Rebecca R.; Ashbourn, Samatha F. M.; Rammer, Thomas A.; Golden, David M.

    2005-01-01

    Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.

  5. Kinetics of atmospheric oxidation of nitrous acid by oxygen in aqueous medium

    NASA Astrophysics Data System (ADS)

    Mudgal, Punit K.; Bansal, S. P.; Gupta, K. S.

    The facts that the high concentrations of nitrous acid have been reported in dew, fog, rain and cloud water and that its oxidation by dissolved oxygen is very fast in freezing conditions have led us to study the kinetics of aqueous phase oxidation of nitrous acid by dissolved oxygen in the pH range 1.0-4.5 at 30 °C. The reaction was followed by measuring [O 2] and under pseudo-first-order conditions the results were in agreement with the rate law: -d[O]t/dt=k0[N]02[H]2[O]t/(K+[H])2, where k0 is third-order composite rate coefficient and Ka is the dissociation constant of HNO 2. The values of k0 and Ka were determined to be 1×10 2 L 2 mol -2 s -1 and 3.84×10 -4, respectively. Consistent with the kinetics results two alternative mechanisms have been considered. The first of these mechanisms assumes an intermediate complex formation, [HNO 2.O 2], by the reaction of HNO 2 and O 2 in a rapid pre-equilibrium, followed by the reaction of this intermediate with another molecule of HNO 2. The second mechanism, originally proposed by Damschen and Martin [1983. Aqueous aerosol oxidation of nitrous acid by O 2, O 3 and H 2O 2. Atmospheric Environment 17, 2005-2011], assumes the formation of a dimer, [HNO 2] 2, in a rapid pre-equilibrium followed by the reaction of the dimer with O 2 to form HNO 3. The application of the mechanisms to fast oxidation of nitrite by dissolved oxygen under freezing conditions is discussed.

  6. Recovery of rare earth elements from the sulfothermophilic red alga Galdieria sulphuraria using aqueous acid.

    PubMed

    Minoda, Ayumi; Sawada, Hitomi; Suzuki, Sonoe; Miyashita, Shin-ichi; Inagaki, Kazumi; Yamamoto, Takaiku; Tsuzuki, Mikio

    2015-02-01

    The demand for rare earth elements has increased dramatically in recent years because of their numerous industrial applications, and considerable research efforts have consequently been directed toward recycling these materials. The accumulation of metals in microorganisms is a low-cost and environmentally friendly method for the recovery of metals present in the environment at low levels. Numerous metals, including rare earth elements, can be readily dissolved in aqueous acid, but the efficiency of metal biosorption is usually decreased under the acidic conditions. In this report, we have investigated the use of the sulfothermophilic red alga Galdieria sulphuraria for the recovery of metals, with particular emphasis on the recovery of rare earth metals. Of the five different growth conditions investigated where G. sulphuraria could undergo an adaptation process, Nd(III), Dy(III), and Cu(II) were efficiently recovered from a solution containing a mixture of different metals under semi-anaerobic heterotrophic condition at a pH of 2.5. G. sulphuraria also recovered Nd(III), Dy(III), La(III), and Cu(II) with greater than 90% efficiency at a concentration of 0.5 ppm. The efficiency remained unchanged at pH values in the range of 1.5-2.5. Furthermore, at pH values in the range of 1.0-1.5, the lanthanoid ions were collected much more efficiently into the cell fractions than Cu(II) and therefore successfully separated from the Cu(II) dissolved in the aqueous acid. Microscope observation of the cells using alizarin red suggested that the metals were accumulating inside of the cells. Experiments using dead cells suggested that this phenomenon was a biological process involving specific activities within the cells.

  7. Ion-recognizable hydrogels for efficient removal of cesium ions from aqueous environment.

    PubMed

    Yu, Hai-Rong; Hu, Jia-Qi; Liu, Zhuang; Ju, Xiao-Jie; Xie, Rui; Wang, Wei; Chu, Liang-Yin

    2017-02-05

    At present, selective and efficient removal of cesium ions (Cs(+)) from nuclear waste is of significant importance but still challenging. In this study, an easy-to-get and low-cost hydrogel adsorbent has been developed for effective adsorption and removal of Cs(+) from aqueous environment. The novel Cs(+)-recognizable poly(acrylic acid-co-benzo-18-crown-6-acrylamide) (poly(AAc-co-B18C6Am)) hydrogel is specifically designed with a synergistic effect, in which the AAc units are designed to attract Cs(+) via electrostatic attraction and the B18C6Am units are designed to capture the attracted Cs(+) by forming stable 2:1 "sandwich" complexes. The poly(AAc-co-B18C6Am) hydrogels are simply synthesized by thermally initiated free-radical copolymerization and display excellent Cs(+) adsorption from commonly coexisting metal ions. Important parameters affecting the adsorption are investigated comprehensively, and the adsorption kinetics and adsorption isotherms are also discussed systematically. The poly(AAc-co-B18C6Am) hydrogels exhibit rapid Cs(+) adsorption within 30min and the adsorption process is governed by the pseudo-second order model. Adsorption isotherm results demonstrate that the equilibrium data are well fitted by the Langmuir isotherm model, indicating that the Cs(+) adsorption is probably a monolayer adsorption process. Such Cs(+)-recognizable hydrogel materials based on the host-guest complexation are promising as efficient and feasible candidates for adsorption and removal of radioactive Cs(+) from nuclear contaminants.

  8. Arsenic(V) biosorption by charred orange peel in aqueous environments.

    PubMed

    Abid, Muhammad; Niazi, Nabeel Khan; Bibi, Irshad; Farooqi, Abida; Ok, Yong Sik; Kunhikrishnan, Anitha; Ali, Fawad; Ali, Shafaqat; Igalavithana, Avanthi Deshani; Arshad, Muhammad

    2016-01-01

    Biosorption efficiency of natural orange peel (NOP) and charred orange peel (COP) was examined for the immobilization of arsenate (As(V)) in aqueous environments using batch sorption experiments. Sorption experiments were carried out as a function of pH, time, initial As(V) concentration and biosorbent dose, using NOP and COP (pretreated with sulfuric acid). Arsenate sorption was found to be maximum at pH 6.5, with higher As(V) removal percentage (98%) by COP than NOP (68%) at 4 g L(-1) optimum biosorbent dose. Sorption isotherm data exhibited a higher As(V) sorption (60.9 mg g(-1)) for COP than NOP (32.7 mg g(-1)). Langmuir model provided the best fit to describe As(V) sorption. Fourier transform infrared spectroscopy and scanning electron microscopy combined with energy dispersive X-ray spectroscopy analyses revealed that the -OH, -COOH, and -N-H surface functional groups were involved in As(V) biosorption and the meso- to micro-porous structure of COP sequestered significantly (2-times) higher As(V) than NOP, respectively. Arsenate desorption from COP was found to be lower (10%) than NOP (26%) up to the third regeneration cycle. The results highlight that this method has a great potential to produce unique 'charred' materials from the widely available biowastes, with enhanced As(V) sorption properties.

  9. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment.

    PubMed

    Kroning, Annika; Furchner, Andreas; Aulich, Dennis; Bittrich, Eva; Rauch, Sebastian; Uhlmann, Petra; Eichhorn, Klaus-Jochen; Seeber, Michael; Luzinov, Igor; Kilbey, S Michael; Lokitz, Bradley S; Minko, Sergiy; Hinrichs, Karsten

    2015-06-17

    The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes containing poly(N-isopropylacrylamide) and poly(acrylic acid) with high potential for biosensing and biomedical applications are studied by in situ infrared-spectroscopic ellipsometry (IRSE). IRSE is a highly sensitive nondestructive technique that allows protein adsorption on polymer brushes to be investigated in an aqueous environment as external stimuli, such as temperature and pH, are varied. These changes are relevant to conditions for regulation of protein adsorption and desorption for biotechnology, biocatalysis, and bioanalytical applications. Here brushes are used as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. The important finding of this work is that IRSE in the in situ experiments in protein solutions can distinguish between contributions of polymer brushes and proteins. The vibrational bands of the polymers provide insights into the hydration state of the brushes, whereas the protein-specific amide bands are related to changes of the protein secondary structure.

  10. Behaviors of acrylamide/itaconic acid hydrogels in uptake of uranyl ions from aqueous solutions

    SciTech Connect

    Karadag, E.; Saraydin, D.; Gueven, O.

    1995-12-01

    In this study, adsorptions of uranyl ions from two different aqueous uranyl solutions by acrylamide-itaconic acid hydrogels were investigated by a spectroscopic method. The hydrogels were prepared by irradiating with {gamma}-radiation. In the experiment of uranyl ions adsorption, Type II adsorption was found. One gram of acrylamide-itaconic acid hydrogels sorbed 178-219 mg uranyl ions from the solutions of uranyl acetate, 42-76 mg uranyl ions from the aqueous solutions of uranyl nitrate, while acrylamide hydrogel did not sorb any uranyl ion. For the hydrogel containing 40 mg of itaconic acid and irradiated to 3.73 kGy, swelling of the hydrogels was observed in water (1660%), in the aqueous solution of uranyl acetate (730%), and in the aqueous solution of uranyl nitrate (580%). Diffusions of water onto hydrogels were a non-Fickian type of diffusion, whereas diffusions of uranyl ions were a Fickian type of diffusion.

  11. Heteroaggregation of engineered nanoparticles and kaolin clays in aqueous environments.

    PubMed

    Wang, Hongtao; Dong, Ya-nan; Zhu, Miao; Li, Xiang; Keller, Arturo A; Wang, Tao; Li, Fengting

    2015-09-01

    The increasing and wide use of nanoparticles (NPs), including TiO2 and Ag NPs, have raised concerns due to their potential toxicity and environmental impacts. Kaolin is a very common mineral in aquatic systems, and there is a very high probability that nanoparticles (NPs) will interact with these clay minerals. We studied the effect of kaolin particles on the aggregation of NPs under different conditions, including the role of pH, ionic strength (IS), and humic acid (HA). We show that kaolin reduces the energy barrier and the Critical Coagulation Concentration (CCC) at pH 4. At pH 8, even though the energy barrier of the system without kaolin increases, kaolin promotes NP aggregation via heteroaggregation. When IS is equal to or greater than the CCC, on the one hand HA promotes aggregation of TiO2 NPs, but on the other hand HA decreases the rate of Ag NP aggregation because the existence of a surface coating may limit the adsorption of HA on these Ag NPs. In addition, the presence of HA increases the energy barrier and the CCC of the binary system (kaolin + NPs). Thus, the complex interactions of clay, NPs, IS, pH, and HA concentration determine the colloidal stability of the NPs. We find that kaolin is a potential coagulant for removal of NPs that behave like Ag and TiO2.

  12. The IUPAC aqueous and non-aqueous experimental pKa data repositories of organic acids and bases

    NASA Astrophysics Data System (ADS)

    Slater, Anthony Michael

    2014-10-01

    Accurate and well-curated experimental pKa data of organic acids and bases in both aqueous and non-aqueous media are invaluable in many areas of chemical research, including pharmaceutical, agrochemical, specialty chemical and property prediction research. In pharmaceutical research, pKa data are relevant in ligand design, protein binding, absorption, distribution, metabolism, elimination as well as solubility and dissolution rate. The pKa data compilations of the International Union of Pure and Applied Chemistry, originally in book form, have been carefully converted into computer-readable form, with value being added in the process, in the form of ionisation assignments and tautomer enumeration. These compilations offer a broad range of chemistry in both aqueous and non-aqueous media and the experimental conditions and original reference for all pKa determinations are supplied. The statistics for these compilations are presented and the utility of the computer-readable form of these compilations is examined in comparison to other pKa compilations. Finally, information is provided about how to access these databases.

  13. The IUPAC aqueous and non-aqueous experimental pKa data repositories of organic acids and bases.

    PubMed

    Slater, Anthony Michael

    2014-10-01

    Accurate and well-curated experimental pKa data of organic acids and bases in both aqueous and non-aqueous media are invaluable in many areas of chemical research, including pharmaceutical, agrochemical, specialty chemical and property prediction research. In pharmaceutical research, pKa data are relevant in ligand design, protein binding, absorption, distribution, metabolism, elimination as well as solubility and dissolution rate. The pKa data compilations of the International Union of Pure and Applied Chemistry, originally in book form, have been carefully converted into computer-readable form, with value being added in the process, in the form of ionisation assignments and tautomer enumeration. These compilations offer a broad range of chemistry in both aqueous and non-aqueous media and the experimental conditions and original reference for all pKa determinations are supplied. The statistics for these compilations are presented and the utility of the computer-readable form of these compilations is examined in comparison to other pKa compilations. Finally, information is provided about how to access these databases.

  14. Mid-Infrared Sensing of Organic Pollutants in Aqueous Environments

    PubMed Central

    Pejcic, Bobby; Myers, Matthew; Ross, Andrew

    2009-01-01

    The development of chemical sensors for monitoring the levels of organic pollutants in the aquatic environment has received a great deal of attention in recent decades. In particular, the mid-infrared (MIR) sensor based on attenuated total reflectance (ATR) is a promising analytical tool that has been used to detect a variety of hydrocarbon compounds (i.e., aromatics, alkyl halides, phenols, etc.) dissolved in water. It has been shown that under certain conditions the MIR-ATR sensor is capable of achieving detection limits in the 10–100 ppb concentration range. Since the infrared spectral features of every single organic molecule are unique, the sensor is highly selective, making it possible to distinguish between many different analytes simultaneously. This review paper discusses some of the parameters (i.e., membrane type, film thickness, conditioning) that dictate MIR-ATR sensor response. The performance of various chemoselective membranes which are used in the fabrication of the sensor will be evaluated. Some of the challenges associated with long-term environmental monitoring are also discussed. PMID:22454582

  15. Covalent triazine-based framework: A promising adsorbent for removal of perfluoroalkyl acids from aqueous solution.

    PubMed

    Wang, Bingyu; Lee, Linda S; Wei, Chenhui; Fu, Heyun; Zheng, Shourong; Xu, Zhaoyi; Zhu, Dongqiang

    2016-09-01

    Perfluoroalkyl acids (PFAAs) are highly stable, persistent, and ubiquitous in the environment with significant concerns growing with regards to both human and ecosystem health. Due to the high stability to both biological and chemical attack, the only currently feasible approach for their removal from water is adsorbent technology. The main objective of this study was to assess a covalent triazine-based framework (CTF) adsorbent for removal from aqueous solutions of perfluoro C4, C6, and C8 carboxylates and sulfonates including the two C8s most commonly monitored, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Adsorption affinity and capacity were quantified and compared to three commonly used sorbents: pulverized microporous activated carbon, single-walled carbon nanotubes, and Amberlite IRA-400 anion-exchange resin. CTF adsorbent exhibited pronouncedly higher adsorption affinity and capacity of PFAAs than other test sorbents. The remarkably strong adsorption to CTF can be attributed to the favored electrostatic interaction between the protonated triazine groups on the inner wall of the hydrophobic CTF pore and the negatively charged head groups of the PFAAs intercalated between the CTF layers. The homogeneous, nanosized pores (1.2 nm) of CTF hindered adsorption of a large-sized dissolved humic acid, thus minimizing the suppression of PFAA adsorption. Additionally, regeneration of CTF was easily accomplished by simply raising pH > 11, which inhibited the electrostatic adsorptive interaction of PFAAs.

  16. Phyllosilicates in Mawrth Vallis: Implications for a Past Aqueous Environment

    NASA Astrophysics Data System (ADS)

    McKeown, N. K.; Bishop, J. L.; Noe Dobrea, E. Z.; Parente, M.; Ehlmann, B. L.; Mustard, J. F.; Murchie, S. L.; Bibring, J.; Silver, E.

    2008-12-01

    impact melt sheet (Al-phyllosilicate unit only). Clay deposits in marine basins typically reflect nearby continental conditions, and the species and volumes of phyllosilicates identified indicate a warm-wet climate. Pedogenesis in a warm-wet environment will produce laterites with alteration horizons of kaolinite and other Al-phyllosilicates and nontronite in the lowermost horizons. Impacts can mobilize frozen water as well as liquid water and the mineral assemblage formed is the same for a given temperature and water to rock ratio, so the climate cannot be determined if the Al-phyllosilicates were formed by an impact melt sheet hydrothermal system. It seems likely that these phyllosilicates formed in a warm-wet climate and are another indicator of a more hospitable environment in Mars' past. [1]Bibring, J.-P., et al. (2006) Science, 312, 400-404. [2]Poulet, F., et al. (2005) Nature, 438, 632-627. [3]Bishop, J. L., et al. (2008) Science, 321, 830-833. [4]Michalski, J. R., et al. (2007) Geology, 35, 951-954. [5]Wray, J. J., et al. (2008) GRL, 35, L12202.

  17. Agglomeration, isolation and dissolution of commercially manufactured silver nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Elzey, Sherrie; Grassian, Vicki H.

    2010-06-01

    The increasing use of manufactured nanoparticles ensures these materials will make their way into the environment. Silver nanoparticles in particular, due to use in a wide range of applications, have the potential to get into water systems, e.g., drinking water systems, ground water systems, estuaries, and/or lakes. One important question is what is the chemical and physical state of these nanoparticles in water? Are they present as isolated particles, agglomerates or dissolved ions, as this will dictate their fate and transport. Furthermore, does the chemical and physical state of the nanoparticles change as a function of size or differ from micron-sized particles of similar composition? In this study, an electrospray atomizer coupled to a scanning mobility particle sizer (ES-SMPS) is used to investigate the state of silver nanoparticles in water and aqueous nitric acid environments. Over the range of pH values investigated, 0.5-6.5, silver nanoparticles with a bimodal primary particle size distribution with the most intense peak at 5.0 ± 7.4 nm, as determined from transmission electron microscopy (TEM), show distinct size distributions indicating agglomeration between pH 6.5 and 3 and isolated nanoparticles at pH values from 2.5 to 1. At the lowest pH investigated, pH 0.5, there are no peaks detected by the SMPS, indicating complete nanoparticle dissolution. Further analysis of the solution shows dissolved Ag ions at a pH of 0.5. Interestingly, silver nanoparticle dissolution shows size dependent behavior as larger, micron-sized silver particles show no dissolution at this pH. Environmental implications of these results are discussed.

  18. ACID GASES IN CO2-RICH SUBSURFACE GEOLOGIC ENVIRONMENTS

    SciTech Connect

    Chialvo, Ariel A; Vlcek, Lukas; Cole, David

    2013-01-01

    The analysis of species behavior involving dilute fluid environments has been crucial for the advance of modern solvation thermodynamics through molecular-based formalisms to guide the development of macroscopic regression tools in the description of fluid behavior and correlation of experimental data (Chialvo 2013). Dilute fluid environments involving geologic formations are of great theoretical and practical relevance regardless of the thermodynamic state conditions. The most challenging systems are those involving highly compressible and reactive confined environments, i.e., where small perturbations of pressure and/or temperature can trigger considerable density changes. This in turn can alter significantly the species solvation, their preferential solvation, and consequently, their reactivity with one another and with the surrounding mineral surfaces whose outcome is the modification of the substrate porosity and permeability, and ultimately, the integrity of the mineral substrates. Considering that changes in porosity and permeability resulting from dissolution and precipitation phenomena in confined environments are at the core of the aqueous CO2-mineral interactions, and that caprock integrity (e.g., sealing capacity) depends on these key parameters, it is imperative to gain fundamental understanding of the mineral-fluid interfacial phenomena and fluid-fluid equilibria under mineral confinement at subsurface conditions. In order to undertand the potential effects of acid gases as contaminants of supercritical CO2 streams, in the next section we will discuss the thermodynamic behavior of CO2 fluid systems by addressing two crucial issues in the context of carbon capture, utilization and sequestration (CCUS) technologies: (i) Why should we consider (acid gas) CO2 impurities? and (ii) Why are CO2 fluid - mineral interactions of paramount relevance?

  19. PELS (Planetary Environmental Liquid Simulator): a new type of simulation facility to study extraterrestrial aqueous environments.

    PubMed

    Martin, Derek; Cockell, Charles S

    2015-02-01

    Investigations of other planetary bodies, including Mars and icy moons such as Enceladus and Europa, show that they may have hosted aqueous environments in the past and may do so even today. Therefore, a major challenge in astrobiology is to build facilities that will allow us to study the geochemistry and habitability of these extraterrestrial environments. Here, we describe a simulation facility (PELS: Planetary Environmental Liquid Simulator) with the capability for liquid input and output that allows for the study of such environments. The facility, containing six separate sample vessels, allows for statistical replication of samples. Control of pressure, gas composition, UV irradiation conditions, and temperature allows for the precise replication of aqueous conditions, including subzero brines under martian atmospheric conditions. A sample acquisition system allows for the collection of both liquid and solid samples from within the chamber without breaking the atmospheric conditions, enabling detailed studies of the geochemical evolution and habitability of past and present extraterrestrial environments. The facility we describe represents a new frontier in planetary simulation-continuous flow-through simulation of extraterrestrial aqueous environments.

  20. Biosorption of acidic textile dyestuffs from aqueous solution by Paecilomyces sp. isolated from acidic mine drainage.

    PubMed

    Çabuk, Ahmet; Aytar, Pınar; Gedikli, Serap; Özel, Yasemin Kevser; Kocabıyık, Erçin

    2013-07-01

    Removal of textile dyestuffs from aqueous solution by biosorption onto a dead fungal biomass isolated from acidic mine drainage in the Çanakkale Region of Turkey was investigated. The fungus was found to be a promising biosorbent and identified as Paecilomyces sp. The optimal conditions for bioremediation were as follows: pH, 2.0; initial dyestuff concentration, 50 mg l(-1) for Reactive Yellow 85 and Reactive Orange 12, and 75 mg l(-1) for Reactive Black 8; biomass dosage, 2 g l(-1) for Reactive Yellow 85, 3 g l(-1) for Reactive Orange 12, 4 g l(-1) for Reactive Black 8; temperature, 25 °C; and agitation rate, 100 rpm. Zeta potential measurements indicated an electrostatic interaction between the binding sites and dye anions. Fourier transform infrared spectroscopy showed that amine, hydroxyl, carbonyl, and amide bonds were involved in the dyestuff biosorption. A toxicity investigation was also carried out before and after the biosorption process. These results showed that the toxicities for the reactive dyestuffs in aqueous solutions after biosorption studies decreased. The Freundlich and Langmuir adsorption models were used for the mathematical description of the biosorption equilibrium, and isotherm constants were evaluated for each dyestuff. Equilibrium data of biosorption of RY85 and RO12 dyestuffs fitted well to both models at the studied concentration and temperature.

  1. Rosmarinic acid content in antidiabetic aqueous extract of Ocimum canum Sims grown in Ghana

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rosmarinic acid (RA) is an important polyphenol that is found in a variety of herbs including Ocimum canum sims (locally called eme or akokobesa in Ghana). Aqueous extracts from the leaves of O.canum are used as an antidiabetic herbal medicine in Ghana. Interestingly, rosmarinic acid content and p...

  2. Treatment of infectious skin defects or ulcers with electrolyzed strong acid aqueous solution.

    PubMed

    Sekiya, S; Ohmori, K; Harii, K

    1997-01-01

    A chronic ulcer with an infection such as methicillin-resistant Staphylococcus aureus is hard to heal. Plastic and reconstructive surgeons often encounter such chronic ulcers that are resistant to surgical or various conservative treatments. We applied conservative treatment using an electrolyzed strong acid aqueous solution and obtained satisfactory results. The lesion was washed with the solution or soaked in a bowl of the solution for approximately 20 min twice a day. Fresh electrolyzed strong acid aqueous solution is unstable and should be stored in a cool, dark site in a sealed bottle. It should be used within a week after it has been produced. Here we report on 15 cases of infectious ulcers that were treated by electrolyzed strong acid aqueous solution. Of these cases, 7 patients were healed, 3 were granulated, and in 5, infection subsided. In most cases the lesion became less reddish and less edematous. Discharge or foul odor from the lesion was decreased. Electrolyzed strong acid aqueous solution was especially effective for treating a chronic refractory ulcer combined with diabetes melitus or peripheral circulatory insufficiency. This clinically applied therapy of electrolyzed strong acid aqueous solution was found to be effective so that this new therapeutic technique for ulcer treatment can now be conveniently utilized.

  3. Influence of pyrolysis temperature on lead immobilization by chemically modified coconut fiber-derived biochars in aqueous environments.

    PubMed

    Wu, Weidong; Li, Jianhong; Niazi, Nabeel Khan; Müller, Karin; Chu, Yingchao; Zhang, Lingling; Yuan, Guodong; Lu, Kouping; Song, Zhaoliang; Wang, Hailong

    2016-11-01

    Biochar has received widespread attention as an eco-friendly and efficient material for immobilization of toxic heavy metals in aqueous environments. In the present study, three types of coconut fiber-derived biochars were obtained by pyrolyzing at three temperatures, i.e., 300, 500, and 700 °C. In addition, nine types of biochars were prepared by chemical modification with ammonia, hydrogen peroxide, and nitric acid, respectively, which were used to investigate changes in physico-chemical properties by inter alia, Fourier transformation infrared spectrophotometry (FTIR), scanning electron microscope (SEM), and BET specific surface area analysis. Batch sorption experiments were carried out to determine the sorption capacity of the biochars for lead (Pb) in aqueous solutions. Results showed that the cation exchange capacity of biochar pyrolyzed at 300 °C and modified with nitric acid increased threefold compared to the control. Loosely corrugated carbon surface and uneven carbon surface of the biochar pyrolyzed at 300 °C were produced during ammonia and nitric acid modifications. Removal rate of Pb by the coconut biochar pyrolyzed at 300 °C and modified with ammonia was increased from 71.8 to 99.6 % compared to the untreated biochar in aqueous solutions containing 100 mg L(-1) Pb. However, chemical modification did not enhance adsorption of Pb of the biochars pyrolyzed at higher temperatures (e.g., 500 or 700 °C), indicating that resistance of biochars to chemical treatment increased with pyrolysis temperature.

  4. Dissociation of equimolar mixtures of aqueous carboxylic acids in ionic liquids: role of specific interactions.

    PubMed

    Shukla, Shashi Kant; Kumar, Anil

    2015-04-30

    Hammett acidity function observes the effect of protonation/deprotonation on the optical density/absorbance of spectrophotometric indicator. In this work, the Hammett acidity, H0, of equimolar mixtures of aqueous HCOOH, CH3COOH, and CH3CH2COOH was measured in 1-methylimidazolium-, 1-methylpyrrolidinium-, and 1-methylpiperidinium-based protic ionic liquids (PILs) and 1-butyl-3-methylimidazolium-based aprotic ionic liquid (AIL) with formate (HCOO(-)) anion. Higher H0 values were observed for the equimolar mixtures of aqueous carboxylic acids in protic ionic liquids compared with those of the aprotic ionic liquid because of the involvement of the stronger specific interactions between the conjugate acid of ionic liquid and conjugate base of carboxylic acids as suggested by the hard-soft acid base (HSAB) theory. The different H0 values for the equimolar mixtures of aqueous carboxylic acids in protic and aprotic ionic liquids were noted to depend on the activation energy of proton transfer (Ea,H(+)). The higher activation energy of proton transfer was obtained in AIL, indicating lower ability to form specific interactions with solute than that of PILs. Thermodynamic parameters determined by the "indicator overlapping method" further confirmed the involvement of the secondary interactions in the dissociation of carboxylic acids. On the basis of the thermodynamic parameter values, the potential of different ionic liquids in the dissociation of carboxylic acids was observed to depend on the hydrogen bond donor acidity (α) and hydrogen bond acceptor basicity (β), characteristics of specific interactions.

  5. A theoretical study on the pH dependence of X-ray emission spectra for aqueous acetic acid

    NASA Astrophysics Data System (ADS)

    Nishida, Naohiro; Tokushima, Takashi; Takahashi, Osamu

    2016-04-01

    We performed theoretical calculations to reproduce the site-selective XES spectra for aqueous acetic acid at the oxygen K-edge. The shape of the experimental XES spectra obtained from aqueous acetic acid drastically changed when the pH value was high. Structure sampling of an aqueous acetic acid cluster model was performed by the ab initio molecular dynamics trajectory. Relative XES peak intensities for the core⿿hole excited state dynamics simulations were calculated using density functional theory. We found that the theoretical XES spectra reproduced well the experimental spectra and that these calculations gave us electronic and molecular structure information about aqueous acetic acid.

  6. Laccase-mediated transformation of triclosan in aqueous solution with metal cations and humic acid.

    PubMed

    Sun, Kai; Kang, Fuxing; Waigi, Michael Gatheru; Gao, Yanzheng; Huang, Qingguo

    2017-01-01

    Triclosan (TCS) is a broad-spectrum antimicrobial agent that is found extensively in natural aquatic environments. Enzyme-catalyzed oxidative coupling reactions (ECOCRs) can be used to remove TCS in aqueous solution, but there is limited information available to indicate how metal cations (MCs) and natural organic matter (NOM) influence the environmental fate of TCS during laccase-mediated ECOCRs. In this study, we demonstrated that the naturally occurring laccase from Pleurotus ostreatus was effective in removing TCS during ECOCRs, and the oligomerization of TCS was identified as the dominant reaction pathway by high-resolution mass spectrometry (HRMS). The growth inhibition studies of green algae (Chlamydomonas reinhardtii and Scenedesmus obliquus) proved that laccase-mediated ECOCRs could effectively reduce the toxicity of TCS. The presence of dissolved MCs (Mn(2+), Al(3+), Ca(2+), Cu(2+), and Fe(2+) ions) influenced the removal and transformation of TCS via different mechanisms. Additionally, the transformation of TCS in systems with NOM derived from humic acid (HA) was hindered, and the apparent pseudo first-order kinetics rate constants (k) for TCS decreased as the HA concentration increased, which likely corresponded to the combined effect of both noncovalent (sorption) and covalent binding between TCS and humic molecules. Our results provide a novel insight into the fate and transformation of TCS by laccase-mediated ECOCRs in natural aquatic environments in the presence of MCs and NOM.

  7. Phosphorylation of glyceric acid in aqueous solution using trimetaphosphate

    NASA Astrophysics Data System (ADS)

    Kolb, Vera; Orgel, Leslie E.

    1996-02-01

    The phosphorylation of glyceric acid is an interesting prebiotic reaction because it converts a simple, potentially prebiotic organic molecule into phosphate derivatives that are central to carbohydrate metabolism. We find that 0.05 M glyceric acid in the presence of 0.5 M trimetaphosphate in alkaline solution gives a mixture of 2- and 3-phosphoglyceric acids in combined yields of up to 40%.

  8. Phosphorylation of Glyceric Acid in Aqueous Solution Using Trimetaphosphate

    NASA Technical Reports Server (NTRS)

    Kolb, Vera; Orgel, Leslie E.

    1996-01-01

    The phosphorylation of glyceric acid is an interesting prebiotic reaction because it converts a simple, potentially prebiotic organic molecule into phosphate derivatives that are central to carbohydrate metabolism. We find that 0.05 M glyceric acid in the presence of 0.5 M trimetaphosphate in alkaline solution gives a mixture of 2- and 3-phosphoglyceric acids in combined yields of up to 40%.

  9. Adsorption of organic acids from dilute aqueous solution onto activated carbon

    SciTech Connect

    Wang, S.W.

    1980-06-01

    The radioisotope technique was used to study the removal of organic acid contaminants from dilute aqueous solutions onto activated carbon. Acetic acid, propionic acid, n-butyric acid, n-hexanoic acid and n-heptanoic acid were studied at 278, 298, and 313/sup 0/K. Three bi-solute acid mixtures (acetic and propionic acids, acetic and butanoic acids, and propionic and butanoic acids) were studied at 278 and 298/sup 0/K. Isotherms of the single-solute systems were obtained at three different temperatures in the very dilute concentration region (less than 1% by weight). These data are very important in the prediction of bi-solute equilibrium data. A Polanyi-based competitive adsorption potential theory was used to predict the bi-solute equilibrium uptakes. Average errors between calculated and experimental data ranges from 4% to 14%. It was found that the competitive adsorption potential theory gives slightly better results than the ideal adsorbed solution theory.

  10. Aggregation and Colloidal Stability of Commercially Available Al2O3 Nanoparticles in Aqueous Environments

    PubMed Central

    Mui, Julie; Ngo, Jennifer; Kim, Bojeong

    2016-01-01

    The aggregation and colloidal stability of three, commercially-available, gamma-aluminum oxide nanoparticles (γ-Al2O3 NPs) (nominally 5, 10, and 20–30 nm) were systematically examined as a function of pH, ionic strength, humic acid (HA) or clay minerals (e.g., montmorillonite) concentration using dynamic light scattering and transmission electron microscopy techniques. NPs possess pH-dependent surface charges, with a point of zero charge (PZC) of pH 7.5 to 8. When pH < PZC, γ-Al2O3 NPs are colloidally stable up to 100 mM NaCl and 30 mM CaCl2. However, significant aggregation of NPs is pronounced in both electrolytes at high ionic strength. In mixed systems, both HA and montmorillonite enhance NP colloidal stability through electrostatic interactions and steric hindrance when pH ≤ PZC, whereas their surface interactions are quite limited when pH > PZC. Even when pH approximates PZC, NPs became stable at a HA concentration of 1 mg·L−1. The magnitude of interactions and dominant sites of interaction (basal planes versus edge sites) are significantly dependent on pH because both NPs and montmorillonite have pH-dependent (conditional) surface charges. Thus, solution pH, ionic strength, and the presence of natural colloids greatly modify the surface conditions of commercial γ-Al2O3 NPs, affecting aggregation and colloidal stability significantly in the aqueous environment. PMID:28335218

  11. The ecological effects of trichloroacetic acid in the environment.

    PubMed

    Lewis, T E; Wolfinger, T F; Barta, M L

    2004-10-01

    Trichloroacetic acid (TCAA) is a member of the family of compounds known as chloroacetic acids, which includes mono-, di- and trichloroacetic acid. The significant property these compounds share is that they are all phytotoxic. TCAA once was widely used as a potent herbicide. However, long after TCAA's use as a herbicide was discontinued, its presence is still detected in the environment in various compartments. Methods for quantifying TCAA in aqueous and solid samples are summarized. Concentrations in various environmental compartments are presented, with a discussion of the possible formation of TCAA through natural processes. Concentrations of TCAA found to be toxic to aquatic and terrestrial organisms in laboratory and field studies were compiled and used to estimate risk quotients for soil and surface waters. TCAA levels in most water bodies not directly affected by point sources appear to be well below toxicity levels for the most sensitive aquatic organisms. Given the phytotoxicity of TCAA, aquatic plants and phytoplankton would be the aquatic species to monitor for potential effects. Given the concentrations of TCAA measured in various soils, there appears to be a risk to terrestrial organisms. Soil uptake of TCAA by plants has been shown to be rapid. Also, combined uptake of TCAA from soil and directly from the atmosphere has been shown. Therefore, risk quotients derived from soil exposure may underestimate the risk TCAA poses to plants. Moreover, TCE and TCA have been shown to be taken up by plants and converted to TCAA, thus leading to an additional exposure route. Mono- and di-chloroacetic acids can co-occur with TCAA in the atmosphere and soil and are more phytotoxic than TCAA. The cumulative effects of TCAA and compounds with similar toxic effects found in air and soil must be considered in subsequent terrestrial ecosystem risk assessments.

  12. Photocatalytic Oxidation of Sulfurous Acid in an Aqueous Medium

    ERIC Educational Resources Information Center

    Romero, Alicia; Hernandez, Willie; Suarez, Marco F.

    2005-01-01

    The effect of some parameters on sulfurous acid and sulfur oxidation kinetics such as initial concentration of sulfurous acid, oxygen, TiO[2] crystalline concentration, the power of black light, and quantity of TiO[2] is investigated. The experiments can be performed in an undergraduate physical chemistry laboratory with an inexpensive…

  13. Multi-walled carbon nanotubes in aqueous phytic acid for enhancing biosensor

    NASA Astrophysics Data System (ADS)

    Guo, Xiaoyu; Miao, Yun; Ye, Pingping; Wen, Ying; Yang, Haifeng

    2014-04-01

    The poor dispersion of carbon based nanomaterials without strong acid pretreatment in aqueous solution is a fundamental problem, limiting its applications in biology-related fields. A good dispersion of multi-walled carbon nanotubes (MWCNTs) in water was realized by 50 wt.% phytic acid (PA) solution. As an application case, the PA-MWCNTs dispersion in aqueous solution was used for the immobilization of horseradish peroxidase (HRP) and its direct electrochemistry was realized. The constructed biosensor has a sound limit of detection, wide linear range, and high affinity for hydrogen peroxide (H2O2) as well as being free from interference of co-existing electro-active species.

  14. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOEpatents

    Dietz, Mark L.; Horwitz, E. Philip; Bartsch, Richard A.; Barrans, Jr., Richard E.; Rausch, David

    1999-01-01

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution.

  15. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOEpatents

    Dietz, M.L.; Horwitz, E.P.; Bartsch, R.A.; Barrans, R.E. Jr.; Rausch, D.

    1999-03-30

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution. 4 figs.

  16. Measurement of high carrier mobility in graphene in an aqueous electrolyte environment

    NASA Astrophysics Data System (ADS)

    Brown, Morgan A.; Crosser, Michael S.; Leyden, Matthew R.; Qi, Yabing; Minot, Ethan D.

    2016-08-01

    Graphene is a promising material for applications in aqueous electrolyte environments. To explore the impact of such environments on graphene's electrical properties, we performed Hall bar measurements on electrolyte-gated graphene. Assuming a Drude model, we find that the room temperature carrier mobility in water-gated, SiO2-supported graphene reaches 7000 cm2/Vs, comparable to the best dry SiO2-supported graphene devices. Our results show that the electrical performance of graphene is robust, even in the presence of dissolved ions that introduce an additional mechanism for Coulomb scattering.

  17. Ferroelectric Thin Films for the Manipulation of Interfacial Forces in Aqueous Environments

    NASA Astrophysics Data System (ADS)

    Ferris, Robert

    Ferroelectric thin films (FETFs) offer a promising new platform for advancing liquid-phase interfacial sensing devices. FETFs are capable of expressing surface charge densities that are an order of magnitude higher than those of traditional charged surfaces in liquid environments (e.g., common oxides, self-assembled monolayers, or electrets). Furthermore, the switchable polarization state of FETFs enables patterning of charge-heterogeneous surfaces whose charge patterns persist over a range of environmental conditions. Integration of FETFs into liquid-phase interfacial sensing devices, however, requires the fabrication of films with nanometer-scale surface roughness, high remnant polarization values, and interfacial stability during prolonged exposure. The objectives of my research were to i) fabricate ferroelectric ultra-smooth lead zirconium titanate (US-PZT) thin films with nanometer-scale surface roughness, ii) establish the interfacial stability of these films after prolonged exposure to aqueous environments, iii) measure the interfacial forces as a function of film polarization and ionic strength, iv) calculate the surface potential of the US-PZT surface using electric double layer (EDL) theory, and v) demonstrate the guided deposition of charged colloidal particles onto locally polarized US-PZT thin films from solution. I demonstrate the use of ferroelectric US-PZT thin films to manipulate EDL interaction forces in aqueous environments. My work conclusively shows that the polarization state of US-PZT controls EDL formation and can be used to induce the guided deposition of charged colloidal particles in solution. I present a robust fabrication scheme for making ferroelectric US-PZT thin films from a sol-gel precursor. By optimizing critical thermal processing steps I am able to minimize the in-plane stress of the film and reliably produce US-PZT thin films on the wafer-scale with mean surface roughness values of only 2.4 nm over a 25 μm2 area. I then

  18. Histological effects of aqueous acids and gaseous hydrogen chloride on bean leaves

    SciTech Connect

    Swiecki, T.J.; Endress, A.G.; Taylor, O.C.

    1982-01-01

    Primary leaves of Phaseoulus vulgaris L. (pinto bean), 9 or 12 days from sowing, were exposed to aqueous acids, chloride salts, or hydrogen chloride gas. Leaves were examined for the presence and severity of resultant visible injury and samples for light and scanning electron microscopy. Exposure to 0.06 N HCl, HNO/sub 3/, H/sub 2/SO/sub 4/ or 14.5-19.0 mg m/sup -3/ gaseous HCl for 20 min evoked similar foliar injury including glazing and necrosis of the laminas. This injury appeared to result initially from plasmolysis and collapse of the epidermis and subsequently of the underlying mesophyll. Cellular injury was accompanied by various cytoplasmic alterations. Microscopic symptoms observed in leaves exposed to gaseous HCl or aqueous acids included vesicles and particulates within the larger vacuoles. Similar symptoms were present in leaves exposed to polyethylene glycol 6000. Differential effects included formation of necrotic pits and preferential injury to paravascular tissues in leaves treated with aqueous acids and crystalline chloroplast inclusions in gaseous HCl-treated and water-stressed leaves. The visible and microscopic appearances of leaves exposed to aqueous acids or gaseous HCl were compared and related to injury stemming from acid precipitation and a possible mechanism of action for gaseous HCl phytotoxicity.

  19. Acid gas treating by aqueous alkanolamines. Annual report, January-December 1994

    SciTech Connect

    Sandall, O.C.; Rinker, E.B.; Ashour, S.

    1994-12-01

    The objective of this work is to investigate the simulateneous absorption or desorption of CO2 and H2S into and from a mixed aqueous amine solvent consisting of methyldiethanolamine (MDEA) and diethanolamine (DEA). In work completed this year the authors have measured the density, viscosity and surface tension of pure MDEA and DEA over a range in temperatures. The diffusivity of N2O was measured in aqueous blends of MDEA and DEA at 50 wt% total amine for various ratios of DEA to MDEA over the temperature range 20 to 80 deg. C. A theoretically-based model has been developed for the correlation of the physical solubility of N2O in aqueous amine solutions. A penetration theory type model which was developed to describe acid gas absorption in aqueous amine solutions was used to carry out a sensitivity analysis for the various parameters affecting the rate of absorption of CO2 in MDEA solutions.

  20. [Sorption of amino acids from aqueous solutions on activated charcoal].

    PubMed

    Nekliudov, A D; Tsibanov, V V

    1985-03-01

    Various methods for quantitative description of amino acid sorption from solutions for parenteral nutrition on activated charcoal were studied under dynamic and static conditions. With the use of the well-known Freindlich and Langmuir absorption isotherms it was shown to be possible to describe in a simplified way the complex multicomponent process of sorption of the amino acids and to estimate their loss at the filtration stage.

  1. Acid gas absorption in aqueous solutions of mixed amines

    SciTech Connect

    Rinker, E.B.; Ashour, S.S.; Sandall, O.C.

    1996-12-31

    A mass transfer model has been developed to describe the rate of absorption (or desorption) of H{sub 2}S and CO{sub 2} in aqueous blends of a tertiary and a secondary or a primary amine. The model is based on penetration theory, and all significant chemical reactions are incorporated in the model. The reactions are taken to be reversible, with reactions involving only a proton transfer considered to be at equilibrium. The particular amines studied in this research were methyldiethanolamine (MDEA), a tertiary amine, and diethanolamine (DEA), a secondary amine. Key physicochemical data needed in the model, such as diffusion coefficients, kinetic rate constants, and gas solubilities, were measured. Experimental absorption rates of CO{sub 2} and H{sub 2}S were measured in a model gas-liquid contacting device and were compared with model predictions. Experiments were carried out for single amine solutions (both MDEA and DEA) and for amine blends.

  2. The effect of thermal treatment on the fracture properties of alloy X-750 in aqueous environments

    SciTech Connect

    Ballinger, R.; Elliott, C.S.; Hwang, I.S.; Prybylowski, J.

    1993-05-01

    Alloy X-750 is a high strength, age hardenable nickel-base alloy used in light water nuclear reactors. The excellent corrosion resistance and high temperature strength of alloy X-750 make it suitable for use in a variety of structure components in both pressurized water reactors and boiling water reactors. These applications involve exposure of highly stressed material to aqueous media. Operational stresses are subject to low frequency thermally induced fluctuations and high frequency flow induced fluctuations. In general, alloy X-750 has performed well in light water reactors. However, an economically significant number of components have failed unexpectedly due to localized forms of attack such as corrosion fatigue and stress corrosion cracking. Thermal processing history is known to play a significant role in the fracture properties of alloy X-750 in aqueous environments. While thermal treatments have been developed recently to improve performance, in many cases the reason for improved performance remains unclear. Therefore, identification of the mechanisms responsible for the degradation of fracture properties in aqueous environments is necessary. As a corollary it is necessary to achieve an understanding of how thermal treatment influences microstructure and, in turn, how microstructure influences fracture properties in aqueous environments. This report discusses five thermal treatments which were studied: (1) SA-1 hr at 1093{degree}C, (2) AH - 24 hr at 885{degree}C + 20 hr at 704{degree}C, (3) HTH - 1 hr at 1093{degree}C + 20 hr at 704{degree}C, (4) AHTH - 1 hr at 1093{degree}C + 24 hr at 885{degree}C + 20 hr at 704{degree}C, and (5) HOA - 1 hr at 1093{degree}C + 100 hrs at 760{degree}C. Microstructural characterization of these materials was accomplished through the use of optical microscopy, transmission electron microscopy,scanning transmission electron microscopy, energy dispersive x-ray spectroscopy, and x-ray diffractometry.

  3. STABILITY OF MFI ZEOLITE-FILLED PDMS MEMBRANES DURING PERVAPORATIVE ETHANOL RECOVERY FROM AQUEOUS MIXTURES CONTAINING ACETIC ACID

    EPA Science Inventory

    Pervaporation is a potential process for recovering bioethanol produced from biomass fermentation. Fermentation broths contain ethanol, water, and a variety of other compounds, often including carboxylic acids. The effects of acetic acid on long-term pervaporation of aqueous et...

  4. Boron removal from aqueous solutions by activated carbon impregnated with salicylic acid.

    PubMed

    Celik, Z Ceylan; Can, B Z; Kocakerim, M Muhtar

    2008-03-21

    In this study, the removal of boric acid from aqueous solution by activated carbon impregnated with salicylic acid was studied in batch system. pH, adsorbent amount, initial boron concentration, temperature, shaking rate and salicylic acid film thickness were chosen as parameters. Boron removal efficiencies increased with increasing adsorbent amount, temperature and pH, decreasing initial boron concentration. As thickness of salicylic acid film on activated carbon becomes thin up to 0.088nm, the efficiency increased, and then, the efficiency decreased with becoming thinner than 0.088nm of salicylic acid film. Shaking rate was no effect on removal efficiency. In result, it was determined that the use of salicylic acid as an impregnant for activated carbon led to the increase of the amount of boron adsorbed. A lactone ring, being the most appropriate conformation, forms between boric acid and -COOH and -OH groups of salicylic acid.

  5. Comparison of XAD macroporous resins for the concentration of fulvic acid from aqueous solution

    USGS Publications Warehouse

    Aiken, G.R.

    1979-01-01

    Five macroreticular, nonlonlc AmberlHe XAD resins were evaluated for concentration and Isolation of fulvlc acid from aqueous solution. The capacity of each resin for fulvlc acid was measured by both batch and column techniques. Elution efficiencies were determined by desorptlon with 0.1 N NaOH. Highest recoveries were obtained with the acrylic ester resins which proved to be most efficient for both adsorption and elution of fulvlc acid. Compared to the acrylic ester resins, usefulness of the styrene dvlnybenzene resins to remove fulvlc acid is limited because of slow diffusion-controlled adsorption and formation of charge-transfer complexes, which hinders elution. ?? 1979 American Chemical Society.

  6. Mechanism of carboxylic acid photooxidation in atmospheric aqueous phase: Formation, fate and reactivity

    NASA Astrophysics Data System (ADS)

    Charbouillot, Tiffany; Gorini, Sophie; Voyard, Guillaume; Parazols, Marius; Brigante, Marcello; Deguillaume, Laurent; Delort, Anne-Marie; Mailhot, Gilles

    2012-09-01

    In the first part of the work, we investigated the reactivity toward photogenerated hydroxyl radicals (rad OH) of seven monocarboxylic acids and six dicarboxylic acids found in natural cloud water. This leads to the proposition of a schematic degradation pathway linking glutaric acid (C5) to complete mineralization into CO2. We report a detailed mechanism on the succinic acid reactivity toward rad OH leading to the formation of malonic, glyoxylic and consequently oxalic acids and a comparison with reported pathways proposed by the CAPRAM (Chemical Aqueous Phase RAdical Mechanism) is discussed. We also investigated the photooxidation of formic acid under atmospherically relevant conditions leading to the possible formation of oxalic acid via radical mediated recombination. The second part focuses on the polychromatic irradiation (closed to solar irradiation) of a collected cloud aqueous phase showing that irradiation of cloud water leads to the formation of both formic and acetic acids. Carboxylic acid formation increases in the presence of photogenerated hydroxyl radicals from hydrogen peroxide, showing that photooxidation could play a key role in the formation of carboxylic acids under atmospherically relevant conditions.

  7. Synthesis of S-linked glycosyl amino acids in aqueous solution with unprotected carbohydrates.

    PubMed

    Cohen, S B; Halcomb, R L

    2001-02-08

    [figure: see text] The cyclic sulfamidate 5 was synthesized in 60% overall yield from L-serine benzyl ester. Compound 5 reacted cleanly with the sodium thiolate salt of a variety of unprotected 1-thio sugars in aqueous buffer to afford the corresponding S-linked amino acid glycoconjugates in good yields after hydrolysis of the N-sulfates.

  8. POLYSTYRENE SULFONIC ACID CATALYZED GREENER SYNTHESIS OF HYDRAZONES IN AQUEOUS MEDIUM USING MICROWAVES

    EPA Science Inventory

    An environmentally benign aqueous protocol for the synthesis of cyclic, bi-cyclic, and heterocyclic hydrazones using polystyrene sulfonic acid (PSSA) as a catalyst has been developed; the simple reaction proceeds efficiently in water in the absence of any organic solvent under mi...

  9. Aqueous-phase hydrogenation of acetic acid over transition metal catalysts

    SciTech Connect

    Olcay, Hakan; Xu, Lijun; Xu, Ye; Huber, George

    2010-01-01

    Catalytic hydrogenation of acetic acid to ethanol has been carried out in aqueous phase on several metals, with ruthenium being the most active and selective. DFT calculations suggest that the initial CO bond scission yielding acetyl is the key step and that the intrinsic reactivity of the metals accounts for the observed activity.

  10. Rosmarinic acid content in antidiabetic aqueous extract from ocimum canum sims in Ghana

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Rosmarinic acid (RA) is an important polyphenol that is found in a variety of herbs including Ocimum canum sims (locally called eme or akokobesa in Ghana). Aqueous extracts from the leaves of O. canum are used as an antidiabetic herbal medicine in Ghana. Analytical TLC was used to examine the compos...

  11. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  12. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  13. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  14. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  15. 49 CFR 173.195 - Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution).

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Hydrogen cyanide, anhydrous, stabilized... Hazardous Materials Other Than Class 1 and Class 7 § 173.195 Hydrogen cyanide, anhydrous, stabilized (hydrocyanic acid, aqueous solution). (a) Hydrogen cyanide, anhydrous, stabilized, must be packed...

  16. THE ROLE OF SELECTED CATIONS IN THE FORMATION OF PSEUDOMICELLES IN AQUEOUS HUMIC ACID (R822832)

    EPA Science Inventory

    The fluorescence intensity enhancement of a pyrene probe in aqueous humic acid solutions was assessed in terms of added lanthanide and thorium cations. Among the trivalent ions it was found that size played a role, with the small Lu3+ ion producing the greatest increase in pyrene...

  17. ROS Initiated Oxidation of Dopamine under Oxidative Stress Conditions in Aqueous and Lipidic Environments

    PubMed Central

    2011-01-01

    Dopamine is known to be an efficient antioxidant and to protect neurocytes from oxidative stress by scavenging free radicals. In this work, we have carried out a systematic quantum chemistry and computational kinetics study on the reactivity of dopamine toward hydroxyl (•OH) and hydroperoxyl (•OOH) free radicals in aqueous and lipidic simulated biological environments, within the density functional theory framework. Rate constants and branching ratios for the different paths contributing to the overall reaction, at 298 K, are reported. For the reactivity of dopamine toward hydroxyl radicals, in water at physiological pH, the main mechanism of the reaction is proposed to be the sequential electron proton transfer (SEPT), whereas in the lipidic environment, hydrogen atom transfer (HAT) and radical adduct formation (RAF) pathways contribute almost equally to the total reaction rate. In both environments, dopamine reacts with hydroxyl radicals at a rate that is diffusion-controlled. Reaction with the hydroperoxyl radical is much slower and occurs only by abstraction of any of the phenolic hydrogens. The overall rate coefficients are predicted to be 2.23 × 105 and 8.16 × 105 M–1 s–1, in aqueous and lipidic environment, respectively, which makes dopamine a very good •OOH, and presumably •OOR, radical scavenger. PMID:21919526

  18. The standard enthalpies of formation of crystalline N-(carboxymethyl)aspartic acid and its aqueous solutions

    NASA Astrophysics Data System (ADS)

    Lytkin, A. I.; Chernyavskaya, N. V.; Volkov, A. V.; Nikol'Skii, V. M.

    2007-07-01

    The energy of combustion of N-(carboxymethyl)aspartic acid (CMAA) was determined by bomb calorimetry in oxygen. The standard enthalpies of combustion and formation of crystalline N-(carboxymethyl)aspartic acid were calculated. The heat effects of solution of crystalline CMAA in water and a solution of sodium hydroxide were measured at 298.15 K by direct calorimetry. The standard enthalpies of formation of CMAA and its dissociation products in aqueous solution were determined.

  19. Relative Amino Acid Composition Signatures of Organisms and Environments

    PubMed Central

    Moura, Alexandra; Savageau, Michael A.; Alves, Rui

    2013-01-01

    Background Identifying organism-environment interactions at the molecular level is crucial to understanding how organisms adapt to and change the chemical and molecular landscape of their habitats. In this work we investigated whether relative amino acid compositions could be used as a molecular signature of an environment and whether such a signature could also be observed at the level of the cellular amino acid composition of the microorganisms that inhabit that environment. Methodologies/Principal Findings To address these questions we collected and analyzed environmental amino acid determinations from the literature, and estimated from complete genomic sequences the global relative amino acid abundances of organisms that are cognate to the different types of environment. Environmental relative amino acid abundances clustered into broad groups (ocean waters, host-associated environments, grass land environments, sandy soils and sediments, and forest soils), indicating the presence of amino acid signatures specific for each environment. These signatures correlate to those found in organisms. Nevertheless, relative amino acid abundance of organisms was more influenced by GC content than habitat or phylogeny. Conclusions Our results suggest that relative amino acid composition can be used as a signature of an environment. In addition, we observed that the relative amino acid composition of organisms is not highly determined by environment, reinforcing previous studies that find GC content to be the major factor correlating to amino acid composition in living organisms. PMID:24204807

  20. Curcumin-cysteine and curcumin-tryptophan conjugate as fluorescence turn on sensors for picric Acid in aqueous media.

    PubMed

    Gogoi, Bedanta; Sen Sarma, Neelotpal

    2015-06-03

    Rapid detection of picric acid in real sample is of outmost importance from the perspective of health, safety, and environment. In this study, a very simple and cost-effective detection of picric acid is accomplished by developing a couple of biobased conjugates curcumin-cysteine (CC) and curcumin-tryptophan (CT), which undergo efficient fluorescence turn on toward picric acid in aqueous media. Both the probes experience about 26.5-fold fluorescence enhancements at 70 nM concentration of the analyte. Here, the fluorescence turn on process is governed by the aggregation induced emission, which is induced from the electrostatic interaction between the conjugates with picric acid. The detection limit of CC and CT are about 13.51 and 13.54 nM of picric acid, respectively. Importantly, both the probes exhibit high selectivity and low interference of other analogues toward the detection of picric acid. In addition, the probes are highly photostable, show low response time and are practically applicable for sensing picric acid in real environmental samples, which is the ultimate goal of this work.

  1. Photodecomposition of tetrabromobisphenol A in aqueous humic acid suspension by irradiation with light of various wavelengths.

    PubMed

    Han, Sang Kuk; Yamasaki, Toshihide; Yamada, Ken-ichi

    2016-03-01

    The reactive species generated in aqueous 3,3',5,5'-tetrabromobisphenol A (TBBPA)/humic acid (HA) suspensions above the TBBPA pKa (∼7.4), under various light-irradiation conditions, namely ambient and ultraviolet light, were investigated using electron paramagnetic resonance (EPR) spectroscopy and liquid chromatography-mass spectrometry (LC-MS). We confirmed that singlet oxygen and OH radicals are the key reactive oxygen species generated at wavelengths greater than 400 and 300 nm, respectively. The amount of 2,6-dibromo-p-benzosemiquinone anion radicals (2,6-DBSQ(•-)) formed under irradiation at 400 nm increased linearly with respect to irradiation time; the initial reaction rate was 7.03 × 10(-9) mol g(-1) HA s(-1). The rate increased with increasing pH and light intensity. LC-MS and EPR spectroscopy showed that tribromohydroxybisphenol A was formed under irradiation at 300 nm via reaction of OH radicals with TBBPA. This study, for the first time, shows that the main byproducts formed during irradiation at wavelengths above 300 nm are 2,6-DBSQ(•-) and tribromohydroxybisphenol A, generated from singlet oxygen ((1)O2) and OH radicals, respectively. Photodecomposition of TBBPA in the environment may occur by formation of (1)O2 and OH radicals.

  2. IMMOBILIZATION OF AQUEOUS PYRENE BY DISSOLVED HUMIC ACID (R822832)

    EPA Science Inventory

    Abstract

    Pyrene is frequently used as a fluorescent probe in the study of solution environments. Purging with nitrogen is a common practice for the elimination of oxygen from solutions, but this procedure leads to the loss of pyrene through carry-over in the nitrogen s...

  3. Interaction between oxalic acid and titania in aqueous ethanol dispersions.

    PubMed

    Dahlsten, Per; Rosenholm, Jarl B

    2013-02-15

    The charging effects resulting from adsorption of oxalic acid and oxalate anions on titania (anatase) surfaces in anhydrous or mixed water-ethanol suspensions is summarized. The suddenly enhanced electrical conductance with respect to titania free solutions has previously been explained in terms of surface-induced electrolytic dissociation (SIED) of weak acids. A recently published model has previously been found to successfully characterize the complex SIED effect. The model is evaluated experimentally by recording the conductance and pH of the dispersion and the zeta potential of the particles. The experimental results can be condensed to master curves, which reveal the major properties of the systems and facilitate further modeling of extensive experimental results. The equilibrium and transport properties of solutions and particles were related, but different mechanisms was found to be active in each case. The results suggest that at least three adsorption equilibria should be considered in order to improve the model.

  4. Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

    NASA Astrophysics Data System (ADS)

    Tan, Y.; Lim, Y. B.; Altieri, K. E.; Seitzinger, S. P.; Turpin, B. J.

    2012-01-01

    Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM-10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

  5. Stability of titania nanotube arrays in aqueous environment and the related factors

    NASA Astrophysics Data System (ADS)

    Cao, Can; Yan, Jun; Zhang, Yumei; Zhao, Lingzhou

    2016-03-01

    Titania nanotube arrays (NTAs) on titanium (Ti) fabricated by electrochemical anodization have attracted tremendous interest for diverse applications, of which most perform in aqueous environment or related to interaction with water. The NTAs are widely studied however the related factor of stability of NTAs when applied in such environment has rarely been concerned. We report that the annealed anatase NTAs are stable but the non-annealed amorphous NTAs are unstable to undergo specific structural change accompanied with a process of amorphous TiO2 dissolution and anatase TiO2 recrystallization. Quite unexpectedly, the non-annealed NTAs still show good stability without structural change in the cell culture media, possibly due to the presence of inorganics that may interfere with the TiO2 dissolution/redeposition process. The pH value of the aqueous environment is not a determinant factor for the structural change for non-annealed NTAs or not, while the temperature and the existence of F‑ can accelerate the structural change process. F‑ may play a very important role in the change process.

  6. Regeneration of an aqueous solution from an acid gas absorption process by matrix stripping

    DOEpatents

    Rochelle, Gary T.; Oyenekan, Babatunde A.

    2011-03-08

    Carbon dioxide and other acid gases are removed from gaseous streams using aqueous absorption and stripping processes. By replacing the conventional stripper used to regenerate the aqueous solvent and capture the acid gas with a matrix stripping configuration, less energy is consumed. The matrix stripping configuration uses two or more reboiled strippers at different pressures. The rich feed from the absorption equipment is split among the strippers, and partially regenerated solvent from the highest pressure stripper flows to the middle of sequentially lower pressure strippers in a "matrix" pattern. By selecting certain parameters of the matrix stripping configuration such that the total energy required by the strippers to achieve a desired percentage of acid gas removal from the gaseous stream is minimized, further energy savings can be realized.

  7. Impact of humic/fulvic acid on the removal of heavy metals from aqueous solutions using nanomaterials: a review.

    PubMed

    Tang, Wang-Wang; Zeng, Guang-Ming; Gong, Ji-Lai; Liang, Jie; Xu, Piao; Zhang, Chang; Huang, Bin-Bin

    2014-01-15

    Nowadays nanomaterials have been widely used to remove heavy metals from water/wastewater due to their large surface area and high reactivity. Humic acid (HA) and fulvic acid (FA) exist ubiquitously in aquatic environments and have a variety of functional groups which allow them to complex with metal ions and interact with nanomaterials. These interactions can not only alter the environmental behavior of nanomaterials, but also influence the removal and transportation of heavy metals by nanomaterials. Thus, the interactions and the underlying mechanisms involved warrant specific investigations. This review outlined the effects of HA/FA on the removal of heavy metals from aqueous solutions by various nanomaterials, mainly including carbon-based nanomaterials, iron-based nanomaterials and photocatalytic nanomaterials. Moreover, mechanisms involved in the interactions were discussed and potential environmental implications of HA/FA to nanomaterials and heavy metals were evaluated.

  8. Ion Pair in Extreme Aqueous Environments, Molecular-Based and Electric Conductance Approaches

    SciTech Connect

    Chialvo, Ariel A; Gruszkiewicz, Miroslaw {Mirek} S; Simonson, J Michael {Mike}; Palmer, Donald; Cole, David R

    2009-01-01

    We determine by molecular-based simulation the density profiles of the Na+!Cl! ion-pair association constant in steam environments along three supercritical isotherms to interrogate the behavior of ion speciation in dilute aqueous solutions at extreme conditions. Moreover, we describe a new ultra-sensitive flow-through electric conductance apparatus designed to bridge the gap between the currently lowest steam-density conditions at which we are experimentally able to attain electric conductance measurements and the theoretically-reachable zero-density limit. Finally, we highlight important modeling challenges encountered near the zero-density limit and discuss ways to overcome them.

  9. Smectite Formation in Acid Sulfate Environments on Mars

    NASA Technical Reports Server (NTRS)

    Peretyazhko, T. S.; Niles, P. B.; Sutter, B.; Clark, J. V.; Morris, R. V.; Ming, D. W.

    2017-01-01

    Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars were hypothesized to form under aqueous conditions that were globally neutral to alkaline. These pH conditions and the presence of a CO2-rich atmosphere should have been favorable for the formation of large carbonate deposits. However, large-scale carbonate deposits have not been detected on Mars. We hypothesized that smectite deposits are consistent with perhaps widespread acidic aqueous conditions that prevented carbonate precipitation. The objective of our work was to investigate smectite formation under acid sulfate conditions in order to provide insight into the possible geochemical conditions required for smectite formation on Mars. Hydrothermal batch incubation experiments were performed with Mars-analogue, glass-rich, basalt simulant in the presence of sulfuric acid of variable concentration.

  10. Ruthenium-catalyzed oxidation of alkenes, alkynes, and alcohols to organic acids with aqueous hydrogen peroxide.

    PubMed

    Che, Chi-Ming; Yip, Wing-Ping; Yu, Wing-Yiu

    2006-09-18

    A protocol that adopts aqueous hydrogen peroxide as a terminal oxidant and [(Me3tacn)(CF3CO2)2Ru(III)(OH2)]CF3CO2 (1; Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) as a catalyst for oxidation of alkenes, alkynes, and alcohols to organic acids in over 80% yield is presented. For the oxidation of cyclohexene to adipic acid, the loading of 1 can be lowered to 0.1 mol %. On the one-mole scale, the oxidation of cyclohexene, cyclooctene, and 1-octanol with 1 mol % of 1 produced adipic acid (124 g, 85% yield), suberic acid (158 g, 91% yield), and 1-octanoic acid (129 g, 90% yield), respectively. The oxidative C=C bond-cleavage reaction proceeded through the formation of cis- and trans-diol intermediates, which were further oxidized to carboxylic acids via C-C bond cleavage.

  11. Gamma-irradiation of malic acid in aqueous solutions. [prebiotic significance

    NASA Technical Reports Server (NTRS)

    Negron-Mendoza, A.; Graff, R. L.; Ponnamperuma, C.

    1980-01-01

    The gamma-irradiation of malic acid in aqueous solutions was studied under initially oxygenated and oxygen-free conditions in an attempt to determine the possible interconversion of malic acid into other carboxylic acids, specifically those associated with Krebs cycle. The effect of dose on product formation of the system was investigated. Gas-liquid chromatography combined with mass spectrometry was used as the principal means of identification of the nonvolatile products. Thin layer chromatography and direct probe mass spectroscopy were also employed. The findings show that a variety of carboxylic acids are formed, with malonic and succinic acids in greatest abundance. These products have all been identified as being formed in the gamma-irradiation of acetic acid, suggesting a common intermediary. Since these molecules fit into a metabolic cycle, it is strongly suggestive that prebiotic pathways provided the basis for biological systems.

  12. Conversion of Aqueous Ammonia-Treated Corn Stover to Lactic Acid by Simultaneous Saccharification and Cofermentation

    NASA Astrophysics Data System (ADS)

    Zhu, Yongming; Lee, Y. Y.; Elander, Richard T.

    Treatment of corn stover with aqueous ammonia removes most of the structural lignin, whereas retaining the majority of the carbohydrates in the solids. After treatment, both the cellulose and hemicellulose in corn stover become highly susceptible to enzymatic digestion. In this study, corn stover treated by aqueous ammonia was investigated as the substrate for lactic acid production by simultaneous saccharification and cofermentation (SSCF). A commercial cellulase (Spezyme-CP) and Lactobacillus pentosus American Type Culture Collection (ATCC) 8041 (Spanish Type Culture Collection [CECT]-4023) were used for hydrolysis and fermentation, respectively. In batch SSCF operation, the carbohydrates in the treated corn stover were converted to lactic acid with high yields, the maximum lactic acid yield reaching 92% of the stoichiometric maximum based on total fermentable carbohydrates (glucose, xylose, and arabinose). A small amount of acetic acid was also produced from pentoses through the phosphoketolase pathway. Among the major process variables for batch SSCF, enzyme loading and the amount of yeast extract were found to be the key factors affecting lactic acid production. Further tests on nutrients indicated that corn steep liquor could be substituted for yeast extract as a nitrogen source to achieve the same lactic acid yield. Fed-batch operation of the SSCF was beneficial in raising the concentration of lactic acid to a maximum value of 75.0 g/L.

  13. [Catalytic ozonation by ceramic honeycomb for the degradation of oxalic acid in aqueous solution].

    PubMed

    Zhao, Lei; Sun, Zhi-Zhong; Ma, Jun

    2007-11-01

    Comparative experiments for the degradation of oxalic acid in aqueous solution were carried out in the three processes of ozonation alone, ceramic honeycomb-catalyzed ozonation and ceramic honeycomb adsorption. The results show that the degradation rates of oxalic acid in the ceramic honeycomb-catalyzed ozonation, ozonation alone and ceramic honeycomb adsorption systems are 37.6%, 2.2% and 0.4%, and the presence of ceramic honeycomb catalyst significantly improves the degradation rate of oxalic acid compared to the results from non-catalytic ozonation and adsorption. With the addition of tert-butanol, the degradation rates of oxalic acid in catalytic ozonation system decrease by 24.1%, 29.0% and 30.1%, respectively, at the concentration of 5, 10 and 15 mg x L(-1). This phenomenon indicates that ceramic honeycomb-catalyzed ozonation for the degradation of oxalic acid in aqueous solution follows the mechanism of *OH oxidation, namely the heterogeneous surface of catalyst enhances the initiation of *OH. The results of TOC analysis demonstrate that the process of ceramic honeycomb-catalyzed ozonation can achieve the complete mineralization level without the formation of intermediary degradation products. The experimental results suggest that the reaction temperature has positive relationship with the degradation rate of oxalic acid. The degradation rates of oxalic acid in the ceramic honeycomb-catalyzed ozonation system are 16.4%, 37.6%, 61.3% and 68.2%, at the respective reaction temperature of 10, 20, 30 and 40 degrees C.

  14. Thermochemical study of the reactions of acid-base interaction in an aqueous solution of α-aminobutyric acid

    NASA Astrophysics Data System (ADS)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.; Skvortsov, I. A.; Korchagina, A. S.

    2017-01-01

    The heat effects of the interaction between a solution of α-aminobutyric acid and solutions of HNO3 and KOH are measured by means of calorimetry in different ranges of pH at 298.15 K and values of ionic strength of 0.25, 0.5, and 0.75 (KNO3). The heat effects of the stepwise dissociation of the amino acid are determined. Standard thermodynamic characteristics (Δr H 0, Δr G 0, and Δr S 0) of the reactions of acid-base interaction in aqueous solutions of α-aminobutyric acid are calculated. The connection between the thermodynamic characteristics of the dissociation of the amino acid and the structure of this compound is considered.

  15. Subcritical crack growth in glasses under cyclic loads: Effect of hydrodynamic pressure in aqueous environments

    SciTech Connect

    Yi, K.S.; Dill, S.J.; Dauskardt, R.H.

    1997-07-01

    The effect of hydrodynamic pressure developed in the wake of a crack growing in a brittle material under cyclic loads in an aqueous environment is considered. The pressure acts in opposition to the movement of the crack faces, thus shielding the crack up from the applied loads. A general hydrodynamic fluid pressure relation based on a one-dimensional Reynolds equation, which applicable to a crack with an arbitrary crack opening profile, is developed. The model is modified to account for side flow through the thickness of the sample and cavitation near the crack tip. Both effects significantly modify the hydrodynamic pressure distribution. Finally, the resulting hydrodynamic pressure relations are combined with a fracture mechanics model to account for the change in the near-tip stress intensity. Resulting predictions of the cyclic crack-growth rate are found to be in good agreement with measured values for a borosilicate glass tested at various frequencies in a water environment.

  16. Energy band alignment and electronic states of amorphous carbon surfaces in vacuo and in aqueous environment

    SciTech Connect

    Caro, Miguel A.; Määttä, Jukka; Lopez-Acevedo, Olga; Laurila, Tomi

    2015-01-21

    In this paper, we obtain the energy band positions of amorphous carbon (a–C) surfaces in vacuum and in aqueous environment. The calculations are performed using a combination of (i) classical molecular dynamics (MD), (ii) Kohn-Sham density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, and (iii) the screened-exchange hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE). PBE allows an accurate generation of a-C and the evaluation of the local electrostatic potential in the a-C/water system, HSE yields an improved description of energetic positions which is critical in this case, and classical MD enables a computationally affordable description of water. Our explicit calculation shows that, both in vacuo and in aqueous environment, the a-C electronic states available in the region comprised between the H{sub 2}/H{sub 2}O and O{sub 2}/H{sub 2}O levels of water correspond to both occupied and unoccupied states within the a-C pseudogap region. These are localized states associated to sp{sup 2} sites in a-C. The band realignment induces a shift of approximately 300 meV of the a-C energy band positions with respect to the redox levels of water.

  17. Evaluation of the Capability of Ionic Liquid-Amino Acid Aqueous Systems for the Formation of Aqueous Biphasic Systems and Their Applications in Extraction.

    PubMed

    Noshadi, Sajjad; Sadeghi, Rahmat

    2017-03-03

    In order to obtain further experimental evidence for better understanding of the molecular mechanisms responsible for the soluting-out effect phenomena in the ternary systems composed of ionic liquid (IL), amino acid and water, systematic studies on the vapor-liquid, liquid-liquid and solid-liquid equilibrium behavior of aqueous solutions of several ILs were carried out in the presence of a range of amino acids. Water activities for binary and ternary aqueous solutions containing 1-butyl-3-methylimidazolium chloride, [C4mim]Cl, 1-hexyl-3-methylimidazolium chloride, [C6mim]Cl, 1-butyl-3-methyl-imidazolium trifluoromethanesulfonate, [C4mim][CF3SO3], l-serine, glycine, alanine, and l-proline were measured using both vapor pressure osmometry and isopiestic methods. All the ternary IL + amino acid + water systems show the negative deviations from the semi-ideal behavior and therefore the soluting-out effects have been seen in these systems. In the case of [C4mim][CF3SO3] + amino acids aqueous systems, the IL is soluted-out by the amino acids and the soluting-out effect appears by aqueous biphasic systems formation. For these systems, the phase diagram and partition coefficient of caffeine were measured at 298.15 K. However, for the [C4mim]Cl and [C6mim]Cl containing systems, the amino acids are soluted-out by the ILs and the soluting-out effect appears by precipitation of the amino acids from the solution and solubilities of the amino acids in aqueous solutions decrease in the presence of [C4mim]Cl and [C6mim]Cl.

  18. Adipic and malonic acid aqueous solutions: surface tensions and saturation vapor pressures.

    PubMed

    Riipinen, Ilona; Koponen, Ismo K; Frank, Göran P; Hyvärinen, Antti-Pekka; Vanhanen, Joonas; Lihavainen, Heikki; Lehtinen, Kari E J; Bilde, Merete; Kulmala, Markku

    2007-12-20

    The surface tension of adipic aqueous solutions was measured as a function of temperature (T=278-313 K) and adipic acid mole fraction (X=0.000-0.003) using the Wilhelmy plate method. A parametrization fitted to these data is presented. The evaporation rates of binary water-malonic and water-adipic acid droplets were measured with a TDMA technique at different temperatures (T=293-300 K) and relative humidities (58-80%), and the saturation vapor pressures of subcooled liquid malonic and adipic acids were derived from the data using a binary evaporation model. The temperature dependence of the vapor pressures was obtained as least-squares fits to the derived vapor pressures: ln(Psat,l) (Pa)=220.2389-22634.96/T (K)-26.66767 ln T (K) for malonic acid and ln(Psat,l) (Pa)=140.6704-18230.97/T (K)-15.48011 ln T (K) for adipic acid.

  19. Enhanced removal of Hg(II) from acidic aqueous solution using thiol-functionalized biomass.

    PubMed

    Chai, Liyuan; Wang, Qingwei; Li, Qingzhu; Yang, Zhihui; Wang, Yunyan

    2010-01-01

    Spent grain, the low-cost and abundant biomass produced in the brewing industry, was functionalized with thiol groups to be used as an adsorbent for Hg(II) removal from acidic aqueous solution. The adsorbents were characterized by the energy-dispersive X-ray analysis (EDAX) and Fourier transform infrared (FTIR) spectroscopy. Optimum pH for Hg(II) adsorption onto the thiol-functionalized spent grain (TFSG) was 2.0. The equilibrium and kinetics of the adsorption of Hg(II) onto TFSG from acidic aqueous solution were investigated. From the Langmuir isotherm model the maximum adsorption capacity of TFSG for Hg(II) was found to be 221.73 mg g(-1), which was higher than that of most various adsorbents reported in literature. Moreover, the adsorption of Hg(II) onto TFSG followed pseudo-second-order kinetic model.

  20. Mechanistic study of fulvic acid assisted propranolol photodegradation in aqueous solution.

    PubMed

    Makunina, Maria P; Pozdnyakov, Ivan P; Chen, Yong; Grivin, Vyacheslav P; Bazhin, Nikolay M; Plyusnin, Victor F

    2015-01-01

    Laser flash (355 nm) and stationary (365 nm) photolysis were used to study the mechanisms of propranolol photolysis in the presence of fulvic acid in aqueous solutions. The FA-assisted photodegradation of propranolol was observed using UV-A irradiation (where propranolol is stable). Direct evidence indicated that the photodegradation resulted from the static quenching of the FA triplet state by propranolol via the electron transfer mechanism. The triplet state yield (ϕT≈0.6%) and the T-T absorption coefficient (ɛT(620 nm)≈5×10(4) M(-1) cm(-1)) were estimated for the first time by modeling the yields of the FA triplet state in the presence of propranolol. Thus, fulvic acid is a promising agent for accelerating propranolol photodegradation in aqueous solutions under UV-A light irradiation.

  1. Effective Removal of Tetracycline from Aqueous Solution by Organic Acid-Coated Magnetic Nanoparticles.

    PubMed

    Guo, Liang; Liang, Yuyan; Chen, Xuelan; Xu, Wei; Wu, Kesheng; Wei, Hua; Xiong, Yonghua

    2016-03-01

    Self-assembled iron oxide nanocomposites are good magnetic nano-adsorbents that can be prepared using simple methods. Four types of organic acid-functionalised (oleic acid, undecenoic acid, caprylic acid or hexanoic acid) magnetic nanoparticles (MNPs) were synthesised through a one-pot chemisorption method for the removal of tetracycline (TC) from aqueous solution. The undecenoic acid-coated MNPs (UA-MNPs) exhibited the highest adsorption efficiency and can be easily retrieved with a low-gradient magnetic separator (0.4 Tesla) at pH 5.0 aqueous solution. The TC adsorption process on the UA-MNPs followed the Langmuir isotherm and the maximum adsorption capacities increased from 86.96 mg g(-1) to 222.2 mg g(-1) with the increase in temperature from 288 K to 318 K. The kinetics of adsorption fits pseudo-second-order model perfectly with a rate constant, 5.946 g mg(-1) min(-1) at 298 K. The positive values of the enthalpy (AH) and the negative value of the free energy (AG) indicated an endothermic and spontaneous adsorption process of TC on the UA-MNPs. Moreover, the UA-MNPs possessed excellent ability to adsorb the other three major types of TC antibiotics, including chlortetracycline, oxytetracycline and doxycycline.

  2. Influence of humic acid on the uptake of aqueous metals by the killifish Fundulus heteroclitus.

    PubMed

    Dutton, Jessica; Fisher, Nicholas S

    2012-10-01

    The role of humic acids, over a concentration range of 0 to 20 mg L(-1) , was investigated in the uptake of three metals (Cd, Cr, and Hg-as both inorganic Hg [Hg(II)] and methylmercury [MeHg]) and a metalloid (As) from the aqueous phase by the killifish (Fundulus heteroclitus). Cadmium uptake showed no relationship with humic acid concentration, whereas Cr, Hg(II), and MeHg uptake showed an inverse relationship, and As uptake increased with increasing humic acid concentration. Concentration factors were >1 for Cd, Hg(II), and MeHg at all humic acid concentrations, indicating killifish were more enriched in the metal than the experimental media, whereas As and Cr generally had concentration factors <1 at the end of a 72-h exposure. The uptake of As and Cr reached steady state within the 72-h exposure, whereas uptake of Cd, Hg(II), and MeHg did not. Uptake rate constants (k(u) s; ml g(-1)  d(-1) ) were highest for MeHg (91-3,936), followed by Hg(II), Cd, and Cr, and lowest for As (0.17-0.29). Dissection data revealed that the gills generally had the highest concentration of all metals under all humic acid treatments. The present study concludes that changes in humic acid concentration can influence the accumulation of aqueous metals in killifish and should be considered when modeling metal bioaccumulation.

  3. Zeolite-type metal organic frameworks immobilized Eu³⁺ for cation sensing in aqueous environment.

    PubMed

    Liu, Chang; Yan, Bing

    2015-12-01

    A novel luminescent lanthanide metal organic framework (Ln-MOF) is synthesized by in situ encapsulating Eu(3+) ions to partial replace the transition-metal clusters in the channels of CPM-17-Zn nanocrystals. The Eu(3+) functionalized zeolite-type MOF hybrid system shows excellent luminescence property and photo-stability in aqueous environment for the sensitization and protection from the host framework. Subsequently, as a highly selective and sensitive sensor, its nanocrystals can be used to detect Cd(2+) in aqueous solution. In addition, the possible sensing mechanism based on ion exchange is discussed in detail. This work is one of the few cases for detecting Cd(2+) in aqueous solution based on a zeolite-type MOF. The good fluorescence stability, low detection limit and broad linear range in aqueous environment make this probe to be expected to have potential application in intracellular sensing and imaging of Cd(2+) potentially.

  4. Impact of acid mine drainage on benthic communities in streams: the relative roles of substratum vs. aqueous effects.

    PubMed

    DeNicol, Dean M; Stapleton, Michael G

    2002-01-01

    Restoration of streams impacted by acid mine drainage (AMD) focuses on improving water quality, however precipitates of metals on the substrata can remain and adversely affect the benthos. To examine the effects of AMD precipitates independently of aqueous effects, four substrata treatments, clean sandstone, clean limestone, AMD precipitate-coated sandstone and coated limestone, were placed in a circumneutral stream of high water quality for 4 weeks. Iron and Al were the most abundant metals on rocks with AMD precipitate. and significantly decreased after the exposure. Precipitate on the substrata did not significantly affect macroinvertebrate or periphyton density and species composition. In an additional experiment, percent survival of caged live caddisflies was significantly lower when exposed in situ for 5 days in an AMD affected stream than in a reference stream. Caddisfly whole-body concentrations of all combined metals and Fe alone were significantly higher in the AMD stream. Whole-body metal concentrations were higher in killed caddisflies than in live, indicating the importance of passive uptake. The results suggest the aqueous chemical environment of AMD had a greater affect on organisms than a coating of recent AMD precipitate on the substrata (ca. 0.5 mm thick), and treatment that improves water quality in AMD impacted streams has the potential to aid in recovery of the abiotic and biotic benthic environment.

  5. Removal of transition metals from dilute aqueous solution by carboxylic acid group containing absorbent polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new carboxylic acid group containing resin with cation exchange capacity, 12.67 meq/g has been used to remove Cu2+, Co2+ and Ni2+ ions from dilute aqueous solution. The resin has Cu2+, Co2+ and Ni2+ removal capacity, 216 mg/g, 154 mg/g and 180 mg/g, respectively. The selectivity of the resin to ...

  6. Distributed All-Optical Sensor to Detect dCO2 in Aqueous Environments

    NASA Astrophysics Data System (ADS)

    Bhatia, S.; Coelho, J.; Melo, L.; Davies, B.; Ahmed, F.; Bao, B.; Wild, P.; Risk, D. A.; Sinton, D.; Jun, M.

    2012-12-01

    Already a proven technology for temperature and stress measurements, an all-optical sensor to detect dCO2 is being developed for deployment in challenging environments. Optical sensors function under high pressure, do not require electronics and therefore experience no magnetic interference. They are also able to transmit signals over long distances with minimal losses. The dCO2 sensor's principal application is in measurement monitoring and verification of carbon capture and storage sites; however, it could also be useful in ocean, fresh water, and transition environments. The objective for the first phase of development was to detect a CO2 signal in laboratory tests. The developmental program incorporated experiments to detect CO2 under high pressure (1400 psi) in aqueous environments. Laboratory testing involved a custom pressure cell, off-the-shelf and custom long period gratings written in SMF125 fiber. Femptosecond laser micromachining was used to test alternative long period grating (LPG) and cutout shapes to maximize evanescent field interaction with the environment. A comprehensive program of geochemical modeling using PHREEQC 2 was used to identify the diversity of species in environments of interest that could exert confounding influence. Purchased UV-LPG responded to changes in concentration of scCO2 in brine at high pressure. Signal differences between CO2-saturated brine and pure brine were also noted under the same, high pressure conditions. Geochemical modeling software, PHREEQC 2, revealed a diversity of species in environments of interest whose concentrations varied strongly with temperature and pH. The modeling program's detailed characterization of environments informed work currently being undertaken as part of Phase 2, to develop a CO2-selective membrane to filter out measurement artifact.

  7. Insights Into the Aqueous History of Mars from Acid-Sulfate Weathered Phyllosilicates

    NASA Technical Reports Server (NTRS)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.; Morris, R. V.

    2016-01-01

    Phyllosilicates on Mars are thought to have formed during Mars' earliest Noachian geologic era (approx. 4.1-3.7 Ga). Sulfate formation, on the other hand, requires more acidic conditions which are thought to have occurred later during Mars' Hesperian era (approx. 3.7-3.0 Ga). Therefore, regions on Mars where phyllosilicates and sulfates are found in close proximity to each other provide evidence for the aqueous conditions during this global transition. Both phyllosilicates and sulfates form in the presence of water and thus give clues to the aqueous history of Mars and its potential for habitability. Phyllosilicates that formed during the Noachian era would have been weathered by the prevailing acidic conditions that define the Hesperian. Therefore, the purpose of this study is to characterize the alteration products of acid-sulfate weathered phyllosilicates in laboratory experiments, focusing on the Fe/Mg-smectites commonly identified on Mars. We also compare our results to observations of phyllosilicates and sulfates on Mars in regions such as Endeavour Crater and Mawrth Vallis to understand the formation process of sulfates and constrain the aqueous history of these regions.

  8. Sulfate Mineral Formation from Acid-Weathered Phyllosilicates: Implications for the Aqueous History of Mars

    NASA Technical Reports Server (NTRS)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.; Morris, R. V.

    2015-01-01

    Phyllosilicates on Mars are thought to have formed under neutral to alkaline conditions during Mars' earliest Noachian geologic era (approx. 4.1-3.7 Gya). Sulfate formation, on the other hand, requires more acidic conditions which are thought to have occurred later during Mars' Hesperian era (approx. 3.7-3.0 Gya). Therefore, regions on Mars where phyllosilicates and sulfates are found in close proximity to each other provide evidence for the geologic and aqueous conditions during this global transition. Both phyllosilicates and sulfates form in the presence of water and thus give clues to the aqueous history of Mars and its potential for habitability. Phyllosilicates that formed during the Noachian era may have been weathered by the prevailing acidic conditions that characterize the Hesperian. Therefore, the purpose of this study is to characterize the alteration products resulting from acid-sulfate weathered phyllosilicates in laboratory experiments. This study focuses on two phyllosilicates commonly identified with sulfates on Mars: nontronite and saponite. We also compare our results to observations of phyllosilicates and sulfates on Mars to better understand the formation process of sulfates in close proximity to phyllosilicates on Mars and constrain the aqueous conditions of these regions on Mars.

  9. Human skin permeability enhancement by lauric acid under equilibrium aqueous conditions.

    PubMed

    Smith, S W; Anderson, B D

    1995-05-01

    An in vitro method was developed to investigate the enhancement of hydrocortisone transport across human stratum corneum (SC) by a model enhancer, lauric acid, in aqueous solutions under equilibrium conditions with respect to the enhancer. In contrast to classical (i.e., nonequilibrium) loading techniques, in which the enhancer is applied only to the donor side of SC either in pure form or in an organic solvent while enhancer-free aqueous buffers are placed in the receptor phase, this method allowed the investigation of pH effects, concentration effects, and reversibility of both enhancer uptake and enhancement of drug transport under thermodynamically well-defined conditions. The SC-buffer partition coefficients for lauric acid were linear with concentration and sigmoidal with pH, suggesting that both the neutral species and laurate anion partition into SC. Comparisons of partition coefficients in delipidized and untreated SC as a function of pH indicated that the uptake of lauric acid in neutral form is governed primarily by the lipid domain, whereas the protein domain accounts for anion uptake. The effects of lauric acid on skin permeability were > 80% reversible upon extraction of the enhancer from the membrane. However, the degree of enhancement of hydrocortisone permeability was nonlinearly dependent on the equilibrium concentration of lauric acid in either the aqueous buffer or the membrane, exhibiting thresholds in the appearance of enhancement with concentration. The enhancer concentration necessary to achieve isoenhancement of about 6-fold varied from approximately 1 x 10(-5) M at pH < pKa to approximately 1 x 10(-2) M at high pH (pH > 8) demonstrating the higher influence of the free acid species.(ABSTRACT TRUNCATED AT 250 WORDS)

  10. Uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide.

    PubMed

    Liu, Ze; Ge, Maofa; Wang, Weigang

    2012-01-01

    Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol formation from isoprene and its gas-phase oxidation products, but the lack of kinetics data significantly limited the evaluation of this process in the atmosphere. Here we report the first measurement of the uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide. Isoprene cannot readily partition into the solution because of its high volatility and low solubility, which hinders its further liquid-phase oxidation. Both methacrylic acid and methyl methacrylate can enter the solutions and be oxidized by hydrogen peroxide, and steady-state uptake was observed with the acidity of solution above 30 wt.% and 70 wt.%, respectively. The steady-state uptake coefficient of methacrylic acid is much larger than that of methyl methacrylate for a solution with same acidity. These observations can be explained by the different reactivity of these two compounds caused by the different electron-withdrawing conjugation between carboxyl and ester groups. The atmospheric lifetimes were estimated based on the calculated steady-state uptake coefficients. These results demonstrate that the multiphase acid-catalyzed oxidation of methacrylic acid plays a role in secondary organic aerosol formation, but for isoprene and methyl methacrylate, this process is not important in the troposphere.

  11. Compartmentalization of amino acids in surfactant aggregates - Partitioning between water and aqueous micellar sodium dodecanoate and between hexane and dodecylammonium propionate trapped water in hexane

    NASA Technical Reports Server (NTRS)

    Fendler, J. H.; Nome, F.; Nagyvary, J.

    1975-01-01

    The partitioning of amino acids (glycine, alanine, leucine, phenylalanine, histidine, aspartic acid, glutamic acid, lysine, isoleucine, threonine, serine, valine, proline, arginine) in aqueous and nonaqueous micellar systems was studied experimentally. Partitioning from neat hexane into dodecylammonium propionate trapped water in hexane was found to be dependent on both electrostatic and hydrophobic interactions, which implies that the interior of dodecylammonium propionate aggregates is negatively charged and is capable of hydrogen bonding in addition to providing a hydrophobic environment. Unitary free energies of transfer of amino acid side chains from hexane to water were determined and solubilities of amino acids in neat hexane substantiated the amino acid hydrophobicity scale. The relevance of the experiments to prebiotic chemistry was examined.

  12. Adsorption of acid dyes from aqueous solution on activated bleaching earth.

    PubMed

    Tsai, W T; Chang, C Y; Ing, C H; Chang, C F

    2004-07-01

    In the present study, activated bleaching earth was used as clay adsorbent for an investigation of the adsorbability and adsorption kinetics of acid dyes (i.e., acid orange 51, acid blue 9, and acid orange 10) with three different molecular sizes from aqueous solution at 25 degrees C in a batch adsorber. The rate of adsorption has been investigated under the most important process parameters (i.e., initial dye concentration). A simple pseudo-second-order model has been tested to predict the adsorption rate constant, equilibrium adsorbate concentration, and equilibrium adsorption capacity by the fittings of the experimental data. The results showed that the adsorbability of the acid acids by activated bleaching earth follows the order: acid orange 51 > acid blue 9 > acid orange 10, parallel to the molecular weights and molecular sizes of the acid dyes. The adsorption removals (below 3%) of acid blue 9 and acid orange 10 onto the clay adsorbent are far lower than that (approximately 24%) of acid orange 51. Further, the adsorption kinetic of acid orange 51 can be well described by the pseudo-second-order reaction model. Based on the isotherm data obtained from the fittings of the adsorption kinetics, the Langmuir model appears to fit the adsorption better than the Freundlich model. The external coefficients of mass transfer of the acid orange 51 molecule across the boundary layer of adsorbent particle have also been estimated at the order of 10(-4)-10(-5) cm s(-1) based on the film-pore model and pseudo-second-order reaction model.

  13. Superhydrophobic copper surfaces fabricated by fatty acid soaps in aqueous solution for excellent corrosion resistance

    NASA Astrophysics Data System (ADS)

    Xu, Wenlong; Hu, Yuanyuan; Bao, Wenda; Xie, Xiaoyu; Liu, Yiran; Song, Aixin; Hao, Jingcheng

    2017-03-01

    A simple and safe one-step immersion method was developed to obtain the stable superhydrophobic copper surfaces with excellent corrosion resistance ability using fatty acids in water-medium instead of ethanol. An organic alkali, N,N-dimethylcyclohexylamine (DMCHA), was chosen to solve the poor solubility of fatty acids in water and the high Krafft point of carboxylate salts with inorganic counterions. The superhydrophobic property can be realized in a much quicker process (7.5 min) in aqueous solution than in ethanol (more than 2 d), which is universally feasible for the fabrication of superhydrophobic metal surfaces in industry scale, thereby greatly increasing the safety in industrial manufacture.

  14. Radical-driven carbonyl-to-acid conversion and acid degradation in tropospheric aqueous systems studied by CAPRAM

    NASA Astrophysics Data System (ADS)

    Tilgner, A.; Herrmann, H.

    2010-12-01

    Model studies on the aqueous phase radical-driven processing of carbonyl compounds and acids in clouds and deliquescent particles were performed. The model exposed that aqueous radical conversions of carbonyl compounds and its oxidation products can contribute potentially to the formation of functionalised organic acids. The main identified C 2-C 4 organic gas phase precursors are ethylene glycol, glycolaldehyde, glyoxal, methylglyoxal and 1,4-butenedial. The aqueous phase is shown to contribute significantly with about 93%/63%, 47%/8%, 31%/4%, 7%/4%, 36%/8% to the multiphase oxidative fate of these compounds under remote/urban conditions. Interestingly, the studies revealed that aqueous chemical processing is not only limited to in-cloud conditions but also proceeds in deliquescent particle phase with significant fluxes. Oxalic acid is shown to be formed preferably in deliquescent particles subsequent to the in-cloud oxidations. Mean aqueous phase oxalate formation fluxes of about 12, 42 and 0.4 ng m -3 h -1 in the remote, urban and maritime scenario, respectively. Additionally, the turnovers of the oxidation of organics such as methylglyoxal by NO 3 radical reactions are identified to be competitive to their OH pendants. At the current state of CAPRAM, mean C 2-C 4 in-cloud oxidation fluxes of about 0.12 and 0.5 μg m -3 h -1 are modelled under the idealised remote and urban cloud conditions. Finally, turnovers from radical oxidations were compared with those of thermal reactions. It is demonstrated that, based on the sparse kinetic data available organic accretion reaction might be of interest in just a few cases for cloud droplets and aqueous particles but generally do not reach the oxidative conversion rates of the main radical oxidants OH and NO 3. Interestingly, oxidation reactions of H 2O 2 are shown to be competitive to the OH radical conversions in cases when H 2O 2 is not readily used up by the S(IV) oxidation.

  15. Changing interfaces: Photoluminescent ZnO nanoparticle powders in different aqueous environments

    NASA Astrophysics Data System (ADS)

    Kocsis, Krisztina; Niedermaier, Matthias; Bernardi, Johannes; Berger, Thomas; Diwald, Oliver

    2016-10-01

    We transformed vapor phase grown ZnO nanoparticle powders into aqueous ZnO nanoparticle dispersions and studied the impact of associated microstructure and interface property changes on their spectroscopic properties. With photoluminescence (PL) spectroscopy, we probed oxygen interstitials Oi2 - in the near surface region and tracked their specific PL emission response at hvEM = 2.1 eV during the controlled conversion of the solid-vacuum into the solid-liquid interface. While oxygen adsorption via the gas phase does affect the intensity of the PL emission bands, the O2 contact with ZnO nanoparticles across the solid-liquid interface does not. Moreover, we found that the near band edge emission feature at hvEM = 3.2 eV gains relative intensity with regard to the PL emission features in the visible light region. Searching for potential PL indicators that are specific to early stages of particle dissolution, we addressed for aqueous ZnO nanoparticle dispersions the effect of formic acid adsorption. In the absence of related spectroscopic features, we were able to consistently track ZnO nanoparticle dissolution and the concomitant formation of solvated Zinc formate species by means of PL and FT-IR spectroscopy, dynamic light scattering, and zeta potential measurements. For a more consistent and robust assessment of nanoparticle properties in different continuous phases, we discuss characterization challenges and potential pitfalls that arise upon replacing the solid-gas with the solid-liquid interface.

  16. The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

    USGS Publications Warehouse

    Bennett, P.C.; Melcer, M.E.; Siegel, D.I.; Hassett, J.P.

    1988-01-01

    The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH.The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

  17. The dissolution of quartz in dilute aqueous solutions of organic acids at 25 degree C

    SciTech Connect

    Bennett, P.C.; Melcer, M.E.; Siegel, D.I.; Hassett, J.P. )

    1988-06-01

    The dissolution of quartz in dilute aqueous solutions of organic acids at 25{degree}C and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 {mu}mole/Kg compared to 50 {mu}mole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

  18. Regeneration of basic sorbents used in the recovery of acetic acid from dilute aqueous solution

    SciTech Connect

    Ng, M.; King, C.J.

    1988-10-01

    The regeneration of basic sorbents used in the recovery of dilute aqueous acetic acid was explored. The regeneration methods studied were solvent leaching and vaporization. The resins used were weak base anion exchange resins, Dow Chemical Company's Dowex MWA-1 (tertiary amine resin) and Celanese Corporation's Aurorez (polybenzimidazole resin). The equilibrium between the aqueous acetic acid solution and the resins was measured in batch experiments. The composite isotherms calculated from these data wee comparable to those of other researchers. Methanol was used as the solvent to leach acetic acid from the resin. The equilibrium data from the batch experiments were used in the local-equilibrium theory of fixed-bed devices to model the desorption behavior of acetic acid in methanol. Both sorption and desorption equilibrium data were used in chemical complexation models to obtain sorption affinities and capacities of the resin for acetic acid. However, the amount of methanol needed to achieve a high degree of regeneration was too large to be economical. 15 refs., 25 figs., 3 tabs.

  19. Prospecting nanomaterials in aqueous environments by cloud-point extraction coupled with transmission electron microscopy.

    PubMed

    Yang, Yu; Reed, Robert; Schoepf, Jared; Hristovski, Kiril; Herckes, Pierre; Westerhoff, Paul

    2017-04-15

    Increasing application of engineered nanomaterials (ENMs) in industry and consumer products inevitably lead to their release into and impact on aquatic environments. To characterize the NMs efficiently in surface water, a fast and simple method is needed to separate and concentrate nanomaterials from the aqueous matrix without altering their shape and size. Applying cloud-point extraction (CPE) using the surfactant Triton 114 to an array of NMs (titanium dioxide, gold, silver, and silicon dioxide) with different sizes or capping agents in nanopure water resulted in extraction efficiency of 83%-107%. Additional CPE experiments were conducted to extract NMs from surface, potable, and sewage waters, and NMs enriched in the surfactant phase were characterized using transmission electron microscopy coupled with energy dispersive x-ray spectroscopy. The most abundant nanoparticles identified in surface water were silica, titanium dioxide, and iron oxide with 4-99nm diameter. The extraction efficiencies of CPE for silicon, titanium, and iron elements from environmental water samples were 51%, 15%, and 99%, respectively. This study applied CPE with TEM to enrich and analyze popular nanoparticles such as SiO2 and TiO2 from natural waters, which has not been well addressed by previous researches. Overall, CPE coupled with transmission electron microscopy (TEM) can be an effective method to characterize NMs in aqueous water samples, and further optimization will increase the extraction efficiency of NMs in complicated surface water matrix.

  20. Aqueous Phase Photo-Oxidation of Succinic Acid: Changes in Hygroscopic Properties and Reaction Products

    NASA Astrophysics Data System (ADS)

    Hudson, P. K.; Ninokawa, A.; Hofstra, J.; de Lijser, P.

    2013-12-01

    Atmospheric aerosol particles have been identified as important factors in understanding climate change. The extent to which aerosols affect climate is determined, in part, by hygroscopic properties which can change as a result of atmospheric processing. Dicarboxylic acids, components of atmospheric aerosol, have a wide range of hygroscopic properties and can undergo oxidation and photolysis reactions in the atmosphere. In this study, the hygroscopic properties of succinic acid aerosol, a non-hygroscopic four carbon dicarboxylic acid, were measured with a humidified tandem differential mobility analyzer (HTDMA) and compared to reaction products resulting from the aqueous phase photo-oxidation reaction of hydrogen peroxide and succinic acid. Reaction products were determined and quantified using gas chromatography-flame ionization detection (GC-FID) and GC-mass spectrometry (GC-MS) as a function of hydrogen peroxide:succinic acid concentration ratio and photolysis time. Although reaction products include larger non-hygroscopic dicarboxylic acids (e.g. adipic acid) and smaller hygroscopic dicarboxylic acids (e.g. malonic and oxalic acids), comparison of hygroscopic growth curves to Zdanovskii-Stokes-Robinson (ZSR) predictions suggests that the hygroscopic properties of many of the product mixtures are largely independent of the hygroscopicity of the individual components. This study provides a framework for future investigations to fully understand and predict the role of chemical reactions in altering atmospheric conditions that affect climate.

  1. Radiolysis of aqueous solutions of acetic acid in the presence of Na-montmorillonite

    NASA Technical Reports Server (NTRS)

    Navarro-Gonzalez, R.; Negron-Mendoza, A.; Ramos, S.; Ponnamperuma, C.

    1990-01-01

    The gamma-irradiation of 0.8 mol dm-3 aqueous, oxygen-free acetic acid solutions was investigated in the presence or absence of Na-montmorillonite. H2, CH4, CO, CO2, and several polycarboxylic acids were formed in all systems. The primary characteristics observed in the latter system were: (1) Higher yield of the decomposition of acetic acid; (2) Lower yield of the formation of polycarboxylic acids; (3) No effect on the formation of methane; (4) Higher yield of the formation of carbon dioxide; and (5) The reduction of Fe3+ in the octahedral sites of Na-montmorillonite. A possible reaction scheme was proposed to account for the observed changes. The results are important in understanding heterogeneous processes in radiation catalysis and might be significant to prebiotic chemistry.

  2. [Studies on carbonization of saccharides by using aqueous solution of various acids].

    PubMed

    Zhang, Xin; He, An-Qi; Kang, Ting-Guo; Xia, Jin-Ming; Weng, Shi-Fu; Xu, Yi-Zhuang; Wu, Jin-Guang

    2014-09-01

    The authors tried to establish an approach to use acids to convert biomass into a fuel with higher carbon content and lower oxygen content in a zero-energy-consumption fashion. Considering that biomass is composed of monosaccharide, we used aqueous solutions of variation acids including hydrochloric acid, sulfuric acid and perchloric acid to treat 2-deoxy-ribose and fructose at ambient temperature and pressure. Black substances were produced after a period of time when 2-deoxy-ribose and fructose were mixed with aqueous solutions containing 8 mol · L(-1) acids. The black substance was collected and characterized by using elemental analysis, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Elemental analysis results indicate that the contents of carbon increases significantly in the black substances in comparison with 2-deoxy-ribose and fructose. Moreover, XPS results indicate that the content of oxygen in the black substance undergoes a significant decrease compared with pure 2-deoxy-ribose and fructose. In the XPS spectra, the is peaks of 2-deoxy-ribose, strong sub peak at 286. 05 eV, which is assigned to carbon linked to oxygen directly, dominate in the C is peak envelop. After treatment by HClO4, the peak decreased dramatically. This result also supports the conclusion that the content of oxygen in mono-saccharide is significantly reduced after treatment by acids. In the FTIR spectra of the black substances, strong peaks can be observed around 1 600 cm(-1), indicating that C==C bond is formed in the product. The above results suggest that treatments with acids may be developed as a new zero-energy-consumption approach to convert biomass in a new fuel with improved energy output efficiency.

  3. Synthesis of antimicrobial silver nanoparticles through a photomediated reaction in an aqueous environment

    PubMed Central

    Banasiuk, Rafał; Frackowiak, Joanna E; Krychowiak, Marta; Matuszewska, Marta; Kawiak, Anna; Ziabka, Magdalena; Lendzion-Bielun, Zofia; Narajczyk, Magdalena; Krolicka, Aleksandra

    2016-01-01

    A fast, economical, and reproducible method for nanoparticle synthesis has been developed in our laboratory. The reaction is performed in an aqueous environment and utilizes light emitted by commercially available 1 W light-emitting diodes (λ =420 nm) as the catalyst. This method does not require nanoparticle seeds or toxic chemicals. The irradiation process is carried out for a period of up to 10 minutes, significantly reducing the time required for synthesis as well as environmental impact. By modulating various reaction parameters silver nanoparticles were obtained, which were predominantly either spherical or cubic. The produced nanoparticles demonstrated strong antimicrobial activity toward the examined bacterial strains. Additionally, testing the effect of silver nanoparticles on the human keratinocyte cell line and human peripheral blood mononuclear cells revealed that their cytotoxicity may be limited by modulating the employed concentrations of nanoparticles. PMID:26855570

  4. Removal of polycyclic aromatic hydrocarbons in aqueous environment by chemical treatments: a review.

    PubMed

    Rubio-Clemente, Ainhoa; Torres-Palma, Ricardo A; Peñuela, Gustavo A

    2014-04-15

    Due to their carcinogenic, mutagenic and teratogenic potential, the removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous environment using physical, biological and chemical processes has been studied by several researchers. This paper reviews the current state of knowledge concerning PAHs including their physico-chemical properties, input sources, occurrence, adverse effects and conventional and alternative chemical processes applied for their removal from water. The mechanisms and reactions involved in each treatment method are reported, and the effects of various variables on the PAH degradation rate as well as the extent of degradation are also discussed. Extensive literature analysis has shown that an effective way to perform the conversion and mineralization of this type of substances is the application of advanced oxidation processes (AOPs). Furthermore, combined processes, particularly AOPs coupled with biological treatments, seem to be one of the best solutions for the treatment of effluents containing PAHs.

  5. Development of tannic acid/chitosan/pullulan composite nanofibers from aqueous solution for potential applications as wound dressing.

    PubMed

    Xu, Fenghua; Weng, Baicheng; Gilkerson, Robert; Materon, Luis Alberto; Lozano, Karen

    2015-01-22

    This study presents the successful development of biocompatible tannic acid (TA)/chitosan (CS)/pullulan (PL) composite nanofibers (NFs) with synergistic antibacterial activity against the Gram-negative bacteria Escherichia coli. The NFs were developed utilizing the forcespinning(®) (FS) technique from CS-CA aqueous solutions to avoid the usage of toxic organic solvents. The ternary nanofibrous membranes were crosslinked to become water stable for potential applications as wound dressing. The morphology, structure, water solubility, water absorption capability and thermal properties of the NFs were characterized. The ternary composite membrane exhibits good water absorption ability with rapid uptake rate. This novel membrane favors fibroblast cell attachment and growth by providing a 3D environment which mimics the extracellular matrix (ECM) in skin and allows cells to move through the fibrous structure resulting in interlayer growth throughout the membrane, thus favoring potential for deep and intricate wound healing.

  6. Influence of Acidity on Uranyl Nitrate Association in Aqueous Solutions: A Molecular Dynamics Simulation Study

    SciTech Connect

    de Almeida, Valmor F; Cui, Shengting; Khomami, Bamin; Ye, Xianggui; Smith, Rodney Bryan

    2010-01-01

    Uranyl ion complexation with water and nitrate is a key aspect of the uranium/plutonium extraction process. We have carried out a molecular dynamics simulation study to investigate this complexation process, including the molecular composition of the various complex species, the corresponding structure, and the equilibrium distribution of the complexes. The observed structures of the complexes suggest that in aqueous solution, uranyls are generally hydrated by 5 water molecules in the equatorial plane. When associating with nitrate ions, a water molecule is replaced by a nitrate ion, preserving the five-fold coordination and planar symmetry. Analysis of the pair correlation function between uranyl and nitrate suggests that nitrates bind to uranyl in aqueous solution mainly in a monodentate mode, although a small portion of bidentates occur. Dynamic association and dissociation between uranyls and nitrates take place in aqueous solution with a substantial amount of fluctuation in the number of various uranyl nitrate species. The average number of the uranyl mononitrate complexes shows a dependence on acid concentration consistent with equilibrium-constant analysis, namely, the concentration of [UO2NO3]+ increases with nitric acid concentration.

  7. Optical characterization of ultrasmall, hydrogen-terminated and carboxyl-functionalized silicon nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Eckhoff, Dean Alan

    The primary theme of this dissertation is to characterize the optical and chemical properties of ultrasmall (˜1 nm) silicon nanoparticles (Si-np) in aqueous environments, focusing on their potential for use as luminescent markers in biophysical and biological applications. Two systems are presented in detail: hydrogen-terminated Si-np prepared through electrochemical dispersion of a crystalline Si wafer and carboxyl-functionalized Si-np prepared via thermal hydrosilylation of surface Si-H bonds with an o-ester 1-alkene. Chemical and physical characterizations are done using nuclear magnetic resonance, size exclusion chromatography, and infrared spectroscopy. Optical characterization is done via absorption and steady-state photoluminescence (PL) and using capillary electrophoresis coupled with laser-induced fluorescence detection. The behavior of the hydrogen-terminated Si-np is studied over time as-prepared in isopropanol and during treatments with water, NaOH, HCl, and H2O 2. The PL spectra show three distinct, near-Gaussian states with a FWHM ˜0.45 eV and their respective emissions in the UV-B (˜305 nm), UV-A (˜340 nm), and 'hard-blue' (˜400 nm) regions of the spectrum. The 'hard-blue' emission is shown to have a simple pH dependence with a pKa ˜3, demonstrating the possibility of using Si-np as environmental probes. These results offer some promise for tailoring the PL properties of ultrasmall Si-np through control of their surface chemistry. In the second part, three central elements establish that the carboxyl-functionalized Si-np have excellent potential for use as a luminescent marker in aqueous systems. First, they are shown to be ultrasmall, with a diameter of ˜1 nm, comparable to that of common organic fluorophores. Second, they are shown to have narrow PL in the near-UV with a nearly-symmetric lineshape and a FWHM as small as 30 nm. Third, it is shown that standard chemical means can be used to functionalize the Si-np with carboxyl groups, giving

  8. Microstructural dependence of aqueous-environment-assisted crack growth and hydrogen uptake in AA 7050

    NASA Astrophysics Data System (ADS)

    Young, Lisa Marie

    This goal of this research was to explain the effects of heat treatment, Cu content, and electrode potential (EApp) on short-transverse aqueous environment assisted cracking (EAC) in a precipitation hardened Al-Zn-Mg-(Cu) alloy. Substantial intergranular EAC susceptibility was observed in several underaged (UA) and peak aged (PA) tempers of AA 7050, where increasing E App produced a slow crack growth rate (da/dt) incubation and transition to fast da/dt. Above the transition potential, da/dt was dramatically increased by further increases in EApp. In contrast the overaged (OA) condition was highly EAC resistant, exhibiting transgranular da/dt ≤2 x 10-8 mm/sec or ≈ 10,000 times slower than PA. Crack growth rates in the low Cu alloy were several orders of magnitude higher than those exhibited by the high Cu material at similar EApp and were only slightly reduced on overaging. Thermal desorption spectroscopy (TDS) results showed enhanced hydrogen uptake in fast-cracking EAC regions compared to as-received hydrogen concentrations. Hydrogen analyses were complicated by the dependence of H-production and uptake on wake exposure time and a pH gradient in the occluded crack environment. Trends between applied anodic potential, crack wake H concentration (normalized by the wake exposure time), and aqueous da/dt were observed. Nuclear reaction analysis revealed unexpectedly high near-surface H concentrations ( ≈ 2000 wppm). The H-concentration profiles indicate that the observed da/dt can be rate-limited by bulk H-diffusion into the crack tip process zone, where EAC is promoted by a hydrogen embrittlement mechanism. The transition potential to fast da/dt increased in the anodic direction with increased isothermal aging time. Additionally, the presence of large Cu-containing second phase particles (S-phase) on high angle grain boundaries partially negated the beneficial effect of overaging on EAC in the Cu-containing alloy, an effect not observed in humid air cracking

  9. Stable organic field-effect transistors for continuous and nondestructive sensing of chemical and biologically relevant molecules in aqueous environment.

    PubMed

    Yun, Minseong; Sharma, Asha; Fuentes-Hernandez, Canek; Hwang, Do Kyung; Dindar, Amir; Singh, Sanjeev; Choi, Sangmoo; Kippelen, Bernard

    2014-02-12

    The use of organic field-effect transistors (OFETs) as sensors in aqueous media has gained increased attention for environmental monitoring and medical diagnostics. However, stable operation of OFETs in aqueous media is particularly challenging because of electrolytic hydrolysis of water, high ionic conduction through the analyte, and irreversible damage of organic semiconductors when exposed to water. To date, OFET sensors have shown the capability of label-free sensing of various chemical/biological species, but they could only be used once because their operational stability and lifetime while operating in aqueous environments has been poor, and their response times typically slow. Here, we report on OFETs with unprecedented water stability. These OFETs are suitable for the implementation of reusable chemical/biological sensors because they primarily respond to charged species diluted in an aqueous media by rapidly shifting their threshold voltage. These OFET sensors present stable current baselines and saturated signals which are ideal for detection of low concentration of small or large molecules that alter the pH of an aqueous environment. The overall response of these OFET sensors paves the way for the development of continuous chemical/biological nondestructive sensor applications in aqueous media.

  10. Radiation-induced degradation of cyclohexanebutyric acid in aqueous solutions by gamma ray irradiation

    NASA Astrophysics Data System (ADS)

    Jia, Wenbao; He, Yanquan; Ling, Yongsheng; Hei, Daqian; Shan, Qing; Zhang, Yan; Li, Jiatong

    2015-04-01

    The radiation-induced degradation of cyclohexanebutyric acid under gamma ray irradiation was investigated. Degradation experiments were performed with 100 mL sealed Pyrex glass vessels loaded with 80 mL of cyclohexanebutyric acid solutions at various initial concentrations of 10, 20, and 40 mg L-1. The absorbed doses were controlled at 0, 0.65, 1.95, 3.25, 6.5, 9.75, and 13 kGy. The results showed that gamma ray irradiation could effectively degrade cyclohexanebutyric acid in aqueous solutions. The removal rate of cyclohexanebutyric acid increased significantly with the increase of absorbed dose and the decrease of its initial concentration. At the same time, the removal of chemical oxygen demand (COD) was as effective as that of cyclohexanebutyric acid. The kinetic studies showed that the degradation of cyclohexanebutyric acid followed pseudo first-order reaction. Above all, the proposed mechanism obtained when NaNO2, NaNO3 and tert-butanol were added showed that the •OH radical played a major role in the gamma degradation process of cyclohexanebutyric acid, while •H and eaq- played a minor role in the gamma degradation process. The degradation products were identified by Fourier transform infrared spectroscopy (FTIR) and gas chromatography/mass spectrometry (GC/MS) during cyclohexanebutyric acid degradation.

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

    PubMed

    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.

  12. 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

  13. Hydrolysis of ionized deoxycholic acid in the aqueous phase and rate analysis for transfer of neutralized deoxycholic acid into the benzene phase across the benzene/water interface.

    PubMed

    Ohno, Ryo; Nakamura, Shohei; Moroi, Yoshikiyo; Isoda-Yamashita, Teruyo

    2008-11-13

    Sodium deoxycholate in water dissociates into sodium cation and deoxycholate anion in the aqueous phase, and then, the latter anions partially hydrolyze to form deionized deoxycholic acids. The acids move into the benzene phase, when liquid benzene is placed upon the aqueous phase, and finally the partition equilibrium is reached. The above processes were traced by pH change in the aqueous phase by a pH meter or the change in [OH-] with time, from which the rate for transfer of neutralized acid to the organic phase was analyzed. From the trace, the rate constants for hydrolysis of acid anion ( kf), neutralization of acid ( kb), transfer of neutralized acid from the aqueous phase to the organic phase ( kin*), and its back-transfer from the organic phase to the aqueous phase ( kut*) were evaluated; kf = 2.18 x 10 (-4) mol (-1) dm (3) min (-1), kb = 1.24 x 10 (5) mol (-1) dm (3) min (-1), kin* = 4.06 x 10 (-1) min (-1) cm (-2), and kout*) = 8.00 x 10 (-2) min (-1) cm (-2). The above values are supported by the partition constant of deoxycholic acid between the benzene phase and the aqueous phase.

  14. The infrared optical constants of sulfuric acid at 250 K. [spectral reflectance measurement of aqueous solutions

    NASA Technical Reports Server (NTRS)

    Pinkley, L. W.; Williams, D.

    1976-01-01

    Results are presented for measurements of the IR spectral reflectance at near-normal incidence of aqueous solutions of sulfuric acid with acid concentrations of 75% and 95.6% by weight. Kramers-Kronig analyses of the reflectance data are employed to obtain values of the optical constants n(nu) and k(nu) in the spectral range from 400 to 6000 cm to the -1 power. The optical constants of these solutions at 250 K and 300 K are compared. It is found that in spectral regions remote from strong absorption bands, the values of the n(nu) indices obtained at 250 K agree with the values given by Lorentz-Lorenz correction of the same indices at 300 K. All absorption bands observed at 300 K are found to be present at 250 K with slight shifts in frequency and with significant differences in the k(nu) indices at the band maxima. Based on these results, it is concluded that the clouds of Venus probably consist of droplets of aqueous solutions of sulfuric acid with acid concentrations of about 75% by weight.

  15. Engineered metal based nanomaterials in aqueous environments: Interactions, transformations and implications

    NASA Astrophysics Data System (ADS)

    Mudunkotuwa, Imali Ama

    Nanoscience and nanotechnology offer potential routes towards addressing critical issues such as clean and sustainable energy, environmental protection and human health. Specifically, metal and metal oxide nanomaterials are found in a wide range of applications and therefore hold a greater potential of possible release into the environment or for the human to be exposed. Understanding the aqueous phase behavior of metal and metal oxide nanomaterials is a key factor in the safe design of these materials because their interactions with living systems are always mediated through the aqueous phase. Broadly the transformations in the aqueous phase can be classified as dissolution, aggregation and adsorption which are dependent and linked processes to one another. The complexity of these processes at the liquid-solid interface has therefore been one of the grand challenges that has persisted since the beginning of nanotechnology. Although classical models provide guidance for understanding dissolution and aggregation of nanoparticles in water, there are many uncertainties associated with the recent findings. This is often due to a lack of fundamental knowledge of the surface structure and surface energetics for very small particles. Therefore currently the environmental health and safety studies related to nanomaterials are more focused on understanding the surface chemistry that governs the overall processes in the liquid-solid interfacial region at the molecular level. The metal based nanomaterials focused on in this dissertation include TiO2, ZnO, Cu and CuO. These are among the most heavily used in a number of applications ranging from uses in the construction industry to cosmetic formulation. Therefore they are produced in large scale and have been detected in the environment. There is debate within the scientific community related to their safety as a result of the lack of understanding on the surface interactions that arise from the detailed nature of the surfaces

  16. Determination of hydroxyl radicals with salicylic acid in aqueous nitrate and nitrite solutions.

    PubMed

    Yang, Xi; Zhan, Man-jun; Kong, Ling-ren; Wang, Lian-sheng

    2004-01-01

    The qualitative and quantitative analyses of reactive oxygen species are essential to determine their steady-state concentration and related reaction mechanisms in environmental aquatic systems. In this study, salicylic acid was employed as an innovative molecular probe of hydroxyl radical(OH) generated in aqueous nitrate and nitrite solutions through photochemical reactions. Kinetic studies showed that the steady-state concentrations of OH in aqueous NO3- (10 mmol/L, pH = 5) and NO2- (10 mmol/L, pH = 5) solutions under ultraviolet irradiation were at a same magnitude, 10(-15) mol/L. Apparent quantum yields of OH at 313 nm were measured as 0.011 and 0.07 for NO3- and NO2- respectively, all comparable to the results of previous studies.

  17. Yeast fermentation of carboxylic acids obtained from pyrolytic aqueous phases for lipid production.

    PubMed

    Lian, Jieni; Garcia-Perez, Manuel; Coates, Ralph; Wu, Hongwei; Chen, Shulin

    2012-08-01

    The presence of very reactive C1-C4 molecules adversely affects the quality bio-oils produced from the pyrolysis of lignocellulosic materials. In this paper a scheme to produce lipids with Cryptococcus curvatus from the carboxylic acids in the pyrolytic aqueous phase collected in fractional condensers is proposed. The capacities of three oleaginous yeasts C. curvatus, Rhodotorula glutinis, Lipomyces starkeyi to ferment acetate, formate, hydroxylacat-aldehyde, phenol and acetol were investigated. While acetate could be a good carbon source for lipid production, formate provides additional energy and contributes to yeast growth and lipid production as auxiliary energy resource. Acetol could slightly support yeast growth, but it inhibits lipid accumulation. Hydroxyacetaldehyde and phenols showed high yeast growth and lipid accumulation inhibition. A pyrolytic aqueous phase with 20 g/L acetate was fermented with C. curvatus, after neutralization and detoxification to produce 6.9 g/L dry biomass and 2.2 g/L lipid.

  18. Self-assembling of poly(aspartic acid) with bovine serum albumin in aqueous solutions.

    PubMed

    Nita, L E; Chiriac, A P; Bercea, M; Asandulesa, M; Wolf, Bernhard A

    2017-02-01

    Macromolecular co-assemblies built up in aqueous solutions, by using a linear polypeptide, poly(aspartic acid) (PAS), and a globular protein, bovine serum albumin (BSA), have been studied. The main interest was to identify the optimum conditions for an interpenetrated complex formation in order to design materials suitable for biomedical applications, such as drug delivery systems. BSA surface possesses several amino- and carboxylic groups available for covalent modification, and/or bioactive substances attachment. In the present study, mixtures between PAS and BSA were investigated at 37°C in dilute aqueous solution by viscometry, dynamic light scattering and zeta potential determination, as well as in solid state by AFM microscopy and dielectric spectroscopy. The experimental data have shown that the interpolymer complex formation occurs for a PAS/BSA molar ratio around 0.541.

  19. Ab initio aqueous thermochemistry: application to the oxidation of hydroxylamine in nitric acid solution.

    PubMed

    Ashcraft, Robert W; Raman, Sumathy; Green, William H

    2007-10-18

    Ab initio molecular orbital calculations were performed and thermochemical parameters estimated for 46 species involved in the oxidation of hydroxylamine in aqueous nitric acid solution. Solution-phase properties were estimated using the several levels of theory in Gaussian03 and using COSMOtherm. The use of computational chemistry calculations for the estimation of physical properties and constants in solution is addressed. The connection between the pseudochemical potential of Ben-Naim and the traditional standard state-based thermochemistry is shown, and the connection of these ideas to computational chemistry results is established. This theoretical framework provides a basis for the practical use of the solution-phase computational chemistry estimates for real systems, without the implicit assumptions that often hide the nuances of solution-phase thermochemistry. The effect of nonidealities and a method to account for them is also discussed. A method is presented for estimating the solvation enthalpy and entropy for dilute aqueous solutions based on the solvation free energy from the ab initio calculations. The accuracy of the estimated thermochemical parameters was determined through comparison with (i) enthalpies of formation in the gas phase and in solution, (ii) Henry's law data for aqueous solutions, and (iii) various reaction equilibria in aqueous solution. Typical mean absolute deviations (MAD) for the solvation free energy in room-temperature water appear to be ~1.5 kcal/mol for most methods investigated. The MAD for computed enthalpies of formation in solution was 1.5-3 kcal/mol, depending on the methodology employed and the type of species (ion, radical, closed-shell) being computed. This work provides a relatively simple and unambiguous approach that can be used to estimate the thermochemical parameters needed to build detailed ab initio kinetic models of systems in aqueous solution. Technical challenges that limit the accuracy of the estimates are

  20. ''Pulling'' Nanoparticles into Water: Phase Transfer of Oleic Acid Stabilized Monodisperse Nanoparticles into Aqueous Solutions of alpha-Cyclodextrin

    SciTech Connect

    Wang, Y.; Wong, J.F.; Teng, X.; Lin, X.Z.; Yang, H.

    2003-10-18

    (B204)This paper describes a general method to drastically improve the disparity of oleic acid stabilized nanoparticles in aqueous solutions. We use oleic acid stabilized monodisperse nanoparticles of iron oxides and silver as model systems, and have modified the surface properties of these nanoparticles through the formation of an inclusion complex between surface-bound surfactant molecules and alpha-cyclodextrin (alpha-CD). After the modification, the nanoparticles of both iron oxide and Ag can transfer from hydrophobic solvents, such as hexane, to alpha-CD aqueous phase. The efficiency of the phase transfer to the aqueous solutions depend son the initial alpha-CD concentration. The alpha-CD/oleic acid complex stabilized nanoparticles can be stable for long periods of time in aqueous phase under ambient atmospheric conditions. Transmission electron microscopy (TME), ultraviolet-visible (UV-vis) spectroscopy, Fourier transform-infrared (FT-IR) spectroscopy, and colorimetric methods have been used in the characterization of these nanoparticles.

  1. Vine-shoot waste aqueous extract applied as foliar fertilizer to grapevines: Effect on amino acids and fermentative volatile content.

    PubMed

    Sánchez-Gómez, R; Garde-Cerdán, T; Zalacain, A; Garcia, R; Cabrita, M J; Salinas, M R

    2016-04-15

    The aim of this work was to study the influence of foliar applications of different wood aqueous extracts on the amino acid content of musts and wines from Airén variety; and to study their relationship with the volatile compounds formed during alcoholic fermentation. For this purpose, the foliar treatments proposed were a vine-shoot aqueous extract applied in one and two times, and an oak extract which was only applied once. Results obtained show the potential of Airén vine-shoot waste aqueous extracts to be used as foliar fertilizer, enhancing the wine amino acid content especially when they were applied once. Similar results were observed with the aqueous oak extract. Regarding wine fermentative volatile compounds, there is a close relationship between musts and their wines amino acid content allowing us to discuss about the role of proline during the alcoholic fermentation and the generation of certain volatiles.

  2. Enhanced stability and dissolution of CuO nanoparticles by extracellular polymeric substances in aqueous environment

    NASA Astrophysics Data System (ADS)

    Miao, Lingzhan; Wang, Chao; Hou, Jun; Wang, Peifang; Ao, Yanhui; Li, Yi; Lv, Bowen; Yang, Yangyang; You, Guoxiang; Xu, Yi

    2015-10-01

    Stability of engineered nanoparticles in aquatic environment is an essential parameter to evaluate their fate, bioavailability, and potential toxic effects toward living organisms. As CuO NPs enter the wastewater systems, they will encounter extracellular polymeric substances (EPS) from microbial community before directly interacting with bacterial cells. EPS may play an important role in affecting the stability and the toxicity of CuO NPs in aquatic environment. In this study, the influences of flocculent sludge-derived EPS, as well as model protein (BSA) and natural polysaccharides (alginate) on the dissolution kinetics and colloidal stability of CuO NPs were investigated. Results showed that the presence of NOMs strongly suppressed CuO NPs aggregation, confirmed by DLS, zeta potentials, and TEM analysis. The enhanced stability of CuO NPs in the presence of EPS and alginate were attributed to the electrostatic combined with steric repulsion, while the steric-hindrance effect may be the predominant mechanism retarding nano-CuO aggregation for BSA. Higher degrees of copper release were achieved with the increasing concentrations of NOMs. EPS are more effective than alginate and BSA in releasing copper, probably due to the abundant functional groups and the excellent metal-binding capacity. The ratio of free-Cu2+/total dissolved Cu significantly decreased in the presence of EPS, indicating that EPS may affect the speciation and Cu bioavailability in aqueous environment. These results may be important for assessing the fate and transport behaviors of CuO NPs in the environment as well as for setting up usage regulation and treatment strategy.

  3. [Adsorption of acid orange II from aqueous solution onto modified peat-resin particles].

    PubMed

    Sun, Qing-Ye; Yang, Lin-Zhang

    2007-06-01

    The adsorption of acid orange II onto modified peat-resin particles was examined in aqueous solution in a batch system. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. The pseudo-first-order, pseudo-second-order kinetic and the intraparticle diffusion models were used to describe the kinetic data. The results showed that both Langmuir and Freundlich adsorption models could be used to describe the adsorption of acid orange II onto modified peat-resin particles. The maximum adsorption capacity was 71.43 mg x g(-1). The data analysis indicated that the intraparticle diffusion model could fit the results of kinetic experiment well. The adsorption rate of acid orange II onto modified peat-resin particles is affected by the initial dye concentrations, sizes and doses of modified peat-resin particles and agitation rates. The surface of modified peat-resin particle is the major adsorption area.

  4. The γ-irradiation of aqueous acetic acid-clay suspensions

    NASA Astrophysics Data System (ADS)

    Negrón-Mendoza, Alicia; Navarro-González, Rafael

    1990-09-01

    γ-radiolysis of 0.8 mol dm-3 aqueous, oxygen-free acetic acid solutions was investigated in the presence or absence of Na-montmorillonite (1 3 g per 10 cm-3). The systems were irradiated at their natural pH (3.5), and 25 °C in a dose range from 0.01 to 500 kGy. H2, CH4, CO, CO2, and a variety of polycarboxylic acids were formed in all systems. The major features of the radiolysis in the presence of clays were: (1) More solute molecules were decomposed; (2) Carbon dioxide was produced in higher yield; (3) The yield of methane was unaffected; and (4) 44% less polycarboxylic acids were formed. Three possible mechanisms that could account for the observed changes are suggested. The results are important in understanding heterogeneous processes in radiation catalysis and might be significant to prebiotic chemistry.

  5. Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

  6. Thermosensitivity of bile acid-based oligo(ethylene glycol) stars in aqueous solutions.

    PubMed

    Strandman, Satu; Le Dévédec, Frantz; Zhu, X X

    2011-08-03

    Amphiphilic star-shaped oligo(ethylene glycol)s with a hydrophobic bile acid core and varying number of hydrophilic arms have been made. Their thermal behavior in aqueous solutions depends on the number rather than the length of the arms. The two-armed lithocholate derivative showed the strongest tendency for association and exhibited the lowest cloud point (79 °C) of the oligomers made, as well as another phase separation at a lower temperature (31 °C). The "double thermosensitivity" arising both from the salt-dependent LCST of the oligo(ethylene glycol) segments and the temperature-responsive self-assembly of amphiphilic bile acid derivative provides an interesting path in the design of bile acid-based smart materials.

  7. Toxicity of aqueous C70-gallic acid suspension in Daphnia magna.

    PubMed

    Seda, Brandon C; Ke, Pu-Chun; Mount, Andrew S; Klaine, Stephen J

    2012-01-01

    The present study assessed the toxic effects of stable aqueous colloidal suspensions of gallic-acid-stabilized C(70) fullerene on Daphnia magna. The suspensions were stabilized through noncovalent surface modification with gallic acid. In addition to whole-organism responses, changes in antioxidative processes in D. magna were quantified. Acute toxicity was observed with 96LC50 for C(70) -gallic acid of 0.4 ± 0.1 mg/L C(70) . Daphnia magna fecundity was significantly reduced in 21-d bioassays at C(70) -gallic aqcid concentrations below quantifiable limits. Antioxidant enzyme activities of glutathione peroxidase and superoxide dismutase as well as lipid peroxidation suggested that exposed organisms experienced oxidative stress. Microscopic techniques used to determine cellular toxicity via apoptosis proved unsuccessful.

  8. Isolation and separation of transplutonium elements from other actinides on ion exchange resins from aqueous and aqueous ethanol solutions of sulfuric acid

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1987-11-01

    The behavior of Am, Cm, Bk, Cf, Es, and other actinides, as well as Zr, on an anion exchange resin and a cation exchange resin in aqueous and aqueous alcohol solutions of sulfuric acid was investigated as a function of the concentration of various components of the solution. It was found that the presence of alcohol in sulfuric acid solutions leads to an increase in the distribution coefficients both on cation exchange resins and on anion exchange resins. The possibility of using ion exchange resins for the concentration and separation of transplutonium elements from U, Np, Pu, Zr, and other elements that form strong complexes with sulfate ions in a wide range of sulfuric acid concentrations was demonstrated.

  9. Low Pressure Tolerance by Methanogens in an Aqueous Environment: Implications for Subsurface Life on Mars.

    PubMed

    Mickol, R L; Kral, T A

    2016-09-23

    The low pressure at the surface of Mars (average: 6 mbar) is one potentially biocidal factor that any extant life on the planet would need to endure. Near subsurface life, while shielded from ultraviolet radiation, would also be exposed to this low pressure environment, as the atmospheric gas-phase pressure increases very gradually with depth. Few studies have focused on low pressure as inhibitory to the growth or survival of organisms. However, recent work has uncovered a potential constraint to bacterial growth below 25 mbar. The study reported here tested the survivability of four methanogen species (Methanothermobacter wolfeii, Methanosarcina barkeri, Methanobacterium formicicum, Methanococcus maripaludis) under low pressure conditions approaching average martian surface pressure (6 mbar - 143 mbar) in an aqueous environment. Each of the four species survived exposure of varying length (3 days - 21 days) at pressures down to 6 mbar. This research is an important stepping-stone to determining if methanogens can actively metabolize/grow under these low pressures. Additionally, the recently discovered recurring slope lineae suggest that liquid water columns may connect the surface to deeper levels in the subsurface. If that is the case, any organism being transported in the water column would encounter the changing pressures during the transport.

  10. Low Pressure Tolerance by Methanogens in an Aqueous Environment: Implications for Subsurface Life on Mars

    NASA Astrophysics Data System (ADS)

    Mickol, R. L.; Kral, T. A.

    2016-09-01

    The low pressure at the surface of Mars (average: 6 mbar) is one potentially biocidal factor that any extant life on the planet would need to endure. Near subsurface life, while shielded from ultraviolet radiation, would also be exposed to this low pressure environment, as the atmospheric gas-phase pressure increases very gradually with depth. Few studies have focused on low pressure as inhibitory to the growth or survival of organisms. However, recent work has uncovered a potential constraint to bacterial growth below 25 mbar. The study reported here tested the survivability of four methanogen species (Methanothermobacter wolfeii, Methanosarcina barkeri, Methanobacterium formicicum, Methanococcus maripaludis) under low pressure conditions approaching average martian surface pressure (6 mbar - 143 mbar) in an aqueous environment. Each of the four species survived exposure of varying length (3 days - 21 days) at pressures down to 6 mbar. This research is an important stepping-stone to determining if methanogens can actively metabolize/grow under these low pressures. Additionally, the recently discovered recurring slope lineae suggest that liquid water columns may connect the surface to deeper levels in the subsurface. If that is the case, any organism being transported in the water column would encounter the changing pressures during the transport.

  11. Corrosion studies in fuel element reprocessing environments containing nitric acid

    SciTech Connect

    Beavers, J A; White, R R; Berry, W E; Griess, J C

    1982-04-01

    Nitric acid is universally used in aqueous fuel element reprocessing plants; however, in the processing scheme being developed by the Consolidated Fuel Reprocessing Program, some of the equipment will be exposed to nitric acid under conditions not previously encountered in fuel element reprocessing plants. A previous report presented corrosion data obtained in hyperazeotropic nitric acid and in concentrated magnesium nitrate solutions used in its preparation. The results presented in this report are concerned with the following: (1) corrosion of titanium in nitric acid; (2) corrosion of nickel-base alloys in a nitric acid-hydrofluoric acid solution; (3) the formation of Cr(VI), which enhances corrosion, in nitric acid solutions; and (4) corrosion of mechanical pipe connectors in nitric acid. The results show that the corrosion rate of titanium increased with the refreshment rate of boiling nitric acid, but the effect diminished rapidly as the temperature decreased. The addition of iodic acid inhibited attack. Also, up to 200 ppM of fluoride in 70% HNO/sub 3/ had no major effect on the corrosion of either titanium or tantalum. In boiling 8 M HNO/sub 3/-0.05 M HF, Inconel 671 was more resistant than Inconel 690, but both alloys experienced end-grain attack. In the case of Inconel 671, heat treatment was very important; annealed and quenched material was much more resistant than furnace-cooled material.The rate of oxidation of Cr(III) to Cr(VI) increased significantly as the nitric acid concentration increased, and certain forms of ruthenium in the solution seemed to accelerate the rate of formation. Mechanical connectors of T-304L stainless steel experienced end-grain attack on the exposed pipe ends, and seal rings of both stainless steel and a titanium alloy (6% Al-4% V) underwent heavy attack in boiling 8 M HNO/sub 3/.

  12. ESTIMATION OF HYDROLYSIS RATE CONSTANTS OF CARBOXYLIC ACID ESTER AND PHOSPHATE ESTER COMPOUNDS IN AQUEOUS SYSTEMS FROM MOLECULAR STRUCTURE BY SPARC

    EPA Science Inventory

    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate hydrolysis rate constants for carboxylic acid ester and phosphate ester compounds in aqueous non- aqueous and systems strictly from molecular structure. The energy diffe...

  13. Aqueous extracts of Mozambican plants as alternative and environmentally safe acid-base indicators.

    PubMed

    Macuvele, Domingos Lusitaneo Pier; Sithole, Gerre Zebedias Samo; Cesca, Karina; Macuvele, Suzana Lília Pinare; Matsinhe, Jonas Valente

    2016-06-01

    Indicators are substances that change color as the pH of the medium. Many of these substances are dyes of synthetic origin. The mulala plant (Euclea natalensis), which roots are commonly used by rural communities for their oral hygiene, and roseira (Hibiscus rosa-sinensis), an ornamental plant, are abundant in Mozambique. Currently, synthetic acid-base indicators are most commonly used but have environmental implications and, on the other hand, are expensive products, so the demand for natural indicators started. This study investigated the applicability of aqueous extracts of H. rosa-sinensis and E. natalensis as acid-base indicators. Ground on this work, the extracts can be used as acid-base indicators. On the basis of the absorption spectroscopy in both the UV-Vis region and previous studies, it was possible to preliminarily pinpoint anthocyanins and naphthoquinones as responsible for the shifting of colors depending on the pH range of aqueous extracts of H. rosa-sinensis and E. natalensis. These natural indicators are easily accessible, inexpensive, easy to extract, environmentally safe, and locally available.

  14. Synthesis of pH-sensitive and recyclable magnetic nanoparticles for efficient separation of emulsified oil from aqueous environments

    NASA Astrophysics Data System (ADS)

    Lü, Ting; Zhang, Shuang; Qi, Dongming; Zhang, Dong; Vance, George F.; Zhao, Hongting

    2017-02-01

    Emulsified oil wastewaters, arisen from oil industry and oil spill accidents, cause severe environmental and ecological problems. In this study, a series of pH-sensitive magnetic nanomaterials (MNPs) were synthesized and characterized for their evaluation in separation of emulsified oil from aqueous environments. A coprecipitation method was used to produce Fe3O4 magnetic nanoparticles that were coated in a 2-step process with first silica to form a surface for anchoring an (3-aminopropyl)triethoxysilane (APTES) molecular layer. Detailed studies were conducted on effects of MNPs dosage, APTES anchoring density (DA) and pH on oil-water separation performance of the synthetic MNPs. Results showed that, under both acidic and neutral conditions, MNPs with high DA exhibited enhanced oil-water separation performance, while under alkaline condition, the oil-water separation process was minimal. Alkaline conditions allowed the MNPs to be recycled up to 9 cycles without showing any significant decrease in oil-water separation efficiency. An examination of the oil-water separation mechanism found that electrostatic interaction and interfacial activity both played important roles in oil-water separation. In conclusion, pH-sensitive MNPs can be easily synthesized and recycled, providing a promising, cost-effective and environmentally-friendly process for the efficient treatment of emulsified oil wastewater.

  15. Sulfate Mineral Formation from Acid-weathered Phyllosilicates: Implications for the Aqueous History of Mars

    NASA Astrophysics Data System (ADS)

    Craig, Patricia; Ming, Douglas; Rampe, Elizabeth

    2014-11-01

    Phyllosilicates on Mars are common in Noachian terrains whereas sulfates are found in the younger Hesperian terrains and suggest alteration under more acidic conditions. Phyllosilicates that formed during the Noachian era would have been exposed to the prevailing acidic conditions during the Hesperian. The purpose of this project is to characterize the effects of acid-weathering on phyllosilicates to better understand the aqueous history of Mars. Nontronite, montmorillonite, and saponite were exposed to H2SO4 solutions at water-rock (WR) ratios of 50 and 25.X-ray diffraction (XRD) patterns of all three acid-treated minerals showed progressive collapse of the phyllosilicate basal spacing with increasing acid concentration. Bassanite formed as an intermediate phase in weathered nontronite and montmorillonite from extracted interlayer Ca. The octahedral cation determined which sulfate formed at high acid concentration: rhomboclase from nontronite, alunogen from montmorillonite, hexahydrite and kieserite from saponite. Gypsum and anhydrite also formed as intermediate phases in nontronite treated at WR=25, showing a change in sulfate hydration state with changing acid concentration (i.e. water activity). Scanning electron microscopy analyses detected phases not identified by XRD. Al-sulfate was found in nontronite weathered at WR=25 and Ca-sulfate in weathered saponite. Near-infrared reflectance spectra of the weathered samples showed decreasing intensity of the hydration/hydroxylation bands and a change or disappearance of metal-OH bands indicating dehydration and dissociation of the interlayers and octahedral layers, respectively, with increased acid weathering.Sulfate mineral formation from acid-weathered phyllosilicates may explain the presence of phyllosilicates and sulfates in close proximity to each other on Mars, such as in Gale Crater. The CheMin XRD instrument on Curiosity may find evidence for acid-weathered phyllosilicates in Mt. Sharp by comparing the 001

  16. Reactivity of aminophosphonic acids. Oxidative dephosphonylation of 1-aminoalkylphosphonic acids by aqueous halogens.

    PubMed

    Drabowicz, Józef; Jordan, Frank; Kudzin, Marcin H; Kudzin, Zbigniew H; Stevens, Christian V; Urbaniak, Paweł

    2016-02-07

    The reactions of 1-aminoalkylphosphonic acids with bromine-water, chlorine-water and iodine-water were investigated. The formation of phosphoric(v) acid, as a result of a halogen-promoted cleavage of the Cα-P bond, accompanied by nitrogen release, was observed. The dephosphonylation of 1-aminoalkylphosphonic acids was found to occur quantitatively. In the reactions of 1-aminoalkylphosphonic acids with other halogen-water reagents investigated by (31)P NMR, scission of the Cα-P bond was also observed, the reaction rates being comparable for bromine and chlorine, but much slower for iodine.

  17. [Forensic-medical diagnostics of an electrical mark resulting from the injury inflicted by technical electricity in the aqueous environment].

    PubMed

    Pigolkin, Iu I; Skovorodnikov, S V; Dubrovin, I A

    2014-01-01

    The objective of the present study was to develop the criteria for forensic-medical diagnostics of an electrical injury inflicted in the aqueous environment based on the characteristics of the electrical mark. The specific morphological features of the electrical injuries inflicted in the aqueous environment that were discovered in the materials available for the forensic medical expertise were analysed taking into consideration the results of the relevant research reported in the forensic medical literature. It was shown that an electrical injury inflicted in the aqueous environment results in the formation of an unusual mark in the form of blisters containing no watery liquid associated with electrogenic oedema in the surrounding tissues. Macroscopic and microscopic studies of the electrical mark failed to reveal the signs of grade III and IV grade thermal burning or thermally affected hair. It is concluded that the consistent characteristics of the electrical mark resulting from the injury inflicted by technical electricity in the aqueous environment include cell lengthening, blister formation inside the corneal layer, and the separation of epidermis from the skin proper.

  18. Leaching of lead from zinc leach residue in acidic calcium chloride aqueous solution

    NASA Astrophysics Data System (ADS)

    Wang, Le; Mu, Wen-ning; Shen, Hong-tao; Liu, Shao-ming; Zhai, Yu-chun

    2015-05-01

    A process with potentially reduced environmental impacts and occupational hazards of lead-bearing zinc plant residue was studied to achieve a higher recovery of lead via a cost-effective and environmentally friendly process. This paper describes an optimization study on the leaching of lead from zinc leach residue using acidic calcium chloride aqueous solution. Six main process conditions, i.e., the solution pH value, stirring rate, concentration of CaCl2 aqueous solution, liquid-to-solid (L/S) ratio, leaching temperature, and leaching time, were investigated. The microstructure and components of the residue and tailing were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). On the basis of experimental results, the optimum reaction conditions were determined to be a solution pH value of 1, a stirring rate of 500 r·min-1, a CaCl2 aqueous solution concentration of 400 g·L-1, a liquid-to-solid mass ratio of 7:1, a leaching temperature of 80°C, and a leaching time of 45 min. The leaching rate of lead under these conditions reached 93.79%, with an iron dissolution rate of 19.28%. Silica did not take part in the chemical reaction during the leaching process and was accumulated in the residue.

  19. Preparation of monodisperse aqueous microspheres containing high concentration of l-ascorbic acid by microchannel emulsification.

    PubMed

    Khalid, Nauman; Kobayashi, Isao; Neves, Marcos A; Uemura, Kunihiko; Nakajima, Mitsutoshi; Nabetani, Hiroshi

    2015-01-01

    Monodisperse aqueous microspheres containing high concentrations of l-ascorbic acid with different concentrations of sodium alginate (Na-ALG) and magnesium sulfate (MgSO4) were prepared by using microchannel emulsification (MCE). The continuous phase was water-saturated decane containing a 5% (w/w) hydrophobic emulsifier. The flow rate of the continuous phase was maintained at 10 mL h(-1), whereas the pressure applied to the disperse phase was varied between 3 and 25 kPa. The disperse phase optimized for successfully generating aqueous microspheres included 2% (w/w) Na-ALG and 1% (w/w) MgSO4. At a higher MgSO4 concentration, the generated microspheres resulted in coalescence and subsequent bursting. At a lower MgSO4 concentration, unstable and polydisperse microspheres were obtained. The aqueous microspheres generated from the MCs under optimized conditions had a mean particle diameter (dav) of 14-16 µm and a coefficient of variation (CV) of less than 8% at the disperse phase pressures of 5-15 kPa.

  20. [Efficient killing of anthrax spores using aqueous and alcoholic peracetic acid solutions].

    PubMed

    Nattermann, H; Becker, S; Jacob, D; Klee, S R; Schwebke, I; Appel, B

    2005-08-01

    We analysed the sporicidal effect of different concentrations of aqueous and alcoholic peracetic acid (PAA) solutions on anthrax spores in suspension and germ carrier tests. In activation of anthrax spores in suspension assays was achieved in less than 2 min using 1% PAA solution and in less than 3 min using 0.5% PAA solution, respectively. In contrast, in germ carrier as says, a test under practical conditions, spores on 38% of the germ carriers survived treatment with 1% PAA solution for 15 min. The use of PAA in 80% ethyl alcohol outclassed the sporicidal effect of aqueous PAA solutions in both suspension and germ carrier assays. Anthrax spores on 14% of germ carriers tested survived 30 min of treatment with a 1% aqueous PAA solution. In contrast anthrax spores were reliably inactivated under the same test procedure using a 1% alcoholic PAA solution for 30 min. The proven enhancement of the sporicidal effect of alcoholic PAA solutions should be kept in mind when using disinfectants in practice. In further surveys we will optimise the test conditions.

  1. Visible Wavelength Spectroscopy of Ferric Minerals: A Key Tool for Identification of Ancient Martian Aqueous Environments

    NASA Technical Reports Server (NTRS)

    Murchie, Scott L.; Bell, J. F., III; Morris, Richard V.

    2000-01-01

    The mineralogic signatures of past aqueous alteration of a basaltic Martian crust may include iron oxides and oxyhydroxides, zeolites, carbonates, phyllosilicates, and silica. The identities, relative abundances, and crystallinities of the phases formed in a particular environment depend on physicochemical conditions. At one extreme, hot spring environments may be characterized by smectite-chlorite to talc-kaolinite silicate assemblages, plus crystalline ferric oxides dominated by hematite. However, most environments, including cold springs, pedogenic layers, and ponded surface water, are expected to deposit iron oxides and oxyhydroxides, carbonates, and smectite-dominated phyllosilicates. A substantial fraction of the ferric iron is expected to occur in nanophase form, with the exact mineralogy strongly influenced by Eh-pH conditions. Detection of these phases has been an objective of a large body of terrestrial telescopic, Mars orbital, and landed spectral investigations and in situ compositional measurements. However, clear identifications of many of these phases is lacking. Neither carbonate nor silica has been unequivocally detected by any method. Although phyllosilicates may occur near the limit of detection by remote sensing, in general they appear to occur in only poorly crystalline form. In contrast, compelling evidence for ferric iron minerals has been gathered by recent telescopic investigations, the Imager for Mars Pathfinder (IMP), and the Thermal Emission Spectrometer (TES) on the Mars Global Surveyor (MGS). These data yield two crucial findings: (1) In the global, high spatial resolution TES data set, highly crystalline ferric iron (as coarse-grained 'gray' hematite) has been recognized but with only very limited spatial occurrence and (2) Low-resolution telescopic reflectance spectroscopy, very limited orbital reflectance spectroscopy, and landed multispectral imaging provide strong indications that at least two broad classes of ferric iron minerals

  2. Extraction of p-coumaric acid and ferulic acid using surfactant-based aqueous two-phase system.

    PubMed

    Dhamole, Pradip B; Demanna, Dhanashree; Desai, S A

    2014-09-01

    Ferulic acid (FA) and p-coumaric acid (pCA) are high-value products that can be obtained by alkaline hydrolysis of lignocellulose. Present work explores the potential of surfactant-based cloud-point extraction (CPE) for FA and pCA extraction from corn cob hydrolysate. More than 90 % (w/w) extraction of both FA and pCA was achieved from model system with L92. The partition coefficient of FA and pCA in L92 aqueous phase system was 35 and 55, respectively. A significant enrichment (8-10-fold) of both FA and pCA was achieved in surfactant-rich phase. Furthermore, the downstream process volume was reduced by 10 to 13 times. Optimized conditions (5 % v/v L92 and pH 3.0) resulted into 85 and 89 % extraction of FA and p-CA, respectively, from alkaline corn cob hydrolysate. Biocompatibility tests were carried out for L92 for ethanol fermentation and found to be biocompatible. Thus, the new surfactant-based CPE system not only concentrated FA and pCA but also reduced the process volume significantly. Further, aqueous phase containing sugars can be used for ethanol fermentation.

  3. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-01-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic aerosols (BA), for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2) and malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment, except for ω-oxooctanoic acid (ωC8) that showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids dominates their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  4. Laboratory photochemical processing of aqueous aerosols: formation and degradation of dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls

    NASA Astrophysics Data System (ADS)

    Pavuluri, C. M.; Kawamura, K.; Mihalopoulos, N.; Swaminathan, T.

    2015-07-01

    To better understand the photochemical processing of dicarboxylic acids and related polar compounds, we conducted batch UV irradiation experiments on two types of aerosol samples collected from India, which represent anthropogenic (AA) and biogenic (BA) aerosols, for time periods of 0.5 to 120 h. The irradiated samples were analyzed for molecular compositions of diacids, oxoacids and α-dicarbonyls. The results show that photochemical degradation of oxalic (C2), malonic (C3) and other C8-C12 diacids overwhelmed their production in aqueous aerosols, whereas succinic acid (C4) and C5-C7 diacids showed a significant increase (ca. 10 times) during the course of irradiation experiments. The photochemical formation of oxoacids and α-dicarbonyls overwhelmed their degradation during the early stages of experiment except for ω-oxooctanoic acid (ωC8), which showed a similar pattern to that of C4. We also found a gradual decrease in the relative abundance of C2 to total diacids and an increase in the relative abundance of C4 during prolonged experiment. Based on the changes in concentrations and mass ratios of selected species with the irradiation time, we hypothesize that iron-catalyzed photolysis of C2 and C3 diacids controls their concentrations in Fe-rich atmospheric waters, whereas photochemical formation of C4 diacid (via ωC8) is enhanced with photochemical processing of aqueous aerosols in the atmosphere. This study demonstrates that the ambient aerosols contain abundant precursors that produce diacids, oxoacids and α-dicarbonyls, although some species such as oxalic acid decompose extensively during an early stage of photochemical processing.

  5. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

    SciTech Connect

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  6. Studies on equilibrium of anthranilic acid in aqueous solutions and in two-phase systems: aromatic solvent-water.

    PubMed

    Zapała, Lidia; Kalembkiewicz, Jan; Sitarz-Palczak, Elzbieta

    2009-03-01

    The acid-base equilibria of anthranilic acid have been characterized in terms of macro- and microdissociation constants (dissociation constants K(a1), K(a2) and tautomeric constant K(z)). On the basis of spectrophotometric investigations the values of the distribution ratio D of anthranilic acid in the two-phase systems: aromatic solvent (benzene, ethylbenzene, toluene, chlorobenzene, bromobenzene)-aqueous solution were obtained. Employing the results of potentiometric titration in the two-phase systems: aromatic solvent-aqueous solution the distribution constant K(D) and dimerization constant K(dim) values were calculated. The influence of organic solvent polarity and pH of the aqueous phase on the contents of the particular forms of the acid in the two-phase systems were analyzed.

  7. Contribution of diffuse inputs to the aqueous mass load of perfluoroalkyl acids in river and stream catchments in Korea.

    PubMed

    Kim, Seung-Kyu; Li, Dong-Hao; Shoeib, Mahiba; Zoh, Kyung-Duk

    2014-02-01

    Recent studies disagree regarding the contributions of point versus non-point sources to the aqueous mass loads of perfluoroalkyl acids (PFAAs). This study investigated the longitudinal change in PFAA mass load from upstream to downstream stations along rivers and/or streams to assess the relative contributions of point versus nonpoint inputs. With concentrations 10 to 100 times higher than running water, point sources such as wastewater treatment plants (WWTPs) effluent and airport ditch-outlet (ADO) water were separated from neighboring upstream and downstream running waters using principal component analysis. Source waters were characterized by certain predominant components [e.g., perfluorobutylsulfonate (PFBS) and perfluorooctanoic acid (PFOA) in WWTP effluent and perfluorohexylsulfonate (PFHxS) and perfluorooctylsulfonate (PFOS) in ADO water], which were minor components of running water. From a mass balance assessment of PFAA mass load, certain compounds such as PFOA and PFBS dominated the contribution of point sources to the mass load in the running water at downstream stations or in small catchment basins with high levels of industrial activity. Most of the mass load in the investigated catchments was attributable to upstream running water with a minor influence from industrial, commercial, and domestic human activities. Furthermore, the negative relationship of per capita emission factors (hereafter, EFs) with population density and a lower contribution of PFAA from WWTPs (~30% on average) compared to the running water-derived mass load at the national level indicated that diffuse inputs were more important contributors to aqueous PFAA contamination in each catchment basin as well as the entire watershed of the country (Korea). Volatile precursor compounds, which are readily dispersed to neighboring basins and transformed to PFAAs in the ambient environment, can be an important source of these diffuse inputs and will become more significant over time.

  8. Effect of Humic Acid on Migration, Distribution and Remediation of Dense Non-aqueous Phase Liquids: A laboratory investigation

    NASA Astrophysics Data System (ADS)

    Cheng, Z.; Wu, J.; Xu, H.; Gao, Y.

    2014-12-01

    Over the last decades, dense non-aqueous phase liquids (DNAPLs) contamination in the subsurface increases with the rapid development of oil industry and becomes the focus of many studies. The migration, distribution and remediation efficiency of DNAPLs in the subsurface environment are greatly affected by the solution chemistry besides the physical heterogeneities of aquifers. Humic acid (HA), which is ubiquitous in natural environments, is a surface active substance exhibiting solubility enhancement behavior for hydrophobic organic compounds such as DNAPLs. Here we reported a laboratory investigation to study the effects of HA on the infiltration, immobilization and subsequent recovery of DNAPL in porous media. Tetrachloroethylene (PCE) was selected as the representative DNAPL in this study. Two-dimensional (2-D) sandbox experiments were conducted to investigate the effects of different HA concentrations on the transport, distribution of PCE and the remediation of PCE using surfactant (Tween 80) flushing in a saturated porous media system. The surfactant flushing of PCE was performed after the PCE transport and distribution had reached equilibrium. A light transmission visualization method with charge-coupled device (CCD) camera was adopted to visualize PCE distribution and quantify its saturation. In addition, the experiments were also designed to gather data for the validation of multiphase flow models. Effluent samples were collected to determine dissolved PCE concentrations. PCE solubilization and PCE-water interfacial tension were experimentally determined in aqueous solutions of varying HA concentrations. The experimental results showed that the presence of HA can have a dramatic impact on PCE flow and entrapment, and significantly improved the recovery of PCE during surfactant enhanced aquifer remediation (SEAR). The findings are of use for better understanding of the migration and entrapment of DNAPLs and developing of SEAR technology.

  9. Competitive adsorption of boric acid and chromate onto alumina in aqueous solutions.

    PubMed

    Demetriou, A; Pashalidis, I

    2014-01-01

    The competitive adsorption of boric acid and chromate from aqueous solutions by alumina has been investigated by spectrophotometry at pH 8, ionic strength = 0.0, 0.1 and 1.0 M NaClO4, T = 22 ± 3 °C and under normal atmospheric conditions. The experimental data show that addition of excess boric acid in the system leads to the increase of Cr(VI) concentration in solution, indicating the replacement of adsorbed chromate by boron on the alumina surface. Data evaluation results in the determination of the competition reaction constant and the formation constant of the Cr(VI) surface complexes, which are logKCr(VI)-B(III) = -3.5 ± 0.2 and logβ*Cr = 7.6 ± 0.3, respectively.

  10. Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid

    PubMed Central

    Niskanen, Johannes; Sahle, Christoph J.; Ruotsalainen, Kari O.; Müller, Harald; Kavčič, Matjaž; Žitnik, Matjaž; Bučar, Klemen; Petric, Marko; Hakala, Mikko; Huotari, Simo

    2016-01-01

    In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range. PMID:26888159

  11. Separation of glycols from dilute aqueous solutions via complexation with boronic acids

    SciTech Connect

    Randel, L.A.; King, C.J.

    1991-07-01

    This work examines methods of separating low molecular weight glycols from dilute aqueous solution. Extraction into conventional solvents is generally not economical, since, in the literature reviewed, distribution ratios for the two- to four-carbon glycols are all less than one. Distribution ratios can be increased, however, by incorporating into the organic phase an extracting agent that will complex with the solute of interest. The extracting agent investigated in this work is 3-nitrophenylboronic acid (NPBA). NPBA, a boric acid derivative, reversibly complexes with many glycols. The literature on complexation of borate and related compounds with glycols, including mechanistic data, measurement techniques, and applications to separation processes, provides information valuable for designing experiments with NPBA and is reviewed herein. 88 refs., 15 figs., 24 tabs.

  12. Extraction and isolation of TPE from other elements on ion exchangers in aqueous and aqueous-organic solutions of phosphoric acid

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1988-07-01

    The behavior of Am-Es and other actinides on anion and cation exchange resins in aqueous and aqueous-organic solutions of phosphoric acid has been studied in a wide range of concentration of various components of the solution. The sorptivity of transplutonium elements (TPE) on anion exchangers from dilute H/sub 3/PO/sub 4/ with a concentration less than or equal to 1 M in presence of organic solvents (alcohols, ketones, etc.) and on cation exchangers from concentrated H/sub 3/PO/sub 4/ has been found to be significant. The possibility of use of phosphoric acid solutions for isolation of TPE from Th, Pa, U, Np, Pu, and Zr and separation of TPE in different oxidation states in presence of a high-purity oxidant has been shown.

  13. Adsorption equilibrium, kinetics and thermodynamics of dichloroacetic acid from aqueous solution using mesoporous carbon.

    PubMed

    Ding, Ying; Zhu, Jianzhong; Cao, Yang; Chen, Shenglu

    2014-08-01

    The presence of disinfection by-products, such as trihalomethanes and haloacetic acids in water, is believed to be harmful to human health. In this work, mesoporous carbon was synthesized with the evaporation-induced self-assembly method and employed to evaluate the effects of initial concentration, contact time, pH and temperature on the removal of dichloroacetic acid in batch experiments. Adsorption equilibrium was established in 480 min and the maximum adsorption (350mg/g) of dichloroacetic acid on the mesoporous carbon was observed to occur at 308 K and pH 3.0. Freundlich and Langmuir isotherms were used to analyse the equilibrium data at different temperatures; kinetic data were fitted to the pseudo-first-order and pseudo-second-order models and found that the adsorption capacity, mass transfer coefficient and diffusivity of dichloroacetic acid were directly affected by the physical and chemical parameters. In addition, the various thermodynamic parameters, such as Gibbs free energy (Delta G), enthalpy (Delta H = 54.35 kJmol-1) and entropy (Delta S = 258.36 Jmol-1 K-1) were calculated to analyse the adsorption process. The experimental results indicated that the mesoporous carbon was an excellent adsorbent for dichloroacetic acid removal from aqueous solutions.

  14. UV irradiation and humic acid mediate aggregation of aqueous fullerene (nC₆₀) nanoparticles.

    PubMed

    Qu, Xiaolei; Hwang, Yu Sik; Alvarez, Pedro J J; Bouchard, Dermont; Li, Qilin

    2010-10-15

    The transport and fate of engineered nanomaterials is affected by multiple environmental factors, including sunlight and natural organic matter. In this study, the initial aggregation kinetics of aqueous fullerene (nC(60)) nanoparticles before and after UVA irradiation was investigated in solutions varying in ionic strength, ionic composition, and humic acid concentration. In NaCl solutions, surface oxidation induced by UV irradiation remarkably increased nC(60) stability due to the increased negative surface charge and reduced particle hydrophobicity; although humic acid greatly enhanced the stability of pristine nC(60) via the steric hindrance effect, it had little influence on the stability of UV-irradiated nC(60) in NaCl due to reduced adsorption on oxidized nC(60) surface. In contrast, UV irradiation reduced nC(60) stability in CaCl(2) due to specific interactions of Ca(2+) with the negatively charged functional groups on UV-irradiated nC(60) surface and the consequent charge neutralization. By neutralizing surface charges of both UV-irradiated nC(60) and humic acid as well as forming intermolecular bridges, Ca(2+) facilitated humic acid adsorption on UV-irradiated nC(60), resulting in enhanced stability in the presence of humic acid. These results demonstrate the critical role of nC(60) surface chemistry in its environmental transport and fate.

  15. Sulfate Formation From Acid-Weathered Phylosilicates: Implications for the Aqueous History of Mars

    NASA Technical Reports Server (NTRS)

    Craig, P. I.; Ming, D. W.; Rampe, E. B.

    2014-01-01

    Most phyllosilicates on Mars are thought to have formed during the planet's earliest Noachian era, then Mars underwent a global change making the planet's surface more acidic [e.g. 1]. Prevailing acidic conditions may have affected the already existing phyllosilicates, resulting in the formation of sulfates. Both sulfates and phyllosilicates have been identified on Mars in a variety of geologic settings [2] but only in a handful of sites are these minerals found in close spatial proximity to each other, including Mawrth Vallis [3,4] and Gale Crater [5]. While sulfate formation from the acidic weathering of basalts is well documented in the literature [6,7], few experimental studies investigate sulfate formation from acid-weathered phyllosilicates [8-10]. The purpose of this study is to characterize the al-teration products of acid-weathered phyllosilicates in laboratory experiments. We focus on three commonly identified phyllosilicates on Mars: nontronite (Fe-smectite), saponite (Mg-smectite), and montmorillonite (Al-smectite) [1, and references therein]. This information will help constrain the formation processes of sulfates observed in close association with phyllosilicates on Mars and provide a better understanding of the aqueous history of such regions as well as the planet as a whole.

  16. Removal of lead from aqueous solutions by a poly(acrylic acid)/bentonite nanocomposite

    NASA Astrophysics Data System (ADS)

    Rafiei, H. R.; Shirvani, M.; Ogunseitan, O. A.

    2016-11-01

    We synthesized a novel poly acrylic acid-organobentonite (PAA-Bent) nanocomposite by successive intercalation of cetyltrimethylammonium (CTA) surfactant and polyacrylic acid (PAA) into the bentonite (Bent) interlayer spaces. The surfactant-modified clay (CTA-Bent) and PAA-Bent nanocomposite were characterized by XRD and FT-IR techniques and used for removal of Pb(II) from aqueous solution. The XRD results confirmed the intercalation of CTA and PAA into the interlayer spaces of the bentonite increasing the d 001 spacing of the clay from 12.2 up to 38.9 Å. FT-IR analysis of the modified clay samples revealed the functional groups of CTA and PAA constituents alighted on the bentonite surfaces. Maximum Pb sorption capacity of the Bent and PAA-Bent predicted by Langmuir model were 52.3 and 93.0 mg g-1, respectively, showing that the synthesized nanocomposite superiorly adsorbed Pb from the solution as compared to the Bent. The maximum Pb removal efficiency of 99.6 % was achieved by the nanocomposite at 25 °C with <30 min contact time for a 7.5 g L-1 solid-to-liquid ratio and an initial metal concentration of 400 mg L-1. The results indicated that PAA-Bent nanocomposite can be efficiently used as a superadsorbent for the removal of Pb(II) from aqueous solution.

  17. EXAFS study of the speciation of protactinium(V) in aqueous hydrofluoric acid solutions.

    PubMed

    De Sio, Stéphanie M; Wilson, Richard E

    2014-12-01

    The speciation of protactinium(V) in hydrofluoric acid (HF) solutions was studied using X-ray absorption spectroscopy. Extended X-ray absorption fine structure measurements were performed on an aqueous solution of 0.05 M protactinium(V) with various HF concentrations ranging from 0.5 to 27 M in order to probe the protactinium coordination sphere with respect to the identity and number of coordinating ligands. The resulting fits to the spectra suggest the presence of an eight-coordinate homoleptic fluoro complex in highly concentrated fluoride solutions (27 M), with equilibrium between seven- and eight-coordinate fluoro complexes at moderate acidities, and in more dilute solutions, results indicate that one water molecule is likely to replace a fluoride in the first coordination sphere, at a distance of 2.54-2.57 Å. Comparisons of this chemistry with group V metals, niobium and tantalum, are presented, and the potential implications for these results on the hydrolytic behavior of protactinium in aqueous systems are discussed.

  18. Removal of Se(IV) from aqueous solution using sulphuric acid-treated peanut shell.

    PubMed

    El-Shafey, E I

    2007-09-01

    A carbonaceous sorbent was prepared from peanut shell via sulphuric acid treatment. Se(IV) removal from aqueous solution on the sorbent was studied varying time, pH, Se(IV) concentration, temperature and sorbent status (wet and dry). Se(IV) removal was faster using the wet sorbent than the dry sorbent following a pseudo-first-order model. Se(IV) removal increases at low pH values, and decreases as pH increases until pH 7. Sorption was found to fit the Langmuir equation and sorption capacity for the wet sorbent was higher than that for the dry one. Both sorbents showed an increased selenium sorption by rising the temperature. Redox processes between Se(IV) and the carbon sorbent are involved. Analysis by scanning electron microscope and X-ray powder diffraction for the sorbent after the reaction with acidified Se(IV) confirmed the availability of elemental selenium as particles on the sorbent surface as a result of Se(IV) reduction. Physicochemical tests showed an increase in sorbent acidity, cation exchange capacity (CEC) and surface functionality after the reaction with acidified Se(IV), indicating the oxidation processes occurring on the sorbent surface. Due to its reduction properties, the sorbent seems efficient for Se(IV) removal from aqueous solution.

  19. Adsorptions of some heavy metal ions in aqueous solutions by acrylamide/maleic acid hydrogels

    SciTech Connect

    Saraydin, D.; Karadag, E.; Gueven, O.

    1995-10-01

    In this study, acrylamide-maleic acid (AAm/MA) hydrogels in the form of rod have been prepared by {gamma}-radiation. They have been used for adsorption of some heavy metal ions such as uranium, iron, and copper. For the hydrogel containing 40 mg of maleic acid and irradiated at 3.73 kGy, maximum and minimum swellings in the aqueous solutions of the heavy metal ions have been observed with water (1480%) and the aqueous solution of iron(III) nitrate (410%), respectively. Diffusions of water and heavy metal ions onto hydrogels have been found to be of the non-Fickian type of diffusion. In experiments of uranyl ions adsorption, Type II adsorption has been found. One gram of AAa/MA hydrogels sorbed 14-86 mg uranyl ions from solutions of uranyl acetate, 14-90 mg uranyl ions from solutions of uranyl nitrate, 16-39 mg iron ions from solutions of iron(IV) nitrate, and 28-81 mg copper ions from solutions of copper acetate, while acrylamide hydrogel did not sorb any heavy metals ions.

  20. Adsorption of Crystal violet on raw and acid-treated montmorillonite, K10, in aqueous suspension.

    PubMed

    Sarma, Gautam Kumar; Sen Gupta, Susmita; Bhattacharyya, Krishna G

    2016-04-15

    Crystal violet is used as a dye in cotton and silk textiles, paints and printing ink. The dye is hazardous and exposure to it may cause permanent injury to the cornea and conjunctiva including permanent blindness, and in severe cases, may lead to respiratory and kidney failure. The present work describes removal of Crystal violet from aqueous solution by adsorption on raw and acid-treated montmorillonite, K10. The clay mineral was treated with 0.25 and 0.50 M sulfuric acid and the resulting materials were characterized by XRD, zeta potential, SEM, FTIR, cation exchange capacity, BET surface area and pore volume measurements. The influences of pH, interaction time, adsorbent amount, and temperature on adsorption were monitored and explained on the basis of physico-chemical characteristics of the materials. Basic pH generally favors adsorption but considerable removal was possible even under neutral conditions. Adsorption was very rapid and equilibrium could be attained in 180 min. The kinetics conformed to second order model. Langmuir monolayer adsorption capacity of raw montmorillonite K10 was 370.37 mg g(-1) whereas 0.25 M and 0.50 M acid treated montmorillonite K10 had capacities of 384.62 and 400.0 mg g(-1) respectively at 303 K. Adsorption was exothermic and decreased in the temperature range of 293-323 K. Thermodynamically, the process was spontaneous with Gibbs energy decreasing with rise in temperature. The results suggest that montmorillonite K10 and its acid treated forms would be suitable for removing Crystal violet from aqueous solution.

  1. Development and validation of non-aqueous capillary electrophoresis methods to analyze boronic esters and acids.

    PubMed

    Forst, Mindy B; Warner, Anne M

    2012-05-01

    Boronic esters and acids are potential intermediates in the manufacture of many active pharmaceutical ingredients (API). Accurate quantitation of the intermediate is necessary to assure the stoichiometry of the reaction. The analysis of these compounds is challenging due to their labile nature. For example, the boronic ester can hydrolyze to the acid during storage, when exposed to moisture in the air, during sample preparation and analysis, and thus give erroneous ester results. Traditional analytical techniques like gas chromatography (GC), normal phase chromatography (NPLC), hydrophilic interaction chromatography (HILIC), and reversed phase liquid chromatography (RPLC) have been utilized but with noted limitations such as poor peak shape, variation in retention times, and evidence of hydrolysis. All of these limitations impact accurate quantitation needed for selected situations. For the proprietary boronic ester evaluated here, these traditional techniques were insufficient for the accurate determination of assay and residual boronic acid. Non-aqueous capillary electrophoresis (NACE) is an accurate quantitative technique that can be used to analyze boronic esters and their corresponding acids without the limitations noted for traditional analytical techniques. The present study describes the development of methodology for the determination of the potency of a proprietary boronic ester as well as methodology for the determination of residual boronic acid in the ester. In addition, nine model boronic ester and acid pairs with a range in polarity, based on the electronic properties of the attached side group, were tested to evaluate and demonstrate the general applicability of these conditions. Under the conditions used for potency, all ten pairs had a resolution between the boronic ester and acid of greater than 1.5, acceptable peak shape for the boronic ester (tailing factor of less than 2.0), and a run time of less than 3 min. In addition, this work describes

  2. Stress-corrosion behavior of aluminum-lithium alloys in aqueous environments

    NASA Technical Reports Server (NTRS)

    Pizzo, P. P.; Galvin, R. P.; Nelson, H. G.

    1983-01-01

    The stress corrosion susceptibility of two powder metallurgy (P/M) alloys, Al-Li-Cu and Al-Li-Cu-Mg two mechanically attrited (M/A) alloys, Al-Li-Cu and Al-Li-Mg; and two wrought, ingot alloys, X-2020 and AA7475, are compared. Time-dependent fracture in an aqueous sodium chloride environment under alternate immersion condition was found to vary significantly between alloys. The stress corrosion behavior of the two powder metallurgy processed alloys was studied in detail under conditions of crack initiation, static crack growth, and fatigue crack growth. A variety of stress corrosion tests were performed including smooth surface, time-to-failure tests; potentiostatic tests on smooth surfaces exposed to constant applied strain rates; and fracture mechanics-type tests under static and cyclic loads. Both alloys show surface pitting and subsequent intergranular corrosion. Pitting is more severe in the magnesium-bearing alloy and is associated with stringer particles strung along the extrusion direction as a result of P/M processing.

  3. CO 2 and CO utilization: radiation-induced carboxylation of aqueous chloroacetic acid to malonic acid

    NASA Astrophysics Data System (ADS)

    Getoff, Nikola

    2003-07-01

    CO 2 and CO in addition to HCOOH/HCOO - can be used to produce the carboxylating radical rad COOH/ rad COO - under the influence of ionizing radiation. The carboxylation of ClCH 2COOH/ClCH 2COO - to malonic acid/malonate was studied at the pH range 2-7. A maximum yield G(malonic acid)=85 at pH=3 was observed by using 5×10 -2 mol dm -3 ClCH 2COOH, 1×10 -2 mol dm -3 HCOOH and 1×10 -3 mol dm -3 CO at a dose of 4.8 kGy. Oxalic and succinic acids were found as byproducts. The yield of the formed Cl - ions passes two maxima, at pH=3 ( G=7.5) and 7 ( G=15). Reaction mechanisms for the carboxylation process are presented.

  4. Hydroxyl Radical (OH•) Reaction with Guanine in an Aqueous Environment: A DFT Study

    PubMed Central

    Kumar, Anil; Pottiboyina, Venkata; Sevilla, Michael D.

    2011-01-01

    The reaction of hydroxyl radical (OH•) with DNA accounts for about half of radiation-induced DNA damage in living systems. Previous literature reports point out that the reaction of OH• with DNA proceeds mainly through the addition of OH• to the C=C bond of the DNA bases. However, recently it has been reported that the principal reaction of OH• with dGuo (deoxyguanosine) is the direct hydrogen atom abstraction from its exocyclic amine group rather than addition of OH• to the C=C bond. In the present work, these two reaction pathways of OH• attack on guanine (G) in the presence of water molecules (aqueous environment) are investigated using the density functional theory (DFT) B3LYP method with 6-31G* and 6-31++G** basis sets. The calculations show that the initial addition of the OH• at C4=C5 double bond of guanine is barrier free and the adduct radical (G-OH•) has only a small activation barrier of ca. 1 – 6 kcal/mol leading to the formation of a metastable ion-pair intermediate (G•+---OH−). The formation of ion-pair is a result of the highly oxidizing nature of the OH• in aqueous media. The resulting ion-pair (G•+---OH−) deprotonates to form H2O and neutral G radicals favoring G(N1-H)• with an activation barrier of ca. 5 kcal/mol. The overall process from the G(C4)-OH• (adduct) to G(N1-H)• and water is found to be exothermic in nature by more than 13 kcal/mol. (G-OH•), (G•+---OH−), and G(N1-H)• were further characterized by the CAM-B3LYP calculations of their UV-visible spectra and good agreement between theory and experiment is achieved. Our calculations for the direct hydrogen abstraction pathway from N1 and N2 sites of guanine by the OH• show that this is also a competitive route to produce G(N2-H)•, G(N1-H)• and H2O. PMID:22050033

  5. Sphingosine-1-Phosphate as an Amphipathic Metabolite: Its Properties in Aqueous and Membrane Environments

    PubMed Central

    García-Pacios, Marcos; Collado, M. Isabel; Busto, Jon V.; Sot, Jesús; Alonso, Alicia; Arrondo, José-Luis R.; Goñi, Félix M.

    2009-01-01

    Abstract Sphingosine-1-phosphate (S1P) is currently considered to be an important signaling molecule in cell metabolism. We studied a number of relevant biophysical properties of S1P, using mainly Langmuir balance, differential scanning calorimetry, 31P-NMR, and infrared (IR) spectroscopy. We found that, at variance with other, structurally related sphingolipids that are very hydrophobic, S1P may occur in either an aqueous dispersion or a bilayer environment. S1P behaves in aqueous media as a soluble amphiphile, with a critical micelle concentration of ≈12 μM. Micelles give rise to larger aggregates (in the micrometer size range) at and above a 1 mM concentration. The aggregates display a thermotropic transition at ∼60°C, presumably due to the formation of smaller structures at the higher temperatures. S1P can also be studied in mixtures with phospholipids. Studies with dielaidoylphosphatidylethanolamine (DEPE) or deuterated dipalmitoylphosphatidylcholine (DPPC) show that S1P modifies the gel-fluid transition of the glycerophospholipids, shifting it to lower temperatures and decreasing the transition enthalpy. Low (<10 mol %) concentrations of S1P also have a clear effect on the lamellar-to-inverted hexagonal transition of DEPE, i.e., they increase the transition temperature and stabilize the lamellar versus the inverted hexagonal phase. IR spectroscopy of natural S1P mixed with deuterated DPPC allows the independent observation of transitions in each molecule, and demonstrates the existence of molecular interactions between S1P and the phospholipid at the polar headgroup level that lead to increased hydration of the carbonyl group. The combination of calorimetric, IR, and NMR data allowed the construction of a temperature-composition diagram (“partial phase diagram”) to facilitate a comparative study of the properties of S1P and other related lipids (ceramide and sphingosine) in membranes. In conclusion, two important differences between S1P and ceramide

  6. Liquefaction of Douglas Fir wood slurries: titration of acids and anions in aqueous product and feed slurries

    SciTech Connect

    Davis, H.G.

    1981-03-01

    After hydrolytic pretreatment, wood slurries contain substantial amounts of organic acids. Additional acids are produced during the liquefaction step whether or not there is prehydrolysis. The acids have pH's in the range of about 3 to 5 and are easily titrated potentiometrically with sodium hydroxide. Anions present in neutralized slurry or in aqueous product can be titrated with hydrogen chloride solution with appropriate corrections for sulfate if present, and for excess titrant at the low pH of the endpoint.

  7. The effects of humic acid on the uptake and depuration of fullerene aqueous suspensions in two aquatic organisms.

    PubMed

    Chen, Qiqing; Yin, Daqiang; Li, Jing; Hu, Xialin

    2014-05-01

    The authors investigated the uptake and depuration of fullerene aqueous suspensions (nC(60)) in 2 aquatic organisms: Daphnia magna and zebrafish. The effects of humic acid were examined to elucidate its possible mechanisms in the aquatic environment. The uptake was concentration-dependent in both organisms, and the maximum uptake concentration of nC(60) in Daphnia (2268 ± 158 mg/kg) was approximately 1 order of magnitude higher than that in zebrafish (222 ± 30 mg/kg) because of the larger gut volume ratio to the mass of Daphnia or its high uptake efficiency. Humic acid reduced the uptake of nC(60) in Daphnia and zebrafish as a result of the size effect and the polarity alternation of nC(60). The depuration patterns were rapid for Daphnia and slow for zebrafish, and the differences were most likely the result of different water exchange frequencies between organisms. The remaining nC(60) percentages were approximately 20% for Daphnia and 30% for zebrafish after 48-h depuration, suggesting that a large nC(60) burden still existed for both aquatic organisms and that there is a need for further studies on the potential for trophic transfer.

  8. Statistical mechanics of hydrophobic amino acids in aqueous solution: A joint experimental scattering and computational study

    NASA Astrophysics Data System (ADS)

    Song, Lingshuang; Yang, Lin; Huang, Wei; Meng, Jie; Yang, Sichun

    How hydrophobic amino acids interact with each other is still a fundamental question in understanding protein dynamics and folding. Here, we describe an integrative experimental-computational approach of combining x-ray solution scattering and atomistic molecular simulations to determine the molecular properties of a hydrophobic leucine amino acid in an aqueous solution. First, scattering data were acquired at a series of amino acid and salt concentrations and these scattering profiles were further used to calibrate atomistic molecular simulations via a single parameter for solute-solvent interaction. Second, these accurate data of atomistic leucine simulations were used to quantify the effective interacting potentials via a structural simplification of one-bead-per-residue and two-bead-per-residue representations. Third, comparative energetic analyses between the one-bead and two-bead representations were performed to reach a simple picture of residue-residue interactions with an accurate energy function. Taken together, this joint experimental-computational study provides critical insights into microscopic interactions of hydrophobic amino acids in solution with a profound application for studying molecular dynamics of, e.g., intrinsically disordered proteins and their folding.

  9. Removal of fluoride in aqueous solution by adsorption on acid activated water treatment sludge

    NASA Astrophysics Data System (ADS)

    Vinitnantharat, Soydoa; Kositchaiyong, Sriwilai; Chiarakorn, Siriluk

    2010-06-01

    This paper reports the use of a pellet of adsorbent made from water treatment sludge (S) and acid activated water treatment sludge (SH) for removal of fluoride in the batch equilibration technique. The influence of pH, adsorbent dosage, temperature and effect of other ions were employed to find out the feasibility of acid activated adsorbent to remove fluoride to the permissible concentration of 0.7 mg/L. The results from the adsorption isotherm followed both Langmuir and Freundlich models and the highest fluoride removal was found for adsorbent activated with acetic acid at 2.0 mol/L. The optimum adsorbent dosage was found at 40 g/L, 0.01 mol/L acid activated adsorbent which was able to adsorb fluoride from 10 down to 0.11 mg/L. The adsorption capacity was decreased when the temperature increased. This revealed that the adsorption of fluoride on SH was exothermic. In the presence of nitrate and carbonate ions in the aqueous solution, fluoride removal efficiency of SH decreased from 94.4% to 86.6% and 90.8%, respectively. However, there is no significant effect in the presence of sulfate and chloride ions.

  10. Population and size distribution of solute-rich mesospecies within mesostructured aqueous amino acid solutions.

    PubMed

    Jawor-Baczynska, Anna; Moore, Barry D; Lee, Han Seung; McCormick, Alon V; Sefcik, Jan

    2013-01-01

    Aqueous solutions of highly soluble substances such as small amino acids are usually assumed to be essentially homogenous systems with some degree of short range local structuring due to specific interactions on the sub-nanometre scale (e.g. molecular clusters, hydration shells), usually not exceeding several solute molecules. However, recent theoretical and experimental studies have indicated the presence of much larger supramolecular assemblies or mesospecies in solutions of small organic and inorganic molecules as well as proteins. We investigated both supersaturated and undersaturated aqueous solutions of two simple amino acids (glycine and DL-alanine) using Dynamic Light Scattering (DLS), Brownian Microscopy/Nanoparticles Tracking Analysis (NTA) and Cryogenic Transmission Electron Microscopy (Cryo-TEM). Colloidal scale mesospecies (nanodroplets) were previously reported in supersaturated solutions of these amino acids and were implicated as intermediate species on non-classical crystallization pathways. Surprisingly, we have found that the mesospecies are also present in significant numbers in undersaturated solutions even when the solute concentration is well below the solid-liquid equilibrium concentration (saturation limit). Thus, mesopecies can be observed with mean diameters ranging from 100 to 300 nm and a size distribution that broadens towards larger size with increasing solute concentration. We note that the mesospecies are not a separate phase and the system is better described as a thermodynamically stable mesostructured liquid containing solute-rich domains dispersed within bulk solute solution. At a given temperature, solute molecules in such a mesostructured liquid phase are subject to equilibrium distribution between solute-rich mesospecies and the surrounding bulk solution.

  11. Degradation of hydroxycinnamic acid mixtures in aqueous sucrose solutions by the Fenton process.

    PubMed

    Nguyen, Danny M T; Zhang, Zhanying; Doherty, William O S

    2015-02-11

    The degradation efficiencies and behaviors of caffeic acid (CaA), p-coumaric acid (pCoA), and ferulic acid (FeA) in aqueous sucrose solutions containing the mixture of these hydroxycinnamic acids (HCAs) were studied by the Fenton oxidation process. Central composite design and multiresponse surface methodology were used to evaluate and optimize the interactive effects of process parameters. Four quadratic polynomial models were developed for the degradation of each individual acid in the mixture and the total HCAs degraded. Sucrose was the most influential parameter that significantly affected the total amount of HCA degraded. Under the conditions studied there was a <0.01% loss of sucrose in all reactions. The optimal values of the process parameters for a 200 mg/L HCA mixture in water (pH 4.73, 25.15 °C) and sucrose solution (13 mass %, pH 5.39, 35.98 °C) were 77% and 57%, respectively. Regression analysis showed goodness of fit between the experimental results and the predicted values. The degradation behavior of CaA differed from those of pCoA and FeA, where further CaA degradation is observed at increasing sucrose and decreasing solution pH. The differences (established using UV/vis and ATR-FTIR spectroscopy) were because, unlike the other acids, CaA formed a complex with Fe(III) or with Fe(III) hydrogen-bonded to sucrose and coprecipitated with lepidocrocite, an iron oxyhydroxide.

  12. Efficient synthesis of 2,3-disubstituted-2,3-dihydroquinazolin-4(1H)-ones catalyzed by dodecylbenzenesulfonic acid in aqueous media under ultrasound irradiation.

    PubMed

    Chen, Bao-Hua; Li, Ji-Tai; Chen, Guo-Feng

    2015-03-01

    Synthesis of 2,3-disubstituted-2,3-dihydroquinazolin-4(1H)-one derivatives catalyzed by dodecylbenzenesulfonic acid was carried out in 80-92% yields at 40-42 °C within 1-2 h in aqueous media via one-pot three-component condensation of isatoic anhydride, aromatic aldehyde and amine under ultrasound irradiation. Convenient work-up procedures, mild reaction conditions, avoiding the use of organic solvents, and friendly to environment are the salient features of this protocol.

  13. Electrochemical treatment of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) in groundwater impacted by aqueous film forming foams (AFFFs).

    PubMed

    Schaefer, Charles E; Andaya, Christina; Urtiaga, Ana; McKenzie, Erica R; Higgins, Christopher P

    2015-09-15

    Laboratory experiments were performed to evaluate the use of electrochemical treatment for the decomposition of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), as well as other perfluoroalkyl acids (PFAAs), in aqueous film forming foam (AFFF)-impacted groundwater collected from a former firefighter training area and PFAA-spiked synthetic groundwater. Using a commercially-produced Ti/RuO2 anode in a divided electrochemical cell, PFOA and PFOS decomposition was evaluated as a function of current density (0-20 mA/cm(2)). Decomposition of both PFOA and PFOS increased with increasing current density, although the decomposition of PFOS did not increase as the current density was increased above 2.5 mA/cm(2). At a current density of 10 mA/cm(2), the first-order rate constants, normalized for current density and treatment volume, for electrochemical treatment of both PFOA and PFOS were 46 × 10(-5) and 70 × 10(-5) [(min(-1)) (mA/cm(2))(-1) (L)], respectively. Defluorination was confirmed for both PFOA and PFOS, with 58% and 98% recovery as fluoride, respectively (based upon the mass of PFOA and PFOS degraded). Treatment of other PFAAs present in the groundwater also was observed, with shorter chain PFAAs generally being more recalcitrant. Results highlight the potential for electrochemical treatment of PFAAs, particularly PFOA and PFOS, in AFFF-impacted groundwater.

  14. Context of ancient aqueous environments on Mars from in situ geologic mapping at Endeavour Crater

    USGS Publications Warehouse

    Crumpler, L.S.; Arvidson, R. E.; Bell, J.; Clark, B. C.; Cohen, B. A.; Farrand, W. H.; Gellert, Ralf; Golombek, M.; Grant, J. A.; Guinness, E.; Herkenhoff, Kenneth E.; Johnson, J. R.; Jolliff, B.; Ming, D. W.; Mittlefehldt, D. W.; Parker, T.; Rice, J. W.; Squyres, S. W.; Sullivan, R.; Yen, A. S.

    2015-01-01

    Using the Mars Exploration Rover Opportunity, we have compiled one of the first field geologic maps on Mars while traversing the Noachian terrain along the rim of the 22 km diameter Endeavour Crater (Latitude −2°16′33″, Longitude −5°10′51″). In situ mapping of the petrographic, elemental, structural, and stratigraphic characteristics of outcrops and rocks distinguishes four mappable bedrock lithologic units. Three of these rock units predate the surrounding Burns formation sulfate-rich sandstones and one, the Matijevic Formation, represents conditions on early Mars predating the formation of Endeavour Crater. The stratigraphy assembled from these observations includes several geologic unconformities. The differences in lithologic units across these unconformities record changes in the character and intensity of the Martian aqueous environment over geologic time. Water circulated through fractures in the oldest rocks over periods long enough that texturally and elementally significant alteration occurred in fracture walls. These oldest pre-Endeavour rocks and their network of mineralized and altered fractures were preserved by burial beneath impact ejecta and were subsequently exhumed and exposed. The alteration along joints in the oldest rocks and the mineralized veins and concentrations of trace metals in overlying lithologic units is direct evidence that copious volumes of mineralized and/or hydrothermal fluids circulated through the early Martian crust. The wide range in intensity of structural and chemical modification from outcrop to outcrop along the crater rim shows that the ejecta of large (>8 km in diameter) impact craters is complex. These results imply that geologic complexity is to be anticipated in other areas of Mars where cratering has been a fundamental process in the local and regional geology and mineralogy.

  15. Fabrication and characterization of ultrathin dextran layers: Time dependent nanostructure in aqueous environments revealed by OWLS.

    PubMed

    Saftics, Andras; Kurunczi, Sándor; Szekrényes, Zsolt; Kamarás, Katalin; Khánh, Nguyen Quoc; Sulyok, Attila; Bősze, Szilvia; Horvath, Robert

    2016-10-01

    Surface coatings of the polysaccharide dextran and its derivatives are key ingredients especially in label-free biosensors for the suppression of non-specific binding and for receptor immobilization. Nevertheless, the nanostructure of these ultrathin coatings and its tailoring by the variation of the preparation conditions have not been profoundly characterized and understood. In this work carboxymethylated dextran (CMD) was prepared and used for fabricating ultrathin surface coatings. A grafting method based on covalent coupling to aminosilane- and epoxysilane-functionalized surfaces was applied to obtain thin CMD layers. The carboxyl moiety of the CMD was coupled to the aminated surface by EDC-NHS reagents, while CMD coupling through epoxysilane molecules was performed without any additional reagents. The surface analysis following the grafting procedures consisted of X-ray photoelectron spectroscopy (XPS), attenuated total reflection infrared spectroscopy (ATR-IR), spectroscopic ellipsometry, atomic force microscopy (AFM) and optical waveguide lightmode spectroscopy (OWLS). The XPS and AFM measurements showed that the grafting resulted in a very thin dextran layer of a few nanometers. The OWLS method allowed devising the structure of the interfacial dextran layers by the evaluation of the optogeometrical parameters. The alteration in the nanostructure of the CMD layer with the chemical composition of the silane coverage and the pH of the grafting solution was revealed by in situ OWLS, specifically, lain down chains were found to be prevalent on the surface under neutral and basic conditions on epoxysilylated surfaces. The developed methodologies allowed to design and fabricate nanometer scale CMD layers with well-controlled surface structure, which are very difficult to characterize in aqueous environments using present instrumentations and highly hydrated surface layers.

  16. Plant viruses in aqueous environment - survival, water mediated transmission and detection.

    PubMed

    Mehle, Nataša; Ravnikar, Maja

    2012-10-15

    The presence of plant viruses outside their plant host or insect vectors has not been studied intensively. This is due, in part, to the lack of effective detection methods that would enable their detection in difficult matrixes and in low titres, and support the search for unknown viruses. Recently, new and sensitive methods for detecting viruses have resulted in a deeper insight into plant virus movement through, and transmission between, plants. In this review, we have focused on plant viruses found in environmental waters and their detection. Infectious plant pathogenic viruses from at least 7 different genera have been found in aqueous environment. The majority of the plant pathogenic viruses so far recovered from environmental waters are very stable, they can infect plants via the roots without the aid of a vector and often have a wide host range. The release of such viruses from plants can lead to their dissemination in streams, lakes, and rivers, thereby ensuring the long-distance spread of viruses that otherwise, under natural conditions, would remain restricted to limited areas. The possible sources and survival of plant viruses in waters are therefore discussed. Due to the widespread use of hydroponic systems and intensive irrigation in horticulture, the review is focused on the possibility and importance of spreading viral infection by water, together with measures for preventing the spread of viruses. The development of new methods for detecting multiple plant viruses at the same time, like microarrays or new generation sequencing, will facilitate the monitoring of environmental waters and waters used for irrigation and in hydroponic systems. It is reasonable to expect that the list of plant viruses found in waters will thereby be expanded considerably. This will emphasize the need for further studies to determine the biological significance of water-mediated transport.

  17. Context of ancient aqueous environments on Mars from in situ geologic mapping at Endeavour Crater

    NASA Astrophysics Data System (ADS)

    Crumpler, L. S.; Arvidson, R. E.; Bell, J.; Clark, B. C.; Cohen, B. A.; Farrand, W. H.; Gellert, R.; Golombek, M.; Grant, J. A.; Guinness, E.; Herkenhoff, K. E.; Johnson, J. R.; Jolliff, B.; Ming, D. W.; Mittlefehldt, D. W.; Parker, T.; Rice, J. W., Jr.; Squyres, S. W.; Sullivan, R.; Yen, A. S.

    2015-03-01

    Using the Mars Exploration Rover Opportunity, we have compiled one of the first field geologic maps on Mars while traversing the Noachian terrain along the rim of the 22 km diameter Endeavour Crater (Latitude -2°16'33", Longitude -5°10'51"). In situ mapping of the petrographic, elemental, structural, and stratigraphic characteristics of outcrops and rocks distinguishes four mappable bedrock lithologic units. Three of these rock units predate the surrounding Burns formation sulfate-rich sandstones and one, the Matijevic Formation, represents conditions on early Mars predating the formation of Endeavour Crater. The stratigraphy assembled from these observations includes several geologic unconformities. The differences in lithologic units across these unconformities record changes in the character and intensity of the Martian aqueous environment over geologic time. Water circulated through fractures in the oldest rocks over periods long enough that texturally and elementally significant alteration occurred in fracture walls. These oldest pre-Endeavour rocks and their network of mineralized and altered fractures were preserved by burial beneath impact ejecta and were subsequently exhumed and exposed. The alteration along joints in the oldest rocks and the mineralized veins and concentrations of trace metals in overlying lithologic units is direct evidence that copious volumes of mineralized and/or hydrothermal fluids circulated through the early Martian crust. The wide range in intensity of structural and chemical modification from outcrop to outcrop along the crater rim shows that the ejecta of large (>8 km in diameter) impact craters is complex. These results imply that geologic complexity is to be anticipated in other areas of Mars where cratering has been a fundamental process in the local and regional geology and mineralogy.

  18. Molecular interactions of α-amino acids insight into aqueous β-cyclodextrin systems.

    PubMed

    Ekka, Deepak; Roy, Mahendra Nath

    2013-10-01

    Qualitative and quantitative analysis of molecular interaction prevailing in glycine, L-alanine, L-valine and aqueous solution of β-cyclodextrin (β-CD) have been probed by thermophysical properties. Density (ρ), viscosity (η), and ultrasonic speed (u) measurements have been reported at different temperatures. The extent of interaction (solute-solvent interaction) is expressed in terms of the limiting apparent molar volume ([Formula: see text]), viscosity B-coefficient and limiting apparent molar adiabatic compressibility ([Formula: see text]). The changes on the enthalpy ([Formula: see text]) and entropy ([Formula: see text]) of the encapsulation analysis give information about the driving forces governing the inclusion. The temperature dependence behaviour of partial molar quantities and group contributions to partial molar volumes has been determined for the amino acids. The trends in transfer volumes, [Formula: see text], have been interpreted in terms of solute-cosolute interactions based on a cosphere overlap model. The role of the solvent (aqueous solution of β-CD) and the contribution of solute-solute and solute-solvent interactions to the solution complexes have also been analyzed through the derived properties.

  19. Aqueous Dispersions of Silica Stabilized with Oleic Acid Obtained by Green Chemistry

    PubMed Central

    Nistor, Cristina Lavinia; Ianchis, Raluca; Ghiurea, Marius; Nicolae, Cristian-Andi; Spataru, Catalin-Ilie; Culita, Daniela Cristina; Pandele Cusu, Jeanina; Fruth, Victor; Oancea, Florin; Donescu, Dan

    2016-01-01

    The present study describes for the first time the synthesis of silica nanoparticles starting from sodium silicate and oleic acid (OLA). The interactions between OLA and sodium silicate require an optimal OLA/OLANa molar ratio able to generate vesicles that can stabilize silica particles obtained by the sol-gel process of sodium silicate. The optimal molar ratio of OLA/OLANa can be ensured by a proper selection of OLA and respectively of sodium silicate concentration. The titration of sodium silicate with OLA revealed a stabilization phenomenon of silica/OLA vesicles and the dependence between their average size and reagent’s molar ratio. Dynamic light scattering (DLS) and scanning electron microscopy (SEM) measurements emphasized the successful synthesis of silica nanoparticles starting from renewable materials, in mild condition of green chemistry. By grafting octadecyltrimethoxysilane on the initial silica particles, an increased interaction between silica particles and the OLA/OLANa complex was achieved. This interaction between the oleyl and octadecyl chains resulted in the formation of stable gel-like aqueous systems. Subsequently, olive oil and an oleophylic red dye were solubilized in these stable aqueous systems. This great dispersing capacity of oleosoluble compounds opens new perspectives for future green chemistry applications. After the removal of water and of the organic chains by thermal treatment, mesoporous silica was obtained.

  20. Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution

    NASA Astrophysics Data System (ADS)

    Park, Sunghak; Chang, Woo Je; Lee, Chan Woo; Park, Sangbaek; Ahn, Hyo-Yong; Nam, Ki Tae

    2017-01-01

    The solar-driven splitting of hydrohalic acids (HX) is an important and fast growing research direction for H2 production. In addition to the hydrogen, the resulting chemicals (X2/X3-) can be used to propagate a continuous process in a closed cycle and are themselves useful products. Here we present a strategy for photocatalytic hydrogen iodide (HI) splitting using methylammonium lead iodide (MAPbI3) in an effort to develop a cost-effective and easily scalable process. Considering that MAPbI3 is a water-soluble ionic compound, we exploit the dynamic equilibrium of the dissolution and precipitation of MAPbI3 in saturated aqueous solutions. The I- and H+ concentrations of the aqueous solution are determined to be the critical parameters for the stabilization of the tetragonal MAPbI3 phase. Stable and efficient H2 production under visible light irradiation was demonstrated. The solar HI splitting efficiency of MAPbI3 was 0.81% when using Pt as a cocatalyst.

  1. Poly (vinylsulfonic acid) assisted synthesis of aqueous solution stable vaterite calcium carbonate nanoparticles.

    PubMed

    Nagaraja, Ashvin T; Pradhan, Sulolit; McShane, Michael J

    2014-03-15

    Calcium carbonate nanoparticles of the vaterite polymorph were synthesized by combining CaCl2 and Na2CO3 in the presence of poly (vinylsulfonic acid) (PVSA). By studying the important experimental parameters we found that controlling PVSA concentration, reaction temperature, and order of reagent addition the particle size, monodispersity, and surface charge can be controlled. By increasing PVSA concentration or by decreasing temperature CCNPs with an average size from ≈150 to 500 nm could be produced. We believe the incorporation of PVSA into the reaction plays a dual role to (1) slow down the nucleation rate by sequestering calcium and to (2) stabilize the resulting CCNPs as the vaterite polymorph, preventing surface calcification or aggregation into microparticles. The obtained vaterite nanoparticles were found to maintain their crystal structure and surface charge after storage in aqueous buffer for at least 5 months. The aqueous stable vaterite nanoparticles could be a useful platform for the encapsulation of a large variety of biomolecules for drug delivery or as a sacrificial template toward capsule formation for biosensor applications.

  2. Determination of acidity constants of curcumin in aqueous solution and apparent rate constant of its decomposition.

    PubMed

    Bernabé-Pineda, Margarita; Ramírez-Silva, María Teresa; Romero-Romo, Mario; González-Vergara, Enrique; Rojas-Hernández, Alberto

    2004-04-01

    The stability of curcumin (H3Cur) in aqueous media is improved when the systems in which it is present are at high pH values (higher than 11.7), fitting a model describable by a pseudo-zero order with a rate constant k' for the disappearance of the Cur3- species of 1.39 (10(-9)) Mmin(-1). There were three acidity constants measured for the curcumin as follows: pKA3 = 10.51 +/- 0.01 corresponding to the equilibrium HCur2- = Cur3- + H+, a pKA2 = 9.88 +/- 0.02 corresponding to the equilibrium H2Cur- = HCur-(2) + H+. These pKA values were attributed to the hydrogen of the phenol part of the curcumin, while the pKA1 = 8.38 +/- 0.04 corresponds to the equilibrium H3Cur = H2Cur- + H+ and is attributed the acetylacetone type group. Formation of quinoid structures play an important role in the tautomeric forms of the curcumin in aqueous media, which makes the experimental values differ from the theoretically calculated ones, depending on the conditions adopted in the study.

  3. Investigation of secondary formation of formic acid: urban environment vs. oil and gas producing region

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Veres, P. R.; Warneke, C.; Roberts, J. M.; Gilman, J. B.; Koss, A.; Edwards, P. M.; Graus, M.; Kuster, W. C.; Li, S.-M.; Wild, R. J.; Brown, S. S.; Dubé, W. P.; Lerner, B. M.; Williams, E. J.; Johnson, J. E.; Quinn, P. K.; Bates, T. S.; Lefer, B.; Hayes, P. L.; Jimenez, J. L.; Weber, R. J.; Zamora, R.; Ervens, B.; Millet, D. B.; Rappenglück, B.; de Gouw, J. A.

    2014-09-01

    Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site in June-July of 2010 during CalNex and a site in an oil and gas producing region in January-February of 2013 during UBWOS 2013 will be discussed. Although the VOC compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 ppb in UBWOS 2013 and 2.0 ± 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (> 8%). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of > 10). Inclusion of recent findings on additional precursors and formation pathways of formic acid in the box model increases modeled formic acid concentrations for UBWOS 2013 and CalNex by a factor of 6.4 and 4.5, respectively. A comparison of measured and modeled HCOOH/acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 21 and 47% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be -7 and 0-6% in UBWOS 2013 and CalNex, respectively. We observe that air-snow exchange processes and morning fog events may also contribute to ambient formic acid concentrations during UBWOS 2013 (∼20% in total). In total, 50-57% in UBWOS 2013 and 48-53% in CalNex of secondary formation of formic acid remains unexplained. More work on formic acid formation pathways is needed to reduce the uncertainties in the sources and budget of formic

  4. Modeling photodegradation kinetics of three systemic neonicotinoids-dinotefuran, imidacloprid, and thiamethoxam-in aqueous and soil environment.

    PubMed

    Kurwadkar, Sudarshan; Evans, Amanda; DeWinne, Dustan; White, Peter; Mitchell, Forrest

    2016-07-01

    Environmental presence and retention of commonly used neonicotinoid insecticides such as dinotefuran (DNT), imidacloprid (IMD), and thiamethoxam (THM) are a cause for concern and prevention because of their potential toxicity to nontarget species. In the present study the kinetics of the photodegradation of these insecticides were investigated in water and soil compartments under natural light conditions. The results suggest that these insecticides are fairly unstable in both aqueous and soil environments when exposed to natural sunlight. All 3 insecticides exhibit strong first-order degradation rate kinetics in the aqueous phase, with rate constants kDNT , kIMD , and kTHM of 0.20 h(-1) , 0.30 h(-1) , and 0.18 h(-1) , respectively. However, in the soil phase, the modeled photodegradation kinetics appear to be biphasic, with optimal rate constants k1DNT and k2DNT of 0.0198 h(-1) and 0.0022 h(-1) and k1THM and k2THM of 0.0053 h(-1) and 0.0014 h(-1) , respectively. Differentially, in the soil phase, imidacloprid appears to follow the first-order rate kinetics with a kIMD of 0.0013 h(-1) . These results indicate that all 3 neonicotinoids are photodegradable, with higher degradation rates in aqueous environments relative to soil environments. In addition, soil-encapsulated imidacloprid appears to degrade slowly compared with dinotefuran and thiamethoxam and does not emulate the faster degradation rates observed in the aqueous phase. Environ Toxicol Chem 2016;35:1718-1726. © 2015 SETAC.

  5. The aqueous photolysis of α-pinene in solution with humic acid

    USGS Publications Warehouse

    Goldberg, Marvin C.; Cunningham, Kirkwood M.; Aiken, George R.; Weiner, Eugene R.; ,

    1992-01-01

    Terpenes are produced abundantly by environmental processes but are found in very low concentrations in natural waters. Aqueous photolysis of solutions containing α-pinene, a representative terpene, in the presence of humic acid resulted in degradation of the pinene. Comparison of this reaction to photolysis of α-pinene in the presence of methylene blue leads to the conclusion that the reactive pathway for the abiotic degradation of α-pinene is due to reaction with singlet oxygen produced by irradiation of the humic material. The initial product of single oxygen and α-pinene is a hydroperoxide. Since humic materials are prevalent in most natural waters, this mechanism of photodecomposition for α-pinene probably also applies to other terpenes in surface waters and may be reasonably considered to contribute to their low environmental concentration.

  6. Cementation and Aqueous Alteration of a Sandstone Unit Under Acidic Conditions in Gale Crater, Mars

    NASA Technical Reports Server (NTRS)

    Yen, A. S.; Blake, D. F.; Ming, D. W.; Morris, R. V.; Gellert, R.; Clark, B.; Vaniman, D. T.; Chipera, S. J.; Thompson, L. M.; Bristow, T. F.; Rampe, E. B.; Crisp, J. A.

    2016-01-01

    The Curiosity rover landed on Mars in August 2012 to explore the sedimentary history and to assess the habitability of Gale Crater. After 1200 sols of surface operations and over 12 km of traverse distance, the mineralogy of 10 samples has been determined by the CheMin X-ray diffractometer (XRD) and the chemical composition of nearly 300 targets has been established by the Alpha Particle X-ray Spectrometer (APXS). Light-toned fracture zones containing elevated concentrations of silica have been studied by Curiosity's instruments to determine the nature of the fluids that resulted in the enrichment of SiO2. Multiple fluid exposures are evident, and the chemistry and mineralogy data indicate at least two aqueous episodes may have occurred under acidic conditions.

  7. Comparison of aqueous ammonia and dilute acid pretreatment of bamboo fractions: Structure properties and enzymatic hydrolysis.

    PubMed

    Xin, Donglin; Yang, Zhong; Liu, Feng; Xu, Xueru; Zhang, Junhua

    2015-01-01

    The effect of two pretreatments methods, aqueous ammonia (SAA) and dilute acid (DA), on the chemical compositions, cellulose crystallinity, morphologic change, and enzymatic hydrolysis of bamboo fractions (bamboo yellow, timber, green, and knot) was compared. Bamboo fractions with SAA pretreatment had better hydrolysability than those with DA pretreatment. High crystallinity index resulted in low hydrolysis yield in the conversion of SAA pretreated bamboo fractions, not DA pretreated fractions. The increase of cellulase loading had modestly positive effect in the hydrolysis of both SAA and DA pretreated bamboo fractions, while supplement of xylanase significantly increased the hydrolysis of the pretreated bamboo fractions, especially after SAA pretreatment. The results indicated that SAA pretreatment was more effective than DA pretreatment in conversion of bamboo fractions, and supplementation of xylanase was necessary in effective conversion of the SAA pretreated fractions into fermentable sugars.

  8. Pervaporation of Water from Aqueous Hydriodic Acid and Iodine Mixtures Using Nafion (R) Membranes

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart

    2007-11-01

    The sulfur-iodine (S-I) process for generation of hydrogen has been proposed as a thermochemical cycle for study due to its predicted high efficiencies. Improvements in the cycle that will yield the greatest gain in both operating and capital costs involve chemical separations. To date, membrane processes have been largely unexplored. In this work, a materials compatibility study into the application of Nafion-117® and Nafion-112® as membranes for the pervaporation of water from aqueous mixtures of hydriodic acid (HI) and HI/iodine at 134 ºC was conducted. Significant fluxes of water were measured with respect to feed water concentration and high separation factors were calculated. Most surprisingly, HI and HI/iodine feeds acted very differently in that HI-iodine complexes formed result in higher fluxes and separation factors than what was observed for HI alone.

  9. Terahertz microfluidic chips for detection of amino acids in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Su, Bo; Zhang, Cong; Fan, Ning; Zhang, Cunlin

    2016-11-01

    Microfluidic technology can control the fluidic thickness accurately in less than 100 micrometers. So the combination of terahertz (THz) and microfluidic technology becomes one of the most interesting directions towards biological detection. We designed microfluidic chips for terahertz spectroscopy of biological samples in aqueous solutions. Using the terahertz time-domain spectroscopy (THz-TDS) system, we experimentally measured the transmittance of the chips and the THz absorption spectra of L-threonine and L-arginine, respectively. The results indicated the feasibility of performing high sensitivity THz spectroscopy of amino acids solutions. Therefore, the microfluidic chips can realize real-time and label-free measurement for biochemistry samples in THz-TDS system.

  10. Electrodeposited Films from Aqueous Tungstic Acid-Hydrogen Peroxide Solutions for Electrochromic Display Devices

    NASA Astrophysics Data System (ADS)

    Yamanaka, Kazusuke

    1987-11-01

    Electrodeposited tungsten oxide films from aqueous tungstic acid-hydrogen peroxide solutions were investigated for applications to electrochromic devices. These films exhibited electrochromism in aprotic electrolyte solutions containing Li-salts. When the films were heat-treated for an hour at temperatures between 100 and 200°C, the electrochromic reactions were rich in reversibility. The coloring efficiency and response rate for the films were favorable and comparable to those for tungsten trioxide evaporated films. A cell life-test was performed on several clock-size cells by applying a 1.2-V, 1-Hz, continuous square wave. The typical amount of charge required for coloration was about 50 C / m2 and remained unchanged even after 107 coloration-bleaching cycles.

  11. Characterization of potassium bromide crystals grown in the aqueous solution of picric acid

    NASA Astrophysics Data System (ADS)

    Maheswari, J. Uma; Krishnan, C.; Kalyanaraman, S.; Selvarajan, P.

    2016-12-01

    Potassium bromide crystals were grown in the aqueous solution of picric acid by slow evaporation technique at room temperature. X-ray Diffraction (XRD) analysis ensures that the grown sample is in Fm3m space group and FCC structure. Energy Dispersive X-ray Spectroscopy (EDX) reveals the presence of elements in the title compound. UV-Vis-NIR spectrum reveals that the grown sample is a promising nonlinear optical (NLO) material. FTIR analysis confirms the functional groups present in the sample. The thermogravimetric (TG) and differential thermogravimetric (DTA) analyses ensure that the sample material is thermally stable up to 160 °C. The second harmonic efficiency of the sample is 1.3 times greater than that of standard KDP. The mechanical strength of the grown sample is estimated by Vickers microhardness tester. The electrical properties were investigated by impedance analysis and the results of various studies of the grown crystals are discussed.

  12. Aqueous Hydricity from Calculations of Reduction Potential and Acidity in Water.

    PubMed

    Brereton, Kelsey R; Bellows, Sarina M; Fallah, Hengameh; Lopez, Antonio A; Adams, Robert M; Miller, Alexander J M; Jones, William D; Cundari, Thomas R

    2016-12-22

    Hydricity, or hydride donating ability, is a thermodynamic value that helps define the reactivity of transition metal hydrides. To avoid some of the challenges of experimental hydricity measurements in water, a computational method for the determination of aqueous hydricity values has been developed. With a thermochemical cycle involving deprotonation of the metal hydride (pKa), 2e(-) oxidation of the metal (E°), and 2e(-) reduction of the proton, hydricity values are provided along with other valuable thermodynamic information. The impact of empirical corrections (for example, calibrating reduction potentials with 2e(-) organic versus 1e(-) inorganic potentials) was assessed in the calculation of the reduction potentials, acidities, and hydricities of a series of iridium hydride complexes. Calculated hydricities are consistent with electronic trends and agree well with experimental values.

  13. Acid-catalysed autoreduction of ferrylmyoblobin in aqueous solution studied by freeze quenching and ESR spectroscopy.

    PubMed

    Kröger-Ohlsen, M V; Andersen, M L; Skibsted, L H

    1999-04-01

    Decay of the hypervalent muscle pigment ferrylmyoglobin, formed by activation of metmyoglobin by hydrogen peroxide, was found, when studied by a combination of ESR and UV/VIS spectroscopy in aqueous solution at physiological pH, to proceed by parallel second- and first-order kinetics. At pH below 6.5 a sharp ESR signal (g = 2.003) with an increasing intensity for decreasing pH were observed in solutions frozen in liquid nitrogen, and a broad signal (g = 2.005) was seen throughout the studied pH range also in frozen solutions. The g = 2.005 signal is suggested to arise from an intermediate formed in an intramolecular rate-determining electron-transfer in ferrylmyoglobin, whereas the g 2.003 signal is caused by a radical formed in a proton-assisted electron-transfer initiating the specific acid-catalysed autoreduction.

  14. Removal of Basic Violet 14 from aqueous solution using sulphuric acid activated materials.

    PubMed

    Suresh, S

    2016-01-01

    In this study the adsorption of Basic Violet, 14 from aqueous solution onto sulphuric acid activated materials prepared from Calophyllum inophyllum (CS) and Theobroma cacao (TS) shells were investigated. The experimental data were analysed by Langmuir, Freundlich and Temkin isotherm models. The results showed that CS has a superior adsorption capacity compared to the TS. The adsorption capacity was found to be 1416.43 mg/g for CS and 980.39 mg/g for TS. The kinetic data results at different concentrations were analysed using pseudo first-order and pseudo-second order model. Boyd plot indicates that the dye adsorption onto CS and TS is controlled by film diffusion. The adsorbents were characterised by scanning electron microscopy. The materials used in this study were economical waste products and hence can be an attractive alternative to costlier adsorbents for dye removal in industrial wastewater treatment processes.

  15. pH-switchable structural evolution in aqueous surfactant-aromatic dibasic acid system.

    PubMed

    Rose J, Linet; Tata, B V R; Aswal, V K; Hassan, P A; Talmon, Yeshayahu; Sreejith, Lisa

    2015-01-01

    Structural transitions triggered by pH in an aqueous micellar system comprising of a cationic surfactant (cetylpyridinium chloride) and an aromatic dibasic acid (phthalic acid) was investigated. Reversible switching between liquid-like and gel-like states was exhibited by the system on adjusting the solution pH. Self-assembled structures, responsible for the changes in flow properties were identified using rheology, light scattering techniques and cryogenic Transmission Electron Microscopy (cryo-TEM). High-viscosity, shear-thinning behavior and Maxwell-type dynamic rheology shown by the system at certain pH values suggested the growth of spheroidal/short cylindrical micelles into long and entangled structures. Light scattering profiles also supported the notion of pH-induced microstructural transitions in the solution. Cryo-TEM images confirmed the presence of spheroidal/short cylindrical micelles in the low-viscosity sample whereas very long and entangled thread-like micelles in the peak viscosity sample. pH-dependent changes in the micellar binding ability of phthalic acid is proposed as the key factor regulating the morphological transformations and related flow properties of the system.

  16. Aromatic ionene topology and counterion-tuned gelation of acidic aqueous solutions.

    PubMed

    Bachl, Jürgen; Bertran, Oscar; Mayr, Judith; Alemán, Carlos; Díaz Díaz, David

    2017-04-04

    Unusual gelation of acidic solutions was achieved using polycations bearing quaternary ammonium moieties. These ionene polymers are based on a disubstituted phenylene dibenzamide core, which allows the construction of different topomers (i.e. ortho-1, meta-2 and para-3). The topology of the polymers was found to play a key role on their aggregation behaviour both in pure water and in a variety of aqueous acidic solutions leading to the formation of stable acidic gels. Specifically, ortho-1 showed superior gelation ability than the analogues meta-2 and para-3 in numerous solutions of different pH and ionic strengths. Lower critical gelation concentrations, higher gel-to-sol transition temperatures and faster gelation were usually observed for ortho-1 regardless the solvent system. Detailed computational molecular dynamic simulations revealed a major role of the counterion (Cl(-)) and specific polymerpolymer interactions. In particular, hydrogen bonds, N-Hπ interactions and intramolecular π-π stacking networks are distinctive in ortho-1. In addition, counterions located at internal hydration regions also affect to such polymerpolymer interactions, acting as binders and, therefore, providing additional stability.

  17. The adsorption of cationic dye from aqueous solution onto acid-activated andesite.

    PubMed

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

    2007-08-25

    The adsorption of cationic dye (i.e., methylene blue) onto acid-activated andesite in aqueous solution was studied in a batch system with respect to its kinetics as a function of agitation speed, initial adsorbate concentration, pH, and adsorbent mass. It was found that the resulting acid-activated adsorbent possessed a mesoporous structure with BET surface areas at around 60m(2)/g. The surface characterization of acid-activated andesite was also performed using the zeta-potential measurements, indicating that the charge sign on the surface of the andesite should be negative in a wide pH range (i.e., 3-11). Furthermore, a simplified kinetic model, pseudo-second-order, was tested to investigate the adsorption behaviors of methylene blue onto the clay samples treated under different process conditions. It was found that the adsorption process could be well described with the model. The adsorption capacity parameter of the model obtained in the present work was significantly in line with the process parameters.

  18. Phenolic compounds extracted by acidic aqueous ethanol from berries and leaves of different berry plants.

    PubMed

    Tian, Ye; Liimatainen, Jaana; Alanne, Aino-Liisa; Lindstedt, Anni; Liu, Pengzhan; Sinkkonen, Jari; Kallio, Heikki; Yang, Baoru

    2017-04-01

    Phenolic compounds of berries and leaves of thirteen various plant species were extracted with aqueous ethanol and analyzed with UPLC-DAD-ESI-MS, HPLC-DAD, and NMR. The total content of phenolics was consistently higher in leaves than in berries (25-7856 vs. 28-711mg/100g fresh weight). Sea buckthorn leaves were richest in phenolic compounds (7856mg/100g f.w.) with ellagitannins as the dominant compound class. Sea buckthorn berries contained mostly isorhamnetin glycosides, whereas quercetin glycosides were typically abundant in most samples investigated. Anthocyanins formed the dominating group of phenolics in most dark-colored berries but phenolic acid derivatives were equally abundant in saskatoon and chokeberry berries. Caffeoylquinic acids constituted 80% of the total phenolic content (1664mg/100g f.w.) in bilberry leaves. B-type procyanidins and caffeoylquinic acids were the major phenolic compounds in hawthorn and rowanberry, respectively. Use of leaves of some species with prunasin, tyramine and β-p-arbutin, may be limited in food applications.

  19. Effects of ultrasonic processing on degradation of salvianolic acid B in aqueous solution.

    PubMed

    Guo, Y X; Zhang, L; Lu, L; Liu, E H; Shi, C Z

    2016-09-10

    To evaluate the stability of salvianolic acid B (Sal B) under ultrasound-assisted extraction in the pharmaceutical industry, degradation of Sal B under ultrasonic irradiation was investigated as the function of buffer concentration, pH, and temperature. With regard to Sal-B concentration, a first-order degradation process was determined, with 10% change in assay from its initial concentration as t90=4.81h, under maximum stability acidic conditions (pH 2.0) and at 25°C. The logkpH-pH profile described by specific acid-base catalysis and water molecules supported the experimental results. Liquid chromatography-mass spectrometry (LC-MS) analyses revealed 7 major degradation products whose structures were characterized by electrospray ionization/mass spectrometry. A primary degradation pathway involved cleavage of the ester bond and ring-opening of benzofuran in Sal B was proposed. The complete degradation pathway of Sal B was also proposed. Results showed that ultrasonic irradiation leads to degradation of Sal B in aqueous solution.

  20. Removal of boron from aqueous solution using magnetic carbon nanotube improved with tartaric acid

    PubMed Central

    2014-01-01

    Boron removal capacity of multi-walled carbon nanotubes (MWCNTs) modified with tartaric acid was investigated in this study. Modification of MWCNTs with tartaric acid was confirmed by Boehm surface chemistry method and fourier transform infra-red (FT-IR) spectroscopy. Experiments were performed to determine the adsorption isotherm and adsorption thermodynamic parameters of boron adsorption on tartaric acid modified MWCNTs (TA-MWCNTs). The effect of variables including initial pH, dosage of adsorbent, contact time and temperature was investigated. Analysis of data showed that adsorption equilibrium could be better described by Freundlich isotherm and the maximum adsorption capacities obtained at the pH of 6.0 was 1.97 mg/g. The estimated thermodynamic values of free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) indicated a spontaneous and an endothermic process. Furthermore, the TA-MWCNTs was magnetized for separation of boron-contaminated adsorbent from aqueous solution by applying magnetic field. The results showed that magnetic TA-MWCNTs particles were separated effectively after adsorption from contaminated water. PMID:24393401

  1. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    SciTech Connect

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  2. Mineralogy and Organic Geochemistry of Acid Sulfate Environments from Valles Caldera, New Mexico: Habitability, Weathering and Biosignatures

    NASA Astrophysics Data System (ADS)

    Vogel, M. B.; Des Marais, D. J.; Jahnke, L. L.; Kubo, M.

    2009-12-01

    We report on the mineralogy, organic preservation potential and habitability of sulfate deposits in acid sulfate volcanic settings at Valles Caldera, New Mexico. Fumaroles and acidic springs are potential analogs for aqueous environments on Mars and may offer insights into habitability of sulfate deposits such as those at Meridiani Planum. Sulfates recently detected on Mars are posited to have formed from fluids derived from basaltic weathering and igneous volatile input, ultimately precipitating from acidic brines subjected to desiccation and freeze-thaw cycles (McClennan and Grotzinger, 2008). Key issues concerning martian sulfate deposits are their relationship to aqueous clay deposits, and whether or not specific sulfates deposits represent former habitable environments (see Soderblum and Bell, 2008; Tosca et al., 2008). Modern terrestrial volcanic fumaroles and hot springs precipitate various Ca-, Mg- and Fe- sulfates along with clays, and can help clarify whether certain acid sulfate mineral assemblages reflect habitable environments. Valles caldera is a resurgent caldera last active in the Pleistocene (1.4 - 1.0 Ma) that hosts several active fumaroles and over 40 geothermal exploration wells (see Goff, 2009). Fumaroles and associated mudpots and springs at Valles range from pH < 1 to 3, and affect argillic alteration upon rhylolitic tuffs and sedimentary deposits (Charles et al., 1986). We identified assemblages containing gypsum, quartz, Al-sulfates, elemental sulfur, clays and other minerals using XRD and SEM-EDS. Our previous research has shown that sulfates from different marine depositional environments display textural and morphological traits that are indicative of biological influence, or specific conditions in the depositional environments (Vogel et al., 2009). Gypsum crystals that develop in the presence of microbial biofilms in marine environments may have distorted crystal morphologies, biofilm - associated dissolution features, and accessory

  3. Investigation of secondary formation of formic acid: urban environment vs. oil and gas producing region

    NASA Astrophysics Data System (ADS)

    Yuan, B.; Veres, P. R.; Warneke, C.; Roberts, J. M.; Gilman, J. B.; Koss, A.; Edwards, P. M.; Graus, M.; Kuster, W. C.; Li, S.-M.; Wild, R. J.; Brown, S. S.; Dubé, W. P.; Lerner, B. M.; Williams, E. J.; Johnson, J. E.; Quinn, P. K.; Bates, T. S.; Lefer, B.; Hayes, P. L.; Jimenez, J. L.; Weber, R. J.; Zamora, R.; Ervens, B.; Millet, D. B.; Rappenglück, B.; de Gouw, J. A.

    2015-02-01

    Formic acid (HCOOH) is one of the most abundant carboxylic acids in the atmosphere. However, current photochemical models cannot fully explain observed concentrations and in particular secondary formation of formic acid across various environments. In this work, formic acid measurements made at an urban receptor site (Pasadena) in June-July 2010 during CalNex (California Research at the Nexus of Air Quality and Climate Change) and a site in an oil and gas producing region (Uintah Basin) in January-February 2013 during UBWOS 2013 (Uintah Basin Winter Ozone Studies) will be discussed. Although the VOC (volatile organic compounds) compositions differed dramatically at the two sites, measured formic acid concentrations were comparable: 2.3 ± 1.3 in UBWOS 2013 and 2.0 ± 1.0 ppb in CalNex. We determine that concentrations of formic acid at both sites were dominated by secondary formation (> 99%). A constrained box model using the Master Chemical Mechanism (MCM v3.2) underestimates the measured formic acid concentrations drastically at both sites (by a factor of > 10). Compared to the original MCM model that includes only ozonolysis of unsaturated organic compounds and OH oxidation of acetylene, when we updated yields of ozonolysis of alkenes and included OH oxidation of isoprene, vinyl alcohol chemistry, reaction of formaldehyde with HO2, oxidation of aromatics, and reaction of CH3O2 with OH, the model predictions for formic acid were improved by a factor of 6.4 in UBWOS 2013 and 4.5 in CalNex, respectively. A comparison of measured and modeled HCOOH/acetone ratios is used to evaluate the model performance for formic acid. We conclude that the modified chemical mechanism can explain 19 and 45% of secondary formation of formic acid in UBWOS 2013 and CalNex, respectively. The contributions from aqueous reactions in aerosol and heterogeneous reactions on aerosol surface to formic acid are estimated to be 0-6 and 0-5% in UBWOS 2013 and CalNex, respectively. We observe that

  4. Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

    USGS Publications Warehouse

    Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.

    1993-01-01

    Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

  5. Chemistry in the Venus clouds: Sulfuric acid reactions and freezing behavior of aqueous liquid droplets

    NASA Astrophysics Data System (ADS)

    Delitsky, M. L.; Baines, K. H.

    2015-11-01

    Venus has a thick cloud deck at 40-70 km altitude consisting of liquid droplets and solid particles surrounded by atmospheric gases. The liquid droplets are highly concentrated aqueous solutions of sulfuric acid ranging in concentration from 70-99 wt%. Weight percent drops off with altitude (Imamura and Hashimoto 2001). There will be uptake of atmospheric gases into the droplet solutions and the ratios of gas-phase to liquid-phase species will depend on the Henry’s Law constant for those solutions. Reactions of sulfuric acid with these gases will form products with differing solubilities. For example, uptake of HCl by H2SO4/H2O droplets yields chlorosulfonic acid, ClSO3H (Robinson et al 1998) in solution. This may eventually decompose to thionyl- or sulfuryl chlorides, which have UV absorbances. HF will also uptake, creating fluorosulfonic acid, FSO3H, which has a greater solubility than the chloro- acid. As uptake continues, there will be many dissolved species in the cloudwaters. Baines and Delitsky (2013) showed that uptake will have a maximum at ~62 km and this is very close to the reported altitude for the mystery UV absorber in the Venus atmosphere. In addition, at very strong concentrations in lower altitude clouds, sulfuric acid will form hydrates such as H2SO4.H2O and H2SO4.4H2O which will have very different freezing behavior than sulfuric acid, with much higher freezing temperatures (Carslaw et al, 1997). Using temperature data from Venus Express from Tellmann et al (2009), and changes in H2SO4 concentrations as a function of altitude (James et al 1997), we calculate that freezing out of sulfuric acid hydrates can be significant down to as low as 56 km altitude. As a result, balloons, aircraft or other probes in the Venus atmosphere may be limited to flying below certain altitudes. Any craft flying at altitudes above ~55 km may suffer icing on the wings, propellers, balloons and instruments which could cause possible detrimental effects (thermal

  6. Understanding the interaction of amorphous calcium polyphosphate with aqueous environments to optimize its use as a localized drug delivery matrix

    NASA Astrophysics Data System (ADS)

    Djogbenou, Nancy

    Amorphous calcium polyphosphate (CPP) shows potential as an implantable drug delivery matrix through a simple gelling protocol that has been shown to eliminate burst release and extend drug release time from the matrix. The nature of the interaction of CPP with aqueous environments and different drugs is not yet well understood. For this reason, CPP samples were manufactured using two different methods: the established gelation protocol, with and without drug, and mixing CPP with different volumes of aqueous solutions to better understand the effect of water exposure on the structural and drug release properties of CPP. Exposure to aqueous systems caused a reduction in the chain length of CPP that was dependant on gel time and mode of exposure. Longer gel times or increased volume of water used during exposure also caused the formation of crystalline material upon drying. In general, drug release was a function of aqueous exposure and the therapeutic agent used. Drug elution studies showed an increase in the burst release of vancomycin (VCM) from CPP gelled for extended periods. When total gel time was 10 hours or below samples that were gelled for only a short time during drug loading performed best. CPP loaded with BSA had a much slower release rate than VCM and appeared to release BSA by a different mechanism. Overall, this thesis shows that CCP drug delivery matrices can be produced with tailored properties simply by controlling processing conditions.

  7. A GREEN CHEMISTRY APPROACH TO PREPARATION OF CORE (FE OR CU)-SHELL (NOBLE METALS) NANOCOMPOSITES USING AQUEOUS ASCORBIC ACID

    EPA Science Inventory

    A greener method to fabricate novel core (Fe or Cu)-shell (noble metals) nanocomposites of transition metals such as Fe and Cu and noble metals such as Au, Pt, Pd, and Ag using aqueous ascorbic acid is described. Transition metal salts such as Cu and Fe were reduced using ascor...

  8. The role of hydrogen bonds in an aqueous solution of acetylsalicylic acid: a molecular dynamics simulation study.

    PubMed

    Donnamaria, Maria Cristina; de Xammar Oro, Juan Roberto

    2011-10-01

    This work focuses on the role of the dynamic hydrogen bonds (HB) formed in an aqueous solution of aspirin using molecular dynamics simulation. The statistics reveal the existence of internal HB that inhibit the rotational movements of the acetyl and the carboxylic acid groups, forcing the molecule to adopt a closed conformer structure in water, and playing an important role in stabilizing this conformation.

  9. Sorption of As(V) from aqueous solution using acid modified carbon black.

    PubMed

    Borah, Dipu; Satokawa, Shigeo; Kato, Shigeru; Kojima, Toshinori

    2009-03-15

    The sorption performance of a modified carbon black was explored with respect to arsenic removal following batch equilibrium technique. Modification was accomplished by refluxing the commercial carbon black with an acid mixture comprising HNO(3) and H(2)SO(4). Modification resulted in the substantial changes to the inherent properties like surface chemistry and morphology of the commercial carbon black to explore its potential as sorbent. The suspension pH as well as the point of zero charge (pH(pzc)) of the material was found to be highly acidic. The material showed excellent sorption performance for the removal of arsenic from a synthetic aqueous solution. It removed approximately 93% arsenic from a 50mg/L solution at equilibration time. The modified carbon black is capable of removing arsenic in a relatively broad pH range of 3-6, invariably in the acidic region. Both pseudo-first-order and second-order kinetics were applied to search for the best fitted kinetic model to the sorption results. The sorption process is best described by the pseudo-second-order kinetic. It has also been found that intra-particle diffusion is the rate-controlling step for the initial phases of the reaction. Modelling of the equilibrium data with Freundlich and Langmuir isotherms revealed that the correlation coefficient is more satisfactory with the Langmuir model although Freundlich model predicted a good sorption process. The sorption performance has been found to be strongly dependent on the solution pH with a maximum display at pH of 5.0. The temperature has a positive effect on sorption increasing the extent of removal with temperature up to the optimum temperature. The sorption process has been found to be spontaneous and endothermic in nature, and proceeds with the increase in randomness at the solid-solution interface. The spent sorbent was desorbed with various acidic and basic extracting solutions with KOH demonstrating the best result ( approximately 85% desorption).

  10. UV – INDUCED SYNTHESIS OF AMINO ACIDS FROM AQUEOUS STERILIZED SOLUTION OF AMMONIUM FORMATE AND AMMONIA UNDER HETROGENEOUS CONDITIONS

    PubMed Central

    Bisht, G.; Bisht, L. S.

    1990-01-01

    Irradiation of sterilized aqueous solution of ammonium formate and ammonia with UV light in the presence and or absence of certain inorganic sensitizers for 25 hrs. gave six ninhydrin positive products in appreciable amounts. Out of the six products observed fiver were characterized as lysine, serine, glutemic acid, n-amino butyric acid and leucine. The sensitizing effect of additives on ammonium formate was observed in the order; uranium oxide > ammonium formate > ferric oxide > arsenic oxide. PMID:22556511

  11. Electrochemical treatment of acidic aqueous ferrous sulfate and copper sulfate as models for acid mine drainage.

    PubMed

    Bunce, N J; Chartrand, M; Keech, P

    2001-12-01

    Acid mine drainage (AMD) is a serious environmental problem in the mining industry. The present work describes electrolytic reduction of solutions of synthetic AMD, comprising FeSO4/H2SO4 and CuSO4/H2SO4, in flow-through cells whose anode and cathode compartments were separated using ion exchange membranes. In the case of FeSO4/H2SO4 at constant flow rate, the pH of the effluent from the catholyte increased progressively with current at a variety of cathodes, due to electrolytic reduction of H+ ions to elemental hydrogen. Near-quantitative removal of iron was achieved by sparging air into the catholyte effluent, thereby precipitating iron outside the electrochemical cell, and avoiding fouling of the electrodes. The anode reaction was the oxidation of water to O2, a proton-releasing process. Using cation exchange membranes and sodium sulfate as the supporting electrolyte in the anode compartment, the efficiency of the process was compromised at high currents by transport of H+ competitively with Na+ from the anode to the cathode compartments. Higher efficiencies were obtained when anion exchange membranes were used, and in this case no additional supporting electrolyte other than dilute H2SO4 was needed, the net reaction being the electrochemically driven transfer of the elements of H2SO4 from the cathode to the anode compartments. Current efficiencies approximately 50% were achieved, the loss of efficiency being accounted for by ohmic heating of the solutions. In the case of CuSO4/H2SO4 and anion exchange membranes at high currents, reduction of Cu2+ and H+ ions and transport of SO4(2-) ions out of the catholyte caused unacceptably high potentials to be generated.

  12. Removal of Cr(VI) from Aqueous Environments Using Micelle-Clay Adsorption

    PubMed Central

    Qurie, Mohannad; Khamis, Mustafa; Manassra, Adnan; Ayyad, Ibrahim; Nir, Shlomo; Scrano, Laura; Bufo, Sabino A.; Karaman, Rafik

    2013-01-01

    Removal of Cr(VI) from aqueous solutions under different conditions was investigated using either clay (montmorillonite) or micelle-clay complex, the last obtained by adsorbing critical micelle concentration of octadecyltrimethylammonium ions onto montmorillonite. Batch experiments showed the effects of contact time, adsorbent dosage, and pH on the removal efficiency of Cr(VI) from aqueous solutions. Langmuir adsorption isotherm fitted the experimental data giving significant results. Filtration experiments using columns filled with micelle-clay complex mixed with sand were performed to assess Cr(VI) removal efficiency under continuous flow at different pH values. The micelle-clay complex used in this study was capable of removing Cr(VI) from aqueous solutions without any prior acidification of the sample. Results demonstrated that the removal effectiveness reached nearly 100% when using optimal conditions for both batch and continuous flow techniques. PMID:24222757

  13. Removal of Cr(VI) from aqueous environments using micelle-clay adsorption.

    PubMed

    Qurie, Mohannad; Khamis, Mustafa; Manassra, Adnan; Ayyad, Ibrahim; Nir, Shlomo; Scrano, Laura; Bufo, Sabino A; Karaman, Rafik

    2013-01-01

    Removal of Cr(VI) from aqueous solutions under different conditions was investigated using either clay (montmorillonite) or micelle-clay complex, the last obtained by adsorbing critical micelle concentration of octadecyltrimethylammonium ions onto montmorillonite. Batch experiments showed the effects of contact time, adsorbent dosage, and pH on the removal efficiency of Cr(VI) from aqueous solutions. Langmuir adsorption isotherm fitted the experimental data giving significant results. Filtration experiments using columns filled with micelle-clay complex mixed with sand were performed to assess Cr(VI) removal efficiency under continuous flow at different pH values. The micelle-clay complex used in this study was capable of removing Cr(VI) from aqueous solutions without any prior acidification of the sample. Results demonstrated that the removal effectiveness reached nearly 100% when using optimal conditions for both batch and continuous flow techniques.

  14. Biosorption of methyl blue onto tartaric acid modified wheat bran from aqueous solution.

    PubMed

    Yao, Shuhua; Lai, Hong; Shi, Zhongliang

    2012-12-05

    Tartaric acid modified wheat bran was utilized as adsorbent to remove methyl blue, a basic dye from aqueous solution. Batch experiments were carried out to study the effect of various experimental parameters such as initial solution pH, contact time, initial dye concentration and adsorbent dosage, on dye adsorption. The results showed that the modification of wheat bran by tartaric acid significantly improved its adsorption capacity, and made this material a suitable adsorbent to remove methyl blue. The adsorption capacity of modified wheat bran was about 1.6 times higher than that of unmodified one. The amount of methyl blue adsorbed was found to vary with initial solution pH, adsorbent dosage, contact time and initial methyl blue concentration. Kinetics study showed that the overall adsorption rate of methyl blue was illustrated by pseudo-second-order kinetic model. The applicability of the Langmuir and Freundlich models for the data was tested. Both models adequately described the experimental data of the biosorption of methyl blue. The maximum adsorption capacity for methyl blue calculated from Langmuir model was 25.18 mg/g. The study has shown the effectiveness of modified wheat bran in the removal of methyl blue, and that it can be considered as an attractive alternative to the more expensive technologies used in wastewater treatment.

  15. Adsorption of Acid Red 57 from aqueous solutions onto polyacrylonitrile/activated carbon composite.

    PubMed

    El-Bindary, Ashraf A; Diab, Mostafa A; Hussien, Mostafa A; El-Sonbati, Adel Z; Eessa, Ahmed M

    2014-04-24

    The adsorption of Acid Red 57 (AR57) onto Polyacrylonitrile/activated carbon (PAN/AC) composite was investigated in aqueous solution in a batch system with respect to contact time, pH and temperature. Physical characteristics of (PAN/AC) composite such as fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) were obtained. Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The activation energy of adsorption was also evaluated for the adsorption of AR57 onto (PAN/AC) composite. The pseudo-first-order and pseudo-second-order kinetic models were used to describe the kinetic data. The dynamic data fitted the pseudo-second-order kinetic model well. The activation energy, change of free energy, enthalpy and entropy of adsorption were also evaluated for the adsorption of AR57 onto (PAN/AC) composite. The thermodynamics of the adsorption indicated spontaneous and exothermic nature of the process. The results indicate that (PAN/AC) composite could be employed as low-cost material for the removal of acid dyes from textile effluents.

  16. Biosorption of methyl blue onto tartaric acid modified wheat bran from aqueous solution

    PubMed Central

    2012-01-01

    Tartaric acid modified wheat bran was utilized as adsorbent to remove methyl blue, a basic dye from aqueous solution. Batch experiments were carried out to study the effect of various experimental parameters such as initial solution pH, contact time, initial dye concentration and adsorbent dosage, on dye adsorption. The results showed that the modification of wheat bran by tartaric acid significantly improved its adsorption capacity, and made this material a suitable adsorbent to remove methyl blue. The adsorption capacity of modified wheat bran was about 1.6 times higher than that of unmodified one. The amount of methyl blue adsorbed was found to vary with initial solution pH, adsorbent dosage, contact time and initial methyl blue concentration. Kinetics study showed that the overall adsorption rate of methyl blue was illustrated by pseudo-second-order kinetic model. The applicability of the Langmuir and Freundlich models for the data was tested. Both models adequately described the experimental data of the biosorption of methyl blue. The maximum adsorption capacity for methyl blue calculated from Langmuir model was 25.18 mg/g. The study has shown the effectiveness of modified wheat bran in the removal of methyl blue, and that it can be considered as an attractive alternative to the more expensive technologies used in wastewater treatment. PMID:23369295

  17. Removal of humic acid from aqueous solution by cetylpyridinium bromide modified zeolite.

    PubMed

    Zhan, Yanhui; Zhu, Zhiliang; Lin, Jianwei; Qiu, Yanling; Zhao, Jianfu

    2010-01-01

    Natural zeolite was modified by loading cetylpyridinium bromide (CPB) to create more efficient sites for humic acid (HA) adsorption. The natural and CPB modified zeolites were characterized with X-ray diffraction, field emission scanning electron microscopy, Fourier transform infrared spectroscopy and elemental analysis. The effects of various experimental parameters such as contact time, initial HA concentration, solution pH and coexistent Ca2+, upon HA adsorption onto CPB modified zeolites were evaluated. The results showed that natural zeolite had negligible affinity for HA in aqueous solutions, but CPB modified zeolites exhibited high adsorption efficiency for HA. A higher CPB loading on natural zeolites exhibited a larger HA adsorption capacity. Acidic pH and coexistent Ca2+ were proved to be favorable for HA adsorption onto CPB modified zeolite. The kinetic process was well described by pseudo second-order model. The experimental isotherm data fitted well to Langmuir and Sips models. The maximum monolayer adsorption capacity of CPB modified zeolite with surfactant bilayer coverage was found to be 92.0 mg/g.

  18. Determination of acidity constants of sparingly soluble drugs in aqueous solution by the internal standard capillary electrophoresis method.

    PubMed

    Cabot, Joan Marc; Fuguet, Elisabet; Rosés, Martí

    2014-12-01

    A set of 33 drugs with different solubilities, ranging from soluble to very insoluble, has been chosen in order to evaluate the performance of the internal standard CE method to determine acidity constants of compounds with limited solubility. The set of drugs tested in this work has been chosen as a function of their intrinsic solubility. For the most insoluble compounds, several analytical conditions to overcome the insolubility in aqueous buffers have been tested. This paper assesses the compound solubility limits for the IS-CE method in aqueous pKa determinations, and also compares the determined pKa s with the results from the literature data obtained by other methods. It is proved that IS-CE method determines acidity constants of sparingly soluble drugs in aqueous media (compounds with logS down to around -6), whereas other reference methods require the use of aqueous-organic solvent buffers and extrapolation procedures to obtain the aqueous pKa for the same compounds.

  19. Formation of 4(5)-Methylimidazole in Aqueous d-Glucose-Amino Acids Model System.

    PubMed

    Karim, Faris; Smith, J Scott

    2016-01-01

    The International Agency for Research on Cancer (IRAC) has classified 4(5)-methylimidazole (4-MeI) as a group 2B possible human carcinogen. Thus, how 4-MeI forms in a D-glucose (Glu) amino acids (AA) model system is important, as it is how browning is affected. An aqueous solution of Glu was mixed individually in equimolar amounts at 3 concentrations (0.05, 0.1, and 0.15 M) with aqueous solutions of L-Alanine (Ala), L-Arginine (Arg), Glycine (Gly), L-Lysine (Lys), and L-Serine (Ser). The Glu-AA mixtures were reacted at 60, 120, and 160 °C for 1 h. The 4-MeI levels were measured by gas chromatography-mass spectrometry after derivatization with isobutylchloroformate. No 4-MeI was formed at 60 °C for any treatment combination; however, at 120 °C and 0.05 M, Glu-Arg and Glu-Lys produced 0.13 and 0.14 mg/kg of 4-MeI. At 160 °C and 0.05 M all treatment combinations formed 4-MeI. At 160 °C and 0.15 M, the observed levels of Glu-Ala, Glu-Arg, Glu-Gly, Glu-Lys, and Glu-Ser were 0.21, 1.00, 0.15, 0.22, and 0.16 mg/kg. The AA type, reactant concentrations, and temperature significantly affected (P < 0.001) formation of 4-MeI as well as browning. Glu-Lys treatment in all combinations produced the most browning, but Glu-Arg produced the most 4-MeI. This method showed that foods processed using low temperatures may have reduced levels of 4-MeI.

  20. Novel acid resistance genes from the metagenome of the Tinto River, an extremely acidic environment.

    PubMed

    Guazzaroni, María-Eugenia; Morgante, Verónica; Mirete, Salvador; González-Pastor, José E

    2013-04-01

    Microorganisms that thrive in acidic environments are endowed with specialized molecular mechanisms to survive under this extremely harsh condition. In this work, we performed functional screening of six metagenomic libraries from planktonic and rhizosphere microbial communities of the Tinto River, an extremely acidic environment, to identify genes involved in acid resistance. This approach has revealed 15 different genes conferring acid resistance to Escherichia coli, most of which encoding putative proteins of unknown function or previously described proteins not known to be related to acid resistance. Moreover, we were able to assign function to one unknown and three hypothetical proteins. Among the recovered genes were the ClpXP protease, the transcriptional repressor LexA and nucleic acid-binding proteins such as an RNA-binding protein, HU and Dps. Furthermore, nine of the retrieved genes were cloned and expressed in Pseudomonas putida and Bacillus subtilis and, remarkably, most of them were able to expand the capability of these bacteria to survive under severe acid stress. From this set of genes, four presented a broad-host range as they enhance the acid resistance of the three different organisms tested. These results expand our knowledge about the different strategies used by microorganisms to survive under extremely acid conditions.

  1. On the vibrational behavior of single- and double-walled carbon nanotubes under the physical adsorption of biomolecules in the aqueous environment: a molecular dynamics study.

    PubMed

    Ajori, S; Ansari, R; Darvizeh, M

    2016-03-01

    The adsorption of biomolecules on the walls of carbon nanotubes (CNTs) in an aqueous environment is of great importance in the field of nanobiotechnology. In this study, molecular dynamics (MD) simulations were performed to understand the mechanical vibrational behavior of single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) under the physical adsorption of four important biomolecules (L-alanine, guanine, thymine, and uracil) in vacuum and an aqueous environment. It was observed that the natural frequencies of these CNTs in vacuum reduce under the physical adsorption of biomolecules. In the aqueous environment, the natural frequency of each pure CNT decreased as compared to its natural frequency in vacuum. It was also found that the frequency shift for functionalized CNTs as compared to pure CNTs in the aqueous environment was dependent on the radius and the number of walls of the CNT, and could be positive or negative.

  2. Partial molar volumes of some alpha-amino acids in aqueous sodium acetate solutions at 308.15 K.

    PubMed

    Wang, J; Yan, Z; Zhuo, K; Lu, J

    1999-08-30

    The apparent molar volumes V(2,phi) have been determined for glycine, DL-alpha-alanine, DL-alpha-amino-n-butyric acid, DL-valine and DL-leucine in aqueous solutions of 0.5, 1.0, 1.5 and 2.0 mol kg(-1) sodium acetate by density measurements at 308.15 K. These data have been used to derive the infinite dilution apparent molar volumes V(0)(2,phi) for the amino acids in aqueous sodium acetate solutions and the standard volumes of transfer, Delta(t)V(0), of the amino acids from water to aqueous sodium acetate solutions. It has been observed that both V(0)(2,phi) and Delta(t)V(0) vary linearly with increasing number of carbon atoms in the alkyl chain of the amino acids. These linear correlations have been utilized to estimate the contributions of the charged end groups (NH(3)(+), COO(-)), CH(2) group and other alkyl chains of the amino acids to V(0)(2,phi) and Delta(t)V(0). The results show that V(0)(2,phi) values for (NH(3)(+), COO(-)) groups increase with sodium acetate concentration, and those for CH(2) are almost constant over the studied sodium acetate concentration range. The transfer volume increases and the hydration number of the amino acids decreases with increasing electrolyte concentrations. These facts indicate that strong interactions occur between the ions of sodium acetate and the charged centers of the amino acids. The volumetric interaction parameters of the amino acids with sodium acetate were calculated in water. The pair interaction parameters are found to be positive and decreased with increasing alkyl chain length of the amino acids, suggesting that sodium acetate has a stronger dehydration effect on amino acids which have longer hydrophobic alkyl chains. These phenomena are discussed by means of the co-sphere overlap model.

  3. Acidic pH environment induces autophagy in osteoblasts

    PubMed Central

    Zhang, Zhichao; Lai, Qingguo; Li, Yanan; Xu, Chao; Tang, Xiaopeng; Ci, Jiangbo; Sun, Shaolong; Xu, Bingbing; Li, Yan

    2017-01-01

    Osteoblasts (OBs) play an important role in bone fracture healing, yet the extreme adverse microenvironment in fracture sites has a negative impact on the survival of OBs. Therefore, it is important to study how OBs behave in the complex fracture microenvironment. Studies have shown that autophagy plays a pivotal role in maintaining cellular homeostasis and defending the cell against adverse microenvironments. In this study we found the induction of autophagy in OBs at femoral bone fracture sites, which may be a result of ischemia, oxidative stress and hypoxia within the local area. At fracture sites a low pH environment also developed. Until now it has been unclear whether the induction of autophagy in osteoblasts is triggered by the acidic pH environment. Therefore, we cultured OBs in vitro in media of different pH values, and found both autophagy and apoptosis increased in OBs in acidic conditions. However, when autophagy inhibitor chloroquine (CQ) was used, apoptosis increased significantly compared with that without CQ. Thus indicating that inhibition of autophagy may promote apoptosis in OBs in an acidic environment, which may provide a new therapeutic strategy to decrease cell apoptosis in OBs through the use of drugs that modulate the autophagic state. PMID:28382973

  4. Surface Hydrophilicity and Functional Group-Driven Iron(III) Hydroxide Nucleation on Organic-Coated Substrates in Aqueous Environments

    NASA Astrophysics Data System (ADS)

    Ray, J.; Lee, B.; Baltrusaitis, J.; Jun, Y.

    2012-12-01

    Homogeneous and heterogeneous iron hydroxide nanoparticle nucleation can occur continuously in both natural and complex aqueous systems. Iron oxide nanoparticles can act as sinks and/or carriers for heavy metal contaminants; therefore, it is important to develop a better understanding of factors affecting their formation. Organic coatings are ubiquitous in aqueous environments where they can exist on mineral surfaces (e.g., biofilm), as nanoparticle surface coatings (e.g., natural organic matter), or be introduced as coagulants in water treatment systems. These surface coatings could influence the formation of iron oxide nanoparticles and thus, the mobility of aqueous contaminants. Therefore, to better understand the fate and transport of contaminants in complex aqueous environments, we need more accurate information about mechanisms governing heterogeneous and homogeneous nucleation and growth of iron(III) hydroxide nanoparticles in the presence of organic surface coatings. In this work, we used a unique measurement technique allowing for simultaneous small-angle X-ray scattering (SAXS) and grazing incidence (GISAXS) analysis to monitor nanoparticle nucleation in solution and at substrate surfaces. Clean quartz, and polyaspartate- and alginate-coated substrates were chosen as model substrates to represent mineral coatings, engineered organic coatings and natural organic coatings. Polyaspartate was determined to be the most negatively charged substrate and quartz to be the least negatively charged substrate; however, after 2 h of reaction, the total nanoparticle volume calculations—determined from GISAXS—indicate that precipitation of positively-charged iron(III) hydroxide nanoparticles is 10 times higher on the quartz substrate than on the polyaspartate substrate. This implies that electrostatics do not govern iron(III) hydroxide nucleation. Furthermore, homogeneous nucleation approximately 250 μm above the substrate surface was highest in the presence of the

  5. MODELING SMALL-SCALE SPILLS OF AQUEOUS SOLUTIONS IN THE INDOOR ENVIRONMENT

    EPA Science Inventory

    A mass transfer model is proposed to estimate the rates of chemical emissions from aqueous solutions spilled on hard surfaces inside buildings. The model is presented in two forms: a set of four ordinary differential equations and a simplified exact solution. The latter can be ...

  6. Adsorption of chloridazon from aqueous solution on heat and acid treated sepiolites.

    PubMed

    González-Pradas, E; Socías-Viciana, M; Ureña-Amate, M D; Cantos-Molina, A; Villafranca-Sánchez, M

    2005-05-01

    The adsorption of chloridazon on heat treated sepiolite samples at 110 degrees C (S-110), 200 degrees C (S-200), 400 degrees C (S-400), 600 degrees C (S-600) and acid treated samples with H2SO4 solutions of two different concentrations (0.25 and 1.0M) (S-0.25 and S-1.0, respectively) from pure water at 25 degrees C has been studied by using batch experiments. In addition, column experiments were carried out with the natural (S-110) and 600 degrees C (S-600) heat treated samples, using a 10.30 mg l-1 aqueous solution of chloridazon. The adsorption experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (Kf) of the samples; Kf values range from 2.89 mg kg-1 for the S-1.0 sample up to 164 mg kg-1 for the S-600 sample; so, the heat treatment given to the sepiolite greatly increases its adsorption capacity for the herbicide chloridazon whereas the acid treatment produces a clear decrease in the amount of chloridazon adsorbed. The removal efficiency (R) has also been calculated; R values ranging from 5.08% for S-1.0 up to 60.9% for S-600. The batch experiments showed that the strongest heat treatment is more effective than the natural and acid treated sepiolite in relation to adsorption of chloridazon. The column experiments also showed that 600 degrees C heat treated sepiolite might be reasonably used in removing chloridazon from water. Thus, as this type of clay is relatively plentiful, these activated samples might be reasonably used in order to remove chloridazon from water.

  7. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments.

    PubMed

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  8. Energetics of Amino Acid Synthesis in Alkaline Hydrothermal Environments

    NASA Astrophysics Data System (ADS)

    Kitadai, Norio

    2015-12-01

    Alkaline hydrothermal systems have received considerable attention as candidates for the origin and evolution of life on the primitive Earth. Nevertheless, sufficient information has not yet been obtained for the thermodynamic properties of amino acids, which are necessary components for life, at high temperatures and alkaline pH. These properties were estimated using experimental high-temperature volume and heat capacity data reported in the literature for several amino acids, together with correlation algorithms and the revised Helgeson-Kirkham-Flowers (HKF) equations of state. This approach enabled determination of a complete set of the standard molal thermodynamic data and the revised HKF parameters for the 20 protein amino acids in their zwitterionic and ionization states. The obtained dataset was then used to evaluate the energetics of amino acid syntheses from simple inorganic precursors (CO2, H2, NH3 and H2S) in a simulated alkaline hydrothermal system on the Hadean Earth. Results show that mixing between CO2-rich seawater and the H2-rich hydrothermal fluid can produce energetically favorable conditions for amino acid syntheses, particularly in the lower-temperature region of such systems. Together with data related to the pH and temperature dependences of the energetics of amino acid polymerizations presented in earlier reports, these results suggest the following. Hadean alkaline hydrothermal settings, where steep pH and temperature gradients may have existed between cool, slightly acidic Hadean ocean water and hot, alkaline hydrothermal fluids at the vent-ocean interface, may be energetically the most suitable environment for the synthesis and polymerization of amino acids.

  9. Synthesis, characterization and adsorption properties of diethylenetriamine-modified hypercrosslinked resins for efficient removal of salicylic acid from aqueous solution.

    PubMed

    Huang, Jianhan; Jin, Xiaoying; Mao, Jinglin; Yuan, Bin; Deng, Rujie; Deng, Shuguang

    2012-05-30

    We report an effective approach for tailoring the pore textural properties and surface polarity of a hypercrosslinked resin to enhance its adsorption capacity and selectivity for removing salicylic acid from aqueous solution. Four hypercrosslinked resins were synthesized by controlling the reaction time of the self Friedel-Crafts reaction of chloromethylated polystyrene-co-divinylbenzene, and then modified with diethylenetriamine to adjust their surface polarity. The resins were characterized with N(2) adsorption for pore textural properties, Fourier transform infrared spectroscopy (FT-IR) for surface functional groups, chemical analysis for residual chlorine content and weak basic exchange capacity. Adsorption equilibrium, kinetics and breakthrough performance were determined for the removal of salicylic acid from aqueous solution on a selected resin HJ-M01. The equilibrium adsorption capacity of salicylic acid on HJ-M01 is significantly higher than that on its precursor HJ-11 and a few commercial adsorbents including AB-8, XAD-4 and XAD-7. The dynamic adsorption capacity of salicylic acid on HJ-M01 was found to be 456.4 mg/L at a feed concentration of 1000 mg/L and 294 K. The used resin could be fully regenerated with 1% sodium hydroxide solution. The hypercrosslinked resins being developed were promising alternatives to commercial adsorbents for removing salicylic acid and other volatile organic compounds (VOCs) from aqueous solution.

  10. Effects of low molecular weight organic acids on the immobilization of aqueous Pb(II) using phosphate rock and different crystallized hydroxyapatite.

    PubMed

    Wei, Wei; Cui, Jing; Wei, Zhenggui

    2014-06-01

    Understanding the effects of low molecular weight organic acids (LMWOAs) on the transformation of Pb(II) to geochemically stable pyromorphite (PY) by apatite materials (AMs), has considerable benefits for risk assessment and remediation strategies for contaminated water and soil. In this study, we systematically investigated the immobilization of Pb(II) from aqueous solution by natural phosphate rock (PR) and different crystallized hydroxyapatite (HAp) in the absence and presence of LMWOAs (oxalic, malic and citric acids). The results indicated that the effectiveness of PR and HAp in immobilizing Pb(II) followed in descending order by HAp2 (the poorly crystallized HAp), HAp1 (the well crystallized HAp) and PR, regardlessof the presence of LMWOAs. The presence of malic and citric acids significantly decreased the immobilizationefficiency of Pb(II) by HAp1 and PR, clarifying the lower adsorption affinities of Pb(II)-organic acid complexes on HAp1 and PR rather than Pb(II) ion. On thecontrary, oxalic acid could markedly enhance the removal of Pb(II) from aqueous solution by HAp1 and PR through the formation of lead oxalate, which was confirmed by FT-IR and XRDanalysis. Results also showed that LMWOAs had little promoting or inhibiting effect on the immobilization of Pb(II) by HAp2. This study suggested that the ubiquity of LMWOAs in natural environments could retard the transformation efficiency of Pb(II) to PY by AMs, especiallyin thepresenceof oxalic acid, and the poorly crystallized HAp2 had great potential to remediate Pb(II)-contaminated water and soil due to its insusceptibility to LMWOAs.

  11. Peptide synthesis in aqueous environments: the role of extreme conditions on peptide bond formation and peptide hydrolysis.

    PubMed

    Schreiner, Eduard; Nair, Nisanth N; Marx, Dominik

    2009-09-30

    The mechanisms and free energetics underlying the formation of peptides from alpha-amino acids and alpha-amino acid N-carboxyanhydrides (NCAs) in bulk water at both ambient and extreme temperature and pressure conditions were investigated using accelerated ab initio molecular dynamics. In particular, peptide bond formation using an activated amino acid in form of its NCA, subsequent decarboxylation, as well as hydrolysis of the formed peptide were studied using glycine. It is shown to what extent thermodynamic conditions affect the reaction mechanisms qualitatively and the energetics quantitatively in solution. In particular, the zwitterionic intermediate in the peptidization step found in ambient water degenerates into a transient species in hot-pressurized water, whereas the hydrolysis reaction is found to follow qualitatively different pathways at ambient and extreme conditions. The work also quantifies the impact of extreme solvent conditions on both peptide bond formation and peptide hydrolysis in aqueous media. Beyond the specific case, the results provide important insights into how elevated temperatures and increased pressures affect organic reactions in aqueous solutions.

  12. A CALPHAD study on the thermodynamic stability of calcium-, zinc-, and yttrium-doped magnesium in aqueous environments

    SciTech Connect

    Wu, Kaisheng; Dogan, Omar N.; Velikokhatnyl, Oleg I.; Kumta, Prashant N.

    2011-12-15

    Magnesium has attracted the attention of the biomaterials community as a potential biodegradable metallic candidate for use in stents and orthopedic applications. Alloying of Mg with metals such as Ca, Y and Zn, etc., to form alloy precursors is important to optimize its corrosion rate in electrolytic and aqueous environments to understand the alloy response in body fluid environments. In the current study, the chemical reactions of Mg–Me alloys (Me = Ca, Y, and Zn) with pure water have been investigated using the CALPHAD technique. A qualitative agreement between CALPHAD and first-principles results has been obtained. The CALPHAD method has also been employed to study the reactions of Mg alloys in the human blood fluid environment. The effects of alloying elements and compositions on the reaction enthalpies, reaction products, amount of gas release and gas compositions as well as the pH of the fluids have been systematically discussed and reported.

  13. A CALPHAD Study on the Thermodynamic Stability of Calcium-, Zinc-, and Yttrium-Doped Magnesium in Aqueous Environments

    SciTech Connect

    Wu, Kaisheng

    2011-12-15

    Magnesium has attracted the attention of the biomaterials community as a potential biodegradable metallic candidate for use in stents and orthopedic applications. Alloying of Mg with metals such as Ca, Y and Zn, etc., to form alloy precursors is important to optimize its corrosion rate in electrolytic and aqueous environments to understand the alloy response in body fluid environments. In the current study, the chemical reactions of Mg–Me alloys (Me = Ca, Y, and Zn) with pure water have been investigated using the CALPHAD technique. A qualitative agreement between CALPHAD and first-principles results has been obtained. The CALPHAD method has also been employed to study the reactions of Mg alloys in the human blood fluid environment. The effects of alloying elements and compositions on the reaction enthalpies, reaction products, amount of gas release and gas compositions as well as the pH of the fluids have been systematically discussed and reported.

  14. Experimental and Theoretical Studies of the Acid-Catalyzed Conversion of Furfuryl Alcohol to Levulinic Acid in Aqueous Solution

    SciTech Connect

    Gonzalez Maldonado, Gretchen M.; Assary, Rajeev S.; Dumesic, James A.; Curtiss, Larry A.

    2012-02-14

    The conversion of furfuryl alcohol (FAL) to levulinic acid over Amberlyst TM 15 in aqueous media was investigated using a combination of liquid chromatography-mass spectrometry (LC-MS) measurements, isotopic labeling studies, nuclear magnetic resonance (NMR) spectroscopy, and ab initio quantum chemical calculations using the G4MP2 method. The results of these combined studies showed that one of the major reaction pathways takes place via a geminal diol species (4,5,5- trihydroxypentan-2-one, denoted as intermediate A), formed by the addition of two water molecules to FAL, where two of the oxygen atoms from FAL are retained. This geminal diol species can also be produced from another intermediate found to be a dimer-like species, denoted as intermediate B. This dimer-like species is formed at the early stages of reaction, and it can also be converted to intermediate A, indicating that intermediate B is the product of the reaction of FAL with another early intermediate. Quantum chemical calculations suggested this to be a protonated acyclic species. Reaction of this early intermediate with water produces intermediate A, while reaction with FAL produces intermediate B.

  15. Experimental and Theoretical Studies of the Acid-Catalyzed Conversion of Furfuryl Alcohol to Levulinic Acid in Aqueous Solution

    SciTech Connect

    González Maldonado, Gretchen M.; Assary, Rajeev S.; Dumesic, James; Curtiss, Larry A.

    2012-01-01

    The conversion of furfuryl alcohol (FAL) to levulinic acid over AmberlystTM 15 in aqueous media was investigated using a combination of liquid chromatography-mass spectrometry (LC-MS) measurements, isotopic labeling studies, nuclear magnetic resonance (NMR) spectroscopy, and ab initio quantum chemical calculations using the G4MP2 method. The results of these combined studies showed that one of the major reaction pathways takes place via a geminal diol species (4,5,5-trihydroxypentan-2-one, denoted as intermediate A), formed by the addition of two water molecules to FAL, where two of the oxygen atoms from FAL are retained. This geminal diol species can also be produced from another intermediate found to be a dimer-like species, denoted as intermediate B. This dimer-like species is formed at the early stages of reaction, and it can also be converted to intermediate A, indicating that intermediate B is the product of the reaction of FAL with another early intermediate. Quantum chemical calculations suggested this to be a protonated acyclic species. Reaction of this early intermediate with water produces intermediate A, while reaction with FAL produces intermediate B.

  16. Lewis Acid Pairs for the Activation of Biomass-derived Oxygenates in Aqueous Media

    SciTech Connect

    Roman, Yuriy

    2015-09-14

    The objective of this project is to understand the mechanistic aspects behind the cooperative activation of oxygenates by catalytic pairs in aqueous media. Specifically, we will investigate how the reactivity of a solid Lewis acid can be modulated by pairing the active site with other catalytic sites at the molecular level, with the ultimate goal of enhancing activation of targeted functional groups. Although unusual catalytic properties have been attributed to the cooperative effects promoted by such catalytic pairs, virtually no studies exist detailing the use heterogeneous water-tolerant Lewis pairs. A main goal of this work is to devise rational pathways for the synthesis of porous heterogeneous catalysts featuring isolated Lewis pairs that are active in the transformation of biomass-derived oxygenates in the presence of bulk water. Achieving this technical goal will require closely linking advanced synthesis techniques; detailed kinetic and mechanistic investigations; strict thermodynamic arguments; and comprehensive characterization studies of both materials and reaction intermediates. For the last performance period (2014-2015), two technical aims were pursued: 1) C-C coupling using Lewis acid and base pairs in Lewis acidic zeolites. Tin-, zirconium-, and hafnium containing zeolites (e.g., Sn-, Zr-, and Hf-Beta) are versatile solid Lewis acids that selectively activate carbonyl functional groups. In this aim, we demonstrate that these zeolites catalyze the cross-aldol condensation of aromatic aldehydes with acetone under mild reaction conditions with near quantitative yields. NMR studies with isotopically labeled molecules confirm that acid-base pairs in the Si-O-M framework ensemble promote soft enolization through α-proton abstraction. The Lewis acidic zeolites maintain activity in the presence of water and, unlike traditional base catalysts, in acidic solutions. 2) One-pot synthesis of MWW zeolite nanosheets for activation of bulky substrates. Through

  17. One-pot synthesis of amino acid precursors with insoluble organic matter in planetesimals with aqueous activity.

    PubMed

    Kebukawa, Yoko; Chan, Queenie H S; Tachibana, Shogo; Kobayashi, Kensei; Zolensky, Michael E

    2017-03-01

    The exogenous delivery of organic molecules could have played an important role in the emergence of life on the early Earth. Carbonaceous chondrites are known to contain indigenous amino acids as well as various organic compounds and complex macromolecular materials, such as the so-called insoluble organic matter (IOM), but the origins of the organic matter are still subject to debate. We report that the water-soluble amino acid precursors are synthesized from formaldehyde, glycolaldehyde, and ammonia with the presence of liquid water, simultaneously with macromolecular organic solids similar to the chondritic IOM. Amino acid products from hydrothermal experiments after acid hydrolysis include α-, β-, and γ-amino acids up to five carbons, for which relative abundances are similar to those extracted from carbonaceous chondrites. One-pot aqueous processing from simple ubiquitous molecules can thus produce a wide variety of meteoritic organic matter from amino acid precursors to macromolecular IOM in chondrite parent bodies.

  18. One-pot synthesis of amino acid precursors with insoluble organic matter in planetesimals with aqueous activity

    PubMed Central

    Kebukawa, Yoko; Chan, Queenie H. S.; Tachibana, Shogo; Kobayashi, Kensei; Zolensky, Michael E.

    2017-01-01

    The exogenous delivery of organic molecules could have played an important role in the emergence of life on the early Earth. Carbonaceous chondrites are known to contain indigenous amino acids as well as various organic compounds and complex macromolecular materials, such as the so-called insoluble organic matter (IOM), but the origins of the organic matter are still subject to debate. We report that the water-soluble amino acid precursors are synthesized from formaldehyde, glycolaldehyde, and ammonia with the presence of liquid water, simultaneously with macromolecular organic solids similar to the chondritic IOM. Amino acid products from hydrothermal experiments after acid hydrolysis include α-, β-, and γ-amino acids up to five carbons, for which relative abundances are similar to those extracted from carbonaceous chondrites. One-pot aqueous processing from simple ubiquitous molecules can thus produce a wide variety of meteoritic organic matter from amino acid precursors to macromolecular IOM in chondrite parent bodies. PMID:28345041

  19. Modified Mesoporous Silica (SBA–15) with Trithiane as a new effective adsorbent for mercury ions removal from aqueous environment

    PubMed Central

    2014-01-01

    Background Removal of mercury from aqueous environment has been highly regarded in recent years and different methods have been tested for this purpose. One of the most effective ways for mercury ions (Hg+2) removal is the use of modified nano porous compounds. Hence, in this work a new physical modification of mesoporous silica (SBA-15) with 1, 3, 5 (Trithiane) as modifier ligand and its application for the removal of Hg+2 from aqueous environment has been investigated. SBA-15 and Trithiane were synthesized and the presence of ligand in the silica framework was demonstrated by FTIR spectrum. The amounts of Hg+2 in the samples were determined by cold vapor generation high resolution continuum source atomic absorption spectroscopy. Also, the effects of pH, stirring time and weight of modified SBA-15 as three major parameters for effective adsorption of Hg+2 were studied. Results The important parameter for the modification of the adsorbent was Modification ratio between ligand and adsorbent in solution which was 1.5. The results showed that the best Hg+2 removal condition was achieved at pH = 5.0, stirring time 15 min and 15.0 mg of modified adsorbent. Moreover, the maximum percentage removal of Hg+2 and the capacity of adsorbent were 85% and 10.6 mg of Hg+2/g modified SBA-15, respectively. Conclusions To sum up, the present investigation introduced a new modified nano porous compound as an efficient adsorbent for removal of Hg+2 from aqueous environment. PMID:25097760

  20. Aggregation of TiO2-graphene nanocomposites in aqueous environment: Influence of environmental factors and UV irradiation.

    PubMed

    Hua, Zulin; Zhang, Jianan; Bai, Xue; Ye, Zhengfang; Tang, Zhiqiang; Liang, Lu; Liu, Yuqi

    2016-01-01

    The aggregation kinetics of TiO2-graphene nanocomposites in aqueous solution affected by solution pH, salt types (NaCl, CaCl2) and concentrations of electrolytes, and stability induced by UV irradiation was investigated in this study. The zeta potentials and hydrodynamic diameter of the nanoparticles were used as bases to assess the aggregation behavior, and stability of nanocomposites exposed to UV irradiation was expressed in terms of supernatant concentration. The aggregation of TiO2-graphene nanoparticles in aqueous media followed the colloidal theory. TiO2-graphene nanoparticles were significantly aggregated in the presence of a diavalent cation compared with monovalent cation because the former was more capable of effective charge screening and neutralization. The calculated Hamaker constant of the TiO2-graphene nanocomposites in aqueous solution prepared in the lab was 2.31×10(-20)J. The stability of this composite nanoparticles was between those of pure TiO2 and graphene. A known intensity of UV irradiation was beneficial in the formation of TiO2-graphene nanoparticle aggregates. However, prolonged UV irradiation may stabilize the nanoparticles. These results provided critical information about the colloidal properties of the new TiO2-graphene nanocomposites and were useful in predicting the fate and transport of TiO2-graphene nanocomposites in natural water environments.

  1. Unusual red shift of the sensor while detecting the presence of Cd2+ in aqueous environment.

    PubMed

    Sarkar, Santu; Shunmugam, Raja

    2013-08-14

    A norbornene derived 8-hydroxyquinoline (N8HQ) is designed and synthesized. A "turn-on" ratiometric fluorescent response is observed for Cd(2+) in aqueous solution upon binding with N8HQ with a characteristic huge red shift of 164 nm. A lowest detection limit of 1.6 nM of Cd(2+) is achieved in the presence of other heavy metals.

  2. Combination of best promoter and micellar catalyst for chromic acid oxidation of 1-butanol to 1-butanal in aqueous media at room temperature.

    PubMed

    Saha, Rumpa; Ghosh, Aniruddha; Saha, Bidyut

    2014-04-24

    In aqueous acidic media, picolinic acid, 2,2'-bipyridine and 1,10-phenanthroline promoted Cr(VI) oxidation of 1-butanol produces 1-butanal. 1-butanal is separated from mixture by fractional distillation. The anionic surfactant (SDS) and neutral surfactant (TX-100) accelerate the process while the cationic surfactant (CPC) retards the reaction. Combination of bipy and SDS is the best choice for chromic acid oxidation of 1-butanol to 1-butanal in aqueous media.

  3. Hydrocarbon adsorption in an aqueous environment: A computational study of alkyls on Cu(111)

    NASA Astrophysics Data System (ADS)

    Montemore, Matthew M.; Andreussi, Oliviero; Medlin, J. Will

    2016-08-01

    Hydrocarbon chains are important intermediates in various aqueous-phase surface processes, such as CO2 electroreduction, aqueous Fischer-Tropsch synthesis, and aqueous phase reforming of biomass-derived molecules. Further, the interaction between water and adsorbed hydrocarbons represents a difficult case for modern computational methods. Here, we explore various methods for calculating the energetics of this interaction within the framework of density functional theory and explore trade-offs between the use of low water coverages, molecular dynamics approaches, and minima hopping for identification of low energy structures. An effective methodology for simulating low temperature processes is provided by using a unit cell in which the vacuum space is filled with water, employing the minima hopping algorithm to search for low-lying minima, and including dispersion (van der Waals) interactions. Using this methodology, we show that a high coverage of adsorbed alkyls is destabilized by the presence of water, while a low coverage of alkyls is stabilized. Solvation has a small effect on the energetics of hydrocarbon chain growth, generally decreasing its favorability at low temperatures. We studied higher temperatures by running molecular dynamics simulations starting at the minima found by the minima hopping algorithm and found that increased temperatures facilitate chain growth. The self-consistent continuum solvation method effectively describes the alkyl-water interaction and is in general agreement with the explicit solvation results in most cases, but care should be taken at high alkyl coverage.

  4. Adsorption of copper ions from aqueous solution by citric acid modified soybean straw.

    PubMed

    Zhu, Bo; Fan, Tongxiang; Zhang, Di

    2008-05-01

    The objectives of the present study were to convert soybean straw to a metal ion adsorbent and further to investigate the potential of using the adsorbent for the removal of Cu(2+) from aqueous solution. The soybean straw was water or base washed and citric acid (CA) modified to enhance its nature adsorption capacity. The morphological and chemical characteristics of the adsorbent were evaluated by spectroscopy and N(2)-adsorption techniques. The porous structure, as well as high amounts of introduced free carboxyl groups of CA modified soybean straw makes the adsorbent be good to retain Cu(2+). The adsorption capacities increased when the solution pH increased from 2 to 6 and reached the maximum value at pH 6 (0.64 mmol g(-1) for the base washed, CA modified soybean straw (CA-BWSS)). The Cu(2+) uptake increased and percentage adsorption of the Cu(2+) decreased with the increase in initial Cu(2+) concentration from 1 mM to 20 mM. Both the Langmuir and Freundlich adsorption isotherms were tested, and the Freundlich model fited much better than the Langmuir model. It was found that CA-BWSS have the highest adsorption capacity of the four kinds of pretreated soybean straw.

  5. Preparation and characterization of aqueous dispersions of high amylose starch and conjugated linoleic acid complex.

    PubMed

    Seo, Tae-Rang; Kim, Hee-Young; Lim, Seung-Taik

    2016-11-15

    Crystalline starch-CLA complexes were prepared by blending an alcoholic solution of conjugated linoleic acid (CLA) in an aqueous high-amylose maize starch dispersion. Recovery yield of CLA in the precipitates obtained by centrifuging the dispersion was dependent on reaction conditions such as temperature, time and pH. The CLA recovery reached a maximum when the reaction was performed at 90°C for 6h at neutral pH, with 67.7% of the initial CLA being co-precipitated with starch. The precipitates contained amylose-CLA complex exhibiting a V6I-type crystalline structure under X-ray diffraction analysis and a type II polymorph under DSC analysis. Ultrasonic treatment for the re-dispersed starch-CLA complex in water resulted in the reduction of hydrodynamic diameter of the complex particles to 201.5nm. The dispersion exhibited a zeta potential of -27.0mV and remained stable in an ambient storage without forming precipitates for more than 4weeks.

  6. Adsorption removal of tannic acid from aqueous solution by polyaniline: Analysis of operating parameters and mechanism.

    PubMed

    Sun, Chencheng; Xiong, Bowen; Pan, Yang; Cui, Hao

    2017-02-01

    Polyaniline (PANI) prepared by chemical oxidation was studied for adsorption removal of tannic acid (TA) from aqueous solution. Batch adsorption studies were carried out under different adsorbent dosages, pH, ionic strength, initial TA concentration and coexisting anions. Solution pH had an important impact on TA adsorption onto PANI with optimal removal in the pH range of 8-11. TA adsorption on PANI at three ionic strength levels (0.02, 0.2 and 2molL(-1) NaCl) could be well described by Langmuir model (monolayer adsorption process) and the maximum adsorption capacity was 230, 223 and 1023mgg(-1), respectively. Kinetic data showed that TA adsorption on PANI fitted well with pseudo-second-order model (controlled by chemical process). Among the coexisting anions tested, PO4(3-) significantly inhibited TA adsorption due to the enhancement of repulsive interaction. Continuous flow adsorption studies indicated good flexibility and adaptability of the PANI adsorbent under different flow rates and influent TA concentrations. The mechanism controlling TA adsorption onto PANI under different operating conditions was analyzed with the combination of electrostatic interactions, hydrogen bonding, π-π interactions and Van der Waals interactions.

  7. [Mechanism of action of combined extremely weak magnetic field on aqueous solution of amino acid].

    PubMed

    Zhadin, M N; Bakharev, B V; Bobkova, N V

    2014-01-01

    The fundamental physical mechanisms of resonance action of an extremely weak (40 nT) alternating magnetic field at the cyclotron frequency combined with a weak (40 μT) static magnetic field, on living systems are analyzed in the present work. The experimental effects of such sort of magnetic fields were described in different papers: the very narrow resonant peaks in electrical conductivity of the aqueous solutions in the in vitro experiments and the biomedical in vivo effects on living animals of magnetic fields with frequencies tuned to some amino acids. The existing experimental in vitro data had a good repeatability in different laboratories and countries. Unfortunately, for free ions such sort of effects are absolutely impossible because the dimensions of an ion rotation radius should be measured by meters at room temperature and at very low static magnetic fields used in all the above experiments. Even for bound ions these effects should be also absolutely impossible from the positions of classic physics because of rather high viscosity of biological liquid media (blood plasma, cerebrospinal liquid, cytoplasm). Only modern quantum electrodynamics of condensed media opens the new ways for solving these problems. The proposed article is devoted to analysis of quantum mechanisms of these effects.

  8. Aqueous acidities of primary benzenesulfonamides: Quantum chemical predictions based on density functional theory and SMD.

    PubMed

    Aidas, Kęstutis; Lanevskij, Kiril; Kubilius, Rytis; Juška, Liutauras; Petkevičius, Daumantas; Japertas, Pranas

    2015-11-05

    Aqueous pK(a) of selected primary benzenesulfonamides are predicted in a systematic manner using density functional theory methods and the SMD solvent model together with direct and proton exchange thermodynamic cycles. Some test calculations were also performed using high-level composite CBS-QB3 approach. The direct scheme generally does not yield a satisfactory agreement between calculated and measured acidities due to a severe overestimation of the Gibbs free energy changes of the gas-phase deprotonation reaction by the used exchange-correlation functionals. The relative pK(a) values calculated using proton exchange method compare to experimental data very well in both qualitative and quantitative terms, with a mean absolute error of about 0.4 pK(a) units. To achieve this accuracy, we find it mandatory to perform geometry optimization of the neutral and anionic species in the gas and solution phases separately, because different conformations are stabilized in these two cases. We have attempted to evaluate the effect of the conformer-averaged free energies in the pK(a) predictions, and the general conclusion is that this procedure is highly too costly as compared with the very small improvement we have gained.

  9. Formation of an 8-hydroxyguanine moiety in deoxyribonucleic acid on gamma-irradiation in aqueous solution

    SciTech Connect

    Dizdaroglu, M.

    1985-07-30

    Isolation and characterization of a novel radiation-induced product, i.e., the 8-hydroxyguanine residue, produced in deoxyribonucleic acid (DNA), 2'-deoxyguanosine, and 2'-deoxyguanosine 5'-monophosphate by gamma-irradiation in aqueous solution, are described. For this purpose, gamma-irradiated DNA was first hydrolyzed with a mixture of four enzymes, i.e., DNase I, spleen and snake venom exonucleases, and alkaline phosphatase. Analysis of the resulting mixture by capillary gas chromatography-mass spectrometry after trimethylsilylation revealed the presence of a product, which was identified as 8-hydroxy-2'-deoxyguanosine on the basis of the typical fragment ions of its trimethylsilyl (Me3Si) derivative. This product was then isolated by using reversed-phase high-performance liquid chromatography. The UV and proton nuclear magnetic resonance spectra taken from the isolated product confirmed the structure suggested by the mass spectrum of its Me3Si derivative. The yield of 8-hydroxyguanine was also measured. Its mechanism of formation is believed to involve OH radical addition to the C-8 position of guanine followed by oxidation of the radical adduct.

  10. Adsorption of Benzoic Acid in Aqueous Solution by Bagasse Fly Ash

    NASA Astrophysics Data System (ADS)

    Suresh, S.

    2012-09-01

    This paper reports the studies on the benzoic acid (BA) onto bagasse fly ash (BFA) was studied in aqueous solution in a batch system. Physico-chemical properties including surface area, surface texture of the GAC before and after BA adsorption onto BFA were analysed using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The optimum initial pH for the adsorption of BA was found to be 5.56. The adsorbent dose was 10 g/l for BFA and the equilibrium time 8 h of reaction. Pseudo first and second order models were used to find the adsorption kinetics. It was found that intraparticle diffusion played important role in the adsorption mechanisms of BA and the adsorption kinetics followed pseudo-second order kinetic model rather than the pseudo first order kinetic model. Isotherm data were generated for BA solution having initial concentrations of BA in the range of 10-200 mg/l for the BFA dosage of 10 g/l at temperatures of 288, 303, and 318 K. The adsorption of BA onto BFA was favorably influenced by an increase in temperature. Equilibrium data were well represented by the Redlich-Peterson isotherm model. Values of the change in entropy ( ΔS 0), heat of adsorption ( ΔH 0) for adsorption of BA on BFA was found to be 120.10 and 19.61 kJ/mol respectively. The adsorption of BA onto BFA was an endothermic reaction. Desorption of BA from BFA was studied by various solvents method. Acetic acid was found to be a better eluant for desorption of BA with a maximum desorption efficiency of 55.2 %. Owing to its heating value, spent BFA can be used as a co-fuel for the production of heat in boiler furnaces.

  11. Action of combined magnetic fields on aqueous solution of glutamic acid: the further development of investigations.

    PubMed

    Giuliani, Livio; Grimaldi, Settimio; Lisi, Antonella; D'Emilia, Enrico; Bobkova, Natalia; Zhadin, Mikhail

    2008-01-25

    In the present work the results of the known investigation of the influence of combined static (40 microT) and alternating (amplitude of 40 nT) parallel magnetic fields on the current through the aqueous solution of glutamic acid, were successfully replicated. Fourteen experiments were carried out by the application of the combined magnetic fields to the solution placed into a Plexiglas reaction vessel at application of static voltage to golden electrodes placed into the solution. Six experiments were carried out by the application of the combined magnetic fields to the solution placed in a Plexiglas reaction vessel, without electrodes, within an electric field, generated by means of a capacitor at the voltage of 27 mV. The frequency of the alternating field was scanned within the bounds of 1.0 Hz including the cyclotron frequency corresponding to a glutamic acid ion and to the applied static magnetic field. In this study the prominent peaks with half-width of approximately 0.5 Hz and with different heights (till 80 nA) were registered at the alternating magnetic field frequency equal to the cyclotron frequency (4.2 Hz). The general reproducibility of the investigated effects was 70% among the all solutions studied by us and they arose usually after 40-60 min. after preparation of the solution. In some made-up solutions the appearance of instability in the registered current was noted in 30-45 min after the solution preparation. This instability endured for 20-40 min. At the end of such instability period the effects of combined fields action appeared practically every time. The possible mechanisms of revealed effects were discussed on the basis of modern quantum electrodynamics.

  12. Lipase in biphasic alginate beads as a biocatalyst for esterification of butyric acid and butanol in aqueous media.

    PubMed

    Ng, Choong Hey; Yang, Kun-Lin

    2016-01-01

    Esterification of organic acids and alcohols in aqueous media is very inefficient due to thermodynamic constraints. However, fermentation processes used to produce organic acids and alcohols are often conducted in aqueous media. To produce esters in aqueous media, biphasic alginate beads with immobilized lipase are developed for in situ esterification of butanol and butyric acid. The biphasic beads contain a solid matrix of calcium alginate and hexadecane together with 5 mg/mL of lipase as the biocatalyst. Hexadecane in the biphasic beads serves as an organic phase to facilitate the esterification reaction. Under optimized conditions, the beads are able to catalyze the production of 0.16 mmol of butyl butyrate from 0.5 mmol of butyric acid and 1.5 mmol of butanol. In contrast, when monophasic beads (without hexadecane) are used, only trace amount of butyl butyrate is produced. One main application of biphasic beads is in simultaneous fermentation and esterification (SFE) because the organic phase inside the beads is very stable and does not leach out into the culture medium. SFE is successfully conducted with an esterification yield of 6.32% using biphasic beads containing iso-octane even though the solvent is proven toxic to the butanol-producing Clostridium spp.

  13. Binding affinities of amino acid analogues at the charged aqueous titania interface: implications for titania-binding peptides.

    PubMed

    Sultan, Anas M; Hughes, Zak E; Walsh, Tiffany R

    2014-11-11

    Despite the extensive utilization of biomolecule-titania interfaces, biomolecular recognition and interactions at the aqueous titania interface remain far from being fully understood. Here, atomistic molecular dynamics simulations, in partnership with metadynamics, are used to calculate the free energy of adsorption of different amino acid side chain analogues at the negatively-charged aqueous rutile TiO2 (110) interface, under conditions corresponding with neutral pH. Our calculations predict that charged amino acid analogues have a relatively high affinity to the titania surface, with the arginine analogue predicted to be the strongest binder. Interactions between uncharged amino acid analogues and titania are found to be repulsive or weak at best. All of the residues that bound to the negatively-charged interface show a relatively stronger adsorption compared with the charge-neutral interface, including the negatively-charged analogue. Of the analogues that are found to bind to the titania surface, the rank ordering of the binding affinities is predicted to be "arginine" > "lysine" ≈ aspartic acid > "serine". This is the same ordering as was found previously for the charge-neutral aqueous titania interface. Our results show very good agreement with available experimental data and can provide a baseline for the interpretation of peptide-TiO2 adsorption data.

  14. Sorption of carboxylic acid from carboxylic salt solutions at pHs close to or above the pK[sub a] of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

    DOEpatents

    King, C.J.; Tung, L.A.

    1992-07-21

    Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH[sub a] into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. The acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carboxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia. 8 figs.

  15. Sorption of carboxylic acid from carboxylic salt solutions at PHS close to or above the pK.sub.a of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine

    DOEpatents

    King, C. Judson; Tung, Lisa A.

    1992-01-01

    Carboxylic acids are sorbed from aqueous feedstocks at pHs close to or above the acids' pH.sub.a into a strongly basic organic liquid phase or onto a basic solid adsorbent or moderately basic ion exchange resin. the acids are freed from the sorbent phase by treating it with aqueous alkylamine or ammonia thus forming an alkylammonium or ammonium carobxylate which dewatered and decomposed to the desired carboxylic acid and the alkylamine or ammonia.

  16. Characterisation of weak magnetic field effects in an aqueous glutamic acid solution by nonlinear dielectric spectroscopy and voltammetry

    PubMed Central

    Pazur, Alexander

    2004-01-01

    Background Previous reports indicate altered metabolism and enzyme kinetics for various organisms, as well as changes of neuronal functions and behaviour of higher animals, when they were exposed to specific combinations of weak static and alternating low frequency electromagnetic fields. Field strengths and frequencies, as well as properties of involved ions were related by a linear equation, known as the formula of ion cyclotron resonance (ICR, abbreviation mentioned first by Liboff). Under certain conditions already a aqueous solution of the amino acid and neurotransmitter glutamate shows this effect. Methods An aqueous solution of glutamate was exposed to a combination of a static magnetic field of 40 μT and a sinusoidal electromagnetic magnetic field (EMF) with variable frequency (2–7 Hz) and an amplitude of 50 nT. The electric conductivity and dielectric properties of the solution were investigated by voltammetric techniques in combination with non linear dielectric spectroscopy (NLDS), which allow the examination of the dielectric properties of macromolecules and molecular aggregates in water. The experiments target to elucidate the biological relevance of the observed EMF effect on molecular level. Results An ion cyclotron resonance (ICR) effect of glutamate previously reported by the Fesenko laboratory 1998 could be confirmed. Frequency resolution of the sample currents was possible by NLDS techniques. The spectrum peaks when the conditions for ion cyclotron resonance (ICR) of glutamate are matched. Furthermore, the NLDS spectra are different under ICR- and non-ICR conditions: NLDS measurements with rising control voltages from 100–1100 mV show different courses of the intensities of the low order harmonics, which could possibly indicate "intensity windows". Furthermore, the observed magnetic field effects are pH dependent with a narrow optimum around pH 2.85. Conclusions Data will be discussed in the context with recent published models for the

  17. Light-induced multiphase chemistry of gas phase ozone on aqueous pyruvic and oxalic acids: Aerosol chamber study

    NASA Astrophysics Data System (ADS)

    Gligorovski, S.; Grgic, I.; Net, S.; Böge, O.; Iinuma, Y.; Kahnt, A.; Scheinhardt, S.; Herrmann, H.; Wortham, H.

    2010-12-01

    The light-absorbing organic compounds present in and on condensed aerosol particles interacting with trace gases such as ozone can initiate a new and potentially important photo-induced multiphase chemistry. However, investigations of light induced multiphase processes are very scarce at present. We have launched the idea of pyruvic acid (PA) acting as a photosensitizer in the multiphase reactions between gas-phase ozone and aqueous oxalic acid (OA). The performed photochemical batch experiments yielded a complex suite of organic molecules which resulted primarily from the oligomerization of OA/PA and subsequent reactions, including decarboxylation and cycloadition (Grgic et al., 2010). In the atmosphere, pyruvic acid will always be accompanied by other carboxylic acids (and also other organics) which are constituents of either aerosol particles or aqueous droplets the effects of a possible photochemistry triggered by pyruvic acid should be experimentally studied in depth and under natural conditions as far as possible. Hence, in a very recent study experiments in the aerosol chamber facility LEAK at IFT, Leipzig, were performed to verify the influence of pyruvic on the multiphase (photo)oxidation of oxalic acid. The aim of these experiments was to study the multiphase photo-induced oxidation reactions with airborne deliquescent particles to demonstrate the applicability of the reactions mentioned above under more realistic conditions than in a batch reactor. State of the art sampling and analytical tools were applied for the analysis of the ongoing chamber runs and the formed particulate products which include denuder sampling, carbonyl compound derivatisation, PTR-MS measurements, GC-MS measurements and HPLC-MS and CE-MS for the particle phase. First results from these joint complex chamber experiments will be presented and discussed. Reference: Grgić I., Nieto-Gligorovski L.I., Net S., Temime-Roussel B., Gligorovski S., Wortham H. Light induced multiphase

  18. Dynamic interfacial behavior of viscoelastic aqueous hyaluronic acid: effects of molecular weight, concentration and interfacial velocity.

    PubMed

    Vorvolakos, Katherine; Coburn, James C; Saylor, David M

    2014-04-07

    An aqueous hyaluronic acid (HA(aq)) pericellular coat, when mediating the tactile aspect of cellular contact inhibition, has three tasks: interface formation, mechanical signal transmission and interface separation. To quantify the interfacial adhesive behavior of HA(aq), we induce simultaneous interface formation and separation between HA(aq) and a model hydrophobic, hysteretic Si-SAM surface. While surface tension γ remains essentially constant, interface formation and separation depend greatly on concentration (5 ≤ C ≤ 30 mg mL(-1)), molecular weight (6 ≤ MW ≤ 2000 kDa) and interfacial velocity (0 ≤ V ≤ 3 mm s(-1)), each of which affect shear elastic and loss moduli G′ and G′′, respectively. Viscoelasticity dictates the mode of interfacial motion: wetting-dewetting, capillary necking, or rolling. Wetting-dewetting is quantified using advancing and receding contact angles θ(A) and θ(R), and the hysteresis between them, yielding data landscapes for each C above the [MW, V] plane. The landscape sizes, shapes, and curvatures disclose the interplay, between surface tension and viscoelasticity, which governs interfacial dynamics. Gel point coordinates modulus G and angular frequency ω appear to predict wetting-dewetting (G < 75 ω0.2), capillary necking (75 ω0.2 < G < 200 ω0.075) or rolling (G > 200ω0.075). Dominantly dissipative HA(aq) sticks to itself and distorts irreversibly before separating, while dominantly elastic HA(aq) makes contact and separates with only minor, reversible distortion. We propose the dimensionless number (G′V)/(ω(r)γ), varying from 10(-5) to 10(3) in this work, as a tool to predict the mode of interface formation-separation by relating interfacial kinetics with bulk viscoelasticity. Cellular contact inhibition may be thus aided or compromised by physiological or interventional shifts in [C, MW, V], and thus in (G′V)/(ω(r)γ), which affect both mechanotransduction and interfacial dynamics. These observations

  19. Identification and measurement of nitrous acid in an indoor environment

    NASA Astrophysics Data System (ADS)

    Pttts, James N.; Wallington, Timothy J.; Biermann, Heinz W.; Winer, Arthur M.

    We report here direct observation by differential optical absorption spectroscopy (DOAS) of the formation of ppb levels of gaseous nitrous acid (MONO) from the reaction of ppm levels of nitrogen dioxide (NO 2) with water vapor, in an indoor environment. The rate of formation of HONO displayed first order kinetics with respect to NO 2 with a rate of (0.25 ±0.04) ppb min -1 per ppm of NO 2 present. Assuming a lifetime of l h with respect to both physical and chemical removal processes for HONO, this leads to an estimated steady state concentration of ~ 15 ppb of HONO per ppm of NO 2 present. This relatively high level of HONO associated with NO 2-air mixtures raises new questions concerning the health implications of elevated NO 2 concentrations in indoor environments e.g. HONO is a respirable nitrite known to convert secondary amines invitro to carcinogenic nitrosamines.

  20. Interaction of model aryl- and alkyl-boronic acids and 1,2-diols in aqueous solution.

    PubMed

    Marinaro, William A; Prankerd, Richard; Kinnari, Kaisa; Stella, Valentino J

    2015-04-01

    The goal of this work was to quantitate ester formation between alkyl and aryl boronic acids and vicinal-diols or 1,2-diols in aqueous solution. As used here, 1,2-diols includes polyols with one or more 1,2-diol pairs. Multiple techniques were used including apparent pKa shifts of the boronic acids using UV spectrophotometry (for aryl acids) and titration (for aryl and alkyl acids). Isothermal microcalorimetry was also used, with all reactions being enthalpically favored. For all the acids and 1,2-diols and the conditions studied, evidence only supported 1:1 ester formation. All the esters formed were found to be significantly more acidic, as Lewis acids, by 3-3.5 pKa units than the corresponding nonesterified boronic acid. The equilibrium constants for ester formation increased with increasing number of 1,2-diol pairs but stereochemistry may also play a role as sorbitol with five possible 1,2-diol pairs and five isomers (taking into account the stereochemistry of the alcohol groups) was twice as efficient at ester formation compared with mannitol, also with five possible 1,2-diol pairs but only three isomers. Alkyl boronic acids formed esters to a greater extent than aryl acids. Although some quantitative differences were seen between the various techniques used, rank ordering of the structure/reactivity was consistent. Formulation implications of ester formation between boronic acids and 1,2-diols are discussed.

  1. Evidence for compounds hydrolyzable to amino acids in aqueous extracts of apollo 11 and apollo 12 lunar fines.

    PubMed

    Harada, K; Hare, P E; Windsor, C R; Fox, S W

    1971-07-30

    Hydrolyzates of aqueous extracts of Apollo 11 fines, an Apollo 12 trench sample, and an Apollo 12 surface sample have been analyzed on an ultrasensitive amino acid analyzer. The total content of amino acids recovered ranged from 20 to 70 parts per billion of lunar soil. Amino acids are not recovered by the direct hydrolysis of lunar fines, presumably because of decomposition in the presence of the large excess of lunar mineral. As judged by retention time, glycine is the dominant amino acid found; alanine is secondarily present in each case in the profile. Only a few amino acids have been recorded in each analysis. The pattern is relatively consistent in the samples from the three locations; the pattern from either hydrolyzed or unhydrolyzed extracts differs markedly from that of hydrolyzed or unhydrolyzed handprints. The evidence is not consistent with contamination of the kind expected by many investigators.

  2. Design of aqueous two-phase systems for purification of hyaluronic acid produced by metabolically engineered Lactococcus lactis.

    PubMed

    Rajendran, Vivek; Puvendran, Kirubhakaran; Guru, Bharath Raja; Jayaraman, Guhan

    2016-02-01

    Hyaluronic acid has a wide range of biomedical applications and its commercial value is highly dependent on its purity and molecular weight. This study highlights the utility of aqueous two-phase separation as a primary recovery step for hyaluronic acid and for removal of major protein impurities from fermentation broths. Metabolically engineered cultures of a lactate dehydrogenase mutant strain of Lactococcus lactis (L. lactis NZ9020) were used to produce high-molecular-weight hyaluronic acid. The cell-free fermentation broth was partially purified using a polyethylene glycol/potassium phosphate system, resulting in nearly 100% recovery of hyaluronic acid in the salt-rich bottom phase in all the aqueous two-phase separation experiments. These experiments were optimized for maximum removal of protein impurities in the polyethylene glycol rich top phase. The removal of protein impurities resulted in substantial reduction of membrane fouling in the subsequent diafiltration process, carried out with a 300 kDa polyether sulfone membrane. This step resulted in considerable purification of hyaluronic acid, without any loss in recovery and molecular weight. Diafiltration was followed by an adsorption step to remove minor impurities and achieve nearly 100% purity. The final hyaluronic acid product was characterized by Fourier-transform IR and NMR spectroscopy, confirming its purity.

  3. Long-term aging of Ag/a-C:H:O nanocomposite coatings in air and in aqueous environment.

    PubMed

    Drábik, Martin; Pešička, Josef; Biederman, Hynek; Hegemann, Dirk

    2015-04-01

    Nanocomposite coatings of silver particles embedded in a plasma polymer matrix possess interesting properties depending on their microstructure. The film microstructure is affected among others also by the RF power supplied during the deposition, as shown by transmission electron microscopy. The optical properties are characterized by UV-vis-NIR spectroscopy. An anomalous optical absorption peak from the Ag nanoparticles is observed and related to the microstructure of the nanocomposite films. Furthermore, a long-term aging of the coatings is studied in-depth in ambient air and in aqueous environments. It is shown that the studied films are not entirely stable. The deposition conditions and the microstructure of the films affect the processes taking place during their aging in both environments.

  4. A modular diffusion barrier based on phase separation for localized delivery of discrete drug volumes in aqueous environments.

    PubMed

    Steigert, Juergen; Strasser, Monika; Wangler, Nicolai; Brett, Olivia; Streule, Wolfgang; Koltay, Peter; Daub, Martina; Zengerle, Roland

    2009-06-21

    We present a new tool for the precisely controlled transfer of individual picoliter (pL) droplets in the range of 150-950 pL at user defined local positions within aqueous liquid environments while avoiding any leakage by diffusion. This is achieved by a low-cost, disposable and biocompatible cap that can be placed on top of any pL-dispenser and generates a phase-gap between dispensing agent and target liquid when the dispenser is dipped into the latter. We developed two different working modes: (i) the standard mode enables an instant injection (< 1 ms) of the droplet into the liquid environment and (ii) the focus mode further increases the spatial resolution from 100 microm to 50 microm at the cost of slowing down the injection time. For the phase-gap we have proven an excellent long-term stability of more than 30 hours against capillary priming.

  5. Long-term aging of Ag/a-C:H:O nanocomposite coatings in air and in aqueous environment

    PubMed Central

    Pešička, Josef; Biederman, Hynek; Hegemann, Dirk

    2015-01-01

    Nanocomposite coatings of silver particles embedded in a plasma polymer matrix possess interesting properties depending on their microstructure. The film microstructure is affected among others also by the RF power supplied during the deposition, as shown by transmission electron microscopy. The optical properties are characterized by UV–vis–NIR spectroscopy. An anomalous optical absorption peak from the Ag nanoparticles is observed and related to the microstructure of the nanocomposite films. Furthermore, a long-term aging of the coatings is studied in-depth in ambient air and in aqueous environments. It is shown that the studied films are not entirely stable. The deposition conditions and the microstructure of the films affect the processes taking place during their aging in both environments. PMID:27877774

  6. The aqueous photodegradation of fenitrothion under various agricultural plastics: implications for pesticide longevity in agricultural 'micro-environments'.

    PubMed

    Weber, Jan; Halsall, Crispin J; Wargent, Jason J; Paul, Nigel D

    2009-06-01

    Plastic cladding is increasingly used in agriculture to create micro-environments to improve crop yield/growth. Many of these plastics can alter the solar light spectrum by inhibiting or reducing the transmittance of certain parts of the solar spectrum. In this study, we investigated the aqueous photolysis of fenitrothion, under a selection of different plastic films commonly used in agriculture. Three different grades of polyethylene film were used: 'standard', 'transparent' and 'opaque'. The transmittance of light wavelengths in the UV region (290-400 nm), measured with a spectroradiometer, was found to decrease in the order of transparent>standard>opaque. Fenitrothion, an organophosphorothioate insecticide possesses molar absorptivity in the solar wavelength range of 290-400 nm. Aqueous first order degradation rate constants for fenitrothion determined over a 12 h period were found to be considerably less for those experiments conducted under the standard and opaque plastic films, compared to the transparent film and no-film control. The experiments were conducted in an Atlas Suntest solar simulator using a UV-filtered Xenon arc lamp to simulate sunlight. The first order half-life for fenitrothion was 100 and 250 h under the standard and opaque films, respectively, compared to approximately 10 h for the transparent film and no-film experiments. Our results suggest that pesticide longevity could be greatly extended within these plastic micro-environments, especially for those chemicals which may degrade/transform via photolytic or photochemical pathways.

  7. Insulated gold scanning tunneling microscopy probes for recognition tunneling in an aqueous environment.

    PubMed

    Tuchband, Michael; He, Jin; Huang, Shuo; Lindsay, Stuart

    2012-01-01

    Chemically functionalized probes are required for tunneling measurements made via chemical contacts ("Recognition Tunneling"). Here, we describe the etching of gold STM probes suitable for chemical functionalization with moieties bearing thiol groups. Insulated with high density polyethylene, these probes may be used in aqueous electrolytes with sub pA leakage currents. The area of the exposed probe surface was characterized via the saturation current in an electroactive solution (0.1 M K(3)Fe(CN)(6)). Twenty five percent of the probes had an exposed region of 10 nm radius or less.

  8. Interactions of Organic Surfactants With Oxide Nanoparticles Grown in Aqueous Environments

    DTIC Science & Technology

    2007-02-01

    growth of oxide nanoparticles (e.g., TiO2, ZnO ) in aqueous solutions. It is generally known that particles grow from solution into shapes that minimize...Table 4. Absorption bands for different Ti coordinations and hydroxyl groups probed with CO, NH2, and SO2 ...coordinations and hydroxyl groups probed with CO, NH2, and SO2 . State Molecule Bands Anatase Ti4+cus CO 2188,2208 Anatase Ti3+cus CO 2115 Anatase Ti4+5C

  9. Concentration effects in the nucleophilic reactions of tertiary amines in aqueous solutions: Alkylation of amines with chloroacetic acid

    NASA Astrophysics Data System (ADS)

    Kazantsev, O. A.; Baruta, D. S.; Shirshin, K. V.; Sivokhin, A. P.; Kamorin, D. M.

    2011-03-01

    In alkylations of tertiary amines with chloroacetic acid in aqueous solutions, an increase in the initial concentrations of reagents to a certain level led to an abrupt increase in the initial rates and conversions attained during the control time. Viscosimetric and refractometric data showed that association with reagents occurred in these systems. The structures of associates that determine the character of the concentration effects of the Menschutkin reaction in water were suggested.

  10. Spectrophotometric Study of the Interaction Np(VI) with Orthosilicic Acid and Polymeric Silicic Acids in Aqueous Solutions

    SciTech Connect

    Yusov, A. B.; Shilov, V. P.; Fedoseev, A. M.; Astafurova, L. N.; Delegard, Calvin H.

    2005-07-15

    Spectrophotometric methods were used to investigate the interaction of the NpO22+ ion with orthosilicic acid, Si(OH)4, and polymeric silicic acids (PSA) in aqueous solutions. At рН ≤ 4.5, the interaction is described by the reaction NpO22+ + Si(OH)4 = NpO2OSi(OH)3+ + H+ with an equilibrium constant of lg K = -2.88 ± 0.12 (ionic strength I = 0.1-0.2). Recalculation to I = 0 gives lg K0 =-2.61 ± 0.12; the stability constant of the complex NpO2OSi(OH)3+ is lg β0 = 7.20 ± 0.12. Polymerization of Si(OH)4 does not lead to an apparent increase in the constant K. In solutions with рН higher than 5, and with silicate concentration more than 0.02 mole/l, leads to formation of a second complex, whose structure probably is described by the formula NpO2(≡SiO)2(≡SiOH)m-2, where (≡SiOH)m designates the PSA molecule with superficial Si-OH groups. The factors influencing the apparent equilibrium constants in forming of complexes NpO2OSi(OH)3+ and NpO2(≡SiO)2(≡SiOH)m-2 are considered upon polymerization of Si(OH)4. Absorption spectra of complexes NpO2OSi(OH)3+ and NpO2(≡SiO)2(≡SiOH)m-2 were obtained. Molar extinction coefficients at the maxima (500-600 nanometers) are much higher than those of the Np(VI) aquo ion and are about 25-30 l/mol∙cm. The stabilities of silicate complexes of all types - MO2OSi(OH)3+, MO2(≡SiO)2(≡SiOH)m-2, or MO2SiO3 (M = U, Np, or Pu) - decrease in order U> Np> Pu with the greatest difference occurring between Np and Pu.

  11. Stability of Rosmarinic Acid in Aqueous Extracts from Different Lamiaceae Species after in vitro Digestion with Human Gastrointestinal Enzymes

    PubMed Central

    Zorić, Zoran; Markić, Joško; Pedisić, Sandra; Bučević-Popović, Viljemka; Generalić-Mekinić, Ivana; Grebenar, Katarina

    2016-01-01

    Summary The present study compares the gastrointestinal stability of rosmarinic acid in aqueous extracts of thyme, winter savory and lemon balm with the stability of pure rosmarinic acid. The stability of rosmarinic acid was detected after two-phase in vitro digestion process (gastric and duodenal) with human gastrointestinal enzymes. The concentration of rosmarinic acid in undigested and digested samples was detected using HPLC-DAD. Results showed that gastrointestinal stability of pure rosmarinic acid was significantly higher than that of rosmarinic acid from plant extracts after both gastric and intestinal phases of digestion. Among plant extracts, rosmarinic acid was the most stable in lemon balm after gastric (14.10%) and intestinal digestion phases (6.5%). The temperature (37 °C) and slightly alkaline medium (pH=7.5) did not affect the stability of rosmarinic acid, while acid medium (pH=2.5) significantly decreased its stability (≥50%). In addition, the stability rate of rosmarinic acid is influenced by the concentration of human gastrointestinal juices. PMID:27904398

  12. Stability of Rosmarinic Acid in Aqueous Extracts from Different Lamiaceae Species after in vitro Digestion with Human Gastrointestinal Enzymes.

    PubMed

    Zorić, Zoran; Markić, Joško; Pedisić, Sandra; Bučević-Popović, Viljemka; Generalić-Mekinić, Ivana; Grebenar, Katarina; Kulišić-Bilušić, Tea

    2016-03-01

    The present study compares the gastrointestinal stability of rosmarinic acid in aqueous extracts of thyme, winter savory and lemon balm with the stability of pure rosmarinic acid. The stability of rosmarinic acid was detected after two-phase in vitro digestion process (gastric and duodenal) with human gastrointestinal enzymes. The concentration of rosmarinic acid in undigested and digested samples was detected using HPLC-DAD. Results showed that gastrointestinal stability of pure rosmarinic acid was significantly higher than that of rosmarinic acid from plant extracts after both gastric and intestinal phases of digestion. Among plant extracts, rosmarinic acid was the most stable in lemon balm after gastric (14.10%) and intestinal digestion phases (6.5%). The temperature (37 °C) and slightly alkaline medium (pH=7.5) did not affect the stability of rosmarinic acid, while acid medium (pH=2.5) significantly decreased its stability (≥50%). In addition, the stability rate of rosmarinic acid is influenced by the concentration of human gastrointestinal juices.

  13. Phenol Removal from Aqueous Environment by Adsorption onto Pomegranate Peel Carbon

    PubMed Central

    Afsharnia, Mojtaba; Saeidi, Mahdi; Zarei, Amin; Narooie, Mohammad Reza; Biglari, Hamed

    2016-01-01

    Introduction Phenol and its derivatives are the most common poisonous compounds which are stable in aqueous media and lead to many health issues. In this study, application of the carbon resulted from pomegranate peel is investigated in removal of phenol by adsorption method. Methods to perform this cross-sectional study, first, samples of phenol with concentrations of 10 to 100 mg/L were prepared for six months in 2016. Then, the impacts of parameters such as pH, adsorbent dosage, contact time, and initial concentration of phenol in adsorption process were investigated independently in Gonabad Chemistry Lab using a spectrophotometer at 505 nm as the wavelength. Furthermore, adherence of the samples to the isotherm models of Langmuir and Freundlich was determined by Excel 2016 and descriptive statistical methods were then reported. Results The obtained results demonstrated a maximum adsorption capacity (ash) of 148.38 mgg-1 at pH 7, initial concentration of 100 mg L−1, and temperature of 23 ± 2 °C. The phenol removal rate was found to correlate directly to the adsorbent dosage and contact time, and inversely to the initial concentration of phenol. In addition, the investigations showed that the adsorption of phenol on the pomegranate peel ash follows the Freundlich model well with a correlation coefficient of R2 0.9056. Conclusion Pomegranate peel ash could be used as an efficient and low-cost adsorbent for phenol removal from aqueous media. PMID:28070259

  14. Cd(II) removal from aqueous solution by adsorption on α-ketoglutaric acid-modified magnetic chitosan

    NASA Astrophysics Data System (ADS)

    Yang, Guide; Tang, Lin; Lei, Xiaoxia; Zeng, Guangming; Cai, Ye; Wei, Xue; Zhou, Yaoyu; Li, Sisi; Fang, Yan; Zhang, Yi

    2014-02-01

    The present study developed an α-ketoglutaric acid-modified magnetic chitosan (α-KA-Fe3O4/CS) for highly efficient adsorption of Cd(II) from aqueous solution. Several techniques, including transmission electron microscopy (TEM), Fourier transform infrared (FTIR) and vibrating sample magnetometer (VSM), were applied to characterize the adsorbent. Batch tests were conducted to investigate the Cd(II) adsorption performance of α-KA-Fe3O4/CS. The maximum adsorption efficiency of Cd(II) appeared at pH 6.0 with the value of 93%. The adsorption amount was large and even reached 201.2 mg/g with the initial Cd(II) concentration of 1000 mg/L. The adsorption equilibrium was reached within 30 min and commendably described by pseudo-second-order model, and Langmuir model fitted the adsorption isotherm better. Furthermore, thermodynamic parameters, free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) of Cd(II) adsorption were also calculated and showed that the overall adsorption process was endothermic and spontaneous in nature because of positive ΔH values and negative ΔG values, respectively. Moreover, the Cd(II)-loaded α-KA-Fe3O4/CS could be regenerated by 0.02 mol/L NaOH solution, and the cadmium removal capacity could still be kept around 89% in the sixth cycle. All the results indicated that α-KA-Fe3O4/CS was a promising adsorbent in environment pollution cleanup.

  15. Hydrolysis mechanism of anticancer drug lobaplatin in aqueous medium under neutral and acidic conditions: A DFT study

    NASA Astrophysics Data System (ADS)

    Reddy B., Venkata P.; Mukherjee, Subhajit; Mitra, Ishani; Mahata, Sujay; Linert, Wolfgang; Moi, Sankar Ch.

    2016-10-01

    We have studied the hydrolysis mechanism of lobaplatin in aqueous medium under neutral and acidic conditions using density functional theory combining with CPCM model. The stationary states located on potential energy surface were fully optimized and characterised. The rate limiting step in neutral conditions, ring opening reaction with an activation energy of 110.21 kJ mol-1. The completely hydrolysed complex is expected to be the reactive species towards the DNA purine bases. In acidic conditions, ligand detachment is the rate limiting step with an activation energy of 113.82 kJ mol-1. Consequently, monohydrated complex is expected to be the species reacting with DNA.

  16. Effect of synthesis and acid purification methods on the microwave dielectric properties of single-walled carbon nanotube aqueous dispersions

    NASA Astrophysics Data System (ADS)

    Xie, Shawn X.; Gao, Fuqiang; Patel, Sunny C.; Booske, John H.; Hagness, Susan C.; Sitharaman, Balaji

    2013-09-01

    We characterized the microwave-frequency (0.5-6 GHz) dielectric properties of aqueous dispersions of pristine and purified single-walled carbon nanotubes (SWCNTs). SWCNTs were synthesized by two CVD-based methods and purified using two acid-based purification methods. We characterized the structural and chemical differences across SWCNT samples using Raman analysis, UV-Vis spectroscopy, atomic force microscopy, and thermogravimetric analysis. We found that the dielectric properties of the pristine SWCNT dispersions did not vary with synthesis method, but the dielectric properties of purified SWCNT dispersions were variably impacted by acid purification due to different degrees of morphological and chemical changes in the SWCNTs.

  17. Oxidation of hydroxyurea with oxovanadium(V) ions in acidic aqueous solution.

    PubMed

    Gabricević, Mario; Besić, Erim; Birus, Mladen; Zahl, Achim; Eldik, Rudi van

    2006-10-01

    Hydroxyurea (HU) effectively reduces vanadium(V) into vanadium(IV) species (hereafter V(V) and V(IV) species, respectively) in acidic aqueous solution via the formation of a transient complex followed by an electron transfer process that includes the formation and subsequent fading out of a free radical, U* (U* identical with H(2)N-C(=O)N(H)O*). The electron paramagnetic resonance (EPR) spectra of U* in H(2)O/D(2)O solutions suggest that the unpaired electron is located predominantly on the hydroxamate hydroxyl-oxygen atom. Visible and V(IV)-EPR spectroscopic data reveal HU as a two-electron donor, whereas formation of U*, which reduces a second V(V), indicates that electron transfer occurs in two successive one-electron steps. At the molarity ratio [V(V)]/[HU]=2, the studied reaction can be formulated as: 2 V(V)+HU-->2 V(IV)+0.98 CO(2)+0.44 N(2)O+1.1 NH(3)+0.1 NH(2)OH. Lack of evidence for the formation of NO is suggested to be a consequence of the slow oxidation of HNO due to the too low reduction potential of the V(V)/V(IV) couple under the experimental conditions used. The nuclear magnetic resonance ((51)V-NMR) spectral data indicate protonation of (H(2)O)(4)V(V)O(2)(+), and the protonation equilibrium constant was determined to be K=0.7 M(-1). Spectrophotometric titration data for the V(V)-HU system reveal formation of (H(2)O)(2)V(V)O(OH)U(+) and (H(2)O)(3)V(V)OU(2+). Their stability constants were calculated as K(110)=5 M(-1) and K(111)=22 M(-2), where the subscript digits refer to (H(2)O)(4)V(V)O(2)(+), HU and H(+), respectively.

  18. Drin pesticides removal from aqueous solutions using acid-treated date stones.

    PubMed

    El Bakouri, H; Usero, J; Morillo, J; Rojas, R; Ouassini, A

    2009-05-01

    This work describes the potential applicability of chemically and thermally treated date stones for removing drin pesticides (aldrin, dieldrin and endrin) from aqueous solutions. The effect of several parameters, such as sorbent particle size, adsorbent dose, shaking speed, shaking time, concentration of pesticide solution and temperature, was evaluated by batch experiments. Pesticide determination was carried out using stir bar sorptive extraction and gas chromatography coupled with mass spectroscopy. Maximum removal efficiency (93%) was reached using 0.1 g of acid-treated date stones (ATDS) (63-100 microm) and 100 mL of aldrin (0.5 mg L(-1)). The removal efficiency of drin pesticides decreased in the order of aldrin, dieldrin and endrin, and decreased as the temperature rose. Adsorption data were processed according to various kinetic models. Lagergren and Morris-Weber equations were applied to fit the kinetic results. The second order model was the most suitable on the whole, and intra-particle diffusion was found to be the rate-controlling the adsorption process. According to adsorption kinetic data, 3.5h were considered as the equilibrium time for determining adsorption isotherms. Adsorption data were analyzed by the Langmuir, Freundlich and Dubinin-Radushkevich adsorption approaches. Experimental results showed that the Freundlich isotherm model best described the adsorption process. In addition, thermodynamic parameters such as DeltaH, DeltaS and DeltaG were calculated. Negative values of DeltaH and DeltaG indicate the exothermic and spontaneous nature of pesticide adsorption on ATDS.

  19. On the selective growth of titania polymorphs in acidic aqueous medium

    SciTech Connect

    Li, Haoguang; Afanasiev, Pavel

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Mutual influence of peptizing and anions addition of titania hydrothermal growth was studied. Black-Right-Pointing-Pointer Sulfate and chloride control TiO{sub 2} phase or particles shape depending on the order of introduction. Black-Right-Pointing-Pointer A rationale of difference between sulfate and chloride effect was provided. Black-Right-Pointing-Pointer Ground state DFT and semi-empirical calculations of Ti species support the conclusions. -- Abstract: The influence of preparation conditions on the phase composition and morphology of titania was studied for the solids synthesized by hydrothermal treatment (HT) and peptizing of hydrous TiO{sub 2} sols in acidic medium. Mutual influence of peptizing and of additive anions (SO{sub 4}{sup 2-}, Cl{sup -}) on the nature of obtained polymorphs was for the first time systematically studied and coherently explained. The solids were characterized by XRD, Raman spectroscopy, and transmission electron microscopy. It was found that peptizing step preceding HT and the presence of anions play a crucial role for the selective formation of TiO{sub 2} anatase or rutile polymorphs. Low temperature peptizing leads to acicular rutile particles, whereas HT produces highly dispersed anatase. However if the HT was preceded by peptizing step, rutile was obtained in most cases. The influence of additives strongly depends on the moment of their introduction. Sulfate and chloride species can act as phase growth controllers, or as morphology modifiers. Sulfate hindered formation of rutile and favored anatase al low temperatures, but for already formed rutile seed, sulfate acted only as a shape controller. By contrast, chloride showed a strong tendency to promote rutile growth, whatever the conditions. A qualitative model was proposed explaining the effects observed, supported by ground state DFT and semi-empirical calculations of the aqueous Ti species.

  20. Removal of Pb(II) ions from aqueous solutions by sulphuric acid-treated wheat bran.

    PubMed

    Ozer, A

    2007-03-22

    Sulphuric acid-treated wheat bran (STWB) was used as an adsorbent to remove Pb(II) ions from aqueous solution. It was observed that the adsorption yield of Pb(II) ions was found to be pH dependent. The equilibrium time for the process was determined as 2h. STWB gave the highest adsorption yield at around pH 6.0. At this pH, adsorption percentage for an initial Pb(II) ions concentration of 100mg/L was found to be 82.8 at 25 degrees C for contact time of 2h. The equilibrium data obtained at different temperatures fitted to the non-linear form of Langmuir, Freundlich and Redlich-Peterson and linear form of Langmuir and Freundlich models. Isotherm constants were calculated and compared for the models used. The maximum adsorption capacity (q(max)) which was obtained linear form of Langmuir model increased from 55.56 to 79.37mg/g with increasing temperature from 25 to 60 degrees C. Similar trend was observed for other isotherm constants related to the adsorption capacity. Linear form of Langmuir isotherm data was evaluated to determine the thermodynamic parameters for the process. Thermodynamic parameters show that adsorption process of Pb(II) ions is an endothermic and more effective process at high temperatures. The pseudo nth order kinetic model was successfully applied to the kinetic data and the order (n) of adsorption reaction was calculated at the range from 1.711 to 1.929. The values of k(ad) were found to be 5.82x10(-4) and 21.81x10(-4)(min(-1))(mg/g)(1-n) at 25 and 60 degrees C, respectively. Activation energy was determined as 29.65kJ/mol for the process. This suggest that the adsorption Pb(II) ions by STWB is chemically controlled.

  1. Degradation of dichloroacetic acid in homogeneous aqueous media employing ozone and UVC radiation.

    PubMed

    Lovato, María Eugenia; Martín, Carlos A; Cassano, Alberto E

    2011-03-02

    A tentative workable mechanism for dichloroacetic acid decomposition (DCA) in aqueous media employing ozone and UVC radiation has been developed. All experiments were made in a homogeneous medium under assured kinetic control regime. Under no circumstances did a headspace exist in the reactor volume. The starting point of the reaction with UVC radiation was always under the prerequisite of a confirmed state of initial equilibrium conditions for the mixture water-ozone-oxygen at 20 °C. The explored variables were: (i) DCA initial concentration, (ii) ozone concentration and (iii) fluence rate at the reactor window. The model comprises three parallel reactions: (1) direct photolysis, (2) direct ozonation and (3) ozone + UVC degradation. Complete DCA removal was achieved, and the mass balance, considering DCA disappearance and chloride ion formation, closed within very small error. The combination of ozone and UVC radiation produces a significant amount of hydrogen peroxide as an important reaction by-product. The direct photolysis can be well represented with a six step reaction sequence. The direct ozonation mechanism comprises 22 steps and, with the entire set of kinetic constants completed in this work, it is independent of the reaction pH in the range from 3 to 6.3. Lastly, the associated use of ozone and UVC radiation becomes necessary to consider the existence of radiation absorption by three species, namely DCA, ozone and hydrogen peroxide. The developed system, including the three parallel reactions, led to the proposal of a 37 step reaction mechanism. Finally the reaction kinetics, the mass balances and the radiation field corresponding to this complex system were rigorously modeled and the most significant features of the mathematical representation are briefly described. The simulation results rendered from this model agree very well with the measured experimental data. This outcome will be essential for deriving a complete reactor model that must be

  2. Surface Changes and Impurity Release Kinetics of Titanium Dioxide Nanoparticles in Aqueous Environment

    EPA Science Inventory

    Previous studies have found the significant role of impurities (i.e., silicon, phosphorus) in the aggregation and sedimentation of TiO2 nanoparticles in water environment. However, it is not understood whether dissolution of the impurities potentially impacts the environment or t...

  3. Acid gas treating by aqueous alkanolamines. Annual report, January-December 1993

    SciTech Connect

    Sandall, O.C.; Rinker, E.B.; Ashour, S.

    1993-12-01

    The objective of the work is to investigate the simultaneous absorption or desorption of CO2 and H2S into and from a mixed aqueous amine solvent consisting of methyldiethanolamine (MDEA) and diethanolamine (DEA). In work completed thus far, density, viscosity, gas diffusivity, gas solubility, surface tension, and amine solution vapor pressure have been measured for aqueous MDEA, DEA, and MDEA/DEA mixtures over the temperature range 20 to 100 deg. C and for concentrations up to 50 weight %. A mathematical model, based on the penetration theory, for the simultaneous absorption (desorption) of CO2 and H2S into (from) aqueous solutions of MDEA and DEA has been developed.

  4. Using Australian Acidic Playa Lakes as Analogs for Phyllosilicate and Sulfate Depositional Environments on Mars

    NASA Astrophysics Data System (ADS)

    Baldridge, A. M.; Michalski, J.; Kargel, J.; Hook, S.; Marion, G.; Crowley, J.; Bridges, N.; Brown, A.; Ribeiro da Luz, B.; de Souza Filho, C. R.; Thomson, B.

    2008-12-01

    Recent work on the origin of martian sulfates and their relationship to phyllosilicate deposits suggest that these deposits formed in different eras of Mars' history, under distinct environmental conditions. In southwestern Meridiani Planum phyllosilicates exist in close proximity to sulfate deposits. One possible explanation for this relationship is that it is an unconformable stratigraphic sequence, representing a significant change in aqueous geochemical conditions over time. Specifically, it may be interpreted to record a change in environment from neutral pH aqueous alteration in the Noachian to an acidic evaporitic system in the late Noachian to the Hesperian. On Earth, two different geochemical systems need not be evoked to explain such chemical variation. Acidic playa lakes in Western Australia have large pH differences separated by only a few tens of meters and demonstrate how highly variable chemistries can coexist over short distances in natural environments. Playa lakes on Earth tend to be dominated by lateral flow of water and salts leading to lateral chemical variation. Heterogeneity of playa mineralogy in Australia is due to the varied source rocks of brines and the mixing of dilute oxidizing brines and freshwater with the saturated evaporitic brines. This is evidenced by the ferricretes in the near-shore environment and more soluble phases in basin interiors. Playa lakes on Mars would be much larger than their terrestrial counterparts, leading to the prevalence of large-scale surface and crustal advection of water and salt rather than short-distance lateral flow, except at lake boundaries. Little or no influx of freshwater would preclude the formation of playa rim (e.g., crater rim) ferricretes and silcretes. Instead, we expect to see mainly vertical facies changes, and any diachronous lateral facies changes are expected to occur on very large spatial scales. Comparison of high spatial resolution, hyperspectral airborne data for Australian playa

  5. Evidence for a Morin Type Intramolecular Cyclization of an Alkene with a Phenylsulfenic Acid Group in Neutral Aqueous Solution

    PubMed Central

    Keerthi, Kripa; Sivaramakrishnan, Santhosh; Gates, Kent S.

    2009-01-01

    Sulfenic acids (RSOH) are among the most common sulfur-centered reactive intermediates generated in biological systems. Given the biological occurrence of sulfenic acids, it is important to explore the reactivity of these intermediates under physiological conditions. The Morin rearrangement is a synthetic process developed for the conversion of penicillin derivatives into cephalosporins that proceeds via nucleophilic attack of an alkene on a sulfenic acid intermediate. In its classic form, the Morin reaction involves initial elimination of a sulfenic acid from a cyclic sulfoxide, followed by intramolecular cyclization of the resulting alkene and sulfenic acid groups to generate an episulfonium ion intermediate that undergoes further reaction to yield ring-expanded products. On the basis of the existing literature, it is difficult to assess whether the reaction between an alkene and a sulfenic group can occur under mild conditions because the conditions required to generate the sulfenic acid from the sulfoxide precursor in the Morin reaction typically involve high temperatures and strong acid. In the work described here, β-sulfinylketone precursors were used to generate a “Morin type” sulfenic acid intermediate under mild conditions. This approach made it possible to demonstrate that the intramolecular cyclization of an alkene with a phenylsulfenic acid to generate an episulfonium ion intermediate can occur in neutral aqueous solution at room temperature. PMID:18500784

  6. Multi-Scale Studies of Transport and Adsorption Phenomena of Cement-based Materials in Aqueous and Saline Environment

    NASA Astrophysics Data System (ADS)

    Yoon, Se Yoon

    The transport and adsorption phenomena in cement-based materials are the most important processes in the durability of concrete structures or nuclear waste containers, as they are precursors to a number of deterioration processes such as chloride-induced corrosion, sulfate attack, carbonation, etc. Despite this importance, our understanding of these processes remains limited because the pore structure and composition of concrete are complex. In addition, the range of the pore sizes, from nanometers to millimeters, requires the multi-scale modeling of the transport and adsorption processes. Among the various environments that cement-based materials are exposed to, aqueous and saline environments represent the most common types. Therefore, this dissertation investigates the adsorption and transport phenomena of cement-based materials exposed to an aqueous and saline environment from atomic to macro-scales using different arrays of novel spectroscopic techniques and simulation methods, such as scanning transmission X-ray microscopy (STXM), X-ray absorption near edge structure (XANES), molecular dynamics (MD), and finite element method (FEM). The structure and transport of water molecules through interlayer spacing of tobermorite was investigated using MD simulations because the interlayer water of calcium silicate hydrate (C-S-H) gel influences various material properties of concrete. The adsorption processes of cementitious phases interacting with sodium and chloride ions at the nano-scale were identified using STXM and XANES measurements. A mathematical model and FEM procedure were developed to identify the effect of surface treatments at macro-scale on ionic transport phenomena of surface-treated concrete. Finally, this dissertation introduced a new material, calcined layered double hydroxide (CLDH), to prevent chloride-induced deterioration.

  7. Optimization of polyphenol extraction from red grape pomace using aqueous glycerol/tartaric acid mixtures and response surface methodology.

    PubMed

    Makris, Dimitris P; Passalidi, Vassiliki; Kallithraka, Stamatina; Mourtzinos, Ioannis

    2016-01-01

    Grape pomace is a food industry waste containing a high burden of antioxidant polyphenols and several methodologies have been developed for their efficient extraction. However, a sustainable and environmentally friendly process should involve recovery means composed of benign, non-toxic solvents, such as tartaric acid and glycerol, which are natural food constituents. In this line, this study examined the extraction of polyphenols using aqueous tartaric acid/glycerol solutions. The aim was to assess the role of acid and glycerol concentration in the extraction yield, employing a Box-Behnken experimental design and response surface methodology. The results showed that solutions containing only glycerol (20%, w/v) are more suitable for retrieving polyphenols, flavonoids, and pigments from grape pomace, while tartaric acid exerted a negative effect in this regard, when tested at concentrations up to 2% (w/v).

  8. Boronic acid-containing aminopyridine- and aminopyrimidinecarboxamide CXCR1/2 antagonists: Optimization of aqueous solubility and oral bioavailability.

    PubMed

    Schuler, Aaron D; Engles, Courtney A; Maeda, Dean Y; Quinn, Mark T; Kirpotina, Liliya N; Wicomb, Winston N; Mason, S Nicholas; Auten, Richard L; Zebala, John A

    2015-09-15

    The chemokine receptors CXCR1 and CXCR2 are important pharmaceutical targets due to their key roles in inflammatory diseases and cancer progression. We have previously identified 2-[5-(4-fluoro-phenylcarbamoyl)-pyridin-2-ylsulfanylmethyl]-phenylboronic acid (SX-517) and 6-(2-boronic acid-5-trifluoromethoxy-benzylsulfanyl)-N-(4-fluoro-phenyl)-nicotinamide (SX-576) as potent non-competitive boronic acid-containing CXCR1/2 antagonists. Herein we report the synthesis and evaluation of aminopyridine and aminopyrimidine analogs of SX-517 and SX-576, identifying (2-{(benzyl)[(5-boronic acid-2-pyridyl)methyl]amino}-5-pyrimidinyl)(4-fluorophenylamino)formaldehyde as a potent chemokine antagonist with improved aqueous solubility and oral bioavailability.

  9. Unraveling the Diversity of Early Aqueous Environments and Climate on Mars Through the Phyllosilicate Record

    NASA Technical Reports Server (NTRS)

    Bishop, J. L.; Baker, L. L.; Fairén, A. G.; Gross, C.; Velbel, M. A.; Rampe, E. B.; Michalski, J. R.

    2017-01-01

    Were Martian phyllosilicates formed on the surface or subsurface? Was early Mars warm or cold? How long was liquid water present on the surface of Mars? These are some of the many open questions about our neighboring planet. We propose that the mineralogy of the clay-bearing outcrops on Mars can help address these questions. Abundant phyllosilicates and aqueous minerals are observed nearly everywhere we can see the ancient rocks on Mars. Most bountiful among these is Fe/Mg-smectite. In this study we evaluate the nature and stratigraphy of clay outcrops observed on Mars and the presence of mixtures of other clays or other minerals with the ubiquitous Fe/Mg-smectite.

  10. In situ evidence for an ancient aqueous environment at Meridiani Planum, Mars

    USGS Publications Warehouse

    Squyres, S. W.; Grotzinger, J.P.; Arvidson, R. E.; Bell, J.F.; Calvin, W.; Christensen, P.R.; Clark, B. C.; Crisp, J.A.; Farrand, W. H.; Herkenhoff, K. E.; Johnson, J. R.; Klingelhofer, G.; Knoll, A.H.; McLennan, S.M.; McSween, H.Y.; Morris, R.V.; Rice, J. W.; Rieder, R.; Soderblom, L.A.

    2004-01-01

    Sedimentary rocks at Eagle crater in Meridiani Planum are composed of fine-grained siliciclastic materials derived from weathering of basaltic rocks, sulfate minerals (including magnesium sulfate and jarosite) that constitute several tens of percent of the rock by weight, and hematite. Cross-stratification observed in rock outcrops indicates eolian and aqueous transport. Diagenetic features include hematite-rich concretions and crystal-mold vugs. We interpret the rocks to be a mixture of chemical and siliciclastic sediments with a complex diagenetic history. The environmental conditions that they record include episodic inundation by shallow surface water, evaporation, and desiccation. The geologic record at Meridiani Planum suggests that conditions were suitable for biological activity for a period of time in martian history.

  11. Stress-Corrosion Cracking of AISI 4340 Steel in Aqueous Environments

    NASA Astrophysics Data System (ADS)

    Kalnaus, Sergiy; Zhang, Jixi; Jiang, Yanyao

    2011-02-01

    Stress corrosion cracking of the high-strength martensitic steel AISI 4340 (yield stress = 1503 MPa) in NaCl aqueous solutions of different concentrations was studied experimentally using compact tension specimens in free corroding conditions. The experiments were conducted under the controls of constant load, constant crack opening displacement (COD), constant loading rate, and constant COD rate. Despite the differences in controlling conditions, the experiments yielded similar results for the threshold stress intensity factor and the plateau velocity in the 3.5 wt pct NaCl solution. Dependence of the plateau velocity on the NaCl concentration was observed, whereas the values of the threshold stress intensity factors seem to be independent of the NaCl concentration in distilled water.

  12. A potentiodynamic study of aluminum-lithium alloys in an aqueous sodium chloride environment

    NASA Technical Reports Server (NTRS)

    Tsao, C.-H. T.; Pizzo, P. P.

    1985-01-01

    The characteristics of the potentiodynamic curves for Al-Li alloys in 3.5 percent NaCl aqueous solution are explained and the electrochemical parameters of the potentiodynamic technique are correlated to observed pitting and intergranular cracking behavior. It is shown that the oxygen content of the sodium chloride electrolyte plays an important role in the electrochemical behavior of Al-Li alloys. The potentiodynamic behavior of the alloys is found to be insensitive to variation in compositional content and heat treatment, both of which affect the stress-corrosion behavior. Stringer oxide particle attack and random pitting are observed. It is shown that alternate-immersion exposure prior to potentiodynamic polarization may offer a means of assessing susceptibility to stress-corrosion cracking.

  13. Atmospheric pressure resistive barrier air plasma jet induced bacterial inactivation in aqueous environment

    NASA Astrophysics Data System (ADS)

    Thiyagarajan, Magesh; Sarani, Abdollah; Gonzales, Xavier

    2013-03-01

    An atmospheric pressure resistive barrier air plasma jet is designed to inactivate bacteria in aqueous media in direct and indirect exposure modes of treatment. The resistive barrier plasma jet is designed to operate at both dc and standard 50-60 Hz low frequency ac power input and the ambient air at 50% humidity level was used as the operating gas. The voltage-current characteristics of the plasma jet were analyzed and the operating frequency of the discharge was measured to be 20 kHz and the plasma power was measured to be 26 W. The plasma jet rotational temperatures (Trot) are obtained from the optical emission spectra, from the N2C-B(2+) transitions by matching the experimental spectrum results with the Spectra Air (SPECAIR) simulation spectra. The reactive oxygen and nitrogen species were measured using optical emission spectroscopy and gas analyzers, for direct and indirect treatment modes. The nitric oxides (NO) were observed to be the predominant long lived reactive nitrogen species produced by the plasma. Three different bacteria including Staphylococcus aureus (Gram-positive), Escherichia coli (Gram-negative), and Neisseria meningitidis (Gram-negative) were suspended in an aqueous media and treated by the resistive barrier air plasma jet in direct and indirect exposure modes. The results show that a near complete bacterial inactivation was achieved within 120 s for both direct and indirect plasma treatment of S. aureus and E. coli bacteria. Conversely, a partial inactivation of N. meningitidis was observed by 120 s direct plasma exposure and insignificant inactivation was observed for the indirect plasma exposure treatment. Plasma induced shifts in N. meningitidis gene expression was analyzed using pilC gene expression as a representative gene and the results showed a reduction in the expression of the pilC gene compared to untreated samples suggesting that the observed protection against NO may be regulated by other genes.

  14. Removal characteristics of As(III) and As(V) from acidic aqueous solution by steel making slag.

    PubMed

    Oh, Chamteut; Rhee, Sungsu; Oh, Myounghak; Park, Junboum

    2012-04-30

    This study focused on the environmental risk of steel making slag itself, arsenic removal mechanism and re-leaching possibility of arsenic to aqueous state after the adsorption. The purpose of the study is to promote the use of steel making slag as a low-cost adsorbent for arsenic in aqueous system. Calcium was easily dissolved out from the slag and become the dominant substance in the leachate. Some of the calcium could form amorphous calcium carbonate in alkaline condition, and arsenic in the aqueous solution would be removed by being co-precipitated with or adsorbed onto the amorphous calcium carbonate. Most of the amorphous calcium carbonate containing arsenic would be bound to amorphous iron oxide of the slag. When the slag was used as an adsorbent for arsenic removal, a little amount of toxic chemicals were leached from the slag itself under pH 0.8 to 13.6. Also, 70-80% of arsenic laden on the slag was bound to amorphous iron oxide which would not easily desorb unless given a reducing and complexing condition. Showing 95-100% removal efficiency near initial pH 2, the slag, therefore, could be used as an appropriate adsorbent for eliminating arsenic in acidic aqueous solution.

  15. In situ decarboxylation of acetic and formic acids in aqueous inclusions as a possible way to produce excess CH4

    NASA Astrophysics Data System (ADS)

    Ong, Anthony; Pironon, Jacques; Robert, Pascal; Dubessy, Jean; Caumon, Marie-Camille; Randi, Aurélien; Chailan, Olivier; Girard, Jean-Pierre

    2013-04-01

    Accurate reconstruction of diagenetic P-T conditions in petroleum reservoirs from fluid inclusion data relies on valid measurements of methane concentration in aqueous inclusions. Techniques have been developed (Raman spectrometry) to provide sufficiently accurate data, assuming measured methane concentration has not been modified after aqueous inclusion entrapment. In petroleum reservoirs, acetic (CH3COOH) and formic (HCOOH) acids are the most commonly reported organic acids, and the concentration of the total organic acids can be as high as 10,000 ppm at temperature below 120°C. This study investigates the likelihood that organic acids derived from petroleum fluids and dissolved in formation water might suffer decarboxylation upon post-entrapment heating within the fluid inclusion chamber upon post-entrapment heating, thereby generating excess CH4 in the inclusions. Four different experiments were conducted in Fused Silica Capillary Capsules (FSCCs), mimicking fluid inclusions. The capsules were loaded with acetic (CH3COOH) or formic (HCOOH) acid solution and were heated to 250°C for short durations (< 72hrs) in closed system conditions, with or without applying a fixed PH2. Reaction products were characterized by Raman and FT-IR spectrometry. The beginning of the decarboxylation of acetic acid is reached in 32 h at 250°C, with production of CH4 and CO2. Complete decarboxylation of formic acid is reached in 5 h at 250°C, with production of CO2, CO and H2. The lack of CH4 production in experiments with formic acid may be attributed to the relatively short duration of the experiments and/or the loss of H2 through the FSCC by diffusion during the experiment. Further experiments with a longer heating duration should be performed to assess the possibility of reducing the CO2 into CH4 from the formic acid. 2) The injection of H2 in the FSCC as a way to promote CO2 reduction did not promote decarboxylation in the duration of our experiment. These results suggest

  16. A Simple Purification of Indole-3-Acetic Acid and Abscisic Acid for GC-SIM-MS Analysis by Microfiltration of Aqueous Samples through Nylon

    PubMed Central

    Dunlap, James R.; Guinn, Gene

    1989-01-01

    A simple procedure was developed for the partial purification of plant tissue samples to be analyzed simultaneously for indole-3-acetic acid (IAA) and abscisic acid (ABA). The procedure relies on removal of contaminants by filtration through nylon and partitioning into dichloromethane. This procedure successfully purified both IAA and ABA from muskmelon, cotton, and broccoli tissue. Twenty individual samples can be purified and methylated in 8 h for analysis of free IAA and ABA with gas chromatography-selected ion monitoring-mass spectrometry. The use of microfiltration of aqueous samples through nylon offers new opportunities for improving the efficiency of existing sample purification procedures. PMID:16666735

  17. An optical fiber-based sensor array for the monitoring of zinc and copper ions in aqueous environments.

    PubMed

    Kopitzke, Steven; Geissinger, Peter

    2014-02-17

    Copper and zinc are elements commonly used in industrial applications as aqueous solutions. Before the solutions can be discharged into civil or native waterways, waste treatment processes must be undertaken to ensure compliance with government guidelines restricting the concentration of ions discharged in solution. While currently there are methods of analysis available to monitor these solutions, each method has disadvantages, be it high costs, inaccuracy, and/or being time-consuming. In this work, a new optical fiber-based platform capable of providing fast and accurate results when performing solution analysis for these metals is described. Fluorescent compounds that exhibit a high sensitivity and selectivity for either zinc or copper have been employed for fabricating the sensors. These sensors demonstrated sub-part-per-million detection limits, 30-second response times, and the ability to analyze samples with an average error of under 10%. The inclusion of a fluorescent compound as a reference material to compensate for fluctuations from pulsed excitation sources has further increased the reliability and accuracy of each sensor. Finally, after developing sensors capable of monitoring zinc and copper individually, these sensors are combined to form a single optical fiber sensor array capable of simultaneously monitoring concentration changes in zinc and copper in aqueous environments.

  18. Pattern recognition and data mining software based on artificial neural networks applied to proton transfer in aqueous environments

    NASA Astrophysics Data System (ADS)

    Amani, Tahat; Jordi, Marti; Ali, Khwaldeh; Kaher, Tahat

    2014-04-01

    In computational physics proton transfer phenomena could be viewed as pattern classification problems based on a set of input features allowing classification of the proton motion into two categories: transfer ‘occurred’ and transfer ‘not occurred’. The goal of this paper is to evaluate the use of artificial neural networks in the classification of proton transfer events, based on the feed-forward back propagation neural network, used as a classifier to distinguish between the two transfer cases. In this paper, we use a new developed data mining and pattern recognition tool for automating, controlling, and drawing charts of the output data of an Empirical Valence Bond existing code. The study analyzes the need for pattern recognition in aqueous proton transfer processes and how the learning approach in error back propagation (multilayer perceptron algorithms) could be satisfactorily employed in the present case. We present a tool for pattern recognition and validate the code including a real physical case study. The results of applying the artificial neural networks methodology to crowd patterns based upon selected physical properties (e.g., temperature, density) show the abilities of the network to learn proton transfer patterns corresponding to properties of the aqueous environments, which is in turn proved to be fully compatible with previous proton transfer studies.

  19. Biosorption of formic and acetic acids from aqueous solution using activated carbon from shea butter seed shells

    NASA Astrophysics Data System (ADS)

    Adekola, Folahan A.; Oba, Ismaila A.

    2016-10-01

    The efficiency of prepared activated carbon from shea butter seed shells (SB-AC) for the adsorption of formic acid (FA) and acetic acid (AA) from aqueous solution was investigated. The effect of optimization parameters including initial concentration, agitation time, adsorbent dosage and temperature of adsorbate solution on the sorption capacity were studied. The SB-AC was characterized for the following parameters: bulk density, moisture content, ash content, pH, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The optimal conditions for the adsorption were established and the adsorption data for AA fitted Dubinin-Radushkevich (D-R) isotherm well, whereas FA followed Langmuir isotherm. The kinetic data were examined. It was found that pseudo-second-order kinetic model was found to adequately explain the sorption kinetic of AA and FA from aqueous solution. It was again found that intraparticle diffusion was found to explain the adsorption mechanism. Adsorption thermodynamic parameters were estimated and the negative values of ∆G showed that the adsorption process was feasible and spontaneous in nature, while the negative values of ∆H indicate that the adsorption process was exothermic. It is therefore established that SB-AC has good potential for the removal of AA and FA from aqueous solution. Hence, it should find application in the regular treatment of polluted water in aquaculture and fish breeding system.

  20. Synthesis, spectra, and electron-transfer reaction of aspartic acid-functionalized water-soluble perylene bisimide in aqueous solution.

    PubMed

    Zhong, Lina; Xing, Feifei; Shi, Wei; Yan, Liuming; Xie, Liqing; Zhu, Shourong

    2013-04-24

    An aspartic acid-functionalized water-soluble perylene bisimide, N,N'-di(2-succinic acid)-perylene-3,4,9,10-tetracarboxylic bisimide (PASP) was synthesized and characterized. It has absorbance maximum A(0-0) and A(0-1) at 527 and 498 nm (ε ≈ 1.7 × 10(4) L cm(-1) mol(-1)) respectively in pH 7.20 HEPES buffer. Two quasi-reversible redox processes with E1/2 at -0.17 and -0.71 V (vs Ag/AgCl) respectively in pH 7-12.5 aqueous solutions. PASP can react with Na2S in pure aqueous solution to form monoanion radical and dianion species consecutively. PASP(-•) has EPR signal with g = 1.998 in aqueous solution, whereas PASP(2-) is EPR silent. The monoanion radical formation is a first-order reaction with k = 8.9 × 10(-2) s(-1). Dianion species formation is a zero-order reaction and the rate constant is 4.3 × 10(-8) mol L(-1) s(-1). The presence of H2O2 greatly increases the radical formation rate constant. PASP as a two-electron transfer reagent is expected to be used in the water photolysis.

  1. Study of monoprotic acid-base equilibria in aqueous micellar solutions of nonionic surfactants using spectrophotometry and chemometrics.

    PubMed

    Babamoradi, Hamid; Abdollahi, Hamid

    2015-10-05

    Many studies have shown the distribution of solutes between aqueous phase and micellar pseudo-phase in aqueous micellar solutions. However, spectrophotometric studies of acid-base equilibria in these media do not confirm such distribution because of the collinearity between concentrations of chemical species in the two phases. The collinearity causes the number of detected species to be equal to the number of species in a homogenous solution that automatically misinterpreted as homogeneity of micellar solutions, therefore the collinearity is often neglected. This interpretation is in contradiction to the distribution theory in micellar media that must be avoided. Acid-base equilibrium of an indicator was studied in aqueous micellar solutions of a nonionic surfactant to address the collinearity using UV/Visible spectrophotometry. Simultaneous analysis (matrix augmentation) of the equilibrium and solvation data was applied to eliminate the collinearity from the equilibrium data. A model was then suggested for the equilibrium that was fitted to the augmented data to estimate distribution coefficients of the species between the two phases. Moreover, complete resolution of concentration and spectral profiles of species in each phase was achieved.

  2. Effect of Loading History on Stress Corrosion Cracking of 7075-T651 Aluminum Alloy in Saline Aqueous Environment

    NASA Astrophysics Data System (ADS)

    Zhang, Jixi; Kalnaus, Sergiy; Behrooz, Majid; Jiang, Yanyao

    2011-02-01

    An experimental study of stress corrosion cracking (SCC) was conducted on 7075-T651 aluminum alloy in a chromate-inhibited, acidic 3.5 pct sodium chloride aqueous solution using compact tension specimens with a thickness of 3.8 mm under permanent immersion conditions. The effects of loading magnitude, overload, underload, and two-step high-low sequence loading on incubation time and crack growth behavior were investigated. The results show that the SCC process consists of three stages: incubation, transient crack growth, and stable crack growth. The incubation time is highly dependent on the load level. Tensile overload or compressive underload applied prior to SCC significantly altered the initiation time of corrosion cracking. Transition from a high to a low loading magnitude resulted in a second incubation but much shorter or disappearing transient stage. The stable crack growth rate is independent of stress intensity factor in the range of 10 to 22 MPa sqrt {{m}}.

  3. Salt Effect Model for Aqueous Solubility of TBP in a 5 to 100% TBP/n-Dodecane-Nitric Acid-Water Biphasic System at 298.2 K

    SciTech Connect

    Kumar, Shekhar; Koganti, Sudhir Babu

    2000-02-15

    The solubilities of nonelectrolytes in aqueous electrolyte solutions have traditionally been modeled by using the Setschenow equation for salt effect. The aqueous solubility of tri-n-butyl phosphate (TBP) during operating conditions of the Purex process is an important parameter for safety considerations. Use of the Setschenow equation for aqueous solubility of TBP under limited conditions has been reported in the literature. However, there is no general model available to account for the presence of the diluent and for the case of multicomponent electrolyte solutions in which only some electrolytes are solvated and extracted by TBP. An extended salt effect model is proposed for predicting the aqueous solubility of TBP in a 5 to 100% TBP/n-dodecane-nitric acid-water biphasic system at 298.2 K. The literature data on TBP solubility were correlated to aqueous acid concentration, diluent concentration in the solvents, and an interaction parameter for electrolytic solutes (extracted or not extracted by TBP)

  4. Thermodynamic studies of ionic hydration and interactions for amino acid ionic liquids in aqueous solutions at 298.15 K.

    PubMed

    Dagade, Dilip H; Madkar, Kavita R; Shinde, Sandeep P; Barge, Seema S

    2013-01-31

    Amino acid ionic liquids are a special class of ionic liquids due to their unique acid-base behavior, biological significance, and applications in different fields such as templates in synthetic chemistry, stabilizers for biological macromolecules, etc. The physicochemical properties of these ionic liquids can easily be altered by making the different combinations of amino acids as anion along with possible cation modification which makes amino acid ionic liquids more suitable to understand the different kinds of molecular and ionic interactions with sufficient depth so that they can provide fruitful information for a molecular level understanding of more complicated biological processes. In this context, volumetric and osmotic coefficient measurements for aqueous solutions containing 1-ethyl-3-methylimidazolium ([Emim]) based amino acid ionic liquids of glycine, alanine, valine, leucine, and isoleucine are reported at 298.15 K. From experimental osmotic coefficient data, mean molal activity coefficients of ionic liquids were estimated and analyzed using the Debye-Hückel and Pitzer models. The hydration numbers of ionic liquids in aqueous solutions were obtained using activity data. Pitzer ion interaction parameters are estimated and compared with other electrolytes reported in the literature. The nonelectrolyte contribution to the aqueous solutions containing ionic liquids was studied by calculating the osmotic second virial coefficient through an application of the McMillan-Mayer theory of solution. It has been found that the second osmotic virial coefficient which includes volume effects correlates linearly with the Pitzer ion interaction parameter estimated independently from osmotic data as well as the hydrophobicity of ionic liquids. The enthalpy-entropy compensation effect, explained using the Starikov-Nordén model of enthalpy-entropy compensation, and partial molar entropy analysis for aqueous [Emim][Gly] solutions are made by using experimental Gibb

  5. Raman spectra and structures of 1-methyl-4-(4-diethylaminophenylazo)-pyridinium iodide in neutral and acidic aqueous solutions

    NASA Astrophysics Data System (ADS)

    Iwase, Akitaka; Ueda, Atsushi; Kuwae, Akio; Hanai, Kazuhiko; Kunimoto, Ko-Ki

    2013-09-01

    Fourier transform (FT) and resonance Raman spectra of 1-methyl-4-(4-diethylaminophenylazo)-pyridinium iodide (MDP) and its four deuterated and three 15N stable isotopic compounds have been measured in neutral and acidic aqueous solutions, and the molecular structures have been discussed on the basis of detailed vibrational assignments using the isotope shifts. No Raman band due to the azo Ndbnd N group is observed in a neutral aqueous solution and also in the solid state of MDP; therefore, this finding suggests that double bond character of the azo group becomes weak and, consequently, the structures of both benzene and pyridinium rings are close to that of a quinoid. The Raman and the 15N NMR spectra indicate that the Nβ of the azo group is protonated in an acidic solution of MDP. Comparison of the spectra of the two solutions suggests that the benzene ring has more quinoid character in the acidic than in the neutral solution. The chromophore structures have been revealed in each of the neutral (purple) and the acidic (yellow) solution.

  6. Quantitative evaluation of noncovalent interactions between polyphosphate and dissolved humic acids in aqueous conditions.

    PubMed

    Fang, Wei; Sheng, Guo-Ping; Wang, Long-Fei; Ye, Xiao-Dong; Yu, Han-Qing

    2015-12-01

    As one kind of phosphorus species, polyphosphate (poly-P) is ubiquitous in natural environments, and the potential interactions between poly-P and humic substances in the sediments or natural waters would influence the fate of poly-P in the environments. However, the mechanism of the interactions has not yet been understood clearly. In this work, the characteristics and mechanisms of the interactions between humic acids (HA) and two model poly-P compounds with various chain lengths have been investigated. Results show that a stable polyphosphate-HA complex would be formed through the noncovalent interactions, and hydrogen bond might be the main driving force for the binding process, which might be formed between the proton-accepting groups of poly-P (e.g., PO and P-O(-)) and the oxygen containing functional groups in HA. Our findings implied that the presence of humic substances in natural waters, soils and sediments would influence the potential transport and/or mobility of environmental poly-P.

  7. A comparison of dilute aqueous p-toluenesulfonic and sulfuric acid pretreatments and saccharification of corn stover at moderate temperatures and pressures.

    PubMed

    Amarasekara, Ananda S; Wiredu, Bernard

    2012-12-01

    Single step pretreatment-saccharification of corn stover was investigated in aqueous p-toluenesulfonic and sulfuric acid media. Dilute aqueous solution of p-toluenesulfonic acid was a better catalyst than aqueous sulfuric acid of the same H(+) ion concentration for single step pretreatment-saccharification of corn stover at moderate temperatures and pressures. For example, 100mg corn stover heated at 150°C for 1h in 0.100 M H(+) aqueous sulfuric acid produced 64 μmol of total reducing sugars (TRS), whereas the sample heated in 0.100 M H(+)p-toluenesulfonic acid produced 165 μmol of TRS under identical conditions. Glucose yield showed a similar trend, as aq. sulfuric acid and p-toluene sulfonic acid media produced 29 and 35 μmol of glucose respectively after 2.5h. Higher catalytic activity of p-toluenesulfonic acid may be due to an interaction with biomass, supported by repulsion of hydrophobic tolyl group by the aqueous phase.

  8. Activities of microorganisms and enzymes in water-restricted environments: biological activities in aqueous compartments at micron scale

    NASA Astrophysics Data System (ADS)

    Hoppert, Michael; Mlejnek, Klaus; Seiffert, Beatrix; Mayer, Frank

    1997-07-01

    In water-in-oil microemulsions, microdroplets of water, surrounded by a layer of surfactant molecules (reversed micelles), are dispersed in an organic solvent. Various microorganisms (unicellular algae and cyanobacteria) and isolated enzymes were dispersed in microemulsions without loss of biological activity. Each biological system needed a defined quantity of water in the microemulsion for maximum activity. Under optimum conditions, microbial enzymes for various sources (hydrogenases, dehydrogenases) exhibited, besides ten-fold increase in specific activity, a temperature optimum up to 16 degree(s)C higher as compared to aqueous solutions. These experimental findings, together with theoretical considerations, imply that water structure inside reversed micelles is very different from free water, but similar to water in narrow compartments with polar or ionic surfaces. These compartments may represent a model system for environments, where (liquid) water is not available in bulk amounts, but embedded in an anhydrous matrix.

  9. Synchrotron X-ray bio-imaging of natural and synthetic bone-graft materials in an aqueous environment

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Gun; Bark, Chung Wung

    2014-11-01

    Bone-graft materials in dentistry have osteoinductive and osteoconductive abilities, which depend on their microstructural characteristics, such as their porosity, particle size, micro channels, and absorption. These characteristics have been observed using various imaging techniques, such as optical microscopy and scanning electron microscopy (SEM). However, most techniques cannot provide images in water, even though graft materials in vivo are invariably in contact with different water-based fluids. Synchrotron X-ray imaging allows sample microenvironments to be controlled as X-ray beams easily penetrate air and water. In this report, we used the synchrotron X-ray imaging technique to provide in-situ images of various bone-graft materials in aqueous environments. We observed internal microstructural images of bone-graft materials in real-time in 0.9% saline solution and interactions between bone-graft materials and saline, that is, hydration patterns and bone-graft expansion.

  10. Sources and interrelations of oxidants (peroxides and {sup {center_dot}}OH), iron(II), and organic acids formed from aqueous-phase photochemical reactions in clouds, fogs, and aqueous aerosols

    SciTech Connect

    Faust, B.C.; Arakaki, T.; Shu P.G.

    1995-12-31

    Based on studies of cloud waters from Whiteface Mountain, New York, the aqueous photoformation of OH is attributed to two different mechanisms. One of these mechanisms involves the direct photolysis of nitrate, and the other mechanism involves an HOOH-Fe(II) photo-Fenton reaction. Separate studies of well-defined aqueous solutions (pH=3.7) of Fe(III)-dicarboxylate complexes, for dicarboxylates commonly found in atmospheric waters (oxalate, malonate, succinate, glutarate), reveals that these complexes rapidly form Fe(II) and HOOH with 313-nm illumination. Finally, studies of the aqueous (pH=3.7) photolysis of biacetyl, which is commonly found in fogs and clouds, produces acetic acid, peroxyacetic acid, HOOH, CH{sub 3}OOH, and pyruvic acid. The peroxylacetyl radical is proposed as a key intermediate; it is the most strongly oxidizing organic peroxyl radical known to date.

  11. A novel liquid plasma AOP device integrating microwaves and ultrasounds and its evaluation in defluorinating perfluorooctanoic acid in aqueous media.

    PubMed

    Horikoshi, Satoshi; Sato, Susumu; Abe, Masahiko; Serpone, Nick

    2011-09-01

    A simplified and energy-saving integrated device consisting of a microwave applicator and an ultrasonic homogenizer has been fabricated to generate liquid plasma in a medium possessing high dielectric factors, for example water. The microwave waveguide and the ultrasonic transducer were interconnected through a tungsten/titanium alloy stick acting both as the microwave antenna and as the horn of the ultrasonic homogenizer. Both microwaves and ultrasonic waves are simultaneously transmitted to the aqueous media through the tungsten tip of the antenna. The microwave discharge liquid plasma was easily generated in solution during ultrasonic cavitation. The simple device was evaluated by carrying out the degradation of the perfluorooctanoic acid (PFOA), a system highly recalcitrant to degradation by conventional advanced oxidation processes (AOPs). PFOA is 59% degraded in an aqueous medium after only 90 s of irradiation by the plasma. Intermediates were identified by electrospray mass spectral techniques in the negative ion mode.

  12. Free energy surface for Brønsted acid-catalyzed glucose ring-opening in aqueous solution.

    PubMed

    Qian, Xianghong

    2013-10-03

    Car-Parrinello-based molecular dynamics coupled with metadynamics simulations were used to determine the mechanism and associated free energy surface for opening the ring structure of cyclic glucopyranose in acidic aqueous solutions. The ring-opening process is initiated by the protonation of the ring oxygen atom and the breakage of the C1-O5 bond. The barrier for this process is about 25 kcal/mol, in good agreement with experimental measurements. Moreover, the glucose cyclic conformation is found to be more stable than the open chain form. The barrier for proton-catalyzed ring-opening in aqueous solution appears to be largely solvent induced due to the high affinity of water molecules for protons.

  13. in situ formation of rGO quantum dots during GO reduction via interaction with citric acid in aqueous medium

    NASA Astrophysics Data System (ADS)

    Ortega-Amaya, R.; Matsumoto, Y.; Flores-Conde, A.; Pérez-Guzmán, M. A.; Ortega-López, M.

    2016-10-01

    Chemical methods represent an economical approach to the mass production of graphene. Their main drawback is the use of environmentally harmful reagents. This work describes a simple, green method to prepare reduced graphene oxide (rGO) sheets and rGO quantum dots (rGOQD) in a single step using citric acid (CA) as the reductant in aqueous medium at room temperature. The reduction level of the nanocomposite obtained depends strongly on the processing time; the sample treated for 24 h demonstrate significant reduction. It is found that CA not only reduces GO but also functionalizes it to produce well-stabilized rGO aqueous dispersions. Additionally, a mechanism for the reduction and functionalization of GO by CA is proposed.

  14. Amino Acid Synthesis in Seafloor Environments on Icy Worlds

    NASA Astrophysics Data System (ADS)

    Flores, Erika; Barge, Laura; VanderVelde, David; Kallas, Kayo; Baum, Marc M.; Russell, Michael J.; Kanik, Isik

    2016-10-01

    In 2005, the Cassini mission detected plumes erupting from Enceladus' surface, containing carbon dioxide, methane, silica, and possibly ammonia. Subsequent laboratory experiments indicated that the silica particles in the plumes were generated under alkaline conditions and at moderate temperatures of ~90°C (Hsu et al., 2015); one scenario for such conditions would be the existence of alkaline (serpentinization-driven) hydrothermal activity within Enceladus. Alkaline vents are significant since they have been proposed as a likely environment for the emergence of metabolism on the early Earth (Russell et al. 2014) and thus could also provide a mechanism for origin of life on ocean worlds with a water-rock interface. Alkaline vents in an acidic, iron-containing ocean could produce mineral precipitates that could act as primitive enzymes or catalysts mediating organic reactions; for example, metal sulfides can catalyze the reductive amination of pyruvate to alanine (Novikov and Copley 2013). We have conducted experiments testing the synthesis of amino acids catalyzed by other iron minerals that might be expected to precipitate on the seafloor of early Earth or Enceladus. Preliminary results indicate that amino acids as well as other organic products can be synthesized in 1-3 days under alkaline hydrothermal conditions. We also find that the yield and type of organic products is highly dependent on pH and temperature, implying that understanding the specifics of the geochemical hydrothermal gradients on Enceladus (or other ocean worlds) will be significant in determining their potential for synthesizing building blocks for life.Hsu, H.-W. et al. (2015), Nature 519, 207-210.Russell, M. J. et al. (2014), Astrobiology, 14, 308-43.Novikov Y. and Copley S. D. (2013) PNAS 110, 33, 13283-13288.

  15. Polyethylene glycol-coated blue-emitting silicon dots with improved properties for uses in aqueous and biological environments

    NASA Astrophysics Data System (ADS)

    Rodríguez Sartori, Damián; Lillo, Cristian R.; Romero, Juan J.; Dell‧Arciprete, María Laura; Miñán, Alejandro; de Mele, Mónica Fernández Lorenzo; Gonzalez, Mónica C.

    2016-11-01

    Grafting of polyethylene glycol (PEG) to ultrasmall photoluminescent silicon dots (SiDs) is expected to improve and expand the applications of these particles to aqueous environments and biological systems. Herein we report a novel one-pot synthesis of robust, highly water compatible PEG-coated SiDs (denoted as PEG-SiDs) of (3.3 ± 0.5) nm size. The nanoparticles’ synthesis is based on the liquid phase oxidation of magnesium silicide using PEG as reaction media and leading to high PEG density grafting. PEG-SiDs enhanced photophysical, photosensitising, and solution properties in aqueous environments are described and compared to those of 2 nm size PEG-coated SiDs with low PEG density grafting (denoted as PEG-NHSiDs) obtained from a multistep synthesis strategy. PEG-SiDs form highly dispersed suspensions in water showing stable photoluminescence and quantum yields of Φ = 0.13 ± 0.04 at 370 nm excitation in air-saturated suspensions. These particles exhibited the capacity of photosensitising the formation of singlet molecular oxygen, not observed for PEG-NHSiDs. PEG robust shielding of the silicon core luminescent properties is further demonstrated in bio-imaging experiments stressing the strong interaction between PEG-SiDs and Staphylococcus aureus smears by observing the photoluminescence of particles. PEG-SiDs were found to be nontoxic to S. aureus cells at concentrations of 100 mg ml-1, though a bacteriostatic effect on S. aureus biofilms was observed upon UV-A irradiation under conditions where light alone has no effect.

  16. Behavior of transplutonium elements on ion-exchange materials in mixed aqueous-organic solutions of mineral acids

    SciTech Connect

    Guseva, L.I.; Tikhomirov, G.S.; Stepushkina, V.V.

    1987-03-01

    Systematic studies are reported on the behavior of transplutonium elements (TPE) on cation-exchange and anion-exchange materials in mixed aqueous-organic solutions of mineral acids (HClO/sub 4/, HCl, HNO/sub 3/, H/sub 2/SO/sub 4/, H/sub 3/PO/sub 4/) as affected by solution composition, nature of acid, and nature of organic solvent. With all these acids, replacing most of the water by alcohol increases the TPE uptake on the ion exchangers, and the effect occurs for the cation exchangers at lower contents of the organic component. Optimum conditions have been identified for concentrating and separating TPE from numerous elements. The most effective system consists of anion exchanger with HNO/sub 3/ and alcohol.

  17. Simultaneous determination of nitric acid and uranium concentrations in aqueous solution from measurements of electrical conductivity, density, and temperature

    SciTech Connect

    Spencer, B.B.

    1991-01-01

    Nuclear fuel reprocessing plants handle aqueous solutions of nitric acid and uranium in large quantities. Automatic control of process operations requires reliable measurements of these solutes concentration, but this is difficult to directly measure. Physical properties such as solution density and electrical conductivity vary with solute concentration and temperature. Conductivity, density and temperature can be measured accurately with relatively simple and inexpensive devices. These properties can be used to determine solute concentrations will good correlations. This paper provides the appropriate correlations for solutions containing 2 to 6 Molar (M) nitric acid and 0 to 300 g/L uranium metal at temperatures from 25--90{degrees}C. The equations are most accurate below 5 M nitric acid, due to a broad maximum in the conductivity curve at 6 M. 12 refs., 9 figs., 6 tabs.

  18. Recovery of transplutonium elements from aqueous and water-ethanol solutions of sulfuric acid and their separation from other actinides

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1988-05-01

    The behavior of Am, Cm, Bk, Cf, Es, and other actinides, as well as Zr, on anion and cation exchangers in aqueous and water-ethanol solutions of sulfuric acid as a function of the various components of the solution has been investigated. It has been discovered that the presence of ethanol in sulfuric acid solutions causes an increase in the distribution coefficients both on cation exchangers and on anion exchangers. The possibility of the use of ion exchangers for the preconcentration and separation of transplutonium elements from U, Np, Pu, Zr, and other elements which form strong complexes with sulfate ions over a broad range of concentrations of sulfuric acid has been demonstrated.

  19. Acid gas treating by aqueous alkanolamines. Annual report, July-December 1992

    SciTech Connect

    Sandall, O.C.; Rinker, E.B.; Tamimi, A.; Davis, R.A.; Oelschlager, D.W.

    1992-12-01

    The objective of the work is to investigate the simultaneous absorption or desorption of CO2 and H2S into and from a mixed aqueous amine solvent consisting of methyldiethanolamine (MDEA) and diethanolamine (DEA). In work completed thus far models have been developed for single gas (either H2S or CO2) absorption into a single amine solution (MDEA or DEA). Density and viscosity measurements have been made for aqueous MDEA, DEA and MDEA/DEA mixtures over the temperature range 20 to 100 C and for concentrations up to 50 weight %.

  20. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part II. Recovery of Ammonia from Sour Waters

    SciTech Connect

    Poole, L.J.; King, C.J.

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO{sub 2} and H{sub 2}S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, SUCCiOlC acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The concentration

  1. Automatically purification of aqueous CdTe nanocrystals in water-ethanol co-environment.

    PubMed

    Jiang, Yuan; Wang, Chunlei; Xu, Shuhong; Shao, Haibao; Lin, Xiaoyan; Wang, Zhuyuan; Cui, Yiping

    2014-01-01

    Purification is a separated post-treatment step after the synthesis of nanocrystals (NCs) in order to exclude excess ligands and monomers in NC solution. The common purification process involves many manipulations, such as concentrating, addition of anti-solvents and centrifugation, which are troublesome and time consuming. In this work, we originally integrate NC synthesis and NC purification in one-pot via selecting water-ethanol co-environment for NC synthesis and NC purification. Our research shows that NCs can grow in water-ethanol mixture. When growing into critical size, NCs will automatically precipitate from the solution. Element analysis demonstrates that precipitates fraction fits well with stoichiometric of ligand-capped NCs. Excess monomers are left in supernatant, and thus achieving automatically purification of NCs in the water-ethanol co-environment. By adjusting the volume ratios of water and ethanol in bi-solvent system, different-sized purified NCs can be controlled. Besides, this water-ethanol co-environment can be used in both thermal-promoted and hydrazine-promoted growth.

  2. Capillary electrophoresis of some free fatty acids using partially aqueous electrolyte systems and indirect UV detection. Application to the analysis of oleic and linoleic acids in peanut breeding lines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study has shown for the first time the suitability of CE with a partially aqueous electrolyte system for the analysis of free fatty acids (FFA's) in small portions of single peanut seeds. The partially aqueous electrolyte system consisted of 40 mM Tris, 2.5 mM adenosine-5'-monophosphate (AMP) ...

  3. Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

    SciTech Connect

    Gomez-Gonzalez, Sergio Efrain; Carbajal-Arizaga, Gregorio Guadalupe; Manriquez-Gonzalez, Ricardo; De la Cruz-Hernandez, Wencel; Gomez-Salazar, Sergio

    2014-11-15

    Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH{sub 3}COO){sub 2}Cr{sup +} ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. {sup 13}C, {sup 29}Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level.

  4. Atomic force microscopy based nanoindentation study of onion abaxial epidermis walls in aqueous environment

    NASA Astrophysics Data System (ADS)

    Xi, Xiaoning; Kim, Seong H.; Tittmann, Bernhard

    2015-01-01

    An atomic force microscopy based nanoindentation method was employed to study how the structure of cellulose microfibril packing and matrix polymers affect elastic modulus of fully hydrated primary plant cell walls. The isolated, single-layered abaxial epidermis cell wall of an onion bulb was used as a test system since the cellulose microfibril packing in this cell wall is known to vary systematically from inside to outside scales and the most abundant matrix polymer, pectin, can easily be altered through simple chemical treatments such as ethylenediaminetetraacetic acid and calcium ions. Experimental results showed that the pectin network variation has significant impacts on the cell wall modulus, and not the cellulose microfibril packing.

  5. Atomic force microscopy based nanoindentation study of onion abaxial epidermis walls in aqueous environment

    SciTech Connect

    Xi, Xiaoning; Tittmann, Bernhard; Kim, Seong H.

    2015-01-14

    An atomic force microscopy based nanoindentation method was employed to study how the structure of cellulose microfibril packing and matrix polymers affect elastic modulus of fully hydrated primary plant cell walls. The isolated, single-layered abaxial epidermis cell wall of an onion bulb was used as a test system since the cellulose microfibril packing in this cell wall is known to vary systematically from inside to outside scales and the most abundant matrix polymer, pectin, can easily be altered through simple chemical treatments such as ethylenediaminetetraacetic acid and calcium ions. Experimental results showed that the pectin network variation has significant impacts on the cell wall modulus, and not the cellulose microfibril packing.

  6. Intermolecular interactions in aqueous solutions of gallic acid at 296-306 K according to spectrofluorimetry and densimetry data

    NASA Astrophysics Data System (ADS)

    Grigoryan, K. R.; Sargsyan, L. S.

    2015-12-01

    Features of intermolecular interactions in aqueous solutions of gallic acid (GA) are studied by means of densimetry and fluorescence spectroscopy (intrinsic fluorescence, 2D spectra, and excitation/ emission matrix fluorescence spectra, 3D) at 296.15, 301.15, and 306.15 K in the concentration range of 5.88 × 10-4-5.88 × 10-2 mol L-1. It is shown by analyzing the concentration and temperature dependences of the apparent molar volumes and fluorescence parameters of GA that the equilibrium between nonassociated and associated species in the solution and the hydration of these species undergo changes.

  7. Experimental and theoretical evaluation on the microenvironmental effect of dimethyl sulfoxide on adrenaline in acid aqueous solution

    NASA Astrophysics Data System (ADS)

    Yu, Zhang-Yu; Liu, Tao; Guo, Dao-Jun; Liu, Yong-Jun; Liu, Cheng-Bu

    2010-12-01

    The microenvironmental effect of dimethyl sulfoxide (DMSO) on adrenaline was studied by several approaches including the cyclic voltammetry (CV) of adrenaline at a platinum electrode in acid aqueous solution, the chemical shift of 1H nuclear magnetic resonance ( 1H NMR) of adrenaline, and the change of diffusion coefficient of adrenaline. The experimental results demonstrated that DMSO has significant microenvironmental effect on adrenaline, which was confirmed by the density functional theory (DFT) study on the hydrogen bond (H-bond) complexes of adrenaline with water and DMSO.

  8. Chemiluminescence studies between aqueous phase synthesized mercaptosuccinic acid capped cadmium telluride quantum dots and luminol-H2O2

    NASA Astrophysics Data System (ADS)

    Kaviyarasan, Kulandaivelu; Anandan, Sambandam; Mangalaraja, Ramalinga Viswanathan; Asiri, Abdullah M.; Wu, Jerry J.

    2016-08-01

    Mercaptosuccinic acid capped Cadmium telluride quantum dots have been successfully synthesized via aqueous phase method. The products were well characterized by a number of analytical techniques, including FT-IR, XRD, HRTEM, and a corrected particle size analysis by the statistical treatment of several AFM measurements. Chemiluminescence experiments were performed to explore the resonance energy transfer between chemiluminescence donor (luminol-H2O2 system) and acceptor CdTe QDs. The combination of such donor and acceptor dramatically reduce the fluorescence while compared to pristine CdTe QDs without any exciting light source, which is due to the occurrence of chemiluminescence resonance energy transfer (CRET) processes.

  9. Unexpectedly Enhanced Solubility of Aromatic Amino Acids and Peptides in an Aqueous Solution of Divalent Transition-Metal Cations

    NASA Astrophysics Data System (ADS)

    Shi, Guosheng; Dang, Yaru; Pan, Tingting; Liu, Xing; Liu, Hui; Li, Shaoxian; Zhang, Lijuan; Zhao, Hongwei; Li, Shaoping; Han, Jiaguang; Tai, Renzhong; Zhu, Yiming; Li, Jichen; Ji, Qing; Mole, R. A.; Yu, Dehong; Fang, Haiping

    2016-12-01

    We experimentally observed considerable solubility of tryptophan (Trp) in a CuCl2 aqueous solution, which could reach 2-5 times the solubility of Trp in pure water. Theoretical studies show that the strong cation-π interaction between Cu2 + and the aromatic ring in Trp modifies the electronic distribution of the aromatic ring to enhance significantly the water affinity of Trp. Similar solubility enhancement has also been observed for other divalent transition-metal cations (e.g., Zn2 + and Ni2 + ), another aromatic amino acid (phenylalanine), and three aromatic peptides (Trp-Phe, Phe-Phe, and Trp-Ala-Phe).

  10. Aspartic acid interaction with cobalt(II) in dilute aqueous solution: A 57Co emission Mössbauer spectroscopic study

    NASA Astrophysics Data System (ADS)

    Kamnev, Alexander A.; Tugarova, Anna V.; Kovács, Krisztina; Homonnay, Zoltan; Kuzmann, Erno; Vértes, Attila

    2012-03-01

    Emission (57Co) Mössbauer spectra of the aspartic acid—57CoCl2 system were measured at T = 80 K in frozen aqueous solution and in the form of a dried residue of this solution. The Mössbauer spectra, besides a weak contribution from after-effects, showed two Fe2 + /Co2 + components which were ascribed to octahedrally and tetrahedrally coordinated 57CoII microenvironments in the Asp-cobalt(II) complex. This dual coordination mode may be due to the involvement of the second terminal carboxylic group of aspartic acid in the coordination sphere of Co.

  11. UV Irradiation and Humic Acid Mediate Aggregation of Aqueous Fullerene (nC60) Nanoparticles

    EPA Science Inventory

    The transport and fate of engineered nanomaterials is affected by multiple environmental factors, including sunlight and natural organic matter. In this study, the initial aggregation kinetics of aqueous fullerene (nC60) nanoparticles before and after UVA irradiation was investig...

  12. Quantitative extraction and concentration of synthetic water-soluble acid dyes from aqueous media using a quinine-chloroform solution

    SciTech Connect

    Kobayashi, F.; Ozawa, N.; Hanai, J.; Isobe, M.; Watabe, T.

    1986-12-01

    Twenty-one water-soluble acid dyes, including eleven azo, five triphenylmethane four xanthene, one naphthol derivatives, used at practical concentrations for food coloration, were quantitatively extracted from water and various carbonated beverages into a 0.1 M quinine-chloroform solution in the presence of 0.5 M boric acid by brief shaking. Quantitative extraction of these dyes was also accomplished by the 0.1 M quinine-chloroform solution made conveniently from chloroform, quinine hydrochloride, and sodium hydroxide added successively to water or beverages containing boric acid. Quinine acted as a countercation on the dyes having sulfonic and/or carboxylic acid group(s) to form chloroform-soluble ion-pair complexes. The diacidic base alkaloid interacted with each acid group of mono-, di-, tri-, and tetrasulfonic acid dyes approximately in the ratio 0.8-0.9 to 1. The dyes in the chloroform solution were quantitatively concentrated into a small volume of sodium hydroxide solution also by brief shaking. The convenient quinine-chloroform method was applicable to the quantitative extraction of a mixture of 12 dyes from carbonated beverages, which are all currently used for food coloration. A high-pressure liquid chromatographic method is also presented for the systematic separation and determination of these 12 dyes following their concentration into the aqueous alkaline solution. The chromatogram was monitored by double-wavelength absorptiometry in the visible and ultraviolet ray regions.

  13. Steric structure and thermodynamic aspects of the complexes of dysprosium (III) with aminobenzoic acids in aqueous solutions

    SciTech Connect

    Kondrashina, Yu, G.; Mustafina, A.R.; Vul`fson, S.G.

    1994-10-01

    Steric structures of dysprosium (III) aminobenzoate complexes with the 1:1 and 1:2 molar ratio in aqueous solutions were determined on the basis of pH-metric and paramagnetic birefringence data. An increase in conjugation observed for the series of the acids, viz., benzoic, meta-, ortho-, and para-aminobenzoic acids, results in the increased stability of the complexes with the 1:1 and 1:2 composition. In the case of para-aminobenzoic acid, the polyhedra [DyL(H{sub 2}O){sub 6}]{sup 2+} and [DyL{sub 2}(H{sub 2}O){sub 4}]{sup +} are cubes with the ligands coordinated to one and two edges, respectively. In the case of meta-aminobenzoic acid, the polyhedra [DyL(H{sub 2}O){sub 6}]{sup 2+} and [DyL{sub 2}(H{sub 2}O){sub 4}]{sup +} are a dodecahedron with the ligand coordinated to one edge and a square anti-prism with the ligands coordinated to two edges, respectively. In the case of ortho-aminobenzoic acid, both the 1:1 and 1:2 complexes have structures that are intermediate between the structures of meta- and para-aminobenzoic acids.

  14. Studies on estrification and sulphonation of riboflavin in the environment of highly concentrated sulphuric acid.

    PubMed

    Pajak, Wojciech; Brzezińska, Elzbieta

    2003-01-01

    The article presents investigations of riboflavin reactions in aqueous solutions of sulphuric acid. Analysis of UV/VIS, 1H NMR spectra and TLC indicates that at the beginning of the reaction ester of riboflavin were obtained and then sulphonation reaction took place. From the analysis of UV/VIS spectra the kinetics of the reaction was calculated, using own computer program.

  15. Formation of Amino Acids on the Sonolysis of Aqueous Solutions Containing Acetic Acid, Methane, or Carbon Dioxide, in the Presence of Nitrogen Gas.

    PubMed

    Dharmarathne, Leena; Grieser, Franz

    2016-01-21

    The sonolysis of aqueous solutions containing acetic acid, methane, or carbon dioxide in the presence of nitrogen gas was found to produce a number of different amino acids at a rate of ∼1 to 100 nM/min, using ultrasound at an operating power of 70 W and 355 kHz. Gas-phase elementary reactions are suggested, and discussed, to account for the formation of the complex biomolecules from the low molar mass solutes used. On the basis of the results, a new hypothesis is presented to explain the formation of amino acids under primitive atmospheric conditions and how their formation may be linked to the eventual abiotic genesis of life on Earth.

  16. Water-Gated n-Type Organic Field-Effect Transistors for Complementary Integrated Circuits Operating in an Aqueous Environment

    PubMed Central

    2017-01-01

    The first demonstration of an n-type water-gated organic field-effect transistor (WGOFET) is here reported, along with simple water-gated complementary integrated circuits, in the form of inverting logic gates. For the n-type WGOFET active layer, high-electron-affinity organic semiconductors, including naphthalene diimide co-polymers and a soluble fullerene derivative, have been compared, with the latter enabling a high electric double layer capacitance in the range of 1 μF cm–2 in full accumulation and a mobility–capacitance product of 7 × 10–3 μF/V s. Short-term stability measurements indicate promising cycling robustness, despite operating the device in an environment typically considered harsh, especially for electron-transporting organic molecules. This work paves the way toward advanced circuitry design for signal conditioning and actuation in an aqueous environment and opens new perspectives in the implementation of active bio-organic interfaces for biosensing and neuromodulation. PMID:28180187

  17. Water-Gated n-Type Organic Field-Effect Transistors for Complementary Integrated Circuits Operating in an Aqueous Environment.

    PubMed

    Porrazzo, Rossella; Luzio, Alessandro; Bellani, Sebastiano; Bonacchini, Giorgio Ernesto; Noh, Yong-Young; Kim, Yun-Hi; Lanzani, Guglielmo; Antognazza, Maria Rosa; Caironi, Mario

    2017-01-31

    The first demonstration of an n-type water-gated organic field-effect transistor (WGOFET) is here reported, along with simple water-gated complementary integrated circuits, in the form of inverting logic gates. For the n-type WGOFET active layer, high-electron-affinity organic semiconductors, including naphthalene diimide co-polymers and a soluble fullerene derivative, have been compared, with the latter enabling a high electric double layer capacitance in the range of 1 μF cm(-2) in full accumulation and a mobility-capacitance product of 7 × 10(-3) μF/V s. Short-term stability measurements indicate promising cycling robustness, despite operating the device in an environment typically considered harsh, especially for electron-transporting organic molecules. This work paves the way toward advanced circuitry design for signal conditioning and actuation in an aqueous environment and opens new perspectives in the implementation of active bio-organic interfaces for biosensing and neuromodulation.

  18. A systematic investigation and insight into the formation mechanism of bilayers of fatty acid/soap mixtures in aqueous solutions.

    PubMed

    Xu, Wenlong; Song, Aixin; Dong, Shuli; Chen, Jingfei; Hao, Jingcheng

    2013-10-08

    Vesicles are the most common form of bilayer structures in fatty acid/soap mixtures in aqueous solutions; however, a peculiar bilayer structure called a "planar sheet" was found for the first time in the mixtures. In the past few decades, considerable research has focused on the formation theory of bilayers in fatty acid/soap mixtures. The hydrogen bond theory has been widely accepted by scientists to explain the formation of bilayers. However, except for the hydrogen bond, no other driving forces were proposed systematically. In this work, three kinds of weak interactions were investigated in detail, which could perfectly demonstrate the formation mechanism of bilayer structures in the fatty acid/soap mixtures in aqueous solutions. (i) The influence of hydrophobic interaction was detected by changing the chain length of fatty acid (C(n)H(2n+1)COOH), in which n = 10 to 18, the phase behavior was investigated, and the phase region was presented. With the help of cryogenic transmission electron microscopy (cryo-TEM) observations, deuterium nuclear magnetic resonance ((2)H NMR), and X-ray diffraction (XRD) measurements, the vesicles and planar sheets were determined. The chain length of C(n)H(2n+1)COOH has an important effect on the physical state of the hydrophobic chain, resulting in an obvious difference in the viscoelasticity of the solution samples. (ii) The existence of hydrogen bonds between fatty acids and their soaps in aqueous solutions was demonstrated by Fourier transform infrared (FT-IR) spectroscopy and molecule dynamical simulation. From the pH measurements, the pH ranges of the bilayer formation were at the pKa values of fatty acids, respectively. (iii) Counterions can be embedded in the stern layer of the bilayers and screen the electrostatic repulsion between the COO(-) anionic headgroups. FT-IR characterization demonstrated a bidentate bridging coordination mode between counterions and carboxylates. The conductivity measurements provided the degree

  19. Reproduction potentiated in nematodes (Caenorhabditis elegans) and guppy fish (Poecilia reticulata) by adding a synthetic peptide to their aqueous environment.

    PubMed

    Davies, Keith G; Zimmerman, Brian; Dudley, Ed; Newton, Russell P; Hart, John E

    2015-03-01

    Ambient exposure to a short synthetic peptide has enhanced fecundity (number of offspring) in invertebrates and vertebrates, ostensibly by disinhibiting reproduction. In separate experiments, nematodes (Caenorhabditis elegans) and guppy fish (Poecilia reticulata) were exposed via their aqueous environment to a dissolved synthetic hexamer (6mer) peptide, IEPVFT (EPL036), at a concentration of 1 μmol l(-1). In the case of the worms, peptide was added to their aqueous buffer daily throughout the experiment (14 days); for the guppies, peptide administration was on the first 15 alternate days in a 50 week experiment. Fecundity rose by 79% among the worms. The number of descendants of the treated guppies was more than four times that of controls by week 26 (103 versus 25, including 72 juveniles versus 6), with 15.4% more estimated biomass in the test tank in total (i.e. including founders). It was deduced that treated females bred earlier, at a smaller size, and had larger brood sizes. The total number of fish in the control tank had caught up by termination, but biomass continued to lag the test tank. There were no overt signs of toxicity among either the worms or the fish. Bioinformatics has been unilluminating in explaining these results in terms, for example, of mimicry of an endogenous regulator. A mass spectrometric campaign to identify a receptor, using murine brain for expediency, proved inconclusive. Molecular modelling in silico indicated unexpectedly that the hexamer EPL036 might be acting as an antagonist, to pro-fecundity effect; that is, as a blocker of an inhibitor. This suggests that there awaits discovery an evolutionarily conserved reproductive inhibitor and its (anti-fecundity) receptor.

  20. Corrosion characteristics of seven metals in three aqueous environments for forensic applications

    NASA Astrophysics Data System (ADS)

    Tong, Tianqi

    Corrosion characteristics of seven varieties of metals---zinc, brass C260, stainless steel 302, stainless steel 316, stainless steel 420, stainless steel 430, and stainless steel 440---in three aqueous media---Atlantic Ocean, Charles River, and deionized waters---were assessed via mass loss methods over 32 weeks, with supplemental data in the form of photomicrographic records. Concurrently, tests were conducted to determine the degree of measurement error resulting from the analytical scale used during corrosion assessment. This was accomplished by using reference samples of each type of metal and a glass vial as the container that held the metal and water samples. These error tests indicated that while the mass error associated with the metal samples was low, the error in mass associated with the vial displayed error margins two orders of magnitude larger than the error margins for the smaller metal samples. Further, control tests and statistical analysis indicated that this variation was the result of some quality inherent to the vial. The metal samples involved in the corrosion assessment experiment generally displayed corrosion characteristics in agreement with trends reported in the literature. Zinc produced the greatest quantity of corrosion residues out of all the metals studied. Brass C260 also developed visible corrosion. For example, brass C260 developed dark green/brown adherent residue and whitish blue-tinted nonadherent residue in Atlantic Ocean water, faint greenish tarnishing and some dark green spots and dots over time in Charles River water, and only faint greenish tarnish in deionized water. In contrast with zinc and brass C260, the stainless steels did not exhibit signs of significant corrosion rates excepting stainless steel 420 (SS420), which displayed pitted features surrounded by multi-colored rings on all of its Atlantic Ocean immersion samples and 25% of its Charles River immersion samples. Atlantic Ocean water generally caused the greatest

  1. Biodegradation of Aromatic Hydrocarbons in an Extremely Acidic Environment

    PubMed Central

    Stapleton, Raymond D.; Savage, Dwayne C.; Sayler, Gary S.; Stacey, Gary

    1998-01-01

    The potential for biodegradation of aromatic hydrocarbons was evaluated in soil samples recovered along gradients of both contaminant levels and pH values existing downstream of a long-term coal pile storage basin. pH values for areas greatly impacted by runoff from the storage basin were 2.0. Even at such a reduced pH, the indigenous microbial community was metabolically active, showing the ability to oxidize more than 40% of the parent hydrocarbons, naphthalene and toluene, to carbon dioxide and water. Treatment of the soil samples with cycloheximide inhibited mineralization of the aromatic substrates. DNA hybridization analysis indicated that whole-community nucleic acids recovered from these samples did not hybridize with genes, such as nahA, nahG, nahH, todC1C2, and tomA, that encode common enzymes from neutrophilic bacteria. Since these data suggested that the degradation of aromatic compounds may involve a microbial consortium instead of individual acidophilic bacteria, experiments using microorganisms isolated from these samples were initiated. While no defined mixed cultures were able to evolve 14CO2 from labeled substrates in these mineralization experiments, an undefined mixed culture including a fungus, a yeast, and several bacteria successfully metabolized approximately 27% of supplied naphthalene after 1 week. This study shows that biodegradation of aromatic hydrocarbons can occur in environments with extremely low pH values. PMID:9797263

  2. Design of a Multisensory Probe for Measuring Carbon Cycle Processes in Aqueous Subterranean Environments

    SciTech Connect

    McIntyre, Timothy J; Kisner, Roger; Woodworth, Ken; Lenarduzzi, Roberto; Frank, Steven Shane; McKnight, Timothy E

    2015-01-01

    The global carbon cycle describes the exchange of carbon between the atmosphere, terrestrial vegetation, oceans, and soil. Mechanisms involving carbon in sub-terrestrial ecosystems and their impact on climate are not well understood. This lack of understanding limits current climate models and prevents accurate soil-carbon storage predications for future climate conditions. To address the lack of instrumentation for conducting high fidelity measurements of appropriate parameters in the field, a multi-sensory probe using a mix of optical, fiber optic, and electronic technologies to measure CO2, temperature, dissolved oxygen, redox potential, and water level in subsurface environments has been developed. Details of the design, fabrication and laboratory performance verification are presented. Use cases and the anticipated impacts of such measurements on climate models are discussed.

  3. Plasmon-driven dimerization via S-S chemical bond in an aqueous environment.

    PubMed

    Cui, Lin; Wang, Peijie; Chen, Xiaowei; Fang, Yurui; Zhang, Zhenglong; Sun, Mengtao

    2014-11-27

    The surface-enhanced Raman scattering (SERS) spectra of thioanisole are experimentally investigated in an electrochemical environment in this study. Two Raman peaks, which depend strongly not only on electric potential but also on the local surface plasmon resonances (LSPR), have been observed. Theoretical calculations reveal that thioanisole is first dissociated from thiophenol via the S-CH3 bond; plasmons then drive the dimerisation of thiophenol via the S-S bond, which is strongly potential dependent. One Raman peak corresponds to the S-S vibrational mode of the thiophenol dimer, and the other corresponds to the asymmetric C-C stretching modes of the benzenyl of the thiophenol dimer. The potential-dependent two Raman modes is the potential-dependent dimerisation dynamics of thiophenol via the S-S bond. Our experimental findings provide insight into the structural elucidation of adsorbed molecules and molecular surface reaction dynamics.

  4. Ranking of phenols for abiotic oxidation in aqueous environment: a QSPR approach.

    PubMed

    Gramatica, Paola; Pilutti, Pamela; Papa, Ester

    2005-01-01

    The limited availability and variability of data related to the overall degradation of compounds in the environment is a very relevant issue in studies related to environmental fate and chemical behavior. The studied phenol data set consists of reaction rate constants of different oxidation reactions in surface waters, available either experimentally or, to fill the data gap, from our QSAR models reported herein. A PCA (Principal Component Analysis) model based on these oxidative degradations has been proposed to evaluate the degradability of chemicals. The score of the first Principal Component is modelled by theoretical molecular descriptors to obtain a multiple linear regression (MLR) model with high predictive power, both internally and externally validated. This modeling approach allows a fast and preliminary ranking of phenols according to their tendency to be degraded by oxidants in water, starting only from knowledge of their molecular structure.

  5. Plasmon-driven dimerization via S-S chemical bond in an aqueous environment

    PubMed Central

    Cui, Lin; Wang, Peijie; Chen, Xiaowei; Fang, Yurui; Zhang, Zhenglong; Sun, Mengtao

    2014-01-01

    The surface-enhanced Raman scattering (SERS) spectra of thioanisole are experimentally investigated in an electrochemical environment in this study. Two Raman peaks, which depend strongly not only on electric potential but also on the local surface plasmon resonances (LSPR), have been observed. Theoretical calculations reveal that thioanisole is first dissociated from thiophenol via the S-CH3 bond; plasmons then drive the dimerisation of thiophenol via the S-S bond, which is strongly potential dependent. One Raman peak corresponds to the S-S vibrational mode of the thiophenol dimer, and the other corresponds to the asymmetric C-C stretching modes of the benzenyl of the thiophenol dimer. The potential-dependent two Raman modes is the potential-dependent dimerisation dynamics of thiophenol via the S-S bond. Our experimental findings provide insight into the structural elucidation of adsorbed molecules and molecular surface reaction dynamics. PMID:25427897

  6. A water-soluble polylysine-retinaldehyde Schiff base. Stability in aqueous and nonaqueous environments.

    PubMed

    Viguera, A R; Villa, M J; Goñi, F M

    1990-02-15

    In order to improve the existing models of retinal-protein Schiff bases, a water-soluble polylysine-retinaldehyde imine has been synthesized and its stability assessed under a variety of conditions through changes in the visible absorption spectrum. The compound absorbs at 342 nm and consists of a 90-kDa poly-L-lysine containing a retinal Schiff base in about 2% of the lysyl epsilon-amino ends. Retinal is mostly in the all-trans form; under no conditions is more than 15% of the 13-cis isomer detected. The absorption maximum exhibits a pH-dependent reversible shift to 402 nm, with an apparent pKa approximately 3.4. In the presence of the anionic surfactant sodium dodecyl sulfate, this pKa is shifted to approximately 8.9, probably because of electric neutralization of lysyl epsilon-amino groups. Other detergents (cetyltrimethylammonium bromide, Triton X-100) do not modify the Schiff base pKa, but rather promote its hydrolysis; in this case detergents act in the same way as certain solvent mixtures, by providing an amphiphillic environment to the imine that in turn stabilizes the products of hydrolysis. Our results suggest that once the surfactant reaches the Schiff base, preferential partition of retinal into detergent micelles is the main factor facilitating imine bond breakdown. The response of our synthetic Schiff base to changes in pH or solvent polarity point together to an important role of the supporting polypeptide in providing a suitable environment to the chromophore.

  7. A study of effects of acid activated saw dust on the removal of different dissolved tannery dyes (acid dye) from aqueous solutions.

    PubMed

    Dhar, N R; Khoda, A K M B; Khan, A H; Bala, P; Karim, M F

    2005-04-01

    The effectiveness of acid activated sawdust in absorbing D-Brown EGP and Lurazol Brown PM dyes from aqueous solutions was studied as a function of agitation time and initial dye concentration. The experimental data were fitted to Langmuir and Freundlich isotherm and found that adsorption process follows both the isotherms. The values of Langmuir and Freundlich constants indicate favorable and beneficial adsorption. Saw dust is an excellent low cost adsorbent of colored organic anions and may have significant potential as a color removal from tannery wastewater.

  8. Experimental Design Approach for Methylene Blue Dye Removal in Aqueous Environment by Nitrilotriacetic Modified Banana Pith.

    PubMed

    Lee, Shi-Ling; Liew, Shu-Wei; Ong, Siew-Teng

    2016-01-01

    Native banana pith (NBP) was modified by using nitrilotriacetic acid to increase its efficiency and adsorption capacity for methylene blue (MB) dye. The effect of various parameters such as pH, contact time and initial dye concentration, sorption isotherm and adsorbent dosage were studied. The maximum adsorption capacity of the NBP and NTA-BP is 100 and 142.86 mg/g, respectively. The IR spectrum of NBP and NTA-BP showed the presence of both carboxyl and hydroxyl groups. From the SEM micrographs, the surface morphology of NTA-BP before adsorption appeared to be smoother as compared to that after adsorption process. The pH(pzc) of NBP is 5.6 whereas for NTA-BP is 7.6. The experimental data fitted well into Langmuir isotherm with R(2) of 0.992. Plackett-Burman design was applied to identify the significant factors in affecting the uptake whereas the interaction between the factors and their optimum levels for the maximum percentage uptake of MB were determined using response surface methodology (RSM). Based on the results, the optimum condition for adsorption of MB was by using 0.06 g of NTA-BP in dye solution at pH 6 with 120 minutes contact time. The maximum adsorption of MB by NTA-BP achieved 99.42% under the optimum condition.

  9. Role of low molecular weight organic acids on pyrite dissolution in aqueous systems: implications for catalytic chromium (VI) treatment.

    PubMed

    Kantar, Cetin

    2016-01-01

    A systematic study combining batch experiments with spectroscopic analyses was carried out to better understand the effects of various organic acids on pyrite dissolution and subsequent Cr(VI) removal in aqueous systems. Our results suggest that organic acids had no effect on total Fe dissolution from pyrite relative to systems containing no acid. However, while nearly 100% of total Fe dissolved from pyrite was in Fe(II) form in the absence of ligands, the addition of organic acids led to significant oxidation of Fe(II) species to Fe(III). The degree and extent of Fe(II) oxidation increased in the order: tartrate < salicylate < oxalate ≈ citrate < EDTA. Except for salicylate (an aromatic compound), this stimulatory effect observed in Fe(II) oxidation was well correlated with the strength of Fe-ligand complexes. In systems containing Cr(VI), the amount of Fe dissolved increased significantly relative to non-Cr(VI) containing system, and the ligands enhanced the dissolution of surface oxidation products from pyrite. Overall, it is clear that the dissolution of pyrite with organic acids had very little effect on solution phase Cr(VI) removal, but significantly stimulated surface phase Cr(VI) reduction by removing surface oxidation products, and thus creating new surface sites for extended Cr(VI) removal.

  10. Biosorption of hexavalent chromium by raw and acid-treated green alga Oedogonium hatei from aqueous solutions.

    PubMed

    Gupta, V K; Rastogi, A

    2009-04-15

    The hexavalent chromium, Cr(VI), biosorption by raw and acid-treated Oedogonium hatei were studied from aqueous solutions. Batch experiments were conducted to determine the biosorption properties of the biomass. The optimum conditions of biosorption were found to be: a biomass dose of 0.8 g/L, contact time of 110 min, pH and temperature 2.0 and 318 K respectively. Both Langmuir and Freundlich isotherm equations could fit the equilibrium data. Under the optimal conditions, the biosorption capacities of the raw and acid-treated algae were 31 and 35.2 mg Cr(VI) per g of dry adsorbent, respectively. Thermodynamic parameters showed that the adsorption of Cr(VI) onto algal biomass was feasible, spontaneous and endothermic under studied conditions. The pseudo-first-order kinetic model adequately describe the kinetic data in comparison to second-order model and the process involving rate-controlling step is much complex involving both boundary layer and intra-particle diffusion processes. The physical and chemical properties of the biosorbent were determined and the nature of biomass-metal ions interactions were evaluated by FTIR analysis, which showed the participation of -COOH, -OH and -NH(2) groups in the biosorption process. Biosorbents could be regenerated using 0.1 M NaOH solution, with up to 75% recovery. Thus, the biomass used in this work proved to be effective materials for the treatment of chromium bearing aqueous solutions.

  11. Mechanism of polyol-induced protein stabilization: solubility of amino acids and diglycine in aqueous polyol solutions.

    PubMed

    Gekko, K

    1981-12-01

    The solubilities of several amino acids and diglycine have been measured in water and at several concentrations of methanol and various polyols (glycerol, erythritol, xylitol, sorbitol, and inositol). The solubility data were used to calculate the free energy of transfer of amino acid side chains and peptide group from water to the aqueous alcohol solutions. The results for methanol systems were similar to those reported for ethanol and dioxane systems. The free energy of transfer to aqueous solutions of linear polyols was positive for most nonpolar side chains and peptide group, but high concentrations of the polyols may disrupt the hydrophobic interactions of large nonpolar side chains. Moreover, the linear polyols appeared to stabilize the hydrophobic interaction more effectively and the peptide-peptide hydrogen bond less effectively with increasing hydroxymethyl chain length of polyols. A cyclic polyol, inositol, had a very strong stabilizing ability on hydrophobic interactions of nonpolar side chains, but it may act as a destabilizing reagent for peptide-peptide hydrogen bonds. From these results, it was concluded that the protein stabilization by polyols is a manifestation of polyol-induced strengthening of the hydrophobic interaction of protein molecules.

  12. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

    PubMed Central

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-01-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition. PMID:27222322

  13. Selective Chemical Conversion of Sugars in Aqueous Solutions without Alkali to Lactic Acid Over a Zn-Sn-Beta Lewis Acid-Base Catalyst

    NASA Astrophysics Data System (ADS)

    Dong, Wenjie; Shen, Zheng; Peng, Boyu; Gu, Minyan; Zhou, Xuefei; Xiang, Bo; Zhang, Yalei

    2016-05-01

    Lactic acid is an important platform molecule in the synthesis of a wide range of chemicals. However, in aqueous solutions without alkali, its efficient preparation via the direct catalysis of sugars is hindered by a side dehydration reaction to 5-hydroxymethylfurfural due to Brønsted acid, which originates from organic acids. Herein, we report that a previously unappreciated combination of common two metal mixed catalyst (Zn-Sn-Beta) prepared via solid-state ion exchange synergistically promoted this reaction. In water without a base, a conversion exceeding 99% for sucrose with a lactic acid yield of 54% was achieved within 2 hours at 190 °C under ambient air pressure. Studies of the acid and base properties of the Zn-Sn-Beta zeolite suggest that the introduction of Zn into the Sn-Beta zeolite sequentially enhanced both the Lewis acid and base sites, and the base sites inhibited a series of side reactions related to fructose dehydration to 5-hydroxymethylfurfural and its subsequent decomposition.

  14. Phototransformation of cephalosporin antibiotics in an aqueous environment results in higher toxicity.

    PubMed

    Wang, Xiao-Huan; Lin, Angela Yu-Chen

    2012-11-20

    Photodegradation may be the most important elimination process for cephalosporin antibiotics in surface water. Cefazolin (CFZ) and cephapirin (CFP) underwent mainly direct photolysis (t(1/2) = 0.7, 3.9 h), while cephalexin (CFX) and cephradine (CFD) were mainly transformed by indirect photolysis, which during the process a bicarbonate-enhanced nitrate system contributed most to the loss rate of CFX, CFD, and cefotaxime (CTX) (t(1/2) = 4.5, 5.3, and 1.3 h, respectively). Laboratory data suggested that bicarbonate enhanced the phototransformation of CFD and CFX in natural water environments. When used together, NO(3)(-), HCO(3)(-), and DOM closely simulated the photolysis behavior in the Jingmei River and were the strongest determinants in the fate of cephalosporins. TOC and byproducts were investigated and identified. Direct photolysis led to decarboxylation of CFD, CFX, and CFP. Transformation only (no mineralization) of all cephalosporins was observed through direct photolysis; byproducts were found to be even less photolabile and more toxic (via the Microtox test). CFZ exhibited the strongest acute toxicity after just a few hours, which may be largely attributed to its 5-methyl-1,3,4-thiadiazole-2-thiol moiety. Many pharmaceuticals were previously known to undergo direct sunlight photolysis and transformation in surface waters; however, the synergistic increase in toxicity caused by this cocktail (via pharmaceutical photobyproducts) cannot be ignored and warrants future research attention.

  15. Gas-grain Modeling of Isocyanic Acid (HNCO), Cyanic Acid (HOCN), Fulminic Acid (HCNO), and Isofulminic Acid (HONC) in Assorted Interstellar Environments

    NASA Astrophysics Data System (ADS)

    Quan, Donghui; Herbst, Eric; Osamura, Yoshihiro; Roueff, Evelyne

    2010-12-01

    Isocyanic acid (HNCO) is a well-known interstellar molecule. Evidence also exists for the presence of two of its metastable isomers in the interstellar medium: HCNO (fulminic acid) and HOCN (cyanic acid). Fulminic acid has been detected toward cold and lukewarm sources, while cyanic acid has been detected both in these sources and in warm sources in the Galactic Center. Gas-phase models can reproduce the abundances of the isomers in cold sources, but overproduce HCNO in the Galactic Center. Here we present a detailed study of a gas-grain model that contains these three isomers, plus a fourth isomer, isofulminic acid (HONC), for four types of sources: hot cores, the warm envelopes of hot cores, lukewarm corinos, and cold cores. The current model is partially able to rationalize the abundances of HNCO, HOCN, and HCNO in cold and warm sources. Predictions for HONC in all environments are also made.

  16. Acid-base equilibria in aqueous solutions of meta-cresolsulfophthalein in the temperature range of 25 to 200°C

    NASA Astrophysics Data System (ADS)

    Stepanchikova, S. A.; Galay, G. I.

    2017-01-01

    Values of the second thermodynamic ionization constant of pH indicator m-Cresol Purple are determined spectrophotometrically in slightly alkaline aqueous solutions in the temperature range of 25 to 200°C at saturated vapor pressure. Data required for studies on acid-base equilibria in weakly alkaline aqueous solution of rare-earth elements at elevated temperatures are obtained to characterize their behavior in geochemical systems.

  17. Ionization energies of aqueous nucleic acids: photoelectron spectroscopy of pyrimidine nucleosides and ab initio calculations.

    PubMed

    Slavícek, Petr; Winter, Bernd; Faubel, Manfred; Bradforth, Stephen E; Jungwirth, Pavel

    2009-05-13

    Vertical ionization energies of the nucleosides cytidine and deoxythymidine in water, the lowest ones amounting in both cases to 8.3 eV, are obtained from photoelectron spectroscopy measurements in aqueous microjets. Ab initio calculations employing a nonequilibrium polarizable continuum model quantitatively reproduce the experimental spectra and provide molecular interpretation of the individual peaks of the photoelectron spectrum, showing also that lowest ionization originates from the base. Comparison of calculated vertical ionization potentials of pyrimidine bases, nucleosides, and nucleotides in water and in the gas phase underlines the dramatic effect of bulk hydration on the electronic structure. In the gas phase, the presence of sugar and, in particular, of phosphate has a strong effect on the energetics of ionization of the base. Upon bulk hydration, the ionization potential of the base in contrast becomes rather insensitive to the presence of the sugar and phosphate, which indicates a remarkable screening ability of the aqueous solvent. Accurate aqueous-phase vertical ionization potentials provide a significant improvement to the corrected gas-phase values used in the literature and represent important information in assessing the threshold energies for photooxidation and oxidation free energies of solvent-exposed DNA components. Likewise, such energetic data should allow improved assessment of delocalization and charge-hopping mechanisms in DNA ionized by radiation.

  18. Crystallization of aqueous inorganic-malonic acid particles: nucleation rates, dependence on size, and dependence on the ammonium-to-sulfate ratio.

    PubMed

    Parsons, Matthew T; Riffell, Jenna L; Bertram, Allan K

    2006-07-06

    Using an electrodynamic balance, we determined the relative humidity (RH) at which aqueous inorganic-malonic acid particles crystallized, with ammonium sulfate ((NH(4))(2)SO(4)), letovicite ((NH(4))(3)H(SO(4))(2)), or ammonium bisulfate (NH(4)HSO(4)) as the inorganic component. The results for (NH(4))(2)SO(4)-malonic acid particles and (NH(4))(3)H(SO(4))(2)-malonic acid particles show that malonic acid decreases the crystallization RH of the inorganic particles by less than 7% RH when the dry malonic acid mole fraction is less than 0.25. At a dry malonic acid mole fraction of about 0.5, the presence of malonic acid can decrease the crystallization RH of the inorganic particles by up to 35% RH. For the NH(4)HSO(4)-malonic acid particles, the presence of malonic acid does not significantly modify the crystallization RH of the inorganic particles for the entire range of dry malonic acid mole fractions studied; in all cases, either the particles did not crystallize or the crystallization RH was close to 0% RH. Size dependent measurements show that the crystallization RH of aqueous (NH(4))(2)SO(4) particles is not a strong function of particle volume. However, for aqueous (NH(4))(2)SO(4)-malonic acid particles (with dry malonic acid mole fraction = 0.36), the crystallization RH is a stronger function of particle volume, with the crystallization RH decreasing by 6 +/- 3% RH when the particle volume decreases by an order of magnitude. To our knowledge, these are the first size dependent measurements of the crystallization RH of atmospherically relevant inorganic-organic particles. These results suggest that for certain organic mole fractions the particle size and observation time need to be considered when extrapolating laboratory crystallization results to atmospheric scenarios. For aqueous (NH(4))(2)SO(4) particles, the homogeneous nucleation rate data are a strong function of RH, but for aqueous (NH(4))(2)SO(4)-malonic acid particles (with dry organic mole fraction = 0

  19. Fatigue Crack Propagation from Notched Specimens of 304 SS in elevated Temperature Aqueous Environment

    SciTech Connect

    Wire, G. L.; Mills, W. J.

    2002-08-01

    Fatigue crack propagation (FCP) rates for 304 stainless steel (304SS) were determined in 24 degree C and 288 degree C air and 288 degree C water using double-edged notch (DEN) specimens of 304 stainless steel (304 SS). Test performed at matched loading conditions in air and water at 288 degree C with 20-6- cc h[sub]2/kg h[sub]2O provided a direct comparison of the relative crack growth rates in air and water over a wide range of crack growth rates. The DEN crack extension ranged from short cracks (0.03-0.25 mm) to long cracks up to 4.06 mm, which are consistent with conventional deep crack tests. Crack growth rates of 304 SS in water were about 12 times the air rate. This 12X environmental enhancement persisted to crack extensions up to 4.06 mm, far outside the range associated with short crack effects. The large environmental degradation for 304 SS crack growth is consistent with the strong reduction of fatigue life in high hydrogen water. Further, very similar environmental effects w ere reported in fatigue crack growth tests in hydrogen water chemistry (HWC). Most literature data in high hydrogen water show only a mild environmental effect for 304 SS, of order 2.5 times air or less, but the tests were predominantly performed at high cyclic stress intensity or equivalently, high air rates. The environmental effect in low oxygen environments at low stress intensity depends strongly on both the stress ratio, R, and the load rise time, T[sub]r, as recently reported for austenitic stainless steel in BWR water. Fractography was performed for both tests in air and water. At 288 degree C in water, the fracture surfaces were crisply faceted with a crystallographic appearance, and showed striations under high magnification. The cleavage-like facets on the fracture surfaces suggest that hydrogen embrittlement is the primary cause of accelerated cracking.

  20. Gamma irradiation of isocitric and citric acid in aqueous solution: Relevance in prebiotic chemistry

    NASA Astrophysics Data System (ADS)

    Negrón-Mendoza, A.; Ramos-Bernal, S.

    2015-07-01

    The radiation chemistry of hydroxy acids like citric and isocitric acids is rather scarce, even though they are crucial compounds in biological systems and for food irradiation. The aim of this work is to study the radiolytic behavior of these acids focused on the interconversion induced by radiation of citric and isocitric acid into other members of the Krebs cycle. The results showed that among the products formed were succinic, malonic, malic and other acids related to metabolic pathways, and these results are correlated with its possible role in chemical evolution processes.

  1. Gamma irradiation of isocitric and citric acid in aqueous solution: Relevance in prebiotic chemistry

    SciTech Connect

    Negrón-Mendoza, A. Ramos-Bernal, S.

    2015-07-23

    The radiation chemistry of hydroxy acids like citric and isocitric acids is rather scarce, even though they are crucial compounds in biological systems and for food irradiation. The aim of this work is to study the radiolytic behavior of these acids focused on the interconversion induced by radiation of citric and isocitric acid into other members of the Krebs cycle. The results showed that among the products formed were succinic, malonic, malic and other acids related to metabolic pathways, and these results are correlated with its possible role in chemical evolution processes.

  2. Combination of best promoter and micellar catalyst for more than kilo-fold rate acceleration in favor of chromic acid oxidation of D-galactose to D-galactonic acid in aqueous media at room temperature

    NASA Astrophysics Data System (ADS)

    Saha, Rumpa; Ghosh, Aniruddha; Sar, Pintu; Saha, Indrajit; Ghosh, Sumanta K.; Mukherjee, Kakali; Saha, Bidyut

    2013-12-01

    Picolinic acid, 2,2‧-bipyridine and 1,10-phenanthroline promoted Cr(VI) oxidation of D-galactose to D-galactonic acid in three representative aqueous micellar media has been studied. The anionic surfactant (SDS) accelerated the rate of reaction while the cationic surfactant (CPC) and neutral surfactant (TX-100) retarded the reaction rate. Combination of bipy and SDS is the best choice for chromic acid oxidation of D-galactose to D-galactonic acid in aqueous media although 1,10-phenanthroline is best promoter in absence of micellar catalyst.

  3. THE ECOLOGICAL EFFECTS OF TRICHLORACETIC ACID (TCAA) IN THE ENVIRONMENT

    EPA Science Inventory

    Trichloroacetic acid (TCAA) is a member of the family of compounds known as chloroacetic acids, which includes mono-, di- and trichloroacetic acid. The significant property these compounds share is that they are all phytotoxic. TCAA once was widely used as a potent herbicide. ...

  4. Phase diagrams and water activities of aqueous dicarboxylic acid systems of atmospheric importance.

    PubMed

    Beyer, Keith D; Friesen, Katherine; Bothe, Jameson R; Palet, Benjamin

    2008-11-20

    We have studied liquid/solid phase diagrams and water activities of the dicarboxylic acid/water binary systems for maleic, dl-malic, glutaric, and succinc acids using differential scanning calorimetry, infrared (IR) spectroscopy of thin films, and conductivity analysis of saturated solutions. For each binary system we report the measurements of the ice melting envelope, the acid dissolution envelope, and the ice/acid eutectic temperature and composition. Water activities have been determined by using the freezing point depression of ice. Additionally, an irreversible solid/solid phase transition for maleic acid was observed in both DSC and IR studies likely due to the conversion of a meta-stable crystal form of maleic acid to its most stable crystal form. In general we find good agreement with literature values for temperature-dependent acid solubilities.

  5. Instrumentation and vehicle platform of a miniaturized submersible for exploration of terrestrial and extraterrestrial aqueous environments

    NASA Astrophysics Data System (ADS)

    Jonsson, Jonas; Sundqvist, Johan; Nguyen, Hugo; Berglund, Martin; Ogden, Sam; Palmer, Kristoffer; Smedfors, Katarina; Johansson, Linda; Hjort, Klas; Thornell, Greger

    2012-10-01

    An example of an extraterrestrial environment likely to support life is the vast liquid body believed to hide underneath the frozen crust of Jupiter's moon Europa. The hypothetical exploration of this, as well as the more accessible subglacial lakes on Earth, has been used as model applications for the development of a heavily miniaturized, yet qualified, submersible with the potential to be deployable either in itself through a long and narrow borehole or as the daughter craft of an ice-penetrating cryobot. Onboard the submersible, which is only 20 cm in length and 5 cm in diameter, accommodation of a versatile set of sensors and instruments capable of characterizing and imaging the surroundings, and even collecting water samples with microorganisms for return, is facilitated through the use of miniaturization technologies. For instance, together with a small camera, a laser-based, microoptic device enables the 3-D reconstruction of imaged objects for topographical measurements. As a complement, when the water is turbid or a longer range is wanted, the world's smallest side-scanning sonar, exhibiting centimeter resolution and a range of over 30 m, has been developed. The work on miniaturizing a CTD, which is a widely employed oceanographic instrument used to measure and correlate conductivity, temperature, and depth, has commenced. Furthermore, a device employing acoustics to trap microscopic particles and organisms, and, by this, enrich water samples, is under development. To ensure that the gathered samples are pristine until analyzed at the end of a mission, the device is equipped with high-pressure, latchable valves. Remote operation and transfer of measurement data and images, or even live streaming of video, is made possible through a kilometer-long fiber optic cable being reeled out from the vehicle underway and tethering it to a terminal. To extend the missions, the same fiber shall also be capable of charging the onboard batteries. In this paper, the

  6. Epoxidation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids.

    PubMed

    Dinda, Srikanta; Patwardhan, Anand V; Goud, Vaibhav V; Pradhan, Narayan C

    2008-06-01

    The kinetics of epoxidation of cottonseed oil by peroxyacetic acid generated in situ from hydrogen peroxide and glacial acetic acid in the presence of liquid inorganic acid catalysts were studied. It was possible to obtain up to 78% relative conversion to oxirane with very less oxirane cleavage by in situ technique. The rate constants for sulphuric acid catalysed epoxidation of cottonseed oil were in the range 0.39-5.4 x 10(-6)L mol(-1)s(-1) and the activation energy was found to be 11.7 kcal mol(-1). Some thermodynamic parameters such as enthalpy, entropy, and free energy of activation were determined to be of 11.0 kcal mol(-1), -51.4 cal mol(-1)K(-1) and 28.1 kcal mol(-1), respectively. The order of effectiveness of catalysts was found to be sulphuric acid>phosphoric acid>nitric acid>hydrochloric acid. Acetic acid was found to be superior to formic acid for the in situ cottonseed oil epoxidation.

  7. Multivalent calix[4]arene-based fluorescent sensor for detecting silver ions in aqueous media and physiological environment.

    PubMed

    Lotfi, Behzad; Tarlani, Aliakbar; Akbari-Moghaddam, Peyman; Mirza-Aghayan, Maryam; Peyghan, Ali Ahmadi; Muzart, Jacques; Zadmard, Reza

    2017-04-15

    A new derivative of dipodal 1,3-calix[4]arene-based chemosensor (R), which was containing several binding sites have been synthesized and characterized by NMR, IR and LC-MS spectroscopic methods. The selectivity of Rhas been investigated in aqueous methanol, resulting in fluorescence shift and selective recognition of Ag(+) among 20 various alkali, alkaline earth and transition metal ions. Microstructural features of R and its complex with Ag(+)have been investigated by Atomic Force Microscopy (AFM). AFM images can clearly differentiate R from its complex of Ag(+). Moreover; the complicated binding mode of metal-ligand complex has been explored by UV-Vis, LC-MS, FIR, Fluorescence titration, Job's plot method and theoretical approaches. Density functional theory (DFT) method at B3LYP/LANL2DZ level of theory was employed for computational studies. Theoretical calculations revealed that selectivity and specificity of R toward Ag(+) could be attributed to structural conformation of 1,3-alternate-calix[4]arene scaffold and molecular electrostatic potential of its surface. Furthermore; the competitive experiments were carried out to test sensor's ability for practical uses. Finally, the efficiency of R in matrix of physiological cations was examined and showed gradual emission enhancement which makes R an ideal candidate for monitoring of Ag(+) in physiological environment.

  8. Protective or damage promoting effect of calcium carbonate layers on the surface of cement based materials in aqueous environments

    SciTech Connect

    Schwotzer, M.; Scherer, T.; Gerdes, A.

    2010-09-15

    Cement based materials permanently exposed to aggressive aqueous environments are subject to chemical changes affecting their durability. However, this holds also for tap water that is considered to be not aggressive to cementitious materials, although in that case a formation of covering layers of CaCO{sub 3} on the alkaline surfaces is commonly supposed to provide protection against reactive transport processes. Thus, investigations of the structural and chemical properties of the material/water interface were carried out in laboratory experiments and case studies to elucidate the consequences of surface reactions for the durability of cement based materials exposed to tap water. Focused Ion Beam investigations revealed that a protective effect of a CaCO{sub 3} covering layer depends on its structural properties, which are in turn affected by the hydro-chemical conditions during crystallization. Surface precipitation of CaCO{sub 3} can trigger further chemical degradation, if the required calcium is supplied by the pore solution of the material.

  9. Chemical Processing in High-Pressure Aqueous Environments. 9. Process Development for Catalytic Gasification of Algae Feedstocks

    SciTech Connect

    Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G.; Rotness, Leslie J.; Olarte, Mariefel V.; Zacher, Alan H.

    2012-07-26

    Through the use of a metal catalyst, gasification of wet algae slurries can be accomplished with high levels of carbon conversion to gas at relatively low temperature (350 C). In a pressurized-water environment (20 MPa), near-total conversion of the organic structure of the algae to gases has been achieved in the presence of a supported ruthenium metal catalyst. The process is essentially steam reforming, as there is no added oxidizer or reagent other than water. In addition, the gas produced is a medium-heating value gas due to the synthesis of high levels of methane, as dictated by thermodynamic equilibrium. As opposed to earlier work, biomass trace components were removed by processing steps so that they did not cause processing difficulties in the fixed catalyst bed tubular reactor system. As a result, the algae feedstocks, even those with high ash contents, were much more reliably processed. High conversions were obtained even with high slurry concentrations. Consistent catalyst operation in these short-term tests suggested good stability and minimal poisoning effects. High methane content in the product gas was noted with significant carbon dioxide captured in the aqueous byproduct in combination with alkali constituents and the ammonia byproduct derived from proteins in the algae. High conversion of algae to gas products was found with low levels of byproduct water contamination and low to moderate loss of carbon in the mineral separation step.

  10. Occurrence of cyclophosphamide and ifosfamide in aqueous environment and their removal by biological and abiotic wastewater treatment processes.

    PubMed

    Česen, Marjeta; Kosjek, Tina; Laimou-Geraniou, Maria; Kompare, Boris; Širok, Brane; Lambropolou, Dimitra; Heath, Ester

    2015-09-15

    Cytostatic drug residues in the aqueous environment are of concern due to their possible adverse effects on non-target organisms. Here we report the occurrence and removal efficiency of cyclophosphamide (CP) and ifosfamide (IF) by biological and abiotic treatments including advanced oxidation processes (AOPs). Cyclophosphamide was detected in hospital wastewaters (14-22,000 ng L(-1)), wastewater treatment plant influents (19-27 ng L(-1)) and effluent (17 ng L(-1)), whereas IF was detected only in hospital wastewaters (48-6800 ng L(-1)). The highest removal efficiency during biological treatment (attached growth biomass in a flow through bioreactor) was 59 ± 15% and 35 ± 9.3% for CP and IF, respectively. Also reported are the removal efficiencies of both compounds from wastewater using hydrodynamic cavitation (HC), ozonation (O3) and/or UV, either individually or in combination with hydrogen peroxide (H2O2). Hydrodynamic cavitation did not remove CP and IF to any significant degree. The highest removal efficiencies: 99 ± 0.71% for CP and 94 ± 2.4% for IF, were achieved using UV/O3/H2O2 at 5 g L(-1) for 120 min. When combined with biological treatment, removal efficiencies were >99% for both compounds. This is the first report of combined biological and AOP treatment of CP and IF from wastewater with a removal efficiency >99%.

  11. Graphene-Based Platform for Infrared Near-Field Nanospectroscopy of Water and Biological Materials in an Aqueous Environment.

    PubMed

    Khatib, Omar; Wood, Joshua D; McLeod, Alexander S; Goldflam, Michael D; Wagner, Martin; Damhorst, Gregory L; Koepke, Justin C; Doidge, Gregory P; Rangarajan, Aniruddh; Bashir, Rashid; Pop, Eric; Lyding, Joseph W; Thiemens, Mark H; Keilmann, Fritz; Basov, D N

    2015-08-25

    Scattering scanning near-field optical microscopy (s-SNOM) has emerged as a powerful nanoscale spectroscopic tool capable of characterizing individual biomacromolecules and molecular materials. However, applications of scattering-based near-field techniques in the infrared (IR) to native biosystems still await a solution of how to implement the required aqueous environment. In this work, we demonstrate an IR-compatible liquid cell architecture that enables near-field imaging and nanospectroscopy by taking advantage of the unique properties of graphene. Large-area graphene acts as an impermeable monolayer barrier that allows for nano-IR inspection of underlying molecular materials in liquid. Here, we use s-SNOM to investigate the tobacco mosaic virus (TMV) in water underneath graphene. We resolve individual virus particles and register the amide I and II bands of TMV at ca. 1520 and 1660 cm(-1), respectively, using nanoscale Fourier transform infrared spectroscopy (nano-FTIR). We verify the presence of water in the graphene liquid cell by identifying a spectral feature associated with water absorption at 1610 cm(-1).

  12. Characterization of local hydrophobicity on sapphire (0001) surfaces in aqueous environment by colloidal probe atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Wada, Tomoya; Yamazaki, Kenji; Isono, Toshinari; Ogino, Toshio

    2017-02-01

    Sapphire (0001) surfaces exhibit a phase-separation into hydrophobic and hydrophilic domains upon high-temperature annealing, which were previously distinguished by the thickness of adsorbed water layers in air using atomic force microscopy (AFM). To characterize their local surface hydrophobicity in aqueous environment, we used AFM equipped with a colloidal probe and measured the local adhesive force between each sapphire domain and a hydrophilic SiO2 probe surface, or a hydrophobic polystyrene one. Two data acquisition modes for statistical analyses were used: one is force measurements at different positions of the surface and the other repeated measurement at a fixed position. We found that adhesive force measurements using the polystyrene probe allow us to distinctly separate the hydrophilic and hydrophobic domains. The dispersion in the force measurement data at different positions of the surface is larger than that in the repeated measurements at a fixed position. It indicates that the adhesive force measurement is repeatable although their data dispersion for the measurement positions is relatively large. From these results, we can conclude that the hydrophilic and hydrophobic domains on the sapphire (0001) surfaces are distinguished by a difference in their hydration degrees.

  13. Self-assembly of pi-conjugated peptides in aqueous environments leading to energy-transporting bioelectronic nanostructures

    SciTech Connect

    Tavor, John

    2016-12-06

    The realization of new supramolecular pi-conjugated organic structures inspired and driven by peptide-based self-assembly will offer a new approach to interface with the biotic environment in a way that will help to meet many DOE-recognized grand challenges. Previously, we developed pi-conjugated peptides that undergo supramolecular self-assembly into one-dimensional (1-D) organic electronic nanomaterials under benign aqueous conditions. The intermolecular interactions among the pi-conjugated organic segments within these nanomaterials lead to defined perturbations of their optoelectronic properties and yield nanoscale conduits that support energy transport within individual nanostructures and throughout bulk macroscopic collections of nanomaterials. Our objectives for future research are to construct and study biomimetic electronic materials for energy-related technology optimized for harsher non-biological environments where peptide-driven self-assembly enhances pi-stacking within nanostructured biomaterials, as detailed in the following specific tasks: (1) synthesis and detailed optoelectronic characterization of new pi-electron units to embed within homogeneous self assembling peptides, (2) molecular and data-driven modeling of the nanomaterial aggregates and their higher-order assemblies, and (3) development of new hierarchical assembly paradigms to organize multiple electronic subunits within the nanomaterials leading to heterogeneous electronic properties (i.e. gradients and localized electric fields). These intertwined research tasks will lead to the continued development and fundamental mechanistic understanding of a powerful bioinspired materials set capable of making connections between nanoscale electronic materials and macroscopic bulk interfaces, be they those of a cell, a protein or a device.

  14. Fast and highly-efficient removal of methylene blue from aqueous solution by poly(styrenesulfonic acid-co-maleic acid)-sodium-modified magnetic colloidal nanocrystal clusters

    NASA Astrophysics Data System (ADS)

    Song, Yu-Bei; Lv, Shao-Nan; Cheng, Chang-Jing; Ni, Guo-Li; Xie, Xiao-Wa; Huang, Wei; Zhao, Zhi-Gang

    2015-01-01

    Magnetic colloidal nanocrystal clusters (MCNCs) modified with different amounts of poly(4-styrenesulfonic acid-co-maleic acid) sodium (PSSMA) have been prepared through simple one-step solvothermal method for removal of methylene blue (MB) from aqueous solution. The prepared MCNCs are characterized by Fourier transform infrared (FT-IR) spectra, scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), X-ray diffraction (XRD), nitrogen adsorption-desorption technique and dynamic light scattering (DLS). Moreover, effects of the solution pH, contact time, adsorbent dosage, ionic strength and initial dye concentration on MB adsorption onto the MCNCs are systematically investigated. The PSSMA-modified MCNCs show fast and highly-efficient MB removal capacity, which dramatically depends on the immobilization amounts of PSSMA, solution pH and adsorbent dosage. Their adsorption kinetics and isotherms exhibit that the kinetics and equilibrium adsorptions can be well-described by pseudo-second-order kinetic and Langmuir model, respectively. These magnetic nanocomposites, with high separation efficiency, low production cost and recyclable property, are promising as functional adsorbents for efficient removal of cationic organic pollutants from aqueous solution.

  15. Interaction Between Some Monosaccharides and Aspartic Acid in Dilute Aqueous Solutions

    PubMed Central

    Kulikova, Galina A.

    2008-01-01

    Interaction between aspartic acid and d-glucose, d-galactose, and d-fructose has been studied by isothermal titration calorimetry, calorimetry of dissolution, and densimetry. It has been found that d-glucose and d-fructose form thermodynamically stable associates with aspartic acid, in contrast to d-galactose. The selectivity in the interaction of aspartic acid with monosaccharides is affected by their stereochemical structures. PMID:19669542

  16. Removal of Heavy Metals from Aqueous Solution Using Novel Nanoengineered Sorbents: Self-Assembled Carbamoylphosphonic Acids on Mesoporous Silica

    SciTech Connect

    Yantasee, Wassana; Lin, Yuehe; Fryxell, Glen E.; Busche, Brad J.; Birnbaum, Jerome C.

    2003-08-01

    Self-assembled monolayers of carbamoylphosphonic acids (acetamide phosphonic acid and propionamide phosphonic acid) on mesoporous silica supports were studied as potential absorbents for heavy and transition metal ions in aqueous wastes. The adsorption capacity, selectivity, and kinetics of the materials in sequestering metal ions, including Cd2+, Co2+, Cu2+, Cr3+, Pb2+, Ni2+, Zn2+, and Mn2+, were measured in batch experiments with excess sodium ion. The solution pH ranged from 2.2 to 5.5. The kinetics study shows that the adsorption reached equilibrium in seconds, indicating that there is little resistance to mass transfer, intraparticle diffusion, and surface chemical reaction. The competitive adsorption study found the phosphonic acid-SAMMS to have an affinity for divalent metal ions in decreasing order of Pb2+ > Cu2+ > Mn2+ > Cd2+ > Zn2+ > Co2+ > Ni2+. The measured Cd2+ adsorption isotherm was of the Langmuirian type and had a saturation binding capacity of 0.32 mmol/g.

  17. An In Silico study of TiO2 nanoparticles interaction with twenty standard amino acids in aqueous solution

    PubMed Central

    Liu, Shengtang; Meng, Xuan-Yu; Perez-Aguilar, Jose Manuel; Zhou, Ruhong

    2016-01-01

    Titanium dioxide (TiO2) is probably one of the most widely used nanomaterials, and its extensive exposure may result in potentially adverse biological effects. Yet, the underlying mechanisms of interaction involving TiO2 NPs and macromolecules, e.g., proteins, are still not well understood. Here, we perform all-atom molecular dynamics simulations to investigate the interactions between TiO2 NPs and the twenty standard amino acids in aqueous solution exploiting a newly developed TiO2 force field. We found that charged amino acids play a dominant role during the process of binding to the TiO2 surface, with both basic and acidic residues overwhelmingly preferred over the non-charged counterparts. By calculating the Potential Mean Force, we showed that Arg is prone to direct binding onto the NP surface, while Lys needs to overcome a ~2 kT free energy barrier. On the other hand, acidic residues tend to form “water bridges” between their sidechains and TiO2 surface, thus displaying an indirect binding. Moreover, the overall preferred positions and configurations of different residues are highly dependent on properties of the first and second solvation water. These molecular insights learned from this work might help with a better understanding of the interactions between biomolecules and nanomaterials. PMID:27883086

  18. Simultaneous removal of acid green 25 and mercury ions from aqueous solutions using glutamine modified chitosan magnetic composite microspheres.

    PubMed

    Tao, Xue; Li, Kun; Yan, Han; Yang, Hu; Li, Aimin

    2016-02-01

    In this current work, the magnetic composite microsphere containing glutamine modified chitosan and silica coated Fe3O4 nanoparticles (CS-Gln-MCM) has been successfully prepared and extensively characterized, which is a kind of biodegradable materials. CS-Gln-MCM shows enhanced removal efficiency for both acid green 25 (AG25), an amphoteric dye, and mercury ions (Hg(2+)) from water in the respective while measured pH range compared with chitosan magnetic composite microsphere (CS-MCM) without modification. It is due to the fact that the grafted amino acid provides a variety of additional adsorption active sites and diverse adsorption mechanisms are involved. In AG25 and Hg(2+) aqueous mixture, the modified adsorbents bear preferential adsorption for AG25 over Hg(2+) in strong acidic solutions ascribed to multiple interactions between AG25 and CS-Gln-MCM, such as hydrogen bonding and electrostatic interactions. While, in weak acidic conditions, an efficient simultaneous removal is observed for different adsorption effects involved in aforementioned two pollutants. Besides, CS-Gln-MCM illuminates not only short equilibrium time for adsorption of each pollutant less than 20.0 min but also rapid magnetic separation from water and efficient regeneration after saturated adsorption. Therefore, CS-Gln-MCM bears great application potentials in water treatment.

  19. An In Silico study of TiO2 nanoparticles interaction with twenty standard amino acids in aqueous solution

    NASA Astrophysics Data System (ADS)

    Liu, Shengtang; Meng, Xuan-Yu; Perez-Aguilar, Jose Manuel; Zhou, Ruhong

    2016-11-01

    Titanium dioxide (TiO2) is probably one of the most widely used nanomaterials, and its extensive exposure may result in potentially adverse biological effects. Yet, the underlying mechanisms of interaction involving TiO2 NPs and macromolecules, e.g., proteins, are still not well understood. Here, we perform all-atom molecular dynamics simulations to investigate the interactions between TiO2 NPs and the twenty standard amino acids in aqueous solution exploiting a newly developed TiO2 force field. We found that charged amino acids play a dominant role during the process of binding to the TiO2 surface, with both basic and acidic residues overwhelmingly preferred over the non-charged counterparts. By calculating the Potential Mean Force, we showed that Arg is prone to direct binding onto the NP surface, while Lys needs to overcome a ~2 kT free energy barrier. On the other hand, acidic residues tend to form “water bridges” between their sidechains and TiO2 surface, thus displaying an indirect binding. Moreover, the overall preferred positions and configurations of different residues are highly dependent on properties of the first and second solvation water. These molecular insights learned from this work might help with a better understanding of the interactions between biomolecules and nanomaterials.

  20. Mycogenic Mn(II) oxidation promotes remediation of acid mine drainage and other anthropogenically impacted environments

    NASA Astrophysics Data System (ADS)

    Santelli, C. M.; Chaput, D.; Hansel, C. M.; Burgos, W. D.

    2014-12-01

    Manganese is a pollutant in worldwide environments contaminated with metals and organics, such as acid mine drainage (AMD), freshwater ponds, and agricultural waste storage sites. Microorganisms contribute to the removal of dissolved Mn compounds in the environment by promoting Mn(II) oxidation reactions. The oxidation of Mn(II) results in the precipitation of sparingly soluble Mn(IV) oxide minerals, effectively removing the metal from the aqueous milieu (e.g., groundwater or wastewater streams). In recent years, our research has identified a diversity of Mn(II)-oxidizing fungi inhabiting these polluted environments, however their overall contribution to the remediation process in situ remains poorly understood. Here we present results of culture-based and Next Generation Sequencing (NGS) studies in AMD treatment systems actively remediating Mn and other metals where we profile the bacterial, fungal, algal and archaeal communities to determine the overall community diversity and to establish the relative abundance of known Mn(II) oxidizers. A variety of treatment systems with varying Mn-removal efficiencies were sampled to understand the relationship between remediation efficiency and microbial community composition and activity. Targeted-amplicon sequencing of DNA and RNA of the 16S rRNA genes (bacteria and archaea), 23S rRNA genes (algae) and ITS region (fungi) was performed using both 454 pyrosequencing and Illumina platforms. Results showed that only the fungal taxonomic profiles significantly differed between sites that removed the majority of influent Mn and those that did not. Specifically, Ascomycota (which include known Mn(II) oxidizers isolated from these treatment systems) dominated greater efficiency systems whereas less efficient systems were dominated by Basidiomycota. Furthermore, known Mn(II) oxidizers accounted for only a minor proportion of bacterial sequences but a far greater proportion of fungal sequences. These culture-independent studies lend

  1. Enrichment of the amino acid L-isovaline by aqueous alteration on CI and CM meteorite parent bodies.

    PubMed

    Glavin, Daniel P; Dworkin, Jason P

    2009-04-07

    The distribution and enantiomeric composition of the 5-carbon (C(5)) amino acids found in CI-, CM-, and CR-type carbonaceous meteorites were investigated by using liquid chromatography fluorescence detection/TOF-MS coupled with o-phthaldialdehyde/N-acetyl-L-cysteine derivatization. A large L-enantiomeric excess (ee) of the alpha-methyl amino acid isovaline was found in the CM meteorite Murchison (L(ee) = 18.5 +/- 2.6%) and the CI meteorite Orgueil (L(ee) = 15.2 +/- 4.0%). The measured value for Murchison is the largest enantiomeric excess in any meteorite reported to date, and the Orgueil measurement of an isovaline excess has not been reported previously for this or any CI meteorite. The L-isovaline enrichments in these two carbonaceous meteorites cannot be the result of interference from other C(5) amino acid isomers present in the samples, analytical biases, or terrestrial amino acid contamination. We observed no L-isovaline enrichment for the most primitive unaltered Antarctic CR meteorites EET 92042 and QUE 99177. These results are inconsistent with UV circularly polarized light as the primary mechanism for L-isovaline enrichment and indicate that amplification of a small initial isovaline asymmetry in Murchison and Orgueil occurred during an extended aqueous alteration phase on the meteorite parent bodies. The large asymmetry in isovaline and other alpha-dialkyl amino acids found in altered CI and CM meteorites suggests that amino acids delivered by asteroids, comets, and their fragments would have biased the Earth's prebiotic organic inventory with left-handed molecules before the origin of life.

  2. Enrichment of the Amino Acid L-Isovaline by Aqueous Alteration on CI and CM Meteorite Parent Bodies

    NASA Technical Reports Server (NTRS)

    Glavin, Daniel P.; Dworkin, Jason P.

    2009-01-01

    The distribution and enantiomeric composition of the 5-carbon (C(sub 5)) amino acids found in Cl-, CM-, and CR-type carbonaceous meteorites were investigated by using liquid chromatography fluorescence detection/TOF-MS coupled with o-phthaldialdehyde/Nacetyl- l-cysteine derivatization. A large L-enantiomeric excess (ee) of the a-methyl amino acid isovaline was found in the CM meteorite Murchison (L(sub ee) = 18.5 +/- 2.6%) and the Cl meteorite Orguell (L(sub ee) = 15.2 +/- 4.0%). The measured value for Murchison is the largest enantiomeric excess in any meteorite reported to date, and the Orgueil measurement of an isovaline excess has not been reported previously for this or any Cl meteorite. The L-isovaline enrichments in these two carbonaceous meteorites cannot be the result of interference from other C(sub 5) amino acid isomers present in the samples, analytical biases, or terrestrial amino acid contamination. We observed no L-isovaline enrichment for the most primitive unaltered Antarctic CR meteorites EET 92042 and QUE 99177. These results are inconsistent with UV circularly polarized light as the primary mechanism for L-isovaline enrichment and indicate that amplification of a small initial isovaline asymmetry in Murchison and Orgueil occurred during an extended aqueous alteration phase on the meteorite parent bodies. The large asymmetry in isovaline and other alpha-dialkyl amino acids found in altered Ct and CM meteorites suggests that amino acids delivered by asteroids, comets, and their fragments would have biased the Earth's prebiotic organic inventory with left-handed molecules before the origin of life.

  3. Long-term degradation study of hyaluronic acid in aqueous solutions without protection against microorganisms.

    PubMed

    Simulescu, Vasile; Kalina, Michal; Mondek, Jakub; Pekař, Miloslav

    2016-02-10

    The degradation of hyaluronan (HA) of different molecular weights (Mw 14.3, 267.2 and 1160.6 kDa, measured for fresh solutions, before degradation) was studied in aqueous solutions by SEC-MALLS determination of molecular mass, polydispersity and conformation parameters. The solutions were stored either at laboratory or refrigerator temperatures for two months. After this period the weight average molecular weight decreased by 90% for 14.3 kDa, 95% for 267.2 kDa and 71% for 1160.6 kDa hyaluronan (room temperature) or 5.6% for 14.3 kDa, 6.2% for 267.2 kDa and 7.7% for 1160.6 kDa hyaluronan (refrigerator temperature). The hyaluronan aqueous solutions studied did not contain sodium azide or other protectants against microorganisms, because the aim of our study was to assess the degradation in solutions to be used in medicine or cosmetics (without any compounds that are poisonous or toxic for the human body). The solvent used to prepare the samples was pure water. The polydispersity of all the samples remained unaltered during the entire degradation at both temperatures. This indicates a non-random mechanism of degradation.

  4. Direct quantitative gas chromatographic separation of C2-C6 fatty acids, methanol, and ethyl alcohol in aqueous microbial fermentation media.

    PubMed

    Rogosa, M; Love, L L

    1968-02-01

    A method is described for the direct quantitative gas chromatographic separation of C(2)-C(6) lower fatty acid homologues, methanol, and ethyl alcohol in aqueous microbial fermentation media. A hydrogen flame detector and a single-phase solid column packing, comprising beads of a polyaromatic resin (polystyrene cross-linked with divinyl benzene), were employed. Direct injections of 1 to 10 muliters of aqueous culture supernatant fluids were made. Quantitative recoveries of C(2)-C(6) acids added to culture supernatant fluids were obtained.

  5. Direct Quantitative Gas Chromatographic Separation of C2-C6 Fatty Acids, Methanol, and Ethyl Alcohol in Aqueous Microbial Fermentation Media

    PubMed Central

    Rogosa, M.; Love, L. L.

    1968-01-01

    A method is described for the direct quantitative gas chromatographic separation of C2-C6 lower fatty acid homologues, methanol, and ethyl alcohol in aqueous microbial fermentation media. A hydrogen flame detector and a single-phase solid column packing, comprising beads of a polyaromatic resin (polystyrene cross-linked with divinyl benzene), were employed. Direct injections of 1 to 10 μliters of aqueous culture supernatant fluids were made. Quantitative recoveries of C2-C6 acids added to culture supernatant fluids were obtained. PMID:5645415

  6. Hybrid molecularly imprinted poly(methacrylic acid-TRIM)-silica chemically modified with (3-glycidyloxypropyl)trimethoxysilane for the extraction of folic acid in aqueous medium.

    PubMed

    de Oliveira, Fernanda Midori; Segatelli, Mariana Gava; Tarley, César Ricardo Teixeira

    2016-02-01

    In the present study a hybrid molecularly imprinted poly(methacrylic acid-trimethylolpropane trimethacrylate)-silica (MIP) was synthesized and modified with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) with posterior opening of epoxy ring to provide hydrophilic properties of material in the extraction of folic acid from aqueous medium. The chemical and structural aggregates of hybrid material were characterized by means of Fourier Transform Infrared (FT-IR), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Thermogravimetric analysis (TGA) and textural data. Selectivity data of MIP were compared to non-imprinted polymer (NIP) through competitive sorption studies in the presence of caffeine, paracetamol or 4-aminobenzamide yielding relative selectivity coefficients (k′) higher than one unit, thus confirming the selective character of MIP even in the presence of structurally smaller compounds than the folic acid. The lower hydrophobic sorption by bovine serum albumin (BSA) in the MIP as compared to unmodified MIP proves the hydrophilicity of polymer surface by using GPTMS with opening ring. Under acid medium(pH 1.5) the sorption of folic acid onto MIP from batch experiments was higher than the one achieved for NIP. Equilibrium sorption of folic acid was reached at 120 min for MIP, NIP and MIP without GPTMS and kinetic sorption data were well described by pseudo-second-order, Elovich and intraparticle diffusion models. Thus, these results indicate the existence of different binding energy sites in the polymers and a complex mechanism consisting of both surface sorption and intraparticle transport of folic acid within the pores of polymers.

  7. Fast removal of copper ions from aqueous solution by chitosan-g-poly(acrylic acid)/attapulgite composites.

    PubMed

    Wang, Xiaohuan; Zheng, Yian; Wang, Aiqin

    2009-09-15

    Novel chitosan-g-poly(acrylic acid)/attapulgite (CTS-g-PAA/APT) composites were applied as adsorbents for the removal of Cu(II) from aqueous solution. The effects of the initial pH value (pH(0)) of Cu(II) solution, contact time (t), APT content (wt%) and the initial concentration of Cu(II) solution (C(0)) on the adsorption capacity of the composites were investigated. Results from kinetic experimental data showed that the Cu(II) adsorption rate on the composites with 10, 20 and 30 wt% APT was fast and more than 90% of the maximum adsorption capacity for Cu(II) occurred within the initial 15 min. The adsorption kinetics was better described by the pseudo-second order equation, and their adsorption isotherms were better fitted for the Langmuir equation. The results of the five-time consecutive adsorption-desorption studies showed that the composites had high adsorption and desorption efficiencies, which implies that the composites may be used as quite effective adsorbents for the removal of Cu(II) from aqueous solution.

  8. Extraction of electrolytes from aqueous solutions and their spectrophotometric determination by use of acid-base chromoionophores in lipophylic solvents.

    PubMed

    Barberi, Paola; Giannetto, Marco; Mori, Giovanni

    2004-04-01

    The formation of non-absorbing complexes in an organic phase has been exploited for the spectrophotometric determination of ionic analytes in aqueous solutions. The method is based on liquid-liquid extraction of aqueous solution with lipophylic organic phases containing an acid-base chromoionophore, a neutral lypophilic ligand (neutral carrier) selective to the analyte and a cationic (or anionic) exchanger. The method avoids all difficulties of the preparation of the very thin membranes used in optodes, so that it can advantageously be used for the study of the role physical-chemical parameters of the system in order to optimize them and to prepare, if necessary, an optimized optode. Two lipophylic derivatives of Nile Blue and 4',5-dibromofluorescein have been synthesized, in order to ensure their permanence within organic phase. Two different neutral carriers previously characterized by us as ionophores for liquid-membrane Ion Selective Electrodes have been employed. Three different ionic exchangers have been tested. Furthermore, a model allowing the interpolation of experimental data and the determination of the thermodynamic constant of the ionic-exchange equilibrium has been developed and applied.

  9. Nitrilotriacetic acid functionalized Adansonia digitata biosorbent: Preparation, characterization and sorption of Pb (II) and Cu (II) pollutants from aqueous solution.

    PubMed

    Adewuyi, Adewale; Pereira, Fabiano Vargas

    2016-11-01

    Nitrilotriacetic acid functionalized Adansonia digitata (NFAD) biosorbent has been synthesized using a simple and novel method. NFAD was characterized by X-ray Diffraction analysis technique (XRD), Scanning Electron Microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analyzer, Fourier Transform Infrared spectrometer (FTIR), particle size dispersion, zeta potential, elemental analysis (CHNS/O analyzer), thermogravimetric analysis (TGA), differential thermal analysis (DTA), derivative thermogravimetric analysis (DTG) and energy dispersive spectroscopy (EDS). The ability of NFAD as biosorbent was evaluated for the removal of Pb (II) and Cu (II) ions from aqueous solutions. The particle distribution of NFAD was found to be monomodal while SEM revealed the surface to be heterogeneous. The adsorption capacity of NFAD toward Pb (II) ions was 54.417 mg/g while that of Cu (II) ions was found to be 9.349 mg/g. The adsorption of these metals was found to be monolayer, second-order-kinetic, and controlled by both intra-particle diffusion and liquid film diffusion. The results of this study were compared better than some reported biosorbents in the literature. The current study has revealed NFAD to be an effective biosorbent for the removal of Pb (II) and Cu (II) from aqueous solution.

  10. Magnetic hyaluronic acid nanospheres via aqueous Diels-Alder chemistry to deliver dexamethasone for adipose tissue engineering.

    PubMed

    Jia, Yang; Fan, Ming; Chen, Huinan; Miao, Yuting; Xing, Lian; Jiang, Bohong; Cheng, Qifan; Liu, Dongwei; Bao, Weikang; Qian, Bin; Wang, Jionglu; Xing, Xiaodong; Tan, Huaping; Ling, Zhonghua; Chen, Yong

    2015-11-15

    Biopolymer-based nanospheres have great potential in the field of drug delivery and tissue regenerative medicine. In this work, we present a flexible way to conjugate a magnetic hyaluronic acid (HA) nanosphere system that are capable of vectoring delivery of adipogenic factor, e.g. dexamethasone, for adipose tissue engineering. Conjugation of nanospheres was established by aqueous Diels-Alder chemistry between furan and maleimide of HA derivatives. Simultaneously, a furan functionalized dexamethasone peptide, GQPGK, was synthesized and covalently immobilized into the nanospheres. The magnetic HA nanospheres were fabricated by encapsulating super-paramagnetic iron oxide nanoparticles, which exhibited quick magnetic sensitivity. The aqueous Diels-Alder chemistry made nanospheres high binding efficiency of dexamethasone, and the vectoring delivery of dexamethasone could be easily controlled by a external magnetic field. The potential application of the magnetic HA nanospheres on vectoring delivery of adipogenic factor was confirmed by co-culture of human adipose-derived stem cells (ASCs). In vitro cytotoxicity tests demonstrated that incorporation of dexamethasone into magnetic HA nanospheres showed high efficiency to promote ASCs viabilities, in particular under a magnetic field, which suggested a promising future for adipose regeneration applications.

  11. Removal of dicyclohexyl acetic acid from aqueous solution using ultrasound, ozone and their combination.

    PubMed

    Kumar, Pardeep; Headley, John; Peru, Kerry; Bailey, Jon; Dalai, Ajay

    2014-01-01

    Naphthenic acids are a complex mixture of organic components, some of which include saturated alkyl-substituted cycloaliphatic carboxylic acids and acyclic aliphatic acids. They are naturally found in hydrocarbon deposits like oil sand, petroleum, bitumen and crude oil. In this study, the oxidation of a relatively high molecular weight naphthenic acid (Dicyclohexyl acetic acid) was investigated using ozonation, ultrasonication and hydrogen peroxide alone and their combinations. Effects on oxidation of dicyclohexyl acetic acid (DAA) were measured for different concentrations of ozone ranging between 0.7 to 3.3 mg L(-1) and pH in the range 6 to 10. Ultrasonication and hydrogen peroxide alone were not effective to oxidize dicyclohexyl acetic acid, but combining ultrasonication with H2O2 had a significant effect on oxidation of dicyclohexyl acetic acid with maximum removal reaching to 84 ± 2.2% with 81 ± 2.1% reduction in chemical oxygen demand (COD). Synergistic effects were observed for combining ultrasonication with ozonation and resulted in 100% DAA removal with 98 ± 0.8% reduction in COD within 15 min at 3.3 mg L(-1) ozone concentration and 130 Watts ultrasonication power. The reaction conditions obtained for the maximum oxidation of DAA and COD removal were used for the degradation of naphthenic acids mixture extracted from oil sands process water (OSPW). The percentage oxidation of NAs mixture extracted from OSPW was 89.3 ± 1.1% in ozonation and combined ozonation and ultrasonication, but COD removal observed was 65 ± 1.2% and 78 ± 1.4% for ozonation and combined ozonation and ultrasonication treatments, respectively.

  12. Modeling aqueous ozone/UV process using oxalic acid as probe chemical.

    PubMed

    Garoma, Temesgen; Gurol, Mirat D

    2005-10-15

    A kinetic model that describes the removal of organic pollutants by an ozone/UV process is described. Oxalic acid, which reacts with a very low rate constant with ozone and relatively high rate constant with hydroxyl radical (OH*), was used as the probe chemical to model the process. The model was verified by experimental data on concentrations of oxalic acid and hydrogen peroxide (H202) under various experimental conditions, i.e., ozone gas dosage, UV light intensity, and varying oxalic acid concentrations.

  13. Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.

    PubMed

    Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji

    2014-10-06

    To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)⇌ RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH 5-11: B' + L' (K')⇌ BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution.

  14. Equilibrium and kinetics study on the adsorption of perfluorooctanoic acid from aqueous solution onto powdered activated carbon.

    PubMed

    Qu, Yan; Zhang, Chaojie; Li, Fei; Bo, Xiaowen; Liu, Guangfu; Zhou, Qi

    2009-09-30

    Powdered activated carbon (PAC) was applied to remove perfluorooctanoic acid (PFOA) from the aqueous PFOA solution in this study. Contact time, adsorbent dose and temperature were analyzed as the effect factors in the adsorption reaction. The contact time of maximum PFOA uptake was around 1h while the sorption removal efficiency increased with the PAC concentrations. And the process of adsorption increased from 303 K to 313 K and then decreased from 313 K to 323 K. Among four applied models, the experimental isotherm data were discovered to follow Langmuir isotherm model more closely. Thermodynamically, adsorption was endothermic because enthalpy, entropy and Gibbs constants were 198.5 kJ/mol, 0.709 kJ/mol/K and negative, respectively, which also indicated that the adsorption process was spontaneous and feasible. From kinetic analysis, the adsorption was suggested to be pseudo-second-order model. The adsorption of PFOA on the PAC was mainly controlled by particle diffusion.

  15. Morphological and phase evolution of TiO 2 nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

    NASA Astrophysics Data System (ADS)

    Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

    2009-04-01

    Nanosized anatase and rutile TiO 2 having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H 2O 2) in water/isopropanol media by a facile sol-gel process. The TiO 2 nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO 2 are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given.

  16. Tandem bis-aza-Michael addition reaction of amines in aqueous medium promoted by polystyrenesulfonic Acid

    EPA Science Inventory

    An efficient and environmentally benign tandem bis-aza-Michael addition of amines catalyzed by polystyrene sulfonic acid (PSSA) is described. This operationally simple high yielding microwave assisted synthetic protocol proceeded in water in the absence of any organic solvent.

  17. Spectrofluorimetric study of the interaction of ciprofloxacin with amino acids in aqueous solution following solvatochromic studies

    NASA Astrophysics Data System (ADS)

    Alizadeh, Kamal; Mobarrez, Mahsa; Ganjali, Mohammad Reza; Norouzi, Parviz; Chaichi, Mohammad Javad

    Complexation of a fluoroquinolone derivative (ciprofloxacin), L, and some amino acids has been studied using spectrofluorimetric method. Results indicated that ciprofloxacin have a greater tendency to form a 1:1 complex with aspartic acid and arginine than the other tested molecules. The fluorescence of ciprofloxacin exhibits quenching process while it has been titrated with these amino acids. Formation constant values (Kf) for complex formed between ciprofloxacin and amino acids were also calculated. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were studied too. Possible reasons for the observed stability sequence were discussed based on the structures proposed for the resulting complexes. Besides the solution studies, solvatochromic properties of the ciprofloxacin are discussed by studying its spectra in a selection of different solvents.

  18. Magnetically separable nanoferrite-anchored glutathione: Aqueous homocoupling of arylboronic acids under microwave irradiation

    EPA Science Inventory

    A highly active, stable and magnetically separable glutathione based organocatalyst provided good to excellent yields to symmetric biaryls in the homocoupling of arylboronic acids under microwave irradiation. Symmetrical biaryl motifs are present in a wide range of natural p...

  19. Spectroscopic study of Mg(II) ion influence on the autoxidation of gallic acid in weakly alkaline aqueous solutions

    NASA Astrophysics Data System (ADS)

    Nikolić, G. M.; Veselinović, A. M.; Nikolić, R. S.; Mitić, S. S.

    2011-12-01

    Gallic acid autoxidation in weakly alkaline aqueous solutions was studied by UV-Vis spectrophotometry and ESR spectroscopy under various conditions. Lowering the pH value from 10 to 8.5 probably changes the mechanism of the autoxidation reaction as evidenced by the different time variations of UV-Vis spectra of solutions. The presence of Mg(II) ions greatly influences the autoxidation reaction at pH 8.5. Although the UV-Vis spectral changes with time follow the similar pattern during the gallic acid autoxidation at pH 10 and at pH 8.5 in the presence of Mg(II) ions, some small differences indicate that Mg(II) ions not only affect the electron density of absorbing species but also influence the overall mechanism of the autoxidation reaction. ESR spectra of free radials formed during the initial stage of gallic acid autoxidation at pH 8.5 in the presence of Mg(II) ions were recorded. Computer simulation of ESR spectra allows partial characterization of these free radicals.

  20. S-oxygenation of thiocarbamides IV: Kinetics of oxidation of tetramethylthiourea by aqueous bromine and acidic bromate.

    PubMed

    Ajibola, Risikat O; Simoyi, Reuben H

    2011-04-07

    The kinetics and mechanism of oxidation of tetramethylthiourea (TTTU) by bromine and acidic bromate has been studied in aqueous media. The kinetics of reaction of bromate with TTTU was characterized by an induction period followed by formation of bromine. The reaction stoichiometry was determined to be 4BrO(3)(-) + 3(R)(2)C═S + 3H(2)O → 4Br(-) + 3(R)(2)C═O + 3SO(4)(2-) + 6H(+). For the reaction of TTTU with bromine, a 4:1 stoichiometric ratio of bromine to TTTU was obtained with 4Br(2) + (R)(2)C═S + 5H(2)O → 8Br(-) + SO(4)(2-) + (R)(2)C═O + 10H(+). The oxidation pathway went through the formation of tetramethythiourea sulfenic acid as evidenced by the electrospray ionization mass spectrum of the dynamic reaction solution. This S-oxide was then oxidized to produce tetramethylurea and sulfate as final products of reaction. There was no evidence for the formation of the sulfinic and sulfonic acids in the oxidation pathway. This implicates the sulfoxylate anion as a precursor to formation of sulfate. In aerobic conditions, this anion can unleash a series of genotoxic reactive oxygen species which can explain TTTU's observed toxicity. A bimolecular rate constant of 5.33 ± 0.32 M(-1) s(-1) for the direct reaction of TTTU with bromine was obtained.

  1. Electrical conductivity measurements of aqueous boric acid at 25--350{degree}C at saturation vapor pressure. Final report

    SciTech Connect

    Ho, P.C.; Palmer, D.A.

    1995-09-01

    Electrical conductance measurements of aqueous boric acid solutions (15-110 g/kg-H{sub 2}O {equivalent_to} 0.251--1.815 mol/kg-H{sub 2}O) were measured over the temperature range 25 to 75 C at saturation vapor pressures in glass cells with parallel platinum electrodes. Sixteen series of measurements were made involving three samples of boric acid from different sources. Conductance measurements were also made at 15.5 and 30.5 g/kg-H{sub 2}O over the temperature range 100 to 350 C at 50 C intervals with a metallic cell fitted with concentric platinum electrodes. The specific conductances of H{sub 3}BO{sub 3} (aq)were calculated after correction for the conductance of the solvent (water) and are tabulated in this report. At the specific conditions requested in the project description, namely a concentration of 110 g/kg-H{sub 2}O and 65 C, the specific conductance of boric acid is 293.2 {+-} 1.8 microSiemens/cm based on duplicate measurements of four independent solutions. The results from these tests will be utilized by the Tokamak Physics Experimental Project (TPX).

  2. Photocatalytic decomposition of humic acids in anoxic aqueous solutions producing hydrogen, oxygen and light hydrocarbons.

    PubMed

    Klauson, Deniss; Budarnaja, Olga; Beltran, Ignacio Castellanos; Krichevskaya, Marina; Preis, Sergei

    2014-01-01

    Photocatalytic water splitting for hydrogen and oxygen production requires sacrificial electron donors, for example, organic compounds. Titanium dioxide catalysts doped with platinum, cobalt, tungsten, copper and iron were experimentally tested for the production of hydrogen, oxygen and low molecular weight hydrocarbons from aqueous solutions of humic substances (HS). Platinum-doped catalyst showed the best results in hydrogen generation, also producing methane, ethene and ethane, whereas the best oxygen production was exhibited by P25, followed by copper--and cobalt-containing photocatalysts. Iron-containing photocatalyst produced carbon monoxide as a major product. HS undergoing anoxic photocatalytic degradation produce hydrogen with minor hydrocarbons, and/or oxygen. It appears that better hydrogen yield is achieved when direct HS splitting takes place, as opposed to HS acting as electron donors for water splitting.

  3. Methylene blue adsorption from aqueous solution by activated carbon: effect of acidic and alkaline solution treatments.

    PubMed

    Ijagbemi, Christianah O; Chun, Ji I; Han, Da H; Cho, Hye Y; O, Se J; Kim, Dong S

    2010-01-01

    The removal of Methylene Blue (MB) from aqueous solution using activated carbon (AC) has been investigated. Adsorption experiments were conducted and the maximum adsorption capacity was determined. The effect of experimental parameters such as pH, dye concentration and temperature were studied on the adsorption process. Equilibrium data were mathematically modeled using the Langmuir and Freundlich adsorption models to describe the equilibrium isotherms at different dye concentrations and temperature. Parameters of best-fit model were calculated and discussed. To understand the mechanism of adsorption, kinetic models were employed to follow the adsorption processes; the pseudo-first-order best described the adsorption of MB onto AC. It was found that pH plays a major role in the adsorption process; adsorption capacity was influenced by the physical and surface chemical properties of carbon and the pH of the solution. 99.0% MB removal was achieved at equilibrium.

  4. Adsorption characteristics of malic acid from aqueous solutions by weakly basic ion-exchange chromatography.

    PubMed

    Gao, Qiang; Pan, Chaoqiang; Liu, Fabao; Lu, Fuping; Wang, Depei; Zhang, Jian; Zhu, Yan

    2012-08-17

    In this study, we reported the effects of temperature, malic acid loading concentration, and resin dose on malic acid adsorption by IRA-67 in batch experiments. The kinetic data well fitted the pseudo-second-order kinetic model. Both the equilibrium and ultimate adsorption slightly decreased with increased temperature from 303 to 323 K at 74.7 g/L malic acid loading concentration. The malic acid adsorption was revealed as a homogeneous adsorbent process by the Langmuir model and film diffusion process at loading concentrations of 18.2-94.5 g/L malic acid by the Boyd plot. The values of effective diffusion coefficient D(i) also increased with the temperature. Based on Eq. (15), the negative values of ΔG° and ΔH° revealed that the adsorption process was spontaneous and exothermic. The negative value of ΔS° also indicated the decrease in the solid-liquid interface randomness at this interface when malic acid is adsorbed by IRA-67.

  5. Simple and rapid hydrogenation of p-nitrophenol with aqueous formic acid in catalytic flow reactors.

    PubMed

    Javaid, Rahat; Kawasaki, Shin-Ichiro; Suzuki, Akira; Suzuki, Toshishige M

    2013-01-01

    The inner surface of a metallic tube (i.d. 0.5 mm) was coated with a palladium (Pd)-based thin metallic layer by flow electroless plating. Simultaneous plating of Pd and silver (Ag) from their electroless-plating solution produced a mixed distributed bimetallic layer. Preferential acid leaching of Ag from the Pd-Ag layer produced a porous Pd surface. Hydrogenation of p-nitrophenol was examined in the presence of formic acid simply by passing the reaction solution through the catalytic tubular reactors. p-Aminophenol was the sole product of hydrogenation. No side reaction occurred. Reaction conversion with respect to p-nitrophenol was dependent on the catalyst layer type, the temperature, pH, amount of formic acid, and the residence time. A porous and oxidized Pd (PdO) surface gave the best reaction conversion among the catalytic reactors examined. p-Nitrophenol was converted quantitatively to p-aminophenol within 15 s of residence time in the porous PdO reactor at 40 °C. Evolution of carbon dioxide (CO2) was observed during the reaction, although hydrogen (H2) was not found in the gas phase. Dehydrogenation of formic acid did not occur to any practical degree in the absence of p-nitrophenol. Consequently, the nitro group was reduced via hydrogen transfer from formic acid to p-nitrophenol and not by hydrogen generated by dehydrogenation of formic acid.

  6. Extraction and isolation of lithospermic acid B from Salvia miltiorrhiza Bunge using aqueous two-phase extraction followed by high-performance liquid chromatography.

    PubMed

    Guo, Yong Xue; Shi, Chang Zhi; Zhang, Lei; Lv, Lin; Zhang, Yue Yong

    2016-09-01

    A rapid and effective method integrating separation and purification of lithospermic acid B from Salvia miltiorrhiza Bunge was developed by combining an aqueous two-phase system extraction with preparative chromatography. An aqueous two-phase system of n-butyl alcohol/KH2 PO4 was chosen from seven systems. The influence of parameters including concentration of KH2 PO4 , n-butyl alcohol concentration, pH, and the ratio of an aqueous two-phase system to crude extract were investigated using a single factor design. Response surface methodology was subsequently used to find the optimal compositions of an aqueous two-phase system. Keeping a solvent-to-solid ratio of 10, the final optimized composition of an aqueous two-phase system was 39.1% w/w n-butyl alcohol and 22.6% w/w KH2 PO4 . Under these conditions a recovery yield of 99.8% and a high partition coefficient of 310.4 were obtained. In a pilot-scale experiment using optimized conditions, 18.79 g of lithospermic acid B with a purity of 70.5% and in a yield of 99.8% was separated from 0.5 kg of crude extract. Subsequently, 9.94 g lithospermic acid B with a purity of 99.3% and recovery yield of 70.3% was obtained with a preparative chromatographic process, and the two-step total recovery was 70.1%.

  7. Effects of Relative Humidity and Particle Phase Water on the Heterogeneous OH Oxidation of 2-Methylglutaric Acid Aqueous Droplets.

    PubMed

    Chim, Man Mei; Chow, Chun Yin; Davies, James F; Chan, Man Nin

    2017-03-02

    Organic aerosols can exist as aqueous droplets, with variable water content depending on their composition and environmental conditions (e.g., relative humidity (RH)). Recent laboratory studies have revealed that oxidation kinetics in highly concentrated droplets can be much slower than those in dilute solutions. However, it remains unclear whether aerosol phase water affects the formation of reaction products physically and/or chemically. In this work, we investigate the role of aerosol phase water on the heterogeneous chemistry of aqueous organic droplets consisting of 2-methylglutaric acid (2-MGA), measuring the reaction kinetics and the reaction products upon heterogeneous OH oxidation over a range of RH. An atmospheric pressure soft ionization source (direct analysis in real time, DART) coupled with a high-resolution mass spectrometer is used to obtain real-time molecular information on the reaction products. Aerosol mass spectra show that the same reaction products are formed at all measured RH. At a given reaction extent of the parent 2-MGA, the aerosol composition is independent of RH. These results suggest the aerosol phase water does not alter reaction mechanisms significantly. Kinetic measurements find that the effective OH uptake coefficient, γeff, decreases with decreasing RH below 72%. Isotopic exchange measurements performed using aerosol optical tweezers reveal water diffusion coefficients in the 2-MGA droplets to be 3.0 × 10(-13) to 8.0 × 10(-13) m(2) s(-1) over the RH range of 47-58%. These values are comparable to those of other viscous organic aerosols (e.g., citric acid), indicating that 2-MGA droplets are likely to be viscous at low humidity. Smaller γeff at low RH is likely attributed to the slower diffusion of reactants within the droplets. Taken together, the observed relationship between the γeff and RH is likely attributed to changes in aerosol viscosity rather than changes in reaction mechanisms.

  8. Acid in the environment: lessons learned and future prospects

    SciTech Connect

    Visgilio, Gerald R.; Whitelaw, Diana M.

    2007-07-01

    This book is the result of a conference held biannually at the Goodwin-Niering Center for Conservation Biology and Environmental Studies at Connecticut College. It uses an interdisciplinary approach to focus on important ecological impacts of acid deposition, the transboundary nature of the pollutants that cause acid rain, and domestic and international policies designed to reduce the emission of these pollutants. The book combines research findings and the policy analyses of experts from different academic disciplines with the positions advanced by representatives of various nongovernmental organizations (NGOs). The sixteen papers are arranged in four parts entitled: ecological impacts of acid deposition; acid emissions energy and policy; sulfur dioxide and the market; and lessons learned and future prospects.

  9. Phase diagrams and water activities of aqueous ammonium salts of malonic acid.

    PubMed

    Beyer, Keith D; Richardson, Michael; Reusch, Breanna

    2011-04-14

    Malonic acid has been observed in the free troposphere and as a component of tropospheric aerosol, among other dicarboxylic acids. These aerosols can uptake ammonia, which partially or completely neutralizes the acids. Therefore, the impact of ammoniated dicarboxylic acids on the phases that can exist in aerosols at atmospheric temperatures needs investigation. To that end, the low temperature, solid/liquid phase diagrams of ammonium hydrogen malonate/water, ammonium malonate/water, and triammonium hydrogen malonate/water have been investigated with differential scanning calorimetry and infrared spectroscopy of thin films. Results show that the order of increasing solubility is triammonium hydrogen malonate, ammonium hydrogen malonate, malonic acid, and ammonium malonate. We have also determined a hydrate may form in the ammonium malonate system and decompose below 240 K. We report water activities at the ice melting points for each system up to the respective eutectic concentrations, and find for a given mole fraction of water, increasing ammonium content leads to decreasing water activity coefficients.

  10. Spectroscopic evidence for organic diacid complexation with dissolved silica in aqueous systems—I. Oxalic acid

    USGS Publications Warehouse

    Marley, N.A.; Bennett, P.; Janecky, D.R.; Gaffney, J.S.

    1989-01-01

    Increased solubility of quartz and mobilization in contaminated groundwater due to the complexation with dissolved organic acids has been recently proposed [Bennett and Siegel, Nature326, 684–686 (1987)]. Using laser Raman and Fourier transform infrared spectroscopies, we have examined mixed solutions of oxalic and silicic acids at near neutral pH in the tenth molar concentration ranges in an attempt to directly observe the proposed organo-silicate complexes.In both laser Raman and infrared spectra, product bands were observed that indicate an oxalate/silicic acid ester is being formed in the reaction. These data support the observation that organic diacids can lead to enhanced solubility of quartz in hydrogeological systems.

  11. Pervaporation of Water from Aqueous Sulfuric Acid at Elevated Temperatures Using Nafion® Membranes

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart

    2009-01-01

    The concentration of sulfuric acid by pervaporation has been studied using Nafion-112® and Nafion-117® membranes, which have been characterized in terms of flux, permeability, and selectivity at 100 ºC and 120 ºC. Feed concentrations investigated ranged from 40 to over 80 weight percent. In general, water fluxes ranged from 100-8000 g/m2h, depending on feed acid concentration and separations factors as high as 104 were observed. Membrane stability was probed using Dynamic Mechanical Analysis that revealed some embrittlement of the membranes during use. Further studies showed that the embrittlement was due to an interaction with the acid and was not induced by the operating temperature.

  12. Thermodynamic and ultrasonic properties of ascorbic Acid in aqueous protic ionic liquid solutions.

    PubMed

    Singh, Vickramjeet; Sharma, Gyanendra; Gardas, Ramesh L

    2015-01-01

    In this work, we report the thermodynamic and ultrasonic properties of ascorbic acid (vitamin C) in water and in presence of newly synthesized ammonium based protic ionic liquid (diethylethanolammonium propionate) as a function of concentration and temperature. Apparent molar volume and apparent molar isentropic compression, which characterize the solvation state of ascorbic acid (AA) in presence of protic ionic liquid (PIL) has been determined from precise density and speed of sound measurements at temperatures (293.15 to 328.15) K with 5 K interval. The strength of molecular interactions prevailing in ternary solutions has been discussed on the basis of infinite dilution partial molar volume and partial molar isentropic compression, corresponding volume of transfer and interaction coefficients. Result has been discussed in terms of solute-solute and solute-solvent interactions occurring between ascorbic acid and PIL in ternary solutions (AA + water + PIL).

  13. Removal of 8-quinolinecarboxylic acid pesticide from aqueous solution by adsorption on activated montmorillonites.

    PubMed

    Mekhloufi, M; Zehhaf, A; Benyoucef, A; Quijada, C; Morallon, E

    2013-12-01

    Sodium montmorillonite (Na-M), acidic montmorillonite (H-M), and organo-acidic montmorillonite (Org-H-M) were applied to remove the herbicide 8-quinolinecarboxylic acid (8-QCA). The montmorillonites containing adsorbed 8-QCA were investigated by transmission electron microscopy, FT-IR spectroscopy, X-ray diffraction analysis, X-ray fluorescence thermogravimetric analysis, and physical adsorption of gases. Experiments showed that the amount of adsorbed 8-QCA increased at lower pH, reaching a maximum at pH 2. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The Langmuir model provided the best correlation of experimental data for adsorption equilibria. The adsorption of 8-QCA decreased in the order Org-H-M > H-M > Na-M. Isotherms were also used to obtain the thermodynamic parameters. The negative values of ΔG indicated the spontaneous nature of the adsorption process.

  14. Thermodynamic and Ultrasonic Properties of Ascorbic Acid in Aqueous Protic Ionic Liquid Solutions

    PubMed Central

    Singh, Vickramjeet; Sharma, Gyanendra; Gardas, Ramesh L.

    2015-01-01

    In this work, we report the thermodynamic and ultrasonic properties of ascorbic acid (vitamin C) in water and in presence of newly synthesized ammonium based protic ionic liquid (diethylethanolammonium propionate) as a function of concentration and temperature. Apparent molar volume and apparent molar isentropic compression, which characterize the solvation state of ascorbic acid (AA) in presence of protic ionic liquid (PIL) has been determined from precise density and speed of sound measurements at temperatures (293.15 to 328.15) K with 5 K interval. The strength of molecular interactions prevailing in ternary solutions has been discussed on the basis of infinite dilution partial molar volume and partial molar isentropic compression, corresponding volume of transfer and interaction coefficients. Result has been discussed in terms of solute-solute and solute-solvent interactions occurring between ascorbic acid and PIL in ternary solutions (AA + water + PIL). PMID:26009887

  15. Reduction of Cr(VI) by malic acid in aqueous Fe-rich soil suspensions.

    PubMed

    Zhong, Laiyuan; Yang, Jiewen

    2012-03-01

    Detoxification of Cr(VI) through reduction by organic reductants has been regarded as an effective way for remediation of Cr(VI)-polluted soils. However, such remediation strategy would be limited in practical applications due to the low Cr(VI) reduction rate. In this study, the catalytic effect of two Fe-rich soils (Ultisol and Oxisol) on Cr(VI) reduction by malic acid was evaluated. As the results shown, the two soils could obviously accelerate the reduction of Cr(VI) by malic acid at low pH conditions, while such catalytic effect was gradually suppressed as the increase in pH. After reaction for 48 h at pH 3.2, Oxalic acid was found in the supernatant of Ultisol, suggesting the oxidization of hydroxyl in malic acid to carboxyl and breakage of the bond between C(2) and C(3). It was also found that the catalytic reactivity of Ultisol was more significant than that of Oxisol, which could be partly attributed to the fact that the amount of Fe(II) released from the reductive dissolution of Ultisol by malic acid was larger than that of Oxisol. With addition of Al(III), the catalytic effect from Ultisol was inhibited across the pH range examined. On the contrary, the presence of Cu(II) would increase the catalytic effect of Ultisol, which was more pronounced with the increase in pH. This study proposed a potential way for elimination of the environmental risks posed by the Cr(VI) contamination by use of the natural soil surfaces to catalyze Cr(VI) reduction by the organic reductant such as malic acid, a kind of organic reductant originating from soil organic decomposition process or plant excretion.

  16. Interaction of some metals between marine-origin humic acids and aqueous solutions

    SciTech Connect

    Huljev, D.J.

    1986-08-01

    The interaction of metal ions (carrier-free form) in aquatic medium with humic acids is a complicated process depending on the properties of humic acids (elementary, chemical, and trace element composition), metals studied (valence, charge, chemical form, concentration), and medium used (pH, ionic strength). The use of radionuclides was found to be very suitable for a rapid and precise determination of the distribution coefficient K/sub d/ (ratio of the concentration of a certain trace metal association with a gram of humic acid over the concentration of the same trace metal per milliliter of solution) of the investigated system. Isolated humic acids from offshore sediments from the North Adriatic (Lim channel, near Rovinj, Yugoslavia) were characterized according to their elementary composition, the amount of products of hydrolysis, and the trace elements bound. All experiments were carried out between pH 3 and 5. It was found that conditions usually present at the site where humic acid interacts with metal ions (anaerobic conditions, H/sub 2/S) in brackish (21% S) and standard seawater (38% S) are determined in the pH range 3 to 5. The results of the pick-up (uptake) and replacement (release) experiments are presented as a distribution coefficient (K/sub d/), as a function of contact time. Processes of pick-up and replacement of a number of metals under various physicochemical conditions were investigated and special attention was paid to the influence of salinity. With the increase in NaCl concentration and pH in the system, the fixation of ruthenium, zinc, cobalt, and mercury by humic acids decreased.

  17. Removal of aqueous oxalic acid by heterogeneous catalytic ozonation with MnOx/sewage sludge-derived activated carbon as catalysts.

    PubMed

    Huang, Yuanxing; Sun, Yaru; Xu, Zhihua; Luo, Mengyu; Zhu, Chunlei; Li, Liang

    2017-01-01

    MnOx/sewage sludge-derived activated carbon (MnOx/SAC) was prepared as catalysts to improve the performance of aqueous oxalic acid degradation by ozonation. The results indicated that MnOx/SAC had excellent catalytic activity in mineralization of oxalic acid during heterogeneous catalytic ozonation process. MnOx/SAC with a manganese load of 30% exhibited the strongest catalytic activity under the condition of solution pH3.5, which enhanced the oxalic acid removal from 10.3% to 92.2% in 60min compared with that treated by ozone alone. Increase of catalyst dosage and aqueous ozone concentration was advantageous for oxalic acid removal from water. On the basis of catalyst characterization analysis and the observation of inhibitory effect induced by higher pH, less catalyst dosage as well as the presence of hydroxyl radical scavenger, it was deduced that the reaction mechanism involved both hydroxyl radicals attack and surface reactions.

  18. Survival of the acid-adapted Bacillus cereus in acidic environments.

    PubMed

    Chen, Jui-Lin; Chiang, Ming-Lun; Chou, Cheng-Chun

    2009-01-15

    In this study, the acid tolerance of Bacillus cereus 1-4-1 after adaptation at pH 5.5 for 1, 2 and 4 h was first determined. The survival of acid-adapted and non-adapted cells of B. cereus in phosphate buffer solution (PBS pH 4.0) containing various organic acids such as acetic, propionic, citric, lactic or tartaric acid as well as in a commercial acidic beverage of mixed fruits and vegetables (pH 3.7) was then examined. Results revealed that acid adaptation time influenced the increased tolerance of B. cereus in PBS (pH 4.0). The 2 h-adapted cells exhibited the highest acid tolerance in PBS. The presence of chloramphenicol during the acid adaptation reduced the extent of increased acid tolerance. Acid adaptation was also found to enhance the tolerance of the test organism in the presence of the various organic acids tested. While the extent of increased acid tolerance varied with the organic acid examined. Acid-adapted B. cereus cells exhibited the largest extent of increased tolerance, showing an increased survival of ca. 1000 folds, in the propionic acid-containing PBS. Additionally, a higher survival percentage was noted with the acid-adapted than the non-adapted cells of B. cereus in the acidic beverage stored at 4 or 25 degrees C.

  19. Sampling of Organic Solutes in Aqueous and Heterogeneous Environments Using Oscillating Excess Chemical Potentials in Grand Canonical-like Monte Carlo-Molecular Dynamics Simulations.

    PubMed

    Lakkaraju, Sirish Kaushik; Raman, E Prabhu; Yu, Wenbo; MacKerell, Alexander D

    2014-06-10

    Solute sampling of explicit bulk-phase aqueous environments in grand canonical (GC) ensemble simulations suffer from poor convergence due to low insertion probabilities of the solutes. To address this, we developed an iterative procedure involving Grand Canonical-like Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Each iteration involves GCMC of both the solutes and water followed by MD, with the excess chemical potential (μex) of both the solute and the water oscillated to attain their target concentrations in the simulation system. By periodically varying the μex of the water and solutes over the GCMC-MD iterations, solute exchange probabilities and the spatial distributions of the solutes improved. The utility of the oscillating-μex GCMC-MD method is indicated by its ability to approximate the hydration free energy (HFE) of the individual solutes in aqueous solution as well as in dilute aqueous mixtures of multiple solutes. For seven organic solutes: benzene, propane, acetaldehyde, methanol, formamide, acetate, and methylammonium, the average μex of the solutes and the water converged close to their respective HFEs in both 1 M standard state and dilute aqueous mixture systems. The oscillating-μex GCMC methodology is also able to drive solute sampling in proteins in aqueous environments as shown using the occluded binding pocket of the T4 lysozyme L99A mutant as a model system. The approach was shown to satisfactorily reproduce the free energy of binding of benzene as well as sample the functional group requirements of the occluded pocket consistent with the crystal structures of known ligands bound to the L99A mutant as well as their relative binding affinities.

  20. Efficacy of chlorine, acidic electrolyzed water and aqueous chlorine dioxide solutions to decontaminate Escherichia coli O157:H7 from lettuce leaves

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study compared the efficacy of chlorine (20 – 200 ppm), acidic electrolyzed water (50 ppm chlorine, pH 2.6), acidified sodium chlorite (20 – 200 ppm chlorite ion concentration, Sanova), and aqueous chlorine dioxide (20 – 200 ppm chlorite ion concentration, TriNova) washes in reducing population...