Hematin crystallization from aqueous and organic solvents

NASA Astrophysics Data System (ADS)

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

2013-09-01

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

Perylene Diimide Based Fluorescent Dyes for Selective Sensing of Nitroaromatic Compounds: Selective Sensing in Aqueous Medium Across Wide pH Range.

PubMed

Hariharan, P S; Pitchaimani, J; Madhu, Vedichi; Anthony, Savarimuthu Philip

2016-03-01

Water soluble perylenediimide based fluorophore salt, N,N'-bis(ethelenetrimethyl ammoniumiodide)-perylene-3,4,9,10-tetracarboxylicbisimide (PDI-1), has been used for selective fluorescence sensing of picric acid (PA) and 4-nitroaniline (4-NA) in organic as well as aqueous medium across wide pH range (1.0 to 10.0). PDI-1 showed strong fluorescence in dimethylformamide (DMF) (Φf = 0.26 (DMF) and moderate fluorescence in water. Addition of picric acid (PA) and 4-nitroaniline (4-NA) into PDI-1 in DMF/aqueous solution selectively quenches the fluorescence. The concentration dependent studies showed decrease of fluorescence linearly with increase of PA and 4-NA concentration. The interference studies demonstrate high selectivity for PA and 4-NA. Interestingly, PDI-1 showed selective fluorescence sensing of PA and 4-NA across wide pH range (1.0 to 10.0). Selective fluorescence sensing of PA and 4-NA has also been observed with trifluoroacetate (PDI-2), sulfate (PDI-3) salt of PDI-1 as well as octyl chain substituted PDI (PDI-4) without amine functionality. These studies suggest that PA and 4-NA might be having preferential interaction with PDI aromatic core and quenches the fluorescence. Thus PDI based dyes have been used for selective fluorescent sensing of explosive NACs for the first time to the best our knowledge.

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

NASA Astrophysics Data System (ADS)

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

2009-01-01

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

Aggregation induced emission enhancement (AIEE) characteristics of quinoline based compound - A versatile fluorescent probe for pH, Fe(III) ion, BSA binding and optical cell imaging

NASA Astrophysics Data System (ADS)

Manikandan, Irulappan; Chang, Chien-Huei; Chen, Chia-Ling; Sathish, Veerasamy; Li, Wen-Shan; Malathi, Mahalingam

2017-07-01

Novel benzimidazoquinoline derivative (AVT) was synthesized through a substitution reaction and characterized by various spectral techniques. Analyzing the optical properties of AVT under absorption and emission spectral studies in different environments exclusively with respect to solvents and pH, intriguing characteristics viz. aggregation induced emission enhancement (AIEE) in the THF solvent and 'On-Off' pH sensing were found at neutral pH. Sensing nature of AVT with diverse metal ions and bovine serum albumin (BSA) was also studied. Among the metal ions, Fe3 + ion alone tunes the fluorescence intensity of AVT probe in aqueous medium from ;turn-on; to ;turn-off; through ligand (probe) to metal charge transfer (LMCT) mechanism. The probe AVT in aqueous medium interacts strongly with BSA due to Fluorescence Resonance Energy Transfer (FRET) and the conformational change in BSA was further analyzed using synchronous fluorescence techniques. Docking study of AVT with BSA reveals that the active site of binding is tryptophan residue which is also supported by the experimental results. Interestingly, fluorescent AVT probe in cells was examined through cellular imaging studies using BT-549 and MDA-MB-231 cells. Thus, the single molecule probe based detection of multiple species and stimuli were described.

Filterability of the suspension from germanium precipitation with aqueous tannin extract solution

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

Mikhailov, N.F.; Petropol'skii, V.M.; Semenenko, L.E.

1978-01-01

We have already described the use of a neutral aqueous solution of tannin extract to recover germanium from collecting-mains liquor in coking plants. Further pilot commercial trials have encountered problems with the poor filterability of the precipitate obtained when germanium is extracted with this reagent in alkaline media. There are published references to the colloidal nature of the precipitated tannin-germanium complex. It is also known that the alkalinity of the medium influences the degree of association in colloidal systems to a marked extent. Accordingly, special research was needed to establish the relationship between the pH of the precipitation medium andmore » the filterability of the germanium deposit. Samples of collecting-mains liquor were taken from one of the southern coking plants to determine the optimum filtration behavior. The collecting-mains liquor should first be purged of volatile ammonia and then adjusted to pH = 6.5 to 6.7 for precipitation.« less

Plasma Induced Degradation of Benzidine in Aqueous Solution

NASA Astrophysics Data System (ADS)

Gao, Jinzhang; Gai, Ke; Yang, Wu; Dong, Yanjie

2003-10-01

The degradation of benzidine in aqueous solution by the low temperature plasma was examined. The results showed that the concentration of medium and the value of pH have an appreciable effect on the degradation of benzidine. What is more important is that iron ions acting as a catalyst play an important role in this reaction. For exploring the degradation mechanism of benzidine, some of the intermediate products were recorded by HPLC (high performance liquid chromatography).

A laboratory scale study on arsenic(V) removal from aqueous medium using calcined bauxite ore.

PubMed

Mohapatra, Debasish; Mishra, Debaraj; Park, Kyung Ho

2008-01-01

The present work deals with the As(V) removal from an aqueous medium by calcined refractory grade bauxite (CRB) as a function of solution pH, time, As(V) concentration and temperature. The residual As(V) was lowered from 2 mg/L to below 0.01 mg/L in the optimum pH range 4.0-7.0 using a 5 g/L CRB within 3 h contact time. The adsorption data fits well with Langmuir isotherm and yielded Langmuir monolayer capacity of 1.78 mg As(V)/g of CRB at pH 7.0. Presence of anions such as silicate and phosphate decreased As(V) adsorption efficiency. An increase temperature resulted a decrease in the amount of As(V) adsorbed by 6%. The continuous fixed bed column study showed that at the adsorbent bed depth of 30 cm and residence time of 168 min, the CRB was capable of treating 340 bed volumes of As(V) spiked water (C0 = 2 mg/L) before breakthrough (Ce = 0.01 mg/L). This solid adsorbent, although not reusable, can be considered for design of adsorption columns as an efficiency arsenic adsorption media.

Biomimetic synthesis of silver nanoparticles and evaluation of their catalytic activity towards degradation of methyl orange

NASA Astrophysics Data System (ADS)

Manjari Mishra, Pravat; Bihari Pani, Khirod

2017-11-01

This paper described the significant effect of process variables like reductant concentrations, substrate concentration, reaction pH and reaction temperature on the size, morphology and yield of the silver nanoparticles (AgNPs) synthesized using aqueous leaf extract of a medicinal plant Momordica charantia (Bitter guard). By means of UV-vis spectroscopy, XRD analysis, TEM analysis and Fluorescence analysis, it is observed that the reaction solution containing 10-3 M of AgNO3 of pH 5.3  +  10 ml of aqueous leaf extract at normal room temperature, was optimum for synthesis of stable, polydisperse, predominantly spherical AgNPs with average size of 12.15 nm. FT-IR and TEM studies confirmed the stability of AgNPs was due to the capping of phytoconstituents present in the leaf extract. The aqueous solution of leaf extract containing AgNPs showed remarkable catalytic activity towards degradation of methyl orange (MO) in aqueous medium.

Biosorption of hexavalent chromium from aqueous medium with Opuntia biomass.

PubMed

Fernández-López, José A; Angosto, José M; Avilés, María D

2014-01-01

The biosorption of hexavalent chromium from aqueous solutions by Opuntia cladodes and ectodermis from cactus fruits was investigated. Both types of biomass are considered low-cost, natural, and ecofriendly biosorbents. Batch experiments were carried out to determine Cr(VI) biosorption capacity and the efficiency of the biosorption process under different pH, initial Cr(VI) concentration, and sorbent dosage. The biosorption of Cr(VI) by Opuntia biomass was highly pH dependent, favoring higher metal uptake at low pH. The higher biosorption capacity was exhibited at pH 2. The optimal conditions were obtained at a sorbent dosage of 1 g L(-1) and initial metal concentration of 10 mg L(-1). Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The rate constant, the initial biosorption rate, and the equilibrium biosorption capacity were determined. The experimental equilibrium data obtained were analyzed using two-parameter isotherm models (Langmuir, Freundlich, and Temkin). The Langmuir maximum monolayer biosorption capacity (q max) was 18.5 mg g(-1) for cladodes and 16.4 mg g(-1) for ectodermis. The results suggest that Opuntia biomass could be considered a promising low-cost biosorbent for the ecofriendly removal of Cr(VI) from aqueous systems.

Flotation removal of the microalga Nannochloropsis sp. using Moringa protein-oil emulsion: A novel green approach.

PubMed

Kandasamy, Ganesan; Shaleh, Sitti Raehanah Muhamad

2018-01-01

A new approach to recover microalgae from aqueous medium using a bio-flotation method is reported. The method involves utilizing a Moringa protein extract - oil emulsion (MPOE) for flotation removal of Nannochloropsis sp. The effect of various factors has been assessed using this method, including operating parameters such as pH, MPOE dose, algae concentration and mixing time. A maximum flotation efficiency of 86.5% was achieved without changing the pH condition of algal medium. Moreover, zeta potential analysis showed a marked difference in the zeta potential values when increase the MPOE dose concentration. An optimum condition of MPOE dosage of 50ml/L, pH 8, mixing time 4min, and a flotation efficiency of greater than 86% was accomplished. The morphology of algal flocs produced by protein-oil emulsion flocculant were characterized by microscopy. This flotation method is not only simple, but also an efficient method for harvesting microalgae from culture medium. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

Jelińska, A; Magdziarz, M

2000-01-01

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

Metal-oxide thin-film transistor-based pH sensor with a silver nanowire top gate electrode

NASA Astrophysics Data System (ADS)

Yoo, Tae-Hee; Sang, Byoung-In; Wang, Byung-Yong; Lim, Dae-Soon; Kang, Hyun Wook; Choi, Won Kook; Lee, Young Tack; Oh, Young-Jei; Hwang, Do Kyung

2016-04-01

Amorphous InGaZnO (IGZO) metal-oxide-semiconductor thin-film transistors (TFTs) are one of the most promising technologies to replace amorphous and polycrystalline Si TFTs. Recently, TFT-based sensing platforms have been gaining significant interests. Here, we report on IGZO transistor-based pH sensors in aqueous medium. In order to achieve stable operation in aqueous environment and enhance sensitivity, we used Al2O3 grown by using atomic layer deposition (ALD) and a porous Ag nanowire (NW) mesh as the top gate dielectric and electrode layers, respectively. Such devices with a Ag NW mesh at the top gate electrode rapidly respond to the pH of solutions by shifting the turn-on voltage. Furthermore, the output voltage signals induced by the voltage shifts can be directly extracted by implantation of a resistive load inverter.

Effect of pH and interaction between egg white protein and hydroxypropymethylcellulose in bulk aqueous medium on foaming properties.

PubMed

Sadahira, Mitie S; Lopes, Fernanda C Rezende; Rodrigues, Maria I; Yamada, Aureo T; Cunha, Rosiane L; Netto, Flavia M

2015-07-10

Egg white protein (EW) is used as surface-active ingredient in aerated food and hydroxypropylmethylcellulose (HPMC) is a polysaccharide that behaves as a surfactant. This study aimed at investigating the effects of process parameters biopolymer concentration (2.0-5.0%, w/w), EW:HPMC ratio (2:1-18:1), pH (3.0-6.0), and the influence of biopolymers' behavior in aqueous solution at different pH on the foaming properties (overrun, drainage, and bubble growth rate). Process parameters had effect on foaming properties. The pH was the major factor influencing the type of EW/HPMC interaction and affected the foaming properties of biopolymer mixture. At pH 3.0, EW and HPMC showed thermodynamic compatibility leading to better foaming properties, higher foaming capacity, and stability than without HPMC addition whereas at pH 4.5 and 6.0, EW and HPMC are incompatible that causes lower stability concerning the disproportionation comparing to foam without HPMC. At pH between 3.0 and 4.5, HPMC improves foaming properties of aerated products. Copyright © 2015 Elsevier Ltd. All rights reserved.

Assessing the suitability of the OECD 29 guidance document to investigate the transformation and dissolution of silver nanoparticles in aqueous media.

PubMed

Wasmuth, Claus; Rüdel, Heinz; Düring, Rolf-Alexander; Klawonn, Thorsten

2016-02-01

The OECD guidance document No. 29 was designed to determine the rate and extend to which metals can produce soluble available ionic metal species. This transformation/dissolution protocol was applied to silver nanomaterials. The results prove that concentrations of released Ag(+) at pH 8 were nearly similar at all three different loadings. At pH 6, the concentration of Ag(+) was almost the same at loadings of 10 and 100 mg L(-1) AgNPs. However, the study showed changes in concentrations of nanoparticles and aggregates (operationally defined as the fraction passing a 0.2 µm filter). At the higher pH both the concentrations in the test medium of Ag(+) and of AgNPs (fraction < 0.2 µm) decreased. After 7 days of test duration, 71 µg L(-1) of Ag(+) was found in pH 6 medium (initial loading of 100 mg L(-1)). In pH 8 medium a maximum concentration of 29 µg L(-1) Ag(+) was measured (initial loading of 10 mg L(-1)). The maximum transformation from AgNPs to Ag(+) was 2.7% (27 µg L(-1)) in pH 8 medium (loading of 1 mg L(-1)) after 7 days. At an initial loading of 100 mg L(-1) AgNPs in medium at pH 8, only 0.03% (30 µg L(-1)) were transformed to Ag(+) after 7 days. At the loading of 1 mg L(-1) AgNPs all silver concentrations remain relatively constant for the duration of the test after 7 until 28 days. The results reveal that only low concentrations of Ag(+) are released from AgNPs under the applied conditions. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

[Role of the medium acidity in the complexes formation of pyropheophorbide a with albumin and lipoproteins].

PubMed

Golovina, G V; Ol'shevskaia, V A; Kalinina, V N; Shtil', A A; Kuz'min, V A

2011-01-01

The spectral characteristics of the photosensitizer pyropheophorbide a (PPP) complexes with its carriers, that is, serum albumin and low density lipoproteins, were investigated in aqueous solutions at pH 7.4 and 5.0. The acidic pH had no effect on the quantitative parameters of PPP binding to lipoproteins but reduces its affinity for albumin. Differential role of acidification in the binding of PPP to biomacromolecules should be considered in the design of PPP-based drugs given that pH is frequently lowered in the sites of the disease.

Ultrasound promoted synthesis of 2-imidazolines in water: a greener approach toward monoamine oxidase inhibitors.

PubMed

Sant' Anna, Gabriela da S; Machado, Pablo; Sauzem, Patricia D; Rosa, Fernanda A; Rubin, Maribel A; Ferreira, Juliano; Bonacorso, Helio G; Zanatta, Nilo; Martins, Marcos A P

2009-01-15

A series of sixteen 2-substituted-2-imidazolines (where the substituent R=Ph, Me-4-Ph; MeO-4-Ph; (MeO)(2)-3,4-Ph; (MeO)(3)-3,4,5-Ph; Ph-4-O-C(O)-Ph; Cl-4-Ph; Cl-2-Ph; Cl(2)-2,4-Ph; NO(2)-4-Ph; NO(2)-3-Ph; Naphth-2-yl; Fur-2-yl; Benzofur-2-yl; Pyridin-2-yl; Quinolin-2-yl) has been synthesized from the reaction of the substituted-aldehydes and ethylenediamine by ultrasound irradiation with NBS in an aqueous medium in high yields (80-99%). The 2-imidazoline ability to inhibit the activity of the A and B isoforms of monoamine oxidase (MAO) was investigated and some of them showed potent and selective MAO inhibitory activity especially for the MAO-B isoform and could become promising candidates for future development.

Biosorption of Hexavalent Chromium from Aqueous Medium with Opuntia Biomass

PubMed Central

2014-01-01

The biosorption of hexavalent chromium from aqueous solutions by Opuntia cladodes and ectodermis from cactus fruits was investigated. Both types of biomass are considered low-cost, natural, and ecofriendly biosorbents. Batch experiments were carried out to determine Cr(VI) biosorption capacity and the efficiency of the biosorption process under different pH, initial Cr(VI) concentration, and sorbent dosage. The biosorption of Cr(VI) by Opuntia biomass was highly pH dependent, favoring higher metal uptake at low pH. The higher biosorption capacity was exhibited at pH 2. The optimal conditions were obtained at a sorbent dosage of 1 g L−1 and initial metal concentration of 10 mg L−1. Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The rate constant, the initial biosorption rate, and the equilibrium biosorption capacity were determined. The experimental equilibrium data obtained were analyzed using two-parameter isotherm models (Langmuir, Freundlich, and Temkin). The Langmuir maximum monolayer biosorption capacity (q max) was 18.5 mg g−1 for cladodes and 16.4 mg g−1 for ectodermis. The results suggest that Opuntia biomass could be considered a promising low-cost biosorbent for the ecofriendly removal of Cr(VI) from aqueous systems. PMID:24982975

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

PubMed

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

2017-03-01

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

Removal of oxytetracycline from aqueous solutions by hydroxyapatite as a low-cost adsorbent

NASA Astrophysics Data System (ADS)

Harja, Maria; Ciobanu, Gabriela

2017-11-01

The present paper involved a study of the adsorption process of the oxytetracycline drug from aqueous medium by using the hydroxyapatite nanopowders as adsorbent materials. The batch adsorption experiments were performed by monitoring the solution pH, contact time, adsorbent dosage and drug solution concentration. At pH 8 and ambient temperature, high oxytetracycline removal rates of about 97.58% and 89.95% for the uncalcined and calcined nanohydroxyapatites, respectively, were obtained. The kinetic studies indicate that the oxytetracycline adsorption onto nanohydroxyapatite samples follows a pseudo-second order kinetic model. The maximum adsorption capacities of 291.32 mg/g and 278.27 mg/g for uncalcined and calcined nanohydroxyapatite samples, respectively, have been found. So, the conclusion can be drawn that the hydroxyapatite shows good adsorption ability towards oxytetracycline.

Effect of hydrotalcite-like compounds on the aqueous solubility of some poorly water-soluble drugs.

PubMed

Ambrogi, Valeria; Fardella, Giuseppe; Grandolini, Giuliano; Nocchetti, Morena; Perioli, Luana

2003-07-01

A new approach of improving drug dissolution properties is described. This method exploits the property of a carrier owing to the hydrotalcite-type anionic clays (HTlc). HTlc is an inorganic layered solid that lodges anionic compounds among its layers. As HTlc dissolves at acidic pH values (pH < 4), the anions intercalated among the layers are promptly released in the medium. In this article some nonsteroidal antiinflammatory drugs were chosen as models of poorly water-soluble drugs. They were intercalated in HTlc and solubility measurements in acidic medium were performed. A remarkable improvement of drug solubility was observed especially in the case of indomethacin. Copyright 2003 Wiley-Liss, Inc. and the American Pharmacists Association

Spectral characteristics of ortho, meta and para dihydroxy benzenes in different solvents, pH and beta-cyclodextrin.

PubMed

Stalin, T; Devi, R Anitha; Rajendiran, N

2005-09-01

Spectral characteristics of ortho, meta and para dihydroxy benzenes (DHB's) have been studied in different solvents, pH and beta-cyclodextrin. Solvent study shows that: (i) the interaction of OH group with the aromatic ring is less than that of amino group both in the ground and excited states, (ii) in absorption, the charge transfer interaction of OH group in para position is larger than ortho and meta positions. pH studies reveals that DHB's are more acidic than phenol. The higher pK(a) value of oDHB (monoanion-dianion) indicates that the formed monoanion is more stabilized by intramolecular hydrogen bonding. DHB's forms a 1:1 inclusion complex with beta-CD. In beta-CD medium, absorption spectra of DHB's mono and dianions shows unusual blue shifts, whereas in the excited state, the spectral characteristics of DHB's follow the same trend in both aqueous and beta-CD medium.

Two different forms of metarhodopsin II: Schiff base deprotonation precedes proton uptake and signaling state.

PubMed

Arnis, S; Hofmann, K P

1993-08-15

Rhodopsin is a retinal protein and a G-protein-coupled receptor; it shares with both of these families the seven helix structure. To generate the G-interacting helix-loop conformation, generally identified with the 380-nm absorbing metarhodopsin II (MII) photoproduct, the retinal Schiff base bond to the apoprotein must be deprotonated. This occurs as a key event also in the related retinal proteins, sensory rhodopsins, and the proton pump bacteriorhodopsin. In MII, proton uptake from the aqueous phase must be involved as well, since its formation increases the pH of the aqueous medium and is accelerated under acidic conditions. In the native membrane, the pH effect matches MII formation kinetically, suggesting that intramolecular and aqueous protonation changes contribute in concert to the protein transformation. We show here, however, that proton uptake, as indicated by bromocresol purple, and Schiff base deprotonation (380-nm absorption change) show different kinetics when the protein is solubilized in suitable detergents. Our data are consistent with a two-step reaction:

Aromatic organic contaminant removal from an aqueous environment by p(4-VP)-based materials.

PubMed

Sahiner, Nurettin; Ozay, Ozgur; Aktas, Nahit

2011-10-01

p(4-vinylpyridine) (p(4-VP)) hydrogels were prepared in bulk (macro, 5 × 6 mm) and in nanosizes (370 nm) dimensions. The prepared hydrogels were used to remove organic aromatic contaminates such as 4-nitrophenol (4-NP), 2-nitrophenol (2-NP), phenol (Ph) and nitrobenzene (NB) from an aqueous environment. Important parameters affecting the absorption phenomena, such as the initial concentration of the organic species and the absorbent, absorption rate, absorption capacity, pH and the temperature of the medium, were evaluated for both hydrogel sizes. The absorption capacity of bulk and microgels were found to be 4-NP>2-NP>Ph>NB. Furthermore, p(4-VP) microgels were embedded in poly(acrylamide) (p(AAm)) bulk hydrogel as a microgel-hydrogel interpenetrating polymer network and proved to be very practical in overcoming the difficulty of using the microgels in real applications. Moreover, it was demonstrated that separately prepared magnetic ferrite particles inserted inside p(4-VP) microgels during synthesis allowed for trouble-free removal of p(4-VP)-magnetic composite microgels from the aqueous environment by an externally applied magnetic field upon completion of their task. Copyright © 2011 Elsevier Ltd. All rights reserved.

Efficient photodegradation of methylthioninium chloride dye in aqueous using barium tungstate nanoparticles

NASA Astrophysics Data System (ADS)

AlShehri, Saad M.; Ahmed, Jahangeer; Ahamad, Tansir; Almaswari, Basheer M.; Khan, Aslam

2017-08-01

BaWO4 nanoparticles were successfully used as the photocatalysts in the degradation of methylthioninium chloride (MTC) dye at different pH levels of aqueous solution. Pure phase of barium tungstate (BaWO4) nanoparticles was synthesized by modified molten salt process at 500 °C for 6 h. Structural and morphological characterizations of BaWO4 nanoparticles (average particle size of 40 nm) were studied in details using powder x-ray diffraction (XRD), FTIR, Raman, energy-dispersive, electron microscopic, and x-ray photoelectron spectroscopy (XPS) techniques. Direct band gap energy of BaWO4 nanoparticles was found to be 3.06 eV from the UV-visible absorption spectroscopy followed by Tauc's model. Photocatalytic properties of the nanoparticles were also investigated systematically for the degradation of MTC dye solution in various mediums. BaWO4 nanoparticles claim the significant enhancement of the photocatalytic degradation of aqueous MTC dye to non-hazardous inorganic constitutes under alkaline, neutral, and acidic mediums. [Figure not available: see fulltext.

A hexa-quinoline based C3-symmetric chemosensor for dual sensing of zinc(ii) and PPi in an aqueous medium via chelation induced "OFF-ON-OFF" emission.

PubMed

Sinha, Sanghamitra; Chowdhury, Bijit; Adarsh, Nayarassery N; Ghosh, Pradyut

2018-05-15

A quinoline-based C3-symmetric fluorescent probe (1), N,N',N''-((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(1-(quinolin-2-yl)-N-(quinolin-2-ylmethyl)methanamine), has been developed which can selectively detect Zn2+ without the interference of Cd2+via significant enhancement in emission intensity (fluorescence "turn-ON") associated with distinct fluorescence colour changes and very low detection limits (35.60 × 10-9 M in acetonitrile and 29.45 × 10-8 M in 50% aqueous buffer (10 mM HEPES, pH = 7.4) acetonitrile media). Importantly, this sensor is operative with a broad pH window (pH 4-10). The sensing phenomenon has been duly studied through UV-vis, steady-state, and time-resolved fluorescence spectroscopic methods indicating 1 : 3 stoichiometric binding between 1 and Zn2+ which is further corroborated by 1H NMR studies. Density functional theoretical (DFT) calculations provide the optimized molecular geometry and properties of the zinc complex, 1[Zn(ClO4)]33+, which is proposed to be formed in acetonitrile. The results are in line with the solution-state experimental findings. The single crystal X-ray study provides the solid state structure of the trinuclear Zn2+ complex showing solubility in an aqueous buffer (10 mM HEPES, pH = 7.4). Finally, the resulting trinuclear Zn2+ complex has been utilized as a fluorescence "turn-OFF" sensor for the selective detection of pyrophosphate in a 70% aqueous buffer (10 mM HEPES, pH = 7.4) acetonitrile solvent with a nanomolar detection limit (45.37 × 10-9 M).

Release rate of diazinon from microcapsule based on melamine formaldehyde

NASA Astrophysics Data System (ADS)

Noviana Utami C., S.; Rochmadi

2018-04-01

The microcapsule containing diazinon as the core material and melamine formaldehyde as the membrane material have been synthesized by in situ polymerization method. The microcapsule membrane in this research is melamine formaldehyde (MF). This research aims to study the effect of pH and temperature on the release rate of diazinon from microcapsule based on melamine formaldehyde in aqueous medium. The results showed that pH and temperature has little effect on the release rate of diazinon from microcapsule based on melamine formaldehyde. This is due to the diffusion through the microcapsule membrane is not influenced by the pH and temperature of the solution outside of microcapsule.

Extra cellular pH influences uptake and photodynamic action of pyropheophorbide-a entrapped in folate receptor targeted organically modified silica nanoparticle.

PubMed

Singh, Surya Prakash; Sharma, Mrinalini; Patel, Harishankar; Gupta, Pradeep Kumar

2014-06-01

Photodynamic efficacy of pyropheophorbide-a (PPa) is limited due to poor aqueous solubility. In the present study, organically modified silica nanoparticles (ORMOSIL) entrapping PPa and its folate receptor targeted conjugate (FR-Np-PPa) were prepared and the effect of pH on uptake and photodynamic action of plain and FR-Np-PPa in squamous cell carcinoma (Nt-8e) cells and adenocarcinoma of breast (MCF-7) cells were studied. Nanoformulations of PPa were characterized by absorption and fluorescence spectroscopy. Dynamic light scattering was used for size measurements. The uptake of the two nanoformulations by cells incubated in media of pH 6.5 and 7.4 was studied by confocal fluorescence microscopy and spectrofluoremetrically. Phototoxicity of PPa was studied by MTT assay. In MCF-7 and Nt-8e cells, while the uptake of PPa was observed to increase with a decrease in pH of the incubation media for folate receptor targeted Np, uptake of Np-PPa was not influenced by a change in the pH of the media. Inhibition in the uptake of PPa in presence of free folic acid for cells incubated in a medium of pH 6.5 with targeted nanoparticles was higher compared to physiological pH. Consistent with uptake studies in both the cell lines phototoxicity of PPa delivered through FR-Np-PPa was higher in medium of pH 6.5 as compared to physiological pH and phototoxicity induced by NP-PPa was independent of the pH of medium. Acidic pH enhances the photodynamic efficacy of FR-targeted nanoformulated PPa. Copyright © 2014 Elsevier B.V. All rights reserved.

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

PubMed

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

2010-04-01

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

[Comparative evaluation of stability of benzylpenicillin in acid media of natural solutions and in culture fluid].

PubMed

Peretokina, N S; Lin'kova, O S; Erdman, I E; Sinitsyn, M A

1992-07-01

Inactivation of benzylpenicillin in real media i.e. fermentation broths and their filtrates was studied in comparison with the published data on inactivation of commercial benzylpenicillin in aqueous solutions as dependent on the medium pH and temperature. The lowest constant of benzylpenicillin inactivation was shown to be in the fermentation broths.

Indomethacin-Kollidon VA64 Extrudates: A Mechanistic Study of pH-Dependent Controlled Release.

PubMed

Tres, Francesco; Treacher, Kevin; Booth, Jonathan; Hughes, Leslie P; Wren, Stephen A C; Aylott, Jonathan W; Burley, Jonathan C

2016-03-07

Because of its weakly acidic nature (pKa of 4.5), indomethacin presents an aqueous solubility that significantly increases when changing from acidic to neutral/alkaline pH (1.5 μg/mL at pH 1.2 and 105.2 μg/mL at pH 7.4). We have therefore investigated the impact of the dissolution medium pH on the dissolution performance of indomethacin:Kollidon VA64 extrudates. The impact of the drug loading on the dissolution properties of these systems was also examined (5%, 15%, 30%, 50%, 70%, and 90% drug loading). Time-resolved Raman spectroscopy along with in-line UV-vis spectrophotometry was employed to directly relate changes in dissolution behavior to physicochemical changes that occur to the extrudate during the test. The dissolution tests were performed in pH 2 HCl (to mimic the stomach conditions), and this was then switched during the experiment to pH 6.8 phosphate buffer (to simulate the poststomach conditions). The rotating disc dissolution rate test was also used to simultaneously measure the dissolution rate of both the drug and the polymer. We found that in pH 2 HCl buffer, for the 15% or higher drug-loaded extrudates, Kollidon VA64 preferentially dissolves from the exterior of the compact leaving an amorphous drug-rich hydrophobic shell, which, similarly to an enteric coating, inhibits the drug release. The in situ formation of an enteric coating has been previously hypothesized, and this has been the first time that is directly observed in a pH-variable dissolution test. The dissolution medium switch to pH 6.8 phosphate buffer, due to the large increase of the aqueous solubility of indomethacin at this pH, leads to rapid dissolution of the material forming the coating and therefore total drug release. In contrast, the 5% extrudate is fully hydrated and quickly dissolves at low pH pointing to a dissolution performance dependent on highly water-soluble Kollidon VA64.

The effect of solution pH on the electrochemical performance of nanocrystalline metal ferrites MFe2O4 (M=Cu, Zn, and Ni) thin films

NASA Astrophysics Data System (ADS)

Elsayed, E. M.; Rashad, M. M.; Khalil, H. F. Y.; Ibrahim, I. A.; Hussein, M. R.; El-Sabbah, M. M. B.

2016-04-01

Nanocrystalline metal ferrite MFe2O4 (M=Cu, Zn, and Ni) thin films have been synthesized via electrodeposition-anodization process. Electrodeposited (M)Fe2 alloys were obtained from aqueous sulfate bath. The formed alloys were electrochemically oxidized (anodized) in aqueous (1 M KOH) solution, at room temperature, to the corresponding hydroxides. The parameters controlling the current efficiency of the electrodeposition of (M)Fe2 alloys such as the bath composition and the current density were studied and optimized. The anodized (M)Fe2 alloy films were annealed in air at 400 °C for 2 h. The results revealed the formation of three ferrite thin films were formed. The crystallite sizes of the produced films were in the range between 45 and 60 nm. The microstructure of the formed film was ferrite type dependent. The corrosion behavior of ferrite thin films in different pH solutions was investigated using open circuit potential (OCP) and potentiodynamic polarization measurements. The open circuit potential indicates that the initial potential E im of ZnFe2O4 thin films remained constant for a short time, then sharply increased in the less negative direction in acidic and alkaline medium compared with Ni and Cu ferrite films. The values of the corrosion current density I corr were higher for the ZnFe2O4 films at pH values of 1 and 12 compared with that of NiFe2O4 and CuFe2O4 which were higher only at pH value 1. The corrosion rate was very low for the three ferrite films when immersion in the neutral medium. The surface morphology recommended that Ni and Cu ferrite films were safely used in neutral and alkaline medium, whereas Zn ferrite film was only used in neutral atmospheres.

Colloid-probe AFM studies of the interaction forces of proteins adsorbed on colloidal crystals.

PubMed

Singh, Gurvinder; Bremmell, Kristen E; Griesser, Hans J; Kingshott, Peter

2015-04-28

In recent years, colloid-probe AFM has been used to measure the direct interaction forces between colloidal particles of different size or surface functionality in aqueous media, as one can study different forces in symmerical systems (i.e., sphere-sphere geometry). The present study investigates the interaction between protein coatings on colloid probes and hydrophilic surfaces decorated with hexagonally close packed single particle layers that are either uncoated or coated with proteins. Controlled solvent evaporation from aqueous suspensions of colloidal particles (coated with or without lysozyme and albumin) produces single layers of close-packed colloidal crystals over large areas on a solid support. The measurements have been carried out in an aqueous medium at different salt concentrations and pH values. The results show changes in the interaction forces as the surface charge of the unmodified or modified particles, and ionic strength or pH of the solution is altered. At high ionic strength or pH, electrostatic interactions are screened, and a strong repulsive force at short separation below 5 nm dominates, suggesting structural changes in the absorbed protein layer on the particles. We also study the force of adhesion, which decreases with an increment in the salt concentration, and the interaction between two different proteins indicating a repulsive interaction on approach and adhesion on retraction.

Development of a reduced-graphene-oxide based superparamagnetic nanocomposite for the removal of nickel (II) from an aqueous medium via a fluorescence sensor platform.

PubMed

Nandi, Debabrata; Saha, Indranil; Ray, Suprakas Sinha; Maity, Arjun

2015-09-15

Reduced-graphene-oxide based superparamagnetic nanocomposite (GC) was fabricated and applied for the remediation of Ni(II) from an aqueous medium. The as-prepared GC was extensively characterized by Raman, TEM, AFM, SEM-EDX, SQUID, and BET analyses. Quantitative immobilization of Ni(II) in an aqueous solution by the fluorescent sensor platform of GC was explored at varying pH, doses, contact times, and temperatures. The pseudo-second-order kinetics equation governed the overall sorption process at optimized pH of 5 (±0.2). The superior monolayer sorption capacity was 228mgg(-1) at 300K. Negative ΔG(0) indicated the spontaneous sorption nature, whereas the positive ΔH(0) resulted from an increase in entropy (positive ΔS(0)) at the solid-liquid interface during the endothermic reaction. The lower enthalpy agreed with the relatively high regeneration (approximately 91%) of the GC by 0.1M HCl, because of the formation of stable tetrahedral complex. The physisorption was well corroborated by calculated sorption energy (EDR ∼7kJmol(-1)) and the nature of the Stern-Volmer plot of the fluorescence-quenching data with reaction time. The GC played a pivotal role as a static fluorescent sensor platform (fluorophore) for Ni(II) adsorption. Magnetic property also indicated that GC could be easily separated from fluids by exploiting its superparamagnetic property. Copyright © 2015 Elsevier Inc. All rights reserved.

Sodium sulfite pH-buffering effect for improved xylose-phenylalanine conversion to N-(1-deoxy-d-xylulos-1-yl)-phenylalanine during an aqueous Maillard reaction.

PubMed

Cui, Heping; Duhoranimana, Emmanuel; Karangwa, Eric; Jia, Chengsheng; Zhang, Xiaoming

2018-04-25

The yield of the Maillard reaction intermediate (MRI), prepared in aqueous medium, is usually unsatisfactory. However, the addition of sodium sulfite could improve the conversion of xylose-phenylalanine (Xyl-Phe) to the MRI (N-(1-deoxy-d-xylulos-1-yl)-phenylalanine) in aqueous medium. Sodium sulfite (Na 2 SO 3 ) showed a significant pH-buffering effect during the Maillard reaction, which accounted for its facilitation of the N-(1-deoxy-d-xylulos-1-yl)-phenylalanine yield. The results revealed that the pH could be maintained at a relatively high level (above 7.0) for an optimized pH-buffering effect when Na 2 SO 3 (4.0%) was added before the reaction of Xyl-Phe. Thus, the conversion of Xyl-Phe to N-(1-deoxy-d-xylulos-1-yl)-phenylalanine increased from 47.23% to 74.86%. Furthermore, the addition moment of Na 2 SO 3 and corresponding solution pH were crucial factors in regulating the pH-buffering effect of Na 2 SO 3 on N-(1-deoxy-d-xylulos-1-yl)-phenylalanine yield. Based on the pH-buffering effect of Na 2 SO 3 and maintaining the optimal pH 7.4 relatively stable, the conversion of Xyl-Phe to N-(1-deoxy-d-xylulos-1-yl)-phenylalanine was successfully improved. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Two different forms of metarhodopsin II: Schiff base deprotonation precedes proton uptake and signaling state.

PubMed Central

Arnis, S; Hofmann, K P

1993-01-01

Rhodopsin is a retinal protein and a G-protein-coupled receptor; it shares with both of these families the seven helix structure. To generate the G-interacting helix-loop conformation, generally identified with the 380-nm absorbing metarhodopsin II (MII) photoproduct, the retinal Schiff base bond to the apoprotein must be deprotonated. This occurs as a key event also in the related retinal proteins, sensory rhodopsins, and the proton pump bacteriorhodopsin. In MII, proton uptake from the aqueous phase must be involved as well, since its formation increases the pH of the aqueous medium and is accelerated under acidic conditions. In the native membrane, the pH effect matches MII formation kinetically, suggesting that intramolecular and aqueous protonation changes contribute in concert to the protein transformation. We show here, however, that proton uptake, as indicated by bromocresol purple, and Schiff base deprotonation (380-nm absorption change) show different kinetics when the protein is solubilized in suitable detergents. Our data are consistent with a two-step reaction: Images Fig. 6 PMID:8356093

A rapid, naked-eye detection of hypochlorite and bisulfite using a robust and highly-photostable indicator dye Quinaldine Red in aqueous medium

NASA Astrophysics Data System (ADS)

Dutta, Tanoy; Chandra, Falguni; Koner, Apurba L.

2018-02-01

A ;naked-eye; detection of health hazardous bisulfite (HSO3-) and hypochlorite (ClO-) using an indicator dye (Quinaldine Red, QR) in a wide range of pH is demonstrated. The molecule contains a quinoline moiety linked to an N,N-dimethylaniline moiety with a conjugated double bond. Treatment of QR with HSO3- and ClO-, in aqueous solution at near-neutral pH, resulted in a colorless product with high selectivity and sensitivity. The detection limit was 47.8 μM and 0.2 μM for HSO3- and ClO- respectively. However, ClO- was 50 times more sensitive and with 2 times faster response compared to HSO3-. The detail characterization and related analysis demonstrate the potential of QR for a rapid, robust and highly efficient colorimetric sensor for the practical applications to detect hypochlorite in water samples.

Electrical properties of polycrystalline GaN films functionalized with cysteine and stabilization of GaN nanoparticles in aqueous media.

PubMed

Arízaga, Gregorio Guadalupe Carbajal; Oviedo, Mariana J; López, Oscar Edel Contreras

2012-10-01

GaN was synthesized onto sapphire substrates by chemical vapor deposition, reacting gallium, ammonium chloride and ammonia. The polycrystalline films were immersed in glycine, aspartic acid and cysteine solutions. Cysteine chemisorbed onto GaN films produced detectable changes in conductivity, mobility and Hall coefficient indicating that GaN is capable of detecting and reacting with thiolate groups, which was confirmed by X-ray photoelectron spectroscopy. The Cys-GaN film solution was adjusted to pH 10, upon which the GaN nanoparticles were transferred to the aqueous phase forming a suspension stable for seven days. The alkaline colloid was then further adjusted down to pH 3 retaining stability for three days. The GaN colloid obtained represents a suitable medium to study GaN properties for biological applications. Copyright © 2012 Elsevier B.V. All rights reserved.

Purification of alkali metal nitrates

DOEpatents

Fiorucci, Louis C.; Gregory, Kevin M.

1985-05-14

A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

[Role of the blood bicarbonate buffer system in the mechanism of fish adaptation to different levels of carbonic acid in an aqueous medium].

PubMed

Romanenko, V D; Kotsar', N I

1976-01-01

The role of a bicarbonate buffer system of fish (Cyprinidae family) blood was studied in their organism addaptive reactions to different levels of CO2 in the aqueous medium. The fish is established to prossess rather effective for maintaining blood acid-base balance. It permits the fish to endure for a long time essential fluctuations of carbonic acid concentration in water. In prevention of possible development of carbonic acid acidosis an essential role belongs to formation of bicarbonates as a blood buffer system stablizing pH is shown to be significant for preventing possible development of acidosis. The adaptation potentialities of Cyprinidae family permit them to endure an increase of CO2 in water and are determined by the ability of their organism to formations of bicarbonate and their retaining in blood.

Algorithm for Calculating the Dissociation Constants of Ampholytes in Nonbuffer Systems

NASA Astrophysics Data System (ADS)

Lysova, S. S.; Skripnikova, T. A.; Zevatskii, Yu. E.

2018-05-01

An algorithm for calculating the dissociation constants of ampholytes in aqueous solutions is developed on the basis of spectrophotometric data in the UV and visible ranges without pH measurements of a medium and without buffer solutions. The proposed algorithm has been experimentally tested for five ampholytes of different strengths. The relative error of measuring dissociation constants is less than 5%.

Kinetics of photoinduced electron transfer between DNA bases and triplet 3,3',4,4'-benzophenone tetracarboxylic acid in aqueous solution of different pH's: proton-coupled electron transfer?

PubMed

Nguyen, Truong X; Kattnig, Daniel; Mansha, Asim; Grampp, Günter; Yurkovskaya, Alexandra V; Lukzen, Nikita

2012-11-08

The kinetics of triplet state quenching of 3,3',4,4'-benzophenone tetracarboxylic acid (BPTC) by DNA bases adenine, adenosine, thymine, and thymidine has been investigated in aqueous solution using time-resolved laser flash photolysis. The observation of the BPTC ketyl radical anion at λ(max) = 630 nm indicates that one electron transfer is involved in the quenching reactions. The pH-dependence of the quenching rate constants is measured in detail. As a result, the chemical reactivity of the reactants is assigned. The bimolecular rate constants of the quenching reactions between triplet BPTC and adenine, adenosine, thymine, and thymidine are k(q) = 2.3 × 10(9) (4.7 < pH < 9.9), k(q) = 4.0 × 10(9) (3.5 < pH < 4.7), k(q) = 1.0 × 10(9) (4.7 < pH < 9.9), and k(q) = 4.0 × 10(8) M(-1) s(-1) (4.7 < pH < 9.8), respectively. Moreover, it reveals that in strong basic medium (pH = 12.0) a keto-enol tautomerism of thymine inhibits its reaction with triplet BPTC. Such a behavior is not possible for thymidine because of its deoxyribose group. In addition, the pH-dependence of the apparent electrochemical standard potential of thymine in aqueous solution was investigated by cyclic voltammetry. The ΔE/ΔpH ≈ -59 mV/pH result is characteristic of proton-coupled electron transfer. This behavior, together with the kinetic analysis, leads to the conclusion that the quenching reactions between triplet BPTC and thymine involve one proton-coupled electron transfer.

Kinetics of Photoinduced Electron Transfer between DNA Bases and Triplet 3,3′,4,4′-Benzophenone Tetracarboxylic Acid in Aqueous Solution of Different pH's: Proton-Coupled Electron Transfer?

PubMed Central

2012-01-01

The kinetics of triplet state quenching of 3,3′,4,4′-benzophenone tetracarboxylic acid (BPTC) by DNA bases adenine, adenosine, thymine, and thymidine has been investigated in aqueous solution using time-resolved laser flash photolysis. The observation of the BPTC ketyl radical anion at λmax = 630 nm indicates that one electron transfer is involved in the quenching reactions. The pH-dependence of the quenching rate constants is measured in detail. As a result, the chemical reactivity of the reactants is assigned. The bimolecular rate constants of the quenching reactions between triplet BPTC and adenine, adenosine, thymine, and thymidine are kq = 2.3 × 109 (4.7 < pH < 9.9), kq = 4.0 × 109 (3.5 < pH < 4.7), kq = 1.0 × 109 (4.7 < pH < 9.9), and kq = 4.0 × 108 M–1 s–1 (4.7 < pH < 9.8), respectively. Moreover, it reveals that in strong basic medium (pH = 12.0) a keto–enol tautomerism of thymine inhibits its reaction with triplet BPTC. Such a behavior is not possible for thymidine because of its deoxyribose group. In addition, the pH-dependence of the apparent electrochemical standard potential of thymine in aqueous solution was investigated by cyclic voltammetry. The ΔE/ΔpH ≈ −59 mV/pH result is characteristic of proton-coupled electron transfer. This behavior, together with the kinetic analysis, leads to the conclusion that the quenching reactions between triplet BPTC and thymine involve one proton-coupled electron transfer. PMID:23038981

Sulfomethylation of Di-, Tri-, and polyazamacrocycles: a new route to entry of mixed-side-chain macrocyclic chelates.

PubMed

van Westrenen, J; Sherry, A D

1992-01-01

The sulfomethylation of piperazine and the polyazamacrocycles, [9]aneN3, [12]aneN3, [12]aneN4, and [18]aneN6 with formaldehyde bisulfite in aqueous medium at various pH values is described. The number of methanesulfonate groups introduced into these structures was found to be largely determined by pH. At neutral pH, disubstituted products of [9]aneN3, [12]aneN3, [12]aneN4 are formed and, in the latter case, the trans-1,7-bis(methanesulfonate) isomer was predominant. Similarly, a single, symmetrical trisubstituted product was formed with [18]aneN6 at neutral pH. Monomethanesulfonated products of these same polyaza compounds were formed at more acidic pH's. These sulfomethylated products were used as an entry into a series of mono- and diacetate, phosphonate, and phosphinate derivatives of [9]aneN3, [12]aneN3, and [12]aneN4. The sulfonate groups may be converted to acetates without isolation of intermediates by using cyanide to displace the sulfonate(s) followed by acidic hydrolysis. The aminomethanesulfonates may also be oxidatively hydrolyzed by using aqueous triiodide as a prelude to the preparation of aminomethanephosphonates or aminomethanephosphinates.

Thermally induced degradation of sulfur-containing aliphatic glucosinolates in broccoli sprouts (Brassica oleracea var. italica) and model systems.

PubMed

Hanschen, Franziska S; Platz, Stefanie; Mewis, Inga; Schreiner, Monika; Rohn, Sascha; Kroh, Lothar W

2012-03-07

Processing reduces the glucosinolate (GSL) content of plant food, among other aspects due to thermally induced degradation. Since there is little information about the thermal stability of GSL and formation of corresponding breakdown products, the thermally induced degradation of sulfur-containing aliphatic GSL was studied in broccoli sprouts and with isolated GSL in dry medium at different temperatures as well as in aqueous medium at different pH values. Desulfo-GSL have been analyzed with HPLC-DAD, while breakdown products were estimated using GC-FID. Whereas in the broccoli sprouts structural differences of the GSL with regard to thermal stability exist, the various isolated sulfur-containing aliphatic GSL degraded nearly equally and were in general more stable. In broccoli sprouts, methylsulfanylalkyl GSL were more susceptible to degradation at high temperatures, whereas methylsulfinylalkyl GSL were revealed to be more affected in aqueous medium under alkaline conditions. Besides small amounts of isothiocyanates, the main thermally induced breakdown products of sulfur-containing aliphatic GSL were nitriles. Although they were most rapidly formed at comparatively high temperatures under dry heat conditions, their highest concentrations were found after cooking in acidic medium, conditions being typical for domestic processing.

Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium.

PubMed

Pitman, Catherine L; Brereton, Kelsey R; Miller, Alexander J M

2016-02-24

Aqueous hydride transfer is a fundamental step in emerging alternative energy transformations such as H2 evolution and CO2 reduction. "Hydricity," the hydride donor ability of a species, is a key metric for understanding transition metal hydride reactivity, but comprehensive studies of aqueous hydricity are scarce. An extensive and self-consistent aqueous hydricity scale is constructed for a family of Ru and Ir hydrides that are key intermediates in aqueous catalysis. A reference hydricity is determined using redox potentiometry and spectrophotometric titration for a particularly water-soluble species. Then, relative hydricity values for a range of species are measured using hydride transfer equilibria, taking advantage of expedient new synthetic procedures for Ru and Ir hydrides. This large collection of hydricity values provides the most comprehensive picture so far of how ligands impact hydricity in water. Strikingly, we also find that hydricity can be viewed as a continuum in water: the free energy of hydride transfer changes with pH, buffer composition, and salts present in solution.

Fabrication of silver nanoparticles in pH responsive polymer microgel dispersion for catalytic reduction of nitrobenzene in aqueous medium

NASA Astrophysics Data System (ADS)

Farooqi, Zahoor H.; Begum, Robina; Naseem, Khalida; Rubab, Uma; Usman, Muhammad; Khan, Abbas; Ijaz, Aysha

2016-12-01

Copolymer microgels based on N-isopropylacrylamide (NIPAM) and methacrylic acid (MAA) have been synthesized by free radical emulsion polymerization using N, N-methylenebisacrylamide (BIS) as a cross-linker. Synthesized microgels were characterized by Fourier transform infrared spectroscopy (FTIR). Then silver nanoparticles were fabricated in the synthesized microgels by in-situ reduction of AgNO3 with NaBH4. The formation of silver nanoparticles was confirmed by UV-Vis spectroscopy. The pH sensitivity of the copolymer microgels was investigated using dynamic light scattering technique (DLS). Hydrodynamic radius of P (NIPAM-MAA) microgels increases with increase in pH of the medium at 25°C. Surface plasmon resonance wavelength (λSPR) of silver nanoparticles increases with increase in hydrodynamic radius due to change in pH of the medium. The catalytic activity for the reduction of nitrobenzene (NB), an environmental pollutant, into aniline was investigated by UV-Vis spectroscopy in excess of NaBH4 using hybrid microgels as catalyst. The value of apparent rate constant ( k app) of the reaction was calculated using pseudo first order kinetic model and it was found to be linearly related to the amount of catalyst. The results were compared with literature data. The system was found to be an effective catalyst for conversion of NB into aniline.

Control of continuous phase PH using visible light to activate PH-dependent fibers and gels in a controlled and reversible manner

NASA Astrophysics Data System (ADS)

Zirino, Albert

1994-08-01

A transparent polyelectrolyte fiber or gel, such as crosslinked polyacrylic acid, which contracts and expands upon the addition of an acid or base to an aqueous medium solution, is placed in the same solution with a pH dependent dye, a colored photochromatic indicator dye. The dye preferably has a pAa value that is the same as the pH at a null contraction point of the fiber. By irradiating the solution with light of a wavelength of the absorption band of either the acid or base form of the dye, the solution pH is made to change, and the fiber is made to expand or contract, depending upon the wavelength. Thus, light energy is readily converted to work energy and may be used to power a pump, for example or an artificial muscle can be powered via an optical fiber.

Application of mucilage from Dicerocaryum eriocarpum plant as biosorption medium in the removal of selected heavy metal ions.

PubMed

Jones, Bassey O; John, Odiyo O; Luke, Chimuka; Ochieng, Aoyi; Bassey, Bridget J

2016-07-15

The ability of mucilage from Dicerocaryum eriocarpum (DE) plant to act as biosorption medium in the removal of metals ions from aqueous solution was investigated. Functional groups present in the mucilage were identified using Fourier transform infrared spectroscopy (FTIR). Mucilage was modified with sodium and potassium chlorides. This was aimed at assessing the biosorption efficiency of modified mucilage: potassium mucilage (PCE) and sodium mucilage (SCE) and comparing it with non-modified deionised water mucilage (DCE) in the uptake of metal ions. FTIR results showed that the functional groups providing the active sites in PCE and SCE and DCE include: carboxyl, hydroxyl and carbonyl groups. The chloride used in the modification of the mucilage did not introduce new functional groups but increased the intensity of the already existing functional groups in the mucilage. Results from biosorption experiment showed that DE mucilage displays good binding affinity with metals ions [Zn(II), Cd(II) Ni(II), Cr(III) and Fe(II)] in the aqueous solution. Increase in the aqueous solution pH, metal ions initial concentration and mucilage concentration increased the biosorption efficiency of DE mucilage. The maximum contact time varied with each species of metal ions. Optimum pH for [Zn(II), Cd(II) Ni(II) and Fe(II)] occurred at pH 4 and pH 6 for Cr(III). Kinetic models result fitted well to pseudo-second-order with a coefficient values of R(2) = 1 for Cd(II), Ni(II), Cr(III), Fe(II) and R(2) = 0.9974 for Zn(II). Biosorption isotherms conforms best with Freundlich model for all the metal ions with correlation factors of 0.9994, 0.9987, 0.9554, 0.9621 and 0.937 for Zn(II), Ni(II), Fe(II), Cr(III) and Cd(II), respectively. Biosorption capacity of DE mucilage was 0.010, 2.387, 4.902, 0688 and 0.125 for Zn(II), Cr(III), Fe(II), Cd(II) and Ni(II) respectively. The modified mucilage was found to be highly efficient in the removal of metal ions than the unmodified mucilage. Copyright © 2016 Elsevier Ltd. All rights reserved.

[State of Fungal Lipases of Rhizopus microsporus, Penicillium sp. and Oospora lactis in Border Layers Water-Solid Phase and Factors Affecting Catalytic Properties of Enzymes].

PubMed

Khasanov, Kh T; Davranov, K; Rakhimov, M M

2015-01-01

We demonstrated that a change in the catalytic activity of fungal lipases synthesized by Rhizopus microsporus, Penicillium sp. and Oospora lactis and their ability to absorb on different sorbents depended on the nature of groups on the solid phase surface in the model systems water: lipid and water: solid phase. Thus, the stability of Penicillium sp. lipases increased 85% in the presence ofsorsilen or DEAE-cellulose, and 55% of their initial activity respectively was preserved. In the presence of silica gel and CM-cellulose, a decreased rate of lipid hydrolysis by Pseudomonas sp. enzymes was observed in water medium, and the hydrolysis rate increased by 2.4 and 1.5 times respectively in the presence of aminoaerosil and polykefamid. In an aqueous-alcohol medium, aminoaerosil and polykefamid decreased the rate of substrate hydrolysis by more than 30 times. The addition of aerosil to aqueous and aqueous-alcohol media resulted in an increase in the hydrolysis rate by 1.2-1.3 times. Sorsilen stabilized Penicillium sp. lipase activity at 40, 45, 50 and 55 degrees C. Either stabilization or inactivation of lipases was observed depending on the pH of the medium and the nature of chemical groups localized on the surface of solid phase. The synthetizing activity of lipases also changed depending on the conditions.

METHOD OF PROCESSING MONAZITE SAND

DOEpatents

Welt, M.A.; Smutz, M.

1958-08-26

A process is described for recovering thorium, uranium, and rare earth values from monazite sand. The monazite sand is first digested with sulfuric acid and the resulting "monazite sulfate" solution is adjusted to a pH of between 0.4 and 3.0, and oxalate anions are added causing precipitation of the thorium and the rare earths as the oxalates. The oxalate precipitate is separated from the uranium containing supernatant solution, and is dried and calcined to the oxides. The thorium and rare earth oxides are then dissolved in nitric acid and the solution is contacted with tribntyl phosphate whereby an organic extract phase containing the cerium and thorium values is obtained, together with an aqueous raffinate containing the other rare earth values. The organic phase is then separated from the aqueous raffinate and the cerium and thorium are back extracted with an aqueous medium.

Arsenic removal in conjunction with lime softening

DOEpatents

Khandaker, Nadim R.; Brady, Patrick V.; Teter, David M.; Krumhansl, James L.

2004-10-12

A method for removing dissolved arsenic from an aqueous medium comprising adding lime to the aqueous medium, and adding one or more sources of divalent metal ions other than calcium and magnesium to the aqueous medium, whereby dissolved arsenic in the aqueous medium is reduced to a lower level than possible if only the step of adding lime were performed. Also a composition of matter for removing dissolved arsenic from an aqueous medium comprising lime and one or more sources of divalent copper and/or zinc metal ions.

Spectrophotometric study of the copigmentation of malvidin 3-O-glucoside with p-coumaric, vanillic and syringic acids.

PubMed

Malaj, Naim; De Simone, Bruna Clara; Quartarolo, Angelo Domenico; Russo, Nino

2013-12-15

Anthocyanins are a natural source of pigments in plants and their processed food products have become attractive and excellent candidates to replace the synthetic colourants due to their characteristic intense colours and associated health benefits. The intermolecular copigmentation between anthocyanins and other colourless compounds has been reported to be an important way to enhance and stabilise the colour intensity of aqueous solutions. In the present work we report the equilibrium constant, stoichiometric ratio and the thermodynamic parameters (ΔG°, ΔH° and ΔS°) related to the intermolecular copigmentation reactions of the anthocyanin malvidin 3-O-glucoside with one hydroxycinnamic acid (p-coumaric acid) and two O-methylated hydroxybenzoic acids (vanillic and syringic acid). Different factors which affect their interactions such as copigment concentration, pH and temperature of the medium are examined at two pH levels (pH=2.50 and 3.65) corresponding to those of the major food mediums where these reactions take place (fruit juices, wine, jams etc.). Copyright © 2013 Elsevier Ltd. All rights reserved.

Removal of trivalent chromium from aqueous solution by zeolite synthesized from coal fly ash.

PubMed

Wu, Deyi; Sui, Yanming; He, Shengbing; Wang, Xinze; Li, Chunjie; Kong, Hainan

2008-07-15

The capability of 14 zeolites synthesized from different fly ashes (ZFAs) to sequestrate Cr(III) from aqueous solutions was investigated in a batch mode. The influence of pH on the sorption of Cr(III) was examined. ZFAs had a much greater ability than fly ash to remove Cr(III), due to the high cation exchange capacity (CEC) and the high acid neutralizing capacity (ANC) of ZFAs. The mechanism of Cr(III) removal by ZFAs involved ion exchange and precipitation. A high-calcium content in both the fly ashes and ZFAs resulted in a high ANC value and, as a result, a high immobilization capacity for Cr(III). The pH strongly influenced Cr(III) removal by ZFAs. Inside the solubility range, removal of chromium increased with increasing pH. Hydroxysodalite made from a high-calcium fly ash had a higher sorptive capacity for Cr(III) than the NaP1 zeolite from medium- and low-calcium fly ashes. On the other hand, at pH values above the solubility range, the efficiency of chromium removal by the ZFAs approached 100% due to the precipitation of Cr(OH)3 on the sorbent surfaces. It is concluded that ZFAs and high-calcium fly ashes may be promising materials for the purification of Cr(III) from water/wastewater.

Chemical durability of alkali-borosilicate glasses studied by analytical SEM, IBA, isotopic-tracing and SIMS

NASA Astrophysics Data System (ADS)

Trocellier, P.; Djanarthany, S.; Chêne, J.; Haddi, A.; Brass, A. M.; Poissonnet, S.; Farges, F.

2005-10-01

Simple and complex alkali-borosilicate glasses were submitted to aqueous corrosion at room temperature, 60 and 90 °C in solutions with pH ranging between 0 and 12. Analytical scanning electron microscopy (SEM), ion beam analysis (IBA) techniques, isotopic tracing and secondary ion mass-depth profiling (SIMS) have been used to investigate the variations of the surface composition of glass. In acidic medium, the glass surface is generally covered by a thick hydrated silica layer, mobile elements like Li, Na and B and transition elements (Fe, Zr, Mo, etc.) are strongly depleted. Near pH 7, relative enrichments of aluminium, iron and rare earths are shown together with strong Li, Na and B depletions. In basic medium, the glass surface exhibits relative enrichments of the major part of transition metals (from Cr to U) whereas mobile elements seem to be kept close to their nominal concentration level at the glass surface and Si is severely impoverished. Hydrogen incorporated at the glass surface after leaching is much more immobile in neutral and basic media than in acid medium.

The influence of diesel-truck exhaust particles on the kinetics of the atmospheric oxidation of dissolved sulfur dioxide by oxygen.

PubMed

Meena, Vimlesh Kumar; Dhayal, Yogpal; Saxena, Deepa; Rani, Ashu; Chandel, C P Singh; Gupta, K S

2016-09-01

The automobile exhausts are one of the major sources of particulate matter in urban areas and these particles are known to influence the atmospheric chemistry in a variety of ways. Because of this, the oxidation of dissolved sulfur dioxide by oxygen was studied in aqueous suspensions of particulates, obtained by scraping the particles deposited inside a diesel truck exhaust pipe (DEP). A variation in pH showed the rate to increase with increase in pH from 5.22 to about ∼6.3 and to decrease thereafter becoming very slow at pH = 8.2. In acetate-buffered medium, the reaction rate was higher than the rate in unbuffered medium at the same pH. Further, the rate was found to be higher in suspension than in the leachate under otherwise identical conditions. And, the reaction rate in the blank reaction was the slowest. This appears to be due to catalysis by leached metal ions in leachate and due to catalysis by leached metal ions and particulate surface both in suspensions. The kinetics of dissolved SO2 oxidation in acetate-buffered medium as well as in unbuffered medium at pH = 5.22 were defined by rate law: k obs  = k 0 + k cat [DEP], where k obs and k 0 are observed rate constants in the presence and the absence of DEP and k cat is the rate constant for DEP-catalyzed pathway. At pH = 8.2, the reaction rate was strongly inhibited by DEP in buffered and unbuffered media. Results suggest that the DEP would have an inhibiting effect in those areas where rainwater pH is 7 or more. These results at high pH are of particular significance to the Indian subcontinent, because of high rainwater pH. Conversely, it indicates the DEP to retard the oxidation of dissolved SO2 and control rainwater acidification.

Native, acidic pre-treated and composite clay efficiency for the adsorption of dicationic dye in aqueous medium.

PubMed

Ehsan, Asma; Bhatti, Haq Nawaz; Iqbal, Munawar; Noreen, Saima

2017-02-01

Environmental applications of composites have attracted the interests of researchers due to their excellent adsorption efficiency for pollutants. Native, HCl pre-treated clay and MnFe 2 O 4 /clay composite were investigated as an adsorbent for removal of methyl green from aqueous solution. The adsorption behaviors of dye onto native, HCl pre-treated and composite clays were studied as a function of contact time, adsorbent dose, pH, initial dye concentration and temperature. Maximum dye adsorption of 44 mg/g was achieved at pH of 8, contact time 40 min, adsorbent dose 0.20 g/L and initial dye concentration of 125 mg/L using clay composite. The Langmuir isotherm and pseudo-second-order kinetic model best explained the methyl green dye adsorption onto clay adsorbents. Thermodynamic parameters revealed the endothermic and spontaneous adsorption nature of dye. From results, it is concluded that clay has potential for adsorbing methyl green and can be used for the removal of dyes from industrial effluents.

pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis

PubMed Central

Ansar, Siyam M.; Chakraborty, Saptarshi

2018-01-01

Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride—a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is significant, based on the fact that nanoparticle-catalyzed reactions may occur under different pH conditions. PMID:29772775

Interactions of human hemoglobin with charged ligand-functionalized iron oxide nanoparticles and effect of counterions

NASA Astrophysics Data System (ADS)

Ghosh, Goutam; Panicker, Lata

2014-12-01

Human hemoglobin is an important metalloprotein. It has tetrameric structure with each subunit containing a `heme' group which carries oxygen and carbon dioxide in blood. In this work, we have investigated the interactions of human hemoglobin (Hb) with charged ligand-functionalized iron oxide nanoparticles and the effect of counterions, in aqueous medium. Several techniques like DLS and ζ-potential measurements, UV-vis, fluorescence, and CD spectroscopy have been used to characterize the interaction. The nanoparticle size was measured to be in the range of 20-30 nm. Our results indicated the binding of Hb with both positively as well as negatively charged ligand-functionalized iron oxide nanoparticles in neutral aqueous medium which was driven by the electrostatic and the hydrophobic interactions. The electrostatic binding interaction was not seen in phosphate buffer at pH 7.4. We have also observed that the `heme' groups of Hb remained unaffected on binding with charged nanoparticles, suggesting the utility of the charged ligand-functionalized nanoparticles in biomedical applications.

A fluorescent probe based on nitrogen doped graphene quantum dots for turn off sensing of explosive and detrimental water pollutant, TNP in aqueous medium

NASA Astrophysics Data System (ADS)

Kaur, Manjot; Mehta, Surinder K.; Kansal, Sushil Kumar

2017-06-01

This paper reports the carbonization assisted green approach for the fabrication of nitrogen doped graphene quantum dots (N-GQDs). The obtained N-GQDs displayed good water dispersibility and stability in the wide pH range. The as synthesized N-GQDs were used as a fluorescent probe for the sensing of explosive 2,4,6-trinitrophenol (TNP) in aqueous medium based on fluorescence resonance energy transfer (FRET), molecular interactions and charge transfer mechanism. The quenching efficiency was found to be linear in proportion to the TNP concentration within the range of 0-16 μM with detection limit (LOD) of 0.92 μM. The presented method was successfully applied to the sensing of TNP in tap and lake water samples with satisfactory results. Thus, N-GQDs were used as a selective, sensitive and turn off fluorescent sensor for the detection of perilous water contaminant i.e. TNP.

A fluorescent probe based on nitrogen doped graphene quantum dots for turn off sensing of explosive and detrimental water pollutant, TNP in aqueous medium.

PubMed

Kaur, Manjot; Mehta, Surinder K; Kansal, Sushil Kumar

2017-06-05

This paper reports the carbonization assisted green approach for the fabrication of nitrogen doped graphene quantum dots (N-GQDs). The obtained N-GQDs displayed good water dispersibility and stability in the wide pH range. The as synthesized N-GQDs were used as a fluorescent probe for the sensing of explosive 2,4,6-trinitrophenol (TNP) in aqueous medium based on fluorescence resonance energy transfer (FRET), molecular interactions and charge transfer mechanism. The quenching efficiency was found to be linear in proportion to the TNP concentration within the range of 0-16μM with detection limit (LOD) of 0.92μM. The presented method was successfully applied to the sensing of TNP in tap and lake water samples with satisfactory results. Thus, N-GQDs were used as a selective, sensitive and turn off fluorescent sensor for the detection of perilous water contaminant i.e. TNP. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular complexes of L-phenylalanine with substituted 1,4-benzoquinones in aqueous medium: Spectral and theoretical investigations

NASA Astrophysics Data System (ADS)

Ganesh, K.; El-Mossalamy, E. H.; Satheshkumar, A.; Balraj, C.; Elango, K. P.

2013-12-01

Various spectral techniques such as UV-Vis, FT-IR, and fluorescence have been employed to investigate the charge transfer interaction of L-phenylalanine (LPA) with substituted 1,4-benzoquinones (MQ1-4). Kinetic and thermodynamic properties of the complexes were determined in aqueous medium at physiological condition (pH = 7). The interaction of MQ1-4 with L-phenylalanine (LPA) was found to proceed through the formation of donor-acceptor complex, yielding a radical anion. The stoichiometry of the complexes was determined by Jobs continuous variation method and was found to be 1:1 in all the cases. Fluorescence quenching studies showed that the interaction between the donor and the acceptors is spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The order of the experimentally measured association constant of these complexes was well supported by DFT/B3LYP calculations.

Oxidation of ethylenethiourea in water via ozone enhanced by UV-C: identification of transformation products.

PubMed

Bottrel, Sue Ellen C; Pereira, Pedro C; de Oliveira Pereira, Renata; Leão, Mônica M D; Amorim, Camila C

2018-06-25

Ethylenethiourea (ETU) is a toxic degradation product of one class of fungicide which is largely employed in the world, the ethylenebisdithiocarbamates. In this study, ETU was degraded by ozonation enhanced by UV-C light irradiation (O 3 /UV-C) in aqueous medium. Degradation experiments were conducted at natural pH (6.8) and neutral pH (7.0, buffered). ETU was promptly eliminated from the reactive medium during ozonation in the presence and absence of light. Within the first few minutes of reaction conducted in natural pH, the pH decreased quickly from 6.8 to 3.0. Results show that ETU mineralization occurs only in the reaction conducted in neutral pH and that it takes place in a higher rate when enhanced by UV-C irradiation. Main intermediates formed during the O3/UV-C experiments in different conditions tested were also investigated and three different degradation mechanisms were proposed considering the occurrence of direct and indirect ozone reactions. At pH 7, ethylene urea (EU) was quickly generated and degraded. Meanwhile, at natural pH, besides EU, other compounds originated from the electrophilic attack of ozone to the sulfur atom present in the contaminant molecule were also identified during reaction and EU was detected within 60 min of reaction. Results showed that ozonation enhanced by UV-C promotes a faster reaction than the same system in the absence of light, and investigation of the toxicity is recommended.

FLUX OF IONIC DYES ACROSS MICRONEEDLE-TREATED SKIN: EFFECT OF DYE MOLECULAR CHARACTERISTICS

PubMed Central

Gomaa, Yasmine A.; Garland, Martin J.; McInnes, Fiona; Donnelly, Ryan F.; El-Khordagui, Labiba K.; Wilson, Clive

2014-01-01

Drug flux across microneedle (MN)-treated skin is influenced by the characteristics of the MN array, microconduits and drug molecules in addition to the overall diffusional resistance of microconduits and viable tissue. Relative implication of these factors has not been fully explored. In the present study, the in vitro permeation of a series of six structurally related ionic xanthene dyes with different molecular weights (MW) and chemical substituents, across polymer MN-pretreated full thickness porcine skin was investigated in relation of their molecular characteristics. Phosphate buffer saline pH 7.4, the medium used in skin permeation experiments, was used to determine the equilibrium solubility of the dyes and their partition coefficient both in the isotropic n-octanol/ aqueous system and porcine skin/ aqueous system. Additionally, dissociation constants were determined potentiometrically. Results indicated that for rhodamine dyes, skin permeation of the zwitterionic form which predominates at physiological pH, was significantly reduced by an increase in MW, the presence of the chemically reactive isothiocyanate substituent reported to interact with stratum corneum proteins and the skin thickness. These factors were generally shown to override aqueous solubility, an important determinant of drug diffusion in an aqueous milieu. Findings provided more insight into the mechanism of drug permeation across MN-treated skin, of importance to both the design of MN-based transdermal drug delivery systems and in vitro skin permeation research. PMID:22960319

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

PubMed

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

2008-02-11

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

Photo-catalytic decolourisation of toxic dye with N-doped titania: a case study with Acid Blue 25.

PubMed

Chakrabortty, Dhruba; Gupta, Susmita Sen

2013-05-01

Dyes are one of the hazardous water pollutants. Toxic Acid Blue 25, an anthraquinonic dye, has been decolourised by photo-catalysing it with nitrogen doped titania in aqueous medium. The photo catalyst was prepared from 15% TiCl3 and 25% aqueous NH3 solution as precursor. XRD and TEM revealed the formation of well crystalline anatase phase having particle size in the nano-range. BET surface area of the sample was higher than that of pure anatase TiO2. DRS showed higher absorption of radiation in visible range compared to pure anatase TiO2. XPS revealed the presence of nitrogen in N-Ti-O environment. The experimental parameters, namely, photocatalyst dose, initial dye concentration as well as solution pH influence the decolourisation process. At pH 3.0, the N-TiO2 could decolourise almost 100% Acid Blue 25 within one hour. The influence of N-TiO2 dose, initial concentration of Acid Blue 25 and solution pH on adsorption-desorption equilibrium is also studied. The adsorption process follows Lagergren first order kinetics while the modified Langmuir-Hinselwood model is suitably fitted for photocatalytic decolourisation of Acid Blue 25.

Propham mineralization in aqueous medium by anodic oxidation using boron-doped diamond anode: influence of experimental parameters on degradation kinetics and mineralization efficiency.

PubMed

Ozcan, Ali; Sahin, Yücel; Koparal, A Savaş; Oturan, Mehmet A

2008-06-01

This study aims the removal of a carbamate herbicide, propham, from aqueous solution by direct electrochemical advanced oxidation process using a boron-doped diamond (BDD) anode. This electrode produces large quantities of hydroxyl radicals from oxidation of water, which leads to the oxidative degradation of propham up to its total mineralization. Effect of operational parameters such as current, temperature, pH and supporting electrolyte on the degradation and mineralization rate was studied. The applied current and temperature exert a prominent effect on the total organic carbon (TOC) removal rate of the solutions. The mineralization of propham can be performed at any pH value between 3 and 11 without any loss in oxidation efficiency. The propham decay and its overall mineralization reaction follows a pseudo-first-order kinetics. The apparent rate constant value of propham oxidation was determined as 4.8 x 10(-4)s(-1) at 100 mA and 35 degrees C in the presence of 50mM Na(2)SO(4) in acidic media (pH: 3). A general mineralization sequence was proposed considering the identified oxidation intermediates.

Electrogenerated chemiluminescence reactions between the [Ru(bpy)3](2+) complex and PAMAM GX.0 dendrimers in an aqueous medium.

PubMed

Jimenez-Ruiz, A; Grueso, E; Perez-Tejeda, P

2015-10-01

Electrogenerated chemiluminescence, ECL, reactions between tris(2,2'-bipyridine)ruthenium(II), [Ru(bpy)3](2+), and PAMAM GX.0 (X=1 and 2) dendrimers in an aqueous medium were carried out at pH10 (fully deprotonated dendrimer surface). ECL was detected in the presence of GX.0 dendrimers without addition of any known coreactant. Atomic force microscopy, AFM, measurements for GX.0 dendrimers in the presence of the [Ru(bpy)3](2+) complex were also done. AFM images showed the existence of aggregates (pillars) of globular shape, as well as interdendrimer networks forming fibers in the x-y direction for dendrimer aqueous solutions. ECL and AFM results in cooperation suggest that the coreactant effect of the end amine groups is improved by both the dendritic branched shells and the globular z-type aggregates. The ECL efficiency trends as a function of [GX.0] (whole range) can be interpreted taking into account the coreactant effect modulated by the presence of the z and x-y type aggregates. Importantly, ECL efficiency values can be taken as a measure of the change induced on the dendrimer aggregation in aqueous solutions when their concentrations rise. Redox potentials of the [Ru(bpy)3](3+/2+) couple in the presence of the G1.0 and G2.0 dendrimers were also determined. Copyright © 2015 Elsevier Inc. All rights reserved.

Evolution of Spatial pH Distribution in Aqueous Solution induced by Atmospheric Pressure Plasma

NASA Astrophysics Data System (ADS)

Takahashi, Shigenori; Mano, Kakeru; Hayashi, Yui; Takada, Noriharu; Kanda, Hideki; Goto, Motonobu

2016-09-01

Discharge plasma at gas-liquid interface produces some active species, and then they affect chemical reactions in aqueous solution, where pH of aqueous solution is changed due to redox species. The pH change of aqueous solution is an important factor for chemical reactions. However, spatial pH distribution in a reactor during the discharge has not been clarified yet. Thus, this work focused on spatial pH distribution of aqueous solution when pulsed discharge plasma was generated from a copper electrode in gas phase to aqueous solution in a reactor. Experiments were conducted using positive unipolar pulsed power. The unipolar pulsed voltage at +8.0 kV was applied to the copper electrode and the bottom of the reactor was grounded. The size of the reactor was 80 mm wide, 10 mm deep, and 40 mm high. The electrode was set at distance of 2 mm from the solution surface. Anthocyanins were contained in the aqueous solution as a pH indicator. The change pH solution spread horizontally, and low pH region of 10 mm in depth was formed. After discharge for 10 minutes, the low pH region was diffused toward the bottom of the reactor. After discharge for 60 minutes, the pH of the whole solution decreased.

Optimization and adsorption kinetic studies of aqueous manganese ion removal using chitin extracted from shells of edible Philippine crabs

NASA Astrophysics Data System (ADS)

Quimque, Mark Tristan J.; Jimenez, Marvin C.; Acas, Meg Ina S.; Indoc, Danrelle Keth L.; Gomez, Enjelyn C.; Tabuñag, Jenny Syl D.

2017-01-01

Manganese is a common contaminant in drinking water along with other metal pollutants. This paper investigates the use of chitin, extracted from crab shells obtained as restaurant throwaway, as an adsorbent in removing manganese ions from aqueous medium. In particular, this aims to optimize the adsorption parameters and look into the kinetics of the process. The adsorption experiments done in this study employed the batch equilibration method. In the optimization, the following parameters were considered: pH and concentration of Mn (II) sorbate solution, particle size and dosage of adsorbent chitin, and adsorbent-adsorbate contact time. At the optimal condition, the order of the adsorption reaction was estimated using kinetic models which describes the process best. It was found out that the adsorption of aqueous Mn (II) ions onto chitin obeys the pseudo-second order model. This model assumes that the adsorption occurred via chemisorption

Stimuli-sensitive polymeric micelles as anticancer drug carriers.

PubMed

Na, Kun; Sethuraman, Vijay T; Bae, You Han

2006-11-01

Amphiphilic block copolymers often form core-shell type micelles by self-organization of the blocks in an aqueous medium or under specific experimental conditions. Polymeric micelles constructed from these polymers that contain a segment whose physical or chemical properties respond to small changes in environmental conditions are collectively called 'stimuli-sensitive' micelles. This class of nano-scaled constructs has been investigated as a promising anti-cancer drug carrier because the micelles are able to utilize small environmental changes and modify drug release kinetics, biodistribution and the interactions with tissues and cells. This review summarizes the recent progress in stimuli-sensitive micelles for tumor chemotherapy, particularly for those responding to hyperthermic conditions, tumor pH and endosomal/lysosomal pH.

pH measurements of FET-based (bio)chemical sensors using portable measurement system.

PubMed

Voitsekhivska, T; Zorgiebel, F; Suthau, E; Wolter, K-J; Bock, K; Cuniberti, G

2015-01-01

In this study we demonstrate the sensing capabilities of a portable multiplex measurement system for FET-based (bio)chemical sensors with an integrated microfluidic interface. We therefore conducted pH measurements with Silicon Nanoribbon FET-based Sensors using different measurement procedures that are suitable for various applications. We have shown multiplexed measurements in aqueous medium for three different modes that are mutually specialized in fast data acquisition (constant drain current), calibration-less sensing (constant gate voltage) and in providing full information content (sweeping mode). Our system therefore allows surface charge sensing for a wide range of applications and is easily adaptable for multiplexed sensing with novel FET-based (bio)chemical sensors.

[Studies of local anaesthetics: part 205* studies of stability of heptacainium chloride and carbisocainium chloride using an accelerated non-isothermal test].

PubMed

Stankovičová, Mária; Lašáková, Andrea; Medlenová, Veronika; Bezáková, Zelmíra; Cižmárik, Jozef

2014-08-01

The paper studies the kinetics of alkaline hydrolysis and stability under non-isothermal conditions of heptacainium chloride and carbisocainium chloride in the medium of aqueous-ethanolic solution of sodium hydroxide c = 0.1 mol/l and buffer solutions of values of pH 7.0 and pH 8.0. The results of the study of the kinetics of hydrolysis by means of a non-isothermal test - rate constants and activation energy values served as the basis for exact evaluation of the stability of these potential pharmaceuticals. The objective of the paper links up with the previous studies of these substances.

Evaluation of photosynthetic efficacy and CO2 removal of microalgae grown in an enriched bicarbonate medium.

PubMed

Abinandan, S; Shanthakumar, S

2016-06-01

Bicarbonate species in the aqueous phase is the primary source for CO 2 for the growth of microalgae. The potential of carbon dioxide (CO 2 ) fixation by Chlorella pyrenoidosa in enriched bicarbonate medium was evaluated. In the present study, effects of parameters such as pH, sodium bicarbonate concentration and inoculum size were assessed for the removal of CO 2 by C. pyrenoidosa under mixotrophic condition. Central composite design tool from response surface methodology was used to validate statistical methods in order to study the influence of these parameters. The obtained results reveal that the maximum removal of CO 2 was attained at pH 8 with sodium bicarbonate concentration of 3.33 g/l, and inoculum size of 30 %. The experimental results were statistically significant with R 2 value of 0.9527 and 0.960 for CO 2 removal and accumulation of chlorophyll content, respectively. Among the various interactions, interactive effects between the parameters pH and inoculum size was statistically significant (P < 0.05) for CO 2 removal and chlorophyll accumulation. Based on the studies, the application of C. pyrenoidosa as a potential source for carbon dioxide removal at alkaline pH from bicarbonate source is highlighted.

Novelmetal-organic photocatalysts: Synthesis, characterization and decomposition of organic dyes

NASA Astrophysics Data System (ADS)

Gopal Reddy, N. B.; Murali Krishna, P.; Kottam, Nagaraju

2015-02-01

An efficient method for the photocatalytic degradation of methylene blue in an aqueous medium was developed using metal-organic complexes. Two novel complexes were synthesized using, Schiff base ligand, N‧-[(E)-(4-ethylphenyl)methylidene]-4-hydroxybenzohydrazide (HL) and Ni(II) (Complex 1)/Co(II) (Complex 2) chloride respectively. These complexes were characterized using microanalysis, various spectral techniques. Spectral studies reveal that the complexes exhibit square planar geometry with ligand coordination through azomethine nitrogen and enolic oxygen. The effects of catalyst dosage, irradiation time and aqueous pH on the photocatalytic activity were studied systematically. The photocatalytic activity was found to be more efficient in the presence of Ni(II) complexes than the Co(II) complex. Possible mechanistic aspects were discussed.

Diffusion of water-soluble sorptive drugs in HEMA/MAA hydrogels.

PubMed

Liu, D E; Dursch, T J; Taylor, N O; Chan, S Y; Bregante, D T; Radke, C J

2016-10-10

We measure and, for the first time, theoretically predict four prototypical aqueous-drug diffusion coefficients in five soft-contact-lens material hydrogels where solute-specific adsorption is pronounced. Two-photon fluorescence confocal microscopy and UV/Vis-absorption spectrophotometry assess transient solute concentration profiles and concentration histories, respectively. Diffusion coefficients are obtained for acetazolamide, riboflavin, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA) copolymer hydrogels as functions of composition, equilibrium water content (30-90%), and aqueous pH (2 and 7.4). At pH2, MAA chains are nonionic, whereas at pH7.4, MAA chains are anionic (pKa≈5.2). All studied prototypical drugs specifically interact with HEMA and nonionic MAA (at pH2) moieties. Conversely, none of the prototypical drugs adsorb specifically to anionic MAA (at pH7.4) chains. As expected, diffusivities of adsorbing solutes are significantly diminished by specific interactions with hydrogel strands. Despite similar solute size, relative diffusion coefficients in the hydrogels span several orders of magnitude because of varying degrees of solute interactions with hydrogel-polymer chains. To provide a theoretical framework for the new diffusion data, we apply an effective-medium model extended for solute-specific interactions with hydrogel copolymer strands. Sorptive-diffusion kinetics is successfully described by local equilibrium and Henry's law. All necessary parameters are determined independently. Predicted diffusivities are in good agreement with experiment. Copyright © 2016 Elsevier B.V. All rights reserved.

Immobilization of Lipase from Penicillium sp. Section Gracilenta (CBMAI 1583) on Different Hydrophobic Supports: Modulation of Functional Properties.

PubMed

Turati, Daniela F M; Morais Júnior, Wilson G; Terrasan, César R F; Moreno-Perez, Sonia; Pessela, Benevides C; Fernandez-Lorente, Gloria; Guisan, Jose M; Carmona, Eleonora C

2017-02-22

Lipases are promising enzymes that catalyze the hydrolysis of triacylglycerol ester bonds at the oil/water interface. Apart from allowing biocatalyst reuse, immobilization can also affect enzyme structure consequently influencing its activity, selectivity, and stability. The lipase from Penicillium sp. section Gracilenta (CBMAI 1583) was successfully immobilized on supports bearing butyl, phenyl, octyl, octadecyl, and divinylbenzyl hydrophobic moieties wherein lipases were adsorbed through the highly hydrophobic opened active site. The highest activity in aqueous medium was observed for the enzyme adsorbed on octyl support, with a 150% hyperactivation regarding the soluble enzyme activity, and the highest adsorption strength was verified with the most hydrophobic support (octadecyl Sepabeads), requiring 5% Triton X-100 to desorb the enzyme from the support. Most of the derivatives presented improved properties such as higher stability to pH, temperature, and organic solvents than the covalently immobilized CNBr derivative (prepared under very mild experimental conditions and thus a reference mimicking free-enzyme behavior). A 30.8- and 46.3-fold thermostabilization was achieved in aqueous medium, respectively, by the octyl Sepharose and Toyopearl butyl derivatives at 60 °C, in relation to the CNBr derivative. The octyl- and phenyl-agarose derivatives retained 50% activity after four and seven cycles of p -nitrophenyl palmitate hydrolysis, respectively. Different derivatives exhibited different properties regarding their properties for fish oil hydrolysis in aqueous medium and ethanolysis in anhydrous medium. The most active derivative in ethanolysis of fish oil was the enzyme adsorbed on a surface covered by divinylbenzyl moieties and it was 50-fold more active than the enzyme adsorbed on octadecyl support. Despite having identical mechanisms of immobilization, different hydrophobic supports seem to promote different shapes of the adsorbed open active site of the lipase and hence different functional properties.

New insights on the spectrophotometric determination of melatonin pKa values and melatonin-βCD inclusion complex formation constant

NASA Astrophysics Data System (ADS)

Zafra-Roldán, A.; Corona-Avendaño, S.; Montes-Sánchez, R.; Palomar-Pardavé, M.; Romero-Romo, M.; Ramírez-Silva, M. T.

2018-02-01

Using UV-Vis spectrophotometry a stability study of melatonin at different pH values was done in aqueous media, finding that at acidic pH melatonin is unstable when interacting with the environment, however it becomes stable protecting it from light and oxygen. From the UV-Vis spectra and SQUAD software, melatonin pKa values, in a completely protected aqueous medium, were estimated as 5.777 ± 0.011 and 10.201 ± 0.024. Using the same techniques, the melatonin and β-cyclodextrin inclusion complex formation constants were assessed at pH 3, 7 and 11.5, giving the values of log β = (3.07 ± 0.06), (2.94 ± 0.01) and (3.07 ± 0.06) M- 1, respectively. From the global acidity formation constants and the complexes' formation constants, the molar fractions were determined for each species of MT and MT - βCD, to build the molar fraction-[βCD]-pH 3D diagram and the molar fraction-pH 2D diagrams, where it was possible to observe the predominance of the MT species with and without βCD. A voltammetric study at pH 3, allowed obtaining a value of log β = (3.15 ± 0.01) M- 1, which corroborates that obtained through UV-Vis spectrophotometry, supporting strongly the rationale behind using simple, straightforward techniques.

Carbon dioxide capture using resin-wafer electrodeionization

DOEpatents

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

2015-09-08

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

Production of citrinin-free Monascus pigments by submerged culture at low pH.

PubMed

Kang, Biyu; Zhang, Xuehong; Wu, Zhenqiang; Wang, Zhilong; Park, Sunghoon

2014-02-05

Microbial fermentation of citrinin-free Monascus pigments is of great interest to meet the demand of food safety. In the present work, the effect of various nitrogen sources, such as monosodium glutamate (MSG), cornmeal, (NH4)₂SO₄, and NaNO₃, on Monascus fermentation was examined under different initial pH conditions. The composition of Monascus pigments and the final pH of fermentation broth after Monascus fermentation were determined. It was found that nitrogen source was directly related to the final pH and the final pH regulated the composition of Monascus pigments and the biosynthesis of citrinin. Thus, an ideal nitrogen source can be selected to control the final pH and then the citrinin biosynthesis. Citrinin-free orange pigments were produced at extremely low initial pH in the medium with (NH4)₂SO₄ or MSG as nitrogen source. No citrinin biosynthesis at extremely low pH was further confirmed by extractive fermentation of intracellular pigments in the nonionic surfactant Triton X-100 micelle aqueous solution. This is the first report about the production of citrinin-free Monascus pigments at extremely low pH. Copyright © 2013 Elsevier Inc. All rights reserved.

Powdered Chitin Agar as a Selective Medium for Enumeration of Actinomycetes in Water and Soil1

PubMed Central

Hsu, S. C.; Lockwood, J. L.

1975-01-01

Agar media made with 0.4% colloidal chitin plus mineral salts and adjusted to pH 8.0 was superior to four other commonly used media for the isolation and enumeration of actinomycetes from water samples. More actinomycetes developed on chitin agar, and the development of bacteria and fungi was suppressed. Frozen and vacuum-dried chitin from aqueous colloidal suspensions was finely divided and gave results comparable to those obtained with media prepared from colloidal suspensions. Images PMID:234719

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

Yudoyono, Gatut, E-mail: gyudoyono@physics.its.ac.id; Zharvan, Vicran; Ichzan, Nur

Titanium dioxide (titania) nanoparticle were synthesized by coprecipitation process of titanium trichloride (TiCl{sub 3}) in aqueous medium, with NH{sub 4}OH as pH regulator. The pH solution was varied during the synthesis process between pH 3-8.4, and all samples were calcined temperature at 400°C for 3 hours. Characteristics and properties of the TiO{sub 2} powder were investigated using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM). XRD results show that the single-phase rutile formed when the pH is less than 5, anatase single phase formed began pH 8, and the pH of the solution between 5-8 formed mixed phase rutile-anatase-brookite, rutile-brookite ormore » anatase-brookite. Methylene Blue (MB) photodegradation test were performed in order to evaluate photocatalytic activity. Nanoparticles TiO{sub 2} rutile, anatase phase, and mixed phase rutile-brookite, anatase-brookite used to test the photocatalytic activity by measuring the absorbance spectrum photodegradation using UV-Vis spectrometer. The test results showed that the mixture phase of rutile-brookite provide the greatest photodegradation than other phases.« less

A review on applicability of naturally available adsorbents for the removal of hazardous dyes from aqueous waste.

PubMed

Sharma, Pankaj; Kaur, Harleen; Sharma, Monika; Sahore, Vishal

2011-12-01

The effluent water of many industries, such as textiles, leather, paper, printing, cosmetics, etc., contains large amount of hazardous dyes. There is huge number of treatment processes as well as adsorbent which are available for the processing of this effluent water-containing dye content. The applicability of naturally available low cast and eco-friendly adsorbents, for the removal of hazardous dyes from aqueous waste by adsorption treatment, has been reviewed. In this review paper, we have provided a compiled list of low-cost, easily available, safe to handle, and easy-to-dispose-off adsorbents. These adsorbents have been classified into five different categories on the basis of their state of availability: (1) waste materials from agriculture and industry, (2) fruit waste, (3) plant waste, (4) natural inorganic materials, and (5) bioadsorbents. Some of the treated adsorbents have shown good adsorption capacities for methylene blue, congo red, crystal violet, rhodamine B, basic red, etc., but this adsorption process is highly pH dependent, and the pH of the medium plays an important role in the treatment process. Thus, in this review paper, we have made some efforts to discuss the role of pH in the treatment of wastewater.

Further Studies on the Lyo and Desmo Components of Several Hydrolytic Enzymes and Their Histochemical Significance

PubMed Central

Hannibal, Mark J.; Nachlas, Marvin M.

1959-01-01

This report describes additional studies of the lyo and desmo components of esterase, alkaline phosphatase, acid phosphatase, leucine aminopeptidase, and β-glucuronidase. The techniques used have already been reported (7). Enzyme diffusion occurs to different degrees in different fixatives, and varies somewhat with each enzyme. Loss of enzymatic activity during fixation occurs as a result of both inactivation due to the chemical reaction of the fixative with the enzymic protein, and diffusion of the lyo component into the fixative. The amount of diffusion into formalin can be reduced by the addition of salts, sucrose, or methocel. The pH of the aqueous medium significantly influences the removal of the lyo fraction from the tissue section. A striking similarity can be noted in the proportions of each fraction of enzyme present in the kidney of the rat, dog, and man. The procedure of fixation and paraffin embedding of tissue blocks does not wholly prevent the diffusion of the lyo component from the tissue sections when they are subsequently immersed in the aqueous incubation medium. PMID:13654449

Molecular complexes of l-phenylalanine with substituted 1,4-benzoquinones in aqueous medium: spectral and theoretical investigations.

PubMed

Ganesh, K; El-Mossalamy, E H; Satheshkumar, A; Balraj, C; Elango, K P

2013-12-01

Various spectral techniques such as UV-Vis, FT-IR, and fluorescence have been employed to investigate the charge transfer interaction of L-phenylalanine (LPA) with substituted 1,4-benzoquinones (MQ(1-4)). Kinetic and thermodynamic properties of the complexes were determined in aqueous medium at physiological condition (pH=7). The interaction of MQ(1-4) with L-phenylalanine (LPA) was found to proceed through the formation of donor-acceptor complex, yielding a radical anion. The stoichiometry of the complexes was determined by Jobs continuous variation method and was found to be 1:1 in all the cases. Fluorescence quenching studies showed that the interaction between the donor and the acceptors is spontaneous. The results indicated that the progressive replacement of chlorine atom (-I effect) by methoxy group (+M effect) in the quinone decreased the electron acceptor property of the quinone. The order of the experimentally measured association constant of these complexes was well supported by DFT/B3LYP calculations. Copyright © 2013 Elsevier B.V. All rights reserved.

Dependence of the electronic absorption spectra of aqueous solutions of iodine monochloride on the conditions of dilution and storage time

NASA Astrophysics Data System (ADS)

Klyubin, V. V.; Klyubina, K. A.; Makovetskaya, K. N.

2017-04-01

The electronic absorption spectra of aqueous solutions of iodine monochloride ICl are studied. The spectra of as-prepared solutions display the absorption band associated with hydrated ICl molecules. An additional band indicating that molecular iodine was formed in the solution emerges in the spectrum as dissolution takes place. Only the band belonging to iodine monochloride remains in the absorption spectra, and no additional bands appear after chloride anions Cl- are added to the solution. The absorption spectrum becomes more complex when ICl is dissolved in an alkaline medium. The band belonging to molecular iodine emerges in the spectra at low alkali concentrations, while being transformed to other shorter-wavelength bands at high alkali concentrations (pH ≥ 12).

Fast Potentiometric Analysis of Lead in Aqueous Medium under Competitive Conditions Using an Acridono-Crown Ether Neutral Ionophore.

PubMed

Golcs, Ádám; Horváth, Viola; Huszthy, Péter; Tóth, Tünde

2018-05-03

Lead is a particularly toxic heavy metal that is present above acceptable levels in the water of many countries. This article describes a quick detection method of lead(II) ions using a polyvinyl chloride (PVC)-based ion-selective membrane electrode containing an acridono-crown ether ionophore by potentiometry. The electrochemical cell exhibits a Nernstian response for lead(II) ions between the concentration range of 10 −4 to 10 −2 M, and can be used in the pH range of 4⁻7. The applicability of this sensor was verified by measuring a multicomponent aqueous sample. Under the given conditions, this electrode is suitable for the selective quantitative analysis of lead(II) ions in the presence of many additional metal ions.

Consequences of ions and pH on the supramolecular organization of sphingomyelin and sphingomyelin/cholesterol bilayers.

PubMed

Chemin, Caroline; Bourgaux, Claudie; Péan, Jean-Manuel; Pabst, Georg; Wüthrich, Patrick; Couvreur, Patrick; Ollivon, Michel

2008-06-01

For drug delivery purpose the anticancer drug S12363 was loaded into ESM/Chol-liposomes using either a pH or an ammonium gradient. Association between the drug and the liposome depends markedly on the liposome membrane structure. Thus, ESM and ESM/Chol bilayer organization had been characterized by coupled DSC and XRDT as a function of both cholesterol concentration and aqueous medium composition. ESM bilayers exhibited a ripple lamellar gel phase P(beta') below the melting temperature and adopted a L(beta)-like gel phase upon Chol insertion. Supramolecular organization of ESM and ESM/Chol bilayers was not modified by citrate buffer or ammonium sulfate solution whatever the pH (3< or = pH < or =7). Nevertheless, in ESM bilayer, ammonium sulfate salt induced a peculiar organization of head groups, leading to irregular d-spacing and weakly correlated bilayers. Moreover, in the presence of salts, a weakening of van der Waals attraction forces was seen and led to a swelling of the water layer.

Magnetically recoverable Fe3O4/graphene nanocomposite towards efficient removal of triazine pesticides from aqueous solution: Investigation of the adsorption phenomenon and specific ion effect.

PubMed

Boruah, Purna K; Sharma, Bhagyasmeeta; Hussain, Najrul; Das, Manash R

2017-02-01

Spillage of effluents containing high concentration levels of pesticides into water has been considered as one of the serious environmental problems. In this study Fe 3 O 4 /reduced graphene oxide (rGO) nanocomposite has been efficiently utilized for the adsorption of five harmful pesticides namely ametryn, prometryn, simazine, simeton and atrazine in an aqueous medium. Electrostatic interaction between the pesticides and Fe 3 O 4 /rGO nanocomposite was analyzed by the zeta potential analysis, which is strongly related to the adsorption capacity of the adsorbent. The kinetics parameters of adsorption followed the pseudo second-order linear model. The adsorption isotherm studies show that, the maximum adsorption capacity of 54.8 mg g -1 is achieved at pH 5 and it was enhanced in the presence of different ions (Mg 2+ , Ca 2+ , Na + and SO 4 2 ) and maximum (63.7 mg g -1 ) for ametryn adsorption was found in seawater medium. Thermodynamic parameter shows that, the adsorption process is physisorption and spontaneity in nature. The mechanism of the adsorption process was established by the DRIFT spectroscopy analysis. Efficient adsorption (93.61%) of pesticides was observed due to electrostatic, hydrophobic and π-π interactions of composite towards the heterocyclic conjugation of pesticide molecules. Further, Fe 3 O 4 /rGO nanocomposite was easily and rapidly separated from an aqueous medium using the external magnet for reuse and 88.66% adsorption efficiency was observed up to seven cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Micelles of enzymatically synthesized PEG-poly(amine-co-ester) block copolymers as pH-responsive nanocarriers for docetaxel delivery.

PubMed

Zhang, Xiaofang; Liu, Bo; Yang, Zhe; Zhang, Chao; Li, Hao; Luo, Xingen; Luo, Huiyan; Gao, Di; Jiang, Qing; Liu, Jie; Jiang, Zhaozhong

2014-03-01

A series of PEGylated poly(amine-co-ester) terpolymers were successfully synthesized in one step via lipase-catalyzed copolymerization of ω-pentadecalactone (PDL), diethyl sebacate (DES), and N-methyldiethanolamine (MDEA) comonomers in the presence of poly(ethylene glycol) methyl ether as a chain-terminating agent. The resultant amphiphilic poly(ethylene glycol)-poly(PDL-co-MDEA-co-sebacate) (PEG-PPMS) block copolymers consisted of hydrophilic PEG chain segments and hydrophobic random PPMS chain segments, which self-assembled in aqueous medium to form stable, nanosized micelles at physiological pH of 7.4. Upon decreasing the medium pH from 7.4 to 5.0, the copolymer micelles swell significantly due to protonation of the amino groups in the micelle PPMS cores. Correspondingly, docetaxel (DTX)-encapsulated PEG2K-PPMS copolymer micelles showed gradual sustained drug release at pH of 7.4, but remarkably accelerated DTX release at acidic pH of 5.0. The drug-loaded micelle particles were readily internalized by SK-BR-3 cancer cells and, compared to free DTX drug, DTX-loaded micelles of the copolymers with optimal compositions exhibited enhanced potency against the cells. Biodegradable PEG-PPMS copolymer micelles represent a new type of promising, pH-responsive nanocarriers for anticancer drug delivery, and the drug release rate from the micelles can be systematically controlled by both pH and the copolymer composition. Copyright © 2013 Elsevier B.V. All rights reserved.

Charge-patterning phase transition on a surface lattice of titratable sites adjacent to an electrolyte solution

NASA Astrophysics Data System (ADS)

Shore, Joel; Thurston, George

We discuss a model for a charge-patterning phase transition on a two-dimensional square lattice of titratable sites, here regarded as protonation sites, placed on a square lattice in a dielectric medium just below the planar interface between this medium and an aqueous salt solution. Within Debye-Huckel theory, the analytical form of the electrostatic repulsion between protonated sites exhibits an approximate inverse cubic power-law decrease beyond short distances. The problem can thus be mapped onto the two-dimensional antiferromagnetic Ising model with this longer-range interaction, which we study with Monte Carlo simulations. As we increase pH, the occupation probability of a site decreases from 1 at low pH to 0 at high pH. For sufficiently-strong interaction strengths, a phase transition occurs as the occupation probability of 1/2 is approached: the charges arrange themselves into a checkerboard pattern. This ordered phase persists over a range of pH until a transition occurs back to a disordered state. This state is the analogue of the Neel state in the antiferromagnetic Ising spin model. More complicated ordered phases are expected for sufficiently strong interactions (with occupation probabilities of 1/4 and 3/4) and if the lattice is triangular rather than square. This work was supported by NIH EY018249 (GMT).

Unravelling the pH-dependence of a molecular photocatalytic system for hydrogen production.

PubMed

Reynal, Anna; Pastor, Ernest; Gross, Manuela A; Selim, Shababa; Reisner, Erwin; Durrant, James R

2015-08-01

Photocatalytic systems for the reduction of aqueous protons are strongly pH-dependent, but the origin of this dependency is still not fully understood. We have studied the effect of different degrees of acidity on the electron transfer dynamics and catalysis taking place in a homogeneous photocatalytic system composed of a phosphonated ruthenium tris(bipyridine) dye ( RuP ) and a nickel bis(diphosphine) electrocatalyst ( NiP ) in an aqueous ascorbic acid solution. Our approach is based on transient absorption spectroscopy studies of the efficiency of photo-reduction of RuP and NiP correlated with pH-dependent photocatalytic H 2 production and the degree of catalyst protonation. The influence of these factors results in an observed optimum photoactivity at pH 4.5 for the RuP - NiP system. The electron transfer from photo-reduced RuP to NiP is efficient and independent of the pH value of the medium. At pH <4.5, the efficiency of the system is limited by the yield of RuP photo-reduction by the sacrificial electron donor, ascorbic acid. At pH >4.5, the efficiency of the system is limited by the poor protonation of NiP , which inhibits its ability to reduce protons to hydrogen. We have therefore developed a rational strategy utilising transient absorption spectroscopy combined with bulk pH titration, electrocatalytic and photocatalytic experiments to disentangle the complex pH-dependent activity of the homogenous RuP - NiP photocatalytic system, which can be widely applied to other photocatalytic systems.

Nanocrystalline p-hydroxyacetanilide (paracetamol) and gold core-shell structure as a model drug deliverable organic-inorganic hybrid nanostructure

NASA Astrophysics Data System (ADS)

Das, Subhojit; Paul, Anumita; Chattopadhyay, Arun

2013-09-01

We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release.We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release. Electronic supplementary information (ESI) available: See DOI: 10.1039/c3nr03566b

Injection port derivatization following ion-pair hollow fiber-protected liquid-phase microextraction for determining acidic herbicides by gas chromatography/mass spectrometry.

PubMed

Wu, Jingming; Lee, Hian Kee

2006-10-15

Injection port derivatization following ion-pair hollow fiber-protected liquid-phase microextraction (LPME) for the trace determination of acidic herbicides (2,4-dichlorobenzoic acid, 2,4-dichlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy)propionic acid, 3,5-dichlorobenzoic acid, 2-(2,4,5-trichlorophenoxy)propionic acid) in aqueous samples by gas chromatography/mass spectrometry (GC/MS) was developed. Prior to GC injection port derivatization, acidic herbicides were converted into their ion-pair complexes with tetrabutylammonium chloride in aqueous samples and then extracted by 1-octanol impregnated in the hollow fiber. Upon injection, ion pairs of acidic herbicides were quantitatively derivatized to their butyl esters in the GC injection port. Thus, several parameters related to the derivatization process (i.e., injection temperature, purge-off time) were evaluated, and main parameters affecting the hollow fiber-protected LPME procedure such as extraction organic solvent, ion-pair reagent type, pH of aqueous medium, concentration of ion-pair reagent, sodium chloride concentration added to the aqueous medium, stirring speed, and extraction time profile, optimized. At the selected extraction and derivatization conditions, no matrix effects were observed. This method proved good repeatability (RSDs <12.3%, n = 6) and good linearity (r2 > or = 0.9939) for spiked deionized water samples for five analytes. The limits of detection were in the range of 0.51-13.7 ng x L(-1) (S/N =3) under GC/MS selected ion monitoring mode. The results demonstrated that injection port derivatization following ion-pair hollow fiber-protected LPME was a simple, rapid, and accurate method for the determination of trace acidic herbicides from aqueous samples. In addition, this method proved to be environmentally friendly since it completely avoided open derivatization with potentially hazardous reagents.

Gold nanoparticles prepared by electro-exploding wire technique in aqueous solutions

NASA Astrophysics Data System (ADS)

Kumar, Lalit; Kapoor, Akanksha; Meghwal, Mayank; Annapoorni, S.

2016-05-01

This article presents an effective approach for the synthesis of Au nanoparticles via an environmentally benevolent electro-exploding wire (EEW) technique. In this process, Au nanoparticles evolve through the plasma generated from the parent Au metal. Compared to other typical chemical methods, electro-exploding wire technique is a simple and economical technique which normally operates in water or organic liquids under ambient conditions. Efficient size control was achieved using different aqueous medium like (1mM) NaCl, deionized water and aqueous solution of sodium hydroxide (NaOH, pH 9.5) using identical electro-exploding conditions. The gold nanoparticles exhibited the UV-vis absorption spectrum with a maximum absorption band at 530 nm, similar to that of gold nanoparticles chemically prepared in a solution. The mechanism of size variation of Au nanoparticles is also proposed. The results obtained help to develop methodologies for the control of EEW based nanoparticle growth and the functionalization of nanoparticle surfaces by specific interactions.

Thermodynamic and kinetic studies of biosorption of iron and manganese from aqueous medium using rice husk ash

NASA Astrophysics Data System (ADS)

Adekola, F. A.; Hodonou, D. S. S.; Adegoke, H. I.

2016-11-01

The adsorption behavior of rice husk ash with respect to manganese and iron has been studied by batch methods to consider its application for water and waste water treatment. The optimum conditions of adsorption were determined by investigating the effect of initial metal ion concentration, contact time, adsorbent dose, pH value of aqueous solution and temperature. Adsorption equilibrium time was observed at 120 min. The adsorption efficiencies were found to be pH dependent. The equilibrium adsorption experimental data were found to fit the Langmuir, Freundlich and Temkin isotherms for iron, but fitted only Langmuir isotherm for manganese. The pseudo-second order kinetic model was found to describe the manganese and iron kinetics more effectively. The thermodynamic experiment revealed that the adsorption processes involving both metals were exothermic. The adsorbent was finally applied to typical raw water with initial manganese and iron concentrations of 3.38 mg/l for Fe and 6.28 mg/l, respectively, and the removal efficiency was 100 % for Mn and 70 % for Fe. The metal ions were desorbed from the adsorbent using 0.01 M HCl, it was found to quantitatively remove 67 and 86 % of Mn and Fe, respectively, within 2 h. The results revealed that manganese and iron are considerably adsorbed on the adsorbent and could be an economic method for the removal of these metals from aqueous solutions.

A rhodamine-based turn-on nitric oxide sensor in aqueous medium with endogenous cell imaging: an unusual formation of nitrosohydroxylamine.

PubMed

Alam, Rabiul; Islam, Abu Saleh Musha; Sasmal, Mihir; Katarkar, Atul; Ali, Mahammad

2018-05-10

A new sensor (L3) based on Rhodamine-B-en (2) and 2-(pyridin-2-ylmethoxy)benzaldehyde (1) has been developed for highly sensitive and selective recognition of NO in purely aqueous medium where the reaction of NO with the fluorophore leads to an unusual formation of nitrosohydroxylamine with the selective opening of the spirolactam ring over different cations, anions, amino-acids and other biological species with prominent enhancement in absorption and emission intensities. A large enhancement of fluorescence intensity for NO (11 fold) was observed upon addition of 3 equivalents of NO into the sensor in aqueous HEPES buffer (20 mM) at pH 7.20, μ = 0.05 M NaCl with naked eye detection. The corresponding Kf value was evaluated to be (7.55 ± 2.04) × 104 M-1 from the fluorescence titration plot. Quantum yields of L3 and the [L3 + NO] compound are found to be 0.07 and 0.77, respectively, using Rhodamine-6G as the standard. The LOD for NO was determined by the 3σ method and found to be 83.4 nM. The L3 sensor has low cytotoxicity, and is cell permeable and suitable for in vitro NO sensing. The in vivo compatibility of the sensor was also checked on zebrafish.

Enhancing the recovery of oilseed rape seed oil bodies (oleosomes) using bicarbonate-based soaking and grinding media.

PubMed

De Chirico, Simone; di Bari, Vincenzo; Foster, Tim; Gray, David

2018-02-15

An aqueous process for the recovery of oil bodies from rapeseed using sodium bicarbonate-based soaking and grinding media (pH 9.5) was investigated. The effect of the ratio between seed and mass of media during grinding and molarity of the medium used on oil body integrity, purity and storage stability have been studied. The grinding of seeds in solution at a ratio of 1:7 (w/w) significantly improved the quality of oil body suspension to a size more in-line with that seen in vivo (average D 4,3 of 1.19µm). The purity and the composition of the recovered oil bodies depends on the molarity of medium used; the use of a sodium bicarbonate solution (pH 9.5, 0.1M) in the grinding and washing steps produced oil body preparations with the same purity as that resulting from washing a crude preparation with 9M urea. The resultant emulsion had improved physical stability over a storage period of one month. Copyright © 2017. Published by Elsevier Ltd.

Influences of urea, pH and metal ions on the interaction between cepharanthine and lysozyme by steady state fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Yang, Yumin; Li, Daojin; Xu, Chen

2015-03-01

The study on the binding mode of drug with protein is important to understand the pharmacokinetics and toxicity of the drug as well as the relationship of structure and function of the protein. In the study, the interaction between cepharanthine and lysozyme (Lys) in aqueous solution was first investigated by fluorescence spectroscopic techniques at pH 7.4. The obtained quenching rate constant and binding constant indicated the static quenching mechanism and medium binding force. The effect of cepharanthine on the conformation of Lys was analyzed using synchronous fluorescence and three-dimensional (3D) fluorescence. In addition, the effect of urea on the interaction of cepharanthine with Lys was studied and the binding capacity of cepharanthine to the denatured Lys deceases dramatically, as compared with that of cepharanthine to native Lys. Moreover, influence of pH on the interaction of cepharanthine with Lys was investigated. As compared with that at pH 7.4, the binding abilities of the drug to Lys under other pH conditions (pH 9.0, 5.5, 3.5, and 1.9) deceased. Furthermore, the effect of metal ions on the binding constant of cepharanthine with Lys was investigated.

pH dependent green synthesis of gold nanoparticles by completely C6-carboxylated curdlan under high temperature and various pH conditions.

PubMed

Qiu, Wen-Yi; Wang, Kai; Wang, Yao-Yao; Ding, Zhi-Chao; Wu, Li-Xia; Cai, Wu-Dan; Yan, Jing-Kun

2018-01-01

A C6-carboxylated curdlan (C6-Cc) obtained from 4-acetamido-TEMPO-mediated oxidation of curdlan was used both as a reducing and stabilizing agent for green synthesis of pH-responsive AuNPs, which was carried out by controlling the pH of the C6-Cc solution at a high temperature (100°C). C6-Cc presented a semi-flexible random coil chain in the aqueous medium at pH 5.5 and became more expanded and rigid in alkaline conditions (pH 7.1-12.0), though the primary chemical structure of C6-Cc was virtually unchanged with the pH variation. The AuNPs prepared with C6-Cc at various pHs were characterized by various instrumental measurements. The shapes and sizes of AuNPs were found to be strongly dependent on the pH of the C6-Cc solution. The C6-Cc-decorated AuNPs exhibited a more well-dispersed spherical morphology with smaller particle sizes under alkaline conditions (pH 7.1-12.0). Through this study, a facile, simple, and green method has been demonstrated for preparation of stimuli-sensitive AuNPs using biocompatible polyanionic polysaccharides. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrogen production by sodium borohydride in NaOH aqueous solution

NASA Astrophysics Data System (ADS)

Wang, Q.; Zhang, L. F.; Zhao, Z. G.

2018-01-01

The kinetics of hydrolysis reaction of NaBH4 in NaOH aqueous solution is studied. The influence of pH of the NaOH aqueous solution on the rate of hydrogen production and the hydrogen production efficiency are studied for the hydrolysis reaction of NaBH4. The results show that the activation energy of hydrolysis reaction of NaBH4 increased with the increase of the initial pH of NaOH aqueous solution.With the increasing of the initial pH of NaOH aqueous solution, the rate of hydrogen production and hydrogen production efficiency of NaBH4 hydrolysis decrease.

Use of oxalic acid as inducer in photocatalytic oxidation of cresol red in aqueous solution under natural and artificial light.

PubMed

Seraghni, N; Ghoul, I; Lemmize, I; Reguig, A; Debbache, N; Sehili, T

2017-08-30

This work was carried out in the field of water treatment using advanced oxidation processes (AOPs), especially photolysis of carboxylic acid that leads to the formation in situ of hydroxyl radical (·OH). Cresol red (CR) degradation induced by organic acids/UV system was investigated in aqueous solution. The preliminary study of CR-organic acid mixture in the dark and at room temperature allowed confirming the absence of interaction under our experimental conditions. However, upon irradiation at 365 nm, the proportion of elimination of CR was 89% after 5 h of irradiation. Indeed, the CR degradation efficiency depends on the acid concentration and the pH of the medium. The concentration of acid is optimized to the 5 × 10 -3 M. pH 2.39 was the optimal one when C 2 HO - 4 was the most important species at this pH. The use of i-PrOH as · OH confirmed the involvement of · OH in photodegradation of CR induced by Ox. The addition of metal ions including Zn 2+ and Cu 2+ to the CR-organic acid mixture slowed the CR degradation unlike Fe 2+ , hence an improvement of its disappearance was observed. The results showed a faster degradation of the pollutant under excitation by sunlight. This environmentally friendly method appears to be very effective in the treatment of wastewater.

Unravelling the pH-dependence of a molecular photocatalytic system for hydrogen production† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc01349f Click here for additional data file.

PubMed Central

Pastor, Ernest; Gross, Manuela A.; Selim, Shababa

2015-01-01

Photocatalytic systems for the reduction of aqueous protons are strongly pH-dependent, but the origin of this dependency is still not fully understood. We have studied the effect of different degrees of acidity on the electron transfer dynamics and catalysis taking place in a homogeneous photocatalytic system composed of a phosphonated ruthenium tris(bipyridine) dye (RuP) and a nickel bis(diphosphine) electrocatalyst (NiP) in an aqueous ascorbic acid solution. Our approach is based on transient absorption spectroscopy studies of the efficiency of photo-reduction of RuP and NiP correlated with pH-dependent photocatalytic H2 production and the degree of catalyst protonation. The influence of these factors results in an observed optimum photoactivity at pH 4.5 for the RuP–NiP system. The electron transfer from photo-reduced RuP to NiP is efficient and independent of the pH value of the medium. At pH <4.5, the efficiency of the system is limited by the yield of RuP photo-reduction by the sacrificial electron donor, ascorbic acid. At pH >4.5, the efficiency of the system is limited by the poor protonation of NiP, which inhibits its ability to reduce protons to hydrogen. We have therefore developed a rational strategy utilising transient absorption spectroscopy combined with bulk pH titration, electrocatalytic and photocatalytic experiments to disentangle the complex pH-dependent activity of the homogenous RuP–NiP photocatalytic system, which can be widely applied to other photocatalytic systems. PMID:28717491

Oligonucleoside assisted one pot synthesis and self-assembly of gold nanoparticles

NASA Astrophysics Data System (ADS)

Nimrodh Ananth, A.; Ghosh, Goutam; Umapathy, S.; Jothi Rajan, M. A.

2013-12-01

Gold nanoparticles (AuNPs) were synthesized using two different mono-deoxynucleosides, namely, deoxycytidine (dC) and deoxyadenosine (dA) and the size of the nanoparticles in aqueous dispersions was measured to be approximately 10 and 23 nm, respectively. It was also observed that the AuNPs, synthesized using deoxycytidine (dC), self-assembled to a stable cauliflower-type structure of size approximately 230 nm over a long period of ageing, during which the solution colour was seen continuously changing from pale yellow to deep green. The self-assembly of dC-Au nanoparticles (dC-AuNPs) with time was investigated using UV-visible spectroscopy and dynamic light scattering (DLS) techniques. We have also observed that the self-assembly of dC-AuNPs was dependent on the solution pH; i.e. the aggregates could be dissociated and re-associated upon varying the solution pH which we assumed to be due to breaking and forming of hydrogen bonds between --OH and ==O groups of dC among the neighbouring dC-AuNPs. In contrast, AuNPs synthesized using deoxyadenosine (dA-AuNPs) were quite stable in aqueous medium.

2-Pyridinyl Thermolabile Groups as General Protectants for Hydroxyl, Phosphate, and Carboxyl Functions.

PubMed

Brzezinska, Jolanta; Witkowska, Agnieszka; Kaczyński, Tomasz P; Krygier, Dominika; Ratajczak, Tomasz; Chmielewski, Marcin K

2017-03-02

Application of 2-pyridinyl thermolabile protecting groups (2-PyTPGs) for protection of hydroxyl, phosphate, and carboxyl functions is presented in this unit. Their characteristic feature is a unique removal process following the intramolecular cyclization mechanism and induced only by temperature rise. Deprotection rate of 2-PyTPGs is dependent on certain parameters, such as solvent (aqueous or non-aqueous medium), pH values, and electron distribution in a pyridine ring. The presented approach pertains not only to protecting groups but also to an advanced system of controlling certain properties of 2-pyridinyl derivatives. We improved the "chemical switch" method, allowing us to regulate the protecting group stability by inversing the electron distribution in 2-PyTPG. Together with pH values manipulation, this allows us to regulate the protecting group stability. Moreover, phosphite cyclization to oxazaphospholidine provides a very stable but easily reversible tool for phosphate protection/modifications. For all TPGs we confirmed their utility in a system of protecting groups. This concept can contribute to designing the general protecting group that could be useful in bioorganic chemistry. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

Optimization of biosurfactant production in soybean oil by rhodococcus rhodochrous and its utilization in remediation of cadmium-contaminated solution

NASA Astrophysics Data System (ADS)

Suryanti, Venty; Hastuti, Sri; Andriani, Dewi

2016-02-01

Biosurfactant production by Rhodococcus rhodochrous in soybean oil was developed, where the effect of medium composition and fermentation time were evaluated. The optimum condition for biosurfactant production was achieved when a medium containing 30 g/L TSB (tryptic soy broth) and 20% v/v soybean oil was used as media with 7 days of fermentation. Biosurfactant was identified as glycolipids type biosurfactant which had critical micelle concentration (CMC) value of 896 mg/L. The biosurfactant had oil in water emulsion type and was able to reduce the surface tension of palm oil about 52% which could stabilize the emulsion up to 12 days. The batch removal of cadmium metal ion by crude and partially purified biosurfactants have been examined from synthetic aqueous solution at pH 6. The results exhibited that the crude biosurfactant had a much better adsorption ability of Cd(II) than that of partially purified biosurfactant. However, it was found that there was no significant difference in the adsorption of Cd(II) with 5 and 10 minutes of contact time. The results indicated that the biosurfactant could be used in remediation of heavy metals from contaminated aqueous solution.

Ammonium removal from high-strength aqueous solutions by Australian zeolite.

PubMed

Wijesinghe, D Thushari N; Dassanayake, Kithsiri B; Sommer, Sven G; Jayasinghe, Guttila Y; J Scales, Peter; Chen, Deli

2016-07-02

Removal of ammonium nitrogen (NH4(+)-N) particularly from sources which are highly rich in nitrogen is important for addressing environmental pollution. Zeolites, aluminosilicate minerals, are commonly used as commercial adsorbents and ion-exchange medium in number of commercial applications due to its high adsorption capacity of ammonium (NH4(+)). However, detailed investigations on NH4(+) adsorption and ion exchange capacities of Australian natural zeolites are rare, particularly under higher NH4(+) concentrations in the medium. Therefore, this study was conducted to determine NH4(+) adsorption characteristics of Australian natural zeolites at high NH4(+) concentrations with and without other chemical compounds in an aqueous solution. Results showed that initial NH4(+) concentration, temperature, reaction time, and pH of the solution had significant effects on NH4(+) adsorption capacity of zeolite. Increased retention time and temperature generally had a positive impact on adsorption. Freundlich model fitted well with adsorption process of Australian natural zeolites; however, Langmuir model had best fitted for the adsorption process of sodium (Na(+)) treated zeolites. NaCl treatment increased the NH4(+) adsorption capacity of Australian zeolites by 25% at 1000 mg-N, NH4(+) solution. The maximum adsorption capacity of both natural Australian zeolites and Na(+) treated zeolites were estimated as 9.48 and 11.83 mg-N/g, respectively, which is lower than many zeolites from other sources. Compared to the NH4(+) only medium, presence of other competitive ions and acetic acid in the medium (resembling composition in digested swine manure slurries) reduced NH4(+) removal of natural and Na(+) treated zeolites by 44% and 57%, respectively. This suggests detailed investigations are required to determine practically achievable NH4(+) -N removal potential of zeolites for applications in complex mediums such as animal manure slurries.

Halide removal from aqueous solution by novel silver-polymeric materials.

PubMed

A M S, Polo; I, Velo-Gala; M, Sánchez-Polo; U, von Gunten; J J, López-Peñalver; J, Rivera-Utrilla

2016-12-15

The objective of this study was to analyze the behavior of a new material, silver-doped polymeric cloth (Ag-cloth), in the removal of bromide and iodide from waters. Silver is immobilized on the cloth, guaranteeing selective adsorption of the halide ions as retained silver halides that therefore do not pass into the solution. Results indicate that Ag 0 reacts with H 2 O 2 in the first phases of the process, yielding Ag + and superoxide radical; however, as the process advances, this radical favors Ag + reduction. Increases in the concentration of H 2 O 2 augment the capacity of the Ag-cloth to remove halides from the medium up to a maximum concentration (55μM), above which the removal capacity remains constant (Xm≅1.3-1.8mg halide/g Ag-cloth). Thus, when there is excess H 2 O 2 in the medium, secondary competitive reactions that take place in the process guarantee a constant Ag + concentration, which defines the maximum adsorption capacity of Ag-cloth, reducing its ability to remove halides. Ag-cloth has a higher capacity to remove iodide than bromide, and the presence of organic matter or chloride reduces its capacity to remove iodide or bromide from water. The results obtained shown that the capacity of Ag 0 with H 2 O 2 significantly varies as a function of the medium pH from 1mg Br - /g Ag-cloth at very low pH to 1.6mg/g Ag-cloth at pH9. Copyright © 2016 Elsevier B.V. All rights reserved.

Reaction of benzophenone UV filters in the presence of aqueous chlorine: kinetics and chloroform formation.

PubMed

Duirk, Stephen E; Bridenstine, David R; Leslie, Daniel C

2013-02-01

The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 μM. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M⁻¹s⁻¹ and k(1,DiOxY) = 154 ± 76 M⁻¹s⁻¹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 10⁶ M⁻¹s⁻¹ and k(2_1,DiOxY) = 4.14(±0.68) × 10⁵ M⁻¹s⁻¹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M⁻¹s⁻¹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent; however, chloroform to UV filter molar yields at pH 8 were 0.221 CHCl₃/OXY and 0.212 CHCl₃/DiOXY. Copyright © 2012 Elsevier Ltd. All rights reserved.

Adsorption characteristics of sol gel-derived zirconia for cesium ions from aqueous solutions.

PubMed

Yakout, Sobhy M; Hassan, Hisham S

2014-07-01

Zirconia powder was synthesized via a sol gel method and placed in a batch reactor for cesium removal investigation. X-ray analysis and Fourier transform infrared spectroscopy were utilized for the evaluation of the developed adsorbent. The adsorption process has been investigated as a function of pH, contact time and temperature. The adsorption is strongly dependent on the pH of the medium whereby the removal efficiency increases as the pH turns to the alkaline range. The process was initially very fast and the maximum adsorption was attained within 60 min of contact. A pseudo-second-order model and homogeneous particle diffusion model (HPDM) were found to be the best to correlate the diffusion of cesium into the zirconia particles. Furthermore, adsorption thermodynamic parameters, namely the standard enthalpy, entropy, and Gibbs free energy, were calculated. The results indicate that cesium adsorption by zirconia is an endothermic (ΔH>0) process and good affinity of cesium ions towards the sorbent (ΔS>0) was observed.

Oxidation of SO2 by NO2 and air in an aqueous suspension of carbon

NASA Technical Reports Server (NTRS)

Rogowski, R. S.; Schryer, D. R.; Cofer, W. R., III; Edahl, R. A., Jr.; Munavalli, S.

1982-01-01

A series of experiments has been performed using carbon black as a surrogate for soot particles. Carbon black was suspended in water and gas mixtures were bubbled into the suspensions to observe the effect of carbon particles on the oxidation of SO2 by air and NO2. Identical gas mixtures were bubbled into a black containing only pure water. After exposure each solution was analyzed for pH and sulfate. It was found that NO2 greatly enhances the oxidation of SO2 to sulfate in the presence of carbon black. The amount of sulfate in the blanks was significantly less. Under the conditions of the experiments no saturation of the reaction was observed and SO2 was converted to sulfate even in a highly acid medium (pH not less than 1.5).

[Identity and physicochemical properties of 1-(4-chlorophenyl)-4-morpholino-imidazolin-2-one, AWD 131-138].

PubMed

Heinecke, K; Thiel, W

2001-06-01

The structure of the anticonvulsant 1-(4-chlorophenyl)-4-(4-morpholinyl)-2,5-dihydro-1H-imidazolin-2-one (Code: AWD 131-138, CAS-No.: 188116-07-6) was proved by IR, UV, 1H NMR, 13C NMR and mass spectra. AWD 131-138 is practically insoluble in a neutral aqueous medium at 20 degrees C (S approximately 0.08 g/l). The solubility of the substance in 0.1 N HCl is about 2.7 g/l. In DMF, AWD 131-138 is sparingly soluble (S approximately 28.5 g/l). The pKa-value is about 2.5. The partition coefficients P = COctanol/Cwater at 37 degrees C range from 0.7 at pH approximately 1 to about 20 at pH > or = 6.

Aqueous synthesis of near-infrared highly fluorescent platinum nanoclusters

NASA Astrophysics Data System (ADS)

García Fernández, Jenifer; Trapiella-Alfonso, Laura; Costa-Fernández, José M.; Pereiro, Rosario; Sanz-Medel, Alfredo

2015-05-01

A one-step synthesis of near infrared fluorescent platinum nanoclusters (PtNCs) in aqueous medium is described. The proposed optimized procedure for PtNC synthesis is rather simple, fast and it is based on the direct metal reduction with NaBH4. Bidentated thiol ligands (lipoic acid) were selected as nanoclusters stabilizers in water media. The structural characterization revealed attractive features of the PtNCs, including small size, high water solubility, near-infrared luminescence centered at 680 nm, long-term stability and the highest quantum yield in water reported so far (47%) for PtNCs. Moreover, their stability in different pH media and an ionic strength of 0.2 M NaCl was studied and no significant changes in fluorescence emission were detected. In brief, they offer a new type of fluorescent noble metal nanoprobe with a great potential to be applied in several fields, including biolabeling and imaging experiments.

Heterogeneous semiconductor photocatalysts for hydrogen production from aqueous solutions of electron donors

NASA Astrophysics Data System (ADS)

Kozlova, E. A.; Parmon, V. N.

2017-09-01

Current views on heterogeneous photocatalysts for visible- and near-UV-light-driven production of molecular hydrogen from water and aqueous solutions of inorganic and organic electron donors are analyzed and summarized. Main types of such photocatalysts and methods for their preparation are considered. Particular attention is paid to semiconductor photocatalysts based on sulfides that are known to be sensitive to visible light. The known methods for increasing the quantum efficiency of the target process are discussed, including design of the structure, composition and texture of semiconductor photocatalysts and variation of the medium pH and the substrate and photocatalyst concentrations. Some important aspects of the activation and deactivation of sulfide photocatalysts and the evolution of their properties in the course of hydrogen production processes in the presence of various types of electron donors are analyzed. The bibliography includes 276 references.

Micropellets coated with Kollicoat® Smartseal 30D for taste masking in liquid oral dosage forms.

PubMed

Dashevskiy, Andriy; Mohylyuk, Valentyn; Ahmed, Abid Riaz; Kolter, Karl; Guth, Felicitas; Bodmeier, Roland

2017-09-01

The objective of this study was to develop delivery systems for taste masking based on multiparticulates coated with Kollicoat ® Smartseal 30D formulated as liquid oral suspensions. Coating of particles containing bitter drugs with Kollicoat ® Smartseal reduced drug leaching into aqueous medium, especially when increasing pH, therefore can be used for the formulation of liquid dosage forms. Application of an intermediate layer of ion exchange resins between drug layer and coating can further decrease drug leaching into aqueous vehicle that is beneficial in terms of taste masking. Using optimized compositions of liquid vehicles such as addition of sugar alcohols and ion exchange resin, reconstitutable or ready-to-use liquid dosage forms with micropellets can be developed with bitter taste protection after redispersion lasting longer than 3 weeks, which exceeds the usual period of application.

Effect of environmental and cultural conditions on medium pH and explant growth performance of Douglas-fir ( Pseudotsuga menziesii) shoot cultures

PubMed Central

Chen, Chien-Chih; Bates, Rick; Carlson, John

2015-01-01

The medium pH level of plant tissue cultures has been shown to be essential to many aspects of explant development and growth. Sensitivity or tolerance of medium pH change in vitro varies according to specific requirements of individual species. The objectives of this study are to 1) determine medium pH change over time in storage conditions and with presence of explants, 2) evaluate the effects of medium pH change on explant growth performance and 3) assess the effects of adding a pH stabilizer, 2-(N-morpholino)ethanesulfonic acid (MES) that is commonly used in Douglas-fir micropropagation medium. Vegetative buds were collected in the spring before breaking dormancy from juvenile and mature donor trees for conducting these evaluations. Medium, with or without MES, was pre-adjusted to five pH levels before adding MES, agar and autoclaving. Medium pH changes and explant growth parameters were measured at eight different incubation times. Overall, MES provided a more stable medium pH, relative to starting pH values, under both light and dark storage conditions as well as with presence of explants. A general trend of decreasing medium pH over time was found comparing explants from juvenile and mature donor genotypes. Explant height and weight growth increased over time, but differ among explants from juvenile and mature donor genotypes. Our findings suggest that a 21-day subculture practice may best sustain medium freshness, medium pH level and desirable explant growth. PMID:26535110

Molecular-level elucidation of saccharin-assisted rapid dissolution and high supersaturation level of drug from Eudragit® E solid dispersion.

PubMed

Ueda, Keisuke; Kanaya, Harunobu; Higashi, Kenjirou; Yamamoto, Keiji; Moribe, Kunikazu

2018-03-01

In this work, the effect of saccharin (SAC) addition on the dissolution and supersaturation level of phenytoin (PHT)/Eudragit® E (EUD-E) solid dispersion (SD) at neutral pH was examined. The PHT/EUD-E SD showed a much slower dissolution of PHT compared to the PHT/EUD-E/SAC SD. EUD-E formed a gel layer after the dispersion of the PHT/EUD-E SD into an aqueous medium, resulting in a slow dissolution of PHT. Pre-dissolving SAC in the aqueous medium significantly improved the dissolution of the PHT/EUD-E SD. Solid-state 13 C NMR measurements showed an ionic interaction between the tertiary amino group of EUD-E and the amide group of SAC in the EUD-E gel layer. Consequently, the ionized EUD-E could easily dissolve from the gel layer, promoting PHT dissolution. Solution-state 1 H NMR measurements revealed the presence of ionic interactions between SAC and the amino group of EUD-E in the PHT/EUD-E/SAC solution. In contrast, interactions between PHT and the hydrophobic group of EUD-E strongly inhibited the crystallization of the former from its supersaturated solution. The PHT supersaturated solution was formed from the PHT/EUD-E/SAC SD by the fast dissolution of PHT and the strong crystallization inhibition effect of EUD-E after aqueous dissolution. Copyright © 2018 Elsevier B.V. All rights reserved.

An efficient and sensitive fluorescent pH sensor based on amino functional metal-organic frameworks in aqueous environment.

PubMed

Xu, Xiao-Yu; Yan, Bing

2016-04-28

A pH sensor is fabricated via a reaction between an Al(III) salt and 2-aminoterephthalic acid in DMF which leads to a MOF (Al-MIL-101-NH2) with free amino groups. The Al-MIL-101-NH2 samples show good luminescence and an intact structure in aqueous solutions with pH ranging from 4.0 to 7.7. Given its exceptional stability and pH-dependent fluorescence intensity, Al-MIL-101-NH2 has been applied to fluorescent pH sensing. Significantly, in the whole experimental pH range (4.0-7.7), the fluorescence intensity almost increases with increasing pH (R(2) = 0.99688) which can be rationalized using a linear equation: I = 2.33 pH + 26.04. In addition, error analysis and cycling experiments have demonstrated the accuracy and utilizability of the sensor. In practical applications (PBS and lake water), Al-MIL-101-NH2 also manifests its analytical efficiency in pH sensing. And the samples can be easily isolated from an aqueous solution by incorporating Fe3O4 nanoparticles. Moreover, the possible sensing mechanism based on amino protonation is discussed in detail. This work is on of the few cases for integrated pH sensing systems in aqueous solution based on luminescent MOFs.

Corneal epithelial and aqueous humor acidification during in vivo contact lens wear in rabbits.

PubMed

Giasson, C; Bonanno, J A

1994-03-01

Based on contact lens-induced stromal acidification of the cornea, it has been suggested that the corneal epithelial and endothelial cells also become acidotic during contact lens wear. This alleged acidification may have a role in altered cell appearance and metabolism during contact lens wear. This study investigated the effects of anoxia, carbon dioxide retention, and contact lens gas transmissibility on the epithelial and aqueous humor pH in living rabbits. Epithelial intracellular pH (pHi) and aqueous humor pH were fluorophotometrically measured with a pH sensitive-dye (BCECF) during contact lens wear or exposure to various gas mixtures. Polymethylmethacrylate (PMMA) lens wear acidified epithelial cells by preventing CO2 efflux and by inducing hypoxia. Increasing lens oxygen transmissibility decreased epithelial acidification. After initiation of rigid, gas-permeable (RGP) lens wear or CO2-air exposure, pHi dropped transiently and then recovered partially. This recovery of pHi was not observed during anoxia, whether induced by PMMA lens wear or exposure to 100% N2. The aqueous humor also acidified during PMMA lens wear, a phenomenon not observed during RGP lens wear. Changes in aqueous pH were smaller, slower, and delayed when compared to their epithelial counterparts. Hypoxic contact lens wear acidifies the corneal epithelium and aqueous humor. The aqueous humor pH change indicates a probable endothelial acidification during hypoxic contact lens wear; the pH changes are caused by two separate and additive effects, CO2 retention and hypoxic acidosis. Increases in the oxygen transmissibility of the lens decrease the cellular acidosis, which might minimize cellular complications arising from contact lens wear. We estimate that a lens with an oxygen transmissibility (Dk/L) of 300 x 10(-11) (cm/sec)(ml O2/ml x mm Hg) is needed to prevent epithelial pHi changes in the open eye. In contrast, lenses with Dk/L as low as 18 x 10(-9) (cm/sec)(ml O2/ml x mm Hg) can prevent aqueous humor pH changes.

Water-Soluble Pd8L4 Self-assembled Molecular Barrel as an Aqueous Carrier for Hydrophobic Curcumin.

PubMed

Bhat, Imtiyaz Ahmad; Jain, Ruchi; Siddiqui, Mujahuddin M; Saini, Deepak K; Mukherjee, Partha Sarathi

2017-05-01

A tetrafacial water-soluble molecular barrel (1) was synthesized by coordination driven self-assembly of a symmetrical tetrapyridyl donor (L) with a cis-blocked 90° acceptor [cis-(en)Pd(NO 3 ) 2 ] (en = ethane-1,2-diamine). The open barrel structure of (1) was confirmed by single crystal X-ray diffraction. The presence of a hydrophobic cavity with large windows makes it an ideal candidate for encapsulation and carrying hydrophobic drug like curcumin in an aqueous medium. The barrel (1) encapsulates curcumin inside its molecular cavity and protects highly photosensitive curcumin from photodegradation. The photostability of encapsulated curcumin is due to the absorption of a high proportion of the incident photons by the aromatic walls of 1 with a high absorption cross-sectional area, which helps the walls to shield the guest even against sunlight/UV radiations. As compared to free curcumin in water, we noticed a significant increase in solubility as well as cellular uptake of curcumin upon encapsulation inside the water-soluble molecular barrel (1) in aqueous medium. Fluorescence imaging confirmed that curcumin was delivered into HeLa cancer cells by the aqueous barrel (1) with the retention of its potential anticancer activity. While free curcumin is inactive toward cancer cells in aqueous medium at room temperature due to negligible solubility, the determined IC 50 value of ∼14 μM for curcumin in aqueous medium in the presence of the barrel (1) reflects the efficiency of the barrel as a potential curcumin carrier in aqueous medium without any other additives. Thus, two major challenges of increasing the bioavailability and stability of curcumin in aqueous medium even in the presence of UV light have been addressed by using a new supramolecular water-soluble barrel (1) as a drug carrier.

Morphology Tuning of Strontium Tungstate Nanoparticles

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

Joseph, S.; George, T.; George, K. C.

2007-08-22

Strontium tungstate nanocrystals in two different morphologies are successfully synthesized by controlled precipitation in aqueous and in poly vinyl alcohol (PVA) medium. Structural characterizations are carried out by XRD and SEM. The average particle size calculated for the SrWO4 prepared in the two different solvents ranges 20-24 nm. The SEM pictures show that the surface morphologies of the SrWO4 nanoparticles in aqueous medium resemble mushroom and the SrWO4 nanoparticles in PVA medium resemble cauliflower. Investigations on the room temperature luminescent properties of the strontium tungstate nanoparticles prepared in aqueous and PVA medium shows strong emissions around 425 nm.

The influence of Surelease and sodium alginate on the in-vitro release of tamsulosin hydrochloride in pellet dosage form.

PubMed

Kim, Min-Soo; Jun, Seoung Wook; Lee, Sibeum; Lee, Tae Wan; Park, Jeong-Sook; Hwang, Sung-Joo

2005-06-01

The objective of this study was to prepare controlled-release pellets containing 0.2 mg tamsulosin hydrochloride using a pelletizer-equipped piston extruder and double-arm counter-rotating rollers with Surelease and sodium alginate. The release of tamsulosin HCl from pellets coated with the commercial aqueous ethylcellulose dispersion (Surelease) was investigated at different coating loads. In addition, the effect of sodium alginate on drug release was investigated by varying the ratio of sodium alginate to microcrystalline cellulose (MCC). Dissolution studies were first performed in 500 mL simulated gastric fluid (pH 1.2) containing 0.003% (w/w) polysorbate 80 and then in simulated intestinal fluids (pH 7.2). The morphology of pellet surfaces and cross sections were examined by scanning electron microscopy (SEM). Apparently, the spherical pellets were prepared using a pelletizer-equipped piston extruder and double-arm counter-rotating rollers. The release profiles of tamsulosin HCl from Surelease-coated pellets were significantly affected by changing the content of Surelease, the pH of the dissolution medium and the ratio of sodium alginate to MCC. The drug release rates not only decreased with increase in the coating load, but also increased when the pH of the dissolution medium was increased from 1.2 to 7.2 regardless of the sodium alginate-to-MCC ratio. Moreover, the drug release rate at pH 7.2 was gradually increased by increasing the ratio of sodium alginate to MCC. SEM showed smooth surfaces of Surelease-coated pellets. These results suggest that Surelease and sodium alginate would be useful excipients in the preparation of controlled-release pellets with the desired release profiles.

Synthesis, characterization, and photocatalytic application of Pd/ZrO2 and Pt/ZrO2

NASA Astrophysics Data System (ADS)

Saeed, Khalid; Sadiq, Mohammad; Khan, Idrees; Ullah, Saleem; Ali, Nauman; Khan, Adnan

2018-05-01

Zirconia-supported palladium (Pd/ZrO2) and Zirconia-supported platinum (Pt/ZrO2) nanoparticles (NPs) are synthesized from their precursors via impregnation technique. The Pd/ZrO2 and Pt/ZrO2 NPs were analyzed via SEM and EDX, while the study of indigo disulfonate dye degradation was carried out by UV/VIS spectrophotometer. The SEM micrographs illustrated that the Pd and Pt NPs were well placed on ZrO2 surface. The Pd/ZrO2 and Pt/ZrO2 NPs were also employed as photocatalysts for the photodegradation of indigo disulfonate in an aqueous medium under UV-light irradiation. The photodegradation study presented that Pd/ZrO2 and Pt/ZrO2 NPs degraded 96 and 94% of indigo disulfonate in 14 h, respectively. The effect of pH of medium and catalyst dosage and efficiency of recovered Pd/ZrO2 and Pt/ZrO2 NPs on the photocatalytic degradation were also studied. It was also found that the maximum degradation of dye was found at pH 10 (95-97%) and at 0.02 g weight (40.28%).

Fabrication of luminescent CdS nanoparticles on short-peptide-based hydrogel nanofibers: tuning of optoelectronic properties.

PubMed

Palui, Goutam; Nanda, Jayanta; Ray, Sudipta; Banerjee, Arindam

2009-07-13

The pH-induced self-assembly of three synthetic tripeptides in water medium is used to immobilize luminescent CdS nanoparticles. These peptides form a nanofibrillar network structure upon gelation in aqueous medium at basic pH values (pH 11.0-13.0), and the fabrication of CdS nanoparticles on the gel nanofiber confers the luminescent property to these gels. Atomic force microscopy, field-emission scanning electron microscopy, and high-resolution transmission electron microscopy clearly reveal the presence of CdS nanoparticles in a well-defined array on the gel nanofibers. This is a convenient way to make organic nanofiber-inorganic nanoparticle hybrid nanocomposite systems. The size of the CdS nanoparticles remains almost same before and after deposition on the gel nanofiber. Photoluminescence (PL) measurement of the CdS nanoparticles upon deposition on the gel nanofibers shows a significant blue shift in the emission spectrum of the nanoparticles, and there is a considerable change in the PL gap energy of the CdS nanoparticles after immobilization on different gel nanofibrils. This finding suggests that the optoelectronic properties of CdS nanoparticles can be tuned upon deposition on gel nanofibers without changing the size of the nanoparticles.

Retention of ionisable compounds on high-performance liquid chromatography XVII. Estimation of the pH variation of aqueous buffers with the change of the methanol fraction of the mobile phase.

PubMed

Subirats, Xavier; Bosch, Elisabeth; Rosés, Martí

2007-01-05

The use of methanol-aqueous buffer mobile phases in HPLC is a common election when performing chromatographic separations of ionisable analytes. The addition of methanol to the aqueous buffer to prepare such a mobile phase changes the buffer capacity and the pH of the solution. In the present work, the variation of these buffer properties is studied for acetic acid-acetate, phosphoric acid-dihydrogenphosphate-hydrogenphosphate, citric acid-dihydrogencitrate-hydrogencitrate-citrate, and ammonium-ammonia buffers. It is well established that the pH change of the buffers depends on the initial concentration and aqueous pH of the buffer, on the percentage of methanol added, and on the particular buffer used. The proposed equations allow the pH estimation of methanol-water buffered mobile phases up to 80% in volume of organic modifier from initial aqueous buffer pH and buffer concentration (before adding methanol) between 0.001 and 0.01 mol L(-1). From both the estimated pH values of the mobile phase and the estimated pKa of the ionisable analytes, it is possible to predict the degree of ionisation of the analytes and therefore, the interpretation of acid-base analytes behaviour in a particular methanol-water buffered mobile phase.

Enhanced reactivity of nZVI embedded into supermacroporous cryogels for highly efficient Cr(VI) and total Cr removal from aqueous solution.

PubMed

Jia, Zhenzhen; Shu, Yuehong; Huang, Renlong; Liu, Junguang; Liu, Lingling

2018-05-01

Novel supermacroporous PSA-nZVI composites with nanoscale zero-valent iron particles (nZVI) embedded into poly (sodium acrylate) (PSA) cryogels were synthesized through ion exchange followed by in-situ reduction. The magnetic composites were evaluated for material characterizations and their efficiency for Cr(VI) and total Cr removal from aqueous medium in batch experiments. PSA-nZVI composites with high nZVI loading capacity up to 128.70 mg Fe/g PSA were obtained, and the interconnected macroporous structure of PSA cryogel remained unaltered with nZVI uniformly distributed on PSA cryogel as determined by TGA, SEM, TEM, XRD and XPS analyses. PSA-nZVI composites showed faster reaction rate than free nZVI both for Cr(VI) and total Cr removal, suggesting no mass transfer resistance and the enhanced reactivity of nZVI in PSA carrier. PSA-nZVI composites exhibited much more remarkable performance for Cr(VI) and total Cr removal than free nZVI particles in high removal capacity and broad pH application range (pH 4-10). The reaction mechanisms were also elucidated with XPS analyses before and after Cr(VI) reduction reactions. These results demonstrate that PSA cryogel acts as an excellent carrier and shows multiple functions in nZVI particle dispersion, pH buffering and oxidation resistance in addition to immobilizing nZVI particles from release. Copyright © 2018 Elsevier Ltd. All rights reserved.

Relationship between pH and Medium Dissolved Solids in Terms of Growth and Metabolism of Lactobacilli and Saccharomyces cerevisiae during Ethanol Production

PubMed Central

Narendranath, Neelakantam V.; Power, Ronan

2005-01-01

The specific growth rates of four species of lactobacilli decreased linearly with increases in the concentration of dissolved solids (sugars) in liquid growth medium. This was most likely due to the osmotic stress exerted by the sugars on the bacteria. The reduction in growth rates corresponded to decreased lactic acid production. Medium pH was another factor studied. As the medium pH decreased from 5.5 to 4.0, there was a reduction in the specific growth rate of lactobacilli and a corresponding decrease in the lactic acid produced. In contrast, medium pH did not have any significant effect on the specific growth rate of yeast at any particular concentration of dissolved solids in the medium. However, medium pH had a significant (P < 0.001) effect on ethanol production. A medium pH of 5.5 resulted in maximal ethanol production in all media with different concentrations of dissolved solids. When the data were analyzed as a 4 (pH levels) by 4 (concentrations of dissolved solids) factorial experiment, there was no synergistic effect (P > 0.2923) observed between pH of the medium and concentration of dissolved solids of the medium in reducing bacterial growth and metabolism. The data suggest that reduction of initial medium pH to 4.0 for the control of lactobacilli during ethanol production is not a good practice as there is a reduction (P < 0.001) in the ethanol produced by the yeast at pH 4.0. Setting the mash (medium) with ≥30% (wt/vol) dissolved solids at a pH of 5.0 to 5.5 will minimize the effects of bacterial contamination and maximize ethanol production by yeast. PMID:15870306

Comparison of the Kinetic Rate Law Parameters for the Dissolution of Natural and Synthetic Autunite in the Presence of Aqueous Bicarbonate Ions

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

Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.

2013-08-02

Bicarbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, bicarbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous bicarbonate concentration to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate (0.0005-0.003 M) under the pH range of 6-11 and a temperature range of 5-60oC. Consistentmore » with the results of previous investigation, the rate of uranium release exhibited minimal dependency on temperature; but were strongly dependent on pH. Increasing aqueous bicarbonate concentrations afforded comparable increases in the rate of release of uranium. Most notably under low pH conditions the aqueous bicarbonate resulted in up to 370 fold increases in the rate of uranium release in relative to the rate of uranium release in the absence of bicarbonate. However, the effect of aqueous bicarbonate on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release.« less

Biomimetic Oxidation Studies. 11. Alkane Functionalization in Aqueous Solution Utilizing in Situ Formed [Fe(2)O(eta(1)-H(2)O)(eta(1)-OAc)(TPA)(2)](3+), as an MMO Model Precatalyst, Embedded in Surface-Derivatized Silica and Contained in Micelles.

PubMed

Neimann, Karine; Neumann, Ronny; Rabion, Alain; Buchanan, Robert M.; Fish, Richard H.

1999-07-26

The biomimetic, methane monooxygenase enzyme (MMO) precatalyst, [Fe(2)O(eta(1)-H(2)O)(eta(1)-OAc)(TPA)(2)](3+) (TPA = tris[(2-pyridyl)methyl]amine), 1, formed in situ at pH 4.2 from [Fe(2)O(&mgr;-OAc)(TPA)(2)](3+), 2, was embedded in an amorphous silicate surface modified by a combination of hydrophilic poly(ethylene oxide) and hydrophobic poly(propylene oxide). The resulting catalytic assembly was found to be a biomimetic model for the MMO active site within a hydrophobic macroenvironment, allowing alkane functionalization with tert-butyl hydroperoxide (TBHP)/O(2) in an aqueous reaction medium (pH 4.2). For example, cyclohexane was oxidized to a mixture of cyclohexanone, cyclohexanol, and cyclohexyl-tert-butyl peroxide, in a ratio of approximately 3:1:2. The balance between poly(ethylene oxide) and poly(propylene oxide), tethered on the silica surface, was crucial for maximizing the catalytic activity. The silica-based catalytic assembly showed reactivity somewhat higher in comparison to an aqueous micelle system utilizing the surfactant, cetyltrimethylammonium hydrogen sulfate at its critical micelle concentration, in which functionalization of cyclohexane with TBHP/O(2) in the presence of 1 was also studied at pH 4.2 and was found to provide similar products: cyclohexanol, cyclohexanone, and cyclohexyl-tert-butyl peroxide, in a ratio of approximately 2:3:1. Moreover, the mechanism for both the silica-based catalytic assembly and the aqueous micelle system was found to occur via the Haber-Weiss process, in which redox chemistry between 1 and TBHP provides both the t-BuO(*)() and t-BuOO(*)()( )()radicals. The t-BuO(*)()( )()radical initiates the C-H functionalization reaction to form the carbon radical, followed by O(2) trapping, to provide cyclohexyl hydroperoxide, which produces the cyclohexanol and cyclohexanone in the presence of 1, whereas the coupling product emanates from t-BuOO(*)() and cyclohexyl radicals. A discussion concerning both approaches for alkane functionalization in water will be presented.

The use of gamma radiation for removal of pesticides from waste water

NASA Astrophysics Data System (ADS)

Dessouki, A. M.; Aly, H. F.; Sokker, H. H.

1999-01-01

In the present study, a try was made to explain the degradation kinetics due to irradiation of aqueous solutions of some active ingredient pesticides. These pesticides are as follows: one type of triazine herbicide Ametryn and one type of carbamate insecticide (Applaud) and two types of chlorinated organic pesticides, Aldrin and Chlorothalonil. Factors affecting the radiolysis of these pesticides such as the pesticide concentration, irradiation dose, dose rate and pH of the solutions were studied. Ametryn, Applaud, Chlorothalonil and Aldrin insecticides were degraded by γ-radiation and in the case of the chlorinated pesticides hydrochloric acid was detected. The pH effect has proved to vary according to the type of the pesticide and little degradation was observed in allkaline medium, while more degradation of the pesticides in the neutral medium was observed depending on the type of pesticide and on its chemical structure. However, the degradation in the acid medium was even higher. A drop in pH was observed and may be attributed to the degradation of the pesticide molecules to lower molecular weight compounds, such as organic acids. A combined treatment of gamma irradiation and conventional methods was applied and the effect of different additives such as nitrogen and oxygen showed that nitrogen did not enhance the degradation, while an enhancement in the degradation process was observed when oxygen was added. Experiments on the adsorption of these pesticides on certain polymeric materials and on Granular Activated Carbon (GAC), showed that GAC has the highest adsorption capacity. It may be concluded that the radiation degradation followed by adsorption of the toxic pesticide pollutants and their removal from wastewater down to concentrations not exceeding the maximum permissible concentration (MPC), according to international standards, proved to be better than the conventional methods of purification.

Influence of Calcium on Microbial Reduction of Solid Phase Uranium (VI)

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

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M.

2007-06-27

The effect of calcium on microbial reduction of a solid phase U(VI), sodium boltwoodite (NaUO2SiO3OH ∙1.5H2O), was evaluated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. Batch experiments were performed in a non-growth bicarbonate medium with lactate as electron donor at pH 7 buffered with PIPES. Calcium increased both the rate and extent of Na-boltwoodite dissolution by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) revealed that microbial reductionmore » of solid phase U(VI) is a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. The overall rates of microbial reduction of solid phase U(VI) can be described by the coupled rates of dissolution and microbial reduction that were both influenced by calcium. The results demonstrated that dissolved U(VI) concentration during microbial reduction was a complex function of solid phase U(VI) dissolution kinetics, aqueous U(VI) speciation, and microbial activity.« less

A natural macroalgae consortium for biosorption of copper from aqueous solution: Optimization, modeling and design studies.

PubMed

Deniz, Fatih; Ersanli, Elif Tezel

2018-03-21

In this study, the capacity of a natural macroalgae consortium consisting of Chaetomorpha sp., Polysiphonia sp., Ulva sp. and Cystoseira sp. species for the removal of copper ions from aqueous environment was investigated at different operating conditions, such as solution pH, copper ion concentration and contact time. These environmental parameters affecting the biosorption process were optimized on the basis of batch experiments. The experimentally obtained data for the biosorption of copper ions onto the macroalgae-based biosorbent were modeled using the isotherm models of Freundlich, Langmuir, Sips and Dubinin-Radushkevich and the kinetic models of pseudo-first-order, pseudo-second-order, Elovich and Weber and Morris. The pseudo-first-order and Sips equations were the most suitable models to describe the copper biosorption from aqueous solution. The thermodynamic data revealed the feasibility, spontaneity and physical nature of biosorption process. Based on the data of Sips isotherm model, the biosorption capacity of biosorbent for copper ions was calculated as 105.370 mg g -1 under the optimum operating conditions. A single-stage batch biosorption system was developed to predict the real-scale-based copper removal performance of biosorbent. The results of this investigation showed the potential utility of macroalgae consortium for the biosorption of copper ions from aqueous medium.

Topical drug delivery to the eye: dorzolamide.

PubMed

Loftsson, Thorsteinn; Jansook, Phatsawee; Stefánsson, Einar

2012-11-01

Topically applied carbonic anhydrase inhibitors (CAIs) in eye drop solutions are commonly used to treat glaucoma. However, local eye irritation and multiple daily administrations may hamper their clinical usefulness. Aqueous eye drop formulations that improve their topical bioavailability and reduce their eye irritation can improve their clinical efficacy. Earlier studies showed that dorzolamide and closely related CAIs are more effectively delivered into the eye from acidic eye drop solutions than from comparable neutral solutions. Consequently, dorzolamide was marketed as an aqueous pH 5.6 eye drop solution (Trusopt(®) , Merck). Later, it was shown that increasing the pH of the eye drops from pH 5.6 to physiologic pH significantly reduced their local irritation. Earlier attempts to use cyclodextrins (CDs) as ocular penetration enhancers in dorzolamide eye drop solutions failed since; although the CDs were able to enhance the aqueous solubility of dorzolamide, increasing the pH from 5.6 to physiologic pH reduced the ability of the drug to permeate into the eye. Later, it was discovered that formulating the drug as aqueous dorzolamide/γCD eye drop microparticle suspension resulted in significant bioavailability enhancement. The solid dorzolamide/γCD microparticles are mucoadhesive and release dorzolamide into the aqueous tear fluid for extended time period. Consequently, sustained high dorzolamide concentrations in aqueous humour and various eye tissues were observed after single administration of the aqueous dorzolamide/γCD eye drop microsuspension. The microsuspension has a potential of being developed into a once-a-day eye drop product. This article reviews the physicochemical properties of dorzolamide, its permeation characteristics and topical bioavailability. © 2012 The Authors. Acta Ophthalmologica © 2012 Acta Ophthalmologica Scandinavica Foundation.

Heat aggregation studies of phycobilisomes, ferritin, insulin, and immunoglobulin by dynamic light scattering.

PubMed

Singh, B P; Bohidar, H B; Chopra, S

1991-10-15

Dynamic laser light scattering studies on the heat aggregation behavior of phycobilisomes (PBS), ferritin, insulin, and immunoglobulin (IgG) in dilute aqueous solutions has been reported. Except for PBS, results are reported for heat aggregation trends in these proteins for three different pH environments (4.0, 7.5, 9.1). For PBS, studies were performed only in the neutral buffer medium (pH 7.5). The experiments were performed in the very dilute concentration regime (between 0.23 and 1.8 gL-1). For all these samples heat aggregation and dissociation trends were found to be linear with temperature. Upon temperature reversal (self-cooling), hysteresis-like behavior observed in insulin was found to be predominantly large at pH 7.5. PBS, ferritin, and IgG showed no such behavior at any of three pH values, and retraced their path of aggregation while dissociating on temperature reversal. Heat aggregation and dissociation processes in ferritin were found to be independent of pH. The IgG samples showed smooth aggregation tendency only up to 35 degrees C in the buffer media pH 4.0 and 9.1, whereas for pH 7.0 the same could be observed until 60 degrees C. Low polydispersity in the correlation spectra was observed in case of all these samples.

A combination of grapefruit seed extract and concentrated cranberry juice as a potential antimicrobial preservative for the improvement of microbiological stability of hypromellose gel.

PubMed

Bernatoniene, Jurga; Keraitė, Rasa; Masteiková, Ruta; Pavilonis, Alvydas; Savickas, Arūnas

2013-10-01

Aqueous hypromellose gels are not microbiologically stable - they show signs of microorganism growth during storage. To extend the shelf-life of the gels, antimicrobial preservatives are needed. Some substances of plant origin are known for their antimicrobial properties, and thus they may be used as an alternative to synthetic preservatives. Therefore, the aim of this study was to evaluate the microbiological stability of aqueous hypromellose gel and the effectiveness of natural substances - grapefruit seed extract (GSE), concentrated cranberry juice, and a combination thereof - on the antimicrobial protection of the gel. The evaluation of the antimicrobial activity of GSE and cranberry juice showed that their antimicrobial effects differed. Both cranberry juice and GSE inhibited the growth of the standard gram-positive and gram-negative bacteria, but the effect of GSE was significantly stronger. Candida albicans was sensitive only to GSE. For this reason, in order to affect all the microorganisms studied, either a combination of 0.7% GSE and 10% cranberry juice, or 5% GSE alone may be used. The combination of GSE and cranberry juice was effective only in acidic medium (pH being 2.5-5), while the antimicrobial effect of GSE was not dependent on the pH value.

Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

NASA Astrophysics Data System (ADS)

Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

2018-02-01

The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.

Simple Response Surface Methodology: Investigation on Advance Photocatalytic Oxidation of 4-Chlorophenoxyacetic Acid Using UV-Active ZnO Photocatalyst.

PubMed

Lee, Kian Mun; Hamid, Sharifah Bee Abd

2015-01-19

The performance of advance photocatalytic degradation of 4-chlorophenoxyacetic acid (4-CPA) strongly depends on photocatalyst dosage, initial concentration and initial pH. In the present study, a simple response surface methodology (RSM) was applied to investigate the interaction between these three independent factors. Thus, the photocatalytic degradation of 4-CPA in aqueous medium assisted by ultraviolet-active ZnO photocatalyst was systematically investigated. This study aims to determine the optimum processing parameters to maximize 4-CPA degradation. Based on the results obtained, it was found that a maximum of 91% of 4-CPA was successfully degraded under optimal conditions (0.02 g ZnO dosage, 20.00 mg/L of 4-CPA and pH 7.71). All the experimental data showed good agreement with the predicted results obtained from statistical analysis.

Indirect Manganese Removal by Stenotrophomonas sp. and Lysinibacillus sp. Isolated from Brazilian Mine Water.

PubMed

Barboza, Natália Rocha; Amorim, Soraya Sander; Santos, Pricila Almeida; Reis, Flávia Donária; Cordeiro, Mônica Mendes; Guerra-Sá, Renata; Leão, Versiane Albis

2015-01-01

Manganese is a contaminant in the wastewaters produced by Brazilian mining operations, and the removal of the metal is notoriously difficult because of the high stability of the Mn(II) ion in aqueous solutions. To explore a biological approach for removing excessive amounts of aqueous Mn(II), we investigated the potential of Mn(II) oxidation by both consortium and bacterial isolates from a Brazilian manganese mine. A bacterial consortium was able to remove 99.7% of the Mn(II). A phylogenetic analysis of isolates demonstrated that the predominant microorganisms were members of Stenotrophomonas, Bacillus, and Lysinibacillus genera. Mn(II) removal rates between 58.5% and 70.9% were observed for Bacillus sp. and Stenotrophomonas sp. while the Lysinibacillus isolate 13P removes 82.7%. The catalytic oxidation of Mn(II) mediated by multicopper oxidase was not properly detected; however, in all of the experiments, a significant increase in the pH of the culture medium was detected. No aggregates inside the cells grown for a week were found by electronic microscopy. Nevertheless, an energy-dispersive X-ray spectroscopy of the isolates revealed the presence of manganese in Stenotrophomonas sp. and Lysinibacillus sp. grown in K medium. These results suggest that members of Stenotrophomonas and Lysinibacillus genera were able to remove Mn(II) by a nonenzymatic pathway.

Chlorophyll degradation in aqueous mediums induced by light and UV-B irradiation: An UHPLC-ESI-MS study

NASA Astrophysics Data System (ADS)

Petrović, Sanja; Zvezdanović, Jelena; Marković, Dejan

2017-12-01

Irreversible chlorophyll degradation induced by continuous white light illumination and UV-B irradiation in the aqueous mediums (with 10%, 30% and 50% of methanol) was investigated using the ultrahigh liquid chromatography coupled with diode array and electrospray ionization mass spectrometry detectors (UHPLC-DAD-ESIMS). The degradation was governed by energy input of photons: higher energy of UV-B irradiation induced faster chlorophyll degradation and accordingly faster products formation in comparison to the white light treatment. Main light- or/and UV-B-induced products of chlorophyll in the aqueous mediums were hydroxy-pheophytin a, pheophytin a and hydroxy-lactone-pheophytin a, accompanied with the corresponding epimers. Chlorophylls aggregation dominant in the aqueous medium with the highest methanol content (50%) play a protective role against the UV-B radiation and white light illumination.

Online kinetic studies on intermediates of laccase-catalyzed reaction in reversed micelle.

PubMed

Liu, Zhi-Hong; Shao, Mei; Cai, Ru-Xiu; Shen, Ping

2006-02-01

Using water/AOT/n-octane reversed micelle as the medium, the optical signal of the reactive intermediate of laccase-catalyzed oxidation of o-phenylenediamine, which was indetectable in aqueous solutions, was successfully captured. Thus online kinetic studies of the intermediate were accomplished. Two-way kinetic spectral data were acquired with stopped-flow technique. By resolving the data with global analysis software, both the kinetic curves and the absorption spectra of the components involved in the reaction process were simultaneously obtained. The whole reaction in the reversed micelle was proved to be composed of two successive steps, an enzymatic generation of the intermediate and a following nonenzymatic decay of the intermediate. A consecutive first-order kinetic model of the whole reaction was confirmed. The influences of microenvironmental factors of the medium (such as the pH value of the water pool and the water/AOT ratio) on the detection of the intermediate were also investigated.

Release profile and stability evaluation of optimized chitosan/alginate nanoparticles as EGFR antisense vector

PubMed Central

Azizi, Ebrahim; Namazi, Alireza; Haririan, Ismaeil; Fouladdel, Shamileh; Khoshayand, Mohammad R; Shotorbani, Parisa Y; Nomani, Alireza; Gazori, Taraneh

2010-01-01

Chitosan/alginate nanoparticles which had been optimized in our previous study using two different N/P ratios were chosen and their ability to release epidermal growth factor receptor (EGFR) antisense was investigated. In addition, the stability of these nanoparticles in aqueous medium and after freeze-drying was investigated. In the case of both N/P ratios (5, 25), nanoparticles started releasing EGFR antisense as soon as they were exposed to the medium and the release lasted for approximately 50 hours. Nanoparticle size, shape, zeta potential, and release profile did not show any significant change after the freeze-drying process (followed by reswelling). The nanoparticles were reswellable again after freeze-drying in phosphate buffer with a pH of 7.4 over a period of six hours. Agarose gel electrophoresis of the nanoparticles with the two different N/P ratios showed that these nanoparticles could protect EGFR antisense molecules for six hours. PMID:20957167

Preparation and characterization of fast dissolving flurbiprofen and esomeprazole solid dispersion using spray drying technique.

PubMed

Pradhan, Roshan; Tran, Tuan Hiep; Kim, Sung Yub; Woo, Kyu Bong; Choi, Yong Joo; Choi, Han-Gon; Yong, Chul Soon; Kim, Jong Oh

2016-04-11

We aimed to develop an immediate-release flurbiprofen (FLU) and esomeprazole (ESO) combination formulation with enhanced gastric aqueous solubility and dissolution rate. Aqueous solubility can be enhanced by formulating solid dispersions (SDs) with a polyvinylpyrrolidone (PVP)-K30 hydrophilic carrier, using spray-drying technique. Aqueous and gastric pH dissolution can be achieved by macro-environmental pH modulation using sodium bicarbonate (NaHCO3) and magnesium hydroxide (Mg(OH)2) as the alkaline buffer. FLU/ESO-loaded SDs (FLU/ESO-SDs) significantly improved aqueous solubility of both drugs, compared to each drug powder. Dissolution studies in gastric pH and water were compared with the microenvironmental pH modulated formulations. The optimized FLU/ESO-SD powder formulation consisted of FLU/ESO/PVP-K30/sodium carbonate (Na2CO3) in a weight ratio 1:0.22:1.5:0.3, filled in the inner capsule. The outer capsule consisted of NaHCO3 and Mg(OH)2, which created the macro-environmental pH modulation. Increased aqueous and gastric pH dissolution of FLU and ESO from the SD was attributed to the alkaline buffer effects and most importantly, to drug transformation from crystalline to amorphous SD powder, clearly revealed by scanning electron microscopy, differential scanning calorimetry, and powder X-ray diffraction studies. Thus, the combined FLU and ESO SD powder can be effectively delivered as an immediate-release formulation using the macro-environmental pH modulation concept. Copyright © 2016. Published by Elsevier B.V.

MONITORING THE SPECIATION OF AQUEOUS FREE CHLORINE FROM PH 1-12 WITH RAMAN SPECTROSCOPY TO DETERMINE THE IDENTITY OF THE POTENT LOW-PH OXIDANT

EPA Science Inventory

The speciation of aqueous free chlorine above pH 5 is a well-understood equilibrium of H2O + HOCl (equilibrium) OCl- + H3O+ with a pKa of 7.5. However, the identity of another very potent oxidant present at low pH (below 5) has been attributed by some researchers to Cl2 (aq), a...

Chapter A6. Section 6.4. pH

USGS Publications Warehouse

Wilde, Franceska D.; Busenberg, Eurybiades; Radtke, Dean B.

2006-01-01

Measurement of pH is critical to the understanding of the viability and vulnerability of environmental waters and is considered a master variable in determining the aqueous geochemistry of an aqueous system. pH is a measure that represents the hydrogen-ion concentration (activity) of a solution. This section of the National Field Manual (NFM) describes U.S. Geological Survey (USGS) guidance and protocols for measurement of pH in ground and surface waters.

Porous polymer media

DOEpatents

Shepodd, Timothy J.

2002-01-01

Highly crosslinked monolithic porous polymer materials for chromatographic applications. By using solvent compositions that provide not only for polymerization of acrylate monomers in such a fashion that a porous polymer network is formed prior to phase separation but also for exchanging the polymerization solvent for a running buffer using electroosmotic flow, the need for high pressure purging is eliminated. The polymer materials have been shown to be an effective capillary electrochromatographic separations medium at lower field strengths than conventional polymer media. Further, because of their highly crosslinked nature these polymer materials are structurally stable in a wide range of organic and aqueous solvents and over a pH range of 2-12.

Direct observation and determination of the mechanisms governing mobility of asbestos in porous media

NASA Astrophysics Data System (ADS)

Seiphoori, A.; Ortiz, C. P.; Jerolmack, D. J.

2017-12-01

Transport of asbestos through soil by groundwater is typically considered to be negligible. There are indications, however, that under some conditions of pore-water/soil chemistry asbestos may become mobile, implying that buried contaminants could migrate from a disposal site and surface elsewhere. Shape, size and surface charge may influence the physical and chemical interactions of colloids with the soil matrix, and asbestos consists of elongated particles with different size and unique surface charge properties. Although chemical factors such as pH and ionic strength of pore water may affect the transport properties, the presence of dissolved organic carbon (DOC) has been identified to remarkably enhance the mobility of colloids including asbestos. To date, there is no explanation for how the presence of DOC may facilitate the mobilization of asbestos in soil - mainly because the soil medium has been treated as a black box without the possibility of observing particles within the matrix. Here, we investigated the mobility of chrysotile asbestos particles ( 10 um long) in porous media by developing a flow cell with an optically-transparent porous medium composed of granules of a refractive-index matched material. This enabled us to observe and track the particles within the water-saturated porous medium using in situ microscopy. The aqueous suspension of asbestos fibers was passed through this artificial soil, while the physical and chemical interaction of asbestos particles with the medium and their pore-scale distribution were analyzed. We studied the effects of changing solution chemistry (e.g., ionic strength, pH, and DOC content) on transport, attachment and aggregation of chrysotile particles. Experiments revealed a novel mechanism where the DOC-associated nanoparticles attach to chrysotile fibers by an electrostatic attraction, which facilitates their mobilization through the porous medium while modulating aggregation among fibers. Although pH and ionic strength also influenced aggregation and the attachment rate of particles to the substrate, the effect of DOC was more pronounced. This work may lead to enhanced predictions for the fate and transport of asbestos (as well as other contaminants) in the environment, and has implications for the mobility of asbestos particles in the human body.

Adsorptive removal of phthalate ester (Di-ethyl phthalate) from aqueous phase by activated carbon: a kinetic study.

PubMed

Venkata Mohan, S; Shailaja, S; Rama Krishna, M; Sarma, P N

2007-07-19

Adsorptive studies were carried out on Di-ethyl phthalate (DEP) removal from aqueous phase onto activated carbon. Batch sorption studies were performed and the results revealed that activated carbon demonstrated ability to adsorb DEP. Influence of varying experimental conditions such as DEP concentration, pH of aqueous solution, and dosage of adsorbent were investigated on the adsorption process. Sorption interaction of DEP onto activated carbon obeyed the pseudo second order rate equation. Experimental data showed good fit with both the Langmuir and Freundlich adsorption isotherm models. DEP sorption was found to be dependent on the aqueous phase pH and the uptake was observed to be greater at acidic pH.

The effect of environmental pH on polymeric transfection efficiency.

PubMed

Kang, Han Chang; Samsonova, Olga; Kang, Sun-Woong; Bae, You Han

2012-02-01

Although polymers, polyplexes, and cells are exposed to various extracellular and intracellular pH environments during polyplex preparation and polymeric transfection, the impact of environmental pH on polymeric transfection has not yet been investigated. This study aims to understand the influence of environmental pH on polymeric transfection by modulating the pH of the transfection medium or the culture medium. Changes in the extracellular pH affected polymeric transfection by way of complex factors such as pH-induced changes in polymer characteristics (e.g., proton buffering capacity and ionization), polyplex characteristics (e.g., size, surface charge, and decomplexation), and cellular characteristics (e.g., cellular uptake, cell cycle phases, and intracellular pH environment). Notably, acidic medium delayed endocytosis, endosomal acidification, cytosolic release, and decomplexation of polyplexes, thereby negatively affecting gene expression. However, acidic medium inhibited mitosis and reduced dilution of gene expression, resulting in increased transfection efficiency. Compared to pH 7.4 medium, acidic transfection medium reduced gene expression 1.6-7.7-fold whereas acidic culture medium enhanced transfection efficiency 2.1-2.6-fold. Polymeric transfection was affected more by the culture medium than by the transfection medium. Understanding the effects of extracellular pH during polymeric transfection may stimulate new strategies for determining effective and safe polymeric gene carriers. Copyright © 2011 Elsevier Ltd. All rights reserved.

Self-nanoemulsifying drug delivery system for enhanced bioavailability and improved hepatoprotective activity of biphenyl dimethyl dicarboxylate.

PubMed

El-Laithy, Hanan M

2008-07-01

Biphenyl Dimethyl Dicarboxylate (BDD) is insoluble in aqueous solution and the bioavailability after oral administration is low. Self-nanoemulsifying drug delivery system (SNEDDS) containing BDD has been successfully prepared using carefully selected ingredients which are less affected by pH and ionic strength changes to improve its bioavailability. SNEDDS is an isotropic mixture of lipid, surfactant, and cosurfactant which are spontaneously emulsified in aqueous medium under gentle digestive motility in the gastrointestinal tract. Pseudo ternary phase diagrams composed of various excipients were plotted to identify self -nano -emulsifying area. Droplet size changes upon dilution with aqueous media and in vitro release of BDD from SNEDDS in 0.1N HCl and phosphate buffer (pH 7.4) were studied and compared with commercial chinese pilules and Pennel capsules. The hepatoprotective activity upon oral administration of SNEDDS against carbon tetrachloride-induced oxidative stress in albino rats was assessed by measuring biochemical parameters like serum glutamic oxalacetate transaminase (SGOT), serum glutamic pyruvate transaminase (SGPT) and lactate dehydrogenase (LDH). Results showed that using a proper ratio of Tween 80 to Transcutol as surfactant and co-surfactant respectively and Miglyol 812 as oil to surfactants mixture resulted in production of infinitely diluted formulations in nano droplet size range. BDD self nano emulsified formula composed of 20% Miglyol 812, 60% Tween 80 and 20% Transcutol released 99% of the drug very rapidly within 10-15 minutes regardless of the pH condition. The oral absorption and bioavailability of BDD self nano emulsified formula in albino rats were significantly enhanced (P<0.01) with an average improvement of 1.7 and 6-folds that of commercial chinese pilules and Pennel capsules respectively. This improvement was also confirmed histopathologically in chemically injured rats and by the significant decrease in elevated liver enzymes level.

Monitoring the Rate Solvolytic Decomposition of Benzenediazonium Tetrafluoroborate in Aqueous Media Using a pH Electrode

ERIC Educational Resources Information Center

Wiseman, Floyd L.

2005-01-01

A lab rotary experiment using the pH measurements of an aqueous solution to monitor the course of a solvolytic reaction was conducted. This experiment allowed the students to gain experience in taking precise pH measurement, to use nonlinear analysis techniques for analyzing kinetic data and to use the Arrhenius equation for determination of…

Tertiary-amine-containing thermo- and pH-sensitive hydrophilic ABA triblock copolymers: effect of different tertiary amines on thermally induced sol-gel transitions.

PubMed

Henn, Daniel M; Wright, Roger A E; Woodcock, Jeremiah W; Hu, Bin; Zhao, Bin

2014-03-11

This Article reports on the synthesis of a series of well-defined, tertiary-amine-containing ABA triblock copolymers, composed of a poly(ethylene oxide) (PEO) central block and thermo- and pH-sensitive outer blocks, and the study of the effect of different tertiary amines on thermally induced sol-gel transition temperatures (T(sol-gel)) of their 10 wt % aqueous solutions. The doubly responsive ABA triblock copolymers were prepared from a difunctional PEO macroinitiator by atom transfer radical polymerization of methoxydi(ethylene glycol) methacrylate and ethoxydi(ethylene glycol) methacrylate at a feed molar ratio of 30:70 with ∼5 mol % of either N,N-diethylaminoethyl methacrylate (DEAEMA), N,N-diisopropylaminoethyl methacrylate, or N,N-di(n-butyl)aminoethyl methacrylate. The chain lengths of thermosensitive outer blocks and the molar contents of tertiary amines were very similar for all copolymers. Using rheological measurements, we determined the pH dependences of T(sol-gel) of 10 wt % aqueous solutions of these copolymers in a phosphate buffer. The T(sol-gel) versus pH curves of all polymers exhibited a sigmoidal shape. The T(sol-gel) increased with decreasing pH; the changes were small on both high and low pH sides. At a specific pH, the T(sol-gel) decreased with increasing the hydrophobicity of the tertiary amine, and upon decreasing pH the onset pH value for the T(sol-gel) to begin to increase noticeably was lower for the more hydrophobic tertiary amine-containing copolymer. In addition, we studied the effect of different tertiary amines on the release behavior of FITC-dextran from 10 wt % micellar gels in an acidic medium at 37 and 27 °C. The release profiles for three studied hydrogels at 37 °C were essentially the same, suggesting that the release was dominated by the diffusion of FITC-dextran. At 27 °C, the release was significantly faster for the DEAEMA-containing copolymer, indicating that both diffusion and gel dissolution contributed to the release at this temperature.

Modeling the pH and temperature dependence of aqueousphase hydroxyl radical reaction rate constants of organic micropollutants using QSPR approach.

PubMed

Gupta, Shikha; Basant, Nikita

2017-11-01

Designing of advanced oxidation process (AOP) requires knowledge of the aqueous phase hydroxyl radical ( ● OH) reactions rate constants (k OH ), which are strictly dependent upon the pH and temperature of the medium. In this study, pH- and temperature-dependent quantitative structure-property relationship (QSPR) models based on the decision tree boost (DTB) approach were developed for the prediction of k OH of diverse organic contaminants following the OECD guidelines. Experimental datasets (n = 958) pertaining to the k OH values of aqueous phase reactions at different pH (n = 470; 1.4 × 10 6 to 3.8 × 10 10  M -1  s -1 ) and temperature (n = 171; 1.0 × 10 7 to 2.6 × 10 10  M -1  s -1 ) were considered and molecular descriptors of the compounds were derived. The Sanderson scale electronegativity, topological polar surface area, number of double bonds, and halogen atoms in the molecule, in addition to the pH and temperature, were found to be the relevant predictors. The models were validated and their external predictivity was evaluated in terms of most stringent criteria parameters derived on the test data. High values of the coefficient of determination (R 2 ) and small root mean squared error (RMSE) in respective training (> 0.972, ≤ 0.12) and test (≥ 0.936, ≤ 0.16) sets indicated high generalization and predictivity of the developed QSPR model. Other statistical parameters derived from the training and test data also supported the robustness of the models and their suitability for screening new chemicals within the defined chemical space. The developed QSPR models provide a valuable tool for predicting the ● OH reaction rate constants of emerging new water contaminants for their susceptibility to AOPs.

Risk management and statistical multivariate analysis approach for design and optimization of satranidazole nanoparticles.

PubMed

Dhat, Shalaka; Pund, Swati; Kokare, Chandrakant; Sharma, Pankaj; Shrivastava, Birendra

2017-01-01

Rapidly evolving technical and regulatory landscapes of the pharmaceutical product development necessitates risk management with application of multivariate analysis using Process Analytical Technology (PAT) and Quality by Design (QbD). Poorly soluble, high dose drug, Satranidazole was optimally nanoprecipitated (SAT-NP) employing principles of Formulation by Design (FbD). The potential risk factors influencing the critical quality attributes (CQA) of SAT-NP were identified using Ishikawa diagram. Plackett-Burman screening design was adopted to screen the eight critical formulation and process parameters influencing the mean particle size, zeta potential and dissolution efficiency at 30min in pH7.4 dissolution medium. Pareto charts (individual and cumulative) revealed three most critical factors influencing CQA of SAT-NP viz. aqueous stabilizer (Polyvinyl alcohol), release modifier (Eudragit® S 100) and volume of aqueous phase. The levels of these three critical formulation attributes were optimized by FbD within established design space to minimize mean particle size, poly dispersity index, and maximize encapsulation efficiency of SAT-NP. Lenth's and Bayesian analysis along with mathematical modeling of results allowed identification and quantification of critical formulation attributes significantly active on the selected CQAs. The optimized SAT-NP exhibited mean particle size; 216nm, polydispersity index; 0.250, zeta potential; -3.75mV and encapsulation efficiency; 78.3%. The product was lyophilized using mannitol to form readily redispersible powder. X-ray diffraction analysis confirmed the conversion of crystalline SAT to amorphous form. In vitro release of SAT-NP in gradually pH changing media showed <20% release in pH1.2 and pH6.8 in 5h, while, complete release (>95%) in pH7.4 in next 3h, indicative of burst release after a lag time. This investigation demonstrated effective application of risk management and QbD tools in developing site-specific release SAT-NP by nanoprecipitation. Copyright © 2016 Elsevier B.V. All rights reserved.

Voltammetric studies of hemoglobin-coated polystyrene latex bead films on pyrolytic graphite electrodes.

PubMed

Sun, Hong; Hu, Naifei

2004-08-01

A novel hemoglobin (Hb)-coated polystyrene (PS) latex bead film was deposited on pyrolytic graphite (PG) electrode surface. In the first step, positively charged Hb molecules in pH 5.0 buffers were adsorbed on the surface of negatively charged, 500 nm diameter PS latex beads bearing sulfate groups by electrostatic interaction. The aqueous dispersion of Hb-coated PS particles was then deposited on the surface of PG electrodes and, after evaporation of the solvent, Hb-PS films were formed. The Hb-PS film electrodes exhibited a pair of well-defined, quasi-reversible cyclic voltammetric (CV) peaks at about -0.36 V vs. SCE in pH 7.0 buffers, characteristic of Hb heme Fe(III)/Fe(II) redox couples. Positions of Soret absorption band of Hb-PS films suggest that Hb retains its near-native structure in the films in its dry form and in solution at medium pH. The Hb in PS films was also acted as a catalyst to catalyze electrochemical reduction of various substrates such as trichloroacetic acid (TCA), nitrite, oxygen and hydrogen peroxide.

Biosorption characteristics of Uranium (VI) from aqueous solution by pollen pini.

PubMed

Wang, Feihong; Tan, Lichao; Liu, Qi; Li, Rumin; Li, Zhanshuang; Zhang, Hongsen; Hu, Songxia; Liu, Lianhe; Wang, Jun

2015-12-01

Uranium biosorption from aqueous solutions by pollen pini (Pinus massoniana pollen) was studied in a bath system. The biosorbent was characterized by Fourier-transform infrared spectroscopy and scanning electron microscope. The influences of pH, contact time and initial uranium concentration at room temperature were investigated and the experimental curves were obtained. The pollen pini exhibited the highest uranium sorption capacity at pH 5.0 after 2 h contact. At pH 2.5 pollen pini also exhibited a good uranium loading capacity (>15%). Therefore biosorption characteristics of uranium from aqueous solution onto pollen pini were examined at pH 2.5 as well. The kinetics followed a pseudo-second-order rate equation and adsorption process was well fitted with the Freundlich isotherm at both pH. The adsorption of uranium by the biosorbent was confirmed by energy dispersive spectroscopy. The present study suggested that pollen pini could be a suitable biosorbent for biosorption uranium (VI) from aqueous solution in a fast, low cost and convenient approach. Copyright © 2015 Elsevier Ltd. All rights reserved.

A reversible fluorescent-colorimetric imino-pyridyl bis-Schiff base sensor for expeditious detection of Al(3+) and HSO3(-) in aqueous media.

PubMed

Ghorai, Anupam; Mondal, Jahangir; Chandra, Rukmani; Patra, Goutam K

2015-08-07

A reversible fluorescent-colorimetric imino-pyridyl bis-Schiff base receptor (N(1)E,N(4)E)-N(1),N(4)-bis(pyridine-4-ylmethylene)benzene-1,4-diamine for the detection of both Al(3+) and HSO3(-) in aqueous medium has been developed. Receptor exhibits an excellent selective fluorescent-colorimetric response toward Al(3+). The sensitivity of the fluorescent based assay (0.903 μM) for Al(3+) is far below the limit recommended in the World Health Organization (WHO) guidelines for drinking water (7.41 μM). From (1)H NMR data, the Job plot and the ESI-MS spectrum, 1 : 2 stoichiometric complexation between and Al(3+) has been established. Receptor shows remarkable detection ability in a wide pH range of 4-11 and was successfully utilised in the determination of Al(3+) in aqueous solution of bovine serum albumin protein, and of HSO3(-) in real food samples. Moreover, shows a highly selective colorimetric response to HSO3(-) by changing its colour from yellow to colorless immediately without any interference from other anions.

Aqueous process for recovering sulfur from hydrogen sulfide-bearing gas

DOEpatents

Basu, Arunabha

2015-05-05

A process for recovering sulfur from a hydrogen sulfide-bearing gas utilizes an aqueous reaction medium, a temperature of about 110-150.degree. C., and a high enough pressure to maintain the aqueous reaction medium in a liquid state. The process reduces material and equipment costs and addresses the environmental disadvantages associated with known processes that rely on high boiling point organic solvents.

Low Medium pH Value Enhances Anthocyanin Accumulation in Malus Crabapple Leaves

PubMed Central

Tian, Ji; Jin, Kaina; Yao, Yuncong

2014-01-01

Anthocyanin is a critical factor involved in coloration of plant tissues, but the mechanism how medium pH values affect anthocyanin accumulation in woody plants is unknown. We analyzed anthocyanin composition and the expression of elements encoding anthocyanin and flavonols biosynthesis underlying different medium pH values by using three different leave color type cultivars. HPLC analysis demonstrated that high medium pH values treatment induced a dramatic decrease in the concentration of cyaniding in crabapple leaves. Conversely, the high medium pH values induced up-regulation of the content of flavones and flavonols, suggesting that low pH treatment-induced anthocyanin accumulation. Quantitative real time PCR experiment showed the expression level of anthocyanidin synthase (McANS) and uridine diphosphate glucose flavonoid 3-O-glucosyltransferase (McUFGT) was up-regulated by low pH values treatment, and high medium pH value treatment up-regulate the transcription level of flavonol synthase (McFLS). Meanwhile, several MYB TFs have been suggested in the regulation of pH responses. These results strongly indicate that the low pH treatment-induced anthocyanin accumulation is mediated by the variation of mRNA transcription of the anthocyanin biosynthetic genes. PMID:24914811

Effect of Acidity of a Medium on Riboflavin Photodestruction

NASA Astrophysics Data System (ADS)

Astanov, S. Kh.; Turdiev, M.; Sharipov, M. Z.; Kurtaliev, É. N.; Nizomov, N. N.

2016-03-01

Effect of acidity of a medium on the spectroscopic characteristics of riboflavin aqueous solutions is investigated by the method of fluorescent and absorption spectroscopy. Significant deformation of the electronic spectra of riboflavin aqueous solutions irradiated with unfiltered light of a PRK-2 lamp is observed. It is established that riboflavin photostability in an acid medium is about twice as much as the photostability in a neutral medium, which is caused by the formation of a protonated species.

Incorporation of transmembrane hydroxide transport into the chemiosmotic theory.

PubMed

de Grey, A D

1999-10-01

A cornerstone of textbook bioenergetics is that oxidative ATP synthesis in mitochondria requires, in normal conditions of internal and external pH, a potential difference (delta psi) of well over 100 mV between the aqueous compartments that the energy-transducing membrane separates. Measurements of delta psi inferred from diffusion of membrane-permeant ions confirm this, but those using microelectrodes consistently find no such delta psi--a result ostensibly irreconcilable with the chemiosmotic theory. Transmembrane hydroxide transport necessarily accompanies mitochondrial ATP synthesis, due to the action of several carrier proteins; this nullifies some of the proton transport by the respiratory chain. Here, it is proposed that these carriers' structure causes the path of this "lost" proton flow to include a component perpendicular to the membrane but within the aqueous phases, so maintaining a steady-state proton-motive force between the water at each membrane surface and in the adjacent bulk medium. The conflicting measurements of delta psi are shown to be consistent with the response of this system to its chemical environment.

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 2. Light Lanthanides (Ce-Eu)

NASA Astrophysics Data System (ADS)

Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen

2015-03-01

This is the second part of the volume devoted to the evaluation of experimental solubility data for rare earth metal (REM) fluorides in water as well as in aqueous ternary and multicomponent systems. Fluorides of Ce, Pr, Nd, Pm, Sm, and Eu (so-called light lanthanides), as the main solutes, are covered in the present part, which has thorough coverage of the experimental literature through the end of 2012. The experimentally unknown solubility value for PmF3 in water was predicted by an interpolation of the solubility values for NdF3 and SmF3 at 298 K. General features of the systems, such as the nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, pH, mixed solvent medium on the solubility, quality of the solubility results, and solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.

Growth and maintenance of an embryogenic cell culture of daylily (Hemerocallis) on hormone-free medium

NASA Technical Reports Server (NTRS)

Smith, D. L.; Krikorian, A. D.

1991-01-01

Callus cultures of the diploid daylily (Hemerocallis) clone Autumn Blaze' were initiated and maintained in hormone-containing nutrient medium. At various times (from 6 weeks to 1 year) after being initiated, hormone-derived cultures were evaluated for their ability to be maintained and to multiply on hormone-free medium at low pH (between pH 4 and 4.5). Cultures had to be exposed to hormone-containing medium for at least 12 weeks before they could be maintained on hormone-free medium at low pH. The transition to maintainability on low pH hormone-free medium included the production of many aberrant embryonal forms ( neomorphs'). However, all hormone-derived cultures tested consisted entirely of preglobular stage proembryos (PGSPs) after 12-24 weeks on low pH hormone-free medium. PGSP cultures have been maintained and multiplied as such for over 1 year on low pH hormone-free medium. PGSPs continue their development into various somatic embryo stages when cultured on hormone-free medium buffered at pH 5.8. The production of well-formed somatic embryos was greatly enhanced when PGSPs were plated on activated charcoal impregnated filter papers that were placed on top of the agar surface. The gross morphology and histology of the PGSPs and stages of somatic embryo development are presented. The work shows that the ability of hormone-free medium at low pH to permit PGSP multiplication without development into later stages of embryo development is not restricted to carrot.

Determination of physicochemical properties and degradation kinetics of triamcinolone acetonide palmitate in vitro.

PubMed

Peng, Cuilian; Liu, Cong; Tang, Xing

2010-12-01

Triamcinolone acetonide palmitate (TAP) is a lipophilic prodrug of triamcinolone acetonide (TAA) to improve the insoluble TAA physicochemical properties for the preparation of emulsions. This investigation has focused on the preformulation study of TAP, including its physicochemical properties and hydrolysis kinetics in vitro. The solubility of TAP in medium-chain triglyceride is about twice greater than that in soybean oil (long-chain triglyceride) (19.17 versus 9.55 mg/g) at 25°C, and in all investigated cases, lecithin (80, 160, and 240 mg/g) as solubilizer provided increased solubility of drugs in medium-chain triglyceride and long-chain triglyceride, whereas the maximum water solubility of TAP was 0.10 μg/mL. The partition coefficient (log P) of TAP was 5.79 irrespective of the pH conditions. The hydrolysis of TAP followed pseudo-first-order kinetics in aqueous solutions, and the stable pH range was from pH 5.0 to 9.0. The in vitro enzymolysis kinetics of TAP in rat plasma and liver homogenate was evaluated by measuring the decrease of TAP as well as the increase of TAA at 37°C for 96 hours. The results demonstrated that the TAP may be hydrolyzed mainly by rat plasma esterase and, to a minor extent, by liver esterase, and the hydrolysis half-life of TAP in 100% rat plasma was 17.53 ± 6.85 hours at pH 7.4. All these results indicated that TAP had successfully obtained higher lipid-soluble property for the preparation of intravenous emulsion and may be an effective prodrug for sustained release of TAA in vivo.

Pre-formulation and chemical stability studies of penethamate, a benzylpenicillin ester prodrug, in aqueous vehicles.

PubMed

Jain, Rohit; Wu, Zimei; Bork, Olaf; Tucker, Ian G

2012-01-01

Penethamate (PNT) is a diethylaminoethyl ester prodrug of benzylpenicillin used to treat bovine mastitis via the intramuscular route. Because of its instability, PNT products must be reconstituted before administration and the reconstituted injection has a short shelf life (7 days at 2-8°C). The purpose of this paper was to investigate whether the stability of PNT can be improved in order to achieve a chemically stable ready-to-use aqueous-based PNT formulation or at least to extend the shelf life of the reconstituted suspension. A chemical stability study of PNT in aqueous-based solutions as a function of pH, buffer strength, solvent mixtures and temperature, supported by studies of its solubility in mixed solvents, allowed predictions of the shelf life of PNT solution and suspension formulations. PNT degraded in aqueous solutions by several pathways over the pH range 2.0-9.3 with a V-shaped pH-rate profile and a minimum pH of around 4.5. The stability of PNT solutions in mixed solvents was greater than in aqueous solutions. For example, in propylene glycol:citrate buffer (60:40, v/v, pH 4.5), the half-life of PNT was 4.3 days compared with 1.8 days in aqueous buffer. However, solubility of PNT in the mixed solvent was higher than that in aqueous solution and this had an adverse effect on the stability of suspensions. By judicious choosing of pH and mixed solvent, it is possible to achieve a storage life of a PNT suspension of 5.5 months at 5°C, not sufficient for a ready-to-use product but a dramatic improvement in the storage life of the reconstituted product.

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

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

Travis S. Grimes; Richard D. Tillotson; Leigh R. Martin

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successfulmore » separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.« less

Aqueous biphasic extraction process with pH and particle control

DOEpatents

Chaiko, David J.; Mensah-Biney, R.

1995-01-01

A process for aqueous biphasic extraction of metallic oxides and the like from substances containing silica. Control of media pH enables efficient and effective partition of mixture components. The inventive method may be employed to remove excess silica from kaolin clay.

Electrochemical degradation of the antihypertensive losartan in aqueous medium by electro-oxidation with boron-doped diamond electrode.

PubMed

Salazar, Claudio; Contreras, Nicole; Mansilla, Héctor D; Yáñez, Jorge; Salazar, Ricardo

2016-12-05

In this work the electrochemical oxidation of losartan, an emerging pharmaceutical pollutant, was studied. Electrochemical oxidation was carried out in batch mode, in an open and undivided cell of 100cm(3) using a boron-doped diamond (BDD)/stainless steel system. With Cl(-) medium 56% of mineralization was registered, while with the trials containing SO4(2-) as supporting electrolyte a higher mineralization yield of 67% was reached, even obtaining a total removal of losartan potassium at 80mAcm(-2) and 180min of reaction time at pH 7.0. Higher losartan potassium concentrations enhanced the mineralization degree and the efficiency of the electrochemical oxidation process. During the mineralization up to 4 aromatic intermediates were identified by ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Moreover, short-linear carboxylic acids, like oxalic, succinic and oxamic were detected and quantified by ion-exclusion HPLC. Finally, the ability of the electrochemical oxidation process to mineralize dissolved commercial tablets containing losartan was achieved, obtaining TOC removal up to 71% under optimized conditions (10mAcm(-2), 0.05M Na2SO4, pH 7.0 and 25°C and 360min of electrolysis). Copyright © 2016 Elsevier B.V. All rights reserved.

Dependence of transformation product formation on pH during photolytic and photocatalytic degradation of ciprofloxacin.

PubMed

Salma, Alaa; Thoröe-Boveleth, Sven; Schmidt, Torsten C; Tuerk, Jochen

2016-08-05

Ciprofloxacin (CIP) is a broad-spectrum antibiotic with five pH dependent species in aqueous medium, which makes its degradation behavior difficult to predict. For the identification of transformation products and prediction of degradation mechanisms, a new experimental concept making use of isotopically labeled compounds together with high resolution mass spectrometry was successfully established. The utilization of deuterated ciprofloxacin (CIP-d8) facilitated the prediction of three different degradation pathways and the corresponding degradation products, four of which were identified for the first time. Moreover, two molecular structures of previously reported transformation products were revised according to the mass spectra and product ion spectra of the deuterated transformation products. Altogether, 18 transformation products have been identified during the photolytic and photocatalytic reactions at different pH values (3, 5, 7 and 9). In this work the influence of pH on both reaction kinetics and degradation mechanism was investigated for direct ultraviolet photolysis (UV-C irradiation) and photocatalysis (TiO2/UV-C). It could be shown that the removal rates strongly depended on pH with highest removal rates at pH 9. A comparison with those at pH 3 clearly indicated that under acidic conditions ciprofloxacin cannot be easily excited by UV irradiation. We could confirm that the first reaction step for both oxidative treatment processes is mainly defluorination, followed by degradation at the piperazine ring of CIP. Copyright © 2016 Elsevier B.V. All rights reserved.

Aqueous solubility of a diatomic molecule as a function of its size & electronegativity difference.

PubMed

Al-Malah, Kamal I

2011-02-01

The aqueous solubility of a diatomic molecule as a function of its size & electronegativity difference is investigated. The electronegativity of a diatomic molecule will be calculated using five different electronegativity scales, namely, Pauling [1], Allred-Rochow [2], Mulliken [3, 4], Parr-Yang [5], and Sanderson [6, 7]. It is hypothesized here that at a given pH, temperature, and pressure, the solubility of a diatomic molecule in water will be a function of its polar character; in particular, electronegativity difference and of its molecular size. Different forms of the solubility function were tested; it was found that the solubility model, given by Eq. 3, which is based on different electronegativity scales and the molecular volume, adequately describes the aqueous solubility of alkali halides. The aqueous solubility of alkali halides exhibits maximum at the condition of high electronegativity difference and large molecular volume. On the other hand, the minimum solubility region is observed at very low molecular volume and medium to slightly high values of electronegativity difference. The minimum solubility is also observed at low value of electronegativity difference and high molecular volume. Finally, the general trend of solubility of alkali halides, based on the proposed model (Eq. 3) could be explained in terms of the trade-off between electrostatic interactions (solid lattice side) and the entropic effects (water side).

Aqueous biphasic extraction process with pH and particle control

DOEpatents

Chaiko, D.J.; Mensah-Biney, R.

1995-05-02

A process for aqueous biphasic extraction of metallic oxides and the like from substances containing silica. Control of media pH enables efficient and effective partition of mixture components. The inventive method may be employed to remove excess silica from kaolin clay. 2 figs.

LED-CT Scan for pH Distribution on a Cross-Section of Cell Culture Medium.

PubMed

Higashino, Nobuya; Takayama, Toshio; Ito, Hiroaki; Horade, Mitsuhiro; Yamaguchi, Yasutaka; Dylan Tsai, Chia-Hung; Kaneko, Makoto

2018-01-11

In cell culture, the pH of the culture medium is one of the most important conditions. However, the culture medium may have non-uniform pH distribution due to activities of cells and changes in the environment. Although it is possible to measure the pH distribution with an existing pH meter using distributed electrodes, the method involves direct contact with the medium and would greatly increase the risk of contamination. Here in this paper, we propose a computed tomography (CT) scan for measuring pH distribution using the color change of phenol red with a light-emitting diode (LED) light source. Using the principle of CT scan, we can measure pH distribution without contacting culture medium, and thus, decrease the risk of contamination. We have developed the device with a LED, an array of photo receivers and a rotation mechanism. The system is firstly calibrated with different shapes of wooden objects that do not pass light, we succeeded in obtaining their 3D topographies. The system was also used for measuring a culture medium with two different pH values, it was possible to obtain a pH distribution that clearly shows the boundary.

Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment

DOE PAGES

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira; ...

2016-01-29

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment

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

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

Structural and photodynamic properties of the anti-cancer drug irinotecan in aqueous solutions of different pHs.

PubMed

di Nunzio, Maria Rosaria; Douhal, Yasmin; Organero, Juan Angel; Douhal, Abderrazzak

2018-05-23

This work reports on photophysical studies of the irinotecan (IRT) anti-cancer drug in water solutions of different acidities (pH = 1.11-9.46). We found that IRT co-exists as mono-cationic (C1), di-cationic (C2), or neutral (N) forms. The population of each prototropic species depends on the pH of the solution. At pH = 1.11-3.01, the C1 and C2 structures are stabilized. At pH = 7.00, the most populated species is C1, while at pH values larger than 9.46 the N form is the most stable species. In the 1.11-2.61 pH range, the C1* emission is efficiently quenched by protons to give rise to the emission from C2*. The dynamic quenching constant, KD, is ∼32 M-1. While the diffusion governs the rate of excited-state proton-transfer (ESPT) under these conditions, the reaction rate increases with the proton concentration. A two-step diffusive Debye-Smoluchowski model was applied at pH = 1.11-2.61 to describe the protonation of C1*. The ESPT time constants derived for C1* are 382 and 1720 ps at pH = 1.11 and 1.95, respectively. We found that one proton species is involved in the protonation of C1* to give C2*, in the analyzed acidic pH range. Under alkaline conditions (pH = 9.46), the N form is the most stable structure of IRT. These results indicate the influence of the pH of the medium on the structural and dynamical properties of IRT in water solution. They may help to provide a better understanding on the relationship between the structure and biological activity of IRT.

REVISITING NUCLEOPHILIC SUBSTITUTION REACTIONS: MICROWAVE-ASSISTED SYNTHESIS OF AZIDES, THIOCYANATES AND SULFONES IN AQUEOUS MEDIUM

EPA Science Inventory

A practical, rapid and efficient microwave (MW) promoted synthesis of various azides, thiocyanates and sulfones, is described in aqueous medium. This general and expeditious MW-enhanced nucleophilic substitution approach uses easily accessible starting materials such as halides o...

A facile sol-gel synthesis of impurity-free nanocrystalline titania.

PubMed

Vinogradov, Alexandr V; Ermakova, Al'ena V; Butman, Mikhail F; Hey-Hawkins, Evamarie; Vinogradov, Vladimir V

2014-06-14

This paper reports an original technique that provides a highly pure crystalline sol of titania with controllable particle size by ultrasonic activation of the hydrolysis products of titanium isopropoxide in an aqueous medium at a near-neutral pH, which is potentially promising in impurity-sensitive electronics and biochemical engineering. Optimal conditions (H2O/TIP ratio, sonication time, etc.) for preparation of stable nanocrystalline titania sol were adopted. A new mechanism of regulation of aggregation and polycondensation under ultrasonic irradiation is proposed. Entrapment of human serum albumin (HSA) in the formed porous titania matrix results in high thermal stability of the protein dopants: the denaturation temperature of HSA is shifted by 31 °C.

A novel ethanol-tolerant laccase, Tvlac, from Trametes versicolor.

PubMed

Chen, Lei; Yi, Xiaoming; Deng, Fajun; Fang, Wei; Zhang, Xuecheng; Wang, Xiaotang; Fang, Zemin; Xiao, Yazhong

2016-03-01

To produce and characterize novel laccases with ethanol tolerance from Trametes versicolor using agriculture by-products as energy source. Trametes versicolor 1017 produces two laccase isoenzymes with a total activity of 10 U ml(-1) within 8 days when using wheat bran and peanut powder as energy sources in liquid culture medium. A novel isoenzyme, named Tvlac, was identified, purified and characterized. Its optimum pH and temperature were from 4.5 to 5 and 55 to 60 °C, respectively. Its activity was stimulated by ethanol at 10 % (v/v) which increased the V 0. The biochemical properties of Tvlac substantiate the potential of this enzyme for applications under an aqueous ethanol mixture environment.

Photoproduction of hydroxyl radicals in aqueous solution with algae under high-pressure mercury lamp.

PubMed

Liu, Xianli; Wu, Feng; Deng, Nansheng

2004-01-01

Photoproduction of hydroxyl radicals (*OH) could be induced in aqueous solution with algae (Nitzschia hantzschiana, etc.) and (or not) Fe3+ under high-pressure mercury lamp with an exposure time of 4 h. *OH was determined by HPLC using benzene as a probe. The photoproduction of *OH increased with increasing algae concentration. Fe3+ could enhance the photoproduction of *OH in aqueous solution with algae. The results showed that the photoproduction of *OH in algal solution with Fe3+ was greater than that in algal solution without Fe3+. The light intensity and pH affected the photoproduction of *OH in aqueous solution with algae with/without Fe3+. The photoproduction of *OH in aqueous solution with algae and Fe3+ under 250 W was greater than that under 125 W HPML. The photoproduction of *OH in algal solution (pH ranged from 4.0 to 7.0) with (or not) Fe3+ at pH 4 was the greatest.

Surface Engineering of PAMAM-SDB Chelating Resin with Diglycolamic Acid (DGA) Functional Group for Efficient Sorption of U(VI) and Th(IV) from Aqueous Medium.

PubMed

Ilaiyaraja, P; Deb, A K Singha; Ponraju, D; Ali, Sk Musharaf; Venkatraman, B

2017-04-15

A novel chelating resin obtained via growth of PAMAM dendron on surface of styrene divinyl benzene resin beads, followed by diglycolamic acid functionalization of the dendrimer terminal. Batch experiments were conducted to study the effects of pH, nitric acid concentration, amount of adsorbent, shaking time, initial metal ion concentration and temperature on U(VI) and Th(IV) adsorption efficiency. Diglycolamic acid terminated PAMAM dendrimer functionalized styrene divinylbenzene chelating resin (DGA-PAMAM-SDB) is found to be an efficient candidate for the removal of U(VI) and Th(IV) ions from aqueous (pH >4) and nitric acid media (>3M). The sorption equilibrium could be reached within 60min, and the experimental data fits with pseudo-second-order model. Langmuir sorption isotherm model correlates well with sorption equilibrium data. The maximum U(VI) and Th(IV) sorption capacity onto DGA-PAMAMG 5 -SDB was estimated to be about 682 and 544.2mgg -1 respectively at 25°C. The interaction of actinides and chelating resin is reversible and hence, the resin can be regenerated and reused. DFT calculation on the interaction of U(VI) and Th(IV) ions with chelating resin validates the experimental findings. Copyright © 2017 Elsevier B.V. All rights reserved.

EPR spin trapping evidence of radical intermediates in the photo-reduction of bicarbonate/CO2 in TiO2 aqueous suspensions.

PubMed

Molinari, Alessandra; Samiolo, Luca; Amadelli, Rossano

2015-05-01

Using the EPR spin trapping technique, we prove that simultaneous reactions take place in illuminated suspensions of TiO2 in aqueous carbonate solutions (pH ≈ 7). The adsorbed HCO3(-) is reduced to formate as directly made evident by the detection of formate radicals (˙CO2(-)). In addition, the amount of OH˙ radicals from the photo-oxidation of water shows a linear dependence on the concentration of bicarbonate, indicating that electron scavenging by HCO3(-) increases the lifetime of holes. In a weakly alkaline medium, photo-oxidation of HCO3(-)/CO3(2-) to ˙CO3(-) interferes with the oxidation of water. A comparative analysis of different TiO2 samples shows that formation of ˙CO2(-) is influenced by factors related to the nature of the surface, once expected surface area effects are accounted for. Modification of the TiO2 surface with noble metal nanoparticles does not have unequivocal benefits: the overall activity improves with Pd and Rh but not with Ru, which favours HCO3(-) photo-oxidation even at pH = 7. In general, identification of radical intermediates of oxidation and reduction reactions can provide useful mechanistic information that may be used in the development of photocatalytic systems for the reduction of CO2 also stored in the form of carbonates.

Effect of Medium pH on Rhodosporidium toruloides NCYC 921 Carotenoid and Lipid Production Evaluated by Flow Cytometry.

PubMed

Dias, Carla; Silva, Corália; Freitas, Claudia; Reis, Alberto; da Silva, Teresa Lopes

2016-07-01

The effect of the culture medium pH (3.5-6.0) on the carotenoid and lipid (as fatty acids) production by the yeast Rhodosporidium toruloides NCYC 921 was studied. Flow cytometry was used to evaluate the yeast's physiological response to different culture medium pH values. The yeast biomass concentration and lipid content were maxima at pH 4.0 (5.90 g/L and 21.85 % w/w, respectively), while the maximum carotenoid content (63.37 μg/g) was obtained at pH 5.0. At the exponential phase, the yeast cell size and internal complexity were similar, at different medium pH. At the stationary phase, the yeast cell size and internal complexity decreased as the medium pH increased. At the exponential phase, the proportion of cells with polarized membranes was always high (>80 %) but at the stationary phase, the proportion of yeast cells with depolarized membranes was dominant (>65 %) and increased with the medium pH increase. The results here reported may contribute for yeast bioprocesses optimization. For the first time, multiparameter flow cytometry was used to evaluate the impact of medium pH changes on the yeast cell physiological status, specifically on the yeast membrane potential, membrane integrity, cell size and internal complexity.

Indirect Manganese Removal by Stenotrophomonas sp. and Lysinibacillus sp. Isolated from Brazilian Mine Water

PubMed Central

Barboza, Natália Rocha; Amorim, Soraya Sander; Santos, Pricila Almeida; Reis, Flávia Donária; Cordeiro, Mônica Mendes; Guerra-Sá, Renata; Leão, Versiane Albis

2015-01-01

Manganese is a contaminant in the wastewaters produced by Brazilian mining operations, and the removal of the metal is notoriously difficult because of the high stability of the Mn(II) ion in aqueous solutions. To explore a biological approach for removing excessive amounts of aqueous Mn(II), we investigated the potential of Mn(II) oxidation by both consortium and bacterial isolates from a Brazilian manganese mine. A bacterial consortium was able to remove 99.7% of the Mn(II). A phylogenetic analysis of isolates demonstrated that the predominant microorganisms were members of Stenotrophomonas, Bacillus, and Lysinibacillus genera. Mn(II) removal rates between 58.5% and 70.9% were observed for Bacillus sp. and Stenotrophomonas sp. while the Lysinibacillus isolate 13P removes 82.7%. The catalytic oxidation of Mn(II) mediated by multicopper oxidase was not properly detected; however, in all of the experiments, a significant increase in the pH of the culture medium was detected. No aggregates inside the cells grown for a week were found by electronic microscopy. Nevertheless, an energy-dispersive X-ray spectroscopy of the isolates revealed the presence of manganese in Stenotrophomonas sp. and Lysinibacillus sp. grown in K medium. These results suggest that members of Stenotrophomonas and Lysinibacillus genera were able to remove Mn(II) by a nonenzymatic pathway. PMID:26697496

Removal of tetracycline from aqueous solution by a Fe3O4 incorporated PAN electrospun nanofiber mat.

PubMed

Liu, Qing; Zheng, Yuming; Zhong, Lubin; Cheng, Xiaoxia

2015-02-01

Pollution of antibiotics, a type of emerging contaminant, has become an issue of concern, due to their overuse in human and veterinary application, persistence in environment and great potential risk to human and animal health even at trace level. In this work, a novel adsorbent, Fe3O4 incorporated polyacrylonitrile nanofiber mat (Fe-NFM), was successfully fabricated via electrospinning and solvothermal method, targeting to remove tetracycline (TC), a typical class of antibiotics, from aqueous solution. Field emission scanning electron microscopy and X-ray diffraction spectroscopy were used to characterize the surface morphology and crystal structure of the Fe-NFM, and demonstrated that Fe-NFM was composed of continuous, randomly distributed uniform nanofibers with surface coating of Fe3O4 nanoparticles. A series of adsorption experiments were carried out to evaluate the removal efficiency of TC by the Fe-NFM. The pseudo-second-order kinetics model fitted better with the experimental data. The highest adsorption capacity was observed at initial solution pH4 while relative high adsorption performance was obtained from initial solution pH4 to 10. The adsorption of TC on Fe-NFM was a combination effect of both electrostatic interaction and complexation between TC and Fe-NFM. Freundlich isotherm model could better describe the adsorption isotherm. The maximum adsorption capacity calculated from Langmuir isotherm model was 315.31 mg/g. Compared to conventional nanoparticle adsorbents which have difficulties in downstream separation, the novel nanofiber mat can be simply installed as a modular compartment and easily separated from the aqueous medium, promising its huge potential in drinking and wastewater treatment for micro-pollutant removal. Copyright © 2014. Published by Elsevier B.V.

Phosphate sorption and desorption on pyrite in primitive aqueous scenarios: relevance of acidic --> alkaline transitions.

PubMed

de Souza-Barros, Fernando; Braz-Levigard, Raphael; Ching-San, Yonder; Monte, Marisa M B; Bonapace, José A P; Montezano, Viviane; Vieyra, Adalberto

2007-02-01

Phosphate (P(i)) sorption assays onto pyrite in media simulating primeval aquatic scenarios affected by hydrothermal emissions, reveal that acidic conditions favour P(i) sorption whereas mild alkaline media--as well as those simulating sulfur oxidation to SO(2-) (4)--revert this capture process. Several mechanisms relevant to P(i) availability in prebiotic eras are implicated in the modulation of these processes. Those favouring sorption are: (a) hydrophobic coating of molecules, such as acetate that could be formed in the vicinity of hydrothermal vents; (b) water and Mg(2+) bridging in the interface mineral-aqueous media; (c) surface charge neutralization by monovalent cations (Na+ and K+). The increase of both the medium pH and the SO(2-) (4) trapping by the mineral interface would provoke the release of sorbed P(i) due to charge polarization. Moreover it is shown that P(i) self-modulates its sorption, a mechanism that depends on the abundance of SO(2-) (4) in the interface. The relevance of the proposed mechanisms of P(i) capture, release and trapping arises from the need of abundant presence of this molecule for primitive phosphorylations, since--similarly to contemporary aqueous media--inorganic phosphate concentrations in primitive seas should have been low. It is proposed that the presence of sulphide minerals with high affinity to P(i) could have trapped this molecule in an efficient manner, allowing its concentration in specific niches. In these niches, the conditions studied in the present work would have been relevant for its availability in soluble form, specially in primitive insulated systems with pH gradients across the wall.

Chemical speciation and recovery of gold(I, III) from wastewater and silver by liquid-liquid extraction with the ion-pair reagent amiloride mono hydrochloride and AAS determination.

PubMed

El-Shahawi, M S; Bashammakh, A S; Bahaffi, S O

2007-06-15

A novel and low cost liquid-liquid extraction procedure for the separation of gold(III) at trace level from aqueous medium of pH 5-9 has been developed. The method has been based upon the formation of a yellow colored ternary complex ion associate of tetrachloro gold(III) complex anion, AuCl(4)(-) with the ion-pair reagent 1-(3,5-diamino-6-chloropyrazinecarboxyl) guanidine hydrochloride monohydrate, namely amiloride, DPG(+).Cl(-). The effect of various parameters, e.g. pH, organic solvent, shaking time, etc. on the preconcentration of gold(III) from the aqueous media by the DPG(+).Cl(-) reagent has been investigated. The colored gold species was quantitatively extracted into 4-methyl pentan-2-one. The chemical composition of the ion associate of DPG(+).Cl(-) with AuCl(4)(-) in the organic solvent has been determined by the Job's method. The molar absorptivity (2.19x10(4)Lmol(-1)cm(-1)) of the associate DPG(+).AuCl(4)(-) at 362nm enabled a convenient application of the developed extraction procedure for the separation and AAS determination of traces of aurate ions. Mono-valence gold ions after oxidation to gold(III) with bromine water in HCl (1.0molL(-1)) media have been also extracted quantitatively from the aqueous media by the developed procedure. The chemical speciation of mono- and/or tri-valence gold species spiked to fresh and industrial wastewater samples has been achieved. The method has been also applied successfully from the separation of gold(I) and gold(III) species from metallic ions and silver. The developed method has also the advantage of freedom from most diverse ions.

Effects of •OH and •NO radicals in the aqueous phase on H2O2 and \\text{NO}_{2}^{-} generated in plasma-activated medium

NASA Astrophysics Data System (ADS)

Kurake, Naoyuki; Tanaka, Hiromasa; Ishikawa, Kenji; Takeda, Keigo; Hashizume, Hiroshi; Nakamura, Kae; Kajiyama, Hiroaki; Kondo, Takashi; Kikkawa, Fumitaka; Mizuno, Masaaki; Hori, Masaru

2017-04-01

A plasma-activated medium (PAM), which means a cell-culture medium irradiated with cold atmospheric plasmas or non-equilibrium atmospheric pressure plasma (NEAPP), has shown strong antitumor effects on various kinds of cells such as gastric cancer cells, human lung adenocarcinoma cells, human breast cancer cells and so on. In order to clarify the mechanism, it is extremely important to investigate the behaviors of stable and unstable reactive oxygen nitrogen species in culture medium irradiated by NEAPP. The roles of hydroxyl radicals (•OH) and nitric oxide (•NO) were studied to understand the dominant synthetic pathways of H2O2 and \\text{NO}2- in culture medium irradiated with NEAPP. In the PAM, •OH in the aqueous phase was generated predominantly by photo-dissociation. However, most of the H2O2 nor \\text{NO}2- generated in the PAM did not originate from aqueous •OH and •NO. Pathways for the generation of H2O2 and \\text{NO}2- are suggested based on the high concentrations of intermediates generated at the gas/aqueous-phase interface following NEAPP irradiation. On the basis of these results, the reaction model of chemical species in the culture medium is proposed.

Study of 3-Ethylamino-but-2-enoic acid phenylamide as a new ligand for preconcentration of lanthanides from aqueous media by liquid-liquid extraction prior to ICP-MS analysis.

PubMed

Varbanova, Evelina K; Angelov, Plamen A; Stefanova, Violeta M

2016-11-01

In the present work the potential of a new ligand 3-Ethylamino-but-2-enoic acid phenylamide (representing the class of enaminones) for selective preconcentration of lanthanides (La, Ce, Eu, Gd and Er) from aqueous medium is examined. Liquid-liquid extraction parameters, such as pH of the water phase, type and volume of organic solvent, quantity of ligand and reaction time are optimized on model solutions. Recovery of lanthanides by re-extraction with nitric acid makes the LLE procedure compatible with Inductively Coupled Plasma Mass Spectrometry. Spectral and non-spectral interferences are studied. Two isotopes per element are measured (with exception of La) for dynamic evaluation of the potential risk of spectral interference in variable real samples. The selectivity of complex formation reaction towards concomitant alkali and alkali-earth elements eliminates the interferences from sample matrix. Subjecting the standards to the optimized extraction procedure in combination with Re as internal standard is recommended as calibration strategy. The accuracy of developed method is approved by analysis of CRM Bush branches and leaves (NCS DC 73348) and recovery of spiked water and plant samples. The method's limits of detection for both studied objects are in the ranges from 0.2 ((158)Gd) to 3.7 ((139)La) ngl(-1) and 0.02 ((158)Gd) to 0.37((139)La) ngg(-1) for waters and plants respectively. The studied compound is an effective new ligand for preconcentration/separation of lanthanides from aqueous medium by LLE and subsequent determination by ICP-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

REVISITING CLASSICAL NUCLEOPHILIC SUBSTITUTIONS IN AQUEOUS MEDIUM: MICROWAVE-ASSISTED SYNTHESIS OF ALKYL AZIDES

EPA Science Inventory

An efficient and clean synthesis of alkyl azides using microwave (MW) radiation is described in aqueous medium by reacting alkyl halides or tosylates with alkali azides. This general and expeditious MW-enhanced approach to nucleophilic substitution reactions is applicable to the ...

Influence of the solution pH in the 6-mercaptopurine self-assembled monolayer (6MP-SAM) on a Au(111) single-crystal electrode.

PubMed

Madueño, Rafael; García-Raya, Daniel; Viudez, Alfonso J; Sevilla, José M; Pineda, Teresa; Blázquez, Manuel

2007-10-23

Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) have been prepared on a Au(111) single-crystal electrode by immersion of the metal surface in a 100 microM 6MP and 0.01 M HClO4 solution. The 6MP-SAM Au(111) single-crystal electrodes were transferred to the cell and allowed to equilibrate with the different aqueous working solutions before the electrochemical experiments. The influence of the solution pH was studied by cyclic voltammetry, double layer capacitance curves, and electrochemical impedance spectroscopy. The electrochemical behavior of the 6MP-SAM in acetic acid at pH 4 presents important differences in comparison to that obtained in 0.1 M KOH solutions. Cyclic voltammograms for the reductive desorption process in acid medium are broad and show some features that can be explained by a phase transition between a chemisorbed and a physisorbed state of the 6MP molecules. The low solubility of these molecules in acid medium could explain this phenomenon and the readsorption of the complete monolayer when the potential is scanned in the positive direction. The variation of the double-layer capacitance values in the potential range of monolayer stability with the pH suggests that the acid-base chemistry of the 6MP molecules is playing a role. This fact has been studied by following the variations of the electron-transfer rate constant of the highly charged redox probes as are Fe(CN)(6)-3/-4 and Ru(NH3)(6)+3/+2 as a function of solution pH. The apparent surface pKa value for the 6MP-SAM (pKa approximately 8) is explained by the total conversion of the different 6MP tautomers that exist in solution to the thiol species in the adsorbed state.

Solution pH change in non-uniform alternating current electric fields at frequencies above the electrode charging frequency

PubMed Central

An, Ran; Massa, Katherine

2014-01-01

AC Faradaic reactions have been reported as a mechanism inducing non-ideal phenomena such as flow reversal and cell deformation in electrokinetic microfluidic systems. Prior published work described experiments in parallel electrode arrays below the electrode charging frequency (fc), the frequency for electrical double layer charging at the electrode. However, 2D spatially non-uniform AC electric fields are required for applications such as in plane AC electroosmosis, AC electrothermal pumps, and dielectrophoresis. Many microscale experimental applications utilize AC frequencies around or above fc. In this work, a pH sensitive fluorescein sodium salt dye was used to detect [H+] as an indicator of Faradaic reactions in aqueous solutions within non-uniform AC electric fields. Comparison experiments with (a) parallel (2D uniform fields) electrodes and (b) organic media were employed to deduce the electrode charging mechanism at 5 kHz (1.5fc). Time dependency analysis illustrated that Faradaic reactions exist above the theoretically predicted electrode charging frequency. Spatial analysis showed [H+] varied spatially due to electric field non-uniformities and local pH changed at length scales greater than 50 μm away from the electrode surface. Thus, non-uniform AC fields yielded spatially varied pH gradients as a direct consequence of ion path length differences while uniform fields did not yield pH gradients; the latter is consistent with prior published data. Frequency dependence was examined from 5 kHz to 12 kHz at 5.5 Vpp potential, and voltage dependency was explored from 3.5 to 7.5 Vpp at 5 kHz. Results suggest that Faradaic reactions can still proceed within electrochemical systems in the absence of well-established electrical double layers. This work also illustrates that in microfluidic systems, spatial medium variations must be considered as a function of experiment time, initial medium conditions, electric signal potential, frequency, and spatial position. PMID:25553200

A renaissance of soaps? - How to make clear and stable solutions at neutral pH and room temperature.

PubMed

Wolfrum, Stefan; Marcus, Julien; Touraud, Didier; Kunz, Werner

2016-10-01

Soaps are the oldest and perhaps most natural surfactants. However, they lost much of their importance since "technical surfactants", usually based on sulfates or sulfonates, have been developed over the last fifty years. Indeed, soaps are pH- and salt-sensitive and they are irritant, especially to the eyes. In food emulsions, although authorized, they have a bad taste, and long-chain saturated soaps have a high Krafft temperature. We believe that most or perhaps all of these problems can be solved with modern formulation approaches. We start this paper with a short overview of our present knowledge of soaps and soap formulations. Then we focus on the problem of the lacking soap solubility at neutral pH values. For example, it is well known that with the food emulsifier sodium oleate (NaOl), clear and stable aqueous solutions can only be obtained at pH values higher than 10. A decrease in the pH value leads to turbid and unstable solutions. This effect is not compatible with the formulation of aqueous stable and drinkable formulations with neutral or even acidic pH values. However, the pH value/phase behavior of aqueous soap solutions can be altered by the addition of other surfactants. Such a surfactant can be Rebaudioside A (RebA), a steviol glycoside from the plant Stevia rebaudiana which is used as a natural food sweetener. In a recent paper, we showed the influence of RebA on the apKa value of sodium oleate in a beverage microemulsion and on its clearing temperature. In the present paper, we report on the effect of the edible bio-surfactant RebA, on the macroscopic and microscopic phase behavior of simple aqueous sodium oleate solutions at varying pH values. The macroscopic phase behavior is investigated by visual observation and turbidity measurements. The microscopic phase behavior is analyzed by acid-base titration curves, phase-contrast and electron microscopy. It turned out that even at neutral pH, aqueous NaOl/RebA solutions can be completely clear and stable for more than 50days at room temperature. This is for the first time that a long chain soap could be really solubilized in water at neutral pH at room temperature. At last, these findings were applied to prepare stable, highly translucent and drinkable aqueous solutions of omega-3-fatty acids at a pH value of 7.5. Copyright © 2016 Elsevier B.V. All rights reserved.

Application of Optical Imaging Techniques for Quantification of pH and O2 Dynamicsin Porous Media

NASA Astrophysics Data System (ADS)

Li, B.; Seliman, A. F.; Pales, A. R.; Liang, W.; Sams, A.; Darnault, C. J. G.; DeVol, T. A.

2016-12-01

Understanding the spatial and temporal distribution of physical and chemical parameters (e.g. pH, O2) is imperative to characterize the behavior of contaminants in a natural environment. The objectives of this research are to calibrate pH and O2 sensor foils, to develop a dual pH/O2 sensor foil, and to apply them into flow and transport experiments, in order to understand the physical and chemical parameters that control contaminant fate and transport in an unsaturated sandy porous medium. In addition, demonstration of a sensor foil that quantifies aqueous uranium concentration will be presented. Optical imaging techniques will be conducted with 2D tanks to investigate the influence of microbial exudates and plant roots on pH and O2 parameters and radionuclides transport. As a non-invasive method, the optical imaging technique utilizes optical chemical sensor films and either a digital camera or a spectrometer to capture the changes with high temporal and spatial resolutions. Sensor foils are made for different parameters by applying dyes to generate favorable fluorescence that is proportional to the parameter of interest. Preliminary results suggested that this method could detect pH ranging from 4.5 to 7.5. The result from uranium foil test with different concentrations in the range of 2 to 8 ppm indicated that a higher concentration of uranium resulted in a greater color intensity.

Influence of environmental pH on G2-phase arrest caused by ionizing radiation.

PubMed

Park, Heon Joo; Lee, Sang Hwa; Chung, HyunSook; Rhee, Yun Hee; Lim, Byung Uk; Ha, Sung Whan; Griffin, Robert J; Lee, Hyung Sik; Song, Chang Won; Choi, Eun Kyung

2003-01-01

We investigated the effects of an acidic environment on the G2/M-phase arrest, apoptosis, clonogenic death, and changes in cyclin B1-CDC2 kinase activity caused by a 4-Gy irradiation in RKO.C human colorectal cancer cells in vitro. The time to reach peak G2/M-phase arrest after irradiation was delayed in pH 6.6 medium compared to that in pH 7.5 medium. Furthermore, the radiation-induced G2/M-phase arrest decayed more slowly in pH 6.6 medium than in pH 7.5 medium. Finally, there was less radiation-induced apoptosis and clonogenic cell death in pH 6.6 medium than in pH 7.5 medium. It appeared that the prolongation of G2-phase arrest after irradiation in the acidic environment allowed for greater repair of radiation-induced DNA damage, thereby decreasing the radiation-induced cell death. The prolongation of G2-phase arrest after irradiation in the acidic pH environment appeared to be related at least in part to a prolongation of the phosphorylation of CDC2, which inhibited cyclin B1-CDC2 kinase activity.

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Removal of bisphenol derivatives through quinone oxidation by polyphenol oxidase and subsequent quinone adsorption on chitosan in the heterogeneous system.

PubMed

Kimura, Yuji; Takahashi, Ayumi; Kashiwada, Ayumi; Yamada, Kazunori

2015-01-01

In this study, the combined use of a biopolymer chitosan and an oxidoreductase polyphenol oxidase (PPO) was systematically investigated for the removal of bisphenol derivatives from aqueous medium. The process parameters, such as the pH value, temperature, and PPO concentration, were estimated to conduct the enzymatic quinone oxidation of bisphenol derivatives by as little enzyme as possible. Bisphenol derivatives effectively underwent PPO-catalysed quinone oxidation without H2O2 unlike other oxidoreductases, such as peroxidase and tyrosinase, and the optimum conditions were determined to be pH 7.0 and 40°C for bisphenol B, bisphenol E, bisphenol O, and bisphenol Z; pH 7.0 and 30°C for bisphenol C and bisphenol F; and pH 8.0 and 40°C for bisphenol T. They were completely removed through adsorption of enzymatically generated quinone derivatives on chitosan beads or chitosan powders. Quinone adsorption on chitosan beads or chitosan powders in the heterogeneous system was found to be a more effective procedure than generation of aggregates in the homogeneous system with chitosan solution. The removal time was shortened by increasing the amount of chitosan beads or decreasing the size of the chitosan powders.

Development of Online Spectroscopic pH Monitoring for Nuclear Fuel Reprocessing Plants: Weak Acid Schemes.

PubMed

Casella, Amanda J; Ahlers, Laura R H; Campbell, Emily L; Levitskaia, Tatiana G; Peterson, James M; Smith, Frances N; Bryan, Samuel A

2015-05-19

In nuclear fuel reprocessing, separating trivalent minor actinides and lanthanide fission products is extremely challenging and often necessitates tight pH control in TALSPEAK (Trivalent Actinide-Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Komplexes) separations. In TALSPEAK and similar advanced processes, aqueous pH is one of the most important factors governing the partitioning of lanthanides and actinides between an aqueous phase containing a polyaminopolycarboxylate complexing agent and a weak carboxylic acid buffer and an organic phase containing an acidic organophosphorus extractant. Real-time pH monitoring would significantly increase confidence in the separation performance. Our research is focused on developing a general method for online determination of the pH of aqueous solutions through chemometric analysis of Raman spectra. Spectroscopic process-monitoring capabilities, incorporated in a counter-current centrifugal contactor bank, provide a pathway for online, real-time measurement of solution pH. The spectroscopic techniques are process-friendly and can be easily configured for online applications, whereas classic potentiometric pH measurements require frequent calibration/maintenance and have poor long-term stability in aggressive chemical and radiation environments. Raman spectroscopy discriminates between the protonated and deprotonated forms of the carboxylic acid buffer, and the chemometric processing of the Raman spectral data with PLS (partial least-squares) regression provides a means to quantify their respective abundances and therefore determine the solution pH. Interpretive quantitative models have been developed and validated under a range of chemical composition and pH conditions using a lactic acid/lactate buffer system. The developed model was applied to new spectra obtained from online spectral measurements during a solvent extraction experiment using a counter-current centrifugal contactor bank. The model predicted the pH of this validation data set within 11% for pH > 2, thus demonstrating that this technique could provide the capability of monitoring pH online in applications such as nuclear fuel reprocessing.

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

EPA Science Inventory

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

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

Enrichment and characterization of anaerobic TNT-degrading bacteria

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

Roberts, D.J.; Pendharkar, S.

1995-12-31

Three media constitutions were used to enrich for mixed cultures capable of degrading 2,4,6-trinitrotoluene (TNT) under strictly anaerobic conditions. The media were derived from a mineral salts solution buffered to pH 7 with CO{sub 2}/bicarbonate and all contained TNT. The cultures were enriched in the TNT mineral salts medium or the TNT mineral salts medium supplemented with glucose, yeast extract, or ammonia in various combinations. Inocula were obtained from a treated soil, previously contaminated with dinoseb and then treated using anaerobic procedures, or from a bench-top aqueous culture, maintained with an extract from a munitions-contaminated soil for more than 4more » years. Several cultures reduced TNT, producing 4-amino-2,6-dinitrotoluene and 2,4-diamino-6-nitrotoluene as the major products. The cultures were unable to effectively remove TNT when cross-transferred to the media they were not enriched on, suggesting that different media had enriched different subcultures form the original inoculum. The treated soil provided the most successful inoculum. Two media were chosen for further studies. Medium 1 contained TNT and glucose and produced a culture that might have used TNT as a nitrogen source. Medium 2, containing TNT and yeast extract, enriched cultures that degraded TNT, accumulating small amounts of p-cresol during the degradation.« less

Effect of pH on the Electrophoretic Mobility of Spores of Bacillus anthracis and Its Surrogates in Aqueous Solutions

EPA Science Inventory

Electrophoretic mobility (EPM) of endospores of Bacillus anthracis and surrogates were measured in aqueous solution across a broad pH range and several ionic strengths. EPM values trended around phylogenetic clustering based on the 16S rRNA gene. Measurements reported here prov...

Adsorption of arsenic from aqueous solution using magnetic graphene oxide

NASA Astrophysics Data System (ADS)

Sherlala, A. I. A.; Raman, A. A.; Bello, M. M.

2017-06-01

A binary of graphene oxide (GO) and iron oxide (IO) was prepared and used for the removal of arsenic from aqueous solution. The synthesized compound was characterized using XRD analysis. The prepared composite was used for the adsorption of arsenic from aqueous solution. Central Composite Design was used to design the adsorption experiments and to investigate the effects of operational parameters (initial concentration of arsenic, adsorbent dosage, pH and time) on the adsorption capacity and efficiency. The adsorbent shows a high adsorption capacity for the arsenic. The adsorption efficiency ranges between 33.2 % and 99.95 %. The most significant factors affecting the adsorption capacity were found to be the initial concentration of arsenic and the adsorbent dosage. The initial pH of the solution slightly affects the adsorption capacity, with the maximum adsorption capacity occurring around pH 6 - 7. Thus, the developed adsorbent has a potential for effective removal of arsenic from aqueous solution.

Electronic structures and spectra of two antioxidants: uric acid and ascorbic acid

NASA Astrophysics Data System (ADS)

Shukla, M. K.; Mishra, P. C.

1996-04-01

Electronic absorption and fluorescence spectra of aqueous solutions of two well known antioxidants, uric acid and ascorbic acid (vitamin C), have been studied at different pH. The observed spectra have been interpreted in terms of neutral and anionic forms of the molecules with the help of molecular orbital calculations. The N 3 site of uric acid has been shown to be the most acidic. Fluorescence of uric acid seems to originate from an anion of the molecule in a wide pH range. Around pH 3, both the neutral and anionic forms of ascorbic acid appear to be present in aqueous solutions. In aqueous media, ascorbic acid appears to get converted easily to its dehydro form and this conversion does not seem to be reversible. An anion of dehydroascorbic acid seems to be formed on heating dehydroascorbic acid in aqueous solutions.

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

PubMed

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

2016-05-15

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

Electroactive Film of Myoglobin Incorporated in a 3D-porous Calcium Alginate Film with Polyvinyl Alcohol, Glycerin and Gelatin.

PubMed

Zheng, Xueqin; Sun, Hong; Hou, Shifeng

2015-01-01

In this work, an electroactive porous Mb-CA's composite film was fabricated by incorporating myoglobin (Mb) in a three-dimension (3D) porous calcium alginate (CA) film with polyvinyl alcohol, glycerol, and gelatin. The porous Mb-CA's film modified electrodes exhibited a pair of well-defined, quasi-reversible cyclic voltammetric (CV) peaks at about -0.37 V vs. SCE in pH 7.0 buffers, characteristic of Mb heme Fe((III))/Fe((II)) redox couples. The electrochemical parameters, such as formal potentials (E(o')) and apparent heterogeneous electron-transfer rate constants (ks), were estimated by square-wave voltammetry with nonlinear regression analysis. The porous CA's composite film could form hydrogel in aqueous solution. The positions of the Soret absorbance band suggest that Mb in the CA's composite film kept its native states in the medium pH range. Hydrogen peroxide, oxygen, and nitrite were electrochemically catalyzed by the Mb-CA's composite film with significant lowering of the reduction overpotential.

On spray drying of oxidized corn starch cross-linked gelatin microcapsules for drug release.

PubMed

Dang, Xugang; Yang, Mao; Shan, Zhihua; Mansouri, Shahnaz; May, Bee K; Chen, Xiaodong; Chen, Hui; Woo, Meng Wai

2017-05-01

Spray-dried gelatin/oxidized corn starch (G/OCS) microcapsules were produced for drug release application. The prepared microcapsules were characterized through a scanning electron microscope (SEM) picture and thermogravimetric analysis (TGA). The swelling characteristics of the G/OCS microcapsules and release properties of vitamin C were then investigated. The results from structural analysis indicated that the presence of miscibility and compatibility between oxidized corn starch and gelatin, and exhibits high thermal stability up to 326°C. The swelling of G/OCS microcapsules increased with increasing pH and reduced with decreasing ionic strength, attributed to the cross-linking between gelatin and oxidized corn starch, ionization of functional groups. Vitamin C release characteristic revealed controlled release behavior in the first 3h of contact with an aqueous medium. This release behavior was independent of the swelling behavior indicating the potential of the encapsulating matrix to produce controlled release across a spectrum of pH environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Fabrication of doxorubicin and heparin co-loaded microcapsules for synergistic cancer therapy.

PubMed

Chen, Jing-Xiao; Liang, Yan; Liu, Wen; Huang, Jin; Chen, Jing-Hua

2014-08-01

In this study, a layer-by-layer (LbL) assembly (HEP/CHI)5 microcapsule with doxorubicin hydrochloride (DOX) encapsulating inside was fabricated via alternatively depositing heparin (HEP) and chitosan (CHI) onto DOX-loaded CaCO3 templates. The microcapsules were of stable architecture and had good dispersity in aqueous medium. Fluorescence observation showed that DOX distributed both in the wall and in the cavity of microcapsules, while HEP presented in the capsule wall. The release rate of DOX increased at acidic pH as compared with that at basic pH, suggesting a pH-responsive drug release behavior. The microcapsules with positively charged CHI lying on the outer layer could protect HEP from heparanase degradation and achieve intracellular co-delivery of both DOX and HEP. Thus, the DOX-loaded microcapsules could have improved inhibition activity against A549 cells by combining pharmacological actions of DOX and HEP. Copyright © 2014 Elsevier B.V. All rights reserved.

Development and evaluation of natural gum-based extended release matrix tablets of two model drugs of different water solubilities by direct compression.

PubMed

Ofori-Kwakye, Kwabena; Mfoafo, Kwadwo Amanor; Kipo, Samuel Lugrie; Kuntworbe, Noble; Boakye-Gyasi, Mariam El

2016-01-01

The study was aimed at developing extended release matrix tablets of poorly water-soluble diclofenac sodium and highly water-soluble metformin hydrochloride by direct compression using cashew gum, xanthan gum and hydroxypropylmethylcellulose (HPMC) as release retardants. The suitability of light grade cashew gum as a direct compression excipient was studied using the SeDeM Diagram Expert System. Thirteen tablet formulations of diclofenac sodium (∼100 mg) and metformin hydrochloride (∼200 mg) were prepared with varying amounts of cashew gum, xanthan gum and HPMC by direct compression. The flow properties of blended powders and the uniformity of weight, crushing strength, friability, swelling index and drug content of compressed tablets were determined. In vitro drug release studies of the matrix tablets were conducted in phosphate buffer (diclofenac: pH 7.4; metformin: pH 6.8) and the kinetics of drug release was determined by fitting the release data to five kinetic models. Cashew gum was found to be suitable for direct compression, having a good compressibility index (ICG) value of 5.173. The diclofenac and metformin matrix tablets produced generally possessed fairly good physical properties. Tablet swelling and drug release in aqueous medium were dependent on the type and amount of release retarding polymer and the solubility of drug used. Extended release of diclofenac (∼24 h) and metformin (∼8-12 h) from the matrix tablets in aqueous medium was achieved using various blends of the polymers. Drug release from diclofenac tablets fitted zero order, first order or Higuchi model while release from metformin tablets followed Higuchi or Hixson-Crowell model. The mechanism of release of the two drugs was mostly through Fickian diffusion and anomalous non-Fickian diffusion. The study has demonstrated the potential of blended hydrophilic polymers in the design and optimization of extended release matrix tablets for soluble and poorly soluble drugs by direct compression.

Somatic embryogenesis of carrot in hormone-free medium: external pH control over morphogenesis

NASA Technical Reports Server (NTRS)

Smith, D. L.; Krikorian, A. D.

1990-01-01

Cultures of preglobular stage proembryos (PGSPs) were initiated from mechanically wounded mature zygotic embryos of carrot, Daucus carota, on a hormone-free, semisolid medium. These PGSPs have been maintained and multiplied for extended periods without their progression into later embryo stages on the same hormone-free medium containing 1 mM NH4+ as the sole nitrogen source. Sustained maintenance of cultures comprised exclusively of PGSPs was dependent on medium pH throughout the culture period. Best growth and multiplication of PGSP cultures occurred when the pH of unbuffered, hormone-free medium fell from 4.5 to 4 over a 2-week period or when buffered medium was titrated to pH 4. If the hormone-free medium was buffered to sustain a pH at or above 4.5, PGSPs developed into later embryo stages. Maintenance with continuous multiplication of PGSPs occurred equally well on medium containing NH4+ or NH4+ and NO3-, but growth was poor with NO3- alone. Additional observations on the effects of medium components such as various nitrogen sources and levels, sucrose concentration, semisolid supports, type of buffer, borate concentration, activated charcoal, and initial pH that permit optimum maintenance of the PGSPs or foster their continued developmental progression into mature embryos and plantlets are reported. The influence of the pH of the hormone-free medium as a determinant in maintaining cultures as PGSPs or allowing their continued embryonic development are unequivocally demonstrated by gross morphology, scanning electron microscopy, and histological preparations.

Spectroscopic and thermodynamic study of charge transfer complex formation between cloxacillin sodium and riboflavin in aqueous ethanol media of varying composition

NASA Astrophysics Data System (ADS)

Roy, Dalim Kumar; Saha, Avijit; Mukherjee, Asok K.

2006-03-01

Cloxacillin sodium has been shown to form a charge transfer complex of 2:1 stoichiometry with riboflavin (Vitamin B 2) in aqueous ethanol medium. The enthalpy and entropy of formation of this complex have been determined by estimating the formation constant spectrophotometrically at five different temperatures in pure water medium. Pronounced effect of dielectric constant of the medium on the magnitude of K has been observed by determining K in aqueous ethanol mixtures of varying composition. This has been rationalized in terms of ionic dissociation of the cloxacillin sodium (D -Na +), hydrolysis of the anion D - and complexation of the free acid, DH with riboflavin.

On the pH of Aqueous Attoliter-Volume Droplets

NASA Astrophysics Data System (ADS)

Ramos, Kieran P.; Velpula, Samson S.; Demille, Trevor B.; Pajela, Ryan; Goldner, Lori S.

Droplets of water dispersed in perfluorinated liquids have widespread use including microfluidics, drug delivery and single-molecule measurements. Perfluorinated liquids are distinctly biocompatible due to their stability, low surface tension, lipophobicity, and hydrophobicity. For this reason, the effect of the perfluorinated surface on droplet contents is usually ignored. However, as the droplet diameter is reduced, we expect that any effect of the water/oil interface on droplet contents will become more obvious. We studied the pH of attoliter-volume aqueous droplets in perfluorinated liquids using pH-sensing fluorescent dyes. Droplets were prepared either by sonication or extrusion from buffer and perfluorinated liquids (FC40 or FC77). A non-ionic surfactant was used to stabilize the droplets. Buffer strength, ionic strength, and pH of the aqueous phase were varied and resulting droplet pH compared to the pH of the buffer from which they were formed. Preliminary data are consistent with a pH in droplets that depends on the concentration of non-ionic surfactant. At low surfactant concentrations, the pH in droplets is distinctly lower than the stock buffer. However, as the concentration of non-ionic surfactant is increased the change in pH decreases. This work was funded by NSF/DBI-1152386.

Preliminary study on the photoproduction of hydroxyl radicals in aqueous solution with Aldrich humic acid, algae and Fe(III) under high-pressure mercury lamp irradiation.

PubMed

Liu, Xianli; Xu, Dong; Wu, Feng; Liao, Zhenhuan; Liu, Jiantong; Deng, Nansheng

2004-03-01

Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals (*OH) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that *OH photoproduction increased from 1.80 to 2.74 microM by increasing the HA concentration from 10 to 40 mg L(-1) at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of *OH in the HA solution with Fe(III) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of *OH in HA solution with algae with or without Fe(III) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of *OH in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest *OH photoproduction at pH 4.0.

Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3). [applications to spacecraft fuel cells

NASA Technical Reports Server (NTRS)

Sheridan, P. S.

1980-01-01

A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.

The influence of surface coating on the properties of water-soluble CdSe and CdSe/ZnS quantum dots

NASA Astrophysics Data System (ADS)

Coto-García, Ana María; Fernández-Argüelles, María T.; Costa-Fernández, José M.; Sanz-Medel, Alfredo; Valledor, Marta; Campo, Juan C.; Ferrero, Francisco J.

2013-01-01

It is well-known that ligands coating the surface of luminescent semiconductor nanocrystals (quantum dots [QDs]) play an important role in the preparation, stability and physical properties of the colloidal QDs in both organic and aqueous media. Here we report on the synthesis and characterization of core (CdSe QDs) and core-shell structured QDs (CdSe/ZnS QDs), both of them stabilized in aqueous medium through different mechanisms of modification of their surface chemistry. The approaches evaluated for QDs transfer to aqueous media were ligand exchange and polymer coating. Experiments were performed using two typical thioalkyl acids as ligands, namely mercaptoacetic acid (QDs-MAA) and 2-mercaptoethanesulphonic acid (QDs-MES), and an amphiphilic polymer (PQDs) based on poly(maleic anhydride) functional groups. The effects of pH (buffer solution), illumination and the presence of ions in the QD environment on the spectroscopic properties of the different synthesized QDs are reported. The stability of the prepared QDs has been comparatively evaluated aimed to elucidate which surface chemistry provides the suitable properties to be employed as fluorescence labels in distinct types of applications. The experimental results and conclusions will be useful for the development of sensitive sensors or assays adopting QDs as fluorescence labels.

Calixarene-entrapped nanoemulsion for uranium extraction from contaminated solutions.

PubMed

Spagnul, Aurélie; Bouvier-Capely, Céline; Phan, Guillaume; Rebière, François; Fattal, Elias

2010-03-01

Accidental cutaneous contamination by actinides such as uranium occurring to nuclear power plant workers can lead to their dissemination in other tissues and induce severe damages. Until now, no specific emergency treatment for such contamination has been developed. The aim of the present work was to formulate a tricarboxylic calix[6]arene molecule, known to exhibit good affinity and selectivity for complexing uranium, within a topical delivery system for the treatment of skin contamination. Since calixarene was shown to reduce oil/water interfacial tension, we have designed an oil-in-water nanoemulsion, taking advantage of the small droplet size offering a high contact surface with the contaminated aqueous medium. Characterization of the calixarene nanoemulsion was performed by determination of the oily droplet size, zeta potential and pH, measured as a function of the calixarene concentration. The obtained results have confirmed the surface localization of calixarene molecules being potentially available to extract uranyl ions from an aqueous contaminated solution. In a preliminary experiments, the calixarene nanoemulsion was used for the removal of free uranium from an aqueous contaminated solution. Results showed that the calixarene nanoemulsion extracted up to 80 +/- 5% of uranium, which demonstrates the potential interest of this delivery system for uranium skin decontamination. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

High performance nano-Ni/Graphite electrode for electro-oxidation in direct alkaline ethanol fuel cells

NASA Astrophysics Data System (ADS)

Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Ahmed, Mohamed A.; Hassan, Hamdy H.

2016-09-01

Ni/Graphite electrocatalysts (Ni/G) are successfully prepared through electrodeposition of Ni from acidic (pH = 0.8) and feebly acidic (pH = 5.5) aqueous Ni (II) baths. The efficiencies of such electrodes are investigated as anodes for direct alkaline ethanol fuel cells through their ethanol electrooxidation cyclic voltammetric (CV) response in alkaline medium. A direct proportionality between the amount of the electrodeposited Ni and its CV response is found. The amounts of the deposited Ni from the two baths are recorded using the Electrochemical Quartz Crystal Microbalance (eQCM). The Ni/G electrodes prepared from the feebly acidic bath show a higher electrocatalytic response than those prepared from the acidic bath. Surface morphology of the Ni particles electrodeposited from feebly acidic bath appears in a nano-scale dimension. Various electrochemical experiments are conducted to confirm that the Ni/G ethanol electrooxidation CV response greatly depends on the pH rather than nickel ion concentration of the deposition bath. The eQCM technique is used to detect the crystalline phases of nickel as α-Ni(OH)2/γ-NiOOH and β-Ni(OH)2/β-NiOOH and their in-situ inter-transformations during the potentiodynamic polarization.

Comparative study on Ce (III) and La (III) solvent extraction and separation from a nitric acid medium by D2EHPA and Cyanex272

NASA Astrophysics Data System (ADS)

Habibpour, R.; Dargahi, M.; Kashi, E.; Bagherpour, M.

2018-01-01

The solvent extraction of Cerium(III) and Lanthanum(III) from nitric acid solution using the organophosphorous extractants Di-(2-ethyl hexyl) phosphate (D2EHPA) and di-2,4,4- trimethylpentyl phosphoric acid (Cyanex272) in kerosene was investigated. In this study, the magnitude of the extraction of Ce(III) was found to be more significant with Cyanex272 than D2EHPA. D2EHPA was found to be a better extractant for La(III). Among the two extractants, Cyanex272 was used for the separation of Ce from La in three stages with an extraction efficiency of 90.2% for Ce. A 556 mg/L Ce solution was used for the scrubbing of La with an efficiency of ≈34%, which required multi stage scrubbing. The study of thermodynamic parameters such as enthalpy, entropy, and Gibbs free energy impart the exothermic and non-spontaneous process. The chemical speciation curves for lanthanum and cerium in the aqueous phase as a function of pH showed that the free La(III) and Ce(III) metal ion species were largely predominate between a pH = 0 and pH = 7.

Impact of reaction conditions on the laccase-catalyzed conversion of bisphenol A.

PubMed

Kim, Young-Jin; Nicell, James A

2006-08-01

The oxidative conversion of aqueous BPA catalyzed by laccase from Trametes versicolor was conducted in a closed, temperature-controlled system containing buffer for pH control. The effects of medium pH, buffer concentration, temperature and mediators and the impacts of dissolved wastewater constituents on BPA conversion were investigated. The optimal pH for BPA conversion was approximately 5, with greater than half maximal conversion and good enzyme stability in the range of 4-7. The stability of the enzyme was not impacted by buffer concentration, nor was BPA conversion. Despite the observation that the enzyme tended to be inactivated at elevated temperatures, enhanced conversion of BPA was observed up until a reaction temperature of 45 degrees C. Of the mediators studied, ABTS was most successful at enhancing the conversion of BPA. Dissolved wastewater constituents that were studied included various inorganic salts, organic compounds and heavy metal ions. BPA conversion was inhibited in the presence of anions such as sulfite, thiosulfate, sulfide, nitrite and cyanide. The metal ions Fe(III) and Cu(II) and the halogens chloride and fluoride substantially suppressed BPA conversion, but the presence of selected organic compounds did not significantly reduce the conversion of BPA.

Organic contaminant separator

DOEpatents

Del Mar, P.

1993-12-28

A process is presented of sample preparation prior to analysis for the concentration of an organic contaminant in an aqueous medium by (a) passing an initial aqueous medium including a minor amount of the organic contaminant through a composite tube comprised of a blend of a polyolefin and a polyester, the composite tube having an internal diameter of from about 0.1 to about 2.0 millimeters and being of sufficient length to permit the organic contaminant to adhere to the composite tube, (b) passing a solvent through the composite tube. The solvent is capable of separating the adhered organic contaminant from the composite tube. Further, an extraction apparatus is presented for sample preparation prior to analysis for the concentration of an organic contaminant in an aqueous medium. The apparatus includes a composite tube comprised of a blend of a polyolefin and a polyester. The composite tube has an internal diameter of from about 0.1 to about 2.0 millimeters and has sufficient length to permit an organic contaminant contained within an aqueous medium passed therethrough to adhere to the composite tube. 2 figures.

Great Salt Lake Composition and Rare Earth Speciation Analysis

DOE Data Explorer

Jiao, Yongqin; Lammers, Laura; Brewer, Aaron

2017-04-19

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

EFFECT OF AQUEOUS PHASE PROPERTIES ON CLAY PARTICLE ZETA POTENTIAL AND ELECTRO-OSMOTIC PERMEABILITY: IMPLICATIONS FOR ELECTRO-KINETIC SOIL REMEDIATION PROCESSES

EPA Science Inventory

The influence of aqueous phase properties (pH, ionic strength and divalent metal ion concentration) on clay particle zeta potential and packed-bed electro-osmotic permeability was quantified. Although pH strongly altered the zeta potential of a Georgia kaolinite, it did not signi...

Initial pH of medium affects organic acids production but do not affect phosphate solubilization.

PubMed

Marra, Leandro M; de Oliveira-Longatti, Silvia M; Soares, Cláudio R F S; de Lima, José M; Olivares, Fabio L; Moreira, Fatima M S

2015-06-01

The pH of the culture medium directly influences the growth of microorganisms and the chemical processes that they perform. The aim of this study was to assess the influence of the initial pH of the culture medium on the production of 11 low-molecular-weight organic acids and on the solubilization of calcium phosphate by bacteria in growth medium (NBRIP). The following strains isolated from cowpea nodules were studied: UFLA03-08 (Rhizobium tropici), UFLA03-09 (Acinetobacter sp.), UFLA03-10 (Paenibacillus kribbensis), UFLA03-106 (Paenibacillus kribbensis) and UFLA03-116 (Paenibacillus sp.). The strains UFLA03-08, UFLA03-09, UFLA03-10 and UFLA03-106 solubilized Ca3(PO4)2 in liquid medium regardless of the initial pH, although without a significant difference between the treatments. The production of organic acids by these strains was assessed for all of the initial pH values investigated, and differences between the treatments were observed. Strains UFLA03-09 and UFLA03-10 produced the same acids at different initial pH values in the culture medium. There was no correlation between phosphorus solubilized from Ca3(PO4)2 in NBRIP liquid medium and the concentration of total organic acids at the different initial pH values. Therefore, the initial pH of the culture medium influences the production of organic acids by the strains UFLA03-08, UFLA03-09, UFLA03-10 and UFLA03-106 but it does not affect calcium phosphate solubilization.

Monitoring of bisphenols in canned tuna from Italian markets.

PubMed

Fattore, Margherita; Russo, Giacomo; Barbato, Francesco; Grumetto, Lucia; Albrizio, Stefania

2015-09-01

Monitoring of food contamination from bisphenols is a necessary process for the consumers' risk assessment. A method for the quali-quantitative analysis of Bisphenol A (BPA), Bisphenol B (BPB), Bisphenol A Diglycidyl Ether (BADGE), and Bisphenol F Diglycidyl Ether (BFDGE), by liquid chromatography with fluorescence detection (LC-FD), was performed and validated for their determination in 33 samples of tuna fish, canned in either oil or aqueous medium. Samples were collected in Italian markets. Tuna and the correspondent preservation medium were analyzed separately. Detected levels of bisphenols ranged from 19.1 to 187.0 ng/g in tuna matrix and from 6.3 to 66.9 ng/mL in oil medium. No bisphenols were found in aqueous medium. At least one of the analytes was found in 83% of the tuna samples in oil medium, whereas tuna samples in aqueous medium showed BPA alone in 67% of samples. 21% of the oil medium samples resulted positive for at least one bisphenol. On the basis of measured concentrations and general daily ingestion rate of canned tuna fish, the probable daily intake of BPA for Italian population was calculated. Copyright © 2015 Elsevier Ltd. All rights reserved.

An extended model based on the modified Nernst-Planck equation for describing transdermal iontophoresis of weak electrolytes.

PubMed

Imanidis, Georgios; Luetolf, Peter

2006-07-01

An extended model for iontophoretic enhancement of transdermal drug permeation under constant voltage is described based on the previously modified Nernst-Planck equation, which included the effect of convective solvent flow. This model resulted in an analytical expression for the enhancement factor as a function of applied voltage, convective flow velocity due to electroosmosis, ratio of lipid to aqueous pathway passive permeability, and weighted average net ionic valence of the permeant in the aqueous epidermis domain. The shift of pH in the epidermis compared to bulk caused by the electrical double layer at the lipid-aqueous domain interface was evaluated using the Poisson-Boltzmann equation. This was solved numerically for representative surface charge densities and yielded pH differences between bulk and epidermal aqueous domain between 0.05 and 0.4 pH units. The developed model was used to analyze the experimental enhancement of an amphoteric weak electrolyte measured in vitro using human cadaver epidermis and a voltage of 250 mV at different pH values. Parameter values characterizing the involved factors were determined that yielded the experimental enhancement factors and passive permeability coefficients at all pH values. The model provided a very good agreement between experimental and calculated enhancement and passive permeability. The deduced parameters showed (i) that the pH shift in the aqueous permeation pathway had a notable effect on the ionic valence and the partitioning of the drug in this domain for a high surface charge density and depending on the pK(a) and pI of the drug in relation to the bulk pH; (ii) the magnitude and the direction of convective transport due to electroosmosis typically reflected the density and sign, respectively, of surface charge of the tissue and its effect on enhancement was substantial for bulk pH values differing from the pI of epidermal tissue; (iii) the aqueous pathway predominantly determined passive permeability of the studied compound despite its measurable lipophilicity and therefore the lipid pathway did not notably affect enhancement. Hence, the proposed model can provide a good quantitative insight into the interplay between different phenomena and permeant properties influencing iontophoresis and can potentially be used as a predictive tool of the process.

Process and apparatus for the production of BI-213 cations

DOEpatents

Horwitz, E. Philip; Hines, John J.; Chiarizia, Renato; Dietz, Mark

1998-01-01

A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed.

Process and apparatus for the production of Bi-213 cations

DOEpatents

Horwitz, E.P.; Hines, J.J.; Chiarizia, R.; Dietz, M.

1998-12-29

A process for producing substantially impurity-free Bi-213 cations is disclosed. An aqueous acid feed solution containing Ac-225 cations is contacted with an ion exchange medium to bind the Ac-225 cations and form an Ac-225-laden ion exchange medium. The bound Ac-225 incubates on the ion exchange medium to form Bi-213 cations by radioactive decay. The Bi-213 cations are then recovered from the Ac-225-laden ion exchange medium to form a substantially impurity-free aqueous Bi-213 cation acid solution. An apparatus for carrying out this process is also disclosed. 7 figs.

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics.

PubMed

Anirudhan, T S; Divya, L; Suchithra, P S

2009-01-01

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.

Sorption-desorption of carbamazepine by palygorskite-montmorillonite (PM) filter medium.

PubMed

Berhane, Tedros M; Levy, Jonathan; Krekeler, Mark P S; Danielson, Neil D; Stalcup, Apryll

2015-01-23

Palygorskite-montmorillonite (PM) was studied as a potential sewage treatment effluent filter material for carbamazepine. Batch sorption experiments were conducted as a function of granule size (0.3-0.6, 1.7-2.0 and 2.8mm) and different sewage effluent conditions (pH, ionic strength and temperature). Results showed PM had a mix of fibrous and plate-like morphologies. Sorption and desorption isotherms were fitted to the Freundlich model. Sorption is granule size-dependent and the medium granule size would be an appropriate size for optimizing both flow and carbamazepine retention. Highest and lowest sorption capacities corresponded to the smallest and the largest granule sizes, respectively. The lowest and the highest equilibrium aqueous (Ce) and sorbed (qe) carbamazepine concentrations were 0.4 mg L(-1) and 4.5 mg L(-1), and 0.6 mg kg(-1) and 411.8 mg kg(-1), respectively. Observed higher relative sorption at elevated concentrations with a Freundlich exponent greater than one, indicated cooperative sorption. The sorption-desorption hysteresis (isotherm non-singularity) indicated irreversible sorption. Higher sorption observed at higher rather than at lower ionic strength conditions is likely due to a salting-out effect. Negative free energy and the inverse sorption capacity-temperature relationship indicated the carbamazepine sorption process was favorable or spontaneous. Solution pH had little effect on sorption. Copyright © 2014 Elsevier B.V. All rights reserved.

Radiolysis of aqueous solutions of thiamine

NASA Astrophysics Data System (ADS)

Chijate, C.; Albarran, G.; Negron-Mendoza, A.

1998-06-01

The results of the radiolysis of aqueous solutions of thiamine (vitamin B 1) are presented. The yields for decomposition of thiamine and the product of radiolytic products were determined. The G values decrease as the dose increases. Some radiolytic products were identified. Decomposition of thiamine was slightly dependent on the presence of oxygen and on the pH of the solution. At pH 4.4 with a concentration of 2.5 × 10 -4 mol L -1 of thiamine in an oxygen free aqueous solution, the G 0 value for decomposition is 5.0.

Effect of calcium oxalate on the photocatalytic degradation of Orange II on ZnO surface

NASA Astrophysics Data System (ADS)

Bassaid, S.; Ziane, B.; Badaoui, M.; Chaib, M.; Robert, D.

2013-06-01

The photocatalytic degradation of aqueous solution of Orange II, has been investigated in the presence of ZnO catalyst with calcium oxalate as sacrificial agent. This study demonstrated that the performance of ZnO photocatalyst can be improved by addition of calcium oxalate. Results show that adsorption is an important parameter controlling the degradation phenomena. Indeed, the added oxalate causes a drop in the pH medium, what causes a better adsorption of Orange II on the ZnO surface. The effect of calcium oxalate is to increase the concentration of superoxides (O{2/·-}) and hydroperoxides (HO2·) radicals, which are key intermediaries in the mechanism of photodegradation because of their powerful force of oxidation.

Oxidation of 1,3,7-trimethylxanthine by hypochlorite ion

NASA Astrophysics Data System (ADS)

Kheidorov, V. P.; Ershov, Yu. A.; Chalyi, G. Yu.; Titorovich, O. V.

2011-08-01

The kinetics of the oxidative conversion of 1,3,7-trimethylxanthine upon treatment with hypochlorite ions (OCl-) in aqueous medium at 283-298 K and pH 8.2 was studied. The reaction order with respect to each component was determined and proved to be 1. It was established that the temperature dependence of the reaction rate follows the Arrhenius equation. The activation parameters of the reaction were measured: E a = 33.58 kJ/mol, Δ H ≠ = 31.12 kJ/mol, Δ S ≠ = -170.02 J/(K mol), Δ G ≠ = 81.45 kJ/mol. The stoichiometry of the reaction was studied, and the chemistry of the oxidative conversion of caffeine treated with OCl- is discussed.

Aqueous extract of yellow maca (Lepidium meyenii) improves sperm count in experimental animals but response depends on hypocotyl size, pH and routes of administration.

PubMed

Sanchez-Salazar, L; Gonzales, G F

2018-04-01

Lepidium meyenii, a Peruvian plant growing over 4000 m.a.s.l., has effects on nutrition and fertility. The purpose of this study was to evaluate the sperm count in 105 male mice receiving boiled aqueous extract of yellow maca hypocotyls from different sizes, under different pH conditions and using two different routes of administration. Five mice per group were treated daily for 3 days with vehicle (oral and intraperitoneal) or maca aqueous extracts (5 mg/0.5 ml/day) belonging to the first, second, third and fourth categories, according to their hypocotyl size. On day four, sperm count was evaluated at testis, epididymis and vas deferens. Sperm count was higher in mice receiving maca from the larger sizes (first and second categories). Reduction in maca extract pH increased sperm count, whereas an increase in the pH resulted in a reduction in sperm count. The effect of pH reduction is observed only in maca from the first and second categories. Aqueous extract of maca was effective only after oral administration. In conclusion, the larger size of hypocotyls presented the best biological effect, and the low pH in the extract and the transformation after gastrointestinal passage are both important for its biological action. © 2017 Blackwell Verlag GmbH.

Adsorption of non-ionic ABC triblock copolymers: Surface modification of TiO2 suspensions in aqueous and non-aqueous medium

NASA Astrophysics Data System (ADS)

Lerch, Jean-Philippe; Atanase, Leonard Ionut; Riess, Gérard

2017-10-01

A series of non-ionic ABC triblock copolymers, such as poly(butadiene)-b-poly(2-vinylpyrridine)-b-poly(ethylene oxide) (PB-P2VP-PEO) were synthesized by sequential anionic polymerizations. For these copolymers comprising an organo-soluble PB and a water-soluble PEO block, their P2VP middle block has been selected for its anchoring capacity on solid surfaces. The adsorption isotherms on TiO2 were obtained in heptane and in aqueous medium, as selective solvents. In both of these cases, the P2VP middle block provides the surface anchoring, whereas PB and PEO sequences are acting as stabilizing moieties in heptane and water respectively. By extension to ABC triblock copolymers of the scaling theory developed for diblock copolymers, the density of adsorbed chains could be correlated with the molecular characteristics of the PB-P2VP-PEO triblock copolymers. From a practical point a view, it could be demonstrated that these copolymers are efficient dispersing agents for the TiO2 pigments in both aqueous and non-aqueous medium.

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

DOEpatents

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

1988-01-01

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

Simple Cadmium Sulfide Compound with Stable 95 % Selectivity for Carbon Dioxide Electroreduction in Aqueous Medium.

PubMed

Li, Yu Hang; Cheng, Ling; Liu, Peng Fei; Zhang, Le; Zu, Meng Yang; Wang, Chong Wu; Jin, Yan Huan; Cao, Xiao Ming; Yang, Hua Gui; Li, Chunzhong

2018-05-09

A simple cadmium sulfide nanomaterial is found to be an efficient and stable electrocatalyst for CO 2 reduction in aqueous medium for more than 40 h with a steady CO faradaic efficiency of approximately 95 %. Moreover, it can realize a current density of -10 mA cm -2 at an overpotential of -0.55 V on a porous substrate with similar selectivity. Theoretical and experimental results confirm that the high selectivity for CO 2 reduction is due to its (0 0 0 2) face with sulfur vacancies that prefers CO 2 molecule reduction in aqueous medium. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aqueous Alteration on Mars: Evidence from Landed Missions

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Morris, Richard V.; Clark, Benton C., III; Yen, Albert S.; Gellert, Ralf

2015-01-01

Mineralogical and geochemical data returned by orbiters and landers over the past 15 years have substantially enhanced our understanding of the history of aqueous alteration on Mars. Here, we summarize aqueous processes that have been implied from data collected by landed missions. Mars is a basaltic planet. The geochemistry of most materials has not been “extensively” altered by open-system aqueous processes and have average Mars crustal compositions. There are few examples of open-system alteration, such as Gale crater’s Pahrump Hills mudstone. Types of aqueous alteration include (1) acid-sulfate and (2) hydrolytic (circum-neutral/alkaline pH) with varying water-to-rock ratios. Several hypotheses have been suggested for acid-sulfate alteration including (1) oxidative weathering of ultramafic igneous rocks containing sulfides; (2) sulfuric acid weathering of basaltic materials; (3) acid fog weathering of basaltic materials; and (4) near-neutral pH subsurface solutions rich in Fe (sup 2 plus) that rapidly oxidized to Fe (sup 3 plus) producing excess acidity. Meridiani Planum’s sulfate-rich sedimentary deposit containing jarosite is the most “famous” acid-sulfate environment visited on Mars, although ferric sulfate-rich soils are common in Gusev crater’s Columbia Hills and jarosite was recently discovered in the Pahrump Hills. An example of aqueous alteration under circum-neutral pH conditions is the formation of Fe-saponite with magnetite in situ via aqueous alteration of olivine in Gale crater’s Sheepbed mudstone. Circum-neutral pH, hydrothermal conditions were likely required for the formation of Mg-Fe carbonate in the Columbia Hills. Diagenetic features (e.g., spherules, fracture filled veins) indicate multiple episodes of aqueous alteration/diagenesis in most sedimentary deposits. However, low water-to-rock ratios are prominent at most sites visited by landed missions (e.g., limited water for reaction to form crystalline phases possibly resulting in large amounts of short-range ordered materials and little physical separation of primary and secondary materials). Most of the aqueous alteration appears to have occurred early in the planet’s history; however, minor aqueous alteration may be occurring at the surface today (e.g., thin films of water forming carbonates akin to those discovered by Phoenix).

Analysis of the polyphenols content in medicinal plants based on the reduction of Cu(II)/bicinchoninic complexes.

PubMed

Marino, Daniele Cestari; Sabino, Larissa Zuppardo Lacerda; Armando, José; Ruggiero, Andrea De Andrade; Moya, Horacio Dorigan

2009-12-09

A spectrophotometric method is proposed for the determination of the polyphenols content in aqueous extracts of plants. The method is based on the reduction of Cu(II) to Cu(I) by polyphenols, in the presence of bicinchoninic acid in a buffered medium (ammonium acetate, pH 7.0) with the formation of Cu(I)/BCA complexes. A calibration curve of absorbance (at 558 nm) vs tannic acid concentration is linear (r = 0.995; n = 7) with tannic acid from 0.1 to 0.7 micromol L(-1). The limit of detection and relative standard deviation were 40 nmol L(-1) (99% confidence level) and 3.8% (0.4 micromol L(-1) tannic acid, n = 7), respectively. For the aqueous extracts of Hamamelis virginiana L., Maytenus ilicifolia Mart. ex Reissek, Hydrocotyle bonariensis Lam, Annona muricata L., Myrciaria cauliflora (Mart.) O. Berg., Caesearia sylvestris Sw., Schinus terebinthifolia (Raddi), and Stryphnodendron adstringens (Mart.) Coville, the total polyphenol contents, expressed as tannic acid, were 3.5, 1.3, 2.0, 3.1, 15.4, 3.1, 9.1, and 6.9%, respectively.

Measuring changes in the mass of single subcellular organelles using x-ray microscopy

NASA Astrophysics Data System (ADS)

Goncz, Kaarin K.; Moronne, Mario M.; Lin, W.; Rothman, Stephen S.

1993-01-01

Using quantitative scanning transmission x-ray microscopy, zymogen granules isolated from pancreatic acinar cells were observed suspended in aqueous medium at 50 nm resolution. From 3.64 nm x-ray absorption data, the protein content and rate of protein efflux from individual granules were determined. This was accomplished with a specially designed silicon nitride based wet-cell that allowed continuous perfusion and monitoring of individual granules in a variety of different aqueous environments. Granules suspended in 300 mM sucrose, 5 mM phosphate buffer (pH 6.0) were observed to continuously decrease in size and protein content over a period of several hours. Sudden lysis of the granules was not observed. From the flux data, the apparent protein permeability coefficients for individual granules were determined to range from 1 - 10 X 10-10 cm/sec with an average of 4.78 +/- 3.0 X 10-10 cm/sec. We believe this is the first quantitative population profile determined for a subcellular organelle developed from measurements of individual members of the population.

Zn(II)-cyclam based chromogenic sensors for recognition of ATP in aqueous solution under physiological conditions and their application as viable staining agents for microorganism.

PubMed

Mahato, Prasenjit; Ghosh, Amrita; Mishra, Sanjiv K; Shrivastav, Anupama; Mishra, Sandhya; Das, Amitava

2011-05-02

Two chromogenic complexes, L.Zn (where L is (E)-4-((4-(1,4,8,11-tetraazacyclotetradecan-1-ylsulfonyl)phenyl)diazenyl)-N,N-dimethylaniline) and its [2]pseudorotaxane form (α-CD.L.Zn), were found to bind preferentially to adenosine triphosphate (ATP), among all other common anions and biologically important phosphate (AMP, ADP, pyrophosphate, and phosphate) ions in aqueous HEPES buffer medium of pH 7.2. Studies with live cell cultures of prokaryotic microbes revealed that binding of these two reagents to intercellular ATP, produced in situ, could be used in delineating the gram-positive and the gram-negative bacteria. More importantly, these dyes were found to be nontoxic to living microbes (eukaryotes and prokaryotes) and could be used for studying the cell growth dynamics. Binding to these two viable staining agents to intercellular ATP was also confirmed by spectroscopic studies on cell growth in the presence of different respiratory inhibitors that influence the intercellular ATP generation. © 2011 American Chemical Society

Quercetin loaded biopolymeric colloidal particles prepared by simultaneous precipitation of quercetin with hydrophobic protein in aqueous medium.

PubMed

Patel, Ashok R; Heussen, Patricia C M; Hazekamp, Johan; Drost, Ellen; Velikov, Krassimir P

2012-07-15

Quercetin loaded biopolymeric colloidal particles were prepared by precipitating quercetin (water insoluble polyphenol) and zein (hydrophobic protein), simultaneously, by adding their hydro-alcoholic solution to aqueous solution in presence of sodium caseinate as an electrosteric stabiliser. The presence of protein resulted in altering the shape of quercetin precipitates from needle-like to spherical shape at higher zein proportions, as confirmed by transmission electron microscopy. The average particle size of zein:quercetin composite particles was below 200 nm (130-161 nm) with negative surface charge (-30 to -41 mV), as confirmed by dynamic light scattering and electrophoretic mobility data. Solid state characterisation (X-ray diffraction) and spectroscopic measurements (UV-Vis and IR spectroscopy) confirmed characteristic changes in quercetin due to the entrapment in the biopolymeric matrix of colloidal particles. Results from anti-oxidant study demonstrated the advantage of entrapping quercetin in the colloidal particles in terms of the chemical stability in the alkaline pH and against photodegradation under UV-light irradiation. Copyright © 2012 Elsevier Ltd. All rights reserved.

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 2. Light Lanthanides (Ce–Eu)

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

Mioduski, Tomasz; Gumiński, Cezary, E-mail: cegie@chem.uw.edu.pl; Zeng, Dewen, E-mail: dewen-zeng@hotmail.com

This is the second part of the volume devoted to the evaluation of experimental solubility data for rare earth metal (REM) fluorides in water as well as in aqueous ternary and multicomponent systems. Fluorides of Ce, Pr, Nd, Pm, Sm, and Eu (so-called light lanthanides), as the main solutes, are covered in the present part, which has thorough coverage of the experimental literature through the end of 2012. The experimentally unknown solubility value for PmF{sub 3} in water was predicted by an interpolation of the solubility values for NdF{sub 3} and SmF{sub 3} at 298 K. General features of themore » systems, such as the nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, pH, mixed solvent medium on the solubility, quality of the solubility results, and solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.« less

[Adsorption of Congo red from aqueous solution on hydroxyapatite].

PubMed

Zhan, Yan-Hui; Lin, Jian-Wei

2013-08-01

The adsorption of Congo red (CR) from aqueous solution on hydroxyapatite was investigated using batch experiments. The hydroxyapatite was effective for CR removal from aqueous solution. The adsorption kinetics of CR on hydroxyapatite well followed a pseudo-second-order model. The equilibrium adsorption data of CR on hydroxyapatite could be described by the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated and showed that the adsorption of CR on hydroxyapatite was spontaneous and exothermic in nature. The CR adsorption capacity for hydroxyapatite decreased significantly with increasing pH from 8 to 10. Thermal regeneration showed that hydroxyapatite could be used for six desorption-adsorption cycles with high removal efficiency for CR in each cycle. The mechanisms for CR adsorption on hydroxyapatite with pH value below the pH at point of zero charge (pH(PZC)) include electrostatic attraction, hydrogen bonding and Lewis acid-base interaction. The mechanisms for CR adsorption on hydroxyapatite with pH value above its pH(PZC) include hydrogen bonding and Lewis acid-base interaction. Results of this work indicate that hydroxyapatite is a promising adsorbent for CR removal from aqueous solution.

Relation between the adsorbed quantity and the immersion enthalpy in catechol aqueous solutions on activated carbons.

PubMed

Moreno-Piraján, Juan Carlos; Blanco, Diego; Giraldo, Liliana

2012-01-01

An activated carbon, Carbochem(TM)-PS230, was modified by chemical and thermal treatment in flow of H(2), in order to evaluate the influence of the activated carbon chemical characteristics in the adsorption of the catechol. The catechol adsorption in aqueous solution was studied along with the effect of the pH solution in the adsorption process of modified activated carbons and the variation of immersion enthalpy of activated carbons in the aqueous solutions of catechol. The interaction solid-solution is characterized by adsorption isotherms analysis, at 298 K and pH 7, 9 and 11 in order to evaluate the adsorption value above and below that of the catechol pK(a). The adsorption capacity of carbons increases when the solution pH decreases. The retained amount increases slightly in the reduced carbon to maximum adsorption pH and diminishes in the oxidized carbon. Similar conclusions are obtained from the immersion enthalpies, whose values increase with the solute quantity retained. In granular activated carbon (CAG), the immersion enthalpies obtained are between 21.5 and 45.7 J·g(-1) for catechol aqueous solutions in a range of 20 at 1500 mg·L(-1).

Relation Between the Adsorbed Quantity and the Immersion Enthalpy in Catechol Aqueous Solutions on Activated Carbons

PubMed Central

Moreno-Piraján, Juan Carlos; Blanco, Diego; Giraldo, Liliana

2012-01-01

An activated carbon, CarbochemTM—PS230, was modified by chemical and thermal treatment in flow of H2, in order to evaluate the influence of the activated carbon chemical characteristics in the adsorption of the catechol. The catechol adsorption in aqueous solution was studied along with the effect of the pH solution in the adsorption process of modified activated carbons and the variation of immersion enthalpy of activated carbons in the aqueous solutions of catechol. The interaction solid-solution is characterized by adsorption isotherms analysis, at 298 K and pH 7, 9 and 11 in order to evaluate the adsorption value above and below that of the catechol pKa. The adsorption capacity of carbons increases when the solution pH decreases. The retained amount increases slightly in the reduced carbon to maximum adsorption pH and diminishes in the oxidized carbon. Similar conclusions are obtained from the immersion enthalpies, whose values increase with the solute quantity retained. In granular activated carbon (CAG), the immersion enthalpies obtained are between 21.5 and 45.7 J·g−1 for catechol aqueous solutions in a range of 20 at 1500 mg·L−1. PMID:22312237

Effect of pH on skin permeation enhancement of acidic drugs by l-menthol-ethanol system.

PubMed

Katayama, K; Matsui, R; Hatanaka, T; Koizumi, T

2001-09-11

The effect of pH on the skin permeation enhancement of three acidic drugs by the l-menthol-ethanol system was investigated. The total flux of acidic drugs from the system remarkably varied over the pH range 3.0-8.0, and the permeation enhancement factor depended on the system pH and drug. A skin permeation model, which consists of two permeant (unionized and ionized) species, two system (oily and aqueous) phases, and two permeation (lipid and pore) pathways, was developed. The assumptions were made that only the unionized species can distribute to the oily phase and transport via the lipid pathway. The model explained the relationship between the concentration of drug in the aqueous phase and system pH. The skin permeability data were also described by the model and permeability coefficients corresponding to the physicochemical properties of permeant were calculated for the lipid and pore pathways. The model simulation showed that the permeation of acidic drugs occurred from the aqueous phase and the oily phase acted as a reservoir. Whether the total flux increased with increase of pH was dependent on the lipophilicity of drug. These results suggest that the pH of l-menthol-ethanol system should be given attention to elicit the maximum permeation enhancement.

Advanced oxidation of acridine orange by aqueous alkaline iodine.

PubMed

Azmat, Rafia; Qamar, Noshab; Naz, Raheela; Khursheed, Anum

2016-11-01

The advanced oxidation process is certainly used for the dye waste water treatment. In this continuation a new advanced oxidation via aqueous alkaline iodine was developed for the oxidation of acridine orange (AO) {3, 6 -bis (dimethylamino) acridine zinc chloride double salt}. Oxidation Kinetics of AO by alkaline solution of iodine was investigated spectrophotometrically at λ max 491 nm. The reaction was monitored at various operational parameters like several concentrations of dye and iodine, pH, salt electrolyte and temperature. The initial steps of oxidation kinetics followed fractional order reaction with respect to the dye while depend upon the incremental amount of iodine to certain extent whereas maximum oxidation of AO was achieved at high pH. Decline in the reaction rate in the presence of salt electrolyte suggested the presence of oppositely charged species in the rate determining step. Kinetic data revealed that the de-colorization mechanism involves triodate (I 3 - ) species, instead of hypoidate (OI - ) and hypiodous acid (HOI), in alkaline medium during the photo-excitation of hydrolyzed AO. Alleviated concentration of alkali result in decreasing of rate of reaction, clearly indicate that the iodine species are active oxidizing species instead of OH radical. Activation parameters at elevated temperatures were determined which revealed that highly solvated state of dye complex existed into solution. Reaction mixture was subjected to UV/Visible and GC mass spectrum analysis that proves the secondary consecutive reaction was operative in rate determining step and finally dye complex end into smaller fragments.

Improved specific productivity in cephalexin synthesis by immobilized PGA in silica magnetic micro-particles.

PubMed

Bernardino, Susana M S A; Fernandes, Pedro; Fonseca, Luís P

2010-12-01

There is a marked trend in pharmaceutical industry towards the replacement of classical organic methods by "green" alternatives that minimize or eliminate the generation of waste and avoid, where possible, the use of toxic and/or hazardous reagents and solvents. In this work the kinetically controlled synthesis of cephalexin by soluble and penicillin G acylase immobilized in sol-gel micro-particles with magnetic properties was performed in aqueous media with PGME and 7-ADCA as substrates, at different concentrations of substrate, temperature, pH, enzyme to substrate ratio and acyl donor to nucleophile ratio. Excess acyl donor had a strong effect on cephalexin productivity. A PGME/7-ADCA ratio of 3 was considered optimum. A maximum specific productivity of 5.9 mmol h(-1), gbiocatalyst(-1) at 160 mM 7-ADCA, 480 mM PGME and low enzyme to substrate ratio at 32.5 U mmol(-1) 7-ADCA was obtained with immobilized PGA in full aqueous medium, suggesting that diffusional limitations were minimized when compared with other commercial biocatalysts. A half-life of 133 h for the immobilized biocatalyst was estimated during cephalexin synthesis in the presence of 100 mM 7-ADCA and 300 mM PGME, in 50 mM Tris/HCl at pH 7.2 and 14°C. These results compare quite favorably with those previously reported for the kinetically controlled synthesis of cephalexin. © 2010 Wiley Periodicals, Inc.

Microwave-assisted activated carbon from cocoa shell as adsorbent for removal of sodium diclofenac and nimesulide from aqueous effluents.

PubMed

Saucier, Caroline; Adebayo, Matthew A; Lima, Eder C; Cataluña, Renato; Thue, Pascal S; Prola, Lizie D T; Puchana-Rosero, M J; Machado, Fernando M; Pavan, Flavio A; Dotto, G L

2015-05-30

Microwave-induced chemical activation process was used to prepare an activated carbon from cocoa shell for efficient removal of two anti-inflammatories, sodium diclofenac (DFC) and nimesulide (NM), from aqueous solutions. A paste was obtained from a mixture of cocoa shell and inorganic components; with a ratio of inorganic: organic of 1 (CSC-1.0). The mixture was pyrolyzed in a microwave oven in less than 10 min. The CSC-1.0 was acidified with a 6 mol L(-1) HCl under reflux to produce MWCS-1.0. The CSC-1.0 and MWCS-1.0 were characterized using FTIR, SEM, N2 adsorption/desorption curves, X-ray diffraction, and point of zero charge (pHpzc). Experimental variables such as initial pH of the adsorbate solutions and contact time were optimized for adsorptive characteristics of MWCS-1.0. The optimum pH for removal of anti-inflammatories ranged between 7.0 and 8.0. The kinetic of adsorption was investigated using general order, pseudo first-order and pseu do-second order kinetic models. The maximum amounts of DCF and NM adsorbed onto MWCS-1.0 at 25 °C are 63.47 and 74.81 mg g(-1), respectively. The adsorbent was tested on two simulated hospital effluents. MWCS-1.0 is capable of efficient removal of DCF and NM from a medium that contains high sugar and salt concentrations. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparison of phthalic acid removal from aqueous solution by electrochemical methods: Optimization, kinetic and sludge study.

PubMed

Sandhwar, Vishal Kumar; Prasad, Basheshwar

2017-12-01

In this work, comparative study between electrochemical processes such as electrocoagulation (EC), peroxi-coagulation (PC) and peroxi-electrocoagulation (PEC) was performed for the removal of phthalic acid (PA) and chemical oxygen demand (COD) from aqueous medium. Initially, acid treatment was studied at various pH (1-3) and temperature (10-55 °C). Subsequently, the supernatant was re-treated by electrochemical processes such as EC, PC and PEC separately. Independent parameters viz. pH, current density (CD), electrolyte concentration (m), electrode gap (g), H 2 O 2 concentration and electrolysis time (t) were optimized by Central Composite Design (CCD) for these electrochemical processes. All three processes were compared based on removal, energy consumption, kinetic analysis, operating cost and sludge characteristics. In this study, PEC process was found more efficient among EC, PC and PEC processes in order to get maximum removal, minimum energy consumption and minimum operating cost. Maximum removal of PA- 68.21%, 74.36%, 82.25% & COD- 64.79%, 68.15%, 75.21% with energy consumption - 120.95, 97.51, 65.68 (kWh/kg COD removed) were attained through EC, PC and PEC processes respectively at their corresponding optimum conditions. Results indicated that PA and COD removals are in order of PEC > PC > EC under optimum conditions. First order kinetic model was found able to describe the degradation kinetics and provided best correlation for the removal rate within the acceptable error range. Copyright © 2017 Elsevier Ltd. All rights reserved.

Geochemical interactions between constituents in acidic groundwater and alluvium in an aquifer near Globe, Arizona

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1994-01-01

Acidic water from a copper-mining area has contaminated an alluvial aquifer and stream near Globe, Arizona. The most contaminated groundwater has a pH of 3.3, and contains about 100 mmol/1 SO4, 50 mmol/1 Fe, 11 mmol/1 Al and 3 mmol/1 Cu. Reactions between alluvium and acidic groundwater were first evaluated in laboratory column experiments. A geochemical model was developed and used in the equilibrium speciation program, MINTEQA2, to simulate breakthrough curves for different constituents from the column. The geochemical model was then used to simulate the measured changes in concentration of aqueous constituents along a flow path in the aquifer.The pH was predominantly controlled by reaction with carbonate minerals. Where carbonates had been dissolved, adsorption of H+ by iron oxides was used to simulate pH. Acidic groundwater contained little or no dissolved oxygen, and most aqueous Fe was present as Fe(II). In the anoxic core of the plume, Fe(II) was oxidized by MnO2 to Fe(III), which then precipitated as Fe(OH)3. Attenuation of aqueous Cu, Co, Mn, Ni and Zn was a function of pH and could be quantitatively modeled with the diffuse-layer, surface complexation model in MINTEQA2. Aluminum precipitated as amorphous Al(OH)3 at pH < 4.7 and as AlOHSO4 at pH < 4.7. Aqueous Ca and SO4were close to equilibrium with gypsum.After the alluvium in the column had reached equilibrium with acidic groundwater, uncontaminated groundwater was eluted through the column to evaluate the effect of reactants on groundwater remediation. The concentration of Fe, Mn, Cu, Co, Ni and Zn rapidly decreased to the detection limits within a few pore volumes. All of the gypsum that had precipitated initially redissolved, resulting in elevated Ca and SO4concentrations for about 5 pore volumes. Aluminum and pH exhibited the most potential for continued adverse effects on groundwater quality. As H+ desorbed from Fe(OH)3, pH remained below 4.5 for more than 20 pore volumes, resulting in dissolution of AlOHSO4 and elevated aqueous Al.

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

PubMed

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

Photo-induced degradation of some flavins in aqueous solution

NASA Astrophysics Data System (ADS)

Holzer, W.; Shirdel, J.; Zirak, P.; Penzkofer, A.; Hegemann, P.; Deutzmann, R.; Hochmuth, E.

2005-01-01

The blue-light induced photo-degradation of FMN, FAD, riboflavin, lumiflavin, and lumichrome in aqueous solution at pH 8 is studied by measurement of absorption coefficient spectral changes due to continuous excitation at 428 nm. The quantum yields of photo-degradation determined are ϕD(riboflavin, pH 8) ≈ 7.8 × 10 -3, ϕD(FMN, pH 5.6) ≈ 7.3 × 10 -3, ϕD(FMN, pH 8) ≈ 4.6 × 10 -3, ϕD(FAD, pH 8) ≈ 3.7 × 10 -4, ϕD(lumichrome, pH 8) ≈ 1.8 × 10 -4, and ϕD(lumiflavin, pH 8) ⩽ 1.1 × 10 -5. In a mass-spectroscopic analysis, the photo-products of FMN dissolved in water (solution pH is 5.6) were identified to be lumichrome and the lumiflavin derivatives dihydroxymethyllumiflavin, formyllumiflavin, and lumiflavin-hydroxy-acetaldehyde. An absorption and emission spectroscopic characterisation of the primary photoproducts of FMN at pH 8 is carried out.

Application of pH-sensitive magnetic nanoparticles microgel as a sorbent for the preconcentration of phenoxy acid herbicides in water samples.

PubMed

Tabani, Hadi; Khodaei, Kamal; Bide, Yasamin; Zare, Farzaneh Dorabadi; Mirzaei, Saeed; Fakhari, Ali Reza

2015-08-14

Introducing new sorbents is an interesting and debatable issue in the field of sample preparation. In this study, for the first time, a pH-sensitive magnetic nanoparticles microgel, Fe3O4-SiO2-oly(4-vinylpyridine), was introduced as a new sorbent. The operating mechanism of this sorbent is based on changing the pH value of the sample and consequently the structure of this pH-sensitive microgel is changed. So that, at pH 6.0 the microgel was ready to accept and load the analytes (partial swelling), and when the pH was increased to 8.0, the microgel was closed and analytes were trapped inside the sorbent (deswelling). At pH 2.0 the microgel was opened and the analytes were released from the microgel (swelling). As the adsorption and desorption mechanism is based on changing the pH and only aqueous medium is used as the effluent solvent, this method is introduced as a green extraction method. The use of this microgel resulted in excellent figures of merit. The limits of quantitation and detection for herbicides were obtained within the range of 10-30 and 3-10 ng mL(-1), respectively. Finally, the proposed method was successfully applied to determine the concentration of phenoxy acid herbicides as hazardous materials in water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Stable environmentally sensitive cationic hydrogels for controlled delivery applications.

PubMed

Deo, Namita; Ruetsch, S; Ramaprasad, K R; Kamath, Y

2010-01-01

New thermosensitive, cationic hydrogels were synthesized by the dispersion copolymerization of N-isopropylacrylamide (NIPAM) and (3-acrylamidopropyl)trimethylammonium chloride (AAPTAC). In the polymerization protocol, an amide-based comonomer, (3-acrylamidopropyl)trimethylammonium chloride, was reacted as a new alternative monomer for introducing positive charges into the thermosensitive hydrogel. The hydrogels were synthesized without making any pH adjustment in the aqueous medium. These hydrogel particles exhibited colloidal stability in the pH range of 1.5 to 11.0, while similar cationic hydrogels were reported to be unstable at pHs higher than 6. The stronger cationic character of the selected comonomer provided higher colloidal stability to the poly(NIPAM-co-AAPTAC) hydrogels. Furthermore, these hydrogels displayed sensitivity towards temperature, pH, and salt concentration. Interestingly, the particle size of hydrogels was found to be decreased significantly with an increase in temperature and salt concentration. In addition, using pyrene fluorescence spectroscopy, it was established that the hydrophobicity/hydrophilicity of the hydrogel particles was largely controlled by both pH and temperature. The thermosensitive hydrogels reported in this paper may be suitable for delivering different actives for cosmetic and medical applications. Although direct application of these hydrogel particles in cosmetics has not been shown at this stage, the methodology of making them and controlling their absorption and release properties as a function of temperature and pH has been demonstrated. Furthermore, these hydrogels may also have applications in scavenging organic and inorganic toxics.

Fluorescent chemosensor based on urea/thiourea moiety for sensing of Hg(II) ions in an aqueous medium with high sensitivity and selectivity: A comparative account on effect of molecular architecture on chemosensing

NASA Astrophysics Data System (ADS)

Mishra, Jayanti; Kaur, Harpreet; Ganguli, Ashok K.; Kaur, Navneet

2018-06-01

Mercury is a well-known heavy metal ion which is extremely poisonous to health but is still employed in the form of mercury salts and organomercury compounds in various industrial, anthropological and agricultural activities. Henceforth, its sensing in aqueous medium is an area of great interest in order to avoid its hazardous effect. In the present manuscript, urea/thiourea linkage bearing four organic ligands (1a, 1b, 2a and 2b) are synthesized by a three-step synthetic approach. The organic ligands were then employed to develop organic nanoparticles by re-precipitation method which was further probed for their selective recognition behavior in an aqueous medium using fluorescence spectroscopy. The fluorescence emission profile of the ONPs is used as a tool for the tracking of sensing behavior. The ONPs of 1b has shown selective recognition towards Hg(II) in aqueous medium evidenced by enhancement of fluorescence emission intensity after complexation of 1b ONP with Hg(II), among several alkali, alkaline earth and transition metal ions with a detection limit of the order of 0.84 μM. The ability of the proposed sensor to sense Hg(II) ions with high selectivity and sensitivity could be accounted to photo-induced electron transfer (PET) "OFF" mechanism at λem = 390 nm. This study reveals the application of the proposed thiourea-based sensor for the selective recognition of the Hg(II) ions in an aqueous medium.

Enhanced stability and permeation potential of nanoemulsion containing sefsol-218 oil for topical delivery of amphotericin B.

PubMed

Hussain, Afzal; Samad, Abdus; Singh, Sandeep Kumar; Ahsan, Mohd Neyaz; Faruk, Abdul; Ahmed, Farhan Jalees

2015-05-01

To characterize the enhanced stability and permeation potential of amphotericin B nanoemulsion comprising sefsol-218 oil at varying pH and temperature of aqueous continuous phase. Several batches of amphotericin B loaded nanoemulsion were prepared and evaluated for their physical and chemical stability at different pH and temperature. Also, a comparative study of ex vivo drug permeation across the albino rat skin was investigated with commercial Fungisome® and drug solution at 37 °C for 24 h. The extent of drug penetrated through the rat skin was thereby evaluated using the confocal laser scanning microscopy (CLSM). The optimized nanoemulsion demonstrated the highest flux rate 17.85 ± 0.5 µg/cm(2)/h than drug solution (5.37 ± 0.01 µg/cm(2)/h) and Fungisome® (7.97 ± 0.01 µg/cm(2)/h). Ex vivo drug penetration mechanism from the developed formulations at pH 6.8 and pH 7.4 of aqueous phase pH using the CLSM revealed enhanced penetration. Ex vivo drug penetration studies of developed formulation comprising of CLSM revealed enhanced penetration in aqueous phase at pH 6.8 and 7.4. The aggregation behavior of nanoemulsion at both the pH was found to be minimum and non-nephrotoxic. The stability of amphotericin B was obtained in terms of pH, optical density, globular size, polydispersity index and zeta potential value at different temperature for 90 days. The slowest drug degradation was observed in aqueous phase at pH 7.4 with shelf life 20.03-folds higher when stored at 4 °C (3.8 years) and 5-fold higher at 25 °C (0.951 years) than at 40 °C. The combined results suggested that nanoemulsion may hold an alternative for enhanced and sustained topical delivery system for amphotericin B.

Supercapacitors based on nitrogen-doped reduced graphene oxide and borocarbonitrides

NASA Astrophysics Data System (ADS)

Gopalakrishnan, K.; Moses, Kota; Govindaraj, A.; Rao, C. N. R.

2013-12-01

Nitrogen-doped reduced graphene oxide (RGO) samples with different nitrogen content, prepared by two different methods, as well as nitrogen-doped few-layer graphene have been investigated as supercapacitor electrodes. Two electrode measurements have been carried out both in aqueous (6M KOH) and in ionic liquid media. Nitrogen-doped reduced graphene oxides exhibit satisfactory specific capacitance, the values reaching 126F/g at a scan rate of 10mV/s in aqueous medium. Besides providing supercapacitor characteristics, the study has shown the nitrogen content and surface area to be important factors. High surface-area borocarbonitrides, BxCyNz, prepared by the urea route appear to be excellent supercapacitor electrode materials. Thus, BC4.5N exhibits a specific capacitance of 169F/g at a scan rate of 10mV/s in aqueous medium. In an ionic liquid medium, nitrogen-doped RGO and BC4.5N exhibit specific capacitance values of 258F/g and 240F/g at a scan rate of 5mV/s. The ionic liquid enables a larger operating voltage range of 0.0-2.5V compared to 0.0-1V in aqueous medium.

Quantification of Kinetic Rate Law Parameters of Uranium Release from Sodium Autunite as a Function of Aqueous Bicarbonate Concentrations

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

Gudavalli, Ravi; Katsenovich, Yelena; Wellman, Dawn M.

2013-09-05

ABSTRACT: Hydrogen carbonate is one of the most significant components within the uranium geochemical cycle. In aqueous solutions, hydrogen carbonate forms strong complexes with uranium. As such, aqueous bicarbonate may significantly increase the rate of uranium release from uranium minerals. Quantifying the relationship of aqueous hydrogen carbonate solutions to the rate of uranium release during dissolution is critical to understanding the long-term fate of uranium within the environment. Single-pass flow-through (SPTF) experiments were conducted to estimate the rate of uranium release from Na meta-autunite as a function of bicarbonate solutions (0.0005-0.003 M) under the pH range of 6-11 and temperaturesmore » of 5-60oC. Consistent with the results of previous investigation, the rate of uranium release from sodium autunite exhibited minimal dependency on temperature; but were strongly dependent on pH and increasing concentrations of bicarbonate solutions. Most notably at pH 7, the rate of uranium release exhibited 370 fold increases relative to the rate of uranium release in the absence of bicarbonate. However, the effect of increasing concentrations of bicarbonate solutions on the release of uranium was significantly less under higher pH conditions. It is postulated that at high pH values, surface sites are saturated with carbonate, thus the addition of more bicarbonate would have less effect on uranium release. Results indicate the activation energies were unaffected by temperature and bicarbonate concentration variations, but were strongly dependent on pH conditions. As pH increased from 6 to 11, activation energy values were observed to decrease from 29.94 kJ mol-1 to 13.07 kJ mol-1. The calculated activation energies suggest a surface controlled dissolution mechanism.« less

SYNTHESIS AND IN VITRO CHARACTERIZATION OF HYDROXYPROPYL METHYLCELLULOSE-GRAFT-POLY (ACRYLIC ACID/2-ACRYLAMIDO-2-METHYL-1-PROPANESULFONIC ACID) POLYMERIC NETWORK FOR CONTROLLED RELEASE OF CAPTOPRIL.

PubMed

Furqan Muhammad, Iqbal; Mahmood, Ahmad; Aysha, Rashid

2016-01-01

A super-absorbent hydrogel was developed by crosslinking of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and acrylic acid with hydroxypropyl methylcellulose (HPMC) for controlled release drug delivery of captopril, a well known antihypertensive drug. Acrylic acid and AMPS were polymerized and crosslinked with HPMC by free radical polymerization, a widely used chemical crosslinking method. N,N'-methylenebisacrylamide (MBA) and potassium persulfate (KPS) were added as cross-linker and initiator, respectively. The hydrogel formulation was loaded with captopril (as model drug). The concentration of captopril was monitored at 205 nm using UV spectrophotometer. Equilibrium swelling ratio was determined at pH 2, 4.5 and 7.4 to evaluate the pH responsiveness of the formed hydrogel. The super-absorbent hydrogels were evaluated by FTIR, SEM, XRD, and thermal analysis (DSC and TGA). The formation of new copolymeric network was determined by FTIR, XRD, TGA and DSC analysis. The hydrogel formulations with acrylic acid and AMPS ratio of 4: 1 and lower amounts of crosslinker had shown maximum swelling. Moreover, higher release rate of captopril was observed at pH 7.4 than at pH 2, because of more swelling capacity of copolymer with increasing pH of the aqueous medium. The present research work confirms the development of a stable hydrogel comprising of HPMC with acrylic acid and AMPS. The prepared hydrogels exhibited pH sensitive behav-ior. This superabsorbent composite prepared could be a successful drug carrier for treating hypertension.

Ferrous ion as a reducing agent in the generation of antibiofilm nitric oxide from a copper-based catalytic system.

PubMed

Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

2018-05-01

The work found that the electron-donating properties of ferrous ions (Fe 2+ ) can be used for the conversion of nitrite (NO 2 - ) into the biofilm-dispersing signal nitric oxide (NO) by a copper(II) complex (CuDTTCT) catalyst, a potentially applicable biofilm control technology for the water industries. The availability of Fe 2+ varied depending on the characteristics of the aqueous systems (phosphate- and carbonate-containing nitrifying bacteria growth medium, NBGM and phosphate buffered saline, PBS at pH 6 to 8, to simulate conditions typically present in the water industries) and was found to affect the production of NO from nitrite by CuDTTCT (casted into PVC). Greater amounts of NO were generated from the CuDTTCT-nitrite-Fe 2+ systems in PBS compared to those in NBGM, which was associated with the reduced extent of Fe 2+ -to-Fe 3+ autoxidation by the iron-precipitating moieties phosphates and carbonate in the former system. Further, acidic conditions at pH 6.0 were found to favor NO production from the catalytic system in both PBS and NBGM compared to neutral or basic pH (pH 7.0 or 8.0). Lower pH was shown to stabilize Fe 2+ and reduce its autoxidation to Fe 3+ . These findings will be beneficial for the potential implementation of the NO-generating catalytic technology and indeed, a 'non-killing' biofilm dispersal activity of CuDTTCT-nitrite-Fe 2+ was observed on nitrifying bacteria biofilms in PBS at pH 6. Copyright © 2018 Elsevier Inc. All rights reserved.

Vesicular perylene dye nanocapsules as supramolecular fluorescent pH sensor systems.

PubMed

Zhang, Xin; Rehm, Stefanie; Safont-Sempere, Marina M; Würthner, Frank

2009-11-01

Water-soluble, self-assembled nanocapsules composed of a functional bilayer membrane and enclosed guest molecules can provide smart (that is, condition responsive) sensors for a variety of purposes. Owing to their outstanding optical and redox properties, perylene bisimide chromophores are interesting building blocks for a functional bilayer membrane in a water environment. Here, we report water-soluble perylene bisimide vesicles loaded with bispyrene-based energy donors in their aqueous interior. These loaded vesicles are stabilized by in situ photopolymerization to give nanocapsules that are stable over the entire aqueous pH range. On the basis of pH-tunable spectral overlap of donors and acceptors, the donor-loaded polymerized vesicles display pH-dependent fluorescence resonance energy transfer from the encapsulated donors to the bilayer dye membrane, providing ultrasensitive pH information on their aqueous environment with fluorescence colour changes covering the whole visible light range. At pH 9.0, quite exceptional white fluorescence could be observed for such water-soluble donor-loaded perylene vesicles.

A process for the preparation of cysteine from cystine

DOEpatents

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

1989-01-01

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

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

PubMed

Yongqiang Zhang; Tichang Sun; Tieqiang Lu; Chunhuan Yan

2016-11-25

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

Evaluation of modeled cloud chemistry mechanism against laboratory irradiation experiments: The HxOy/iron/carboxylic acid chemical system

NASA Astrophysics Data System (ADS)

Long, Yoann; Charbouillot, Tiffany; Brigante, Marcello; Mailhot, Gilles; Delort, Anne-Marie; Chaumerliac, Nadine; Deguillaume, Laurent

2013-10-01

Currently, cloud chemistry models are including more detailed and explicit multiphase mechanisms based on laboratory experiments that determine such values as kinetic constants, stability constants of complexes and hydration constants. However, these models are still subject to many uncertainties related to the aqueous chemical mechanism they used. Particularly, the role of oxidants such as iron and hydrogen peroxide in the oxidative capacity of the cloud aqueous phase has typically never been validated against laboratory experimental data. To fill this gap, we adapted the M2C2 model (Model of Multiphase Cloud Chemistry) to simulate irradiation experiments on synthetic aqueous solutions under controlled conditions (e.g., pH, temperature, light intensity) and for actual cloud water samples. Various chemical compounds that purportedly contribute to the oxidative budget in cloud water (i.e., iron, oxidants, such as hydrogen peroxide: H2O2) were considered. Organic compounds (oxalic, formic and acetic acids) were taken into account as target species because they have the potential to form iron complexes and are good indicators of the oxidative capacity of the cloud aqueous phase via their oxidation in this medium. The range of concentrations for all of the chemical compounds evaluated was representative of in situ measurements. Numerical outputs were compared with experimental data that consisted of a time evolution of the concentrations of the target species. The chemical mechanism in the model describing the “oxidative engine” of the HxOy/iron (HxOy = H2O2, HO2rad /O2rad - and HOrad ) chemical system was consistent with laboratory measurements. Thus, the degradation of the carboxylic acids evaluated was closely reproduced by the model. However, photolysis of the Fe(C2O4)+ complex needs to be considered in cloud chemistry models for polluted conditions (i.e., acidic pH) to correctly reproduce oxalic acid degradation. We also show that iron and formic acid lead to a stable complex whose photoreactivity has currently not been investigated. The updated aqueous chemical mechanism was compared with data from irradiation experiments using natural cloud water. The new reactions considered in the model (i.e., iron complex formation with oxalic and formic acids) correctly reproduced the experimental observations.

Magnetic resonance imaging (MRI) and relaxation spectrum analysis as methods to investigate swelling in whey protein gels.

PubMed

Oztop, Mecit H; Rosenberg, Moshe; Rosenberg, Yael; McCarthy, Kathryn L; McCarthy, Michael J

2010-10-01

Effective means for controlled delivery of nutrients and nutraceuticals are needed. Whey protein-based gels, as a model system and as a potential delivery system, exhibit pH-dependent swelling when placed in aqueous solutions. Understanding the physics that govern gel swelling is thus important when designing gel-based delivery platforms. The extent of swelling over time was monitored gravimetrically. In addition to gravimetric measurements, magnetic resonance imaging (MRI) a real-time noninvasive imaging technique that quantified changes in geometry and water content of these gels was utilized. Heat-set whey protein gels were prepared at pH 7 and swelling was monitored in aqueous solutions with pH values of 2.5, 7, and 10. Changes in dimension over time, as characterized by the number of voxels in an image, were correlated to gravimetric measurements. Excellent correlations between mass uptake and volume change (R(2)= 0.99) were obtained for the gels in aqueous solutions at pH 7 and 10, but not for gels in the aqueous solution at pH 2.5. To provide insight into the mechanisms for water uptake, nuclear magnetic resonance (NMR) relaxation times were measured in independent experiments. The relaxation spectrum for the spin-spin relaxation time (T(2)) showed the presence of 3 proton pools for pH 7 and 10 trials and 4 proton pools for pH 2.5 trials. Results demonstrate that MRI and NMR relaxation measurements provided information about swelling in whey protein gels that can constitute a new means for investigating and developing effective delivery systems for foods.

The pH dependent Raman spectroscopic study of caffeine

NASA Astrophysics Data System (ADS)

Kang, Jian; Gu, Huaimin; Zhong, Liang; Hu, Yongjun; Liu, Fang

2011-02-01

First of all the surface enhanced Raman spectroscopy (SERS) and normal Raman spectra of caffeine aqueous solution were obtained at different pH values. In order to obtain the detailed vibrational assignments of the Raman spectroscopy, the geometry of caffeine molecule was optimized by density functional theory (DFT) calculation. By comparing the SERS of caffeine with its normal spectra at different pH values; it is concluded that pH value can dramatically affect the SERS of caffeine, but barely affect the normal Raman spectrum of caffeine aqueous solution. It can essentially affect the reorientation of caffeine molecule to the Ag colloid surface, but cannot impact the vibration of functional groups and chemical bonds in caffeine molecule.

Preparation of novel alkaline pH-responsive copolymers for the formation of recyclable aqueous two-phase systems and their application in the extraction of lincomycin.

PubMed

Liu, Jiali; Cao, Xuejun

2016-02-01

Aqueous two-phase systems have potential industrial application in bioseparation and biocatalysis engineering; however, their practical application is limited primarily because the copolymers involved in the formation of aqueous two-phase systems cannot be recovered. In this study, two novel alkaline pH-responsive copolymers were synthesized and examined for the extraction of lincomycin. The two copolymers could form a novel alkaline aqueous two-phase systems when their concentrations were both 6% w/w and the pH was 8.4(±0.1)-8.7(±0.1). One copolymer was synthesized using acrylic acid, 2-(dimethylamino)ethyl methacrylate, and butyl methacrylate as monomers. Moreover, 98.8% of the copolymer could be recovered by adjusting the solution pH to its isoelectric point (pH 6.29). The other copolymer was synthesized using the monomers methacrylic acid, 2-(dimethylamino)ethyl methacrylate, and methyl methacrylate. In this case, 96.7% of the copolymer could be recovered by adjusting the solution pH to 7.19. The optimal partition coefficient of lincomycin was 0.17 at 30°C in the presence of 10 mM KBr and 5.5 at 40°C in the presence of 80 mM Ti(SO4)2 using the novel alkaline aqueous two-phase systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of hydrothermally prepared supported photocatalytic composite in organic micro-pollutants removal from the water.

PubMed

Shivaraju, H P; Byrappa, K

2012-07-01

This work deals with the non-biodegradable micro-pollutants degradation by supported photocatalyst based heterogeneous photocatalytic reaction. TiO2 based supported photocatalyst was prepared by the hydrothermal technique to improve the photocatalytic performance along with easy recovery of suspended photocatalyst from aqueous medium after photoreaction. TO2 deposited calcium alumino-silicate beads (CASB) supports were prepared under mild hydrothermal conditions (Temparature-200 degrees C, Duration-24 h). In the present study, industrial dyes such as Amaranth and Brilliant Yellow were used as model micro-pollutants in aqueous solution. A real time pesticide industrial effluent was tested for its photocatalytic removal of organic pollutants using TO2 deposited CASB supported photocatalytic composite as an effective photocatalyst. Photocatalytic degradation of micro-pollutants present in aqueous medium was carried out in a batch photoreactor, at atmospheric pressure and temperature (28 degrees C). The influence of different light sources, irradiation time, catalyst load and catalytic performance is discussed. The photocatalytic degradation of micro-pollutants in aqueous medium was evaluated by determination of COD and %T. Easy separation and recovery of suspended photocatalysts from aqueous solution is the major advantage of hydrothermally prepared supported photocatalytic composite.

Use of metallurgical dust for removal chromium ions from aqueous solutions

NASA Astrophysics Data System (ADS)

Pająk, Magdalena; Dzieniszewska, Agnieszka; Kyzioł-Komosińska, Joanna; Chrobok, Michał

2018-01-01

The aim of the study was to determine the potential for the application of dust from steel plant as an effective sorbent for removing Cr(III) and Cr(VI) in the form of simple and complex ions - Acid Blue 193 dye from aqueous solutions. Three isotherms models were used to interpret the experimental results namely: Langmuir, Freundlich, and Dubinin-Radushkevich. Estimated equations parameters allowed to determine the binding mechanism. Based on laboratory studies it was found that the dust was characterized by high sorption capacities for Cr ions and dye from the aqueous solution. The sorption capacity of the dust for Cr(III) and Cr(VI) ions depended on the degree of oxidation, pH of solution and kind of anion and changed in series: Cr(III)-Cl pH=5.0> Cr(III)-SO4 pH=5.0> Cr(III)-Cl pH=3.0> Cr(III)-SO4 pH=3.0> Cr(VI) pH=5.0> Cr(VI) pH=3.0. Dust was also characterized by a high maximum sorption capacity of dye at a range of 38.2 - 91.7 mg/g, depending on the dose of dust. Based on the study it was found that dust from a steel plant, containing iron oxides, can be used as low-cost and effective sorbent to remove pollutions containing chromium ions, especially from acidic wastewater.

Supersaturation of aqueous species and hydrothermal crystal growth of ZnO

NASA Astrophysics Data System (ADS)

Gelabert, M. C.

2015-05-01

Synthesis of ZnO crystals prepared with zinc acetate or chloride, disodium dihydrogen ethylenediaminetetraacetate (EDTA), potassium hydroxide and sodium triflate at 200 °C and variable pH 8-12 is reported. Crystals were imaged and size-analyzed with optical microscopy. Using aqueous speciation modeling software, supersaturation dependence on pH was calculated for five zinc species-Zn2+, Zn(OH)+, Zn(OH)2, Zn(OH)3- and Zn(OH)42- -to investigate connections between predominate crystal habits at different pH and dominant aqueous species. For zinc acetate and chloride systems, the zinc species with highest supersaturation was Zn(OH)42- throughout the pH 8-12 range, and the second highest was Zn2+ or Zn(OH)3-, with a crossover pH of 10.2-10.4 depending on counterion. The prominence of the tetrahydroxyl zinc species in ZnO crystal growth is supported by these calculations, and total supersaturation is inversely proportional to average crystal sizes, as expected. Optical microscopy and size analysis on products revealed crystals with a needle or prismatic habit throughout the studied pH range, and the change in aspect ratio correlates with supersaturation changes for the Zn2+ in this pH range, thus suggesting that growth rates along the [001] crystallographic direction are affected by small concentration changes of this ion.

Predicting the crystallization propensity of carboxylic acid buffers in frozen systems--relevance to freeze-drying.

PubMed

Sundaramurthi, Prakash; Suryanarayanan, Raj

2011-04-01

Selective crystallization of buffer components in frozen solutions is known to cause pronounced pH shifts. Our objective was to study the crystallization behavior and the consequent pH shift in frozen aqueous carboxylic acid buffers. Aqueous carboxylic acid buffers were cooled to -25°C and the pH of the solution was measured as a function of temperature. The thermal behavior of solutions during freezing and thawing was investigated by differential scanning calorimetry. The crystallized phases in frozen solution were identified by X-ray diffractometry. The malate buffer system was robust with no evidence of buffer component crystallization and hence negligible pH shift. In the citrate and tartarate systems, at initial pH

Role of Self-Association and Supersaturation in Oral Absorption of a Poorly Soluble Weakly Basic Drug.

PubMed

Narang, Ajit S; Badawy, Sherif; Ye, Qingmei; Patel, Dhaval; Vincent, Maria; Raghavan, Krishnaswamy; Huang, Yande; Yamniuk, Aaron; Vig, Balvinder; Crison, John; Derbin, George; Xu, Yan; Ramirez, Antonio; Galella, Michael; Rinaldi, Frank A

2015-08-01

Precipitation of weakly basic drugs in intestinal fluids can affect oral drug absorption. In this study, the implications of self-association of brivanib alaninate in acidic aqueous solution, leading to supersaturation at basic pH condition, on its solubility and oral absorption were investigated. Self-association of brivanib alaninate was investigated by proton NMR spectroscopy, surface tension measurement, dynamic light scattering, isothermal titration calorimetry, and molecular modeling. Drug solubility was determined in various pH media, and its tendency to supersaturate upon pH shift was investigated in buffered and biorelevant aqueous solutions. Pharmacokinetic modeling of human oral drug absorption was utilized for parameter sensitivity analyses of input variables. Brivanib alaninate exhibited continuous, and pH- and concentration-dependent self-association. This phenomenon resulted in positive deviation of drug solubility at acidic pH and the formation of a stable supersaturated drug solution in pH-shift assays. Consistent with the supersaturation phenomenon observed in vitro, oral absorption simulations necessitated invoking long precipitation time in the intestine to successfully predict in vivo data. Self-association of a weakly basic drug in acidic aqueous solution can increase its oral absorption by supersaturation and precipitation resistance at the intestinal pH. This consideration is important to the selection of parameters for oral absorption simulation.

Effect of curcumin and Cu 2+/Zn 2+ ions on the fibrillar aggregates formed by the amyloid peptide and other peptides at the organic-aqueous interface

NASA Astrophysics Data System (ADS)

Sanghamitra, Nusrat J. M.; Varghese, Neenu; Rao, C. N. R.

2010-08-01

Characteristic features of a perilous neuro-degenerative disease such as the Alzhiemer's disease is fibrillar plaque formation by the amyloid (Aβ) peptide. We have modelled the formation and disintegration of fibrils by studying the aggregate structures formed by Aβ structural motif diphenylalanine as well as insulin and bovine serum albumin at the organic-aqueous interface. Even small concentrations of curcumin in the organic medium or Cu 2+ and Zn 2+ ions in the aqueous medium are found to break down the fibrillar structures.

Zirconium-modified materials for selective adsorption and removal of aqueous arsenic

DOEpatents

Zhao, Hongting; Moore, Robert C.

2004-11-30

A method, composition, and apparatus for removing contaminant species from an aqueous medium comprising: providing a material to which zirconium has been added, the material selected from one or more of zeolites, cation-exchangeable clay minerals, fly ash, mesostructured materials, activated carbons, cellulose acetate, and like porous and/or fibrous materials; and contacting the aqueous medium with the material to which zirconium has been added. The invention operates on all arsenic species in the form of arsenate, arsenite and organometallic arsenic, with no pretreatment necessary (e.g., oxidative conversion of arsenite to arsenate).

A novel composite material based on antimony(III) oxide and amorphous silica

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

Zemnukhova, Ludmila A.; Panasenko, Alexander E., E-mail: panasenko@ich.dvo.ru

2013-05-01

The composite material nSb₂O₃·mSiO₂·xH₂O was prepared by hydrolysis of SbCl₃ and Na₂SiO₃ in an aqueous medium. It has been shown that the composition of the material is influenced by the ratio of the initial components and the acidity of the reaction medium. The morphology of the material particles and its specific surface area have been determined. The thermal and optic properties were also investigated. - Graphical abstract: Novel composite material containing amorphous silica and crystal antimony(III) oxide has been synthesized by hydrolysis of SbCl₃ and Na₂SiO₃ in an aqueous medium. Highlights: • The composite material nSb₂O₃·mSiO₂·xH₂O was prepared in anmore » aqueous medium. • The composition of the material is controllable by a synthesis conditions. • The morphology of the material and its optic properties have been determined.« less

Oxidation of ascorbic acid by a (salen)ruthenium(VI) nitrido complex in aqueous solution.

PubMed

Wang, Qian; Man, Wai-Lun; Lam, William W Y; Lau, Tai-Chu

2014-12-25

The oxidation of ascorbic acid (H2A) by [Ru(VI)(N)(L)(MeOH)](+) in aqueous acidic solutions has the following stoichiometry: 2[Ru(VI)(N)] + 3H2A → 2[Ru(III)(NH2-HA)](+) + A. Mechanisms involving HAT/N-rebound at low pH (≤2) and nucleophilic attack at the nitride at high pH (≥5) are proposed.

Somatic proembryo production from excised, wounded zygotic carrot embryos on hormone-free medium: evaluation of the effects of pH, ethylene and activated charcoal

NASA Technical Reports Server (NTRS)

Smith, D. L.; Krikorian, A. D.

1990-01-01

Wounded zygotic embryos of cultivated carrot produce somatic proembryos on hormone-free nutrient medium containing 1 mM NH4+ as the sole nitrogen source. Continued maintenance of proembryos on this medium leads to a "pure" culture of preglobular stage proembryos (PGSPs). Ethylene had no effect on this process. Also, somatic embryo production was not affected by growing cultures on activated charcoal-impregnated filter papers. However, somatic proembyros initiated on activated charcoal papers were not maintainable as PGSPs and developed into later embryo stages. Normally, medium pH dropped from 5.7 to 4 during each subculture period, but when using activated charcoal papers the pH endpoint was around 6 - 7 due to a leachable substance(s) within the filter papers. When powdered, activated charcoal was used in the medium as an adsorbent of products potentially released after wounding, pH dropped at the normal rate and to the expected levels; proembryos did not mature into later embryo stages and were maintainable exclusively as PGSPs. Low pH (approximately 4) is detrimental to proembyro production, but is essential to maintaining PGSPs on hormone-free nutrient medium, whereas a sustained pH > or = 5.7 allows continued development of PGSPs into later embryo stages.

Enhanced removal of humic acid from aqueous solution by novel stabilized nano-amorphous calcium phosphate: Behaviors and mechanisms

NASA Astrophysics Data System (ADS)

Jiang, Ling; Li, Yiming; Shao, Yi; Zhang, Yong; Han, Ruiming; Li, Shiyin; Wei, Wei

2018-01-01

Stabilized nano-amorphous calcium phosphate (nACP) was prepared using polyethylene glycol as stabilizer to obtain a nanosized amorphous adsorbent. The produced nACP was evaluated by using XRD, FTIR, SEM and X-ray photoelectron spectroscopy (XPS). The sedimentation test demonstrated that nACP exhibited better stability than crystallized hydroxyapatite. The adsorption efficiency of the nACP material for aqueous humic acid (HA) was evaluated from the point of view of medium pH, adsorption time, temperature, and ionic strength, as well as the presences of metal ions. The results of the study showed very good adsorption performance towards aqueous HA. The Sips modeling results revealed that the stabilized nACP adsorbent had a considerably high adsorption capacity (248.3 mg/g) for HA at 298 K. The adsorption data fitted well into pseudo-second order and Elovich kinetic models. XPS analyses indicated that HA retention on nACP material might be due to the surface complexation reaction between oxygen-containing group and calcium of HA and nACP, respectively. Moreover, the HA adsorption capacity of nACP could still keep more than 86% after four adsorption-desorption cycles. By taking into account all results it was concluded that the nACP adsorbent leveraged its stability in combination with its high uptake capacity to offer a great promise for HA adsorption from water.

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 3. Heavy Lanthanides (Gd–Lu)

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

Mioduski, Tomasz; Gumiński, Cezary, E-mail: cegie@chem.uw.edu.pl; Zeng, Dewen, E-mail: dewen-zeng@hotmail.com

This is the third part of the volume devoted to solubility data for the rare earth metal (REM) fluorides in water and in aqueous ternary and multicomponent systems. It covers experimental results of trivalent fluorides of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu (so-called heavy lanthanides), since no quantitative data on solubilities of TbF{sub 4} and YbF{sub 2} (the most stable compounds at these valencies) are available. The related literature has been covered through the end of 2014. Compilations of all available papers with the solubility data are introduced for each REM fluoride with a corresponding critical evaluation.more » Every such assessment contains a collection of all solubility results in aqueous solution, a selection of suggested solubility data, a solubility equation, and a brief discussion of the multicomponent systems. Only simple fluorides (no complexes or double salts) are treated as the input substances in this report. General features of the systems, such as nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, solution pH, mixed solvent medium on the solubility, quality of the solubility results, and the solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.« less

An experimental study of Au removal from solution by non-metabolizing bacterial cells and their exudates

NASA Astrophysics Data System (ADS)

Kenney, Janice P. L.; Song, Zhen; Bunker, Bruce A.; Fein, Jeremy B.

2012-06-01

In this study, we examine the initial interactions between aqueous Au(III)-hydroxide-chloride aqueous complexes and bacteria by measuring the effects of non-metabolizing cells on the speciation and distribution of Au. We conducted batch Au(III) removal experiments, measuring the kinetics and pH dependence of Au removal, and tracking valence state transformations and binding environments using XANES spectroscopy. These experiments were conducted using non-metabolizing cells of Bacillus subtilis or Pseudomonas putida suspended in a 5 ppm Au(III)-(hydroxide)-chloride starting solution of 0.1 M NaClO4 to buffer ionic strength. Both bacterial species removed greater than 85% of the Au from solution after 2 h of exposure time below approximately pH 5. Above pH 5, the extent of Au removed from solution decreased with increasing pH, with less than approximately 10% removal of Au from solution above pH 7.5. Kinetics experiments indicated that the Au removal with both bacterial species was rapid at pH 3, and slowed with increasing pH. Reversibility experiments demonstrated that (1) once the Au was removed from solution, adjusting 35 the pH alone did not remobilize the Au into solution and (2) the presence of cysteine in solution in the reversibility experiments caused Au to desorb, suggesting that the Au was not internalized within the bacterial cells. Our results suggest that Au removal occurs as a two-step pH-dependent adsorption reduction process. The speciation of the aqueous Au and the bacterial surface appears to control the rate of Au removal from solution. Under low pH conditions, the cell walls are only weakly negatively charged and aqueous Au complexes adsorb readily and rapidly. With increasing pH, the cell wall becomes more negatively charged, slowing adsorption significantly. The XANES data demonstrate that the reduction of Au(III) by bacterial exudates is slower and less extensive than the reduction observed in the bacteria-bearing systems, and we conclude that Au reduction occurs most rapidly and extensively upon interaction with cell wall functional groups.

Geochemical Modeling of Reactions and Partitioning of Trace Metals and Radionuclides during Titration of Contaminated Acidic Sediments

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

Zhang, Fan; Parker, Jack C.; Luo, Wensui

2008-01-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This study was undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cationmore » exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO{sub 4}{sup 2-} for contaminated sediments indicated close agreement, suggesting that the model could potentially be used to predict the acid-base behavior of the sediment-solution system under variable pH conditions.« less

Plasma Induced Degradation of Aniline in Aqueous Solution

NASA Astrophysics Data System (ADS)

Gao, Jin-zhang; Gai, Ke; Lu, Quan-fang; Liu, Yong-jun; Wang, Xiao-yan; Deng, Hua-ling; Hu, Zhong-ai

2002-04-01

In this paper, the degradation of aniline by plasma which was generated in a localized zone between an electrolytic solution and an anode was reported. The influence of the initial concentration, temperature, pH and different mediums of aniline on the reaction kinetic was investigated. The results showed that temperature had a remarkable effect on the degradation of aniline, but the concentration had no appreciable effect on the degradation. There is a maximum elimination rate on the degradation of aniline in neutral condition. Iron (II) and other cations had a remarkable catalytic action on it. On the basis of the detailed analysis of the kinetical consideration, it was demonstrated that the oxidative degradation would be a first-order reaction. Some of the intermediate products of the degradatio process in the solution were detected by HPLC.

Biodegradation of dissolved humic substances by fungi.

PubMed

Collado, Sergio; Oulego, Paula; Suárez-Iglesias, Octavio; Díaz, Mario

2018-04-01

Humic and fulvic acids constitute humic substances, a complex mixture of many different acids containing carboxyl and phenolate groups, which are not only the principal soil fertility factors but also the main pollutants present in landfill leachates or natural organic matter in water. Due to their low bacterial biodegradability, fungal biodegradation processes are key for their removal. The present study compiles and comments all the available literature on decomposition of aqueous humic substances by fungi or by their extracellular enzymes alone, focusing on the influence of the reaction conditions. The biodegradation extent mainly depends on the characteristics and concentration of the humic compounds, the type of microorganisms selected, the inoculation mode, the C and N sources, the presence of certain chemicals in the medium, the availability of oxygen, the temperature, and the pH.

Modeling pH-Responsive Adsorption of Polyelectrolytes at Oil-Water Interfaces

NASA Astrophysics Data System (ADS)

Qin, Shiyi; Yong, Xin

We use dissipative particle dynamics (DPD) to discover the interfacial adsorption of pH-responsive polyelectrolytes in oil-water binary systems under different pH values. The electrostatic interactions between charged beads and the dielectric discontinuity across the interface are modeled by exploiting a modified Particle-Particle-Particle-Mesh (PPPM) method, which uses an iterative method to solve the Poisson equation on a uniform grid. We first model the adsorption behavior of a single linear polyelectrolyte from the aqueous phase. The Henderson-Hasselbalch equation describes the relation between pH and the degree of ionization of the modeled polyelectrolytes. Through changing the degree of ionization, we explore the influence of pH on the adsorption behavior and show that the electrostatic interactions significantly modulate the adsorption. Time evolutions of the position and conformation of the polyelectrolytes and the variation in the oil-water surface tension will be measured to characterize the adsorption behavior. Furthermore, we model the pH-dependent adsorption behavior of polyelectrolytes with more complicated structures, namely, branched polyelectrolytes with hydrophobic backbones and hydrophilic side chains. We also find that the addition of salts in the medium and the lengths of the backbone and ionized side chain affect the adsorption. This research supported by the American Chemical Society Petroleum Research Fund (Award 56884-DNI9).

Harvesting of Chlorella sorokiniana by co-culture with the filamentous fungus Isaria fumosorosea: A potential sustainable feedstock for hydrothermal gasification.

PubMed

Mackay, Stephen; Gomes, Eduardo; Holliger, Christof; Bauer, Rolene; Schwitzguébel, Jean-Paul

2015-06-01

Despite recent advances in down-stream processing, production of microalgae remains substantially limited because of economical reasons. Harvesting and dewatering are the most energy-intensive processing steps in their production and contribute 20-30% of total operational cost. Bio-flocculation of microalgae by co-cultivation with filamentous fungi relies on the development of large structures that facilitate cost effective harvesting. A yet unknown filamentous fungus was isolated as a contaminant from a microalgal culture and identified as Isaria fumosorosea. Blastospores production was optimized in minimal medium and the development of pellets, possibly lichens, was followed when co-cultured with Chlorella sorokiniana under strict autotrophic conditions. Stable pellets (1-2mm) formed rapidly at pH 7-8, clearing the medium of free algal cells. Biomass was harvested with large inexpensive filters, generating wet slurry suitable for hydrothermal gasification. Nutrient rich brine from the aqueous phase of hydrothermal gasification supported growth of the fungus and may increase the process sustainability. Copyright © 2015 Elsevier Ltd. All rights reserved.

Microcapsule Structure with a Tunable Textured Surface via the Assembly of Polyoxomolybdate Clusters: A Bioinspired Strategy and Enhanced Activities in Alkene Oxidation.

PubMed

Chilivery, Rakesh; Rana, Rohit Kumar

2017-01-25

A polyamine-mediated bioinspired strategy to assemble Keggin-type phosphomolybdic acid (PMA) clusters is demonstrated for the fabrication of microcapsule (MC) structures with unique surface textures. It involves supramolecular aggregation of polyamines with multivalent anions, which then allows the assembly of negatively charged PMA into MCs in an aqueous medium under ambient conditions. Resembling the role of polyamines in biosilicification of diatoms, the polyamine-anion interaction is shown to be the key for the assembly process. It not only provides structural stability but also facilitates an interesting transition from a smooth to a wrinkled surface alongside a change in the Keggin form to its lacunary form depending on the pH of the medium. Moreover, the presence of isolated PMA units in the hybrid structure enables them to be active in catalyzing the aerobic oxidation of alkenes under solvent-free conditions with better selectivity and reusability. Hence, the assembly approach represents an effective way for heterogenization of PMA-based materials and is expected to find considerable application in the wider hybrid-cluster field.

Green synthesis of gold and silver nanoparticles using Hibiscus rosa sinensis

NASA Astrophysics Data System (ADS)

Philip, Daizy

2010-03-01

Biological synthesis of gold and silver nanoparticles of various shapes using the leaf extract of Hibiscus rosa sinensis is reported. This is a simple, cost-effective, stable for long time and reproducible aqueous room temperature synthesis method to obtain a self-assembly of Au and Ag nanoparticles. The size and shape of Au nanoparticles are modulated by varying the ratio of metal salt and extract in the reaction medium. Variation of pH of the reaction medium gives silver nanoparticles of different shapes. The nanoparticles obtained are characterized by UV-vis, transmission electron microscopy (TEM), X-ray diffraction (XRD) and FTIR spectroscopy. Crystalline nature of the nanoparticles in the fcc structure are confirmed by the peaks in the XRD pattern corresponding to (1 1 1), (2 0 0), (2 2 0) and (3 1 1) planes, bright circular spots in the selected area electron diffraction (SAED) and clear lattice fringes in the high-resolution TEM image. From FTIR spectra it is found that the Au nanoparticles are bound to amine groups and the Ag nanoparticles to carboxylate ion groups.

Influence of calcium on microbial reduction of solid phase uranium(VI).

PubMed

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M; Wang, Zheming

2007-08-15

The effect of calcium on the dissolution and microbial reduction of a representative solid phase uranyl [U(VI)], sodium boltwoodite (NaUO(2)SiO(3)OH . 1.5H(2)O), was investigated to evaluate the rate-limiting step of microbial reduction of the solid phase U(VI). Microbial reduction experiments were performed in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1, in a bicarbonate medium with lactate as electron donor at pH 6.8 buffered with PIPES. Calcium increased the rate of Na-boltwoodite dissolution and U(VI) bioavailability by increasing its solubility through the formation of a ternary aqueous calcium-uranyl-carbonate species. The ternary species, however, decreased the rates of microbial reduction of aqueous U(VI). Laser-induced fluorescence spectroscopy (LIFS) and transmission electron microscopy (TEM) collectively revealed that microbial reduction of solid phase U(VI) was a sequentially coupled process of Na-boltwoodite dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) to U(IV) that accumulated on bacterial surfaces/periplasm. Under studied experimental conditions, the overall rate of microbial reduction of solid phase U(VI) was limited by U(VI) dissolution reactions in solutions without calcium and limited by microbial reduction in solutions with calcium. Generally, the overall rate of microbial reduction of solid phase U(VI) was determined by the coupling of solid phase U(VI) dissolution, U(VI) aqueous speciation, and microbial reduction of dissolved U(VI) that were all affected by calcium. (c) 2007 Wiley Periodicals, Inc.

Biosorptive removal of inorganic arsenic species and fluoride from aqueous medium by the stem of Tecomella undulate.

PubMed

Brahman, Kapil Dev; Kazi, Tasneem Gul; Baig, Jameel Ahmed; Afridi, Hassan Imran; Arain, Sadaf Sadia; Saraj, Saima; Arain, Muhammad B; Arain, Salma Aslam

2016-05-01

Simultaneous removal of fluoride (F(-)), inorganic arsenic species, As(III) and As(V), from aqueous samples has been performed using an economic indigenous biosorbent (Stem of Tecomella undulata). The inorganic As species in water samples before and after biosorption were determined by cloud point and solid phase extraction methods, while F(-) was determined by ion chromatography. Batch experiments were carried out to evaluate the equilibrium adsorption isotherm studies for As(III), As(V) and F(-) in aqueous solutions. Several parameters of biosorption were optimized such as pH, biomass dosage, analytes concentration, time and temperature. The surface of biosorbent was characterized by SEM and FTIR. The FTIR study indicated the presence of carbonyl and amine functional groups which may have important role in the sorption/removal of these ions. Thermodynamic and kinetic study indicated that the biosorption of As(III), As(V) and F(-) were spontaneous, exothermic and followed by pseudo-second-order. Meanwhile, the interference study revealed that there was no significant effect of co-existing ions for the removal of inorganic As species and F(-) from aqueous samples (p > 0.05). It was observed that the indigenous biosorbent material simultaneously adsorbed As(III) (108 μg g(-1)), As(V) (159 μg g(-1)) and F(-) (6.16 mg g(-1)) from water at optimized conditions. The proposed biosorbent was effectively regenerated and efficiently used for several experiments, to remove the As(III), As(V) and F(-) from real water sample collected from endemic area of Pakistan. Copyright © 2016 Elsevier Ltd. All rights reserved.

The relationship between mantle pH and the deep nitrogen cycle

NASA Astrophysics Data System (ADS)

Mikhail, Sami; Barry, Peter H.; Sverjensky, Dimitri A.

2017-07-01

Nitrogen is distributed throughout all terrestrial geological reservoirs (i.e., the crust, mantle, and core), which are in a constant state of disequilibrium due to metabolic factors at Earth's surface, chemical weathering, diffusion, and deep N fluxes imposed by plate tectonics. However, the behavior of nitrogen during subduction is the subject of ongoing debate. There is a general consensus that during the crystallization of minerals from melts, monatomic nitrogen behaves like argon (highly incompatible) and ammonium behaves like potassium and rubidium (which are relatively less incompatible). Therefore, the behavior of nitrogen is fundamentally underpinned by its chemical speciation. In aqueous fluids, the controlling factor which determines if nitrogen is molecular (N2) or ammonic (inclusive of both NH4+ and NH30) is oxygen fugacity, whereas pH designates if ammonic nitrogen is NH4+ or NH30. Therefore, to address the speciation of nitrogen at high pressures and temperatures, one must also consider pH at the respective pressure-temperature conditions. To accomplish this goal we have used the Deep Earth Water Model (DEW) to calculate the activities of aqueous nitrogen from 1-5 GPa and 600-1000 °C in equilibrium with a model eclogite-facies mineral assemblage of jadeite + kyanite + quartz/coesite (metasediment), jadeite + pyrope + talc + quartz/coesite (metamorphosed mafic rocks), and carbonaceous eclogite (metamorphosed mafic rocks + elemental carbon). We then compare these data with previously published data for the speciation of aqueous nitrogen across these respective P-T conditions in equilibrium with a model peridotite mineral assemblage (Mikhail and Sverjensky, 2014). In addition, we have carried out full aqueous speciation and solubility calculations for the more complex fluids in equilibrium with jadeite + pyrope + kyanite + diamond, and for fluids in equilibrium with forsterite + enstatite + pyrope + diamond. Our results show that the pH of the fluid is controlled by mineralogy for a given pressure and temperature, and that pH can vary by several units in the pressure-temperature range of 1-5 GPa and 600-1000 °C. Our data show that increasing temperature stabilizes molecular nitrogen and increasing pressure stabilizes ammonic nitrogen. Our model also predicts a stark difference for the dominance of ammonic vs. molecular and ammonium vs. ammonia for aqueous nitrogen in equilibrium with eclogite-facies and peridotite mineralogies, and as a function of the total dissolved nitrogen in the aqueous fluid where lower N concentrations favor aqueous ammonic nitrogen stabilization and higher N concentrations favor aqueous N2. Overall, we present thermodynamic evidence for nitrogen to be reconsidered as an extremely dynamic (chameleon) element whose speciation and therefore behavior is determined by a combination of temperature, pressure, oxygen fugacity, chemical activity, and pH. We show that altering the mineralogy in equilibrium with the fluid can lead to a pH shift of up to 4 units at 5 GPa and 1000 °C. Therefore, we conclude that pH imparts a strong control on nitrogen speciation, and thus N flux, and should be considered a significant factor in high temperature geochemical modeling in the future. Finally, our modelling demonstrates that pH plays an important role in controlling speciation, and thus mass transport, of Eh-pH sensitive elements at temperatures up to at least 1000 °C.

Detoxification and fermentation of pyrolytic sugar for ethanol production.

PubMed

Wang, Hui; Livingston, Darrell; Srinivasan, Radhakrishnan; Li, Qi; Steele, Philip; Yu, Fei

2012-11-01

The sugars present in bio-oil produced by fast pyrolysis can potentially be fermented by microbial organisms to produce cellulosic ethanol. This study shows the potential for microbial digestion of the aqueous fraction of bio-oil in an enrichment medium to consume glucose and produce ethanol. In addition to glucose, inhibitors such as furans and phenols are present in the bio-oil. A pure glucose enrichment medium of 20 g/l was used as a standard to compare with glucose and aqueous fraction mixtures for digestion. Thirty percent by volume of aqueous fraction in media was the maximum additive amount that could be consumed and converted to ethanol. Inhibitors were removed by extraction, activated carbon, air stripping, and microbial methods. After economic analysis, the cost of ethanol using an inexpensive fermentation medium in a large scale plant is approximately $14 per gallon.

Removal of phosphate from aqueous solutions and sewage using natural and surface modified coir pith.

PubMed

Krishnan, K Anoop; Haridas, Ajit

2008-04-01

Iron impregnated coir pith (CP-Fe-I) can be effectively used for the removal of phosphate from aqueous streams and sewage. Iron impregnation on natural coir pith was carried out by drop by drop addition method. The effect of various factors such as pH, initial concentration of phosphate, contact time and adsorbent dose on phosphate adsorption was studied by batch technique. The pH at 3.0 favored the maximum adsorption of phosphate from aqueous solutions. The effect of pH on phosphate adsorption was explained by pH(zpc), phosphate speciation in solution and affinity of anions towards the adsorbent sites. A comparative study of the adsorption of phosphate using CP-Fe-I and CP (coir pith) was made and results show that the former one is five to six times more effective than the latter. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Adsorption followed Langmuir isotherm model. Column studies were conducted to examine the utility of the investigated adsorbent for the removal of phosphate from continuously flowing aqueous solutions.

Reaction behaviors of decomposition of monocrotophos in aqueous solution by UV and UV/O processes.

PubMed

Ku, Y; Wang, W; Shen, Y S

2000-02-01

The decomposition of monocrotophos (cis-3-dimethoxyphosphinyloxy-N-methyl-crotonamide) in aqueous solution by UV and UV/O(3) processes was studied. The experiments were carried out under various solution pH values to investigate the decomposition efficiencies of the reactant and organic intermediates in order to determine the completeness of decomposition. The photolytic decomposition rate of monocrotophos was increased with increasing solution pH because the solution pH affects the distribution and light absorbance of monocrotophos species. The combination of O(3) with UV light apparently promoted the decomposition and mineralization of monocrotophos in aqueous solution. For the UV/O(3) process, the breakage of the >C=C< bond of monocrotophos by ozone molecules was found to occur first, followed by mineralization by hydroxyl radicals to generate CO(3)(2-), PO4(3-), and NO(3)(-) anions in sequence. The quasi-global kinetics based on a simplified consecutive-parallel reaction scheme was developed to describe the temporal behavior of monocrotophos decomposition in aqueous solution by the UV/O(3) process.

Effect of medium pH on chemical selectivity of oxalic acid biosynthesis by Aspergillus niger W78C in submerged batch cultures with sucrose as a carbon source.

PubMed

Walaszczyk, Ewa; Podgórski, Waldemar; Janczar-Smuga, Małgorzata; Dymarska, Ewelina

2018-01-01

The pH of the medium is the key environmental parameter of chemical selectivity of oxalic acid biosynthesis by Aspergillus niger . The activity of the enzyme oxaloacetate hydrolase, which is responsible for decomposition of oxaloacetate to oxalate and acetate inside the cell of the fungus, is highest at pH 6. In the present study, the influence of pH in the range of 3-7 on oxalic acid secretion by A. niger W78C from sucrose was investigated. The highest oxalic acid concentration, 64.3 g dm -3 , was reached in the medium with pH 6. The chemical selectivity of the process was 58.6% because of the presence of citric and gluconic acids in the cultivation broth in the amount of 15.3 and 30.2 g dm -3 , respectively. Both an increase and a decrease of medium pH caused a decrease of oxalic acid concentration. The obtained results confirm that pH 6 of the carbohydrate medium is appropriate for oxalic acid synthesis by A. niger , but the chemical selectivity of the process described in this paper was high in comparison to values reported previously in the literature.

The use of physiological solutions or media in calcium phosphate synthesis and processing.

PubMed

Tas, A Cuneyt

2014-05-01

This review examined the literature to spot uses, if any, of physiological solutions/media for the in situ synthesis of calcium phosphates (CaP) under processing conditions (i.e. temperature, pH, concentration of inorganic ions present in media) mimicking those prevalent in the human hard tissue environments. There happens to be a variety of aqueous solutions or media developed for different purposes; sometimes they have been named as physiological saline, isotonic solution, cell culture solution, metastable CaP solution, supersaturated calcification solution, simulated body fluid or even dialysate solution (for dialysis patients). Most of the time such solutions were not used as the aqueous medium to perform the biomimetic synthesis of calcium phosphates, and their use was usually limited to the in vitro testing of synthetic biomaterials. This review illustrates that only a limited number of research studies used physiological solutions or media such as Earle's balanced salt solution, Bachra et al. solutions or Tris-buffered simulated body fluid solution containing 27mM HCO3(-) for synthesizing CaP, and these studies have consistently reported the formation of X-ray-amorphous CaP nanopowders instead of Ap-CaP or stoichiometric hydroxyapatite (HA, Ca10(PO4)6(OH)2) at 37°C and pH 7.4. By relying on the published articles, this review highlights the significance of the use of aqueous solutions containing 0.8-1.5 mMMg(2+), 22-27mM HCO3(-), 142-145mM Na(+), 5-5.8mM K(+), 103-133mM Cl(-), 1.8-3.75mM Ca(2+), and 0.8-1.67mM HPO4(2-), which essentially mimic the composition and the overall ionic strength of the human extracellular fluid (ECF), in forming the nanospheres of X-ray-amorphous CaP. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Kinetics of beta-haematin formation from suspensions of haematin in aqueous benzoic acid.

PubMed

Egan, Timothy J; Tshivhase, Mmboneni G

2006-11-14

Kinetics of beta-haematin (synthetic malaria pigment) formation from haematin have been studied in the presence of aqueous benzoic acid and derivatives of benzoic acid. Formation of the beta-haematin product is demonstrated by X-ray diffraction and IR spectroscopy. Reactions were followed by determining the fraction of unreacted haematin at various time points during the process via reaction of extracted aliquots with pyridine. The kinetics can be fitted to the Avrami equation, indicating that the process involves nucleation and growth. Reaction kinetics in stirred benzoic acid are similar to those previously observed in acetic acid, except that benzoic acid is far more active in promoting the reaction than acetic acid. The reaction reaches completion within 2 h in the presence of 0.050 M benzoic acid (pH 4.5, 60 degrees C). This compares with 1 h in the presence of 4.5 M acetic acid and 4 h in the presence of 2 M acetic acid. The reaction rate in benzoic acid is not affected if the stirring rate is decreased to zero, but very vigorous stirring appears to disrupt nucleation. The rate constant for beta-haematin formation in benzoic acid has a linear dependence on benzoic acid concentration and follows Arrhenius behaviour with temperature. There is a bell-shaped dependence on pH. This suggests that the haematin species in which one propionate group is protonated and the other is deprotonated is optimal for beta-haematin formation. When the reaction is conducted in para-substituted benzoic acid derivatives, the log of the rate constant increases linearly with the Hammett constant. These findings suggest that the role of the carboxylic acid may be to disrupt hydrogen bonding and pi-stacking in haematin, facilitating conversion to beta-haematin. The large activation energy for conversion of precipitated haematin to beta-haematin suggests that the reaction in vivo most likely involves direct nucleation from solution and probably does not occur in aqueous medium.

Valorization of aquaculture waste in removal of cadmium from aqueous solution: optimization by kinetics and ANN analysis

NASA Astrophysics Data System (ADS)

Aditya, Gautam; Hossain, Asif

2018-05-01

Cadmium is one of the most hazardous heavy metal concerning human health and aquatic pollution. The removal of cadmium through biosorption is a feasible option for restoration of the ecosystem health of the contaminated freshwater ecosystems. In compliance with this proposition and considering the efficiency of calcium carbonate as biosorbent, the shell dust of the economically important snail Bellamya bengalensis was tested for the removal of cadmium from aqueous medium. Following use of the flesh as a cheap source of protein, the shells of B. bengalensis made up of CaCO3 are discarded as aquaculture waste. The biosorption was assessed through batch sorption studies along with studies to characterize the morphology and surface structures of waste shell dust. The data on the biosorption were subjected to the artificial neural network (ANN) model for optimization of the process. The biosorption process changed as functions of pH of the solution, concentration of heavy metal, biomass of the adsorbent and time of exposure. The kinetic process was well represented by pseudo second order ( R 2 = 0.998), and Langmuir equilibrium ( R 2 = 0.995) had better fits in the equilibrium process with 30.33 mg g-1 of maximum sorption capacity. The regression equation ( R 2 = 0.948) in the ANN model supports predicted values of Cd removal satisfactorily. The normalized importance analysis in ANN predicts Cd2+ concentration, and pH has the most influence in removal than biomass dose and time. The SEM and EDX studies show clear peaks for Cd confirming the biosorption process while the FTIR study depicts the main functional groups (-OH, C-H, C=O, C=C) responsible for the biosorption process. The study indicated that the waste shell dust can be used as an efficient, low cost, environment friendly, sustainable adsorbent for the removal of cadmium from aqueous solution.

Counterbalancing hydrodynamic sample distortion effects increases resolution of free-flow zone electrophoresis.

PubMed

Weber, G; Bauer, J

1998-06-01

On fractionation of highly heterogeneous protein mixtures, optimal resolution was achieved by forcing proteins to migrate through a preestablished pH gradient, until they entered a medium with a pH similar but not equal to their pIs. For this purpose, up to seven different media were pumped through the electrophoresis chamber so that they were flowing adjacently to each other, forming a pH gradient declining stepwise from the cathode to the anode. This gradient had a sufficiently strong band-focusing effect to counterbalance sample distortion effects of the flowing medium as proteins approached their isoelectric medium closer than 0.5 pH units. Continuous free-flow zone electrophoresis (FFZE) with high throughput capability was applicable if proteins did not precipitate or aggregate in these media. If components of heterogeneous protein mixtures had already started to precipitate or aggregate, in a medium with a pH exceeding their pI by more than 0.5 pH units, the application of interval modus and media forming flat pH gradients appeared advantageous.

Spectrophotometric Determination of Iron(III)-Glycine Formation Constant in Aqueous Medium Using Competitive Ligand Binding

ERIC Educational Resources Information Center

Prasad, Rajendra; Prasad, Surendra

2009-01-01

The formation constant of iron(III) complex with glycine (Gly) ligand in aqueous acidic medium (0.2 M HNO[subscript 3], I = 0.2 M at 28 plus or minus 1 degree C) was determined spectrophotometrically in which a competing color reaction between Fe(III) and SCN[superscript -] was used as an indicator reaction. Under the specified conditions Fe(III)…

Chemoenzymatic one-pot synthesis in an aqueous medium: combination of metal-catalysed allylic alcohol isomerisation-asymmetric bioamination.

PubMed

Ríos-Lombardía, Nicolás; Vidal, Cristian; Cocina, María; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

2015-07-11

The ruthenium-catalysed isomerisation of allylic alcohols was coupled, for the first time, with asymmetric bioamination in a one-pot process in an aqueous medium. In the cases involving prochiral ketones, the ω-TA exhibited excellent enantioselectivity, identical to that observed in the single step. As a result, amines were obtained from allylic alcohols with high overall yields and excellent enantiomeric excesses.

Nanoparticle-supported and magnetically recoverable ruthenium hydroxide catalyst: efficient hydration of nitriles to amides in aqueous medium.

PubMed

Polshettiwar, Vivek; Varma, Rajender S

2009-01-01

Magnetic attraction not filtration: A magnetic nanoparticle-supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.

Organic containment separator

DOEpatents

Del Mar, Peter

1995-01-01

A process of sample preparation prior to analysis for the concentration of an organic contaminant in an aqueous medium by (a) passing an initial aqueous medium including a minor amount of the organic contaminant through a composite tube including a polymeric base material selected from the group of polyolefins and polyfluorocarbons and particles of a carbon allotrope material adfixed to the inner wall of the polymeric base material, the composite tube having an internal diameter of from about 0.1 to about 2.0 millimeters and being of sufficient length to permit the organic contaminant to adhere to the composite tube, (b) passing a solvent through the composite tube, said solvent capable of separating the adhered organic contaminant from the composite tube. Further, an extraction apparatus for sample preparation prior to analysis for the concentration of an organic contaminant in an aqueous medium, said apparatus including a composite tube including a polymeric base material selected from the group of polyolefins and polyfluorocarbons and particles of a carbon allotrope material adfixed to the inner wall of the polymeric base material, the composite tube having an internal diameter of from about 0.1 to about 2.0 millimeters and being of sufficient length to permit an organic contaminant contained within an aqueous medium passed therethrough to adhere to the composite tube is disclosed.

Organic contaminant separator

DOEpatents

Mar, Peter D.

1994-01-01

A process of sample preparation prior to analysis for the concentration of an organic contaminant in an aqueous medium by (a) passing an initial aqueous medium including a minor amount of the organic contaminant through a composite tube including a polymeric base material selected from the group of polyolefins and polyfluorocarbons and particles of a carbon allotrope material adfixed to the inner wall of the polymeric base material, the composite tube having an internal diameter of from about 0.1 to about 2.0 millimeters and being of sufficient length to permit the organic contaminant to adhere to the composite tube, (b) passing a solvent through the composite tube, said solvent capable of separating the adhered organic contaminant from the composite tube. Further, an extraction apparatus for sample preparation prior to analysis for the concentration of an organic contaminant in an aqueous medium, said apparatus including a composite tube including a polymeric base material selected from the group of polyolefins and polyfluorocarbons and particles of a carbon allotrope material adfixed to the inner wall of the polymeric base material, the composite tube having an internal diameter of from about 0.1 to about 2.0 millimeters and being of sufficient length to permit an organic contaminant contained within an aqueous medium passed therethrough to adhere to the composite tube is disclosed.

Effect of pore size of three-dimensionally ordered macroporous chitosan-silica matrix on solubility, drug release, and oral bioavailability of loaded-nimodipine.

PubMed

Gao, Yikun; Xie, Yuling; Sun, Hongrui; Zhao, Qinfu; Zheng, Xin; Wang, Siling; Jiang, Tongying

2016-01-01

To explore the effect of the pore size of three-dimensionally ordered macroporous chitosan-silica (3D-CS) matrix on the solubility, drug release, and oral bioavailability of the loaded drug. 3D-CS matrices with pore sizes of 180 nm, 470 nm, and 930 nm were prepared. Nimodipine (NMDP) was used as the drug model. The morphology, specific surface area, and chitosan mass ratio of the 3D-CS matrices were characterized before the effect of the pore size on drug crystallinity, solubility, release, and in vivo pharmacokinetics were investigated. With the pore size of 3D-CS matrix decreasing, the drug crystallinity decreased and the aqueous solubility increased. The drug release was synthetically controlled by the pore size and chitosan content of 3D-CS matrix in a pH 6.8 medium, while in a pH 1.2 medium the erosion of the 3D-CS matrix played an important role in the decreased drug release rate. The area under the curve of the drug-loaded 3D-CS matrices with pore sizes of 930 nm, 470 nm, and 180 nm was 7.46-fold, 5.85-fold, and 3.75-fold larger than that of raw NMDP respectively. Our findings suggest that the oral bioavailability decreased with a decrease in the pore size of the matrix.

Fate of 2,4,6-Trinitrotoluene in a Simulated Compost System

DTIC Science & Technology

1994-09-01

to the NaOH solution. The insoluble material remaining after the NaOH fractionation con- tained the humin fraction as well as remaining cellulose ...insoluble) (solb) HUMIN + CELLULOSE MIBK (insoluble) (MIBK) (aqueous) ICELLULOSE HUMIN HUMIC ACID + FULVIC ACID +HCI to pH 1 (insoLuble) (soluble...0.5 N NaOH (insoluble) (soluble) HUMIN+ CELLULOSE • MIBK (insoluble) (MIBK) (aqueous) CELLULOSE HUMIN HUMIC ACID + FULVIC ACID + HUMIN +HCl to pH 1

Effects of the microbial siderophore DFO-B on Pb and Cd speciation in aqueous solution.

PubMed

Mishra, Bhoopesh; Haack, Elizabeth A; Maurice, Patricia A; Bunker, Bruce A

2009-01-01

This study investigates the complexation environments of aqueous Pb and Cd in the presence of the trihydroxamate microbial siderophore, desferrioxamine-B (DFO-B) as a function of pH. Complexation of aqueous Pb and Cd with DFO-B was predicted using equilibrium speciation calculation. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy at Pb L(III) edge and Cd K edge was used to characterize Pb and Cd-DFO-B complexes at pH values predicted to best represent each of the metal-siderophore complexes. Pb was not found to be complexed measurably by DFO-B at pH 3.0, but was complexed by all three hydroxamate groups to form a totally "caged" hexadentate structure at pH 7.5-9.0. At the intermediate pH value (pH 4.8), a mixture of Pb-DFOB complexes involving binding of the metal through one and two hydroxamate groups was observed. Cd, on the other hand, remained as hydrated Cd2+ at pH 5.0, occurred as a mixture of Cd-DFOB and inorganic species at pH 8.0, and was bound by three hydroxamate groups from DFO-B at pH 9.0. Overall, the solution species observed with EXAFS were consistent with those predicted thermodynamically. However, Pb speciation at higher pH values differed from that predicted and suggests that published constants underestimate the binding constant for complexation of Pb with all three hydroxamate groups of the DFO-B ligand. This molecular-level understanding of metal-siderophore solution coordination provides physical evidence for complexes of Pb and Cd with DFO-B, and is an important first step toward understanding processes at the microbial- and/or mineral-water interface in the presence of siderophores.

RECOVERY OF ACTINIDES FROM AQUEOUS NITRIC ACID SOLUTIONS

DOEpatents

Ader, M.

1963-11-19

A process of recovering actinides is presented. Tetravalent actinides are extracted from rare earths in an aqueous nitric acid solution with a ketone and back-extracted from the ketone into an aqueous medium. The aqueous actinide solution thus obtained, prior to concentration by boiling, is sparged with steam to reduce its ketone to a maximum content of 3 grams per liter. (AEC)

Experimental results for characterization of a tapered plastic optical fiber sensor based on SPR

NASA Astrophysics Data System (ADS)

Cennamo, N.; Galatus, R.; Zeni, L.

2015-05-01

The experimental results obtained with two different Plastic Optical Fiber (POF) geometries, tapered and not-tapered, for a sensor based on Surface Plasmon Resonance (SPR) are presented. SPR is used for determining the refractive index variations at the interface between a gold layer and a dielectric medium (aqueous medium). In this work SPR sensors in POF configurations, useful for bio-sensing applications, have been realized for the optimization of the sensitivity and experimentally tested. The results show as the sensitivity increases with the tapered POF configuration, when the refractive index of aqueous medium increases.

Performance of Carbon/Polytetrafluoroethylene (PTFE) Air Cathodes from pH 0 to 14 for Li-Air Batteries

DTIC Science & Technology

2007-12-01

aqueous and aqueous electrolytes are kept separate by a non-electronically conducting ceramic membrane impervious to water, but with a high ionic...thought of as being solvated by the ceramic membrane as it passes from non-aqueous to aqueous electrolyte. The half-cell reaction at the lithium...overall charge in the reaction, positive lithium ions flow through an ionically conducting ceramic membrane from the non-aqueous anode compartment to

Spectral changes induced by pH variation of aqueous extracts derived from biomass burning aerosols: Under dark and in presence of simulated sunlight irradiation

NASA Astrophysics Data System (ADS)

Cai, Jing; Zhi, Guorui; Yu, Zhiqiang; Nie, Peng; Gligorovski, Sasho; Zhang, Yuzhe; Zhu, Like; Guo, Xixiang; Li, Pei; He, Tan; He, Youjiang; Sun, Jianzhong; Zhang, Yang

2018-07-01

Water soluble organic carbon (WSOC) can significantly influence the aerosol optical properties and the aqueous phase chemistry in cloudwater, fogwater and aerosol liquid water. Here, we examine how the changing pH (in acidic range) affects the absorption spectra of aqueous extracts from field biomass burning aerosols, under dark conditions and in presence of simulated sunlight illumination. The observation under dark conditions indicates that pH variation from 2 to 5 induces significantly enhanced light absorbance in the wavelength ranges of 235-270 nm and 300-550 nm, whereas the light absorbance decreased in the range of 270-300 nm, which might be partially ascribed to the deprotonation of carboxylic acids and phenols. During the extract photolysis, light absorption exhibits photo-bleaching below 380 nm and photo-enhancement above 380 nm, indicating that at acidic levels (pH = 2-5), the particle extracts could undergo a significant composition evolution leading to a modification of absorptive properties. Meanwhile, after 12 h-photolysis, the acidity ([H+]) normalized by WSOC concentration in aqueous extracts ([WSOCae]) increased with a variation of Δ[H+]/[WSOCae]=(3.7 ± 0.7) × 10-7 mol mgC-1 (mean ± standard deviation), suggesting the formation of new acidic substances. Although these findings were acquired in aqueous solutions more relevant to cloud and fog water, the similar evolution likely occurs in wetted aerosols. This calls more attention to the effect of acidity on the wetted aerosols in order to better estimate the aerosol radiative forcing.

Polymeric nanoparticles of cholesterol-modified glycol chitosan for doxorubicin delivery: preparation and in-vitro and in-vivo characterization.

PubMed

Yu, Jing-Mou; Li, Yong-Jie; Qiu, Li-Yan; Jin, Yi

2009-06-01

Polymeric nanoparticles have been extensively studied as drug carriers. Chitosan and its derivatives have attracted significant attention in this regard but have limited application because of insolubility in biological solution. In this work, we attempted to utilize cholesterol-modified glycol chitosan (CHGC) self-aggregated nanoparticles to increase aqueous solubility, and to reduce side effects and enhance the antitumour efficacy of the anticancer drug doxorubicin. Methods CHGC nanoparticles were loaded with doxorubicin by a dialysis method, and their characteristics were determined by transmission electron microscopy examination, light-scattering study, in-vitro drug-release study, pharmacokinetic study in rats and in-vivo antitumour activity in mice. The resulting doxorubicin-loaded CHGC nanoparticles (DCNs) formed self-assembled aggregates in aqueous medium. From the observation by transmission electron microscopy, DCNs were almost spherical in shape. The mean diameters of these nanoparticles determined by dynamic light scattering were in the range of 237-336 nm as the doxorubicin-loading content increased from 1.73% to 9.36%. In-vitro data indicated that doxorubicin release from DCNs was much faster in phosphate-buffered saline at pH 5.5 than at pH 6.5 and 7.4, and the release rate was dependent on the loading content of doxorubicin in these nanoparticles. It was observed that DCN-16 (drug loaded content: 9.36%) exhibited prolonged circulation time in rat plasma and showed higher antitumour efficacy against S180-bearing mice than free doxorubicin. These results indicated that CHGC nanoparticles had potential as a carrier for insoluble anticancer drugs in cancer therapy.

Product development studies of amino acid conjugate of Aceclofenac.

PubMed

Singh, Ajay Pal; Ramadan, Wafa Mossa; Dahiya, Rajiv; Sarpal, A S; Pathak, Kamla

2009-04-01

The prodrugs designed by classical approach increase lipophilicity of the drug, which decreases the water solubility thus decreasing the concentration gradient, which controls drug absorption. To overcome the limitations of traditional prodrug approach, water soluble prodrugs can be designed by adding selected amino acid to the drug moiety that are the substrates for the enzyme located at the intestinal brush border thus overcoming pharmaceutical problem without compromising bioavailability. ACaa (Amino acid conjugate of Aceclofenac) was synthesized by conjugation with l-phenylalanine by conventional coupling method using N, N-dicyclohexylcarbodiimide and ACaa was characterized by melting point, TLC, photomicrograph, UV, FT-IR, FT-NMR, MS-FAB, XRD and DSC. As a part of product development study ACaa was subjected to studies like In-vivo in albino rats and in-vitro like ACaa reversion to AC (Aceclofenac) in aqueous buffers of pH 1.21, 2.38. 3.10, 6.22 and 7.41, at a constant concentration (0.05M), ionic strength (micro = 0.5) and at a temperature of 37 degrees C +/- 0.5 degrees C, ACaa showed negligible reversion (2.15 %) up to 24 hrs study at acidic pH thus suggesting stability in acidic environment of stomach, the rate of reversion increased as pH of medium increased. pH- partition profile, pH- solubility profile and micromeritic studies were also carried out in comparison to pure drug. The solubility and lipophilicity of ACaa exhibited higher values at all pH range when compared to AC. The micromeritic properties also evaluated in terms of particle shape and size, IQCS and kurtosis. Resulting IQCS value approached zero thus suggesting reducing in the degree of skewness.

Persistence of spiromesifen in soil: influence of moisture, light, pH and organic amendment.

PubMed

Mate, Ch Jamkhokai; Mukherjee, Irani; Das, Shaon Kumar

2015-02-01

Persistence of spiromesifen in soil as affected by varying moisture, light, compost amendment, soil sterilization and pH in aqueous medium were studied. Degradation of spiromesifen in soil followed the first-order reaction kinetics. Effect of different moisture regimes indicated that spiromesifen dissipated faster in submerged soil (t 1/2 14.3-16.7 days) followed by field capacity (t 1/2 18.7-20.0 days), and dry soil (t 1/2 21.9-22.9 days). Dissipation was faster in sterilized submerged (t 1/2 17.7 days) than in sterilized dry (t 1/2 35.8 days). Photo spiromesifen metabolite was not detected under different moisture regimes. After 30 days, enol spiromesifen metabolite was detected under submerged condition and was below detectable limit (<0.001 μg g(-1)) after 90 days. Soil amendment compost (2.5 %) at field capacity enhanced dissipation of the insecticide, and half-life value was 14.3 against 22.4 days without compost amendment. Under different pH condition, residues persisted in water with half-life values 5.7 to 12.5 days. Dissipation in water was faster at pH 9.0 (t 1/2 5.7 days), followed by pH 4.0 (t 1/2 9.7 days) and pH 7.2 (t 1/2 12.5 days). Exposure of spiromesifen to different light conditions indicated that it was more prone to degradation under UV light (t 1/2 3-4 days) than sunlight exposure (t 1/2 5.2-8.1 days). Under sunlight exposure, photo spiromesifen metabolite was detected after 10 and 15 days as compared to 3 and 5 days under UV light exposure.

Isolation and fractionation of soil humin using alkaline urea and dimethylsulphoxide plus sulphuric acid

NASA Astrophysics Data System (ADS)

Song, Guixue; Hayes, Michael H. B.; Novotny, Etelvino H.; Simpson, Andre J.

2011-01-01

Humin, the most recalcitrant and abundant organic fraction of soils and of sediments, is a significant contributor to the stable carbon pool in soils and is important for the global carbon budget. It has significant resistance to transformations by microorganisms. Based on the classical operational definition, humin can include any humic-type substance that is not soluble in water at any pH. We demonstrate in this study how sequential exhaustive extractions with 0.1 M sodium hydroxide (NaOH) + 6 M urea, followed by dimethylsulphoxide (DMSO) + 6% ( v/ v) sulphuric acid (H2SO4) solvent systems, can extract 70-80% of the residual materials remaining after prior exhaustive extractions in neutral and aqueous basic media. Solid-state 13C NMR spectra have shown that the components isolated in the base + urea system were compositionally similar to the humic and fulvic acid fractions isolated at pH 12.6 in the aqueous media. The NMR spectra indicated that the major components isolated in the DMSO + H2SO4 medium had aliphatic hydrocarbon associated with carboxyl functionalities and with lesser amounts of carbohydrate and peptide and minor amounts of lignin-derived components. The major components will have significant contributions from long-chain fatty acids, waxes, to cuticular materials. The isolates in the DMSO + H2SO4 medium were compositionally similar to the organic components that resisted solvation and remained associated with the soil clays. It is concluded that the base + urea system released humic and fulvic acids held by hydrogen bonding or by entrapment within the humin matrix. The recalcitrant humin materials extracted in DMSO + H2SO4 are largely biological molecules (from plants and the soil microbial population) that are likely to be protected from degradation by their hydrophobic moieties and by sorption on the soil clays. Thus, the major components of humin do not satisfy the classical definitions for humic substances which emphasise that these arise from microbial or chemical transformations in soils of the components of organic debris.

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

pH-Dependent solubility and permeability criteria for provisional biopharmaceutics classification (BCS and BDDCS) in early drug discovery.

PubMed

Varma, Manthena V; Gardner, Iain; Steyn, Stefanus J; Nkansah, Paul; Rotter, Charles J; Whitney-Pickett, Carrie; Zhang, Hui; Di, Li; Cram, Michael; Fenner, Katherine S; El-Kattan, Ayman F

2012-05-07

The Biopharmaceutics Classification System (BCS) is a scientific framework that provides a basis for predicting the oral absorption of drugs. These concepts have been extended in the Biopharmaceutics Drug Disposition Classification System (BDDCS) to explain the potential mechanism of drug clearance and understand the effects of uptake and efflux transporters on absorption, distribution, metabolism, and elimination. The objective of present work is to establish criteria for provisional biopharmaceutics classification using pH-dependent passive permeability and aqueous solubility data generated from high throughput screening methodologies in drug discovery settings. The apparent permeability across monolayers of clonal cell line of Madin-Darby canine kidney cells, selected for low endogenous efflux transporter expression, was measured for a set of 105 drugs, with known BCS and BDDCS class. The permeability at apical pH 6.5 for acidic drugs and at pH 7.4 for nonacidic drugs showed a good correlation with the fraction absorbed in human (Fa). Receiver operating characteristic (ROC) curve analysis was utilized to define the permeability class boundary. At permeability ≥ 5 × 10(-6) cm/s, the accuracy of predicting Fa of ≥ 0.90 was 87%. Also, this cutoff showed more than 80% sensitivity and specificity in predicting the literature permeability classes (BCS), and the metabolism classes (BDDCS). The equilibrium solubility of a subset of 49 drugs was measured in pH 1.2 medium, pH 6.5 phosphate buffer, and in FaSSIF medium (pH 6.5). Although dose was not considered, good concordance of the measured solubility with BCS and BDDCS solubility class was achieved, when solubility at pH 1.2 was used for acidic compounds and FaSSIF solubility was used for basic, neutral, and zwitterionic compounds. Using a cutoff of 200 μg/mL, the data set suggested a 93% sensitivity and 86% specificity in predicting both the BCS and BDDCS solubility classes. In conclusion, this study identified pH-dependent permeability and solubility criteria that can be used to assign provisional biopharmaceutics class at early stage of the drug discovery process. Additionally, such a classification system will enable discovery scientists to assess the potential limiting factors to oral absorption, as well as help predict the drug disposition mechanisms and potential drug-drug interactions.

pH recycling aqueous two-phase systems applied in extraction of Maitake β-Glucan and mechanism analysis using low-field nuclear magnetic resonance.

PubMed

Hou, Huiyun; Cao, Xuejun

2015-07-31

In this paper, a recycling aqueous two-phase systems (ATPS) based on two pH-response copolymers PADB and PMDM were used in purification of β-Glucan from Grifola frondosa. The main parameters, such as polymer concentration, type and concentration of salt, extraction temperature and pH, were investigated to optimize partition conditions. The results demonstrated that β-Glucan was extracted into PADB-rich phase, while impurities were extracted into PMDM-rich phase. In this 2.5% PADB/2.5% PMDM ATPS, 7.489 partition coefficient and 96.92% extraction recovery for β-Glucan were obtained in the presence of 30mmol/L KBr, at pH 8.20, 30°C. The phase-forming copolymers could be recycled by adjusting pH, with recoveries of over 96.0%. Furthermore, the partition mechanism of Maitake β-Glucan in PADB/PMDM aqueous two-phase systems was studied. Fourier transform infrared spectra, ForteBio Octet system and low-field nuclear magnetic resonance (LF-NMR) were introduced for elucidating the partition mechanism of β-Glucan. Especially, LF-NMR was firstly used in the mechanism analysis in partition of aqueous two-phase systems. The change of transverse relaxation time (T2) in ATPS could reflect the interaction between polymers and β-Glucan. Copyright © 2015 Elsevier B.V. All rights reserved.

Experiments on the Multiphase Chemistry of Isocyanic Acid, HNCO.

NASA Astrophysics Data System (ADS)

Roberts, J. M.; Liu, Y.

2015-12-01

Isocyanic acid, HNCO, has emerged as a potentially important reduced nitrogen compound that is emitted in wildfires, and may have health effect implications. The extent of the health effects depends on the solubility of HNCO in aqueous and non-aqueous solutions and the relative rates of hydrolysis versus carbamylation reactions (for example: HNCO + ROH => H2NC(O)OR). We report here results of studies of HNCO solubility and its reaction in buffered aqueous solutions (pH3), tridecane, and n-octanol at temperatures over the range 5 to 37°C. From these data, the heats of solution and activation energy of hydrolysis are estimated, and a partition coefficient between n-octanol and water at 25°C is greater than 1 for low pH solutions, indicating appreciable portioning to a non-polar phase, but HNCO will be distributed mostly in the aqueous phase at neutral pH. In addition, it was found that the rate of reaction of HNCO with n-octanol was competitive with hydrolysis under physiologically relevant conditions (pH7.4, 37°C), indicating that carbamylation of ROH groups could be significant. Based on these results, research on the carbamylation of other functional groups, and solubility and reaction studies of other isocyanates (e.g. CH3NCO) are warranted. The implications of this multi-phase chemistry for global exposures to wildfire emissions will be discussed.

Synthesis of poly(aminopropyl/methyl)silsesquioxane particles as effective Cu(II) and Pb(II) adsorbents.

PubMed

Lu, Xin; Yin, Qiangfeng; Xin, Zhong; Li, Yang; Han, Ting

2011-11-30

Poly(aminopropyl/methyl)silsesquioxane (PAMSQ) particles have been synthesized by a one-step hydrolytic co-condensation process using 3-aminopropyltriethoxysilane (APTES) and methyltrimethoxysilane (MTMS) as precursors in the presence of base catalyst in aqueous medium. The amino functionalities of the particles could be controlled by adjusting the organosilanes feed ratio. The compositions of the amino-functionalized polysilsesquioxanes were confirmed by FT-IR spectroscopy, solid-state (29)Si NMR spectroscopy, and elemental analysis. The strong adsorbability of Cu(II) and Pb(II) ions onto PAMSQ particles was systematically examined. The effect of adsorption time, initial metal ions concentration and pH of solutions was studied to optimize the metal ions adsorbability of PAMSQ particles. The kinetic studies indicated that the adsorption process well fits the pseudo-second-order kinetics. Adsorption phenomena appeared to follow Langmuir isotherm. The PAMSQ particles demonstrate the highest Cu(II) and Pb(II) adsorption capacity of 2.29 mmol/g and 1.31 mmol/g at an initial metal ions concentration of 20mM, respectively. The PAMSQ particles demonstrate a promising application in the removal of Cu(II) and Pb(II) ions from aqueous solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

One-step aqueous synthesis of fluorescent copper nanoclusters by direct metal reduction

NASA Astrophysics Data System (ADS)

Fernández-Ujados, Mónica; Trapiella-Alfonso, Laura; Costa-Fernández, José M.; Pereiro, Rosario; Sanz-Medel, Alfredo

2013-12-01

A one-step aqueous synthesis of highly fluorescent water-soluble copper nanoclusters (CuNCs) is here described, based on direct reduction of the metal precursor with NaBH4 in the presence of bidentate ligands (made of lipoic acid anchoring groups, appended with a poly(ethylene glycol) short chain). A complete optical and structural characterization was carried out: the optical emission was centred at 416 nm, with a luminescence quantum yield in water of 3.6% (the highest one reported so far in water for this kind of nanocluster). The structural characterization reveals a homogeneous size distribution (of 2.5 nm diameter) with spherical shape. The CuNCs obtained offer long-term stability (the luminescence emission remained unaltered after more than two months) under a broad range of chemical conditions (e.g. stored at pH 3-12 or even in a high ionic strength medium such as 1 M NaCl) and high photostability, keeping their fluorescence emission intact after more than 2 h of daylight and UV-light exposition. All those advantageous features warrant synthesized CuNCs being promising fluorescent nanoprobes for further developments including (bio)applications.

Composite cryogels for lysozyme purification.

PubMed

Baydemir, Gözde; Türkoğlu, Emir Alper; Andaç, Müge; Perçin, Işık; Denizli, Adil

2015-01-01

Beads-embedded novel composite cryogel was synthesized to purify lysozyme (Lyz) from chicken egg white. The poly(hydroxyethyl methacrylate-N-methacryloyl-L-phenylalanine) (PHEMAPA) beads of smaller than 5 µm size were synthesized by suspension polymerization and then embedded into a poly(hydroxyethyl methacrylate) (PHEMA)-based cryogel column. The PHEMAPA bead-embedded cryogel (BEC) column was characterized by swelling tests, scanning electron microscopy (SEM), surface area measurements by the Brunauer-Emmett-Teller (BET) method, elemental analysis, and flow dynamics. The specific surface area of the PHEMAPA BEC was found as 41.2 m(2) /g using BET measurements. Lyz-binding experiments were performed using aqueous solutions in different conditions such as initial Lyz concentration, pH, flow rate, temperature, and NaCl concentration of an aqueous medium. The PHEMAPA BEC column could be used after 10 adsorption-desorption studies without any significant loss in adsorption capacity of Lyz. The PHEMAPA BEC column was used to purify Lyz from chicken egg white, and gel electrophoresis was used to estimate the purity of Lyz. The chromatographic application of the PHEMAPA BEC column was also performed using fast protein liquid chromatography. © 2014 International Union of Biochemistry and Molecular Biology, Inc.

Synthesis and applications of eco-magnetic nano-hydroxyapatite chitosan composite for enhanced fluoride sorption.

PubMed

Pandi, Kalimuthu; Viswanathan, Natrayasamy

2015-12-10

Adsorption is a significant reaction occurs between adsorbent/water interface for controlling the pollutants in the aqueous environment. In this regard, an eco-magnetic biosorbent was prepared by uniform deposition of magnetic Fe3O4 particles on the surface of nano-hydroxyapatite (n-HAp)/chitosan (CS) nanocomposite namely Fe3O4@n-HApCS composite as versatile sorbent for fluoride sorption. The resulting Fe3O4@n-HApCS nanocomposite was characterized by FTIR and SEM with EDAX techniques. The defluoridation capacity (DC) was found to depend on the contact time, pH, co-existing anions, initial fluoride concentration and temperature. The sorption isotherm was investigated by Freundlich, Langmuir and Temkin isotherm models using the batch method. The thermodynamic parameters revealed the feasibility, spontaneity and endothermic nature of fluoride sorption. The results of this research work designated that Fe3O4@n-HApCS composite having the excellent defluoridation capacity than the individual components and interesting to note that the easy magnetic separation of Fe3O4@n-HApCS composite from aqueous medium. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparing the acidities of aqueous, frozen, and freeze-dried phosphate buffers: Is there a "pH memory" effect?

PubMed

Vetráková, Ľubica; Vykoukal, Vít; Heger, Dominik

2017-09-15

The concept of "pH memory" has been established in the literature for the correlation between the pH of a pre-lyophilization solution and the ionization state of freeze-dried powder (lyophile). In this paper, the concept of "pH memory" is explored for the system of an aqueous solution, a frozen solution, and a lyophile. Sodium and potassium phosphate buffers in the pH range of 5-9 were frozen and lyophilized with sulfonephthalein indicators as acidity probes, and their Hammett acidity functions were compared to the initial pH of the aqueous solution. The results show that the acidities of the lyophiles are somewhat changed compared to the initial pHs, but the acidities in the frozen state differ more substantially. The Hammett acidity functions of the frozen buffers were found to be markedly dissimilar from the initial pH, especially in the sodium phosphate frozen at 233K, where an increase in the initial pH led to a decrease in the Hammett acidity function of the frozen state at a certain pH range. The large acidification observed after freezing the sodium phosphate buffer was not detected in the lyophiles after the sample had been dried; the phenomenon is explained considering the formed crystals analyzed by X-ray powder diffraction. The results suggest that monitoring the final acidity of a lyophile is not sufficient to predict all the acidity changes throughout the whole lyophilization process. The importance of well-controlled freezing and lyophilization conditions follows from the results of the research. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparative Study of the Effect of Defects on Selective Adsorption of Butanol from Butanol/Water Binary Vapor Mixtures in Silicalite-1 Films

DOE PAGES

Farzaneh, Amirfarrokh; DeJaco, Robert F.; Ohlin, Lindsay; ...

2017-08-02

A promising route for sustainable 1-butanol (butanol) production is ABE (acetone, butanol, ethanol) fermentation. However, recovery of the products is challenging because of the low concentrations obtained in the aqueous solution, thus hampering large-scale production of biobutanol. Membrane and adsorbent-based technologies using hydrophobic zeolites are interesting alternatives to traditional separation techniques (e.g., distillation) for energy-efficient separation of butanol from aqueous mixtures. To maximize the butanol over water selectivity of the material, it is important to reduce the number of hydrophilic adsorption sites. This can, for instance, be achieved by reducing the density of lattice defect sites where polar silanol groupsmore » are found. The density of silanol defects can be reduced by preparing the zeolite at neutral pH instead of using traditional synthesis solutions with high pH. In this work, binary adsorption of butanol and water in two silicalite-1 films was studied using in situ attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy under equal experimental conditions. One of the films was prepared in fluoride medium, whereas the other one was prepared at high pH using traditional synthesis conditions. The amounts of water and butanol adsorbed from binary vapor mixtures of varying composition were determined at 35 and 50 °C, and the corresponding adsorption selectivities were also obtained. Both samples showed very high selectivities (100–23 000) toward butanol under the conditions studied. The sample having low density of defects, in general, showed ca. a factor 10 times higher butanol selectivity than the sample having a higher density of defects at the same experimental conditions. This difference was due to a much lower adsorption of water in the sample with low density of internal defects. Analysis of molecular simulation trajectories provides insights on the local selectivities in the zeolite channel network and at the film surface.« less

Comparative Study of the Effect of Defects on Selective Adsorption of Butanol from Butanol/Water Binary Vapor Mixtures in Silicalite-1 Films

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

Farzaneh, Amirfarrokh; DeJaco, Robert F.; Ohlin, Lindsay

A promising route for sustainable 1-butanol (butanol) production is ABE (acetone, butanol, ethanol) fermentation. However, recovery of the products is challenging because of the low concentrations obtained in the aqueous solution, thus hampering large-scale production of biobutanol. Membrane and adsorbent-based technologies using hydrophobic zeolites are interesting alternatives to traditional separation techniques (e.g., distillation) for energy-efficient separation of butanol from aqueous mixtures. To maximize the butanol over water selectivity of the material, it is important to reduce the number of hydrophilic adsorption sites. This can, for instance, be achieved by reducing the density of lattice defect sites where polar silanol groupsmore » are found. The density of silanol defects can be reduced by preparing the zeolite at neutral pH instead of using traditional synthesis solutions with high pH. In this work, binary adsorption of butanol and water in two silicalite-1 films was studied using in situ attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy under equal experimental conditions. One of the films was prepared in fluoride medium, whereas the other one was prepared at high pH using traditional synthesis conditions. The amounts of water and butanol adsorbed from binary vapor mixtures of varying composition were determined at 35 and 50 °C, and the corresponding adsorption selectivities were also obtained. Both samples showed very high selectivities (100–23 000) toward butanol under the conditions studied. The sample having low density of defects, in general, showed ca. a factor 10 times higher butanol selectivity than the sample having a higher density of defects at the same experimental conditions. This difference was due to a much lower adsorption of water in the sample with low density of internal defects. Analysis of molecular simulation trajectories provides insights on the local selectivities in the zeolite channel network and at the film surface.« less

Synthesis and characterization of oxytetracycline imprinted magnetic polymer for application in food

NASA Astrophysics Data System (ADS)

Aggarwal, Sneha; Rajput, Yudhishthir Singh; Singh, Gulab; Sharma, Rajan

2016-02-01

Magnetic imprinted polymer was prepared by polymerization of methacrylate and ethyleneglycoldimethacrylate in the presence of oxytetracycline on the surface of iron magnetite. Selectivity of prepared polymer was calculated from ratio of partition coefficient of oxytetracycline for imprinted and non- imprinted polymer in water, acetonitrile, methanol and at different pH in aqueous buffer. pH of solvent exhibited pronounced effect on selectivity. Selectivity at pH 7.0, 6.0 and 5.0 was 36.0, 2.25 and 1.61 fold higher than at pH 4.0. Imprinted polymer was not selective for oxytetracycline in methanol. However, selectivity in water and acetonitrile was 19.42 and 2.86, respectively. Oxytetracycline did bind to imprinted polymer in water or aqueous buffer (pH 7.0) and could be eluted with methanol. Prepared polymer extracted 75-80 % oxytetracycline from water, honey and egg white.

Camptothecin prodrug nanomicelle based on a boronate ester-linked diblock copolymer as the carrier of doxorubicin with enhanced cellular uptake.

PubMed

Gao, Ya; Xiao, Yi; Liu, Shiyuan; Yu, Jiahui

2018-02-01

A novel pH-sensitive polymeric prodrug of camptothecin (CPT) by polymerizing γ-camptothecin-glutamate N-carboxyanhydride (Glu (CPT)-NCA) on boronate ester-linked poly (ethyleneglycol) (PEG) directly via the amine-initiated ring open polymerization (ROP) has been developed. The resulting amphiphilic prodrug (mPEG-BC-PGluCPT) could self-assemble into nanoparticles and encapsulate doxorubicin (Dox) simultaneously in aqueous solution for dual-drug delivery. The formation of polymeric prodrug micelles (mPEG-BC@PGluCPT) was confirmed by the measurements of critical aggregation concentration (CAC), particle size, and morphology observations. The mPEG-BC@PGluCPT micelles were colloidally stable in solutions for two weeks. Polymeric prodrug micelles mPEG-BC@PGluCPT and Dox-loaded micelles mPEG-BC@PGluCPT⋅Dox showed sustained drug release profiles over 48 h. As expected, drug release was accelerated by the decreasement of pH value from 7.4 to 6.0, which demonstrated pH-dependent manner of drug release. Additionally, it was found that cellular uptake of mPEG-BC@PGluCPT⋅Dox micelles on HepG2 cells was higher than that on HL-7702 cells, especially in culture medium at pH 6.0. The enhanced cellular uptake of mPEG-BC@PGluCPT⋅Dox micelles under acidic condition on HepG2 cells resulted in the higher cytotoxicity of mPEG-BC@PGluCPT⋅Dox micelles at acidic pH than that at pH 7.4.

Aqueous flooding methods for tertiary oil recovery

DOEpatents

Peru, Deborah A.

1989-01-01

A method of aqueous flooding of subterranean oil bearing formation for tertiary oil recovery involves injecting through a well into the formation a low alkaline pH aqueous sodium bicarbonate flooding solution. The flooding solution's pH ranges from about 8.25 to 9.25 and comprises from 0.25 to 5 weight percent and preferably about 0.75 to 3.0 weight percent of sodium bicarbonate and includes a petroleum recovery surfactant of 0.05 to 1.0 weight percent and between 1 and 20 weight percent of sodium chloride. After flooding, an oil and water mixture is withdrawn from the well and the oil is separated from the oil and water mixture.

Experimental measurements of U60 nanocluster stability in aqueous solution

NASA Astrophysics Data System (ADS)

Flynn, Shannon L.; Szymanowski, Jennifer E. S.; Gao, Yunyi; Liu, Tianbo; Burns, Peter C.; Fein, Jeremy B.

2015-05-01

In this study, the aqueous behavior of isolated U60 nanoclusters (K16Li25[UO2(O2)OH]60)-19 was studied under several pH conditions and nanocluster concentrations to determine if the nanoclusters exhibit solid phase buffering behavior or if they exhibit behavior more like aqueous complexes. U60 is a cage cluster consisting of 60 (UO2)(O2)2(OH)2 uranyl polyhedral which share OH and O2 groups with their neighboring uranyl polyhedral, resulting in negatively charged cage clusters whose charge is at least partially offset by K+ and Li+ in the aqueous phase. Batch experiments to monitor nanocluster stability were conducted for 16 days at pH 7.5, 8.0 and 8.5 at nanocluster suspension concentrations of 1.4, 2.8 and 6.0 g/L. The aqueous concentrations of U, Li, and K, determined after 10 kDa molecular weight filtration, achieved steady-state with the nanoclusters within 24 h. The steady-state aqueous U, Li, and K concentrations were independent of solution pH, however they increased with increasing nanocluster concentration, indicating that the nanoclusters do not buffer the aqueous activities as a bulk solid phase would, but exhibit behavior that is more characteristic of dissolved aqueous complexes. The ion activity product (I.A.P.) value was calculated using two approaches: (1) treating the nanoclusters as a solid phase with an activity of one, and (2) treating the nanoclusters as aqueous complexes with a non-unit activity equal to their concentration in solution. The I.A.P. values that were calculated with non-unit activity for the nanoclusters exhibited significantly less variation as a function of nanocluster concentration compared to the I.A.P. values calculated with a nanocluster activity of one. The results yield a calculated log dissociation constant for the U60 nanoclusters of 9.2 + 0.2/-0.3 (1σ). Our findings provide a better understanding of the thermodynamic stability and behavior of U60 nanoclusters in aqueous systems, and can be used to estimate the dissociation behavior of nanoclusters under a range of aqueous conditions.

pH-dependent stability of creatine ethyl ester: relevance to oral absorption.

PubMed

Gufford, Brandon T; Ezell, Edward L; Robinson, Dennis H; Miller, Donald W; Miller, Nicholas J; Gu, Xiaochen; Vennerstrom, Jonathan L

2013-09-01

Creatine ethyl ester hydrochloride (CEE) was synthesized as a prodrug of creatine (CRT) to improve aqueous solubility, gastrointestinal permeability, and ultimately the pharmacodynamics of CRT. We used high-performance liquid chromatography (HPLC) and proton nuclear magnetic resonance (NMR) to characterize the pH-dependent stability of CEE in aqueous solution and compared the permeability of CEE to CRT and creatinine (CRN) across Caco-2 human epithelial cell monolayers and transdermal permeability across porcine skin. CEE was most stable in a strongly acidic condition (half-life = 570 hours at pH 1.0) where it undergoes ester hydrolysis to CRT and ethanol. At pH ≥ 1.0, CEE cyclizes to CRN with the logarithm of the first order rate constant increasing linearly with pH. Above pH 8.0 (half-life = 23 sec) the rate of degradation was too rapid to be determined. The rate of degradation of CEE in cell culture media and simulated intestinal fluid (SIF) was a function of pH and correlated well with the stability in aqueous buffered solutions. The permeability of CEE across Caco-2 monolayers and porcine skin was significantly greater than that of CRT or CRN. The stability of CEE in acidic media together with its improved permeability suggests that CEE has potential for improved oral absorption compared to CRT.

Tuning of "antenna effect" of Eu(III) in ternary systems in aqueous medium through binding with protein.

PubMed

Ghorai, Shyamal Kr; Samanta, Swarna Kamal; Mukherjee, Manini; Saha Sardar, Pinki; Ghosh, Sanjib

2013-02-04

A simple ternary system containing a protein [human serum albumin (HSA)/bovine serum albumin (BSA)], tetracycline hydrochloride (TC), and Eu(III) in suitable aqueous buffer medium at physiological pH (= 7.2) has been shown to exhibit highly efficient "antenna effect" compared to the binary complex of TC with Eu(III) (Eu(3)TC). The ternary system containing E. coli alkaline phosphatase (AP), TC, and Eu(III), however, shows a slight enhancement of Eu(III) emission, although the binding constant of AP with TC is 2 orders of magnitude greater than with BSA/HSA. The enhanced emission of bound TC in the binary systems containing proteins and TC gets quenched in the ternary systems containing HSA/BSA, showing the efficient energy transfer (ET) from TC to Eu(III). Steady state and time-resolved emission studies of each component in all the ternary systems in H(2)O and in D(2)O medium reveal that Eu(III) is very well protected from the O-H oscillator in the ternary system containing HSA/BSA compared to that containing AP. The docking studies locating the binding site of TC in the proteins suggest that TC binds near the surface of AP. In the case of HSA/BSA, TC resides in the interior of the protein resulting in a large shielding effect of Eu(III). The rotational correlation time (θ(c)) determined from the anisotropy decay of bound TC in the complexes and the accessible surface area (ASA) of the ligand in the complexes obtained from the docking studies also support the contention that Eu(3)TC is more exposed to solvent in the case of the ternary system consisting of AP, TC, and Eu(III). The calculated radiative lifetime and the sensitization efficiency ratio of Eu(III) in all the systems clearly demonstrate the protein mediated tuning of "antenna effect" in Eu(III).

Determination of N-vinyl-2-pyrrolidone and N-methyl-2-pyrrolidone in drugs using polypyrrole-based headspace solid-phase microextraction and gas chromatography-nitrogen-phosphorous detection.

PubMed

Mehdinia, Ali; Ghassempour, Alireza; Rafati, Hasan; Heydari, Rouhollah

2007-03-21

A headspace solid-phase microextraction and gas chromatography-nitrogen-phosphorous detection (HS-SPME-GC-NPD) method using polypyrrole (PPy) fibers has been introduced to determine two derivatives of pyrrolidone; N-vinyl-2-pyrrolidone (NVP) and N-methyl-2-pyrrolidone (NMP). Two types of PPy fibers, prepared using organic and aqueous media, were compared in terms of extraction efficiency and thermal stability. It was found that PPy film prepared using organic medium (i.e. acetonitrile) had higher extraction efficiency and more thermal stability compared to the film prepared in aqueous medium. To enhance the sensitivity of HS-SPME, the effects of pH, ionic strength, extraction time, extraction temperature and the headspace volume on the extraction efficiency were optimized. Using the results of this research, high sensitivity and selectivity had been achieved due to the combination of the high extraction efficiency of PPy film prepared in organic medium and the high sensitivity and selectivity of nitrogen-phosphorous detection. Linear range of the analytes was found to be between 1.0 and 1000 microg L(-1) with regression coefficients (R(2)) of 0.998 and 0.997 for NVP and NMP, consequently. Limits of detection (LODs) were 0.074 and 0.081 microg L(-1) for NVP and NMP, respectively. Relative standard deviation (R.S.D.) for five replications of analyses was found to be less than 6.0%. In real samples the mean recoveries were 94.81% and 94.15% for NVP and NMP, respectively. The results demonstrated the suitability of the HS-SPME technique for analyzing NVP and NMP in two different pharmaceutical matrices. In addition, the method was used for simultaneous detection of NVP, 2-pyrrolidone (2-Pyr), gamma-butyrolactone (GBL) and ethanolamine (EA) compounds.

Heat-induced gelation of casein micelles in aqueous suspensions at different pH.

PubMed

Thomar, Peggy; Nicolai, Taco

2016-10-01

Heat-induced gelation of casein micelles in aqueous solution was investigated between pH 5.2 and pH 6.7 over a wide range of protein concentrations (C=25-160gL(-1)). For C≥40gL(-1) the casein micelles rapidly formed a self-supporting gel above a critical temperature (Tc). At C=160gL(-1), Tc decreased from 90°C at pH 6.5 to 30°C at pH 5.4 and increased with decreasing protein concentration. Oscillatory shear measurements during heating showed that the elastic modulus (Gel) of the gels increased strongly with increasing protein concentration, but was insensitive to the pH and the heating temperature except close to Tc where Gel decreased sharply with decreasing temperature. The microstructure of the gels was observed by confocal scanning laser microscopy. Heat-induced gelation of casein micelles was compared with that of sodium caseinate solutions free of calcium phosphate. Copyright © 2016 Elsevier B.V. All rights reserved.

Rational Development of Neutral Aqueous Electrolytes for Zinc–Air Batteries

PubMed Central

Clark, Simon; Latz, Arnulf

2017-01-01

Abstract Neutral aqueous electrolytes have been shown to extend both the calendar life and cycling stability of secondary zinc–air batteries (ZABs). Despite this promise, there are currently no modeling studies investigating the performance of neutral ZABs. Traditional continuum models are numerically insufficient to simulate the dynamic behavior of these complex systems because of the rapid, orders‐of‐magnitude concentration shifts that occur. In this work, we present a novel framework for modeling the cell‐level performance of pH‐buffered aqueous electrolytes. We apply our model to conduct the first continuum‐scale simulation of secondary ZABs using aqueous ZnCl2–NH4Cl as electrolyte. We first use our model to interpret the results of two recent experimental studies of neutral ZABs, showing that the stability of the pH value is a significant factor in cell performance. We then optimize the composition of the electrolyte and the design of the cell considering factors including pH stability, final discharge product, and overall energy density. Our simulations predict that the effectiveness of the pH buffer is limited by slow mass transport and that chlorine‐containing solids may precipitate in addition to ZnO. PMID:28898553

Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

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

O'Hara, Matthew J.; Carter, Jennifer C.; Warner, Cynthia L.

Magnetic nanoparticles are well known to possess chemically active surfaces and large surface areas that can be employed to extract a range of ions from aqueous solutions. In addition, their superparamagnetic properties provide a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. We evaluated two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes for their ability to collect trace levels of a chemically diverse range of alpha emitting radioactive isotopes (polonium (Po), radium (Ra), uranium (U), and americium (Am)) from a wide range of aqueous solutions. The nanomaterials include commerciallymore » available magnetite (Fe3O4) and magnetite modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1. Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the alpha-emitting radionuclide spikes from ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. We show that the uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified ground water was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. In sum, our results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions.« less

Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

DOE PAGES

O'Hara, Matthew J.; Carter, Jennifer C.; Warner, Cynthia L.; ...

2016-10-31

Magnetic nanoparticles are well known to possess chemically active surfaces and large surface areas that can be employed to extract a range of ions from aqueous solutions. In addition, their superparamagnetic properties provide a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. We evaluated two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes for their ability to collect trace levels of a chemically diverse range of alpha emitting radioactive isotopes (polonium (Po), radium (Ra), uranium (U), and americium (Am)) from a wide range of aqueous solutions. The nanomaterials include commerciallymore » available magnetite (Fe3O4) and magnetite modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1. Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the alpha-emitting radionuclide spikes from ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. We show that the uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified ground water was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. In sum, our results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions.« less

Subterahertz Longitudinal Phonon Modes Propagating in a Lipid Bilayer Immersed in an Aqueous Medium

NASA Astrophysics Data System (ADS)

Zakhvataev, V. E.

2018-04-01

The properties of subterahertz longitudinal acoustic phonon modes in the hydrophobic region of a lipid bilayer immersed in a compressible viscous aqueous medium are investigated theoretically. An approximate expression is obtained for the Mandelstam-Brillouin components of the dynamic structure factor of a bilayer. The analysis is based on a generalized hydrodynamic model of the "two-dimensional lipid bilayer + three-dimensional fluid medium" system, as well as on known sharp estimates for the frequencies and lifetimes of long-wavelength longitudinal acoustic phonons in a free hydrated lipid bilayer and in water, obtained from inelastic X-ray scattering experiments and molecular dynamics simulations. It is shown that, for characteristic values of the parameters of the membrane system, subterahertz longitudinal phonon-like excitations in the hydrophobic part of the bilayer are underdamped. In this case, the contribution of the viscous flow of the aqueous medium to the damping of a longitudinal membrane mode is small compared with the contribution of the lipid bilayer. Quantitative estimates of the damping ratio agree well with the experimental results for the vibration mode of the enzyme lysozyme in aqueous solution [1]. It is also shown that a coupling between longitudinal phonon modes of the bilayer and relaxation processes in its fluid environment gives rise to an additional peak in the scattering spectrum, which corresponds to a non-propagating mode.

Optimisation of the Photonic Efficiency of TiO2 Decorated on MWCNTs for Methylene Blue Photodegradation.

PubMed

Abdullahi, Nura; Saion, Elias; Shaari, Abdul Halim; Al-Hada, Naif Mohammed; Keiteb, Aysar

2015-01-01

MWCNTs/TiO2 nanocomposite was prepared by oxidising MWCNT in H2SO4/HNO3 then decorating it with TiO2-p25 nanopowder. The composites were characterised using XRD, TEM, FT-IR PL and UV-vis spectroscopy. The TEM images have shown TiO2 nanoparticles immobilised onto the sidewalls of the MWCNTs. The UV-vis spectrum confirms that the nanocomposites can significantly absorb more light in the visible regions compared with the commercial TiO2 (P25). The catalytic activity of these nanocomposites was determined by photooxidation of MB aqueous solution in the presence of visible light. The MWCNTs/TiO2 (1:3) mass ratio showed maximum degradation efficiency. However, its activity was more favourable in alkaline and a neutral pH than an acidic medium.

Physico-chemical Properties of Supramolecular Complexes of Natural Flavonoids with Biomacromolecules

NASA Astrophysics Data System (ADS)

Barvinchenko, V. M.; Lipkovska, N. O.; Fedyanina, T. V.; Pogorelyi, V. K.

Polyvinylpyrrolidone (a water-soluble biopolymer) and human serum albumin (a globular protein) form supramolecular complexes with natural flavonoids quercetin and rutin in aqueous medium. The interaction with these biomacromolecules (BMM) causes the alteration of flavonoid spectral, protolytic, and other properties; in particular, it essentially increases their solubility. Absorption and solubility measurements revealed the supramolecular compounds of 1:1 stoichiometry for all systems studied. First it was demonstrated experimentally that the interaction with BMM promotes the tautomeric transformation in quercetin molecule. The mechanism of tautomerization via flavonoid molecular structure was discussed. Adsorption of BMM and their supramolecular compounds with flavonoids onto nanosilica was studied as a function of pH, and the properties of the biomacromolecules, flavonoids, and silica surface. It was found that BMM either complexed with quercetin (rutin) or preliminary immobilized on nanosilica increases the flavonoid adsorption.

"Cut-off" effect of antioxidants and/or probes of variable lipophilicity in microheterogeneous media.

PubMed

Aliaga, Carolina; López de Arbina, Amaia; Rezende, Marcos Caroli

2016-09-01

The activities of two hydrophilic (ascorbic acid and Trolox) and two hydrophobic (α-tocopherol and BHT) antioxidants were measured by reaction with a series of 4-alkanoyloxyTEMPO radical probes 1 in buffered (pH 7), aqueous, micellar solutions of reduced Triton-X 100. In all cases, a cut-off effect was observed, in line with previous observations of the same effect for the partitioning of probe series 1 in this medium. These results support an interpretation of the cut-off effect in food emulsions, based on the "amphiphobic" nature of either the antioxidants or probes: competition between two molecular moieties, for the micellar hydrophobic core, tends to expose a reacting fragment differently to a more hydrophilic microenvironment, as the probe or antioxidant hydrophobicity increases. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation of mineral-aqueous chemical equilibria of felsic reservoirs with low-medium temperature: A comparative study in Yangbajing geothermal field and Guangdong geothermal fields

NASA Astrophysics Data System (ADS)

Li, Jiexiang; Sagoe, Gideon; Yang, Guang; Lu, Guoping

2018-02-01

Classical geothermometers are useful tools for estimating reservoir temperatures of geothermal systems. However, their application to low-medium temperature reservoirs is limited because large variations of temperatures calculated by different classical geothermometers are usually observed. In order to help choose the most appropriate classical geothermometer for calculating the temperatures of low-medium temperature reservoirs, this study evaluated the mineral-aqueous equilibria of typical low-medium temperature felsic reservoirs in the Yangbajing geothermal field and Guangdong geothermal fields. The findings of this study support that reservoirs in the Guangdong geothermal fields have no direct magma influence. Also, natural reservoirs may represent the intermediate steady state before reaching full equilibrium, which rarely occurs. For the low-medium temperature geothermal systems without the influence of magma, even with seawater intrusion, the process of minerals reaching mineral-aqueous equilibrium is sequential: chlorite and chalcedony are the first, then followed by K-feldspar, kaolinite and K-mica. Chlorite may reach equilibrium at varying activity values, and the equilibrium between K-feldspar and kaolinite or K-feldspar and K-mica can fix the contents of K and Al in the solutions. Although the SiO2 and Al attain equilibrium state, albite and laumontite remain unsaturated and thus may affect low-medium temperature calculations. In this study, the chalcedony geothermometer was found to be the most suitable geothermometer for low-medium temperature reservoirs. The results of K-Mg geothermometer may be useful to complement that of the chalcedony geothermometer in low-medium temperature reservoir systems. Na-K geothermometer will give unreliable results at low-medium temperatures; and Na-K-Ca will also be unsuitable to calculate reservoir temperatures lower than 180 °C, probably caused by the chemical imbalance of laumontite.

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.

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, W.Y.

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

Kinetic model for the short-term dissolution of a rhyolitic glass

USGS Publications Warehouse

White, A.F.; Claassen, H.C.

1980-01-01

Aqueous dissolution experiments with the vitric phase of a rhyolitic tuff were performed at 25??C and constant pH in the range 4.5-7.5. Results suggest interchange of aqueous hydrogen ions for cations situated both on the surface and within the glass. At time intervals from 24 to 900 hr., dissolution kinetics are controlled by ion transport to and from sites within the glass. Experimental data indicate that parabolic diffusion rate of a chemical species from the solid is a nonlinear function of its aqueous concentration. A numerical solution to Fick's second law is presented for diffusion of sodium, which relates it's aqueous concentration to it's concentration on glass surface, by a Freundlich adsorption isotherm. The pH influence on sodium diffusion in the model can be accounted for by use of a pH-dependent diffusion coefficient and a pH-independent adsorption isotherm. ?? 1980.

Functional magnetic microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Landel, Robert F. (Inventor); Yen, Shiao-Ping S. (Inventor)

1981-01-01

Functional magnetic particles are formed by dissolving a mucopolysaccharide such as chitosan in acidified aqueous solution containing a mixture of ferrous chloride and ferric chloride. As the pH of the solution is raised magnetite is formed in situ in the solution by raising the pH. The dissolved chitosan is a polyelectrolyte and forms micelles surrounding the granules at pH of 8-9. The chitosan precipitates on the granules to form microspheres containing the magnetic granules. On addition of the microspheres to waste aqueous streams containing dissolved ions, the hydroxyl and amine functionality of the chitosan forms chelates binding heavy metal cations such as lead, copper, and mercury and the chelates in turn bind anions such as nitrate, fluoride, phosphate and borate.

pH Neutralization of Aqueous Bio-Oil from Switchgrass Intermediate Pyrolysis Using Process Intensification Devices

DOE PAGES

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira; ...

2017-07-20

Despite the potential carbon-neutrality of switchgrass bio-oil, its high acidity and diverse chemical composition limit its utilization. The objectives of this research are to investigate pH neutralization of bio-oil by adding various alkali solutions in a batch system and then perform neutralization using process intensification devices, including a static mixer and a centrifugal contactor. The results indicate that sodium hydroxide and potassium hydroxide are more appropriate bases for pH neutralization of bio-oil than calcium hydroxide due to the limited solubility of calcium hydroxide in aqueous bio-oil. Mass and total acid number (TAN) balances were performed for both batch and continuous-flowmore » systems. Upon pH neutralization of bio-oil, the TAN values of the system increased after accounting the addition of alkali solution. A bio-oil heating experiment showed that the heat generated during pH neutralization did not cause a significant increase in the acidity of bio-oil. The formation of phenolic compounds during neutralization was initially suspected of increasing the system’s overall TAN value because some of these compounds (e.g., vanillic acid) act as polyprotic acids and have a stronger influence on the TAN value than monoprotic acids (e.g., acetic acid). The amount of phenolics in separated bio-oil phases, however, did not change significantly after pH neutralization. In conclusion, process intensification devices provided sufficient mixing and separation of the organic and aqueous phases, suggesting a scale-up route for the bio-oil pH neutralization process.« less

pH Neutralization of Aqueous Bio-Oil from Switchgrass Intermediate Pyrolysis Using Process Intensification Devices

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

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira

Despite the potential carbon-neutrality of switchgrass bio-oil, its high acidity and diverse chemical composition limit its utilization. The objectives of this research are to investigate pH neutralization of bio-oil by adding various alkali solutions in a batch system and then perform neutralization using process intensification devices, including a static mixer and a centrifugal contactor. The results indicate that sodium hydroxide and potassium hydroxide are more appropriate bases for pH neutralization of bio-oil than calcium hydroxide due to the limited solubility of calcium hydroxide in aqueous bio-oil. Mass and total acid number (TAN) balances were performed for both batch and continuous-flowmore » systems. Upon pH neutralization of bio-oil, the TAN values of the system increased after accounting the addition of alkali solution. A bio-oil heating experiment showed that the heat generated during pH neutralization did not cause a significant increase in the acidity of bio-oil. The formation of phenolic compounds during neutralization was initially suspected of increasing the system’s overall TAN value because some of these compounds (e.g., vanillic acid) act as polyprotic acids and have a stronger influence on the TAN value than monoprotic acids (e.g., acetic acid). The amount of phenolics in separated bio-oil phases, however, did not change significantly after pH neutralization. In conclusion, process intensification devices provided sufficient mixing and separation of the organic and aqueous phases, suggesting a scale-up route for the bio-oil pH neutralization process.« less

The antibacterial activity of chlorhexidine digluconate against Streptococcus mutans biofilms follows sigmoidal patterns.

PubMed

Lee, Dae-Woo; Jung, Ji-Eun; Yang, Yeon-Mi; Kim, Jae-Gon; Yi, Ho-Keun; Jeon, Jae-Gyu

2016-10-01

The aim of this study was to determine the pattern of the antibacterial activity of chlorhexidine digluconate (CHX) against mature Streptococcus mutans biofilms. Streptococcus mutans biofilms were formed on saliva-coated hydroxyapatite discs and then treated with 0-20% CHX, once, three times, or five times (1 min per treatment) during the period of mature biofilm formation (beyond 46 h). After the treatments, the colony-forming unit (CFU) counts of the treated biofilms were determined. The pH values of the spent culture medium were also determined to investigate the change in pH resulting from the antibacterial activity of CHX. The relationships between the concentration of CHX and the CFU counts and the concentration of CHX and culture medium pH, relative to the number of treatments performed, were evaluated using a sigmoidal curve-fitting procedure. The changes in CFU counts and culture medium pH followed sigmoidal curves and were dependent on the concentration of CHX (R 2 = 0.99). The sigmoidal curves were left-shifted with increasing number of treatments. Furthermore, the culture-medium pH of the treated biofilms increased as their CFU counts decreased. The lowest CHX concentration to increase culture-medium pH above the critical pH also decreased as the number of treatments increased. These results may provide fundamental information for selecting the appropriate CHX concentrations to treat S. mutans biofilms. © 2016 Eur J Oral Sci.

Gum karaya based hydrogel nanocomposites for the effective removal of cationic dyes from aqueous solutions

NASA Astrophysics Data System (ADS)

Mittal, Hemant; Maity, Arjun; Ray, Suprakas Sinha

2016-02-01

Biodegradable hydrogel nanocomposites (HNC) of gum karaya (GK) grafted with poly(acrylic acid) (PAA) incorporated silicon carbide nanoparticles (SiC NPs) were synthesized using the in situ graft copolymerization method and tested for the adsorption of cationic dyes from aqueous solution. The structure and morphology of the HNC were characterized using different spectroscopic and microscopic techniques. The results showed that the surface area and porosity of the hydrogel polymer significantly increased after nanocomposite formation with SiC NPs. The HNC was employed for the removal of cationic dyes, i.e., malachite green (MG) and rhodamine B (RhB) from the aqueous solution. The HNC was found to remove 91% (MG) and 86% (RhB) of dyes with a polymer dose of 0.5 and 0.6 g l-1 in neutral medium, respectively. The adsorption process was found to be highly pH dependent and followed the pseudo-second-order rate model. The adsorption isotherm data fitted well with the Langmuir adsorption isotherm with a maximum adsorption capacity of 757.57 and 497.51 mg g-1 for MG and RhB, respectively. Furthermore, the HNC was demonstrated as a versatile adsorbent for the removal of both cationic and anionic dyes from the simulated wastewater. The HNC showed excellent regeneration capacity and was successfully used for the three cycles of adsorption-desorption. In summary, the HNC has shown its potential as an environment friendly and efficient adsorbent for the adsorption of cationic dyes from contaminated water.

Arsenic(V) removal from aqueous solutions using an anion exchanger derived from coconut coir pith and its recovery.

PubMed

Anirudhan, T S; Unnithan, Maya R

2007-01-01

The performance of a new anion exchanger (AE) prepared from coconut coir pith (CP), for the removal of arsenic(V) [As(V)] from aqueous solutions was evaluated in this study. The adsorbent (CP-AE) carrying dimethylaminohydroxypropyl weak base functional group was synthesized by the reaction of CP with epichlorohydrin and dimethylamine followed by treatment of hydrochloric acid. IR spectroscopy results confirm the presence of -NH(+)(CH(3))(2)Cl(-) group in the adsorbent. XRD studies confirm the decrease of crystallinity in CP-AE compared to CP, and it favours the protrusion of the functional group into the aqueous medium. Batch experiments were conducted to examine the efficiency of the adsorbent on As(V) removal. Maximum removal of 99.2% was obtained for an initial concentration of 1 mgl(-1) As(V) at pH 7.0 and an adsorbent dose of 2 gl(-1). The kinetics of sorption of As(V) onto CP-AE was described using the pseudo-second-order model. The equilibrium isotherms were determined for different temperatures and the results were analysed using the Langmuir equation. The temperature dependence indicates an exothermic process. Utility of the adsorbent was tested by removing As(V) from simulated groundwater. Regeneration studies were performed using 0.1N HCl. Batch adsorption-desorption studies illustrate that CP-AE could be used to remove As(V) from ground water and other industrial effluents.

Discoloration of Indigo Carmine Using Aqueous Extracts from Vegetables and Vegetable Residues as Enzyme Sources

PubMed Central

Solís, A.; Perea, F.; Solís, M.; Manjarrez, N.; Pérez, H. I.; Cassani, J.

2013-01-01

Several vegetables and vegetable residues were used as sources of enzymes capable to discolor indigo carmine (IC), completely or partially. Complete discoloration was achieved with aqueous extracts of green pea seeds and peels of green pea, cucumber, and kohlrabi, as well as spring onion leaves. The source of polyphenol oxidase (PPO), pH, time, and aeration is fundamental for the discoloration process catalyzed by PPO. The PPO present in the aqueous extract of green pea seeds was able to degrade 3,000 ppm of IC at a pH of 7.6 and magnetic stirring at 1,800 rpm in about 36 h. In addition, at 1,800 rpm and a pH of 7.6, this extract discolored 300 ppm of IC in 1:40 h; in the presence of 10% NaCl, the discoloration was complete in 5:50 h, whereas it was completed in 4:30 h with 5% NaCl and 2% laundry soap. PMID:24151588

Metal-ion retention properties of water-soluble amphiphilic block copolymer in double emulsion systems (w/o/w) stabilized by non-ionic surfactants.

PubMed

Palencia, Manuel; Rivas, Bernabé L

2011-11-15

Metal-ion retention properties of water-soluble amphiphilic polymers in presence of double emulsion were studied by diafiltration. Double emulsion systems, water-in-oil-in-water, with a pH gradient between external and internal aqueous phases were prepared. A poly(styrene-co-maleic anhydride) (PSAM) solution at pH 6.0 was added to the external aqueous phase of double emulsion and by application of pressure a divalent metal-ion stream was continuously added. Metal-ions used were Cu(2+) and Cd(2+) at the same pH of polymer solution. According to our results, metal-ion retention is mainly the result of polymer-metal interaction. Interaction between PSMA and reverse emulsion globules is strongly controlled by amount of metal-ions added in the external aqueous phase. In addition, as metal-ion concentration was increased, a negative effect on polymer retention capacity and promotion of flocculation phenomena were produced. Copyright © 2011 Elsevier Inc. All rights reserved.

Metal bioavailability and toxicity to fish in low-alkalinity lakes: A critical review

USGS Publications Warehouse

Spry, D.J.; Wiener, James G.

1991-01-01

Fish in low-alkalinity lakes having pH of 6·0–6·5 or less often have higher body or tissue burdens of mercury, cadmium, and lead than do fish in nearby lakes with higher pH. The greater bioaccumulation of these metals in such waters seems to result partly from the greater aqueous abundances of biologically available forms (CH3 Hg+, Cd2+, and Pb2+) at low pH. In addition, the low concentrations of aqueous calcium in low-alkalinity lakes increase the permeability of biological membranes to these metals, which in fish may cause greater uptake from both water and food. Fish exposed to aqueous inorganic aluminum in the laboratory and field accumulate the metal in and on the epithelial cells of the gills; however, there is little accumulation of aluminum in the blood or internal organs. In low-pH water, both sublethal and lethal toxicity of aluminum has been clearly demonstrated in both laboratory and field studies at environmental concentrations. In contrast, recently measured aqueous concentrations of total mercury, methylmercury, cadmium, and lead in low-alkalinity lakes are much lower than the aqueous concentrations known to cause acute or chronic toxicity in fish, although the vast majority of toxicological research has involved waters with much higher ionic strength than that in low-alkalinity lakes. Additional work with fish is needed to better assess (1) the toxicity of aqueous metals in low-alkalinity waters, and (2) the toxicological significance of dietary methylmercury and cadmium.

Synthesis of sub-millimeter calcite from aqueous solution

NASA Astrophysics Data System (ADS)

Reimi, M. A.; Morrison, J. M.; Burns, P. C.

2011-12-01

A novel aqueous synthesis that leads to the formation of calcite (CaCO3) crystals, up to 500μm in diameter, will be used to facilitate the study of contaminant transport in aqueous environmental systems. Existing processes tend to be complicated and often yield nanometer-sized or amorphous CaCO3. The synthesis method presented here, which involves slow mixing of concentrated solutions of CaCl2 ¬and (NH4)2CO3, produces single crystals of rhombohedral calcite in 2 to 4 days. Variations on the experimental method, including changes in pH and solution concentration, were explored to optimize the synthesis. Scanning Electron Microscope images show the differences in size and purity observed when the crystals are grown at pH values ranging from 2 to 6. The crystals grown from solutions of pH 2 were large (up to 500 micrometers in diameter) with minimal polycrystalline calcium carbonate, while crystals grown from solutions with pH values beyond 4 were smaller (up to 100 micrometers in diameter) with significant polycrystalline calcium carbonate. The synthesis method, materials characterization, and use in future actinide contaminant studies will be discussed.

Environmentally friendly system for the degradation of multipesticide residues in aqueous media by the Fenton's reaction.

PubMed

Guimarães, Bruno de S; Kleemann, Natiele; Caldas, Sergiane S; Costa, Fabiane P; Silveira, Maria A K; Duarte, Fabio A; Primel, Ednei G

2014-01-01

A Fenton oxidation system employing zero-valent iron (whose source was swarf, a residue of metallurgical industries, in powder form) and hydrogen peroxide for the treatment of an aqueous solution with six pesticides was developed, and the effect of the iron metal content, pH, and hydrogen peroxide concentration was evaluated. The characterization of the aqueous solution resulted in: pH 5.6, 105 mg L(-1) of dissolved organic carbon, and 44.6 NTU turbidity. In addition, the characterization of the swarf by FAAS and ICP-MS showed 98.43 ± 7.40 % of zero-valent iron. The removal was strongly affected by the content of iron metal, pH, and hydrogen peroxide concentration. The best degradation conditions were 2.0 g swarf, pH 2.0, and 5 mmol L(-1) H2O2. At the end of the treatment, the pesticide degradation ranged from 60 to 100%, leading to 55% mineralization. Besides, all hydrogen peroxide was consumed and the determination of total dissolved iron resulted in 2 mg L(-1). Thus, the advantages of this system are rapid degradation (up to 20 min), high-degradation rates, simple handling, and low cost.

Bovine serum albumin partitioning in an aqueous two-phase system: effect of pH and sodium chloride concentration.

PubMed

Gündüz, U; Korkmaz, K

2000-06-23

The partitioning of bovine serum albumin (BSA) in a polyethylene glycol 3350 (8% w/w)-dextran 37 500 (6% w/w)-0.05 M phosphate aqueous two-phase was investigated at different pHs, at varying concentrations of sodium chloride at 20 degrees C. The effect of NaCl concentration on the partition coefficient of BSA was studied for the PEG-dx systems with initial pH values of 4.2, 5.0, 7.0, 9.0, and 9.8. The NaCl concentrations in the phase systems with constant pH value were 0.06, 0.1, 0.2, 0.3, and 0.34 M. It was observed that the BSA partition coefficient decreased at concentrations smaller than 0.2 M NaCl and increased at concentrations greater than 0.2 M NaCl for all systems with initial pHs of 4.2, 5.0, 7.0, 9.0, and 9.8. It was also seen that the partition coefficient of BSA decreased as the pH of the aqueous two-phase systems increased at any NaCl salt concentration studied.

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.

Benzimidazole acrylonitriles as multifunctional push-pull chromophores: Spectral characterisation, protonation equilibria and nanoaggregation in aqueous solutions

NASA Astrophysics Data System (ADS)

Horak, Ema; Vianello, Robert; Hranjec, Marijana; Krištafor, Svjetlana; Zamola, Grace Karminski; Steinberg, Ivana Murković

2017-05-01

Heterocyclic donor-π-acceptor molecular systems based on an N,N-dimethylamino phenylacrylonitrile benzimidazole skeleton have been characterised and are proposed for potential use in sensing applications. The benzimidazole moiety introduces a broad spectrum of useful multifunctional properties to the system including electron accepting ability, pH sensitivity and compatibility with biomolecules. The photophysical characterisation of the prototropic forms of these chromophores has been carried out in both solution and on immobilisation in polymer films. The experimental results are further supported by computational determination of pKa values. It is noticed that compound 3 forms nanoaggregates in aqueous solutions with aggregation-induced emission (AIE) at 600 nm. All the systems demonstrate spectral pH sensitivity in acidic media which shifts towards near-neutral values upon immobilisation in polymer films or upon aggregation in an aqueous environment (compound 3). The structure-property relationships of these functional chromophores, involving their spectral characteristics, acid-base equilibria, pKa values and aggregation effects have been determined. Potential applications of the molecules as pH and biomolecular sensors are proposed based on their pH sensitivity and AIE properties.

Stability of urea in solution and pharmaceutical preparations.

PubMed

Panyachariwat, Nattakan; Steckel, Hartwig

2014-01-01

The stability of urea in solution and pharmaceutical preparations was analyzed as a function of temperature (25°-60°C), pH (3.11-9.67), and initial urea concentration (2.5%-20%). This study was undertaken to (i) obtain more extensive, quantitative information relative to the degradation of urea in both aqueous and non-aqueous solutions and in pharmaceutical preparations, and (ii) test the effects of initial urea concentration, pH, buffer, and temperature values on urea degradation. The stability analysis shows that urea is more stable at the pH range of 4-8 and the stability of urea decreases by increase in temperature for all pH values. Within the experimental range of temperature and initial urea concentration values, the lowest urea degradation was found with lactate buffer pH 6.0. The urea decomposition rate in solution and pharmaceutical preparations shows the dependence of the initial urea concentrations. At higher initial urea concentrations, the rate of degradation is a decreasing function with time. This suggests that the reverse reaction is a factor in the degradation of concentrated urea solution. For non-aqueous solvents, isopropanol showed the best effort in retarding the decomposition of urea. Since the losses in urea is directly influenced by its stability at a given temperature and pH, the stability analysis of urea by the proposed model can be used to prevent the loss and optimize the operating condition for urea-containing pharmaceutical preparations.

[Study of the interrelations of ethmozine, cordarone and phenycaberan with heparin].

PubMed

Tolstopiatov, B I

1981-01-01

Cordarone, etmozin and phenycaberan form complexes with heparin. Etmozin and phenycaberan form complexes insoluble in an aqueous medium and exhibit a pronounced antiheparin action in in-vitro experiments. Cordarone and heparin form a complex which is soluble in an aqueous medium. This complex potentiates the biological activity of the anticoagulant. In experiments on rabbits cordarone and phenycaberan increase plasma tolerance to heparin followed by its lowering as compared with controls in experiments with phenycaberan. Etmozin decreases plasma tolerance to heparin.

Open-Gated pH Sensor Fabricated on an Undoped-AlGaN/GaN HEMT Structure

PubMed Central

Abidin, Mastura Shafinaz Zainal; Hashim, Abdul Manaf; Sharifabad, Maneea Eizadi; Rahman, Shaharin Fadzli Abd; Sadoh, Taizoh

2011-01-01

The sensing responses in aqueous solution of an open-gated pH sensor fabricated on an AlGaN/GaN high-electron-mobility-transistor (HEMT) structure are investigated. Under air-exposed ambient conditions, the open-gated undoped AlGaN/GaN HEMT only shows the presence of a linear current region. This seems to show that very low Fermi level pinning by surface states exists in the undoped AlGaN/GaN sample. In aqueous solution, typical current-voltage (I-V) characteristics with reasonably good gate controllability are observed, showing that the potential of the AlGaN surface at the open-gated area is effectively controlled via aqueous solution by the Ag/AgCl gate electrode. The open-gated undoped AlGaN/GaN HEMT structure is capable of distinguishing pH level in aqueous electrolytes and exhibits linear sensitivity, where high sensitivity of 1.9 mA/pH or 3.88 mA/mm/pH at drain-source voltage, VDS = 5 V is obtained. Due to the large leakage current where it increases with the negative gate voltage, Nernstian like sensitivity cannot be determined as commonly reported in the literature. This large leakage current may be caused by the technical factors rather than any characteristics of the devices. Surprisingly, although there are some imperfections in the device preparation and measurement, the fabricated devices work very well in distinguishing the pH levels. Suppression of current leakage by improving the device preparation is likely needed to improve the device performance. The fabricated device is expected to be suitable for pH sensing applications. PMID:22163786

Abiotic transformation of high explosives by freshly precipitated iron minerals in aqueous Fe¹¹ solutions

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

Boparai, Hardiljeet K.; Comfort, Steve; Satapanajaru, Tunlawit

Zerovalent iron barriers have become a viable treatment for field-scale cleanup of various ground water contaminants. While contact with the iron surface is important for contaminant destruction, the interstitial pore water within and near the iron barrier will be laden with aqueous, adsorbed and precipitated FeII phases. These freshly precipitated iron minerals could play an important role in transforming high explosives (HE). Our objective was to determine the transformation of RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and TNT (2,4,6-trinitrotoluene) by freshly precipitated iron FeII/FeIII minerals. This was accomplished by quantifying the effects of initial FeII concentration, pH, and the presence of aquifermore » solids (FeIII phases) on HE transformation rates. Results showed that at pH 8.2, freshly precipitated iron minerals transformed RDX, HMX, and TNT with reaction rates increasing with increasing FeII concentrations. RDX and HMX transformations in these solutions also increased with increasing pH (5.8-8.55). By contrast, TNT transformation was not influenced by pH (6.85-8.55) except at pH values <6.35. Transformations observed via LC/MS included a variety of nitroso products (RDX, HMX) and amino degradation products (TNT). XRD analysis identified green rust and magnetite as the dominant iron solid phases that precipitated from the aqueous FeII during HE treatment under anaerobic conditions. Geochemical modeling also predicted FeII activity would likely be controlled by green rust and magnetite. These results illustrate the important role freshly precipitated FeII/FeIII minerals in aqueous FeII solutions play in the transformation of high explosives.« less

Removal of hexavalent chromium upon interaction with biochar under acidic conditions: mechanistic insights and application.

PubMed

Choudhary, Bharat; Paul, Debajyoti; Singh, Abhas; Gupta, Tarun

2017-07-01

Chromium pollution of soil and water is a serious environmental concern due to potential carcinogenicity of hexavalent chromium [Cr(VI)] when ingested. Eucalyptus bark biochar (EBB), a carbonaceous black porous material obtained by pyrolysis of biomass at 500 °C under oxygen-free atmosphere, was used to investigate the removal of aqueous Cr(VI) upon interaction with the EBB, the dominant Cr(VI) removal mechanism(s), and the applicability to treat Cr(VI)-contaminated wastewater. Batch experiments showed complete removal of aqueous Cr(VI) at pH 1-2; sorption was negligible at pH 1, but ~55% of total Cr was sorbed onto the EBB surface at pH 2. Detailed investigations on unreacted and reacted EBB through Fourier transform infrared spectroscopy and X-ray photoelectron spectrometry (XPS) indicate that the carboxylic groups in biochar played a dominant role in Cr(VI) sorption, whereas the phenolic groups were responsible for Cr(VI) reduction. The predominance of sorption-reduction mechanism was confirmed by XPS studies that indicated ~82% as Cr(III) and ~18% as Cr(VI) sorbed on the EBB surface. Significantly, Cr(VI) reduction was also facilitated by dissolved organic matter (DOM) extracted from biochar. This reduction was enhanced by the presence of biochar. Overall, the removal of Cr(VI) in the presence of biochar was affected by sorption due to electrostatic attraction, sorption-reduction mediated by surface organic complexes, and aqueous reduction by DOM. Relative dominance of the aqueous reduction mechanism depended on a critical biochar dosage for a given electrolyte pH and initial Cr(VI) concentration. The low-cost EBB developed here successfully removed all Cr(VI) in chrome tanning acidic wastewater and Cr(VI)-contaminated groundwater after pH adjustment, highlighting its potential applicability in effective Cr(VI) remediation.

Alkaline pH enhances farnesol production by Saccharomyces cerevisiae.

PubMed

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

2009-07-01

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

On the asymmetric adsorption of phenylalanine enantiomers by kaolin.

NASA Technical Reports Server (NTRS)

Bonner, W. A.; Flores, J.

1973-01-01

The attempt is described to verify a recent report that kaolin adsorbs D- and L-phenylalanine enantiomers to different extents from aqueous solutions at both pH 5.8 and pH 2. No evidence whatsoever could be found for the differential adsorption of D- versus L-phenylalanine by kaolin from either pH 6 or pH 2 solutions.

Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems

PubMed Central

Lewis, Scott; Lynch, Andrew; Bachas, Leonidas; Hampson, Steve; Ormsbee, Lindell; Bhattacharyya, Dibakar

2009-01-01

Abstract The primary objective of this research was to model and understand the chelate-modified Fenton reaction for the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. The addition of a nontoxic chelate (L), such as citrate or gluconic acid, allows for operation at near-neutral pH and controlled release of Fe(II)/Fe(III). For the standard Fenton reaction at low pH in two-phase systems, an optimum H2O2:Fe(II) molar ratio was found to be between 1:1 and 2:1. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinated TCE in both the aqueous and organic phases at pH 6–7 using low H2O2:Fe(II) molar ratios (4:1 to 8:1). Increasing the L:Fe ratio was found to decrease the rate of H2O2 degradation in both Fe(II) and Fe(III) systems at near-neutral pH. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using literature-reported hydroxyl radical reaction kinetics and mass transfer relationships. Additional aspects of this work include the reusability of the Fe–citrate complex under repeated H2O2 injections in real water systems as well as packed column studies for simulated groundwater injection. PMID:20418966

Empirical correlation between hydrophobic free energy and aqueous cavity surface area

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

Reynolds, J.A.; Gilbert, D.B.; Tanford, C.

1974-08-01

The unitary free energy of transfer of a hydrocarbon molecule from a hydrocarbon solvent to an aqueous medium is a measure of the hydrophobic interaction in the aqueous medium. We have reexamined available data on this phenomenon and have confirmed that the free energy for saturated hydrocarbons is proportional to the surface area of the cavity created by the solute in the aqueous solution, with the same proportionality constant for linear, branched, and cyclic hydrocarbon molecules. The numerical value of the proportionality constant is uncertain because absolute and self-consistent area measurements are not available. We estimate that it falls betweenmore » 20 and 25 cal/mole per Angstrom/sup 2/ at 25/sup 0/ (for areas measured at the distance of closest approach of water molecules), which is significantly less than the figure of 33 cal/mole per Angstrom/sup 2/ that has been assigned to the same parameter by Hermann.« less

Morinda citrifolia leaves enhance osteogenic differentiation and mineralization of human periodontal ligament cells.

PubMed

Boonanantanasarn, Kanitsak; Janebodin, Kajohnkiart; Suppakpatana, Prapan; Arayapisit, Tawepong; Rodsutthi, Jit-aree; Chunhabundit, Panjit; Boonanuntanasarn, Surintorn; Sripairojthikoon, Wanida

2012-01-01

This present study investigated the potential of Morinda citrifolia leaf aqueous extract to induce osteogenic differentiation and matrix mineralization of human periodontal ligament (hPDL) cells. Human periodontal ligament cells were cultured in complete medium, ascorbic acid with β-glycerophosphate, or Morinda citrifolia leaf aqueous extract. Morinda citrifolia leaf aqueous extract significantly increased alkaline phosphatase activity compared to culturing in complete medium or ascorbic acid with β-glycerophosphate. Matrixcontaining mineralized nodules were formed only when the cells were cultured in the presence of Morinda citrifolia leaf aqueous extract. These nodules showed positive alizarin red S staining and were rich in calcium and phosphorus according to energy dispersive X-ray analysis. In conclusion, Morinda citrifolia leaf extract promoted osteogenic differentiation and matrix mineralization in human periodontal ligament cells, a clear indication of the therapeutic potential of Morinda citrifolia leaves in bone and periodontal tissue regeneration.

Morinda citrifolia leaves enhance osteogenic differentiation and mineralization of human periodontal ligament cells.

PubMed

Boonanantanasarn, Kanitsak; Janebodin, Kajohnkiart; Suppakpatana, Prapan; Arayapisit, Tawepong; Rodsutthi, Jit-aree; Chunhabundit, Panjit; Boonanuntanasarn, Surintorn; Sripairojthikoon, Wanida

2014-01-01

This present study investigated the potential of Morinda citrifolia leaf aqueous extract to induce osteogenic differentiation and matrix mineralization of human periodontal ligament (hPDL) cells. Human periodontal ligament cells were cultured in complete medium, ascorbic acid with β-glycerophosphate, or Morinda citrifolia leaf aqueous extract. Morinda citrifolia leaf aqueous extract significantly increased alkaline phosphatase activity compared to culturing in complete medium or ascorbic acid with β-glycerophosphate. Matrixcontaining mineralized nodules were formed only when the cells were cultured in the presence of Morinda citrifolia leaf aqueous extract. These nodules showed positive alizarin red S staining and were rich in calcium and phosphorus according to energy dispersive X-ray analysis. In conclusion, Morinda citrifolia leaf extract promoted osteogenic differentiation and matrix mineralization in human periodontal ligament cells, a clear indication of the therapeutic potential of Morinda citrifolia leaves in bone and periodontal tissue regeneration.

Photolysis of sulfamethoxypyridazine in various aqueous media: aerobic biodegradation and identification of photoproducts by LC-UV-MS/MS.

PubMed

Khaleel, Nareman D H; Mahmoud, Waleed M M; Hadad, Ghada M; Abdel-Salam, Randa A; Kümmerer, Klaus

2013-01-15

Sulfonamides are one of the most frequently used antibiotics worldwide. Therefore, mitigation processes such as abiotic or biotic degradation are of interest. Photodegradation and biodegradation are the potentially significant removal mechanisms for pharmaceuticals in aquatic environments. The photolysis of sulfamethoxypyridazine (SMP) using a medium pressure Hg-lamp was evaluated in three different media: Millipore water pH 6.1 (MW), effluent from sewage treatment plant pH 7.6 (STP), and buffered demineralized water pH 7.4 (BDW). Identification of transformation products (TPs) was performed by LC-UV-MS/MS. The biodegradation of SMP using two tests from the OECD series was studied: Closed Bottle test (OECD 301 D), and Manometric Respirometry test (OECD 301 F). In biodegradation tests, it was found that SMP was not readily biodegradable so it may pose a risk to the environment. The results showed that SMP was removed completely within 128 min of irradiation in the three media, and the degradation rate was different for each investigated type of water. However, dissolved organic carbon (DOC) was not removed in BDW and only little DOC removal was observed in MW and STP, thus indicating the formation of TPs. Analysis by LC-UV-MS/MS revealed new TPs formed. The hydroxylation of SMP represents the main photodegradation pathway. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis and study of catalytic application of l-methionine protected gold nanoparticles

NASA Astrophysics Data System (ADS)

Raza, Akif; Javed, Safdar; Qureshi, Muhammad Zahid; khan, Muhammad Usman; Khan, Muhammad Saleem

2017-10-01

Gold nanoparticle is growing class of nanotechnology due to large number of uses. We synthesized stable l-methionine protected gold nanoparticles (AuNps) by in situ reduction of HAuCl4 using sodium borohydrate as reducing and l-methionine as stabilizing agent in an aqueous medium. Different parameters (pH, capping agent, precursor salt, and heating time) were optimized to see the effect on the size of particles. Double beam spectrophotometer was used to carry out the spectroscopic studies. It was observed that pH and concentration of reducing salt are deciding factors in controlling the size and morphology of AuNps. Scanning electron microscopy (SEM) verified the formation of AuNPs as predicted by UV-Vis spectra. The interaction of AuNPs with l-methionine was confirmed by Fourier Transform Infrared (FTIR). The reduction of 4-nitrophenol acted as standard of reaction to check the response of AuNps catalyst. Complete reduction of 4-nitrophenol was accomplished by AuNps sol in just 60 s. Fastest reduction rate was observed with smaller spherical particles. This study concluded that size and shape of AuNps can be monitored by controlling the pH, concentration of capping and reducing agent. It also provides an economical solution to aquatic environment in terms of time saving and use of small volume of catalytic solution for reduction of several other toxic organic pollutants.

Reduction of Cr(VI) under acidic conditions by the facultative Fe(III)-reducing bacterium Acidiphilium cryptum

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

David E. Cummings; Scott Fendorf; Rajesh K. Sani

2007-01-01

The potential for biological reduction of Cr(VI) under acidic conditions was evaluated with the acidophilic, facultatively metal-reducing bacterium Acidiphilium cryptum strain JF-5 to explore the role of acidophilic microorganisms in the Cr cycle in low-pH environments. An anaerobic suspension of washed A. cryptum cells rapidly reduced 50 M Cr(VI) at pH 3.2; biological reduction was detected from pH 1.7-4.7. The reduction product, confirmed by XANES analysis, was entirely Cr(III) that was associated predominantly with the cell biomass (70-80%) with the residual residing in the aqueous phase. Reduction of Cr(VI) showed a pH optimum similar to that for growth and wasmore » inhibited by 5 mM HgCl2, suggesting that the reaction was enzyme-mediated. Introduction of O2 into the reaction medium slowed the reduction rate only slightly, whereas soluble Fe(III) (as ferric sulfate) increased the rate dramatically, presumably by the shuttling of electrons from bioreduced Fe(II) to Cr(VI) in a coupled biotic-abiotic cycle. Starved cells could not reduce Cr(VI) when provided as sole electron acceptor, indicating that Cr(VI) reduction is not an energy-conserving process in A. cryptum. We speculate, rather, that Cr(VI) reduction is used here as a detoxification mechanism.« less

Tunable pH and redox-responsive drug release from curcumin conjugated γ-polyglutamic acid nanoparticles in cancer microenvironment.

PubMed

Pillarisetti, Shameer; Maya, S; Sathianarayanan, S; Jayakumar, R

2017-11-01

Tunable pH and redox responsive polymer was prepared using γ-polyglutamic acid (γ-PGA) with linker 3-mercaptopropionic acid (3-MPA) (γ-PGA_SH) via oxidation to obtain redox responsive disulfide (γ-PGA_SS) backbone and adipic acid dihydrazide (ADH) (γ-PGA_SS_ADH) with hydrazide functional group for pH responsiveness. Further curcumin (Cur) was conjugated through hydrazone bond of the γ-PGA_SS_ADH via Schiff base reaction to obtain (γ-PGA_SS_ADH_Cur). The prepared systems were characterized by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Qq-TOF-MS/MS) and Solid state nuclear magnetic resonance (SS NMR) techniques. γ-PGA_SS_ADH_Cur formed self-assembled core shell nanoparticles (NPs) in existence of stabilized aqueous medium. γ-PGA_SS_ADH_Cur NPs maintained its stability in physiological condition. NPs tunable Cur release and cytotoxicity were observed for γ-PGA_SS_ADH_Cur NPs in both acidic and redox conditions mimicking the cancer microenvironment. γ-PGA_SS_ADH_Cur NPs uptake study showed via endocytosis mechanism resulted in the lysosomal entrapment of these NPs within the cell. γ-PGA_SS_ADH_Cur NPs exhibited a dual stimuli responsive drug delivery and can be used as a smart and potential drug delivery system in cancer microenvironment. Copyright © 2017 Elsevier B.V. All rights reserved.

Zr/ZrO2 sensors for in situ measurement of pH in high-temperature and -pressure aqueous solutions.

PubMed

Zhang, R H; Zhang, X T; Hu, S M

2008-04-15

The aim of this study is to develop new pH sensors that can be used to test and monitor hydrogen ion activity in hydrothermal conditions. A Zr/ZrO2 oxidation electrode is fabricated for in situ pH measurement of high-temperature aqueous solutions. This sensor responds rapidly and precisely to pH over a wide range of temperature and pressure. The Zr/ZrO2 electrode was made by oxidizing zirconium metal wire with Na2CO3 melt, which produced a thin film of ZrO2 on its surface. Thus, an oxidation-reduction electrode was produced. The Zr/ZrO2 electrode has a good electrochemical stability over a wide range of pH in high-temperature aqueous solutions when used with a Ag/AgCl reference electrode. Measurements of the Zr/ZrO2 sensor potential against a Ag/AgCl reference electrode is shown to vary linearly with pH between temperatures 20 and 200 degrees C. The slope of the potential versus pH at high temperature is slightly below the theoretical value indicated by the Nernst equation; such deviation is attributed to the fact that the sensor is not strictly at equilibrium with the solution to be tested in a short period of time. The Zr/ZrO2 sensor can be calibrated over the conditions that exist in the natural deep-seawater. Our studies showed that the Zr/ZrO2 electrode is a suitable pH sensor for the hydrothermal systems at midocean ridge or other geothermal systems with the high-temperature environment. Yttria-stabilized zirconia sensors have also been used to investigate the pH of hydrothermal fluids in hot springs vents at midocean ridge. These sensors, however, are not sensitive below 200 degrees C. Zr/ZrO2 sensors have wider temperature range and can be severed as good alternative sensors for measuring the pH of hydrothermal fluids.

Kinetics and mechanism of natural fluorapatite dissolution at 25 °C and pH from 3 to 12

NASA Astrophysics Data System (ADS)

Chaïrat, Claire; Schott, Jacques; Oelkers, Eric H.; Lartigue, Jean-Eric; Harouiya, Najatte

2007-12-01

The dissolution rates of natural fluorapatite (FAP), Ca 10(PO 4) 6F 2, were measured at 25 °C in mixed-flow reactors as a function of pH from 3.0 to 11.7, and aqueous calcium, phosphorus, and fluoride concentration. After an initial preferential Ca and/or F release, stoichiometric Ca, P, and F release was observed. Measured FAP dissolution rates decrease with increasing pH at 3 ⩽ pH ⩽ 7, FAP dissolution rates are pH independent at 7 ⩽ pH ⩽ 10, and FAP dissolution rates again decrease with increasing pH at pH ⩾ 10. Measured FAP dissolution rates are independent of aqueous Ca, P, and F concentration at pH ≈ 3 and pH ≈ 10. Apatite dissolution appears to be initiated by the relatively rapid removal from the near surface of F and the Ca located in the M1 sites, via proton for Ca exchange reactions. Dissolution rates are controlled by the destruction of this F and Ca depleted surface layer. The destruction of this layer is facilitated by the adsorption/penetration of protons into the surface at acidic conditions, and by surface hydration at neutral and basic conditions. Taking into account these two parallel mechanisms, measured fluorapatite forward dissolution rates can be accurately described using r+(molms)=6.61×10-6{aK}/{1+aK+aCa4aF1.4aOH0.6aH6K}+3.69×10-8[tbnd CaOH2+] where ai refers to the activity of the ith aqueous species, [tbnd CaOH2+] denotes the concentration of hydrated calcium sites at the surface of the leached layer (mol m -2), and Kex and Kads stand for the apparent stability constants of the Ca 2+/H + exchange and adsorption/penetration reactions, respectively.

Ocular pharmacokinetics of 0.45% ketorolac tromethamine

PubMed Central

Attar, Mayssa; Schiffman, Rhett; Borbridge, Lisa; Farnes, Quinn; Welty, Devin

2010-01-01

Purpose A new carboxymethylcellulose (CMC)-containing ophthalmic formulation of 0.45% ketorolac, pH 6.8 (Acuvail®) was recently developed for treatment of inflammation and pain after cataract surgery. This study compared pharmacokinetics of the new formulation with that of a prior formulation, 0.4% ketorolac, pH 7.4 (Acular LS®). Methods Ketorolac formulations were administered bilaterally (35 μL) to female New Zealand White rabbits. Samples from aqueous humor and iris-ciliary body were collected at multiple time points, and ketorolac was quantified using liquid chromatography-tandem mass spectrometry. Results In aqueous humor, the peak concentration (Cmax) and area under the concentration-time curve (AUC0–τ) of ketorolac were, respectively, 389 ng/mL and 939 ng·h/mL following administration of the CMC-containing 0.45% ketorolac, pH 6.8, and 211 ng/mL and 465 ng·hr/mL following administration of the 0.4% ketorolac, pH 7.4. In iris-ciliary body, Cmax and AUC0–τ of ketorolac were, respectively 450 ng/g and 2040 ng·h/g after administration of the CMC-containing 0.45% ketorolac, pH 6.8, and 216 ng/g and 699 ng·h/g after administration of the 0.4% ketorolac, pH 7.4. PK simulations predicted an AUC0–τ of 2910 ng·h/g for twice daily, CMC-containing 0.45% ketorolac, pH 6.8, compared to 725 ng·h/g for 4 times daily, 0.4% ketorolac, pH 7.4. Conclusions The CMC-containing formulation of 0.45% ketorolac, pH 6.8, increased ketorolac bioavailability by 2-fold in aqueous humor and by 3-fold in iris-ciliary body in comparison to the 0.4% ketorolac, pH 7.4, allowing a reduced dosing schedule from 4 times daily to twice daily. PMID:21179226

Ocular pharmacokinetics of 0.45% ketorolac tromethamine.

PubMed

Attar, Mayssa; Schiffman, Rhett; Borbridge, Lisa; Farnes, Quinn; Welty, Devin

2010-12-01

A new carboxymethylcellulose (CMC)-containing ophthalmic formulation of 0.45% ketorolac, pH 6.8 (Acuvail(®)) was recently developed for treatment of inflammation and pain after cataract surgery. This study compared pharmacokinetics of the new formulation with that of a prior formulation, 0.4% ketorolac, pH 7.4 (Acular LS(®)). Ketorolac formulations were administered bilaterally (35 μL) to female New Zealand White rabbits. Samples from aqueous humor and iris-ciliary body were collected at multiple time points, and ketorolac was quantified using liquid chromatography-tandem mass spectrometry. In aqueous humor, the peak concentration (C(max)) and area under the concentration-time curve (AUC(0-τ)) of ketorolac were, respectively, 389 ng/mL and 939 ng·h/mL following administration of the CMC-containing 0.45% ketorolac, pH 6.8, and 211 ng/mL and 465 ng·hr/mL following administration of the 0.4% ketorolac, pH 7.4. In iris-ciliary body, C(max) and AUC(0-τ) of ketorolac were, respectively 450 ng/g and 2040 ng·h/g after administration of the CMC-containing 0.45% ketorolac, pH 6.8, and 216 ng/g and 699 ng·h/g after administration of the 0.4% ketorolac, pH 7.4. PK simulations predicted an AUC(0-τ) of 2910 ng·h/g for twice daily, CMC-containing 0.45% ketorolac, pH 6.8, compared to 725 ng·h/g for 4 times daily, 0.4% ketorolac, pH 7.4. The CMC-containing formulation of 0.45% ketorolac, pH 6.8, increased ketorolac bioavailability by 2-fold in aqueous humor and by 3-fold in iris-ciliary body in comparison to the 0.4% ketorolac, pH 7.4, allowing a reduced dosing schedule from 4 times daily to twice daily.

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

PubMed

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

1999-08-05

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

Low external pH replaces 2,4-D in maintaining and multiplying 2,4-D-initiated embryogenic cells of carrot

NASA Technical Reports Server (NTRS)

Smith, D. L.; Krikorian, A. D.

1990-01-01

A mixed culture comprised of both embryonic globules and nonembryogenic callus was derived from seedling hypocotyls of Daucus carota cv. Scarlet Nantes on 2,4-D- containing medium using well-established methods. Then the mixed cultures were transferred to, and serially subcultured on, a hormone-free medium near pH 4. The medium contained 1 mM NH4+ as the sole nitrogen source. When cultured in this way, embryonic globules were able to multiply without development into later embryo stages. Nonembryogenic callus did not survive. Continuous culture of embryonic globules on this low pH hormone-free medium yielded cultures consisting entirely of preglobular stage proembryos (PGSPs). PGSP cultures have been maintained as such with continuous multiplication for nearly 2 years without loss of embryogenic potential. These hormone-free-maintained PGSPs continue their development to later embryo stages when cultured on the same hormone-free medium buffered at pH 5.8. We show that hormone-free medium near pH 4 can replace 2,4-D in its ability to sustain multiplication of 2,4-D-initiated embryogenic cells of carrot at an acceptable growth rate without their development into later embryo stages. This procedure provides selective conditions that do not permit the growth of non-embryogenic cells while providing an adequate environment for embryogenic cell proliferation and should prove invaluable in studying habituation.

[Alterations in tears aqueous layer during cytostatics treatment].

PubMed

Wojciechowska, Katarzyna; Wieckowska-Szakiel, Marzena; Rózalska, Barbara; Jurowski, Piotr

2013-01-01

The aim of the study was to evaluate tears secretion, pH and lysozyme activity in tears aqueous layer during chemotherapy in lung, breast and bowel cancer. 36 patients were enrolled to the study. Depending on the type of cancer and type of chemotherapy patients were divided into three groups. Group I (12 patients) diagnosed with non-small-cell lung cancer treated with PE schema (cisplatin, etoposide), Group II (12 patients) with breast cancer treated with FAC schema (fluorouracil, doxorubicin, cyclophosphamide), Group III (12 patients) with bowel cancer treated with FU/LV schema (fluorouracil, leucovorin). In all the patients: Schirmer's I test, pH measurements and lysozyme test were performed. Patients were examined before chemotherapy, after 2nd, 4th, 6th cycle. In group I and II lowering of tears secretion (p < 0.001) was revealed. In group III there was higher tears secretion (p < 0.001). PH was lowered after 2nd chemotherapy course in group I and II. In further treatment pH value were in the same lower level as after the second course. In group III there was higher pH--more alkaline (p < 0.001) after 2nd cycle of treatment and it was on the same level to the end of the examination process. Lowering of lysozyme activity in the tears film in all groups (p < 0.001) was established. The higher alterations of the lysozyme activity were observed in group treated with FAC schema. Cytostatic treatment has major influence on tears aqueous layer causing alterations of tears secretions. PH alterations depending on type of chemotherapy was observed. Lowering of lysozyme activity in tears was observed. All the deteriorations aggravate with duration of chemotherapy. Alterations of tears film parameters during chemotherapy may influence upon eye surface homeostasis and infectious complication. tears aqueous layer, Schirmer's test, lysozyme activity, tears pH.

Release and skin distribution of silicone-related compound(s) from a silicone gel sheet in vitro.

PubMed

Shigeki, S; Nobuoka, N; Murakami, T; Ikuta, Y

1999-01-01

The efficacy of topical silicone gel sheeting in prevention and/or reduction of keloids and hypertrophic scars is well recognized. In the present study, we reexamined the possible release of silicone-related compound(s) from a commercially available silicone gel sheet (Cica-Care, Smith and Nephew, Hull, England) in aqueous media in vitro. The silicone gel sheet was also applied on the excised skin surface to examine the possible distribution of silicone-related compounds into the skin in vitro. Silicone-related compounds were measured as silicon by an inductively coupled plasma-atomic emission spectrophotometer. When a piece of silicone gel sheet was placed in phosphate buffer solution (pH 3-9) at 37 degrees C for 7 days, the concentration of silicon in the medium increased with time, depending on the pH of the medium. This indicates that the released silicone-related compounds are water-soluble. When Cica-Care was applied on the surface of excised rat skin, human axilla skin and hypertrophic scars under hydrated conditions in vitro, silicon was detected in all skin samples. Greater distribution was observed in rat skin than in human axilla skin and hypertrophic scars. The release of silicone-related compounds from a silicone gel sheet (Cica-Care) and their distribution into the skin were demonstrated in vitro. Silicone-related compounds distributed into the skin may have pharmacological effects on the skin. Further investigation will be necessary to investigate in detail the action of silicone-related compounds on the proliferation of fibroblasts and excessive production of collagen.

Pharmaceutical grade phyllosilicate dispersions: the influence of shear history on floc structure.

PubMed

Viseras, C; Meeten, G H; Lopez-Galindo, A

1999-05-10

The effect of mixing conditions on the flow curves of some clay-water dispersions was studied. Two Spanish fibrous phyllosilicates (sepiolite from Vicálvaro and palygorskite from Turón) and a commercial bentonite (Bentopharm Copyright, UK) were selected as model clays. The disperse systems were made up using a rotor-stator mixer working at two different mixing rates (1000 and 8000 rpm), for periods of 1 and 10 min. Rheological measurements were taken and the corresponding flow curves obtained immediately after interposition and then after a period of 24 h under low shear caused by a roller apparatus. Aqueous sepiolite dispersions showed the highest viscosity and were easily interposed, whereas palygorskite dispersions were more difficult to obtain, resulting in low to medium viscosity gels. Bentonite dispersions provided medium viscosity systems, which greatly increased their viscosity after the low shear treatment (as a result of swelling), whereas the viscosity of the fibrous clays stayed at approximately the same values or even decreased. A linear relation was found between mixing energy and apparent viscosity in the bentonite systems, while apparent viscosity in the sepiolite samples was related to mixing power, with minor influence of mixing times. All the systems studied had thixotropic behaviour, changing from clearly positive to even negative thixotropy in some palygorskite systems. Finally, we studied the effect of drastic pH changes on the system structure. Results showed that rheological properties were highly sensitive to pH in the fibrous dispersions, but less sensitive behaviour was found in the laminar clay systems. Copyright.

Treatment of ferrous-NTA-based NO x scrubber solution by an up-flow anaerobic packed bed bioreactor.

PubMed

Chandrashekhar, B; Sahu, Nidhi; Tabassum, Heena; Pai, Padmaraj; Morone, Amruta; Pandey, R A

2015-06-01

A bench scale system consisting of an up-flow packed bed bioreactor (UAPBR) made of polyurethane foam was used for the treatment and regeneration of aqueous solution of ferrous-NTA scrubbed with nitric oxide (NO). The biomass in the UAPBR was sequentially acclimatized under denitrifying and iron reducing conditions using ethanol as electron donor, after which nitric oxide (NO) gas was loaded continuously to the system by absorption. The system was investigated for different parameters viz. pH, removal efficiency of nitric oxide, biological reduction efficiency of Fe(II)NTA-NO and COD utilization. The Fe(II)NTA-NO reduction efficiency reached 87.8 % at a loading rate of 0.24 mmol L(-1) h(-1), while the scrubber efficiency reached more than 75 % with 250 ppm NO. Stover-Kincannon and a Plug-flow kinetic model based on Michaelis-Menten equation were used to describe the UAPBR performance with respect to Fe(II)NTA-NO and COD removal. The Stover-Kincannon model was found capable of describing the Fe(II)NTA-NO reduction (R m = 8.92 mM h(-1) and K NO = 11.46 mM h(-1)) while plug-flow model provided better fit to the COD utilization (U m = 66.62 mg L(-1) h(-1), K COD = 7.28 mg L(-1)). Analyses for pH, Fe(III)NTA, ammonium, nitrite concentration, and FTIR analysis of the medium samples indicated degradation of NTA, which leads to ammonium and nitrite accumulation in the medium, and affect the regeneration process.

New concept to remove heavy metals from liquid waste based on electrochemical pH-switchable immobilized ligands

NASA Astrophysics Data System (ADS)

Pascal, Viel; Laetitia, Dubois; Joël, Lyskawa; Marc, Sallé; Serge, Palacin

2007-01-01

Absorption on resins is often used as secondary step in the treatment of water-based effluents, in order to reach very low concentrations. The separation of the trapped effluents from the resins and the regeneration of the resins for further use create wide volumes of secondary effluents coming from the washings of the resins with chemical reagents. We propose an alternative solution based on a "surface strategy" through adsorption phenomena and electrical control of the expulsion stage. The final goal is to limit or ideally to avoid the use of chemical reagents at the expulsion (or regeneration) stage of the depolluting process. Heavy metal ions were captured on active filters composed by a conducting surface covered by poly-4-vinylpyridine (P 4VP). Due to pyridine groups those polymer films have chelating properties for copper ions. Our strategy for electrical triggering of the copper expulsion in aqueous medium is based on pH sensitive chelating groups. Applying moderate electro-oxidizing conditions generates acidic conditions in the vicinity of the electrode, i.e. "inside" the polymer film. This allows a "switch-off" of the complexing properties of the film from the basic form of pyridine to pyridinium. Interestingly, no buffer washing is necessary to restore (or "switch-on") the complexing properties of the polymer film because the pH of the external medium is left unchanged by the electrochemical effect that affects only the vicinity of the electrode. Switch-on/switch-off cycles are followed and attested by IR spectroscopy and EQCM method.

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Viers, J.; Emnova, E. E.; Kompantseva, E. I.; Freydier, R.

2008-04-01

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric ( Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic ( Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine ( Skeletonema costatum) and freshwater ( Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ 65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria ( Rhodobacter sp.), cyanobacteria ( Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria ( P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ 65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ 65Cu (solid-solution) = -1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ 65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively. Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu 2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution. Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.

pH-Dependent Stability of Creatine Ethyl Ester: Relevance to Oral Absorption

PubMed Central

Gufford, Brandon T.; Ezell, Edward L.; Robinson, Dennis H.; Miller, Donald W.; Miller, Nicholas J.; Gu, Xiaochen; Vennerstrom, Jonathan L.

2015-01-01

Creatine ethyl ester hydrochloride (CEE) was synthesized as a prodrug of creatine (CRT) to improve aqueous solubility, gastrointestinal permeability, and ultimately the pharmacodynamics of CRT. We used high-performance liquid chromatography (HPLC) and proton nuclear magnetic resonance (NMR) to characterize the pH-dependent stability of CEE in aqueous solution and compared the permeability of CEE to CRT and creatinine (CRN) across Caco-2 human epithelial cell monolayers and transdermal permeability across porcine skin. CEE was most stable in a strongly acidic condition (half-life = 570 hours at pH 1.0) where it undergoes ester hydrolysis to CRT and ethanol. At pH ≥ 1.0, CEE cyclizes to CRN with the logarithm of the first order rate constant increasing linearly with pH. Above pH 8.0 (half-life = 23 sec) the rate of degradation was too rapid to be determined. The rate of degradation of CEE in cell culture media and simulated intestinal fluid (SIF) was a function of pH and correlated well with the stability in aqueous buffered solutions. The permeability of CEE across Caco-2 monolayers and porcine skin was significantly greater than that of CRT or CRN. The stability of CEE in acidic media together with its improved permeability suggests that CEE has potential for improved oral absorption compared to CRT. PMID:23957855

Strong adhesion and cohesion of chitosan in aqueous solutions

PubMed Central

Lee, Dong Woog; Lim, Chanoong; Israelachvili, Jacob N.; Hwang, Dong Soo

2014-01-01

Chitosan, a load-bearing biomacromolecule found in the exoskeletons of crustaceans and insects, is a promising biopolymer for the replacement of synthetic plastic compounds. Here, surface interactions mediated by chitosan in aqueous solutions, including the effects of pH and contact time, were investigated using a surface forces apparatus (SFA). Chitosan films showed an adhesion to mica for all tested pH ranges (3.0–8.5), achieving a maximum value at pH 3.0 after a contact time of 1 hr (Wad ~6.4 mJ/m2). We also found weak or no cohesion between two opposing chitosan layers on mica in aqueous buffer until the critical contact time for maximum adhesion (chitosan-mica) was reached. Strong cohesion (Wco ~8.5 mJ/m2) between the films was measured with increasing contact times up to 1 hr at pH 3.0, which is equivalent to ~60% of the strongest, previously reported, mussel underwater adhesion. Such time-dependent adhesion properties are most likely related to molecular or molecular group reorientations and interdigitations. At high pH (8.5), the solubility of chitosan changes drastically, causing the chitosan-chitosan (cohesion) interaction to be repulsive at all separation distances and contact times. The strong contact time and pH-dependent chitosan-chitosan cohesion and adhesion properties provide new insight into the development of chitosan based load-bearing materials. PMID:24138057

Arsenic release and speciation during the oxidative dissolution of arsenopyrite by O2 in the absence and presence of EDTA.

PubMed

Wang, Shaofeng; Jiao, BeiBei; Zhang, Mingmei; Zhang, Guoqing; Wang, Xin; Jia, Yongfeng

2018-03-15

The oxidative decomposition of arsenopyrite is an important source of As in surface environment. This study investigated the oxidative dissolution of arsenopyrite by O 2 and aqueous arsenic transformation at different pHs, dissolved oxygen (DO) contents, and temperatures in the absence and presence of EDTA. The oxidative dissolution was greatly inhibited at neutral and alkaline pH in the absence of EDTA. However, in the presence of EDTA, the oxidative dissolution rate increased linearly from pH 4 to 7. The highest dissolution rate was 3-4 times higher than that at pH 4 and 1-2 orders of magnitude higher than that at pH 7 in the absence of EDTA. This is possibly due to the lack of Fe oxyhydroxides on the surface of arsenopyrite. In the pH range of 7-10, the oxidative dissolution rate decreased linearly, possibly due to the formation of goethite and/or hematite coating. The oxidation of released arsenite (As III ) to arsenate (As V ) took place simultaneously during the oxidative dissolution of arsenopyrite in the presence of dissolved Fe without EDTA, while no obvious aqueous As III oxidation was observed in the presence of EDTA, indicating that aqueous Fe species play an important role in As III oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

Efficient kinetic resolution of secondary alcohols using an organic solvent-tolerant esterase in non-aqueous medium.

PubMed

Gao, Wenyuan; Fan, Haiyang; Chen, Lifeng; Wang, Hualei; Wei, Dongzhi

2016-07-01

To identify an esterase-mediated kinetic resolution of secondary alcohols in non-aqueous medium. An esterase, EST4, from a marine mud metagenomic library, showed high activity and enantioselectivity for the kinetic resolution of secondary alcohols in non-aqueous medium. Using 1-phenylethanol as the model alcohol, the effects of organic solvents, acyl donors, molar ratio, temperatures and biocatalyst loading on the kinetic resolution catalyzed by the EST4 whole-cell biocatalyst were investigated and optimized. The optimized methodology was effective on resolving 16 various racemic secondary alcohols in neat n-hexane, providing excellent enantiomeric excess (up to 99.9 % ee). Moreover, EST4 exhibited a strong tolerance for high substrate concentration (up to 1 M), and the optical purity of the desired secondary alcohols was kept above 99 % ee. The esterase EST4 is a promising biocatalyst for the enantioselective synthesis of various alcohols and esters with interesting practical applications.

PHOTOREACTION OF VALEROPHENONE IN AQUEOUS SOLUTION

EPA Science Inventory

Kinetics and products of the photoreaction of the phenyl ketone valerophenone were investigated as a function of temperature, pH, and wavelength in aqueous solution. Under these conditions (<10-4M), the photoreactions are pseudo-first-order with respect to valerophenone concentra...

Manufacture and Incorporation of Liposome-Entrapped Ethylenediaminetetraacetic Acid into Model Miniature Gouda-Type Cheese and Subsequent Effect on Starter Viability, pH, and Moisture Content.

PubMed

McAuliffe, Lisa N; Kilcawley, Kieran N; Sheehan, Jeremiah J; McSweeney, Paul L H

2016-10-25

Liposome-encapsulated ethylenediaminetetraacetic acid (EDTA) was incorporated into a model miniature Gouda-type cheese (20 g) in order to assess its effect on rennet gelation, starter viability, pH, and moisture content. EDTA was encapsulated within 2 different food-grade proliposome preparations, Pro-Lipo Duo and Pro-Lipo C (50% and 40% unsaturated soybean phospholipids and 50% and 60% aqueous medium, respectively), using the following high-shear technologies: Ultra-Turrax (5000 rpm), 2-stage homogenization (345 bar), or microfluidization (690 bar). Liposome size distribution was affected by the high-shear technology employed with the proportion of large vesicles (>100 nm) decreasing in the order microfluidization < 2-stage homogenization < Ultra-Turrax. All EDTA-containing liposomes were stable during 28 d refrigerated storage, with no significant (P ≤ 0.05) change in size distribution or EDTA entrapment efficiency (%EE). Liposome composition affected the entrapment of EDTA, with Pro-Lipo C having a significantly greater %EE than Pro-Lipo Duo, 63% and 54%, respectively. For this reason, Pro-Lipo C EDTA liposomes, with and without EDTA, were incorporated into model miniature Gouda-type cheese. Addition of liposome-encapsulated EDTA to milk during cheese making did not impact pH or rennet gel formation. No differences in composition or pH were evident in liposome-treated cheeses. The results of this study show that the incorporation of liposome-encapsulated EDTA into milk during cheese manufacture did not affect milk fermentation, moisture content, or pH, suggesting that this approach may be suitable for studying the effects of calcium equilibrium on the texture of brine-salted cheeses. © 2016 Institute of Food Technologists®.

Biological oxidation of hydrogen sulfide in mineral media using a biofilm airlift suspension reactor.

PubMed

Moghanloo, G M Mojarrad; Fatehifar, E; Saedy, S; Aghaeifar, Z; Abbasnezhad, H

2010-11-01

Hydrogen sulfide (H(2)S) removal in mineral media using Thiobacillus thioparus TK-1 in a biofilm airlift suspension reactor (BAS) was investigated to evaluate the relationship between biofilm formation and changes in inlet loading rates. Aqueous sodium sulfide was fed as the substrate into the continuous BAS-reactor. The reactor was operated at a constant temperature of 30 degrees C and a pH of 7, the optimal temperature and pH for biomass growth. The startup of the reactor was performed with basalt carrier material. Optimal treatment performance was obtained at a loading rate of 4.8 mol S(2-) m(-3) h(-1) at a conversion efficiency as high as 100%. The main product of H(2)S oxidation in the BAS-reactor was sulfate because of high oxygen concentrations in the airlift reactor. The maximum sulfide oxidation rate was 6.7 mol S(2-) m(-3) h(-1) at a hydraulic residence time of 3.3 h in the mineral medium. The data showed that the BAS-reactor with this microorganism can be used for sulfide removal from industrial effluent. Copyright 2010 Elsevier Ltd. All rights reserved.

Effect of light conditions and chemical characteristics of water on dissipation of glyphosate in aqueous medium.

PubMed

Yadav, Veena; Kaur, Pervinder; Kaur, Paawan

2017-11-06

The present study was conducted to determine the effect of light conditions and chemical properties of water on dissipation of glyphosate. The residues of glyphosate and aminomethylphosphonic acid (AMPA) were quantified using fluorescence spectrophotometer after derivatization with 9-fluoroenylmethoxycarbonyl chloride (FMOC-Cl) and orthopthaldehyde (OPA). Average percent recoveries of glyphosate and AMPA from distilled, tap, and ground water ranged from 87.5 to 94.9, 87.3 to 93.7, and 80.6 to 92.0, respectively, with relative standard deviation less than 10%. The limit of detection and limit of quantification of glyphosate and AMPA from different water matrices ranged from 0.001 to 0.03 μg mL -1 and 0.003 to 0.01 μg mL -1 , respectively. The dissipation of glyphosate followed the first-order kinetics, and half-life varied from 1.56 to 14.47 and 13.14 to 42.38 days under UV and sunlight, respectively. The pH and electrical conductivity (EC) of water has differential influence on dissipation of glyphosate, and it increased with increase in pH and EC.

A new approach to evaluate natural zeolite ability to sorb lead (Pb) from aqueous solutions

NASA Astrophysics Data System (ADS)

Drosos, Evangelos I. P.; Karapanagioti, Hrissi K.

2013-04-01

Lead (Pb) is a hazardous pollutant commonly found in aquatic ecosystems. Among several methods available, the addition of sorbent amendments to soils or sediments is attractive, since its application is relatively simple, while it can also be cost effective when a low cost and re-usable sorbent is used; e.g. natural zeolites. Zeolites are crystalline aluminosilicates with a three-dimensional structure composed of a set of cavities occupied by large ions and water molecules. Zeolites can accommodate a wide variety of cations, such as Na+, K+, Ca2+, Mg2+, which are rather loosely held and can readily be exchanged for others in an aqueous solution. Natural zeolites are capable of removing cations, such as lead, from aqueous solutions by ion exchange. There is a wide variation in the cation exchange capacity (CEC) of natural zeolites because of the different nature of various zeolites cage structures, natural structural defects, adsorbed ions, and their associated gangue minerals. Naturally occurring zeolites are rarely pure and are contaminated to varying degrees by other minerals, such as clays and feldspars, metals, quartz, or other zeolites as well. These impurities affect the CEC even for samples originated from the same region but from a different source. CEC of the material increases with decreasing impurity content. Potentially exchangeable ions in such impurities do not necessarily participate in ion exchange mechanism, while, in some cases, impurities may additionally block the access to active sites. For zeoliferous rocks having the same percentage of a zeolitic phase, the CEC increases with decreasing Si/Al ratio, as the more Si ions are substituted by Al ions, the more negative the valence of the matrix becomes. Sodium seems to be the most effective exchangeable ion for lead. On the contrary, it is unlikely that the potassium content of the zeolite would be substituted. A pretreatment with high concentration solutions of Na, such as 2 M NaCl, can significantly improve zeolite CEC by bringing the material to near homoionic form. pH and temperature are the critical parameters for using natural zeolites as sorbents. Zeolites should not be used in extremely acidic, neither in extremely basic pH conditions, except for very short times. The exchange of Pb, requires low solution pH, to avoid precipitation but not too low because the H+ are competitive ions for ion exchange; as a result the zeolite CEC related to Pb removal may be downgraded. If pH enters the basic range (e.g. pH>8), more aquatic complexes with lower positive valence than those prevailing in lower pH are produced; these complexes are less attracted by the negative charged zeolitic matrix. Pb uptake is favored at higher temperatures as ion exchange (including the diffusion of exchangeable ions inside the material and the medium, and vice versa) is an endothermic process. With the increase of temperature there is a decrease in hydration of all available exchangeable cations that eases the movement within the channels of the solid matrix. Additionally, the mobility of the potassium ions, present in the zeolitic material, also increases with the temperature resulting in enhanced CEC.

Methylene-bridged bis(benzimidazolium) salt as a highly efficient catalyst for the benzoin reaction in aqueous media.

PubMed

Iwamoto, Ken-ichi; Kimura, Hitomi; Oike, Masaaki; Sato, Masayuki

2008-03-07

Benzoin reactions are catalyzed effectively by a methylene-bridged bis(benzimidazolium) salt to yield alpha-hydroxy ketones, and the reactions proceed in water as the aqueous medium under mild conditions.

Absorption of nitro-polycyclic aromatic hydrocarbons by biomembrane models: effect of the medium lipophilicity.

PubMed

Castelli, Francesco; Micieli, Dorotea; Ottimo, Sara; Minniti, Zelica; Sarpietro, Maria Grazia; Librando, Vito

2008-10-01

To demonstrate the relationship between the structure of nitro-polycyclic aromatic hydrocarbons and their effect on biomembranes, we have investigated the influence of three structurally different nitro-polycyclic aromatic hydrocarbons, 2-nitrofluorene, 2,7-dinitrofluorene and 3-nitrofluoranthene, on the thermotropic behavior of dimyristoylphosphatidylcholine multilamellar vesicles, used as biomembrane models, by means of differential scanning calorimetry. The obtained results indicate that the studied nitro-polycyclic aromatic hydrocarbons affected the thermotropic behavior of multilamellar vesicles to various extents, modifying the pretransition and the main phase transition peaks and shifting them to lower temperatures. The effect of the aqueous and lipophilic medium on the absorption process of these compounds by the biomembrane models has been also investigated revealing that the process is hindered by the aqueous medium but strongly allowed by the lipophilic medium.

Growth of fluorescence gold clusters using photo-chemically activated ligands

NASA Astrophysics Data System (ADS)

Mishra, Dinesh; Aldeek, Fadi; Michael, Serge; Palui, Goutam; Mattoussi, Hedi

2016-03-01

Ligands made of lipoic acid (LA) appended with a polyethylene glycol (PEG) chain have been used in the aqueous phase growth of luminescent gold clusters with distinct emission from yellow to near-IR, using two different routes. In the first route, the gold-ligand complex was chemically reduced using sodium borohydride in alkaline medium, which gave near- IR luminescent gold clusters with maximum emission around 745 nm. In the second method, LA-PEG ligand was photochemically modified to a mixture of thiols, oligomers and oxygenated species under UV-irradiation, which was then used as both reducing agent and stabilizing ligand. By adjusting the pH, temperature, and time of the reaction, we were able to obtain clusters with two distinct emission properties. Refluxing the gold-ligand complex in alkaline medium in the presence of excess ligand gave yellow emission within the first two hours and the emission shifted to red after overnight reaction. Mass spectrometry and chemical assay were used to understand the photo-chemical transformation of Lipoic Acid (LA). Mass spectroscopic studies showed the photo-irradiated product contains thiols, oligomers (dimers, trimers and tetramers) as well as oxygenated species. The amount of thiol formed under different conditions of irradiation was estimated using Ellman's assay.

Magnetic pH-responsive poly(methacrylic acid-co-acrylic acid)-co-polyvinylpyrrolidone magnetic nano-carrier for controlled delivery of fluvastatin.

PubMed

Amoli-Diva, Mitra; Pourghazi, Kamyar; Mashhadizadeh, Mohammad Hossein

2015-02-01

A novel pH-responsive polymer, poly(methacrylic acid-co-acrylic acid)-co-polyvinyl-pyrrolidone (polymeric nano-carrier) was synthesized and used for encapsulation of 3-aminopropyl triethoxysilane modified Fe3O4 nanoparticles to prepare a new magnetic nano-carrier. The loading and release characteristics of both polymeric and magnetic nano-carriers were investigated using fluvastatin as the model drug. The loading behavior of the carriers was studied by varying concentration of fluvastatin in aqueous medium at 25°C and their release was followed spectrophotometrically (at 304 nm) at 37°C in three different solutions (buffered at pH1.2, 5.5 and 7.2) to simulate gastric and intestine medium. The effect of different parameters on the release of fluvastatin such as the amount of methacrylic acid monomer, cross-linker amount, initiator amount, and magnetic nanoparticles content was also studied. Considering the release kinetics and mechanism of the magnetic nanocarrier besides swelling behavior study of the polymeric nano-carrier reveal Fickian pattern and diffusion controlled mechanism for delivery of fluvastatin. Copyright © 2014 Elsevier B.V. All rights reserved.

Zinc fractionation in contaminated soils by sequential and single extractions: influence of soil properties and zinc content.

PubMed

Voegelin, Andreas; Tokpa, Gerome; Jacquat, Olivier; Barmettler, Kurt; Kretzschmar, Ruben

2008-01-01

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.

[Study of the stability of pyrimido-[5,4-e]-1,2,4-triazine antibiotics in acid-base media by NMR spectroscopy].

PubMed

Esipov, S E; Chernyshev, A I; Shorshnev, S V; Iakushkina, N I; Antonovskiĭ, V L

1985-02-01

A comparative study of the NMR 1H and 13C spectra of reumycin, fervenulin and xanthothricin in aqueous acid-base media showed that at pH or pD ranging from 8.0 to 1.0 the antibiotics were chemically stable. By the ratio of the 1H and 13C chemical shifts of reumycin at pH 4.0-10.0 the pKa values of this antibiotic were determined: 6.7 in aqueous (D2O) solution and 8.76 in dimethylsulfoxide media. Alkalization of the solutions of reumycin (pH 12.0), fervenulin (pH 9.0) and xanthothricin (pH 8.0) resulted in irreversible chemical transformation of the antibiotics. The analysis of the chemical shifts in the PMR spectra of the transformation products revealed transformation of the uracil ring in reumycin and uracil and triazine rings in fervenulin and xanthothricin. Alkalization of the xanthothricin solutions resulted also in demethylation with formation of reumycin.

Atmospheric Processing of Volcanic Glass: Effects on Iron Solubility and Redox Speciation.

PubMed

Maters, Elena C; Delmelle, Pierre; Bonneville, Steeve

2016-05-17

Volcanic ash from explosive eruptions can provide iron (Fe) to oceanic regions where this micronutrient limits primary production. Controls on the soluble Fe fraction in ash remain poorly understood but Fe solubility is likely influenced during atmospheric transport by condensation-evaporation cycles which induce large pH fluctuations. Using glass powder as surrogate for ash, we experimentally simulate its atmospheric processing via cycles of pH 2 and 5 exposure. Glass fractional Fe solubility (maximum 0.4%) is governed by the pH 2 exposure duration rather than by the pH fluctuations, however; pH 5 exposure induces precipitation of Fe-bearing nanoparticles which (re)dissolve at pH 2. Glass leaching/dissolution release Fe(II) and Fe(III) which are differentially affected by changes in pH; the average dissolved Fe(II)/Fetot ratio is ∼0.09 at pH 2 versus ∼0.18 at pH 5. Iron release at pH 2 from glass with a relatively high bulk Fe(II)/Fetot ratio (0.5), limited aqueous Fe(II) oxidation at pH 5, and possibly glass-mediated aqueous Fe(III) reduction may render atmospherically processed ash a significant source of Fe(II) for phytoplankton. By providing new insight into the form(s) of Fe associated with ash as wet aerosol versus cloud droplet, we improve knowledge of atmospheric controls on volcanogenic Fe delivery to the ocean.

Nutritional Capability of and Substrate Suitability for Pseudogymnoascus destructans, the Causal Agent of Bat White-Nose Syndrome

PubMed Central

Raudabaugh, Daniel B.; Miller, Andrew N.

2013-01-01

Pseudogymnoascus destructans, the causal agent of bat white-nose syndrome, has caused nearly six million deaths in North American bats since its introduction into the United States in 2006. Current research has shown that caves can harbor P. destructans even after the infected bats are removed and bats no longer visit or inhabit previously infected caves. Our research focuses on elucidating reservoir requirements by investigating the nutritional capabilities of and substrate suitability requirements for six different P. destructans isolates from various localities including Illinois, Indiana, New York (Type specimen), and Pennsylvania. Enzyme assays implicate that both urease and b-glucosidase appear to be constitutive, lipase and esterase activity were more rapid than proteinase activity on 6% gelatin, gelatin degradation was accompanied by medium alkalinization, the reduction of thiosulfate generated hydrogen sulfide gas, chitinase and manganese dependent peroxidase activity were not visually demonstrated within eight weeks, and keratinase activity was not evident at pH 8 within eight weeks. We demonstrate that all P. destructans isolates are capable of growth and sporulation on dead fish, insect, and mushroom tissues. Sole nitrogen source assays demonstrated that all P. destructans isolates exhibit Class 2 nitrogen utilization and that growth-dependent interactions occur among different pH and nitrogen sources. Substrate suitability assays demonstrated that all isolates could grow and sporulate on media ranging from pH 5–11 and tolerated media supplemented with 2000 mg/L of calcium and 700 mg/L of three separated sulfur compounds: thiosulfate L-cysteine, and sulfite. All isolates were intolerant to PEG-induced matric potential with delayed germination and growth at −2.5 MPa with no visible germination at −5 MPa. Interestingly, decreasing the surface tension with Tween 80 permitted germination and growth of P. destructans in −5 MPa PEG medium within 14 days suggesting a link between substrate suitability and aqueous surface tension altering substances. PMID:24205191

Nutritional capability of and substrate suitability for Pseudogymnoascus destructans, the causal agent of bat white-nose syndrome.

PubMed

Raudabaugh, Daniel B; Miller, Andrew N

2013-01-01

Pseudogymnoascus destructans, the causal agent of bat white-nose syndrome, has caused nearly six million deaths in North American bats since its introduction into the United States in 2006. Current research has shown that caves can harbor P. destructans even after the infected bats are removed and bats no longer visit or inhabit previously infected caves. Our research focuses on elucidating reservoir requirements by investigating the nutritional capabilities of and substrate suitability requirements for six different P. destructans isolates from various localities including Illinois, Indiana, New York (Type specimen), and Pennsylvania. Enzyme assays implicate that both urease and b-glucosidase appear to be constitutive, lipase and esterase activity were more rapid than proteinase activity on 6% gelatin, gelatin degradation was accompanied by medium alkalinization, the reduction of thiosulfate generated hydrogen sulfide gas, chitinase and manganese dependent peroxidase activity were not visually demonstrated within eight weeks, and keratinase activity was not evident at pH 8 within eight weeks. We demonstrate that all P. destructans isolates are capable of growth and sporulation on dead fish, insect, and mushroom tissues. Sole nitrogen source assays demonstrated that all P. destructans isolates exhibit Class 2 nitrogen utilization and that growth-dependent interactions occur among different pH and nitrogen sources. Substrate suitability assays demonstrated that all isolates could grow and sporulate on media ranging from pH 5-11 and tolerated media supplemented with 2000 mg/L of calcium and 700 mg/L of three separated sulfur compounds: thiosulfate L-cysteine, and sulfite. All isolates were intolerant to PEG-induced matric potential with delayed germination and growth at -2.5 MPa with no visible germination at -5 MPa. Interestingly, decreasing the surface tension with Tween 80 permitted germination and growth of P. destructans in -5 MPa PEG medium within 14 days suggesting a link between substrate suitability and aqueous surface tension altering substances.

Phase equilibria in a system of aqueous arginine with an octane solution of sulfonic acid

NASA Astrophysics Data System (ADS)

Kuvaeva, Z. I.; Koval'chuk, I. V.; Vodop'yanova, L. A.; Soldatov, V. S.

2013-05-01

The extraction of arginine (Arg) from aqueous salt (0.1 M NaCl) solutions with a sulfo extractant in a wide range of pH values and amino acid concentrations was studied. The 0.1 M solution of dinonylnaphthalenesulfonic acid (HD) in octane was used as an extractant. The degree of extraction was found to be high at pH 0.8-9.0. This can be explained by the effect of additional intermolecular interactions in the extractant phase involving the guanidine group of Arg.

INFLUENCE OF SOLVENT AND SORBENT CHARACTERISTICS ON DISTRIBUTION OF PENTACHLOROPHENOL IN OCTANOL-WATER AND SOIL-WATER SYSTEMS

EPA Science Inventory

Sorbent and solvent characteristics influencing sorption of pentachlorophenol (PCP) were investigated. Analysis of aqueous sorption data for several sorbents over a broad pH range suggested hydrophobic sorption of neutral PCP predominates at pH 7. At pH > 7, sorption of the penta...

Effectiveness of Mouthrinse formulated from Aqueous Extract of Terminalia chebula on Salivary Streptococcus mutans Count and pH among 8- to 12-year-old School Children of Karnataka: A Randomized Clinical Trial.

PubMed

Palit, Madhuchanda; Hegde, Sundeep K; Bhat, Sham S

2016-01-01

The aim of the present study was to evaluate the anticar-iogenic efficacy of hot and cold aqueous extracts of Terminalia chebula against Streptococcus mutans as an oral rinse and also to discover the acceptability of the mouthwash in children. Sixty children between 8 and 12 years with high caries risk were selected. 10% concentration of hot and cold aqueous extracts were prepared. Children were randomly divided into extract and control group. Baseline salivary samples were taken, and the samples were re-collected at 10, 60, and 90 minutes interval after rinsing. Microbial and pH analysis were done. An acceptability questionnaire was filled. Tukey's multiple comparison test. The results show statistically significant difference in S. mutans counts at 10, 60, and 90 minutes interval when compared with negative control. However, when the hot and cold extracts were compared, there was no significant difference. Acceptability questionnaire showed 65 to 75% overall acceptability for both types of extract. Results of this study showed that both types of aqueous extract of T. chebula may be used as potential anticariogenic mouthwash with acceptable taste in children. Palit MC, Hegde SK, Bhat SS. Effectiveness of Mouthrinse formulated from Aqueous Extract of Terminalia chebula on Salivary Streptococcus mutans Count and pH among 8- to 12-year-old School Children of Karnataka: A Randomized Clinical Trial. Int J Clin Pediatr Dent 2016;9(4):349-354.

α-Tocopherol/chitosan-based nanoparticles: characterization and preliminary investigations for emulsion systems application

NASA Astrophysics Data System (ADS)

Aresta, Antonella; Calvano, Cosima Damiana; Trapani, Adriana; Zambonin, Carlo Giorgio; De Giglio, Elvira

2014-02-01

The processes of lipids oxidation represent a great concern for the consumer health because they are one of the major causes of quality deterioration in fat-containing products. One of the most effective methods of delaying lipid oxidation consists in incorporating antioxidants. The present investigation describes the formulation of chitosan and novel glycol chitosan nanoparticles (NPs) loaded with α-Tocopherol (αToc-NPs). The obtained NPs were characterized by various techniques, such as particle size (showing mean diameters in the range 335-503 nm) and zeta potential measurements, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The NPs were, then, added in the preparation of oil-in-water simple emulsion both to make the lipophilic αToc available in an aqueous medium and to prevent emulsion oxidation. For this purpose, a new highly sensitive, simple and solvent-free method based on a solid phase microextraction (SPME) coupled to gas chromatography mass spectrometry was developed for the determination of αToc in aqueous medium. All the parameters influencing SPME, including fiber coating, time and temperature extraction, pH, ionic strength and desorption conditions, have been carefully screened. The method was successfully applied to the determination of vitamin in the αToc-NPs and its release from NPs-enriched simple emulsion formulations. SPME provided high recovery yields and the limits of detection and of quantification in emulsion were 0.1 and 0.5 μg/mg, respectively. The precision of the method has been also estimated. The delay of the lipid oxidation by the proposed formulations has been evaluated exploiting the Kreis test on αToc-NPs-enriched emulsions.

Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries.

PubMed

Clark, Simon; Latz, Arnulf; Horstmann, Birger

2017-12-08

Neutral aqueous electrolytes have been shown to extend both the calendar life and cycling stability of secondary zinc-air batteries (ZABs). Despite this promise, there are currently no modeling studies investigating the performance of neutral ZABs. Traditional continuum models are numerically insufficient to simulate the dynamic behavior of these complex systems because of the rapid, orders-of-magnitude concentration shifts that occur. In this work, we present a novel framework for modeling the cell-level performance of pH-buffered aqueous electrolytes. We apply our model to conduct the first continuum-scale simulation of secondary ZABs using aqueous ZnCl 2 -NH 4 Cl as electrolyte. We first use our model to interpret the results of two recent experimental studies of neutral ZABs, showing that the stability of the pH value is a significant factor in cell performance. We then optimize the composition of the electrolyte and the design of the cell considering factors including pH stability, final discharge product, and overall energy density. Our simulations predict that the effectiveness of the pH buffer is limited by slow mass transport and that chlorine-containing solids may precipitate in addition to ZnO. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical fate and changes in mutagenic activity of antibiotics nitrofurazone and furazolidone during aqueous chlorination.

PubMed

Nakamura, Hitomi; Kawakami, Tsuyoshi; Niino, Tatsuhiro; Takahashi, Yasuo; Onodera, Sukeo

2008-12-01

Reactions of nitrofuran antibiotics (nitrofurazone (NFZ) and frazolidone (FZD)) with hypochlorite in aqueous solution were investigated under the conditions that simulate wastewater disinfection. The chlorination byproducts were determined by high performance liquid chromatography. At the levels of 5 microM, NFZ reacted rapidly with free chlorine in neutral pH (7.0), while the FZD-hypochlorite reaction was reasonably slow under the same pH. Nevertheless, the strong mutagenic parents disappeared completely after the hypochlorite reactions, and the chlorination byproducts were observed to exert a weak mutagenic effect on Salmonella typhimurium TA100 without S9-mix. The extent of the reactions depended on the chlorine dose, solution pH and compound structures.

The influence of pH on the degradation of phenol and chlorophenols by potassium ferrate.

PubMed

Graham, Nigel; Jiang, Cheng-Chun; Li, Xiang-Zhong; Jiang, Jia-Qian; Ma, Jun

2004-09-01

This paper presents information concerning the influence of solution pH on the aqueous reaction between potassium ferrate and phenol and three chlorinated phenols: 4-chlorophenol (CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP). The redox potential and aqueous stability of the ferrate ion, and the reactivity of dissociating compounds, are known to be pH dependent. Laboratory tests have been undertaken over a wide range of pH (5.8-11) and reactant concentrations (ferrate:compound molar ratios of 1:1 to 8:1). The reactivity of trichloroethylene was also investigated as a reference compound owing to its non-dissociating nature. The extent of compound degradation by ferrate was found to be highly pH dependent, and the optimal pH (maximum degradation) decreased in the order: phenol/CP, DCP, TCP; at the optimal pH the degree of degradation of these compounds was similar. The results indicate that for the group of phenol and chlorophenols studied, the presence of an increasing number of chlorine substituent atoms corresponds to an increasing reactivity of the undissociated compound, and a decreasing reactivity of the dissociated compound.

Development of a C3-symmetric benzohydroxamate tripod: Trimetallic complexation with Fe(III), Cr(III) and Al(III)

NASA Astrophysics Data System (ADS)

Baral, Minati; Gupta, Amit; Kanungo, B. K.

2016-06-01

The design, synthesis and physicochemical characterization of a C3-symmetry Benzene-1,3,5-tricarbonylhydroxamate tripod, noted here as BTHA, are described. The chelator was built from a benzene as an anchor, symmetrically extended by three hydroxamate as ligating moieties, each bearing O, O donor sites. A combination of absorption spectrophotometry, potentiometry and theoretical investigations are used to explore the complexation behavior of the ligand with some trivalent metal ions: Fe(III), Cr(III), and Al(III). Three protonation constants were calculated for the ligand in a pH range of 2-11 in a highly aqueous medium (9:1 H2O: DMSO). A high rigidity in the molecular structure restricts the formation of 1:1 (M/L) metal encapsulation but shows a high binding efficiency for a 3:1 metal ligand stoichiometry giving formation constant (in β unit) 28.73, 26.13 and 19.69 for [M3L]; Mdbnd Fe(III), Al(III) and Cr(III) respectively, and may be considered as an efficient Fe-carrier. The spectrophotometric study reveals of interesting electronic transitions occurred during the complexation. BTHA exhibits a peak at 238 nm in acidic pH and with the increase of pH, a new peak appeared at 270 nm. A substantial shifting in both of the peaks in presence of the metal ions implicates a s coordination between ligand and metal ions. Moreover, complexation of BTHA with iron shows three distinct colors, violet, reddish orange and yellow in different pH, enables the ligand to be considered for the use as colorimetric sensor.

Spectroscopic investigation of the pH controlled inclusion of doxycycline and oxytetracycline antibiotics in cationic micelles and their magnesium driven release.

PubMed

Cesaretti, Alessio; Carlotti, Benedetta; Gentili, Pier Luigi; Clementi, Catia; Germani, Raimondo; Elisei, Fausto

2014-07-24

This work presents a steady-state and time-resolved UV-visible spectroscopic investigation of two antibiotics belonging to the family of tetracyclines (doxycycline and oxytetracycline) in the micellar medium provided by p-dodecyloxybenzyltrimethylammonium bromide (pDoTABr). The spectroscopic analysis has been performed in absorption and emission with femtosecond time resolution, and at pH 5.0 and 8.7 where doxycycline and oxytetracycline are present in their neutral-zwitterionic and monoanionic forms, respectively. The experimental data have been processed by sophisticated data mining methods such as global/target analysis and the maximum entropy method. The results unambiguously indicate that, when doxycycline and oxytetracycline are in their zwitterionic form, they are entrapped within the micelle, while when they are in their monoanionic form, they preferentially show a strong one-to-one interaction with the positively charged surfactant heads. Thus, the pH of the solution controls the inclusion of the investigated drugs into the micelle. When the drugs are entrapped inside the micelles, their spectroscopic and dynamical properties after photoexcitation change appreciably. Interestingly, the entrapped drugs are still able to strongly bind Mg(2+) cations, crucial in determining the biological functioning of tetracyclines. The femtosecond resolved measurements reveal that the drugs are efficiently pulled out of the micelles by Mg(2+). In fact, magnesium-tetracycline complexes are detected in the aqueous phase. The present study suggests the potential promising use of ammonium surfactant micelles embedding doxycycline and oxytetracycline as "smart" drug delivery systems allowing their pH controlled inclusion and Mg(2+) induced release.

Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

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

O'Hara, Matthew J.; Carter, Jennifer C.; Warner, Cynthia L.

Magnetic nanoparticles are well known to possess chemically active surfaces and high surface areas that can be employed to extract a range of ions from aqueous solutions. Additionally, their paramagnetic property provides a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. Herein, two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes, were evaluated for their ability to collect both naturally occurring radioactive isotopes (polonium (Po), radium (Ra), and uranium (U)) as well as the transuranic element americium (Am) from a suite of naturally occurring aqueous matrices. The nanomaterials include commerciallymore » available paramagnetic magnetite (Fe3O4) and magnetite that was modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1 (acidified with HCl). Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the aforementioned alpha-emitting radionuclide spikes from Hanford Site ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. The uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified groundwater was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. Overall, the results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions. These applications may include analytical chemistry, waste water treatment and remediation, mining, and in vitro radiobioassay.« less

Radiation Induced Incorporation of CO in Pure and Aqueous Methanol

NASA Astrophysics Data System (ADS)

Jung, Hak-Jin; Getoff, Nikola; Lorbeer, Eberhard

1994-05-01

Pure and aqueous methanol were used for radiation induced incorporation of CO at elevated pressure (up to 15 bar). The initial yields (Gi) of the main products in pure methanol under 15 bar CO and 1 bar N2O were found to be: Gi(formaldehyde) = 3.80 and Gi(glycolic aldehyde) = 2.0. For aqueous (10-2 mol · dm-3) methanol under 15 bar CO (dose: 0.557 kGy, pH = 2): the yields were G(formaldehyde) = 5.44, G(glycolic aldehyde) = 4.0 and G(oxalic acid) = 7.7. At pH = 7 the yields were essentially lower, namely: G(formaldehyde) = 3.2, G(glycolic aldehyde) = 2.0, G(formate) = 3.8 and G(oxalate) = 5.0. Probable reaction-mechanisms for the product formation are discussed.

Extremophile mediated hydrogen production for hydrogenation of substrates in aqueous media

NASA Astrophysics Data System (ADS)

Anjom, Mouzhgun

Catalytic hydrogenation reactions are pervasive throughout our economy, from production of margarine as food, liquid fuels for transportation and chiral drugs such as L-DOPA. H2 production from non-fossil fuel feedstocks is highly desirable for transition to the "Hydrogen Economy". Also, the rates of hydrogenation reactions that involve a substrate, H 2 gas and a catalyst are often limited by the solubility of H2 in solvent. The present research thus envisioned designing water-soluble catalysts that could effectively utilize biologically produced H2 in a coupled system to hydrogenate substrates in homogeneous mode (two-phase system). Biological production of H2 as an end product or byproduct of the metabolism of organisms that operate under strict anaerobic conditions has been proposed. However, contrary to what was previously observed, Thermotoga neapolitana, belonging to the order of Thermotogales efficiently produces H2 gas under microaerobic conditions (Van Ooteghem et al. 2004). For H2 production by T. neapolitana in the bacterial growth medium (DSM 5068) at an optimum temperature of 70 C, our results in batch mode show that: (1) H2 was produced from glucose though with 16% efficiency, the rest goes to biomass production, (2) H2 gas was produced even when the cultures were inoculated under microaerobic conditions (up to 8% (v/v) O2) suggesting a protective mechanism for one or more [Fe-Fe] hydrogenases in T. neapolitana, (3) H2 production was pH dependent but addition of simple, non-toxic physiological buffering additives such as Methylene succinic acid increased H2 production and (4) H2 production rate varied linearly in the 100--6800 kPa pressure range. We then screened various water-soluble metal catalysts in batch mode and selected the RhCl3.3H2O/TPPTS (TPPTS is a water-soluble ligand) system that achieved 86% hydrogenation of Methylene succinic acid (an olefin) in an aqueous medium pressurized with preformed H2. When water was replaced with the DSM 5068 medium containing cultures of T. neapolitana and no external H2 was added, hydrogenation was observed confirming the possibility of developing an integrated BioCat/ChemCat system. The 1H NMR spectroscopy was used to confirm the identity of Methyl succinic acid, the hydrogenated product of the olefin. The concept was extended to Glycerol, a by-product of biodiesel that was catalytically upgraded to mixed alcohols in an aqueous medium. The next logical step is to evaluate these results in a continuous flow mode. The demonstrated results have implications in the development of next-generation hydrogenation reaction systems that would lead to the production of biofuels and other chemicals, depending on the substrate used.

Production of imidazole alkaloids in cell cultures of jaborandi as affected by the medium pH.

PubMed

Andreazza, N L; Abreu, I N; Sawaya, A C H F; Eberlin, M N; Mazzafera, P

2009-04-01

The effect of pH (from 4.8 to 9.8) on the production of pilosine and pilocarpine and on their partition between cell and medium was studied in two lineages (P and PP) of Pilocarpus microphyllus cell suspension cultures. Highest mass accumulation was observed at high pHs and both lineages produced pilocarpine while only lineage PP produced pilosine. Both alkaloids were released in the medium but higher accumulation occurred in the cells. The highest production of pilocarpine was at pH 8.8-9.8 in both cell lineages. Other imidazole alkaloids were also identified in both lineages. At all pHs tested, the pH in the media cultures tended to stabilize around 6 after 10-15 days of cultivation. NO3(-) and NH4+ variation in the media might partially explain the pH stabilization.

pH regulation of mitochondrial branch chain alpha-keto acid transport and oxidation in rat heart mitochondria.

PubMed

Hutson, S M

1987-07-15

The kinetics of branched chain alpha-keto acid uptake and efflux were studied as a function of varied external and matrix pH. Matrix pH was determined by the distribution of 5,5'-dimethyloxazolidine-2,4-dione. When rat heart mitochondria were incubated under transport conditions at pH 7.0 with succinate as respiratory substrate, the matrix pH was significantly greater than 8.0. Matrix pH remained greater than or equal to 8.0 when the medium pH was varied from 6.3 to 8.3, and it was lowered below 8.0 by addition of 5 mM phosphate or uncoupler. No pH gradient was detectable when mitochondria were incubated in the presence of valinomycin and uncoupler. Efflux of alpha-ketoisocaproate or alpha-ketoisovalerate from rat heart mitochondria obeyed first order kinetics. Varying the external pH from 6.6 to 8.3 had no significant effect on efflux, and at an external pH of 7.0, the first order rate constant for efflux was not affected by decreasing the matrix pH. On the other hand, exchange was sensitive to changes in medium but not matrix pH. The K0.5 for external branched chain alpha-keto acid was lowered by changing the medium pH from 7.6 to 6.3. At medium pH values greater than or equal to 8.0 both K0.5 and Vmax were affected. Uptake was determined either by measuring initial rates or was calculated after measuring the first order approach to a final equilibrium value. Unlike efflux, uptake was sensitive to changes in both external and matrix pH. The rate of branched chain alpha-keto acid uptake was stimulated by decreasing the medium pH from 8.3 to 6.3 and by alkalinization of the mitochondrial matrix. The estimated external pK for proton binding was 6.9. The data indicate that the branched chain alpha-keto acid transporter is asymmetric, that is, binding sites for substrate on the inside and outside of the mitochondrial membrane are not identical. alpha-Ketoisocaproate oxidation was measured at 37 degrees C in isolated mitochondria over the pH range of 6.6 to 8.1. Changes in the rate of branched chain alpha-keto acid oxidation, particularly when ATP was added (increase delta pH), were found to parallel the pH effects observed on branched chain alpha-keto acid uptake. Therefore, transport, and by implication oxidation, can be regulated by pH changes within the physiological range. Furthermore, intracellular pH may affect the degree of compartmentation between the cytosolic and mitochondrial branched chain alpha-keto acid pools.

Regulating Glucose and pH, and Monitoring Oxygen in a Bioreactor

NASA Technical Reports Server (NTRS)

Anderson, Melody M.; Pellis, Neat R.; Jeevarajan, Antony S.; Taylor, Thomas D.; Xu, Yuanhang; Gao, Frank

2006-01-01

A system that automatically regulates the concentration of glucose or pH in a liquid culture medium that is circulated through a rotating-wall perfused bioreactor is described. Another system monitors the concentration of oxygen in the culture medium.

Growth and survival of cowpea rhizobia in acid, aluminum-rich soils

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

Hartel, P.G.; Alexander, M.

1983-01-01

A study was undertaken to determine whether Al-sensitive cowpea Rhizobium survives in acid, Al-rich soils. The lower pH limit for growth of 20 strains in a defined liquid medium varied from pH 4.2 to less than pH 3.6. The mean lower limit for growth was pH 3.9. Several of the strains clumped in this medium at pH 4.5. Of 11 strains that were tested for tolerance to high levels of Al in a defined liquid medium at pH 4.5, nine tolerated 75 ..mu..M Al, and the other two were sensitive to levels above 15 ..mu..M. Three strains, one Al-tolerant, onemore » Al-sensitive, and one Al-tolerant or Al-sensitive depending on the presence of vitamins in the medium, were selected for studies in Al-rich sterile and nonsterile soils. These rhizobia did not survive in soils of less than pH 4.7 sterilized by /sup 60/Co irradiation. When inoculated into sterile soil at pH 4.7, the consistently sensitive strain initially failed to proliferate and then grew slowly, but populations of the other two rhizobia increased rapidly. No consistent relationship was found between the Al tolerance of these three rhizobia and their growth and survival in four acid, Al-rich soils. The data suggest that Al is of minor importance to growth and survival of cowpea Rhizobium strains in acid soils. 16 references, 4 figures, 1 table.« less

Improvement of physicomechanical properties of carbamazepine by recrystallization at different pH values.

PubMed

Javadzadeh, Yousef; Mohammadi, Ameneh; Khoei, Nazaninossadat Seyed; Nokhodchi, Ali

2009-06-01

The morphology of crystals has an appreciable impact role on the physicochemical properties of drugs. Drug properties such as flowability, dissolution, hardness and bioavailability may be affected by crystallinity behaviours of drugs. The objective of this study was to achieve an improved physicomechanical property of carbamazepine powder through recrystallization from aqueous solutions at different pH values. For this purpose, carbamazapine was recrystallized from aqueous solutions at different pH values (1, 7, 11). The morphology of crystals was investigated using scanning electron microscopy; X-ray powder diffraction (XRPD) was used to identify polymorphism; thermodynamic properties were analyzed using differential scanning calorimetery (DSC). Dissolution rate was determined using USP dissolution apparatus. Mechanical behavior of recrystallized carbamazepine powders was investigated by making tablets under different compaction pressure and measuring their hardness. SEM studies showed that the carbamazepine crystallization in different media affected the morphology and size of carbamazepine crystals. The shape of carbamazepine crystals changed from flaky or thin plate-like to needle shape. XRPD and DSC results ruled out any crystallinity changes occurring due to the temperature during recrystallization procedure or pH of crystallization media. The crushing strength of tablets indicated that all of the recrystallized carbamazepine samples had better compactiblity than the original carbamazepine powder. In vitro dissolution studies of carbamazepine samples showed a higher dissolution rate for carbamazepine crystals obtained from media with pH 11 and 1. Carbamazepine particles recrystallized from aqueous solutions of different pH values (all media) appeared to have superior mechanical properties to those of the original carbamazepine sample.

Absorption and emission behaviour of trans- p-coumaric acid in aqueous solutions and some organic solvents

NASA Astrophysics Data System (ADS)

Putschögl, M.; Zirak, P.; Penzkofer, A.

2008-01-01

The absorption and fluorescence behaviour of trans- p-coumaric acid ( trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form ( p-CAH 2) and the single anionic form ( p-CAH -) at low pH (p Kna ≈ 4.9), and between the single anionic and the double anionic form ( p-CA 2-) at high pH (p Kaa ≈ 9.35). In the organic solvents studied trans- p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans- p-coumaric acid in aqueous solution is ϕF ≈ 1.4 × 10 -4 for the neutral and the single anionic form, while it is ϕF ≈ 1.3 × 10 -3 for the double anionic form. For trans- p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 × 10 -5 (acetonitrile) to 1.5 × 10 -4 (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm -1 Stokes shifted in aqueous solution, and 5400-8200 cm -1 Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA 2-, solvent-assisted intra-molecular charge-transfer or ππ ∗ to nπ ∗ transfer and internal conversion for p-CAH 2 and p-CAH -). The solvent dependence of the first ππ ∗ electronic transition frequency and of the fluorescence Stokes shift of p-CAH 2 is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted.

Self-Assembly of a Tripodal Triszwitterion Forms a pH-Switchable Hydrogel that Can Reversibly Encapsulate Hydrophobic Guests in Water.

PubMed

Jana, Poulami; Schmuck, Carsten

2017-01-05

The development of supramolecular smart materials, which exhibit physicochemical structural changes in response to external stimuli is of current interest for various applications. Herein, we have developed the novel tripodal triszwitterion 1, derived from a C 3 -symmetric benzene-1,3,5-tricarboxamide (BTA) core, which forms a thermo-reversible and pH-switchable transparent hydrogel through intermolecular self-complementary zwitterionic interactions at a neutral pH value. The hierarchical supramolecular self-aggregation was fully analyzed by microscopy (AFM, field emission scanning electron microscopy (FESEM)), viscosity, dynamic light scattering (DLS), and rheology studies. Moreover, compound 1 enables to encapsulate hydrophobic guests, such as the dye Nile red in aqueous medium at pH 6, which makes it an interesting candidate for drug delivery and controlled release. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methods for functionalization of microsized polystyrene beads with titania nanoparticles for cathodic electrophoretic deposition.

PubMed

Radice, S; Kern, P; Dietsch, H; Mischler, S; Michler, J

2008-02-15

Functionalization of colloidal particles based on the use of polyelectrolytes and heterocoagulation was combined with electrophoretic deposition (EPD), with the aim of depositing titania-polystyrene (TiO(2)-PS) composite particles on Ti6Al4V substrates. The composite particles were obtained by heterocoagulation of TiO(2) nanoparticles on the surface of monosized polystyrene beads of 4.6 microm in diameter. Two alternative methods were developed for the preparation of the TiO(2)-PS suspensions in organic fluids for cathodic electrodeposition. The first method was carried out in alkaline aqueous medium with the use of polyelectrolytes and intermediate control measurements of zeta potential, conductivity, and pH; the second one was carried out directly in the organic solvent used for EPD, typically isopropanol. Examples of deposits obtained by EPD in both suspensions and a comparative analysis between the two methods are presented.

Emulsions Containing Perfluorocarbon Support Cell Cultures

NASA Technical Reports Server (NTRS)

Ju, Lu-Kwang; Lee, Jaw Fang; Armiger, William B.

1990-01-01

Addition of emulsion containing perfluorocarbon liquid to aqueous cell-culture medium increases capacity of medium to support mammalian cells. FC-40 Fluorinert (or equivalent) - increases average density of medium so approximately equal to that of cells. Cells stay suspended in medium without mechanical stirring, which damages them. Increases density enough to prevent cells from setting, and increases viscosity of medium so oxygen bubbled through it and nutrients stirred in with less damage to delicate cells.

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, Wen Y.

1984-01-01

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

pH-Dependent Conformational Changes in the HCV NS3 Protein Modulate Its ATPase and Helicase Activities

PubMed Central

Ventura, Gustavo Tavares; da Costa, Emmerson Corrêa Brasil; Capaccia, Anne Miranda; Mohana-Borges, Ronaldo

2014-01-01

The hepatitis C virus (HCV) infects 170 to 200 million people worldwide and is, therefore, a major health problem. The lack of efficient treatments that specifically target the viral proteins or RNA and its high chronicity rate make hepatitis C the cause of many deaths and hepatic transplants annually. The NS3 protein is considered an important target for the development of anti-HCV drugs because it is composed of two domains (a serine protease in the N-terminal portion and an RNA helicase/NTPase in the C-terminal portion), which are essential for viral replication and proliferation. We expressed and purified both the NS3 helicase domain (NS3hel) and the full-length NS3 protein (NS3FL) and characterized pH-dependent structural changes associated with the increase in their ATPase and helicase activities at acidic pH. Using intrinsic fluorescence experiments, we have observed that NS3hel was less stable at pH 6.4 than at pH 7.2. Moreover, binding curves using an extrinsic fluorescent probe (bis-ANS) and ATPase assays performed under different pH conditions demonstrated that the hydrophobic clefts of NS3 are significantly more exposed to the aqueous medium at acidic pH. Using fluorescence spectroscopy and anisotropy assays, we have also observed more protein interaction with DNA upon pH acidification, which suggests that the hydrophobic clefts exposure on NS3 might be related to a loss of stability that could lead it to adopt a more open conformation. This conformational change at acidic pH would stimulate both its ATPase and helicase activities, as well as its ability to bind DNA. Taken together, our results indicate that the NS3 protein adopts a more open conformation due to acidification from pH 7.2 to 6.4, resulting in a more active form at a pH that is found near Golgi-derived membranes. This increased activity could better allow NS3 to carry out its functions during HCV replication. PMID:25551442

Experimental investigations of the effect the electrical conductivity of medium has on the performance of pH meters

NASA Astrophysics Data System (ADS)

Rodionov, A. K.; Karashchuk, S. A.

2013-07-01

Results from tests of pH meters carried out in ammonia media having low electric conductivity (less than 5.0 μS/cm) are presented. The check media for the tests were prepared in a special manner the use of which makes it possible to reproduce the pH value of solution with an error not exceeding ˜0.04pH in the range of electrical conductivities above 0.1 μS/cm. The instrument measurement error was determined at different electrical conductivities of medium. Different electrodes were tested, the majority of which were domestically produced ones intended for general industrial applications. Some results were also obtained for one dedicated electrode from a foreign manufacturer. The test results show that the instrument gives a biased pH value for such media. The bias has a random value, which nonetheless is stable in the majority of cases, depends on the electrical conductivity of medium being monitored, and may be quite essential for small electrical conductivities (0.5pH or more). A conclusion is drawn about the need to calibrate the instruments with respect to standard media having electrical conductivity close to that of the medium being monitored. Analytic relations characterizing the check media used fort tests (check solutions) are presented.

Temperature-dependent spectroscopic evidences of curcumin in aqueous medium: a mechanistic study of its solubility and stability.

PubMed

Jagannathan, Ramya; Abraham, Priya Mary; Poddar, Pankaj

2012-12-20

In curcumin, keto-enol-enolate equilibrium of the heptadiene-dione moiety determines its physiochemical and antioxidant properties. However, its poor solubility in water at neutral pH and room temperature decreases its bioavailability. Potential therapeutic applications have triggered an interest in manipulating the solubility of curcumin in water as its stability and solubility in water remains poorly understood. Here, the mechanism behind its solubility at various temperatures and the influence of interplay of temperature, intramolecular H-bonding, and intermolecular forces is reported, which leads to aggregation-disaggregation at various temperatures. Remarkable change is observed in temperature-dependent electronic transition behavior of curcumin, however, the absorption spectra after cooling and heating cycles remain unchanged, hinting much better thermal stability of curcumin in water than previously thought. This study indicates that it is perhaps the breaking of intramolecular hydrogen bonding which leads to exposure of polar groups and hence responsible for the dissolution of curcumin at higher temperature. The formation of intermolecular aggregates might be responsible behind a better room temperature stability of the molecules after cooling its aqueous suspension from 90 to 25 °C. These curcumin solubility studies have great application in biological research with reference to bioavailability and to understand target oriented mode of action of curcumin.

Highly selective stir bar coated with dummy molecularly imprinted polymers for trace analysis of bisphenol A in milk.

PubMed

Zhan, Wen; Wei, Fangdi; Xu, Guanhong; Cai, Zheng; Du, Shuhu; Zhou, Xuemin; Li, Fei; Hu, Qin

2012-04-01

A water compatible molecularly imprinted polymers (MIPs) coated stir bar for bisphenol A(BPA) was prepared with 3,3',5,5'-tetrabromobisphenol A as the dummy template molecule in this study. The dummy molecularly imprinted polymers coated stir bar (DMIPs-SB) showed better selectivity than the bars coated with polydimethylsiloxane or non-imprinted polymers when used to extract BPA and its three analogues. The saturated adsorption amount of the DMIPs coating was 3.0 times over that of the non-imprinted polymers coating. To achieve the optimum extraction performance, several parameters, including extraction and desorption time, pH value, adsorption temperature and stirring speed were investigated. The high-performance liquid chromatography combined with the DMIPs-SB was employed in the analysis of BPA in aqueous solution. The linear range of BPA concentration in aqueous medium was 0.0228-2.28 ng/mL with correlation coefficient of 0.9994 and the detection limit was about 6.84 × 10(-3) ng/mL based on three times ratio of signal to noise. This method was directly applied to the determination of trace BPA in milk with satisfactory results. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Polyethylenimine–Acrylamide/SiO 2 Hybrid Hydrogel Sorbent for Rare-Earth-Element Recycling from Aqueous Sources

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

Wang, Qiuming; Wilfong, Walter C.; Kail, Brian W.

Recycling rare earth elements (REEs) becomes increasingly important due to their supply vulnerability and increasing demands in industry, agriculture, and national security. Hybrid hydrogel sorbents were outstanding due to their high stability and selectivity. Organic-inorganic hybrid hydrogels were synthesized by thermo-polymerization of acrylamide onto PEI polymer chain with N,N’-methylene bisacrylamide as a crosslinker. The grafted network was evidenced by DRIFTS and XPS. The porous structure was observed by SEM. Crosslink degree, PEI grafting degree, and SiO 2 concentration were studied to optimize the REEs adsorption. The pH value of the medium greatly affected REE adsorption capacity, where the nearly neutralmore » conditions gave the strongest bonding of REEs to active sites. Moreover, kinetic studies showed that the rate-determining step of the adsorption process was chemical sorption, and that REE diffusion within micropores was the control step for, specifically, intraparticle diffusion. The adsorbents showed excellent selectivity and recyclability for REEs through 5 adsorption-desorption cycles in contact with synthetic acid mine drainage solution. A high separation toward REEs over fouling metals was achieved by using a citrate-based buffer eluent solution. This hybrid hydrogel shows promise for the recycling of REEs from aqueous solutions.« less

Novel Polyethylenimine–Acrylamide/SiO 2 Hybrid Hydrogel Sorbent for Rare-Earth-Element Recycling from Aqueous Sources

DOE PAGES

Wang, Qiuming; Wilfong, Walter C.; Kail, Brian W.; ...

2017-09-14

Recycling rare earth elements (REEs) becomes increasingly important due to their supply vulnerability and increasing demands in industry, agriculture, and national security. Hybrid hydrogel sorbents were outstanding due to their high stability and selectivity. Organic-inorganic hybrid hydrogels were synthesized by thermo-polymerization of acrylamide onto PEI polymer chain with N,N’-methylene bisacrylamide as a crosslinker. The grafted network was evidenced by DRIFTS and XPS. The porous structure was observed by SEM. Crosslink degree, PEI grafting degree, and SiO 2 concentration were studied to optimize the REEs adsorption. The pH value of the medium greatly affected REE adsorption capacity, where the nearly neutralmore » conditions gave the strongest bonding of REEs to active sites. Moreover, kinetic studies showed that the rate-determining step of the adsorption process was chemical sorption, and that REE diffusion within micropores was the control step for, specifically, intraparticle diffusion. The adsorbents showed excellent selectivity and recyclability for REEs through 5 adsorption-desorption cycles in contact with synthetic acid mine drainage solution. A high separation toward REEs over fouling metals was achieved by using a citrate-based buffer eluent solution. This hybrid hydrogel shows promise for the recycling of REEs from aqueous solutions.« less

Pre-concentration and determination of tartrazine dye from aqueous solutions using modified cellulose nanosponges.

PubMed

Shiralipour, Roohollah; Larki, Arash

2017-01-01

In this study, a new absorbent based on cellulose nanosponges modified with methyltrioctylammonium chloride (aliquat 336) was prepared and used for pre-concentration, removal and determination of tartrazine dye, using UV-vis spectrophotometry. This adsorbent was fully characterized using various instrumental techniques such as SEM, FTIR and XRD spectra. The pre-concentration and removal procedures were studied in column and batch modes, respectively. The effects of parameters such as pH of the aqueous medium, methyltrioctylammounium chloride dose, adsorbent amount, desorbing conditions and interfering ions on the adsorption of tartrazine were investigated and optimized. The fitting experimental data with conventional isotherm models revealed that the adsorption followed the Brunauer-Emmett-Teller (BET) model and the maximum adsorption capacity for tartrazine was 180mg/g with modified nanosponges. Under the optimized conditions, the calibration curve was linear over the range of 2-300ng/mL and the limit of detection was 0.15ng/mL. The relative standard deviation (RSD) for 20 and 100ng/mL of tartrazine were 3.1% and 1.5%, respectively. The proposed method was applied for pre-concentration and determination of tartrazine dye in different water samples. Copyright © 2016 Elsevier Inc. All rights reserved.

Metal ion removal from aqueous solution using physic seed hull.

PubMed

Mohammad, Masita; Maitra, Saikat; Ahmad, Naveed; Bustam, Azmi; Sen, T K; Dutta, Binay K

2010-07-15

The potential of physic seed hull (PSH), Jantropha curcas L. as an adsorbent for the removal of Cd(2+) and Zn(2+) metal ions from aqueous solution has been investigated. It has been found that the amount of adsorption for both Cd(2+) and Zn(2+) increased with the increase in initial metal ions concentration, contact time, temperature, adsorbent dosage and the solution pH (in acidic range), but decreased with the increase in the particle size of the adsorbent. The adsorption process for both metal ions on PSH consists of three stages-a rapid initial adsorption followed by a period of slower uptake of metal ions and virtually no uptake at the final stage. The kinetics of metal ions adsorption on PSH followed a pseudo-second-order model. The adsorption equilibrium data were fitted in the three adsorption isotherms-Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The data best fit in the Langmuir isotherm indication monolayer chemisorption of the metal ions. The adsorption capacity of PSH for both Zn(2+) and Cd(2+) was found to be comparable with other available adsorbents. About 36-47% of the adsorbed metal could be leached out of the loaded PSH using 0.1M HCl as the eluting medium. 2010 Elsevier B.V. All rights reserved.

Coformer selection in pharmaceutical cocrystal development: a case study of a meloxicam aspirin cocrystal that exhibits enhanced solubility and pharmacokinetics.

PubMed

Cheney, Miranda L; Weyna, David R; Shan, Ning; Hanna, Mazen; Wojtas, Lukasz; Zaworotko, Michael J

2011-06-01

Meloxicam is a nonsteroidal anti-inflammatory drug with low aqueous solubility and high permeability. Because of its low solubility under acidic conditions (e.g., pH 1-5), it can take more than 2 h for meloxicam to reach its therapeutic concentration in humans. Although the slow onset of meloxicam does not necessarily impact the current label indications, the slow onset does prevent meloxicam from its potential application for the relief of mild-to-medium-level acute pain. Pharmaceutical cocrystallization of meloxicam, which represents a promising approach to generate diverse novel crystal forms, could be used to improve the aqueous solubility and accelerate the onset of action. In this contribution, we describe how a novel method can be used for coformer selection to enable the efficient and effective development of a pharmaceutical cocrystal with desired physicochemical and pharmacokinetic properties. Aspirin was selected as the coformer for meloxicam based upon this alternative route, which combines the supramolecular synthon approach with findings in the previous pharmacological and toxicological studies of meloxicam. The resulting cocrystal of meloxicam and aspirin exhibited superior kinetic solubility and possessed the potential to significantly decrease the time required to reach the human therapeutic concentration compared with the parent drug, meloxicam. Copyright © 2010 Wiley-Liss, Inc.

Determination of rhodium in metallic alloy and water samples using cloud point extraction coupled with spectrophotometric technique

NASA Astrophysics Data System (ADS)

Kassem, Mohammed A.; Amin, Alaa S.

2015-02-01

A new method to estimate rhodium in different samples at trace levels had been developed. Rhodium was complexed with 5-(4‧-nitro-2‧,6‧-dichlorophenylazo)-6-hydroxypyrimidine-2,4-dione (NDPHPD) as a complexing agent in an aqueous medium and concentrated by using Triton X-114 as a surfactant. The investigated rhodium complex was preconcentrated with cloud point extraction process using the nonionic surfactant Triton X-114 to extract rhodium complex from aqueous solutions at pH 4.75. After the phase separation at 50 °C, the surfactant-rich phase was heated again at 100 °C to remove water after decantation and the remaining phase was dissolved using 0.5 mL of acetonitrile. Under optimum conditions, the calibration curve was linear for the concentration range of 0.5-75 ng mL-1 and the detection limit was 0.15 ng mL-1 of the original solution. The enhancement factor of 500 was achieved for 250 mL samples containing the analyte and relative standard deviations were ⩽1.50%. The method was found to be highly selective, fairly sensitive, simple, rapid and economical and safely applied for rhodium determination in different complex materials such as synthetic mixture of alloys and environmental water samples.

Functional and surface-active membranes from poly(vinylidene fluoride)-graft-poly(acrylic acid) prepared via RAFT-mediated graft copolymerization.

PubMed

Ying, L; Yu, W H; Kang, E T; Neoh, K G

2004-07-06

Poly (vinylidene fluoride) (PVDF) with "living" poly (acrylic acid) (PAAc) side chains (PVDF-g-PAAc) was prepared by reversible addition-fragmentation chain transfer (RAFT)-mediated graft copolymerization of acrylic acid (AAc) with the ozone-pretreated PVDF. The chemical composition and structure of the copolymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The copolymer could be readily cast into pH-sensitive microfiltration (MF) membranes with enriched living PAAc graft chains on the surface (including the pore surfaces) by phase inversion in an aqueous medium. The surface composition of the membranes was determined by X-ray photoelectron spectroscopy. The morphology of the membranes was characterized by scanning electron microscopy. The pore size distribution of the membranes was found to be much more uniform than that of the corresponding membranes cast from PVDF-g-PAAc prepared by the "conventional" free-radical graft copolymerization process. Most important of all, the MF membranes with surface-tethered PAAc macro chain transfer agents, or the living membrane surfaces, could be further functionalized via surface-initiated block copolymerization with N-isopropylacrylamide (NIPAAM) to obtain the PVDF-g-PAAc-b-PNIPAAM MF membranes, which exhibited both pH- and temperature-dependent permeability to aqueous media.

Degradation of quinolone antibiotic, norfloxacin, in aqueous solution using gamma-ray irradiation.

PubMed

Sayed, Murtaza; Khan, Javed Ali; Shah, Luqman Ali; Shah, Noor S; Khan, Hasan M; Rehman, Faiza; Khan, Abdur Rahman; Khan, Asad M

2016-07-01

This study reports the efficiency of gamma-ray irradiation to degrade quinolone antibiotic, norfloxacin, in aqueous solution. Laboratory batch experiments were conducted to determine the "pseudo-first" order degradation kinetics of norfloxacin in the concentration ranges of 3.4-16.1 mg L(-1) by gamma-ray irradiation. The dose constant was found to be dependent on the initial concentration of norfloxacin and gamma-ray irradiation dose rate (D r). The saturation of norfloxacin sample solutions with N2, air or N2O, and the presence of tert-butanol and 2-propanol showed that (•)OH played more crucial role in the degradation of norfloxacin. The second order rate constants of (•)OH, eaq (-), and (•)H with norfloxacin were calculated to be 8.81 × 10(9), 9.54 × 10(8), and 1.10 × 10(9) M(-1) s(-1), respectively. The effects of various additives including CO3 (2-), HCO3 (-), NO3 (-), NO2 (-), and thiourea and the pH of the medium on the degradation of norfloxacin were also investigated. Norfloxacin degradation was lower in surface water and wastewater than in ultrapure water. Several degradation byproducts of norfloxacin were identified from which the possible degradation pathway was proposed.

Focused microwave-assisted extraction combined with solid-phase microextraction and gas chromatography-mass spectrometry for the selective analysis of cocaine from coca leaves.

PubMed

Bieri, Stefan; Ilias, Yara; Bicchi, Carlo; Veuthey, Jean-Luc; Christen, Philippe

2006-04-21

An effective combination of focused microwave-assisted extraction (FMAE) with solid-phase microextraction (SPME) prior to gas chromatography (GC) is described for the selective extraction and quantitative analysis of cocaine from coca leaves (Erythroxylum coca). This approach required switching from an organic extraction solvent to an aqueous medium more compatible with SPME liquid sampling. SPME was performed in the direct immersion mode with a universal 100 microm polydimethylsiloxane (PDMS) coated fibre. Parameters influencing this extraction step, such as solution pH, sampling time and temperature are discussed. Furthermore, the overall extraction process takes into account the stability of cocaine in alkaline aqueous solutions at different temperatures. Cocaine degradation rate was determined by capillary electrophoresis using the short end injection procedure. In the selected extraction conditions, less than 5% of cocaine was degraded after 60 min. From a qualitative point of view, a significant gain in selectivity was obtained with the incorporation of SPME in the extraction procedure. As a consequence of SPME clean-up, shorter columns could be used and analysis time was reduced to 6 min compared to 35 min with conventional GC. Quantitative results led to a cocaine content of 0.70 +/- 0.04% in dry leaves (RSD <5%) which agreed with previous investigations.

Arsenic removal from aqueous solutions using Fe3O4-HBC composite: effect of calcination on adsorbents performance.

PubMed

Baig, Shams Ali; Sheng, TianTian; Sun, Chen; Xue, XiaoQin; Tan, LiSha; Xu, XinHua

2014-01-01

The presence of elevated concentration of arsenic in water sources is considered to be health hazard globally. Calcination process is known to change the surface efficacy of the adsorbent. In current study, five adsorbent composites: uncalcined and calcined Fe3O4-HBC prepared at different temperatures (400°C and 1000°C) and environment (air and nitrogen) were investigated for the adsorptive removal of As(V) and As(III) from aqueous solutions determining the influence of solution's pH, contact time, temperature, arsenic concentration and phosphate anions. Characterizations from FTIR, XRD, HT-XRD, BET and SEM analyses revealed that the Fe3O4-HBC composite at higher calcination temperature under nitrogen formed a new product (fayalite, Fe2SiO4) via phase transformation. In aqueous medium, ligand exchange between arsenic and the effective sorbent site ( = FeOOH) was established from the release of hydroxyl group. Langmuir model suggested data of the five adsorbent composites follow the order: Fe3O4-HBC-1000°C(N2)>Fe3O4-HBC (uncalcined)>Fe3O4-HBC-400°C(N2)>Fe3O4-HBC-400°C(air)>Fe3O4-HBC-1000°C(air) and the maximum As(V) and As(III) adsorption capacities were found to be about 3.35 mg g(-1) and 3.07 mg g(-1), respectively. The adsorption of As(V) and As(III) remained stable in a wider pH range (4-10) using Fe3O4-HBC-1000°C(N2). Additionally, adsorption data fitted well in pseudo-second-order (R2>0.99) rather than pseudo-first-order kinetics model. The adsorption of As(V) and As(III) onto adsorbent composites increase with increase in temperatures indicating that it is an endothermic process. Phosphate concentration (0.0l mM or higher) strongly inhibited As(V) and As(III) removal through the mechanism of competitive adsorption. This study suggests that the selective calcination process could be useful to improve the adsorbent efficiency for enhanced arsenic removal from contaminated water.

Arsenic Removal from Aqueous Solutions Using Fe3O4-HBC Composite: Effect of Calcination on Adsorbents Performance

PubMed Central

Baig, Shams Ali; Sheng, TianTian; Sun, Chen; Xue, XiaoQin; Tan, LiSha; Xu, XinHua

2014-01-01

The presence of elevated concentration of arsenic in water sources is considered to be health hazard globally. Calcination process is known to change the surface efficacy of the adsorbent. In current study, five adsorbent composites: uncalcined and calcined Fe3O4-HBC prepared at different temperatures (400°C and 1000°C) and environment (air and nitrogen) were investigated for the adsorptive removal of As(V) and As(III) from aqueous solutions determining the influence of solution's pH, contact time, temperature, arsenic concentration and phosphate anions. Characterizations from FTIR, XRD, HT-XRD, BET and SEM analyses revealed that the Fe3O4-HBC composite at higher calcination temperature under nitrogen formed a new product (fayalite, Fe2SiO4) via phase transformation. In aqueous medium, ligand exchange between arsenic and the effective sorbent site ( = FeOOH) was established from the release of hydroxyl group. Langmuir model suggested data of the five adsorbent composites follow the order: Fe3O4-HBC-1000°C(N2)>Fe3O4-HBC (uncalcined)>Fe3O4-HBC-400°C(N2)>Fe3O4-HBC-400°C(air)>Fe3O4-HBC-1000°C(air) and the maximum As(V) and As(III) adsorption capacities were found to be about 3.35 mg g−1 and 3.07 mg g−1, respectively. The adsorption of As(V) and As(III) remained stable in a wider pH range (4–10) using Fe3O4-HBC-1000°C(N2). Additionally, adsorption data fitted well in pseudo-second-order (R 2>0.99) rather than pseudo-first-order kinetics model. The adsorption of As(V) and As(III) onto adsorbent composites increase with increase in temperatures indicating that it is an endothermic process. Phosphate concentration (0.0l mM or higher) strongly inhibited As(V) and As(III) removal through the mechanism of competitive adsorption. This study suggests that the selective calcination process could be useful to improve the adsorbent efficiency for enhanced arsenic removal from contaminated water. PMID:24967645

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

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Shabir, Ghulam

2014-12-01

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

The impact of pH on side reactions for aqueous redox flow batteries based on nitroxyl radical compounds

NASA Astrophysics Data System (ADS)

Orita, A.; Verde, M. G.; Sakai, M.; Meng, Y. S.

2016-07-01

Electrochemical and UV-VIS measurements demonstrate that the pH value of a 4-hydroxy-2,2,6,6-tetramethyl-1-pipperidinyloxyl (TEMPOL) electrolyte significantly impacts its redox reversibility. The diffusion coefficient and kinetic rate constant of TEMPOL in neutral aqueous solution are determined and shown to be comparable to those of vanadium ions used for industrially utilized redox flow batteries (RFBs). RFBs that incorporate a TEMPOL catholyte and Zn-based anolyte have an average voltage of 1.46 V and an energy efficiency of 80.4% during the initial cycle, when subject to a constant current of 10 mA cm-2. We demonstrate several factors that significantly influence the concentration and capacity retention of TEMPOL upon cycling; namely, pH and atmospheric gases dissolved in electrolyte. We expand upon the known reactions of TEMPOL in aqueous electrolyte and propose several concepts to improve its electrochemical performance in a RFB. Controlling these factors will be the key to enable the successful implementation of this relatively inexpensive and environmentally friendly battery.

Removal of Copper(II) Ions in Aqueous Solutions Using Tannin-Rich Plants as Natural Bio-Adsorbents

NASA Astrophysics Data System (ADS)

Paksamut, J.; Boonsong, P.

2018-03-01

In this study, the purpose of our interest is to investigatethe adsorption behavior of copper (II) ions in aqueous solution using some tannin-rich plants as natural bio-adsorbents such as mangosteen peels (Garciniamangostana L.), cassava leaves (Manihotesculenta Crantz) and Thai copper pod leaves (Sennasiamea (Lam.)) as powder form in different dosage of adsorbent plant materials.The adsorption capacities at different pH of solution and contact time were performed.All the experiments in this studywere chosen at room temperature by batch technique. From the experimental results showed that cassava leaves gave better adsorbent properties than mangosteen peels and Thai copper pod leaves. The increasing dosage of all adsorbents and contact time have been found to increase adsorption capacities. In this respect, the adsorption capacities depend crucially on the adsorbents and contact time. The optimum pH of copper (II) ions adsorption was pH4. According to this work, it was observed that bioadsorbent materials from tannin-rich plants could be used to remove copper (II) ions from aqueous solutions.

Behavior of soluble and immobilized acid phosphatase in hydro-organic media.

PubMed

Wan, H; Horvath, C

1975-11-20

The hydrolysis of p-nitrophenyl phosphate by wheat germ acid phosphatase (orthophosphoric monoester phosphohydrolase, EC 3.1.3.2) has been investigated in mixtures of aqueous buffers with acetone, dioxane and acetonitrile. The enzyme was either in free solution or immobilized on a pellicular support which consisted of a porous carbonaceous layer on solid glass beads. The highest enzyme activity was obtained in acetone and acetonitrile mixed with citrate buffer over a wide range of organic solvent concentration. In 50% (v/v) acetone both V and Km of the immobilized enzyme were about half of the values in the neat aqueous buffer, but the Ki for inorganic phosphate was unchanged. In 50% (v/v) mixtures of various solvents and citrate buffers of different pH, the enzymic activity was found to depend on the pH of the aqueous buffer component rather than the pH of the hydro-organic mixture as measured with the glass-calomel electrode. The relatively high rates of p-nitrophenol liberation in the presence of glucose even at high organic solvent concentrations suggest that transphosphorylation is facilitated at low water activity.

Adsorption of Cu(II) from aqueous solution on sulfuric acid treated palygorskite

NASA Astrophysics Data System (ADS)

Niu, Yan-Ning; Yuan, Yuan; Gao, Wei-Xin; Qian, Sheng; Sun, Wen

2018-03-01

The absorption behavior of Cu2+ from aqueous solution on sulfuric acid treated palygorskite were investigated, the results showed that palygorskite had high absorption ability for Cu2+ from aqueous solution. Effects of the shaking time, pH and the copper ion concentration on the removal rate were discussed. The absorption behavior of Cu2+ could be well imitated by the Langmuir isothermal equation.

Sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on the surface of porous graphitized carbon

NASA Astrophysics Data System (ADS)

Savchenkova, A. S.; Buryak, A. K.; Kurbatova, S. V.

2015-09-01

The sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on porous graphitized carbon was studied. The effect of the structure of analyte molecules and the eluent composition on the characteristics of retention under the conditions of RP HPLC was analyzed. The effect of pH of the eluent on the shift of equilibrium in aqueous acetonitrile solutions was investigated.

PH adjustment of power plant cooling water with flue gas/fly ash

DOEpatents

Brady, Patrick V.; Krumhansl, James L.

2015-09-22

A system including a vessel including a heat source and a flue; a turbine; a condenser; a fluid conduit circuit disposed between the vessel, the turbine and the condenser; and a diverter coupled to the flue to direct a portion of an exhaust from the flue to contact with a cooling medium for the condenser water. A method including diverting a portion of exhaust from a flue of a vessel; modifying the pH of a cooling medium for a condenser with the portion of exhaust; and condensing heated fluid from the vessel with the pH modified cooling medium.

Influence of formulation properties on chemical stability of captopril in aqueous preparations.

PubMed

Kristensen, S; Lao, Y E; Brustugun, J; Braenden, J U

2008-12-01

The influence of various formulation properties on the chemical stability of captopril in aqueous media at pH 3 was investigated, in order to reformulate and increase the shelf-life of an oral mixture of the drug. At this pH, chemical stability is improved by an increase in drug concentration (1-5 mg/ml) and a decrease in temperature (5-36 degrees C), the latter demonstrated by a linear Arrhenius-plot. The activation energy is low (Ea = 10.2 kcal/mol), thus the Q10 value is only 1.8 in pure aqueous solutions. The degradation at the lowest concentration investigated in pure aqueous solution apparently follows zero order kinetics. The reaction order is changed at higher concentrations. We are presenting a hypothesis of intramolecular proton transfer from the thiol to the ionized carboxylic group as the initial step in the oxidative degradation pathways of captopril. Long-term stability of 1 mg/ml captopril in aqueous solutions at pH 3, stored at 36 degrees C for one year, shows that the sugar alcohol sorbitol accelerates degradation of the drug while Na-EDTA at a concentration as low as 0.01% is sufficient to stabilize these samples. Purging with N2-gas prior to storage is not essential for drug stability, as long as Na-EDTA is present. Only at a low level of Na-EDTA (0.01%) combined with a high level of sorbitol (35%), purging with N2-gas appears to have a small effect. The destabilizing effect of sugar alcohols is confirmed by accelerated degradation also in the presence of glycerol. The efficient stabilization in the presence of Na-EDTA at a low concentration indicates that the metal-ion-catalyzed oxidation pathway dominates the chemical degradation process at low pH, although several mechanisms seem to be involved depending on excipients present.

Optimisation of the expression of a Trametes versicolor laccase gene in Pichia pastoris.

PubMed

O'Callaghan, J; O'Brien, M M; McClean, K; Dobson, A D W

2002-08-01

A cDNA encoding a laccase enzyme was isolated from a Trametes versicolor cDNA library. The gene was subcloned into the Pichia pastoris expression vector pPIC3.5 and transformed into the P. pastoris strains KM71 and GS115. Laccase-secreting transformants were selected by their ability to oxidise the substrate ABTS. No difference in laccase activity was observed between culture supernatants from GS115 (proteolytic) and KM71 (nonproteolytic) strains. The presence of at least 200 microM copper was necessary for optimal laccase activity in the culture supernatants. During growth of P. pastoris on minimal medium the pH of the medium was reduced to <3.0. If alanine was added to the medium the pH reduction was not as pronounced and at alanine concentrations >0.6% w/v the pH was kept constant for >7 days. Cultures in which the pH was maintained by alanine metabolism produced higher levels of laccase activity than those grown in the absence of alanine. This study describes the development of a medium that allows convenient pH control of P. pastoris without the need for continuous neutralisation.

Removal of Mn, Fe, Ni and Cu Ions from Wastewater Using Cow Bone Charcoal

PubMed Central

Moreno, Juan Carlos; Gómez, Rigoberto; Giraldo, Liliana

2010-01-01

Cow bone charcoal (CBC) was synthesized and used for the removal of metals ions (manganese, iron, nickel and copper) from aqueous solutions. Two different adsorption models were used for analyzing the data. Adsorption capacities were determined: copper ions exhibit the greatest adsorption on cow bone charcoal because of their size and pH conditions. Adsorption capacity varies as a function of pH. Adsorption isotherms from aqueous solution of heavy metals on CBC were determined. Adsorption isotherms are consistent with Langmuir´s adsorption model. Adsorbent quantity and immersion enthalpy were studied.

The surface chemistry of multi-oxide silicates

NASA Astrophysics Data System (ADS)

Oelkers, Eric H.; Golubev, Sergey V.; Chairat, Claire; Pokrovsky, Oleg S.; Schott, Jacques

2009-08-01

The surface chemistry of natural wollastonite, diopside, enstatite, forsterite, and albite in aqueous solutions was characterized using both electrokinetic techniques and surface titrations performed for 20 min in batch reactors. Titrations performed in such reactors allow determination of both proton consumption and metal release from the mineral surface as a function of pH. The compositions, based on aqueous solution analysis, of all investigated surfaces vary dramatically with solution pH. Ca and Mg are preferentially released from the surfaces of all investigated divalent metal silicates at pH less than ˜8.5-10 but preferentially retained relative to silica at higher pH. As such, the surfaces of these minerals are Si-rich and divalent metal poor except in strongly alkaline solutions. The preferential removal of divalent cations from these surfaces is coupled to proton consumption. The number of protons consumed by the preferential removal of each divalent cation is pH independent but depends on the identity of the mineral; ˜1.5 protons are consumed by the preferential removal of each Ca atom from wollastonite, ˜3 protons are consumed by the preferential removal of each Mg or Ca atom from diopside or enstatite, and ˜4 protons are consumed by the preferential removal of each Mg from forsterite. These observations are interpreted to stem from the creation of additional 'internal' adsorption sites by the preferential removal of divalent metal cations which can be coupled to the condensation of partially detached Si. Similarly, Na and Al are preferentially removed from the albite surface at 2 > pH > 11; mass balance calculations suggest that three protons are consumed by the preferential removal of each Al atom from this surface over this entire pH range. Electrokinetic measurements on fresh mineral powders yield an isoelectric point (pH IEP) 2.6, 4.4, 3.0, 4.5, and <1, for wollastonite, diopside, enstatite, forsterite, and albite, respectively, consistent with the predominance of SiO 2 in the surface layer of all of these multi-oxide silicates at acidic pH. Taken together, these observations suggest fundamental differences between the surface chemistry of simple versus multi-oxide minerals including (1) a dependency of the number and identity of multi-oxide silicate surface sites on the aqueous solution composition, and (2) the dominant role of metal-proton exchange reactions on the reactivity of multi-oxide mineral surfaces including their dissolution rate variation with aqueous solution composition.

Experimental determination of iron isotope fractionations among Fe aq 2 + -FeSaq-Mackinawite at low temperatures: Implications for the rock record

NASA Astrophysics Data System (ADS)

Wu, Lingling; Druschel, Greg; Findlay, Alyssa; Beard, Brian L.; Johnson, Clark M.

2012-07-01

The Fe isotope fractionation factors among aqueous ferrous iron (Fe aq 2 +), aqueous FeS clusters (FeSaq), and nanoparticulate mackinawite under neutral and mildly acidic and alkaline pH conditions have been determined using the three-isotope method. Combined voltammetric analysis and geochemical modeling were used to determine the Fe speciation in the experimental systems. The equilibrium 56Fe/54Fe fractionation factor at 20 °C and pH 7 has been determined to be -0.32 ± 0.29 (2σ)‰ between Fe aq 2 + (minor FeSaq also present in the experiment) and mackinawite. This fractionation factor was essentially constant when pH was changed to 6 or 8. When equal molarity of HS- and Fe aq 2 + were added to the system, however, the isotopic fractionation at pH 7 changed to -0.64 ± 0.36 (2σ)‰, correlating with a significant increase in the proportion of FeHS+ and FeSaq. These results highlight a more important role of aqueous Fe-S speciation in the equilibrium Fe isotope fractionation factor than recognized in previous studies. The isotopic fractionation remained constant when temperature was increased from 20 °C to 35 °C for fractionation factors between Fe aq 2 + , and mackinawite and between dominantly FeHS+ and mackinawite. Synthesis experiments similar to those of Butler et al. (2005) and Guilbaud et al. (2010) at pH 4 show consistent results: over time, the aqueous Fe-mackinawite fractionation decreases but even after 38 days of aging the fractionation factor is far from the equilibrium value inferred using the three-isotope method. In contrast, at near-neutral pH the fractionation factor for the synthesis experiment reached the equilibrium value in 38 days. These differences are best explained by noting that at low pH the FeS mackinawite particles coarsen more rapidly via particle aggregation, which limits isotopic exchange, whereas at higher pH mackinawite aggregation is limited, and Fe isotope exchange occurs more rapidly, converging on the equilibrium value. These results suggest that mackinawite formed in natural environments at near-neutral or alkaline pH are unlikely to retain kinetic isotope fractionations, but are more likely to reflect equilibrium isotope compositions. This in turn has important implications for interpreting iron isotope compositions of Fe sulfides in natural systems.

Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

PubMed

Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

2015-04-21

Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

Dynamic Mass Transfer of Hemoglobin at the Aqueous/Ionic-Liquid Interface Monitored with Liquid Core Optical Waveguide.

PubMed

Chen, Xuwei; Yang, Xu; Zeng, Wanying; Wang, Jianhua

2015-08-04

Protein transfer from aqueous medium into ionic liquid is an important approach for the isolation of proteins of interest from complex biological samples. We hereby report a solid-cladding/liquid-core/liquid-cladding sandwich optical waveguide system for the purpose of monitoring the dynamic mass-transfer behaviors of hemoglobin (Hb) at the aqueous/ionic liquid interface. The optical waveguide system is fabricated by using a hydrophobic IL (1,3-dibutylimidazolium hexafluorophosphate, BBimPF6) as the core, and protein solution as one of the cladding layer. UV-vis spectra are recorded with a CCD spectrophotometer via optical fibers. The recorded spectra suggest that the mass transfer of Hb molecules between the aqueous and ionic liquid media involve accumulation of Hb on the aqueous/IL interface followed by dynamic extraction/transfer of Hb into the ionic liquid phase. A part of Hb molecules remain at the interface even after the accomplishment of the extraction/transfer process. Further investigations indicate that the mass transfer of Hb from aqueous medium into the ionic liquid phase is mainly driven by the coordination interaction between heme group of Hb and the cationic moiety of ionic liquid, for example, imidazolium cation in this particular case. In addition, hydrophobic interactions also contribute to the transfer of Hb.

Antibacterial properties of the skin mucus of the freshwater fishes, Rita rita and Channa punctatus.

PubMed

Kumari, U; Nigam, A K; Mitial, S; Mitial, A K

2011-07-01

The skin mucus of Rita rita and Channa punctatus was investigated to explore the possibilities of its antibacterial properties. Skin mucus was extracted in acidic solvents (0.1% trifluoroacetic acid and 3% acetic acid) and in triple distilled water (aqueous medium). The antibacterial activity of the mucus extracts was analyzed, using disc diffusion method, against five strains of bacteria--the Gram-positive Staphylococcus aureus and Micrococcus luteus; and the Gram negative Escherichia coli, Pseudomonas aeruginosa and Salmonella typhi. In both Rita rita and Channa punctatus, the skin mucus extracted in acidic solvents as well as in aqueous medium show antibacterial activity against Staphylococcus aureus and Micrococcus luteus. Nevertheless, the activity is higher in acidic solvents than that in aqueous medium. The acidic mucus extracts of Rita rita, show antibacterial activity against Salmonella typhi as well. The results suggest that fish skin mucus have bactericidal properties and thus play important role in the protection of fish against the invasion of pathogens. Fish skin mucus could thus be regarded as a potential source of novel antibacterial components.

Nanodispersed Suspensions of Zeolite Catalysts for Converting Dimethyl Ether into Olefins

NASA Astrophysics Data System (ADS)

Kolesnichenko, N. V.; Yashina, O. V.; Ezhova, N. N.; Bondarenko, G. N.; Khadzhiev, S. N.

2018-01-01

Nanodispersed suspensions that are effective in DME conversion and stable in the reaction zone in a three-phase system (slurry reactor) are obtained from MFI zeolite commercial samples (TsVM, IK-17-1, and CBV) in liquid media via ultrasonic treatment (UST). It is found that the dispersion medium, in which ultrasound affects zeolite commercial sample, has a large influence on particle size in the suspension. UST in the aqueous medium produces zeolite nanoparticles smaller than 50 nm, while larger particles of MFI zeolite samples form in silicone or hydrocarbon oils. Spectral and adsorption data show that when zeolites undergo UST in an aqueous medium, the acid sites are redistributed on the zeolite surface and the specific surface area of the mesopores increases. Preliminary UST in aqueous media of zeolite commercial samples (TsVM, IK-17-1, and CBV) affects the catalytic properties of MFI zeolite nanodispersed suspensions. The selectivity of samples when paraffins and olefins form is largely due to superacid sites consisting of OH groups of hydroxonium ion H3O+.

Stability and Transport of Cerium Oxide Nanoparticles in Aqueous Environment: Effect of pH, Ionic Strength, and Organic Matter.

EPA Science Inventory

This study investigated the stability and transport of CeO2 NPs under the influence of pH, natural/manmade organic matter, and electrolyte (NaCl) concentrations. In column test, effluent concentration of CeO2 NPs was close to the influent at pH 10, while most NPs deposited on san...

Short-column anion-exchange chromatography for soil and peat humic substances profiling by step-wise gradient of high pH aqueous sodium ethylenediaminetetraacetate.

PubMed

Hutta, Milan; Ráczová, Janka; Góra, Róbert; Pessl, Juraj

2015-08-21

Novel anion-exchange liquid chromatographic method with step gradient of aqueous EDTA(4-) based mobile phase elution has been developed to profile available Slovak soil humic substances and alkaline extracts of various soils. The method utilize short glass column (30mm×3mm) filled in with hydrolytically stable particles (60μm diameter) Separon HEMA-BIO 1000 having (diethylamino)ethyl functional groups. Step gradient was programmed by mixing mobile phase composed of aqueous solution of sodium EDTA (pH 12.0; 5mmolL(-1)) and mobile phase constituted of aqueous solution of sodium EDTA (pH 12.0, 500mmolL(-1)). The FLD of HSs was set to excitation wavelength 480nm and emission wavelength 530nm (λem). Separation mechanism was studied by use of selected aromatic acids related to humic acids with the aid of UV spectrophotometric detection at 280nm. The proposed method benefits from high ionic strength (I=5molL(-1)) of the end mobile phase buffer and provides high recovery of humic acids (98%). Accurate and reproducible profiling of studied humic substances, alkaline extracts of various types of soils enables straightforward characterization and differentiation of HSs in arable and forest soils. Selected model aromatic acids were used for separation mechanism elucidation. Copyright © 2015 Elsevier B.V. All rights reserved.

Aqueous photolysis of niclosamide

USGS Publications Warehouse

Graebing, P.W.; Chib, J.S.; Hubert, T.D.; Gingerich, W.H.

2004-01-01

The photodegradation of [14C]niclosamide was studied in sterile, pH 5, 7, and 9 buffered aqueous solutions under artificial sunlight at 25.0 A? 1.0 A?C. Photolysis in pH 5 buffer is 4.3 times faster than in pH 9 buffer and 1.5 times faster than in pH 7 buffer. In the dark controls, niclosamide degraded only in the pH 5 buffer. After 360 h of continuous irradiation in pH 9 buffer, the chromatographic pattern of the degradates was the same regardless of which ring contained the radiolabel. An HPLC method was developed that confirmed these degradates to be carbon dioxide and two- and four-carbon aliphatic acids formed by cleavage of both aromatic rings. Carbon dioxide was the major degradate, comprising 40% of the initial radioactivity in the 360 h samples from both labels. The other degradates formed were oxalic acid, maleic acid, glyoxylic acid, and glyoxal. In addition, in the chloronitroaniline-labeled irradiated test solution, 2-chloro-4-nitroaniline was observed and identified after 48 h of irradiation but was not detected thereafter. No other aromatic compounds were isolated or observed in either labeled test system.

Influence of pH on Drug Absorption from the Gastrointestinal Tract: A Simple Chemical Model

NASA Astrophysics Data System (ADS)

Hickman, Raymond J. S.; Neill, Jane

1997-07-01

A simple model of the gastrointestinal tract is obtained by placing ethyl acetate in contact with water at pH 2 and pH 8 in separate test tubes. The ethyl acetate corresponds to the lipid material lining the tract while the water corresponds to the aqueous contents of the stomach (pH 2) and intestine (pH 8). The compounds aspirin, paracetamol and 3-aminophenol are used as exemplars of acidic, neutral and basic drugs respectively to illustrate the influence which pH has on the distribution of each class of drug between the aqueous and organic phases of the model. The relative concentration of drug in the ethyl acetate is judged by applying microlitre-sized samples of ethyl acetate to a layer of fluorescent silica which, after evaporation of the ethyl acetate, is viewed under an ultraviolet lamp. Each of the three drugs, if present in the ethyl acetate, becomes visible as a dark spot on the silica layer. The observations made in the model system correspond well to the patterns of drug absorption from the gastrointestinal tract described in pharmacology texts and these observations are convincingly explained in terms of simple acid-base chemistry.

Infrared spectrum analysis of the dissociated states of simple amino acids.

PubMed

Sebben, Damien; Pendleton, Phillip

2014-11-11

In this work, we present detailed analyses of the dissociation of dilute aqueous solutions of glycine and of lysine over the range 18 resulted in consistent pKa values for the amino acids. Copyright © 2014 Elsevier B.V. All rights reserved.

Sorption properties of Th(IV) on the raw diatomite--effects of contact time, pH, ionic strength and temperature.

PubMed

Sheng, Guodong; Hu, Jun; Wang, Xiangke

2008-10-01

Diatomite has a number of unique physicochemical properties and has diversified industrial uses. Natural diatomite has been tested as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that sorption of Th(IV) is strongly dependent on ionic strength at pH<3, and is independent of ionic strength at pH>3. Outer-sphere complexation or ion exchange may be the main sorption mechanism of Th(IV) to diatomite at low pH values, whereas the sorption of Th(IV) at pH>3 is mainly dominated by inner-sphere complexation or precipitation. The competition for Th(IV) between aqueous or surface adsorbed anions (e.g., herein ClO(4)(-), NO(3)(-) and Cl(-)) and surface functional groups of diatomite is important for Th(IV) sorption. The thermodynamic data (DeltaH(0), DeltaS(0), DeltaG(0)) are calculated from the temperature-dependent sorption isotherms. The results suggest that sorption process of Th(IV) on diatomite is spontaneous and endothermic.

Unprecedented Selective Oxidation of Styrene Derivatives using a Supported Iron Oxide Nanocatalyst in Aqueous Medium

EPA Science Inventory

Iron oxide nanoparticles supported on mesoporous silica-type materials have been successfully utilized in the aqueous selective oxidation of alkenes under mild conditions using hydrogen peroxide as a green oxidant. Catalysts could be easily recovered after completion of the reac...

O-Allylation of phenols with allylic acetates in aqueous media using a magnetically separable catalytic system

EPA Science Inventory

Allylic ethers were synthesized in water using magnetically recoverable heterogeneous Pd catalyst via O-allylation of phenols with allylic acetates under ambient conditions. Aqueous reaction medium, easy recovery of the catalyst using an external magnet, efficient recycling, and ...

Structural response of phyllomanganates to wet aging and aqueous Mn(II)

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

Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G.

Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates weremore » studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging with Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. In conclusion, such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems, particularly trace metals and redox-active compounds.« less

Structural response of phyllomanganates to wet aging and aqueous Mn(II)

DOE PAGES

Hinkle, Margaret A. G.; Flynn, Elaine D.; Catalano, Jeffrey G.

2016-08-06

Naturally occurring Mn(IV/III) oxides are often formed through microbial Mn(II) oxidation, resulting in reactive phyllomanganates with varying Mn(IV), Mn(III), and vacancy contents. Residual aqueous Mn(II) may adsorb in the interlayer of phyllomanganates above vacancies in their octahedral sheets. The potential for interlayer Mn(II)-layer Mn(IV) comproportionation reactions and subsequent formation of structural Mn(III) suggests that aqueous Mn(II) may cause phyllomanganate structural changes that alters mineral reactivity or trace metal scavenging. Here we examine the effects of aging phyllomanganates with varying initial vacancy and Mn(III) content in the presence and absence of dissolved Mn(II) at pH 4 and 7. Three phyllomanganates weremore » studied: two exhibiting turbostratic layer stacking (δ-MnO2 with high vacancy content and hexagonal birnessite with both vacancies and Mn(III) substitutions) and one with rotationally ordered layer stacking (triclinic birnessite containing predominantly Mn(III) substitutions). Structural analyses suggest that during aging at pH 4, Mn(II) adsorbs above vacancies and promotes the formation of phyllomanganates with rotationally ordered sheets and mixed symmetries arranged into supercells, while structural Mn(III) undergoes disproportionation. These structural changes at pH 4 correlate with reduced Mn(II) uptake onto triclinic and hexagonal birnessite after 25 days relative to 48 h of reaction, indicating that phyllomanganate reactivity decreases upon aging with Mn(II), or that recrystallization processes involving Mn(II) uptake occur over 25 days. At pH 7, Mn(II) adsorbs and causes limited structural effects, primarily increasing sheet stacking in δ-MnO2. These results show that aging-induced structural changes in phyllomanganates are affected by aqueous Mn(II), pH, and initial solid-phase Mn(III) content. In conclusion, such restructuring likely alters manganese oxide reactions with other constituents in environmental and geologic systems, particularly trace metals and redox-active compounds.« less

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

NASA Astrophysics Data System (ADS)

Moon, Ellen M.; Peacock, Caroline L.

2011-11-01

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

pH Regulation of Pectate Lyase Secretion Modulates the Attack of Colletotrichum gloeosporioides on Avocado Fruits†

PubMed Central

Yakoby, Nir; Kobiler, Ilana; Dinoor, Amos; Prusky, Dov

2000-01-01

Growth of Colletotrichum gloeosporioides in pectolytic enzyme-inducing medium (PEIM) increased the pH of the medium from 3.8 to 6.5. Pectate lyase (PL) secretion was detected when the pH reached 5.8, and the level of secretion increased up to pH 6.5. PL gene (pel) transcript production began at pH 5.0 and increased up to pH 5.7. PL secretion was never detected when the pH of the inducing medium was lower than 5.8 or when C. gloeosporioides hyphae were transferred from PL-secreting conditions at pH 6.5 to pH 3.8. This behavior differed from that of polygalacturonase (PG), where pg transcripts and protein secretion were detected at pH 5.0 and continued up to 5.7. Under in vivo conditions, the pH of unripe pericarp of freshly harvested avocado (Persea americana cv. Fuerte) fruits, resistant to C. gloeosporioides attack, was 5.2, whereas in ripe fruits, when decay symptoms were expressed, the pericarp pH had increased to 6.3. Two avocado cultivars, Ardit and Ettinger, which are resistant to C. gloeosporioides attack, had pericarp pHs of less than 5.5, which did not increase during ripening. The present results suggest that host pH regulates the secretion of PL and may affect C. gloeosporioides pathogenicity. The mechanism found in avocado may have equivalents in other postharvest pathosystems and suggests new approaches for breeding against and controlling postharvest diseases. PMID:10698767

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

Casella, Amanda J.; Hylden, Laura R.; Campbell, Emily L.

Knowledge of real-time solution properties and composition is a necessity for any spent nuclear fuel reprocessing method. Metal-ligand speciation in aqueous solutions derived from the dissolved commercial spent fuel is highly dependent upon the acid concentration/pH, which influences extraction efficiency and the resulting speciation in the organic phase. Spectroscopic process monitoring capabilities, incorporated in a counter current centrifugal contactor bank, provide a pathway for on-line real-time measurement of solution pH. The spectroscopic techniques are process-friendly and can be easily configured for on-line applications, while classic potentiometric pH measurements require frequent calibration/maintenance and have poor long-term stability in aggressive chemical andmore » radiation environments. Our research is focused on developing a general method for on-line determination of pH of aqueous solutions through chemometric analysis of Raman spectra. Interpretive quantitative models have been developed and validated under the range of chemical composition and pH using a lactic acid/lactate buffer system. The developed model was applied to spectra obtained on-line during solvent extractions performed in a centrifugal contactor bank. The model predicted the pH within 11% for pH > 2, thus demonstrating that this technique could provide the capability of monitoring pH on-line in applications such as nuclear fuel reprocessing.« less

Germanium precipitation from collecting-mains liquor with tannin extract in an alkaline medium

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

Medvedev, K.P.; Mikhailov, N.F.; Petrapol'skaya, V.M.

1976-01-01

It is proposed to precipitate germanium in a slightly alkaline medium, with a neutral solution of tannin extract in aqueous alkali. The effects of various factors on germanium recovery from collecting-mains liquors have been studied.

Influence of the water molecules near surface of viral protein on virus activation process

NASA Astrophysics Data System (ADS)

Shepelenko, S. O.; Salnikov, A. S.; Rak, S. V.; Goncharova, E. P.; Ryzhikov, A. B.

2009-06-01

The infection of a cell with influenza virus comprises the stages of receptor binding to the cell membrane, endocytosis of virus particle, and fusion of the virus envelope and cell endosome membrane, which is determined by the conformational changes in hemagglutinin, a virus envelope protein, caused by pH decrease within the endosome. The pH value that induces conformation rearrangements of hemagglutinin molecule considerably varies for different influenza virus strains, first and foremost, due to the differences in amino acid structure of the corresponding proteins. The main goal of this study was to construct a model making it possible to assess the critical pH value characterizing the fusogenic activity of influenza virus hemagglutinin from the data on hemagglutinin structure and experimental verification of this model. Under this model, we assume that when the electrostatic force between interacting hemagglutinin molecules in the virus envelop exceeds a certain value, the hemagglutinin HA1 subunits are arranged so that they form a cavity sufficient for penetration of water molecules. This event leads to an irreversible hydration of the inner fragments of hemagglutinin molecule in a trimer and to the completion of conformational changes. The geometry of electrostatic field in hemagglutinin trimer was calculated taking into account the polarization effects near the interface of two dielectrics, aqueous medium and protein macromolecule. The critical pH values for the conformational changes in hemagglutinin were measured by the erythrocyte hemolysis induced by influenza virus particles when decreasing pH. The critical pH value conditionally separating the pH range into the regions with and without the conformational changes was calculated for several influenza virus H1N1 and H3N2 strains based on the data on the amino acid structure of the corresponding hemagglutinin molecules. Comparison of the theoretical and experimental values of critical pH values for influenza virus strains suggests that the proposed model of the interaction between water molecules and influenza virus envelope proteins has a high prediction efficiency.

Liquid-liquid extraction of neodymium(III) by dialkylphosphate ionic liquids from acidic medium: the importance of the ionic liquid cation.

PubMed

Rout, Alok; Kotlarska, Justyna; Dehaen, Wim; Binnemans, Koen

2013-10-21

The ionic liquids 1-hexyl-3-methylimidazolium bis(2-ethylhexyl)phosphate, [C6mim][DEHP], 1-hexyl-1-methylpyrrolidinium bis(2-ethylhexyl)phosphate, [C6mpyr][DEHP], and tetrabutylammonium bis(2-ethylhexyl)phosphate, [N4444][DEHP], were prepared and characterized using (1)H and (13)C NMR spectroscopy. The extraction behavior of neodymium(iii) from nitrate medium by these ionic liquids, diluted with the room temperature ionic liquids 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][NTf2], 1-hexyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C6mpyr][NTf2], and tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N1444][NTf2], was studied. The distribution ratio of neodymium(iii) was measured as a function of various parameters, such as pH, concentration of the ionic liquid extractant, nature of diluents, concentration of ionic liquid cations and nitrate anions in the aqueous phase. The extraction behavior was compared with that obtained for a solution of the molecular extractant bis(2-ethylhexyl)phosphoric acid (DEHPA) in an ionic liquid diluent. The extraction of neodymium(iii) in the ionic liquids [C6mim][DEHP] and [C6mpyr][DEHP] showed markedly different extraction properties in comparison with that of the quaternary ammonium analogue [N4444][DEHP], especially concerning the pH dependence of the extraction process. These results show that the extraction process can be tuned by the selection of the ionic liquid cation. The extraction experiments also included the trivalent rare-earth ions lanthanum(iii), cerium(iii), praseodymium(iii), ytterbium(iii) and yttrium(iii). Studies of the stripping behavior and the reusability of the ionic liquids were carried out, which indicate that the ionic liquids can be reused with no loss in activity.

Enzymatic method for improving the injectability of polysaccharides

DOEpatents

Griffith, William L.; Compere, Alicia L.; Holleman, James W.

1982-01-01

A method for enhancing the ability of polysaccharides in aqueous solution to flow through a porous medium comprises contacting the polysaccharides with an endoenzyme capable of hydrolyzing at least one of the linkages of the sugar units of the polysaccharides and maintaining the polysaccharides in contact with the enzyme under hydrolysis conditions for a time sufficient to decrease the tendency of the polysaccharides to plug the porous medium yet insufficient to decrease the viscosity of the aqueous polysaccharides by more than 25%. The partially hydrolyzed polysaccharides are useful as thickening agents for flooding water used to recover oil from oil-containing subterranean formations.

Best combination of promoter and micellar catalyst for the rapid conversion of sorbitol to glucose

NASA Astrophysics Data System (ADS)

Mukherjee, Kakali; Ghosh, Aniruddha; Saha, Rumpa; Sar, Pintu; Malik, Susanta; Saha, Bidyut

2014-03-01

Kinetic data for oxidation of D-sorbitol to glucose by hexavalent chromium in aqueous medium and aqueous surfactant medium (SDS, TX-100) have been reported. Effect of promoter such as PA, bipy and phenanthroline on the reaction has been investigated. The reaction is performed under pseudo first order condition with an excess of substrate over the oxidant. The reaction is first order with respect to substrate and oxidant. The micelles have a catalytic effect on the reaction. Combination of phen and TX-100 produces almost twelve times increase in rate of oxidation.

Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance

NASA Astrophysics Data System (ADS)

Zhao, H. B.; Hu, C. J.; Cheng, H. W.; Fang, J. H.; Xie, Y. P.; Fang, W. Y.; Doan, T. N. L.; Hoang, T. K. A.; Xu, J. Q.; Chen, P.

2016-05-01

A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g-1 and 96 mAh g-1 at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li+ and Na+. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0-4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries.

Titania-catalyzed radiofluorination of tosylated precursors in highly aqueous medium

DOE PAGES

Sergeev, Maxim E.; Morgia, Federica; Lazari, Mark; ...

2015-04-10

Nucleophilic radiofluorination is an efficient synthetic route to many positron-emission tomography (PET) probes, but removal of water to activate the cyclotron-produced [ 18F]fluoride has to be performed prior to reaction, which significantly increases overall radiolabeling time and causes radioactivity loss. In this paper, we demonstrate the possibility of 18F-radiofluorination in highly aqueous medium. The method utilizes titania nanoparticles, 1:1 (v/v) acetonitrile–thexyl alcohol solvent mixture, and tetra-n-butylammonium bicarbonate as a phase-transfer agent. Efficient radiolabeling is directly performed with aqueous [ 18F]fluoride without the need for a drying/azeotroping step to significantly reduce radiosynthesis time. High radiochemical purity of the target compound ismore » also achieved. Finally, the substrate scope of the synthetic strategy is demonstrated with a range of aromatic, aliphatic, and cycloaliphatic tosylated precursors.« less

Assessment of Fenton's reagent and ozonation as pre-treatments for increasing the biodegradability of aqueous diethanolamine solutions from an oil refinery gas sweetening process.

PubMed

Durán-Moreno, A; García-González, S A; Gutiérrez-Lara, M R; Rigas, F; Ramírez-Zamora, R M

2011-02-28

The aim of this work was to evaluate the efficiency of three chemical oxidation processes for increasing the biodegradability of aqueous diethanolamine solutions (aqueous DEA solutions), to be used as pre-treatments before a biological process. The raw aqueous DEA solution, sourced from a sour gas sweetening plant at a Mexican oil refinery, was first characterized by standardized physico-chemical methods. Then experiments were conducted on diluted aqueous DEA solutions to test the effects of Fenton's reagent, ozone and ozone-hydrogen peroxide on the removal of some physicochemical parameters of these solutions. Lastly, biodegradability tests based on Dissolved Organic Carbon Die Away OECD301-A, were carried out on a dilution of the raw aqueous DEA solution and on the treated aqueous DEA solutions, produced by applying the best experimental conditions determined during the aforementioned oxidation tests. Experimental results showed that for aqueous DEA solutions treated with Fenton's reagent, the best degradation rate (70%) was obtained at pH 2.8, with Fe(2+) and H(2)O(2) at doses of 1000 and 10,000 mg/L respectively. In the ozone process, the best degradation (60%) was observed in aqueous DEA solution (100 mg COD/L), using 100 mg O(3)/L at pH 5. In the ozone-hydrogen peroxide process, no COD or DOC removals were observed. The diluted spent diethanolamine solution showed its greatest increase in biodegradability after a reaction period of 28 days when treated with Fenton's reagent, but after only 15 days in the case of ozonation. Copyright © 2011 Elsevier B.V. All rights reserved.

Magnetic Silica Supported Copper: A Modular Approach to Aqueous Ullmann-type Amination of Aryl Halides

EPA Science Inventory

One-pot synthesis of magnetic silica supported copper catalyst has been described via in situ generated magnetic silica (Fe3O4@SiO2); the catalyst can be used for the efficacious amination of aryl halides in aqueous medium under microwave irradiation.

Impact of lysozyme on stability mechanism of nanozirconia aqueous suspension

NASA Astrophysics Data System (ADS)

Szewczuk-Karpisz, Katarzyna; Wiśniewska, Małgorzata

2016-08-01

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

Electrostatic Interactions Influence Protein Adsorption (but Not Desorption) at the Silica-Aqueous Interface.

PubMed

McUmber, Aaron C; Randolph, Theodore W; Schwartz, Daniel K

2015-07-02

High-throughput single-molecule total internal reflection fluorescence microscopy was used to investigate the effects of pH and ionic strength on bovine serum albumin (BSA) adsorption, desorption, and interfacial diffusion at the aqueous-fused silica interface. At high pH and low ionic strength, negatively charged BSA adsorbed slowly to the negatively charged fused silica surface. At low pH and low ionic strength, where BSA was positively charged, or in solutions at higher ionic strength, adsorption was approximately 1000 times faster. Interestingly, neither surface residence times nor the interfacial diffusion coefficients of BSA were influenced by pH or ionic strength. These findings suggested that adsorption kinetics were dominated by energy barriers associated with electrostatic interactions, but once adsorbed, protein-surface interactions were dominated by short-range nonelectrostatic interactions. These results highlight the ability of single-molecule techniques to isolate elementary processes (e.g., adsorption and desorption) under steady-state conditions, which would be impossible to measure using ensemble-averaging methods.

Removal of methyl orange and methylene blue dyes from aqueous solution using lala clam (Orbicularia orbiculata) shell

NASA Astrophysics Data System (ADS)

Eljiedi, Arwa Alseddig Ahmed; Kamari, Azlan

2017-05-01

Textile effluents are considered as potential sources of water pollution because they contain toxic dyes. In the present study, lala clam shell was used as an alternative low-cost adsorbent for the removal of two harmful dyes, namely methyl orange (MO) and methylene blue (MB) from aqueous solution. Batch adsorption studies were carried out by varying experimental parameters such as solution pH, initial concentration and adsorbent dosage. The optimum pH values for MO and MB removal were pH 2.0 and pH 8.0, respectively. At an initial MO and MB concentration of 20 mg/L, the maximum removal percentage of MO and MB were 18.9 % and 81.3 %, respectively. The adsorption equilibrium data were correlated with both Langmuir and Freundlich isotherm models. The biomass adsorbent was characterised using Field Emission Scanning Electron Microscope (FESEM) and Fourier Transform Infrared Spectrometer (FTIR). Results from this study suggest that lala clam shell, a fishery waste, can be beneficial for water treatment.