Strengthening of the Coordination Shell by Counter Ions in Aqueous Th 4+ Solutions

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

Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.

The presence of counter ions in solutions containing highly charged metal cations can trigger processes such as ion-pair formation, hydrogen bond breakages and subsequent reformation, and ligand exchanges. In this work, it is shown how halide (Cl-, Br-) and perchlorate (ClO4-) anions affect the strength of the primary solvent coordination shells around Th4+ using explicit solvent and finite temperature ab initio molecular dynamics modeling methods. The 9-fold solvent geometry was found to be the most stable hydration structure in each aqueous solution. Relative to the dilute aqueous solution, the presence of the counter ions did not significantly alter the geometrymore » of the primary hydration shell. However, the free energy analyses indicated that the 10-fold hydrated states were thermodynamically accessible in dilute and bromide aqueous solutions within 1 kcal/mol. Analysis of the results showed that the hydrogen bond lifetimes were longer and solvent exchange energy barriers were larger in solutions with counter ions in comparison with the solution with no counter ions. This implies that the presence of the counter ions induces a strengthening of the Th4+ hydration shell.« less

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.

Potential of the octanol-water partition coefficient (logP) to predict the dermal penetration behaviour of amphiphilic compounds in aqueous solutions.

PubMed

Korinth, Gintautas; Wellner, Tanja; Schaller, Karl Heinz; Drexler, Hans

2012-11-23

Aqueous amphiphilic compounds may exhibit enhanced skin penetration compared with neat compounds. Conventional models do not predict this percutaneous penetration behaviour. We investigated the potential of the octanol-water partition coefficient (logP) to predict dermal fluxes for eight compounds applied neat and as 50% aqueous solutions in diffusion cell experiments using human skin. Data for seven other compounds were accessed from literature. In total, seven glycol ethers, three alcohols, two glycols, and three other chemicals were considered. Of these 15 compounds, 10 penetrated faster through the skin as aqueous solutions than as neat compounds. The other five compounds exhibited larger fluxes as neat applications. For 13 of the 15 compounds, a consistent relationship was identified between the percutaneous penetration behaviour and the logP. Compared with the neat applications, positive logP were associated with larger fluxes for eight of the diluted compounds, and negative logP were associated with smaller fluxes for five of the diluted compounds. Our study demonstrates that decreases or enhancements in dermal penetration upon aqueous dilution can be predicted for many compounds from the sign of logP (i.e., positive or negative). This approach may be suitable as a first approximation in risk assessments of dermal exposure. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Permanent physico-chemical properties of extremely diluted aqueous solutions of homeopathic medicines.

PubMed

Elia, V; Baiano, S; Duro, I; Napoli, E; Niccoli, M; Nonatelli, L

2004-07-01

The purpose of this study was to obtain information about the influence of successive dilutions and succussions on the water structure. 'Extremely diluted solutions' (EDS) are solutions obtained through the iteration of two processes: dilution in stages of 1:100 and succussion, typically used in homeopathic medicine. The iteration is repeated until extreme dilutions are reached, so that the chemical composition of the solution is identical to that of the solvent. Nine different preparations, were studied from the 3cH to 30cH (Hahnemannian Centesimal Dilution). Four of those were without the active principle (potentized water). Two different active principles were used: Arsenicum sulphuratum rubrum (ASR), As4S4, 2,4-dichlorophenoxyacetic acid (2,4D). The solvents were: a solution of sodium bicarbonate and of silicic acid at 5 x 10(-5) M (mol/l) each, and solutions of sodium bicarbonate 5 x 10(-5), 7.5 x 10(-5) and 10 x 10(-5) M (mol/l) in double-distilled water. The containers were Pyrex glass to avoid the release of alkaline oxide and silica from the walls. Conductivity measurements of the solutions were carried out as a function of the age of the potencies. We found increases of electrical conductivity compared to untreated solvent. Successive dilution and succussion can permanently alter the physico-chemical properties of the aqueous solvent. But we also detected changes in physio-chemical parameters with time. This has not previously been reported. The modification of the solvent could provide an important support to the validity of homeopathic medicine, that employs 'medicines without molecules'. The nature of the phenomena here described remains still unexplained, nevertheless some significant experimental results were obtained.

Enzyme stabilization by glass-derived silicates in glass-exposed aqueous solutions

USGS Publications Warehouse

Ives, J.A.; Moffett, J.R.; Arun, P.; Lam, D.; Todorov, T.I.; Brothers, A.B.; Anick, D.J.; Centeno, J.; Namboodiri, M.A.A.; Jonas, W.B.

2010-01-01

Objectives: To analyze the solutes leaching from glass containers into aqueous solutions, and to show that these solutes have enzyme activity stabilizing effects in very dilute solutions. Methods: Enzyme assays with acetylcholine esterase were used to analyze serially succussed and diluted (SSD) solutions prepared in glass and plastic containers. Aqueous SSD preparations starting with various solutes, or water alone, were prepared under several conditions, and tested for their solute content and their ability to affect enzyme stability in dilute solution. Results: We confirm that water acts to dissolve constituents from glass vials, and show that the solutes derived from the glass have effects on enzymes in the resultant solutions. Enzyme assays demonstrated that enzyme stability in purified and deionized water was enhanced in SSD solutions that were prepared in glass containers, but not those prepared in plastic. The increased enzyme stability could be mimicked in a dose-dependent manner by the addition of silicates to the purified, deionized water that enzymes were dissolved in. Elemental analyses of SSD water preparations made in glass vials showed that boron, silicon, and sodium were present at micromolar concentrations. Conclusions: These results show that silicates and other solutes are present at micromolar levels in all glass-exposed solutions, whether pharmaceutical or homeopathic in nature. Even though silicates are known to have biological activity at higher concentrations, the silicate concentrations we measured in homeopathic preparations were too low to account for any purported in vivo efficacy, but could potentially influence in vitro biological assays reporting homeopathic effects. ?? 2009 The Faculty of Homeopathy.

Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

DOEpatents

Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.; Presley, Derek J.

2001-01-01

A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

MINTEQA2

EPA Science Inventory

MINTEQA2 is a equilibrium speciation model that can be used to calculate the equilibrium composition of dilute aqueous solutions in the laboratory or in natural aqueous systems. The model is useful for calculating the equilibrium mass distribution among dissolved species, adsorb...

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.

Dilute acid pretreatment of corncob for efficient sugar production

Treesearch

G.S. Wang; Jae-Won Lee; Junyong Zhu; Thomas W. Jeffries

2011-01-01

Aqueous dilute acid pretreatments of corncob were conducted using cylindrical pressure vessels in an oil bath. Pretreatments were conducted in a temperature range of 160–190 °C with acid-solution-to-solid-corncob ratio of 2. The acid concentration (v/v) in the pretreatment solution was varied from 0% to 0.7%, depending on temperature. This gives acid charge on ovendry-...

Surface tension of dilute alcohol-aqueous binary fluids: n-Butanol/water, n-Pentanol/water, and n-Hexanol/water solutions

NASA Astrophysics Data System (ADS)

Cheng, Kuok Kong; Park, Chanwoo

2017-07-01

Surface tension of pure fluids, inherently decreasing with regard to temperature, creates a thermo-capillary-driven (Marangoni) flow moving away from a hot surface. It has been known that few high-carbon alcohol-aqueous solutions exhibit an opposite behavior of the surface tension increasing with regard to temperature, such that the Marangoni flow moves towards the hot surface (self-rewetting effect). We report the surface tensions of three dilute aqueous solutions of n-Butanol, n-Pentanol and n-Hexanol as self-rewetting fluids measured for ranges of alcohol concentration (within solubility limits) and fluid temperatures (25-85 °C). A maximum bubble pressure method using a leak-tight setup was used to measure the surface tension without evaporation losses of volatile components. It was found from this study that the aqueous solutions with higher-carbon alcohols exhibit a weak self-rewetting behavior, such that the surface tensions remain constant or slightly increases above about 60 °C. These results greatly differ from the previously reported results showing a strong self-rewetting behavior, which is attributed to the measurement errors associated with the evaporation losses of test fluids during open-system experiments.

Hypochlorous acid-activated carbon: an oxidizing agent capable of producing hydroxylated polychlorinated biphenyls.

PubMed Central

Voudrias, E A; Larson, R A; Snoeyink, V L; Chen, A S; Stapleton, P L

1986-01-01

Granular activated carbon (GAC), in the presence of dilute aqueous hypochlorite solutions typical of those used in water treatment, was converted to a reagent capable of carrying out free-radical coupling reactions and other oxidations of dilute aqueous solutions of phenols. The products included biphenyls with chlorine and hydroxyl substitution (hydroxylated polychlorinated biphenyls). For example, 2,4-dichlorophenol, a common constituent of wastewaters and also natural waters treated with hypochlorite, was converted to 3,5,5'trichloro-2,4'-dihydroxybiphenyl and several related compounds in significant amounts. It is possible that these products pose more of a health hazard than either the starting phenols or the unhydroxylated polychlorinated biphenyl derivatives. PMID:3028770

Calorimetric study of water's two glass transitions in the presence of LiCl

PubMed Central

Ruiz, Guadalupe N.; Amann-Winkel, Katrin; Bove, Livia E.; Corti, Horacio R.

2018-01-01

A DSC study of dilute glassy LiCl aqueous solutions in the water-dominated regime provides direct evidence of a glass-to-liquid transition in expanded high density amorphous (eHDA)-type solutions. Similarly, low density amorphous ice (LDA) exhibits a glass transition prior to crystallization to ice Ic. Both glass transition temperatures are independent of the salt concentration, whereas the magnitude of the heat capacity increase differs. By contrast to pure water, the glass transition endpoint for LDA can be accessed in LiCl aqueous solutions above 0.01 mole fraction. Furthermore, we also reveal the endpoint for HDA's glass transition, solving the question on the width of both glass transitions. This suggests that both equilibrated HDL and LDL can be accessed in dilute LiCl solutions, supporting the liquid–liquid transition scenario to understand water's anomalies. PMID:29442107

An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range.

PubMed

Dutcher, Cari S; Ge, Xinlei; Wexler, Anthony S; Clegg, Simon L

2013-04-18

In previous studies (Dutcher et al. J. Phys. Chem. C 2011, 115, 16474-16487; 2012, 116, 1850-1864), we derived equations for the Gibbs energy, solvent and solute activities, and solute concentrations in multicomponent liquid mixtures, based upon expressions for adsorption isotherms that include arbitrary numbers of hydration layers on each solute. In this work, the long-range electrostatic interactions that dominate in dilute solutions are added to the Gibbs energy expression, thus extending the range of concentrations for which the model can be used from pure liquid solute(s) to infinite dilution in the solvent, water. An equation for the conversion of the reference state for solute activity coefficients to infinite dilution in water has been derived. A number of simplifications are identified, notably the equivalence of the sorption site parameters r and the stoichiometric coefficients of the solutes, resulting in a reduction in the number of model parameters. Solute concentrations in mixtures conform to a modified Zdanovskii-Stokes-Robinson mixing rule, and solute activity coefficients to a modified McKay-Perring relation, when the effects of the long-range (Debye-Hückel) term in the equations are taken into account. Practical applications of the equations to osmotic and activity coefficients of pure aqueous electrolyte solutions and mixtures show both satisfactory accuracy from low to high concentrations, together with a thermodynamically reasonable extrapolation (beyond the range of measurements) to extreme concentration and to the pure liquid solute(s).

Boiling characteristics of dilute polymer solutions and implications for the suppression of vapor explosions

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

Bang, K.H.; Kim, M.H.

Quenching experiments of hot solid spheres in dilute aqueous solutions of polyethylene oxide polymer have been conducted for the purpose of investigating the physical mechanisms of the suppression of vapor explosions in this polymer solutions. Two spheres of 22.2mm and 9.5mm-diameter were tested in the polymer solutions of various concentrations at 30{degrees}C. Minimum film boiling temperature ({Delta}T{sub MFB}) in this highly-subcooled liquid rapidly decreased from over 700{degrees}c for pure water to about 150{degrees}C as the polymer concentration was increased up to 300ppm for 22.2mm sphere, and it decreased to 350{degrees}C for 9.5mm sphere. This rapid reduction of minimum film boilingmore » temperature in the PEO aqueous solutions can explain its ability of the suppression of spontaneous vapor explosions. The ability of suppression of vapor explosions by dilute polyethylene oxide solutions against an external trigger pressure was tested by dropping molten tin into the polymer solutions at 25{degrees}C. It was observed that in 50ppm solutions more mass fragmented than in pure water, but produced weaker explosion pressures. The explosion was completely suppressed in 300ppm solutions with the external trigger. The debris size distributions of fine fragments smaller than 0.7mm were shown almost identical regardless of the polymer concentrations.« less

Environmental Transport and Fate Process Descriptors for Propellant Compounds

DTIC Science & Technology

2006-06-01

compositional changes that occur when propellant pellets and flakes are immersed in stirred aqueous solutions for 0 to 220 hours. ERDC/EL TR-06-7 2... solution , NQ concen- tration remains constant in heated, dilute hydrochloric acid, but will hydrolyze to NH3, N2O, and CO2 at pH greater than 10...with values between 36 and 300 mg/L (Table 2). Hydrolysis of DPA was inferred from decreased Daphnia toxicity when aged (30-day) aqueous solutions

Structural properties of aqueous metoprolol succinate solutions. Density, viscosity, and refractive index at 311 K

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Kalyankar, T. M.

2013-06-01

Density, viscosity and refractive index of aqueous solutions of metoprolol succinate of different concentrations (0.005-0.05 mol dm-3) were measured at 38°C. Apparent molar volume of resultant solutions were calculated and fitted to the Masson's equation and apparent molar volume at infinite dilution was determined graphically. Viscosity data of solutions has been fitted to the Jone-Dole equation and viscosity A- and B-coefficients were determined graphically. Physicochemical data obtained were discussed in terms of molecular interactions.

DYNAMIC CONDUCTIVITY MEASUREMENTS IN HUMIC AND FULVIC ACID SOLUTIONS. (R828158)

EPA Science Inventory

Conductivity changes of dilute aqueous humic and fulvic acids solutions were monitored after the addition of small quantities of Cu, Cd, Pb, and Zn. The solutions were stirred at a constant and reproducible rate, and measurements proceeded until stable conductivities were atta...

Photoluminescence Spectroscopy of Rhodamine 800 Aqueous Solution and Dye-Doped Polymer Thin-Film: Concentration and Solvent Effects

NASA Astrophysics Data System (ADS)

Le, Khai Q.; Dang, Ngo Hai

2018-05-01

This paper investigates solvent and concentration effects on photoluminescence (PL) or fluorescence properties of Rhodamine 800 (Rho800) dyes formed in aqueous solution and polymer thin-film. Various commonly used organic solvents including ethanol, methanol and cyclopentanol were studied at a constant dye concentration. There were small changes in the PL spectra for the different solvents in terms of PL intensity and peak wavelength. The highest PL intensity was observed for cyclopentanol and the lowest for ethanol. The longest peak wavelength was found in cyclopentanol (716 nm) and the shortest in methanol (708 nm). Dissolving the dye powder in the methanol solvent and varying the dye concentration in aqueous solution from the high concentrated solution to highly dilute states, the wavelength tunability was observed between about 700 nm in the dilute state and 730 nm at high concentration. Such a large shift may be attributed to the formation of dye aggregates. Rho800 dye-doped polyvinyl alcohol (PVA) polymer thin-film was further investigated. The PL intensity of the dye in the form of thin-film is lower than that of the aqueous solution form whereas the peak wavelength is redshifted due to the presence of PVA. This paper, to our best knowledge, reports the first study of spectroscopic properties of Rho800 dyes in various forms and provides useful guidelines for production of controllable organic luminescence sources.

New findings on the influence of carbon surface curvature on energetics of benzene adsorption from aqueous solutions

NASA Astrophysics Data System (ADS)

Wiśniewski, Marek; Werengowska-Ciećwierz, Karolina; Terzyk, Artur P.

2015-01-01

Immersional measurements of benzene adsorption form dilute aqueous solutions are reported for the first time together with the measurements of the enthalpy of benzene adsorption. Benzene adsorption from aqueous solution is an exothermic process. Our results show that with the decrease in carbon nanotube diameter the process becomes more exothermic, and the enthalpy of benzene adsorption correlates with the BET surface area and the electrostatic field strength of the tubes. Possible explanations of the results are proposed, and the most probable is that the change in carbon hybridisation with curvature leads to creation of stronger energetically adsorption sites than observed for graphite.

Vibrational dephasing and frequency shifts of hydrogen-bonded pyridine-water complexes

NASA Astrophysics Data System (ADS)

Kalampounias, A. G.; Tsilomelekis, G.; Boghosian, S.

2015-01-01

In this paper we present the picosecond vibrational dynamics and Raman shifts of hydrogen-bonded pyridine-water complexes present in aqueous solutions in a wide concentration range from dense to extreme dilute solutions. We studied the vibrational dephasing and vibrational frequency modulation by calculating time correlation functions of vibrational relaxation by fits in the frequency domain. The concentration induced variations in bandwidths, band frequencies and characteristic dephasing times have been estimated and interpreted as effects due to solute-solvent interactions. The time-correlation functions of vibrational dephasing were obtained for the ring breathing mode of both "free" and hydrogen-bonded pyridine molecules and it was found that sufficiently deviate from the Kubo model. There is a general agreement in the whole concentration range with the modeling proposed by the Rothschild approach, which applies to complex liquids. The results have shown that the reorientation of pyridine aqueous solutions is very slow and hence in both scattering geometries only vibrational dephasing is probed. It is proposed that the spectral changes depend on the perturbations induced by the dynamics of the water molecules in the first hydration cell and water in bulk, while at extreme dilution conditions, the number of bulk water molecules increases and the interchange between molecules belonging to the first hydration cell may not be the predominant modulation mechanism. The evolution of several parameters, such as the characteristic times, the percentage of Gaussian character in the peak shape and the a parameter are indicative of drastic variations at extreme dilution revealing changes in the vibrational relaxation of the pyridine complexes in the aqueous environment. The higher dilution is correlated to diffusion of water molecules into the reference pyridine system in agreement with the jump diffusion model, while at extreme dilutions, almost all pyridine molecules are elaborated in hydrogen bonding. The results are discussed in the framework of the current phenomenological status of the field.

ELECTRODEPOSITION OF PLUTONIUM

DOEpatents

Wolter, F.J.

1957-09-10

A process of electrolytically recovering plutonium from dilute aqueous solutions containing plutonium ions comprises electrolyzing the solution at a current density of about 0.44 ampere per square centimeter in the presence of an acetate-sulfate buffer while maintaining the pH of the solution at substantially 5 and using a stirred mercury cathode.

"Structure-making" ability of Na+ in dilute aqueous solution: an ONIOM-XS MD simulation study.

PubMed

Sripa, Pattrawan; Tongraar, Anan; Kerdcharoen, Teerakiat

2013-02-28

An ONIOM-XS MD simulation has been performed to characterize the "structure-making" ability of Na(+) in dilute aqueous solution. The region of most interest, i.e., a sphere that includes Na(+) and its surrounding water molecules, was treated at the HF level of accuracy using LANL2DZ and DZP basis sets for the ion and waters, respectively, whereas the rest of the system was described by classical pair potentials. Detailed analyzes of the ONIOM-XS MD trajectories clearly show that Na(+) is able to order the structure of waters in its surroundings, forming two prevalent Na(+)(H(2)O)(5) and Na(+)(H(2)O)(6) species. Interestingly, it is observed that these 5-fold and 6-fold coordinated complexes can convert back and forth with some degrees of flexibility, leading to frequent rearrangements of the Na(+) hydrates as well as numerous attempts of inner-shell water molecules to interchange with waters in the outer region. Such a phenomenon clearly demonstrates the weak "structure-making" ability of Na(+) in aqueous solution.

Removal of uranium from aqueous HF solutions

DOEpatents

Pulley, Howard; Seltzer, Steven F.

1980-01-01

This invention is a simple and effective method for removing uranium from aqueous HF solutions containing trace quantities of the same. The method comprises contacting the solution with particulate calcium fluoride to form uranium-bearing particulates, permitting the particulates to settle, and separting the solution from the settled particulates. The CaF.sub.2 is selected to have a nitrogen surface area in a selected range and is employed in an amount providing a calcium fluoride/uranium weight ratio in a selected range. As applied to dilute HF solutions containing 120 ppm uranium, the method removes at least 92% of the uranium, without introducing contaminants to the product solution.

Nanosized solvent superstructures in ultramolecular aqueous dilutions: twenty years' research using water proton NMR relaxation.

PubMed

Demangeat, Jean-Louis

2013-04-01

proton nuclear magnetic resonance (NMR) relaxation times T1, T2, T1/T2 are sensitive to motion and organization of water molecules. Especially, increase in T1/T2 reflects a higher degree of structuring. My purpose was to look at physical changes in water in ultrahigh aqueous dilutions. Samples were prepared by iterative centesimal (c) dilution with vigorous agitation, ranging between 3c and 24c (Avogadro limit 12c). Solutes were silica-lactose, histamine, manganese-lactose. Solvents were water, NaCl 0.15 M or LiCl 0.15 M. Solvents underwent strictly similar, simultaneous dilution/agitation, for each level of dilution, as controls. NMR relaxation was studied within 0.02-20 MHz. No changes were observed in controls. Increasing T1 and T1/T2 were found in dilutions, which persisted beyond 9c (manganese-lactose), 10c (histamine) and 12c (silica-lactose). For silica-lactose in LiCl, continuous decrease in T2 with increase in T1/T2 within the 12c-24c range indicated growing structuring of water despite absence of the initial solute. All changes vanished after heating/cooling. These findings were interpreted in terms of nanosized (>4-nm) supramolecular structures involving water, nanobubbles and ions, if any. Additional study of low dilutions of silica-lactose revealed increased T2 and decreased T1/T2 compared to solvent, within the 10(-3)-10(-6) range, reflecting transient solvent destructuring. This could explain findings at high dilution. Proton NMR relaxation demonstrated modifications of the solvent throughout the low to ultramolecular range of dilution. The findings suggested the existence of superstructures that originate stereospecifically around the solute after an initial destructuring of the solvent, developing more upon dilution and persisting beyond 12c. Copyright © 2013 The Faculty of Homeopathy. Published by Elsevier Ltd. All rights reserved.

The Electrostatic Screening Length in Concentrated Electrolytes Increases with Concentration.

PubMed

Smith, Alexander M; Lee, Alpha A; Perkin, Susan

2016-06-16

According to classical electrolyte theories interactions in dilute (low ion density) electrolytes decay exponentially with distance, with the Debye screening length the characteristic length scale. This decay length decreases monotonically with increasing ion concentration due to effective screening of charges over short distances. Thus, within the Debye model no long-range forces are expected in concentrated electrolytes. Here we reveal, using experimental detection of the interaction between two planar charged surfaces across a wide range of electrolytes, that beyond the dilute (Debye-Hückel) regime the screening length increases with increasing concentration. The screening lengths for all electrolytes studied-including aqueous NaCl solutions, ionic liquids diluted with propylene carbonate, and pure ionic liquids-collapse onto a single curve when scaled by the dielectric constant. This nonmonotonic variation of the screening length with concentration, and its generality across ionic liquids and aqueous salt solutions, demonstrates an important characteristic of concentrated electrolytes of substantial relevance from biology to energy storage.

Short-time microscopic dynamics of aqueous methanol solutions

NASA Astrophysics Data System (ADS)

Kalampounias, A. G.; Tsilomelekis, G.; Boghosian, S.

2012-12-01

In this paper we present the picosecond vibrational dynamics of a series of methanol aqueous solutions over a wide concentration range from dense to dilute solutions. We studied the vibrational dephasing and vibrational frequency modulation by calculating the time correlation functions of vibrational relaxation by fits in the frequency domain. This method is applied to aqueous methanol solutions xMeOH-(1 - x)H2O, where x = 0, 0.2, 0.4, 0.6, 0.8 and 1. The important finding is that the vibrational dynamics of the system become slower with increasing methanol concentration. The removal of many-body effects by having the molecules in less-crowded environments seems to be the key factor. The interpretation of the vibrational correlation function in the context of Kubo theory, which is based on the assumption that the environmental modulation arises from a single relaxation process and applied to simple liquids, is inadequate for all solutions studied. We found that the vibrational correlation functions of the solutions over the whole concentration range comply with the Rothschild approach, assuming that the environmental modulation is described by a stretched exponential decay. The evolution of the dispersion parameter α with dilution indicates the deviation of the solutions from the model simple liquid and the results are discussed in the framework of the current phenomenological status of the field.

Iodine retention during evaporative volume reduction

DOEpatents

Godbee, H.W.; Cathers, G.I.; Blanco, R.E.

1975-11-18

An improved method for retaining radioactive iodine in aqueous waste solutions during volume reduction is disclosed. The method applies to evaporative volume reduction processes whereby the decontaminated (evaporated) water can be returned safely to the environment. The method generally comprises isotopically diluting the waste solution with a nonradioactive iodide and maintaining the solution at a high pH during evaporation.

The geochemical evolution of aqueous sodium in the Black Creek Aquifer, Horry and Georgetown counties, South Carolina

USGS Publications Warehouse

Zack, Allen L.; Roberts, Ivan

1988-01-01

The Black Creek aquifer contains dilute seawater near the North Carolina State line, probably the result of incomplete flushing of ancient seawater. Data do not indicate that the dilute seawater has migrated toward areas of fresh ground-water withdrawals. The concentration of chloride in ground-water samples ranges from 5 to 720 milligrams per liter and that of sodium from 160 to 690 milligrams per liter. Ion-exchange reactions (sodium for calcium and fluoride for hydroxyl) occur with the calcium carbonate dissolution reaction which produces calcium, bicarbonate, and hydroxyl ions. The reaction sequence and stoichiometry result in an aqueous solution in which the sum of bicarbonate and chloride equivalents per liter is equal to the equivalents per liter of sodium. Calcium ions are exchanged for sodium ions derived from sodium-rich clays upgradient of the dilute seawater. The cation-exchange reaction equilibrates at a sodium concentration of 280 milligrams per liter. Amounts of sodium greater than 280 milligrams per liter are contributed from dilute seawater. The cation-exchange reaction approaches an equilibrium which represents a mass-action limit in terms of the ratio of sodium to calcium in solution versus the ratio of exchangeable sodium to calcium on clay surfaces. Where the limit of calcium carbonate solubility is approached and dissolution ceases, some precipitation of calcite probably takes place. The dissolution of calcite exposes fossil shark teeth which release fluoride ions to the ground water through anion exchange with aqueous hydroxyl ions.

The prediction of the flash point for binary aqueous-organic solutions.

PubMed

Liaw, Horng-Jang; Chiu, Yi-Yu

2003-07-18

A mathematical model, which may be used for predicting the flash point of aqueous-organic solutions, has been proposed and subsequently verified by experimentally-derived data. The results reveal that this model is able to precisely predict the flash point over the entire composition range of binary aqueous-organic solutions by way of utilizing the flash point data pertaining to the flammable component. The derivative of flash point with respect to composition (solution composition effect upon flash point) can be applied to process safety design/operation in order to identify as to whether the dilution of a flammable liquid solution with water is effective in reducing the fire and explosion hazard of the solution at a specified composition. Such a derivative equation was thus derived based upon the flash point prediction model referred to above and then verified by the application of experimentally-derived data.

Dilute acid/metal salt hydrolysis of lignocellulosics

DOEpatents

Nguyen, Quang A.; Tucker, Melvin P.

2002-01-01

A modified dilute acid method of hydrolyzing the cellulose and hemicellulose in lignocellulosic material under conditions to obtain higher overall fermentable sugar yields than is obtainable using dilute acid alone, comprising: impregnating a lignocellulosic feedstock with a mixture of an amount of aqueous solution of a dilute acid catalyst and a metal salt catalyst sufficient to provide higher overall fermentable sugar yields than is obtainable when hydrolyzing with dilute acid alone; loading the impregnated lignocellulosic feedstock into a reactor and heating for a sufficient period of time to hydrolyze substantially all of the hemicellulose and greater than 45% of the cellulose to water soluble sugars; and recovering the water soluble sugars.

Adsorptive separation in bioprocess engineering

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

Huang, E.W.Y.

1987-01-01

The invention and development of an energy-efficient separation technique for recovery of desired chemicals from biomass conversion would greatly enhance the economic viability of this bioprocess. Adsorptive separation of several chemicals from aqueous solution was studied in this thesis. The desired species were recovered from the dilute aqueous solution by using crosslinked polyvinylpyridine resin to effect selective sorption. The sorbed chemicals were then removed from the resin by either thermal regeneration or elution with some appropriate desorbents. The effects of temperature, pH value, and solute concentration on resin swelling were investigated. The adsorption equilibrium isotherms, resin capacities and resin selectivitiesmore » of methanol, ethanol, 1-propanol, isopropanol, glycerol, acetone, 1-butanol, tert-butanol, and 2,3-butanediol were determined to study the homologies. Furthermore, acetic acid, butyric acid, hydrochloric acid, lactic acid, and sulfuric acid were recovered from very dilute aqueous solutions. The concentration of the sorbed chemical in the stationary phase can be many times higher than in the mobile phase for some acids. Finally, different types of equilibrium isotherms were used to fit the experimental data. A mathematical model was developed by using the theory of interference to predict the breakthrough curves and the process efficiency to provide information for large-scale process design and development.« less

Aqueous Phase Non Enzymatic Chemistry of Cyanide, Formaldehyde and RNH2

NASA Technical Reports Server (NTRS)

Lerner, Narcinda R.; Chang, Sherwood (Technical Monitor)

1994-01-01

It is postulated that amino acids were produced on the early earth from dilute aqueous solution of cyanide, carbonyls and ammonia (the Strecker synthesis RNH2 + R"R""C=O + KCN yields H-N(R)-C(R")(R"")-CO2H. We have studied the products obtained from dilute aqueous solutions of cyanide, formaldehyde (R"=R""=H), ammonia (R=H) and amino acids. Solutions in the pH range from 8 to 10. at room temperature and at reactant concentrations from 0.001 M to 0.3 M have been studied. With R= H product yields were low (less than 3%). Only with R"=R""=H and R represented by the following: CH2CO2H (glycine); CH(CH3)CO2H (alanine); CH(CH2CH3)CO2H (a-amino n=butyric acids); C(CH3)2(CO2H) (a-aminoisobutyric acid); CH(CH(CH3)2)CO2H (valine); and CH(CH2CO2H)CO2H (aspartic acid), were product yields high (greater than 10%). The yields of glycine were larger with R not equal to H. The prebiotic implications of these findings will be discussed.

Challenges in analysis of high-molar mass dextrans: comparison of HPSEC, AsFlFFF and DOSY NMR spectroscopy.

PubMed

Maina, Ndegwa Henry; Pitkänen, Leena; Heikkinen, Sami; Tuomainen, Päivi; Virkki, Liisa; Tenkanen, Maija

2014-01-01

Dilute solutions of various dextran standards, a high-molar mass (HMM) commercial dextran from Leuconostoc spp., and HMM dextrans isolated from Weissella confusa and Leuconostoc citreum were analyzed with high-performance size-exclusion chromatography (HPSEC), asymmetric flow field-flow fractionation (AsFlFFF), and diffusion-ordered NMR spectroscopy (DOSY). HPSEC analyses were performed in aqueous and dimethyl sulfoxide (DMSO) solutions, while only aqueous solutions were utilized in AsFlFFF and DOSY. The study showed that all methods were applicable to dextran analysis, but differences between the aqueous and DMSO-based solutions were obtained for HMM samples. These differences were attributed to the presence of aggregates in aqueous solution that were less prevalent in DMSO. The study showed that DOSY provides an estimate of the size of HMM dextrans, though calibration standards may be required for each experimental set-up. To our knowledge, this is the first study utilizing these three methods in analyzing HMM dextrans. Copyright © 2013 Elsevier Ltd. All rights reserved.

PRODUCTION OF TRIFLUOROACETIC ACID COMPOUNDS

DOEpatents

Haworth, W.N.; Stacey, M.

1949-08-30

A process is described for the preparation of trifluoroacetic acid. Acetone vapor diluted wlth nitrogen and fluorine also diluted with nltrogen are fed separately at a temperature of about 210 deg C into a reaction vessel containing a catalyst mass selected from-the group consisting of silver and gold. The temperature in the reaction vessel is maintained in the range of 200 deg to 250 deg C. The reaction product, trifluoroacetyl fluoride, is absorbed in aqueous alkali solution. Trifluoroacetic acid is recovered from the solution by acidification wlth an acid such as sulfuric followed by steam distillation.

Rate constant for reaction of vitamin C with protein radicals in γ-irradiated aqueous albumin solution at 295 K

NASA Astrophysics Data System (ADS)

Miyazaki, Tetsuo; Yoshimura, Toru; Mita, Kazuya; Suzuki, Keiji; Watanabe, Masami

1995-02-01

When an aqueous solution of albumin (0.1 kg dm -3) is irradiated by γ-rays at 295 K, albumin radicals with a long lifetime are observed by ESR. The reaction of vitamin C with the albumin radicals has been studied at 295 K in the albumin solution, which is considered as a model of cells. The rate constant for the reaction of vitamin C with the albumin radicals was measured as 0.014 dm 3 mol -1 s -1, which is much smaller than the reported rate constants (10 6-10 10 dm 3 mol -1 s -1) for the reaction of vitamin C with radicals in a dilute aqueous solution. The small rate constant for the reaction of vitamin C is ascribed to the reaction in polymer coils in the albumin solution, since vitamin C and albumin radicals diffuse very slowly in the coils.

SnS2 Thin Film Deposition by Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Jaber, Abdallah Yahia; Alamri, Saleh Noaiman; Aida, Mohammed Salah

2012-06-01

Tin disulfide (SnS2) thin films have been synthesized using a simplified spray pyrolysis technique using a perfume atomizer. The films were deposited using two different solutions prepared by the dilution of SnCl2 and thiourea in distilled water and in methanol. The obtained films have a microcrystalline structure. The film deposited using methanol as the solvent is nearly stochiometric SnS2 with a spinel phase having a (001) preferential orientation. The film prepared with an aqueous solution is Sn-rich. Scanning electronic microscopy (SEM) images reveal that the film deposited with the aqueous solution is rough and is formed with large wires. However, the film deposited with methanol is dense and smooth. Conductivity measurements indicate that the aqueous solution leads to an n-type semiconductor, while methanol leads to a p-type semiconductor.

CONTINUOUS CHELATION-EXTRACTION PROCESS FOR THE SEPARATION AND PURIFICATION OF METALS

DOEpatents

Thomas, J.R.; Hicks, T.E.; Rubin, B.; Crandall, H.W.

1959-12-01

A continuous process is presented for separating metal values and groups of metal values from each other. A complex mixture. e.g., neutron-irradiated uranium, can be resolved into component parts. In the present process the values are dissolved in an acidic solution and adjusted to the proper oxidation state. Thenceforth the solution is contacted with an extractant phase comprising a fluorinated beta -diketone in an organic solvent under centain pH conditions whereupon plutonium and zirconium are extracted. Plutonium is extracted from the foregoing extract with reducing aqueous solutions or under specified acidic conditions and can be recovered from the aqueous solution. Zirconium is then removed with an oxalic acid aqueous phase. The uranium is recovered from the residual original solution using hexone and hexone-diketone extractants leaving residual fission products in the original solution. The uranium is extracted from the hexone solution with dilute nitric acid. Improved separations and purifications are achieved using recycled scrub solutions and the "self-salting" effect of uranyl ions.

Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution: II. Polycondensations

NASA Technical Reports Server (NTRS)

Kolb, V.; Orgel, L. E.

1995-01-01

We have prepared a [32P]-labeled oligonucleotide probe carrying a ureido (-NH-CO-NH2) function at its 3'-terminus. This labeled oligomer was used to study polycondensations of urea and formaldehyde and of various phenols and formaldehyde in aqueous solution. The formation of formaldehyde copolymers attached to the amido-function of the probe was monitored by gel electrophoresis. Our results are generally in agreement with those obtained using conventional techniques. Our method is suitable for monitoring potentially prebiotic polycondensation reactions involving formaldehyde.

Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution. 2: Polycondensations

NASA Technical Reports Server (NTRS)

Kolb, Vera; Orgel, Leslie E.

1995-01-01

We have prepared a (P-32)-labeled oligonucleotide probe carrying a ureido (-NH-CO-NH2) function at its 3'-terminus. This labeled oligomer was used to study polycondensations of urea and formaldehyde and of various phenols and formaldehyde in aqueous solution. The formation of formaldehyde copolymers attached to the amido-function of the probe was monitored by gel electrophoresis. Our results are generally in agreement with those obtained using conventional techniques. Our method is suitable for monitoring potentially prebiotic polycondensation reactions involving formaldehyde.

Pretreatment of dried distillers grains with solubles by soaking in aqueous ammonia and subsequent enzymatic/dilute acid hydrolysis to produce fermentable sugars

USDA-ARS?s Scientific Manuscript database

Dried distillers grains with solubles (DDGS), a co-product of corn ethanol production in the dry-grind process, was pretreated by soaking in aqueous ammonia (SAA) using a 15% w/w NH4OH solution at a solid:liquid ratio of 1:10. The effect of pretreatment on subsequent enzymatic hydrolysis was studied...

Assessment of boric acid and borax using the IEHR evaluative process for assessing human developmental and reproductive toxicity of agents

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

Moore, J.A.

This document presents an evaluation of the reproductive and developmental effects of boric acid, H3BO3 (CAS Registry No. 10043-35-3) and disodium tetraborate decahydrate or borax, Na2B4O2O(CAS Registry No. 1303-96-4). The element, boron, does not exist naturally. In dilute aqueous solution and at physiological pH (7.4), the predominant species in undissociated boric acid (greater than 98%), irrespective of whether the initial material was boric acid of borax. Therefore, it is both useful and correct to compare exposures and dosages to boric acid and borax in terms of `boron equivalents`, since both materials form equivalent species in dilute aqueous solution with similarmore » systemic effects. In order to be clear in this document, the term `boron` will refer to `boron equivalents` or percent boron in boric acid and borax.« less

Structural and dynamical properties of the V(3+) ion in dilute aqueous solution: An ab initio QM/MM molecular dynamics simulation.

PubMed

Kritayakornupong, Chinapong

2009-12-01

A hybrid ab initio QM/MM molecular dynamics simulation at the Hartree-Fock level has been performed to investigate structural and dynamical parameters of the V(3+) ion in dilute aqueous solution. A distorted octahedral structure with the average V(3+)-O distance of 1.99 A is evaluated from the QM/MM simulation, which is in good agreement with the X-ray data. Several structural parameters such as angular distribution functions, theta- and tilt-angle distributions have been determined to obtain the full description of the hydration structure of the hydrated V(3+). The Jahn-Teller distortions of the V(3+) ion are pronounced in the QM/MM simulation. The mean residence time of 14.5 ps is estimated for the ligand exchange processes in the second hydration shell. (c) 2009 Wiley Periodicals, Inc.

Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

NASA Technical Reports Server (NTRS)

Kolb, V.; Orgel, L. E.; Miller, S. L. (Principal Investigator)

1994-01-01

We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

Application of Molecular Dynamics Simulations in Molecular Property Prediction II: Diffusion Coefficient

PubMed Central

Wang, Junmei; Hou, Tingjun

2011-01-01

In this work, we have evaluated how well the General AMBER force field (GAFF) performs in studying the dynamic properties of liquids. Diffusion coefficients (D) have been predicted for 17 solvents, 5 organic compounds in aqueous solutions, 4 proteins in aqueous solutions, and 9 organic compounds in non-aqueous solutions. An efficient sampling strategy has been proposed and tested in the calculation of the diffusion coefficients of solutes in solutions. There are two major findings of this study. First of all, the diffusion coefficients of organic solutes in aqueous solution can be well predicted: the average unsigned error (AUE) and the root-mean-square error (RMSE) are 0.137 and 0.171 ×10−5 cm−2s−1, respectively. Second, although the absolute values of D cannot be predicted, good correlations have been achieved for 8 organic solvents with experimental data (R2 = 0.784), 4 proteins in aqueous solutions (R2 = 0.996) and 9 organic compounds in non-aqueous solutions (R2 = 0.834). The temperature dependent behaviors of three solvents, namely, TIP3P water, dimethyl sulfoxide (DMSO) and cyclohexane have been studied. The major MD settings, such as the sizes of simulation boxes and with/without wrapping the coordinates of MD snapshots into the primary simulation boxes have been explored. We have concluded that our sampling strategy that averaging the mean square displacement (MSD) collected in multiple short-MD simulations is efficient in predicting diffusion coefficients of solutes at infinite dilution. PMID:21953689

Fragmentation-based QM/MM simulations: length dependence of chain dynamics and hydrogen bonding of polyethylene oxide and polyethylene in aqueous solutions.

PubMed

Li, Hui; Li, Wei; Li, Shuhua; Ma, Jing

2008-06-12

Molecular fragmentation quantum mechanics (QM) calculations have been combined with molecular mechanics (MM) to construct the fragmentation QM/MM method for simulations of dilute solutions of macromolecules. We adopt the electrostatics embedding QM/MM model, where the low-cost generalized energy-based fragmentation calculations are employed for the QM part. Conformation energy calculations, geometry optimizations, and Born-Oppenheimer molecular dynamics simulations of poly(ethylene oxide), PEO(n) (n = 6-20), and polyethylene, PE(n) ( n = 9-30), in aqueous solution have been performed within the framework of both fragmentation and conventional QM/MM methods. The intermolecular hydrogen bonding and chain configurations obtained from the fragmentation QM/MM simulations are consistent with the conventional QM/MM method. The length dependence of chain conformations and dynamics of PEO and PE oligomers in aqueous solutions is also investigated through the fragmentation QM/MM molecular dynamics simulations.

Spontaneous Self-Assembly of Polymeric Nanoparticles in Aqueous Media: New Insights From Microfluidics, In Situ Size Measurements, and Individual Particle Tracking.

PubMed

Li, Xue; Salzano, Giuseppina; Zhang, Jiwen; Gref, Ruxandra

2017-01-01

Supramolecular cyclodextrin-based nanoparticles (CD-NPs) mediated by host-guest interactions have gained increased popularity because of their "green" and simple preparation procedure, as well as their versatility in terms of inclusion of active molecules. Herein, we showed that original CD-NPs of around 100 nm are spontaneously formed in water, by mixing 2 aqueous solutions of (1) a CD polymer and (2) dextran grafted with benzophenone moieties. For the first time, CD-NPs were instantaneously produced in a microfluidic interaction chamber by mixing 2 aqueous solutions of neutral polymers, in the absence of organic solvents. Whatever the mixing conditions, CD-NPs with narrow size distributions were immediately formed upon contact of the 2 polymeric solutions. In situ size measurements showed that the CD-NPs were spontaneously formed. Nanoparticle tracking analysis was used to individually follow the CD-NPs in their Brownian motions, to gain insights on their size distribution, concentration, and stability on extreme dilution. Nanoparticle tracking analysis allowed to establish that despite their non-covalent nature, and the CD-NPs were remarkably stable in terms of concentration and size distribution, even on extreme dilution (concentrations as low as 100 ng/mL). Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Ultrasonic speed, densities and viscosities of xylitol in water and in aqueous tyrosine and phenylalanine solutions at different temperatures

NASA Astrophysics Data System (ADS)

Ali, A.; Bidhuri, P.; Uzair, S.

2014-07-01

Ultrasonic speed u, densities ρ and viscosities η of xylitol in water and in 0.001 m aqueous l-tyrosine (Tyr) and l-phenylalanine (Phe) have been measured at different temperatures. From the density and ultrasonic speed measurements apparent molar isentropic compression κ_{φ}, apparent molar isentropic compressions at infinite dilution κ_{{S,φ}}0 , experimental slope S K , hydration number n H , transfer partial molar isentropic compressibility Δ_{tr} κ_{{S,φ}}0 of xylitol from water to aqueous Tyr and Phe have been obtained. From the viscosity data, B-coefficient and B-coefficient of transfer Δ tr B of xylitol from water to aqueous Phe and Tyr at different temperatures have also been estimated. Gibbs free energies of activation of viscous flow per mole of solvent Δ μ 1 0# and per mole of solute Δ μ 2 0# have been calculated by using Feakins transition state theory for the studied systems. The calculated parameters have been interpreted in terms of solute-solute and solute-solvent interactions and hydration behavior of xylitol.

Cross-linked polyvinyl pyridine coated glass particle catalyst support and aqueous composition or polyvinyl pyridine adducted microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1981-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Protein Aggregation and Molecular Crowding: Perspectives From Multiscale Simulations.

PubMed

Musiani, F; Giorgetti, A

2017-01-01

Cells are extremely crowded environments, thus the use of diluted salted aqueous solutions containing a single protein is too simplistic to mimic the real situation. Macromolecular crowding might affect protein structure, folding, shape, conformational stability, binding of small molecules, enzymatic activity, interactions with cognate biomolecules, and pathological aggregation. The latter phenomenon typically leads to the formation of amyloid fibrils that are linked to several lethal neurodegenerative diseases, but that can also play a functional role in certain organisms. The majority of molecular simulations performed before the last few years were conducted in diluted solutions and were restricted both in the timescales and in the system dimensions by the available computational resources. In recent years, several computational solutions were developed to get close to physiological conditions. In this review we summarize the main computational techniques used to tackle the issue of protein aggregation both in a diluted and in a crowded environment. © 2017 Elsevier Inc. All rights reserved.

Hydration and ion pair formation in aqueous Y(3+)-salt solutions.

PubMed

Rudolph, Wolfram W; Irmer, Gert

2015-11-14

Raman spectra of aqueous yttrium perchlorate, triflate (trifluoromethanesulfonate), chloride and nitrate solutions were measured over a broad concentration range (0.198-3.252 mol L(-1)). The spectra range from low wavenumbers to 4200 cm(-1). A very weak mode at 384 cm(-1) with a full width at half height at 50 cm(-1) in the isotropic spectrum suggests that the Y(3+)- octa-aqua ion is thermodynamically stable in dilute perchlorate solutions (∼0.5 mol L(-1)) while in concentrated perchlorate solutions outer-sphere ion pairs and contact ion pairs are formed. The octa-hydrate, [Y(OH2)8](3+) was also detected in a 1.10 mol L(-1) aqueous Y(CF3SO3)3 solution. Furthermore, very weak and broad depolarized modes could be detected which are assigned to [Y(OH2)8](3+)(aq) at 100, 166, 234 and 320 cm(-1) confirming that a hexa-hydrate is not compatible with the hydrated species in solution. In yttrium chloride solutions contact ion pair formation was detected over the measured concentration range from 0.479-3.212 mol L(-1). The contact ion pairs in YCl3(aq) are fairly weak and disappear with dilution. At a concentration <0.2 mol L(-1) almost all complexes have disappeared. In YCl3 solutions, with additional HCl, chloro-complexes of the type [Y(OH2)8-nCln](+3-n) (n = 1,2) are formed. The Y(NO3)3(aq) spectra were compared with a spectrum of a dilute NaNO3 solution and it was concluded that in Y(NO3)3(aq) over the concentration range from 2.035-0.198 mol L(-1) nitrato-complexes [Y(OH2)8-n(NO3)ln](+3-n) (n = 1,2) are formed. The nitrato-complexes are weak and disappear with dilution <0.1 mol L(-1). DFT geometry optimizations and frequency calculations are reported for both the yttrium-water cluster in the gas phase and the cluster within a polarizable continuum model in order to implicitly describe the presence of the bulk solvent. The bond distance and angle for the square antiprismatic cluster geometry of [Y(OH2)8](3+) with the polarizable dielectric continuum is in good agreement with data from recent structural experimental measurements. The DFT frequency of the Y-O stretching mode of the [Y(OH2)8](3+) cluster, in a polarizable continuum, is at 372 cm(-1) in satisfactory agreement with the experimental value.

SILANE-BASED CONVERSION COATING FOR METALS

EPA Science Inventory

For the past three years, a project to develop new pretreatment rinses for metals was carried out by the U.S. Environmental Protection Agency and the University of Cincinnati. The project involved optimization of laboratory rinses with dilute aqueous solutions organofunctional s...

A concentrated electrolyte for zinc hexacyanoferrate electrodes in aqueous rechargeable zinc-ion batteries

NASA Astrophysics Data System (ADS)

Kim, D.; Lee, C.; Jeong, S.

2018-01-01

In this study, a concentrated electrolyte was applied in an aqueous rechargeable zinc-ion battery system with a zinc hexacyanoferrate (ZnHCF) electrode to improve the electrochemical performance by changing the hydration number of the zinc ions. To optimize the active material, ZnHCF was synthesized using aqueous solutions of zinc nitrate with three different concentrations. The synthesized materials exhibited some differences in structure, crystallinity, and particle size, as observed by X-ray diffraction and scanning electron microscopy. Subsequently, these well-structured materials were applied in electrochemical tests. A more than two-fold improvement in the charge/discharge capacities was observed when the concentrated electrolyte was used instead of the dilute electrolyte. Additionally, the cycling performance observed in the concentrated electrolyte was superior to that in the dilute electrolyte. This improvement in the electrochemical performance may result from a decrease in the hydration number of the zinc ions in the concentrated electrolyte.

Evaporation-based Ge/.sup.68 Ga Separation

DOEpatents

Mirzadeh, Saed; Whipple, Richard E.; Grant, Patrick M.; O'Brien, Jr., Harold A.

1981-01-01

Micro concentrations of .sup.68 Ga in secular equilibrium with .sup.68 Ge in strong aqueous HCl solution may readily be separated in ionic form from the .sup.68 Ge for biomedical use by evaporating the solution to dryness and then leaching the .sup.68 Ga from the container walls with dilute aqueous solutions of HCl or NaCl. The chloro-germanide produced during the evaporation may be quantitatively recovered to be used again as a source of .sup.68 Ga. If the solution is distilled to remove any oxidizing agents which may be present as impurities, the separation factor may easily exceed 10.sup.5. The separation is easily completed and the .sup.68 Ga made available in ionic form in 30 minutes or less.

PROCESS FOR SEPARATING AMERICIUM AND CURIUM FROM RARE EARTH ELEMENTS

DOEpatents

Baybarz, R.D.; Lloyd, M.H.

1963-02-26

This invention relates to methods of separating americium and curium values from rare earth values. In accordance with the invention americium, curium, and rare earth values are sorbed on an anion exchange resin. A major portion of the rare earth values are selectively stripped from the resin with a concentrated aqueous solution of lithium chloride, and americium, curium, and a minor portion of rare earth values are then stripped from the resin with a dilute aqueous solution of lithium chloride. The americium and curium values are further purified by increasing the concentration of lithium chloride in the solution to at least 8 molar and selectively extracting rare earth values from the resulting solution with a monoalkylphosphoric acid. (AEC)

COBALT-60 Gamma Irradiation of Shrimp.

NASA Astrophysics Data System (ADS)

Sullivan, Nancy L. B.

Meta- and ortho-tyrosine were measured using high performance liquid chromatography (HPLC) in conjunction with electrochemical detection in shrimp irradiated using cobalt-60 gamma radiation in the absorbed dose range 0.8 to 6.0 kGy, in nonirradiated shrimp, and in bovine serum albumin (BSA) irradiated in dilute aqueous solution at 25.0 kGy. Ortho-tyrosine was measured in nonirradiated BSA. Para-, meta-, and ortho-tyrosine were measured using HPLC in conjunction with uv-absorption detection in dilute aqueous solutions of phenylalanine irradiated in the absorbed dose range 16.0 to 195.0 kGy. The measured yields of tyrosine isomers were approximately linear as a function of absorbed dose in shrimp, and in irradiated solutions of phenylalanine up to 37.0 kGy. The occurrence of meta- and ortho-tyrosine, which had formerly been considered unique radiolytic products, has not previously been reported in nonirradiated shrimp or BSA. The conventional hydrolyzation and analytical techniques used in the present study to measure meta- and ortho-tyrosine may provide the basis for a method to detect and determine the dose used in food irradiation.

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).

ACTIVATED CARBON PROCESS FOR TREATMENT OF WASTEWATERS CONTAINING HEXAVALENT CHROMIUM

EPA Science Inventory

The removal of hexavalent chromium, Cr(VI), from dilute aqueous solution by an activated carbon process has been investigated. Two removal mechanisms were observed; hexavalent chromium species were removed by adsorption onto the interior carbon surface and/or through reduction to...

SEPARATING HAFNIUM FROM ZIRCONIUM

DOEpatents

Lister, B.A.J.; Duncan, J.F.

1956-08-21

A dilute aqueous solution of zirconyl chloride which is 1N to 2N in HCl is passed through a column of a cation exchange resin in acid form thereby absorbing both zirconium and associated hafnium impurity in the mesin. The cation exchange material with the absorbate is then eluted with aqueous sulfuric acid of a O.8N to 1.2N strength. The first portion of the eluate contains the zirconium substantially free of hafnium.

Gas nanobubbles and aqueous nanostructures: the crucial role of dynamization.

PubMed

Demangeat, Jean-Louis

2015-04-01

Nanobubbles (NBs) have been a subject of intensive research over the past decade. Their peculiar characteristics, including extremely low buoyancy, longevity, enhanced solubility of oxygen in water, zeta potentials and burst during collapse, have led to many applications in the industrial, biological and medical fields. NBs may form spontaneously from dissolved gas but the process is greatly enhanced by gas supersaturation and mechanical actions such as dynamization. Therefore, the formation of NBs during the preparation of homeopathic dilutions under atmospheric pressure cannot be ignored. I suggested in 2009 the involvement of NBs in nanometric superstructures revealed in high dilutions using NMR relaxation. These superstructures seemed to increase in size with dilution, well into the ultramolecular range (>12c). I report here new experiments that confirm the involvement of NBs and prove the crucial role of dynamization to create superstructures specific to the solute. A second dynamization was shown to enhance or regenerate these superstructures. I postulate that superstructures result from a nucleation process of NBs around the solute, with shells of highly organized water (with ions and silicates if any) which protect the solute against out-diffusion and behave as nucleation centres for further dilution steps. The sampling tip may play an active role by catching the superstructures and thus carry the encaged solute across the dilution range, possibly up to the ultramolecular range. The superstructures were not observed at low dilution, probably because of a destructuring of the solvent by the solute and/or of an inadequate gas/solute ratio. Copyright © 2015 The Faculty of Homeopathy. Published by Elsevier Ltd. All rights reserved.

Radiolysis aspects of the aqueous self-cooled blanket concept and the problem of tritium extraction

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

Bruggeman, A.; Snykers, M.; DeRegge, P.

1988-09-01

In the Aqueous Self-Cooled Blanket (ASCB) concept, an aqueous /sup 6/Li solution in a metallic structure is used as a fusion reactor shielding-breeding blanket. Radiolysis effects could be very important for the design and the use of an ASCB. Although many aspects of the radiation chemistry of water and dilute aqueous solutions are now reasonably well understood, it is not possible to predict the radiochemical behaviour of the concentrated candidate ASCB solutions quantitatively. However, by means of a worst case calculation for a possible ASCB for the Next European Torus (NET) it is shown that even with an important ratemore » of water decomposition the ASCB concept is still workable. Gas bubbles and explosive mixtures can be avoided by increasing the pressure in the neutron irradiated zone and by extracting and/or recombining the radiolytically produced hydrogen and oxygen. This could require an additional inert gas loop, which could also be used as part of the tritium extraction installation.« less

Composite polarizability and the construction of an invariant function of refraction and mass density for solutions.

PubMed

Szymański, Krzysztof; Petrache, Horia I

2011-04-14

Re-examination of dynamical ionic polarizabilities in water solutions leads to the formulation of a solution function r(c), which combines the indices of refraction and mass densities of solutions. We show that this function should be independent of ionic concentration if the composite polarizabilities of hydrated solute clusters are constant. Using existing experimental data for a number of aqueous salt and organic solutions, we find that the r(c) function is either constant or varies linearly with concentration, in most cases with negligible slope. We use this function to compare ionic polarizabilities of crystals and aqueous solutions and to highlight how solute polarizabilities at infinite dilution scale with the electronic valence shell of cations and anions. The proposed r(c) function can be used generally to verify the consistency of experimental measurements and of simulation results, and it provides a test of assumptions in current theories of ionic polarizabilities.

Heterogeneity of activated carbons in adsorption of aniline from aqueous solutions

NASA Astrophysics Data System (ADS)

Podkościelny, P.; László, K.

2007-08-01

The heterogeneity of activated carbons (ACs) prepared from different precursors is investigated on the basis of adsorption isotherms of aniline from dilute aqueous solutions at various pH values. The APET carbon prepared from polyethyleneterephthalate (PET), as well as, commercial ACP carbon prepared from peat were used. Besides, to investigate the influence of carbon surface chemistry, the adsorption was studied on modified carbons based on ACP carbon. Its various oxygen surface groups were changed by both nitric acid and thermal treatments. The Dubinin-Astakhov (DA) equation and Langmuir-Freundlich (LF) one have been used to model the phenomenon of aniline adsorption from aqueous solutions on heterogeneous carbon surfaces. Adsorption-energy distribution (AED) functions have been calculated by using an algorithm based on a regularization method. Analysis of these functions for activated carbons studied provides important comparative information about their surface heterogeneity.

Templated cocrystallization of cholesterol and phytosterols from microemulsions

NASA Astrophysics Data System (ADS)

Rozner, Shoshana; Popov, Inna; Uvarov, Vladimir; Aserin, Abraham; Garti, Nissim

2009-08-01

A major cause of cardiovascular disease is high cholesterol (CH) levels in the blood, a potential solution to which is the intake of phytosterols (PS) known as CH-reducing agents. One mechanism proposed for PS activity is the mutual cocrystallization of CH and PS from dietary mixed micelles (DMM), a process that removes excess CH from the transporting micelles. In this study, microemulsions (MEs) were used both as a model system for cocrystallization mimicking DMM and as a possible alternative pathway, based on the competitive solubilization of CH and PS, to reduce solubilized CH transport levels from the ME. The effects of different CH/PS ratios, aqueous dilution, and lecithin-based MEs on sterol crystallization were studied. The precipitated crystals from the ME-loaded system with PS alone and from that loaded with 1:1 or 1:3 CH/PS mixtures were significantly influenced by ME microstructure and by dilution with aqueous phase (X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) results). No new polymorphic structures were detected apart from the corresponding sterol hydrates. Mixed crystal morphology and the habit of the precipitated sterols were strongly affected by the CH/PS ratio and the structures of the diluted ME. As the amount of PS in the mixture increased or as the ME aqueous dilution proceeded, precipitated crystal shape became more needle-like. The mixed sterols seemed to be forming eutectic solids.

Stability of piritramide in patient-controlled analgesia (PCA) solutions.

PubMed

Remane, D; Scriba, G; Meissner, W; Hartmann, M

2009-06-01

For patient controlled analgesia, syringes with solutions of 1.5 mg/ml piritramide in 0.9% aqueous sodium chloride are used. The physical and chemical stability for dilutions of the commercially available preparation of piritramide is limited up to 72 hours by the manufacturer. Since application duration for patient-controlled analgesia can exceed that limited time, stability was investigated by HPLC. Our results show that these solutions are chemically stable over a time period of 60 days.

Partial molar volumes and viscosities of aqueous hippuric acid solutions containing LiCl and MnCl2 · 4H2O at 303.15 K

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Tawde, P. D.; Zinjade, A. B.; Shaikh, A. I.

2015-09-01

Density (ρ) and viscosity (η) of aqueous hippuric acid (HA) solutions containing LiCl and MnCl2 · 4H2O have been studied at 303.15 K in order to understand volumetric and viscometric behavior of these systems. Apparent molar volume (φv) of salts were calculated from density data and fitted to Massons relation and partial molar volumes (φ{v/0}) at infinite dilution were determined. Relative viscosity data has been used to determine viscosity A and B coefficients using Jones-Dole relation. Partial molar volume and viscosity coefficients have been discussed in terms of ion-solvent interactions and overall structural fittings in solution.

Fabrication of Amperometric Glucose Sensor Using Glucose Oxidase-Cellulose Nanofiber Aqueous Solution.

PubMed

Yasuzawa, Mikito; Omura, Yuya; Hiura, Kentaro; Li, Jiang; Fuchiwaki, Yusuke; Tanaka, Masato

2015-01-01

Cellulose nanofiber aqueous solution, which remained virtually transparent for more than one week, was prepared by using the clear upper layer of diluted cellulose nanofiber solution produced by wet jet milling. Glucose oxidase (GOx) was easily dissolved in this solution and GOx-immobilized electrode was easily fabricated by simple repetitious drops of GOx-cellulose solution on the surface of a platinum-iridium electrode. Glucose sensor properties of the obtained electrodes were examined in phosphate buffer solution of pH 7.4 at 40°C. The obtained electrode provided a glucose sensor response with significantly high response speed and good linear relationship between glucose concentration and response current. After an initial decrease of response sensitivity for a few days, relatively constant sensitivity was obtained for about 20 days. Nevertheless, the influence of electroactive compounds such as ascorbic acid, uric acid and acetoaminophen were not negletable.

A viscometric approach of pH effect on hydrodynamic properties of human serum albumin in the normal form.

PubMed

Monkos, Karol

2013-03-01

The paper presents the results of viscosity determinations on aqueous solutions of human serum albumin (HSA) at isoelectric point over a wide range of concentrations and at temperatures ranging from 5°C to 45°C. On the basis of a modified Arrhenius equation and Mooney's formula some hydrodynamic parameters were obtained. They are compared with those previously obtained for HSA in solutions at neutral pH. The activation energy and entropy of viscous flow and the intrinsic viscosity reach a maximum value, and the effective specific volume, the self-crowding factor and the Huggins coefficient a minimum value in solutions at isoelectric point. Using the dimensionless parameter [η]c, the existence of three ranges of concentrations: diluted, semi-diluted and concentrated, was shown. By applying Lefebvre's relation for the relative viscosity in the semi-dilute regime, the Mark-Houvink-Kuhn-Sakurada (MHKS) exponent was established. The analysis of the results obtained from the three ranges of concentrations showed that both conformation and stiffness of HSA molecules in solutions at isoelectric point and at neutral pH are the same.

SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

DOEpatents

Wilson, A.S.

1961-05-01

A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

Enhancements of Nucleate Boiling Under Microgravity Conditions

NASA Technical Reports Server (NTRS)

Zhang, Nengli; Chao, David F.; Yang, W. J.

2000-01-01

This paper presents two means for enhancing nucleate boiling and critical heat flux under microgravity conditions: using micro-configured metal-graphite composites as the boiling surface and dilute aqueous solutions of long-chain alcohols as the working fluid. In the former, thermocapillary force induced by temperature difference between the graphite-fiber tips and the metal matrix plays an important role in bubble detachment. Thus boiling-heat transfer performance does not deteriorate in a reduced-gravity environment. In the latter cases, the surface tension-temperature gradient of the long-chain alcohol solutions turns positive as the temperature exceeds a certain value. Consequently, the Marangoni effect does not impede, but rather aids in bubble departure from the heating surface. This feature is most favorable in microgravity. As a result, the bubble size of departure is substantially reduced at higher frequencies. Based on the existing experimental data, and a two-tier theoretical model, correlation formulas are derived for nucleate boiling on the copper-graphite and aluminum-graphite composite surfaces, in both the isolated and coalesced bubble regimes. In addition, performance equations for nucleate boiling and critical heat flux in dilute aqueous solutions of long-chain alcohols are obtained.

Reversible Condensation of DNA using a Redox-Active Surfactant

PubMed Central

Hays, Melissa E.; Jewell, Christopher M.; Lynn, David M.; Abbott, Nicholas L.

2008-01-01

We report characterization of aqueous solutions of dilute Lambda phage DNA containing the redox-active surfactant (11-ferrocenylundecyl)trimethylammonium bromide (FTMA) as a function of the oxidation state of the FTMA. FTMA undergoes a reversible one-electron oxidation from a reduced state that forms micelles in aqueous solution to an oxidized state (containing the ferrocenium cation) that does not selfassociate in solution. This investigation sought to test the hypothesis that FTMA can be used to achieve reversible control over the conformation of DNA-surfactant complexes in solution. Whereas DNA adopts extended coil conformations in aqueous solutions, our measurements revealed that addition of reduced FTMA (2–5μM) to aqueous solutions of DNA (5 μM in nucleotide units) resulted in coexistence of extended coils and compact globules in solution. At higher concentrations of reduced FTMA (up to 30μM), the DNA was present as compact globules only. In contrast, oxidized FTMA had no measurable effect on the conformation of DNA, allowing DNA to maintain an extended coil state up to a concentration of 75μM oxidized FTMA. We further demonstrate that it is possible to chemically or electrochemically transform the oxidation state of FTMA in preformed complexes of FTMA and DNA, thus achieving in situ control over the conformations of the DNA in solution. These results provide guidance for the design of surfactant systems that permit active control of DNA-surfactant interactions. PMID:17428073

Physicochemical Behavior of Some Amino Acids/Glycylglycine in Aqueous D-Galactose Solutions at Different Temperatures

NASA Astrophysics Data System (ADS)

Ali, Anwar; Patel, Rajan; Shahjahan; Ansari, Nizamul Haque

2010-03-01

The apparent molar volumes {(overline{V_2})} for glycine (Gly), l-alanine (Ala), phenylalanine (Phe), and glycylglycine (Gly-Gly) in 0.10 m aqueous d-galactose solutions have been determined from density measurements at (298.15, 303.15, 308.15, and 313.15) K. The data for {(overline{V_2})} were utilized to estimate the partial molar volume at infinite dilution {(overline{V_2^0})} , and experimental slope {(S_v^ast)} . The transfer volume, {(overline{V2^0}_(tr))} , and hydration number, ( n H) were also evaluated. The viscosity data were used to evaluate A- and B-coefficients of the Jones-Dole equation, the free energy of activation of viscous flow per mole of the solvent {left(Δ μ1^{0ast} right)} and the solute {left(Δ μ 2^{0ast} right)} . The molar refractivity ( R D) was calculated from refractive index data. The results were discussed in terms of hydrophilic-ionic, hydrophilic-hydrophobic, and hydrophobic-hydrophobic interactions, and structure-making/-breaking ability of the solute (AAs/peptide) in aqueous d-galactose solutions.

Mineral induced phosphorylation of glycolate ion--a metaphor in chemical evolution

NASA Technical Reports Server (NTRS)

Kolb, V.; Zhang, S.; Xu, Y.; Arrhenius, G.

1997-01-01

Bilateral surface-active minerals with excess positive charge concentrate glycolate and trimetaphosphate ion from l0(-3) m aqueous solution to half-saturation of the internal surface sites, and induce phosphorylation of glycolate ion in the mineral with trimetaphosphate, sorbed from l0(-2) m solution. By utilizing reactants from dilute solution at near-neutral pH, and eliminating the need for participating organic nitrogen compounds, the reaction comprises several elements considered necessary for geochemical realism in models for molecular evolution.

Precise measurement of the self-diffusion coefficient for poly(ethylene glycol) in aqueous solution using uniform oligomers

NASA Astrophysics Data System (ADS)

Shimada, Kayori; Kato, Haruhisa; Saito, Takeshi; Matsuyama, Shigetomo; Kinugasa, Shinichi

2005-06-01

Uniform poly(ethylene glycol) (PEG) oligomers, with a degree of polymerization n =1-40, were separated by preparative supercritical fluid chromatography from commercial monodispersed samples. Diffusion coefficients, D, for separated uniform PEG oligomers were measured in dilute solutions of deuterium oxide (D2O) at 30 ° C, using pulsed-field gradient nuclear magnetic resonance. The measured D for each molecular weight was extrapolated to infinite dilution. Diffusion coefficients obtained at infinite dilution follow the scaling behavior of Zimm-type diffusion, even in the lower molecular weight range. Molecular-dynamics simulations for PEG in H2O also showed this scaling behavior, and reproduced close hydrodynamic interactions between PEG and water. These findings suggest that diffusion of PEG in water is dominated by hydrodynamic interaction over a wide molecular weight range, including at low molecular weights around 1000.

Aqueous Silicate Polymers: An Alternative to `Supercritical' Fluids as Transport Agents in Subduction Zones

NASA Astrophysics Data System (ADS)

Mannig, C. E.

2005-12-01

The chemistry of subduction-zone fluids is complicated by melt-vapor miscibility and the existence of critical end-points in rock-H2O systems. It is commonly assumed that fluids in subduction zones attain properties intermediate in composition between hydrous silicate liquid and H2O, and that such fluids possess enhanced material transport capabilities. However, the relevance of supercritical, intermediate fluids to subduction zones presents four problems. (1) Albite-H2O is typically used as an analogue system, but the favorable position of its critical curve is not representative; critical curves for polymineralic subduction-zone lithologies lie at substantially higher P. (2) Even if albite-H2O is relevant, jadeite may interfere because of its different solubility and the positive clapeyron slope of its solidus, which points to liquid-structure changes that could cause reappearance of the liquid+vapor field. (3) Critical curves are features of very H2O-rich compositions; low-porosity, H2O-poor natural systems will coexist with intermediate fluids only over a narrow PT interval. (4) Intermediate fluids are expected only over short length scales because their migration will likely result in compositional shifts via reaction and mineral precipitation in the mantle wedge. Although supercritical, intermediate fluids are probably relatively unimportant in subduction zones, they reflect a chemical process that may hold the key to understanding high- P mass transfer. Miscibility in melt-vapor systems is a consequence of polymerization of dissolved components, primarily Si ± Al, Na and Ca. This behavior yields, e.g., aqueous Si-Si, Si-Al, Si-Na-Al, and Si-Ca oxide dimers and other multimers of varying stoichiometry (silicate polymers), even in subcritical, dilute, H2O-rich vapor. Silicate polymers in subcritical aqueous solutions have been inferred from high- P mineral-solubility experiments. The abundance of these species at high P shows that the chemistry of aqueous fluids in subduction-zones differs fundamentally from the more familiar ionic solutions of the upper crust. This has important consequences for minor element transport. Measurements of Fe, phosphorous and Ti solubility reveal that dissolved concentrations rise with increased aqueous albite content at fixed P and T, with maximum enhancements exceeding 10X at melt saturation. Subcritical silicate polymerization thus permits transport of low solubility components via their substitution into sites on aqueous multimers constructed of "polymer formers" such as Na, Al, and Si, even in dilute solutions. The partitioning of elements between the bulk fluid, the polymer network, and the rock matrix likely controls the overall compositional evolution of subduction-zone fluids. Because they form over a wider PT and bulk X range, subcritical silicate polymers in dilute solutions are likely responsible for more mass transfer in subduction zones than intermediate, supercritical fluids.

Hybrid Vapor Stripping-Vapor Permeation Process for Recovery and Dehydration of 1-Butanol and Acetone/Butanol/Ethanol from Dilute Aqueous Solutions. Part 1. Process Simulations

EPA Science Inventory

BACKGROUND: Fermentative production of butanol is limited to low concentrations, typically less than 2 wt% solvent, due to product inhibition. The result is high separation energy demand by conventional distillation approaches, despite favorable vapor-liquid equilibrium and parti...

Polyvinyl pyridine microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1980-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Polyvinyl pyridine microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1979-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Metabolic Compartmentation – A System Level Property of Muscle Cells

PubMed Central

Saks, Valdur; Beraud, Nathalie; Wallimann, Theo

2008-01-01

Problems of quantitative investigation of intracellular diffusion and compartmentation of metabolites are analyzed. Principal controversies in recently published analyses of these problems for the living cells are discussed. It is shown that the formal theoretical analysis of diffusion of metabolites based on Fick's equation and using fixed diffusion coefficients for diluted homogenous aqueous solutions, but applied for biological systems in vivo without any comparison with experimental results, may lead to misleading conclusions, which are contradictory to most biological observations. However, if the same theoretical methods are used for analysis of actual experimental data, the apparent diffusion constants obtained are orders of magnitude lower than those in diluted aqueous solutions. Thus, it can be concluded that local restrictions of diffusion of metabolites in a cell are a system-level properties caused by complex structural organization of the cells, macromolecular crowding, cytoskeletal networks and organization of metabolic pathways into multienzyme complexes and metabolons. This results in microcompartmentation of metabolites, their channeling between enzymes and in modular organization of cellular metabolic networks. The perspectives of further studies of these complex intracellular interactions in the framework of Systems Biology are discussed. PMID:19325782

High-Yield Production of Levulinic Acid from Pretreated Cow Dung in Dilute Acid Aqueous Solution.

PubMed

Su, Jialei; Shen, Feng; Qiu, Mo; Qi, Xinhua

2017-02-14

Agricultural waste cow dung was used as feedstock for the production of a high value-added chemical levulinic acid (LA) in dilute acid aqueous solutions. A high LA yield of 338.9 g/kg was obtained from the pretreated cow dung, which was much higher than that obtained from the crude cow dung (135 g/kg), mainly attributed to the breakage of the lignin fraction in the lignocellulose structure of the cow dung by potassium hydroxide (KOH) pretreatment, and thus enhanced the accessibility of cow dung to the acid sites in the catalytic reaction. Meanwhile, another value-added chemical formic acid could be obtained with a yield of ca. 160 g/kg in the process, implying a total production of ca. 500 g/kg yield for LA and formic acid from the pretreated cow dung with the proposed process. The developed process was shown to be tolerant to high initial substrate loading with a satisfied LA yield. This work provides a promising strategy for the value-increment utilization of liglocellulosic agricultural residues.

Solution behavior of metoclopramide in aqueous-alcoholic solutions at 30°C

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Sawale, R. T.; Tawde, P. D.; Kalyankar, T. M.

2016-07-01

Densities (ρ) and refractive indices ( n D) of solutions of antiemetic drug metoclopramide (4-amino-5-chloro- N-(2-(diethylamino)ethyl)-2-methoxybenzamide hydrochloride hydrate) in methanolwater and ethanol-water mixtures of different compositions were measured at 30°C. Apparent molar volume (φv) of the drug was calculated from density data and partial molar volumes (φ v 0 ) were determined from Massons relation. Concentration dependence of nD has been studied to determine refractive indices of solution at infinite dilution ( n D 0 ). Results have been interpreted in terms of solute-solvent interactions.

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

PubMed

Suzuki, Yoshiharu

2017-08-14

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

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

NASA Astrophysics Data System (ADS)

Suzuki, Yoshiharu

2017-08-01

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

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

Warner-Schmid, D.; Hoshi, Suwaru; Armstrong, D.W.

Aqueous solutions of nonionic surfactants are known to undergo phase separations at elevated temperatures. This phenomenon is known as clouding,' and the temperature at which it occurs is refereed to as the cloud point. Permethylhydroxypropyl-[beta]-cyclodextrin (PMHP-[beta]-CD) was synthesized and aqueous solutions containing it were found to undergo similar cloud-point behavior. Factors that affect the phase separation of PMHP-[beta]-CD were investigated. Subsequently, the cloud-point extractions of several aromatic compounds (i.e., acetanilide, aniline, 2,2[prime]-dihydroxybiphenyl, N-methylaniline, 2-naphthol, o-nitroaniline, m-nitroaniline, p-nitroaniline, nitrobenzene, o-nitrophenol, m-nitrophenol, p-nitrophenol, 4-phenazophenol, 3-phenylphenol, and 2-phenylbenzimidazole) from dilute aqueous solution were evaluated. Although the extraction efficiency of the compounds varied, mostmore » can be quantitatively extracted if sufficient PMHP-[beta]-CD is used. For those few compounds that are not extracted (e.g., o-nitroacetanilide), the cloud-point procedure may be an effective one-step isolation or purification method. 18 refs., 2 figs., 3 tabs.« less

Surface tensions of inorganic multicomponent aqueous electrolyte solutions and melts.

PubMed

Dutcher, Cari S; Wexler, Anthony S; Clegg, Simon L

2010-11-25

A semiempirical model is presented that predicts surface tensions (σ) of aqueous electrolyte solutions and their mixtures, for concentrations ranging from infinitely dilute solution to molten salt. The model requires, at most, only two temperature-dependent terms to represent surface tensions of either pure aqueous solutions, or aqueous or molten mixtures, over the entire composition range. A relationship was found for the coefficients of the equation σ = c(1) + c(2)T (where T (K) is temperature) for molten salts in terms of ion valency and radius, melting temperature, and salt molar volume. Hypothetical liquid surface tensions can thus be estimated for electrolytes for which there are no data, or which do not exist in molten form. Surface tensions of molten (single) salts, when extrapolated to normal temperatures, were found to be consistent with data for aqueous solutions. This allowed surface tensions of very concentrated, supersaturated, aqueous solutions to be estimated. The model has been applied to the following single electrolytes over the entire concentration range, using data for aqueous solutions over the temperature range 233-523 K, and extrapolated surface tensions of molten salts and pure liquid electrolytes: HCl, HNO(3), H(2)SO(4), NaCl, NaNO(3), Na(2)SO(4), NaHSO(4), Na(2)CO(3), NaHCO(3), NaOH, NH(4)Cl, NH(4)NO(3), (NH(4))(2)SO(4), NH(4)HCO(3), NH(4)OH, KCl, KNO(3), K(2)SO(4), K(2)CO(3), KHCO(3), KOH, CaCl(2), Ca(NO(3))(2), MgCl(2), Mg(NO(3))(2), and MgSO(4). The average absolute percentage error between calculated and experimental surface tensions is 0.80% (for 2389 data points). The model extrapolates smoothly to temperatures as low as 150 K. Also, the model successfully predicts surface tensions of ternary aqueous mixtures; the effect of salt-salt interactions in these calculations was explored.

Structure of the enzymatically synthesized fructan inulin.

PubMed

Heyer, A G; Schroeer, B; Radosta, S; Wolff, D; Czapla, S; Springer, J

1998-12-15

Construction, purification and characterization of a fusion protein of maltose-binding protein of Escherichia coli and the fructosyltransferase of Streptococcus mutans is described. With the purified protein, in vitro synthesis of inulin was performed. The obtained polysaccharide was characterized by high-performance size-exclusion chromatography (HPSEC) and static light scattering (SLS) in dilute aqueous and dimethyl sulfoxide solution. For all samples very high molecular weights between 60 x 10(6) and 90 x 10(6) g/mol and a remarkable small polydispersity index of 1.1 have been determined. Small root-mean-square radii of gyration point to a compact conformation in dilute solution. No difference between native and enzymatically synthesized inulin was observed by X-ray powder diffraction and thermoanalysis of solid samples.

Remarkably high apparent quantum yield of the overall photocatalytic H2O splitting achieved by utilizing Zn ion added Ga2O3 prepared using dilute CaCl2 solution.

PubMed

Sakata, Yoshihisa; Hayashi, Takuya; Yasunaga, Ryō; Yanaga, Nobuyuki; Imamura, Hayao

2015-08-21

Remarkably high photocatalytic activity for the overall H2O splitting, where the activity was 32 mmol h(-1) for H2 production and 16 mmol h(-1) for O2 production under irradiation from a 450 W high-pressure Hg lamp and the apparent quantum yield (AQY) was 71% under irradiation at 254 nm, was achieved by utilizing a Rh(0.5)Cr(1.5)O3(Rh; 0.5 wt%)/Zn(3 mol%)-Ga2O3 photocatalyst when Ga2O3 was prepared using dilute CaCl2 aqueous solution having a concentration of 0.001 mol l(-1).

Drop-on-demand drop formation of polyethylene oxide solutions

NASA Astrophysics Data System (ADS)

Yan, Xuejia; Carr, Wallace W.; Dong, Hongming

2011-10-01

The dynamics of drop-on-demand (DOD) drop formation for solutions containing polyethylene oxide (PEO) have been studied experimentally. Using a piezoelectrical actuated inkjet printhead with the nozzle orifice diameter of 53 μm, experiments were conducted for a series of PEO aqueous solutions with molecular weights ranging from 14 to 1000 kg/mol, polydispersity from 1.02 to 2.5, and concentrations from 0.005 to 10 wt. %. The addition of a small amount of PEO can have a significant effect on the DOD drop formation process, increasing breakup time, decreasing primary drop speed, and decreasing the number of satellite drops in some cases. The effects depend on both molecular weight and concentration. At lower molecular weights (14 and 35 kg/mol), the effect of PEO over the dilute solution regime is insignificant even at concentrations large enough that the solution does not fall in the dilute regime. As PEO molecular weight increased, the effects became significant. For monodispersed PEO solutions, breakup time and primary drop speed closely correlated with effective relaxation time but not for polydispersed PEO. Effective relaxation time depended greatly on molecular weight distribution. Viscosity-average molecular weight, used in calculating effective relaxation time for polydispersed PEO solutions, did not adequately account for high molecular fractions in the molecular weight distribution of the polydispersed PEOs. A mixture rule was developed to calculate the effective relaxation times for aqueous solutions containing mixtures of monodispersed PEO, and breakup times and primary drop speeds correlated well with effective relaxation times. For our experiments, DOD drop formation was limited to Deborah number ≲ 23.

Formation of cage-like particles by poly(amino acid)-based block copolymers in aqueous solution.

PubMed Central

Cudd, A; Bhogal, M; O'Mullane, J; Goddard, P

1991-01-01

When dissolved in N,N-dimethylformamide and then dialyzed against phosphate-buffered saline, A-B-A block copolymers composed of poly [N5-(2-hydroxyethyl)-L-glutamine]-block-poly(gamma-benzyl-L-glutamate)- block-poly [N5-(2-hydroxyethyl)-L-glutamine] form particles. The particles are cage-like structures with average diameters of 300 nm (average polydispersity, 0.3-0.5). They are stable in aqueous solution at 4 degrees C for up to 3 weeks, at which time flocculation becomes apparent. Negative staining and freeze-fracture electron microscopy suggest that cage-like particles are formed by selective association of segregated micelle populations. A model of particle formation is presented in which B blocks form micelles in dimethylformamide. On dialysis against an aqueous solution, the extended A blocks then associate intermolecularly to form rod-shaped micelles, which connect the B block micelles. The result is a meshed cage-like particle. The implications of these observations on the aggregation behavior of polymeric surfactants in dilute solution are discussed. Images PMID:11607245

Thermodynamic studies of aqueous and CCl4 solutions of 15-crown-5 at 298.15 K: an application of McMillan-Mayer and Kirkwood-Buff theories of solutions.

PubMed

Dagade, Dilip H; Shetake, Poonam K; Patil, Kesharsingh J

2007-07-05

The density and osmotic coefficient data for solutions of 15-crown-5 (15C5) in water and in CCl4 solvent systems at 298.15 K have been reported using techniques of densitometry and vapor pressure osmometry in the concentration range of 0.01-2 mol kg-1. The data are used to obtain apparent molar and partial molar volumes, activity coefficients of the components as a function of 15C5 concentration. Using the literature heat of dilution data for aqueous system, it has become possible to calculate entropy of mixing (DeltaS(mix)), excess entropy of solution (DeltaS(E)), and partial molar entropies of the components at different concentrations. The results of all these are compared to those obtained for aqueous 18-crown-6 solutions reported earlier. It has been observed that the partial molar volume of 15C5 goes through a minimum and that of water goes through a maximum at approximately 1.2 mol kg(-1) in aqueous solutions whereas the opposite is true in CCl4 medium but at approximately 0.5 mol kg(-1). The osmotic and activity coefficients of 15C5 and excess free energy change for solution exhibit distinct differences in the two solvent systems studied. These results have been explained in terms of hydrophobic hydration and interactions in aqueous solution while weak solvophobic association of 15C5 molecules in CCl4 solutions is proposed. The data are further subjected to analysis by applying McMillan-Mayer and Kirkwood-Buff theories of solutions. The analysis shows that osmotic second virial coefficient value for 15C5 is marginally less than that of 18C6 indicating that reduction in ring flexibility does not affect the energetics of the interactions much in aqueous solution while the same gets influenced much in nonpolar solvent CCl4.

Why is hydrofluoric acid a weak acid?

PubMed

Ayotte, Patrick; Hébert, Martin; Marchand, Patrick

2005-11-08

The infrared vibrational spectra of amorphous solid water thin films doped with HF at 40 K reveal a strong continuous absorbance in the 1000-3275 cm(-1) range. This so-called Zundel continuum is the spectroscopic hallmark for aqueous protons. The extensive ionic dissociation of HF at such low temperature suggests that the reaction enthalpy remains negative down to 40 K. These observations support the interpretation that dilute HF aqueous solutions behave as weak acids largely due to the large positive reaction entropy resulting from the structure making character of the hydrated fluoride ion.

The enthalpies of interactions of Ca2+(aq) and C2O{4/2-} (aq) ions in complexon solutions: Competition between complexation and precipitation

NASA Astrophysics Data System (ADS)

Kustov, A. V.; Smirnova, N. L.; Berezin, B. D.; Trostin, V. N.

2010-04-01

The thermal effects of mixing of aqueous calcium chloride with sodium citrate and ethylenedi-aminetetraacetate in the absence and presence of sodium oxalate have been measured at 25°C. The thermal effects of dilution of aqueous calcium chloride solutions were determined. The thermal effects of calcium oxalate precipitation and formation of calcium complexes with citrate and ethylenediaminetetraacetate ions were calculated. The 1% solution of sodium citrate inhibited the formation of CaC2O4 (s); in a 1% solution of sodium ethylenediaminetetraacetate with [Ca2+][C2O{4/2-}] > 10-5, the endothermal formation of the [CaEdta]2- complex quickly changed to exothermal precipitation. The 3 and 5% solutions of complexons showed a pronounced inhibiting effect on the formation of urinary stones even when the concentration of calcium and oxalate ions in solution exceeded the product of solubility of CaC2O4 by four and more orders of magnitude.

Standard state thermodynamic properties of completely ionized aqueous sodium sulfate using high dilution calorimetry up to 598.15 K.

PubMed

Djamali, Essmaiil; Chen, Keith; Cobble, James W

2009-08-27

Pabalan and Pitzer (Geochim. Cosmochim. Acta 1988, 52, 2393-2404) reported a comprehensive set of thermodynamic properties of aqueous solutions of sodium sulfate without using ion association or hydrolysis. However, there is now ample evidence available indicating that the ion association cannot be ignored at temperatures T>or=373 K. For example, even at the lowest concentration of their studies (m>or=0.05) and at 573.15 K, less than 20% of SO4(2-)(aq) is available as free ions. In the present study, the integral heats of solution of sodium sulfate were measured to very low concentrations (10(-4) m) up to 573.16 K. The data were analyzed correcting for the hydrolysis of SO4(2-)(aq) and the association of Na+(aq) with SO4(2-)(aq) and NaSO4-(aq) in order to obtain the final standard state thermodynamic properties of completely ionized aqueous sodium sulfate, Na2SO4(aq). From these and the available solubility data, the stoichiometric activity coefficients of saturated aqueous solutions of sodium sulfate were calculated up to 573.15 K and compared with literature data. The stoichiometric activity coefficients of aqueous solutions of sodium sulfate, as a function of temperature at all concentrations (0

DESCALING AND DECONTAMINATING METHOD FOR METALS

DOEpatents

Baybarz, R.D.

1961-04-25

Oxide scale is removed from the surface of stainless steels and similar metals by contacting the metal under an inert atmosphere with a dilute sulfuric acid solution containing chromous sulfate. The removed oxide scale is either dissolved or disintegrated into a slurry by the solution. Preferred reagent concentrations are 0.3 to 0.5 M chromous sulfate and 0.4 to 0.6 M sulfuric acid. This process is particularly applicable to decontamination of aqueous homogsneous nuclear reactor systems.

Effect of solution non-ideality on erythrocyte volume regulation.

PubMed

Levin, R L; Cravalho, E G; Huggins, C E

1977-03-01

A non-ideal, hydrated, non-dilute pseudo-binary salt-protein-water solution model of the erythrocyte intracellular solution is presented to describe the osmotic behavior of human erythrocytes. Existing experimental activity data for salts and proteins in aqueous solutions are used to formulate van Laar type expressions for the solvent and solute activity coefficients. Reasonable estimates can therefore be made of the non-ideality of the erythrocyte intracellular solution over a wide range of osmolalities. Solution non-ideality is shown to affect significantly the degree of solute polarization within the erythrocyte intracellular solution during freezing. However, the non-ideality has very little effect upon the amount of water retained within erythrocytes cooled at sub-zero temperatures.

Probing water dynamics with OH -

NASA Astrophysics Data System (ADS)

Corridoni, T.; Sodo, A.; Bruni, F.; Ricci, M. A.; Nardone, M.

2007-07-01

Isotropic Raman spectra of aqueous solutions of LiOH, NaOH and KOH at concentrations ranging from high dilution to saturation have been measured and the frequency and width of the OH - stretching band have been analyzed. The dependence of the bandwidth on solute concentration suggests that the OH - vibration undergoes a transition from fast to slow modulation regimes as the solvent concentration decreases below the value of ˜20 water molecules per solute molecule. A correlation between this finding and structural modifications of the H-bond network of the solvent at similar concentrations is envisaged.

Dilute and Semidilute Solutions of a Nonionic, Rigid, Water-soluble Polymer

NASA Astrophysics Data System (ADS)

Russo, Paul; Huberty, Wayne; Zhang, Donghui; Water-Soluble Rodlike Polymer Team Collaboration

2014-03-01

The solution physics of random polymer chains was established largely on the behavior of commercial polymers such as polystyrene for organic solvents or nonionic poly(ethyleneoxide) for aqueous solvents. Not only are these materials widely available for industrial use, they can be synthesized to be essentially monodisperse. When it comes to stiff polymers, good choices are few and less prone to be used in industrial applications. Much was learned from polypeptides such as poly(benzylglutamate) or poly(stearylglutamate) in polar organic solvents and nonpolar organic solvents, respectively, but aqueous systems generally require charge. Poly(Nɛ-2-[2-(2-Methoxyethoxy) ethoxy]acetyl-L-Lysine) a.k.a. PEGL was pioneered by Deming and coworkers. In principle, PEGL provides a convenient platform from which to study stiff polymer behavior--phase relations, dynamics, liquid crystal formation and gelation--all with good molecular weight control and uniformity and without electrical charge. Still, a large gap in knowledge exists between PEGL and traditional rodlike polymer systems. To narrow this gap, dynamic and static scattering, circular dichroism, and viscosity measurements have been made in dilute and semidilute solutions as necessary preliminaries for lyotropic liquid crystalline and gel phases. Supported by NSF DMR 1306262. Department of Chemistry and Macromolecular Studies Group. Current address: Georgia Institute of Technology, School of Materials Science and Engineering.

Predicting the hydroxymethylation rate of phenols with formaldehyde by molecular orbital calculation.

Treesearch

Tohru Mitsunaga; Anthony H. Conner; Charles G. Hill

2002-01-01

The rates (k) of hydroxymethylation of phenol, resorcinol. phloroglucinol, and several methylphenols in diluted 10% dimethylformamide aqueous alkaline solution were calculated based on the consumption of phenols and formaldehyde. The k values of phloroglucinol and resorcinol relative to that of phenol were about 62000 and 1200 times, respectively. The phenols that have...

Application of molecular dynamics simulations in molecular property prediction II: diffusion coefficient.

PubMed

Wang, Junmei; Hou, Tingjun

2011-12-01

In this work, we have evaluated how well the general assisted model building with energy refinement (AMBER) force field performs in studying the dynamic properties of liquids. Diffusion coefficients (D) have been predicted for 17 solvents, five organic compounds in aqueous solutions, four proteins in aqueous solutions, and nine organic compounds in nonaqueous solutions. An efficient sampling strategy has been proposed and tested in the calculation of the diffusion coefficients of solutes in solutions. There are two major findings of this study. First of all, the diffusion coefficients of organic solutes in aqueous solution can be well predicted: the average unsigned errors and the root mean square errors are 0.137 and 0.171 × 10(-5) cm(-2) s(-1), respectively. Second, although the absolute values of D cannot be predicted, good correlations have been achieved for eight organic solvents with experimental data (R(2) = 0.784), four proteins in aqueous solutions (R(2) = 0.996), and nine organic compounds in nonaqueous solutions (R(2) = 0.834). The temperature dependent behaviors of three solvents, namely, TIP3P water, dimethyl sulfoxide, and cyclohexane have been studied. The major molecular dynamics (MD) settings, such as the sizes of simulation boxes and with/without wrapping the coordinates of MD snapshots into the primary simulation boxes have been explored. We have concluded that our sampling strategy that averaging the mean square displacement collected in multiple short-MD simulations is efficient in predicting diffusion coefficients of solutes at infinite dilution. Copyright © 2011 Wiley Periodicals, Inc.

Exploring the ionic strength effects on the photochemical degradation of pyruvic acid in atmospheric deliquescent aerosol particles

NASA Astrophysics Data System (ADS)

Mekic, Majda; Brigante, Marcello; Vione, Davide; Gligorovski, Sasho

2018-07-01

There is increasing evidence that aqueous-phase atmospheric chemistry is an important source of secondary organic aerosols (SOA), but the related processes are currently not adequately represented in atmospheric chemistry models. Here we show that the absorption spectrum of pyruvic acid (PA) exhibits both an increase of the absorption intensity and a red shift of 13 nm while going from a dilute aqueous phase to a solution containing the inert salt sodium perchlorate (5M NaClO4). If this phenomenon turns out to be more general, many compounds that do not absorb actinic light in clouds and fog could become light absorbers at elevated salt concentrations in aerosol deliquescent particles. Compared to the direct photolysis of PA in dilute aqueous solution, the photolysis rate is increased by three times at high ionic strength (5M NaClO4). Such a considerable enhancement can be rationalized in the framework of the Debye-McAulay approach for reactions of ionic + neutral (or neutral + neutral) species, considering that the PA direct photolysis likely involves interaction between the photogenerated triplet state and water. This is, to our knowledge, the first report of a significant effect of the ionic strength on the rate of an atmospheric photochemical reaction. The phenomenon has important implications for the fate of PA and, potentially, of other organic compounds in atmospheric aerosol deliquescent particles.

CdTe1-x S x (x  ⩽  0.05) thin films synthesized by aqueous solution deposition and annealing

NASA Astrophysics Data System (ADS)

Pruzan, Dennis S.; Hahn, Carina E.; Misra, Sudhajit; Scarpulla, Michael A.

2017-11-01

While CdS thin films are commonly deposited from aqueous solutions, CdTe thin films are extremely difficult to deposit directly from aqueous solution. In this work, we report on polycrystalline CdTe1-x S x thin films synthesized via deposition from aqueous precursor solutions followed by annealing treatments and on their physical properties. The deposition method uses spin-coating of alternating Cd2+ and Te2- aqueous solutions and rinse steps to allow formation of the films but to shear off excess reactants and poorly-bonded solids. Films are then annealed in the presence of CdCl2 as is commonly done for CdTe photovoltaic absorber layers deposited by any means. Scanning electron microscopy (SEM) reveals low void fractions and grain sizes up to 4 µm and x-ray diffraction (XRD) shows that the films are primarily cubic CdTe1-x S x (x  ⩽  0.05) with random crystallographic orientation. Optical transmission yields bandgap absorption consistent with a CdTe1-x S x dilute alloy and low-temperature photoluminescence (PL) consists of an emission band centered at 1.35 eV consistent with donor-acceptor pair (DAP) transitions in CdTe1-x S x . Together, the crystalline quality and PL yield from films produced by this method represent an important step towards electroless, ligand-free solution processed CdTe and related alloy thin films suitable for optoelectronic device applications such as thin film heterojunction or nanodipole-based photovoltaics.

Efficient adsorption and photocatalytic degradation of organic pollutants diluted in water using fluoride-modified hydrophobic mesoporous silica

NASA Astrophysics Data System (ADS)

Yamashita, Hiromi; Maekawa, Kazuhiro; Nakao, Hidetoshi; Anpo, Masakazu

2004-10-01

Using a mixture of tetraethylammonium fluoride and dodecylamine as templates, hydrophobic mesoporous silica supports were prepared. The fine anatase TiO 2 photocatalysts were prepared on the fluoride-modified hydrophobic mesoporous silica and the adsorption properties and the photocatalytic degradation of an aqueous 2-propanol or 2-hexanol solution into CO 2 and H 2O have been studied. The amount of adsorption and the photocatalytic reactivities increased with increasing the content of fluoride ions on these photocatalysts. 2-Hexanol diluted in water was adsorbed on the hydrophobic catalysts more efficiently than 2-propanol.

Dynamics of falling droplet and elongational properties of dilute nonionic surfactant solutions with drag-reducing ability

NASA Astrophysics Data System (ADS)

Tamano, Shinji; Ohashi, Yota; Morinishi, Yohei

2017-05-01

The dynamics of the falling droplet through a nozzle for dilute nonionic surfactant (oleyl-dimethylamine oxide, ODMAO) aqueous solutions with viscoelastic and drag-reducing properties were investigated at different concentrations of ODMAO solutions Cs = 500, 1000, and 1500 ppm by weight. The effects of the flow rate and tube outer diameter on the length of the filament, which was the distance between the tube exit and the lower end of a droplet at the instant when the droplet almost detached from the tube, were clarified by flow visualization measurements by a high-speed video camera. Two types of breaking-off processes near the base of the droplet and within the filament were classified by the Ohnesorge number Oh and the Weber number We. In the regime of the higher Oh and We, the length of the filament became drastically larger at Cs = 1000 and 1500 ppm, whose high spinnability represented the strong viscoelasticity of ODMAO solutions. In the case where the filament was broken up near the lower end of the neck and thinning in time, the thinning of the diameter of the filament was measured by a light-emitting diode micrometer. As for the elasto-capillary thinning of dilute nonionic surfactant solutions, the initial necking process was similar to that of Newtonian fluids and then followed the exponential thinning like polymer solutions. The apparent elongational viscosity of the dilute nonionic surfactant solution was evaluated in the elasto-capillary thinning regime, in which the elongation rate was almost constant. At Cs = 1000 and 1500 ppm, the Trouton ratio, which was the ratio of the apparent elongational viscosity to the shear viscosity, was found to be several orders of magnitude larger than that of Newtonian fluids, while the shear viscosity measured by the capillary viscometer was almost the same order of the Newtonian fluids. The higher elongational property would be closely related to the higher drag-reducing ability of dilute nonionic surfactant solutions.

Dielectric dispersion of short single-stranded DNA in aqueous solutions with and without added salt.

PubMed

Katsumoto, Yoichi; Omori, Shinji; Yamamoto, Daisuke; Yasuda, Akio; Asami, Koji

2007-01-01

Dielectric spectroscopy measurements were performed for aqueous solutions of short single-stranded DNA with 30 to 120 bases of thymine over a frequency range of 10;{5} to 10;{8}Hz . Dielectric dispersion was found to include two relaxation processes in the ranges from 10;{5} to 10;{6} and from 10;{6} to 10;{8}Hz , respectively, with the latter mainly discussed in this study. The dielectric increment and the relaxation time of the high-frequency relaxation of DNA in solutions without added salt exhibited concentration and polymer-length dependences eventually identical to those for dilute polyion solutions described in previous studies. For solutions with added salt, on the other hand, those dielectric parameters were independent of salt concentration up to a certain critical value and started to decrease with further increasing salt concentration. This critical behavior is well explained by our newly extended cell model that takes into account the spatial distribution of loosely bound counterions around DNA molecules as a function of salt concentration.

Catalysis of the Oligomerization of O-Phospho-Serine, Aspartic Acid, or Glutamic Acid by Cationic Micelles

NASA Technical Reports Server (NTRS)

Bohler, Christof; Hill, Aubrey R., Jr.; Orgel, Leslie E.

1996-01-01

Treatment of relatively concentrated aqueous solutions of 0-phospho-serine (50 mM), aspartic acid (100 mM) or glutamic acid (100 mM) with carbonyldiimidazole leads to the formation of an activated intermediate that oligomerizes efficiently. When the concentration of amino acid is reduced tenfold, few long oligomers can be detected. Positively-charged cetyltrimethyl ammonium bromide micelles concentrate the negatively-charged activated intermediates of the amino acids at their surfaces and catalyze efficient oligomerization even from dilute solutions.

Catalysis of the Oligomerization of O-Phospho-Serine, Aspartic Acid, or Glutamic Acid by Cationic Micelles

NASA Technical Reports Server (NTRS)

Boehler, Christof; Hill, Aubrey R., Jr.; Orgel, Leslie E.

1996-01-01

Treatment of relatively concentrated aqueous solutions of O-phospho-serine (50 mM), aspartic acid (100 mM) or glutamic acid (100 mM) with carbonyldiimidazole leads to the formation of an activated intermediate that oligomerizes efficiently. When the concentration of amino acid is reduced tenfold, few long oligomers can be detected. Positively-charged cetyltrimethyl ammonium bromide micelles concentrate the negatively-charged activated intermediates of the amino acids at their surfaces and catalyze efficient oligomerization even from dilute solutions.

Pervaporation separation of ethanol-water mixtures using polyethylenimine composite membranes

DOEpatents

Neidlinger, H.H.; Schissel, P.O.; Orth, R.A.

1987-04-21

Synthetic, organic, polymeric membranes were prepared from polyethylenimine for use with pervaporation apparatus in the separation of ethanol-water mixtures. The polymeric material was prepared in dilute aqueous solution and coated onto a polysulfone support film, from which excess polymeric material was subsequently removed. Cross-links were then generated by limited exposure to toluene-2,4-diisocyanate solution, after which the prepared membrane was heat-cured. The resulting membrane structures showed high selectivity in permeating ethanol or water over a wide range of feed concentrations.

Pervaporation separation of ethanol-water mixtures using polyethylenimine composite membranes

DOEpatents

Neidlinger, Hermann H.; Schissel, Paul O.; Orth, Richard A.

1987-01-01

Synthetic, organic, polymeric membranes were prepared from polyethylenimine for use with pervaporation apparatus in the separation of ethanol-water mixtures. The polymeric material was prepared in dilute aqueous solution and coated onto a polysulfone support film, from which excess polymeric material was subsequently removed. Cross-links were then generated by limited exposure to toluene-2,4-diisocyanate solution, after which the prepared membrane was heat-cured. The resulting membrane structures showed high selectivity in permeating ethanol or water over a wide range of feed concentrations.

Hybrid Vapor Stripping-Vapor Permeation Process for Recovery and Dehydration of 1-Butanol and Acetone/Butanol/Ethanol from Dilute Aqueous Solutions. Part 2. Experimental Validation with Simple Mixtures and Actual Fermentation Broth

EPA Science Inventory

BACKGROUND: In Part1 of this work, a process integrating vapor stripping, vapor compression, and a vapor permeation membrane separation step, Membrane Assisted Vapor Stripping (MAVS), was predicted to produce energy savings compared to traditional distillation systems for separat...

Photochemical induced growth and aggregation of metal nanoparticles in diode-array spectrophotometer via excited dimethyl-sulfoxide.

PubMed

Zidki, Tomer; Cohen, Haim; Meyerstein, Dan

2010-10-21

Ag(0) and Au(0) nanoparticles suspended in dilute aqueous solutions containing (CH(3))(2)SO are photochemically unstable. The light source of a diode-array spectrophotometer induces, within less than a minute, particle growth and aggregation. The results indicate that this process is triggered by UV light absorption by the (CH(3))(2)SO.

Bimaterial Microcantilevers as a Hybrid Sensing Platform

DTIC Science & Technology

2008-01-01

cantilevers are immersed in dilute solution (milli molar) of desired organic molecule (e.g., alkanethiols) in aqueous or organic solvent (e.g., water... active layers, and some of the im- portant applications. Emphasizing the material design aspects, the review underscores the most important findings... active sensing materials in microelectromechanical systems (MEMS), soft matter-inclusive sensors bring a desir- able diversity in signal transduction

Temperature of maximum density and excess thermodynamics of aqueous mixtures of methanol

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

González-Salgado, D.; Zemánková, K.; Noya, E. G.

In this work, we present a study of representative excess thermodynamic properties of aqueous mixtures of methanol over the complete concentration range, based on extensive computer simulation calculations. In addition to test various existing united atom model potentials, we have developed a new force-field which accurately reproduces the excess thermodynamics of this system. Moreover, we have paid particular attention to the behavior of the temperature of maximum density (TMD) in dilute methanol mixtures. The presence of a temperature of maximum density is one of the essential anomalies exhibited by water. This anomalous behavior is modified in a non-monotonous fashion bymore » the presence of fully miscible solutes that partly disrupt the hydrogen bond network of water, such as methanol (and other short chain alcohols). In order to obtain a better insight into the phenomenology of the changes in the TMD of water induced by small amounts of methanol, we have performed a new series of experimental measurements and computer simulations using various force fields. We observe that none of the force-fields tested capture the non-monotonous concentration dependence of the TMD for highly diluted methanol solutions.« less

Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. The solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl from 0 to 50 °C, including extrapolations to very low temperature and to the pure liquid state, and NaHSO4, NaOH, and NH3 at 25 °C.

PubMed

Clegg, S L; Wexler, A S

2011-04-21

Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer) model has been used to calculate apparent molar volumes of H(2)SO(4) in 0-3 mol kg(-1) aqueous solutions of the pure acid and to represent directly the effect of the HSO(4)(-) ↔ H(+) + SO(4)(2-) reaction. The results are incorporated into the treatment of aqueous H(2)SO(4) density described here. Densities and apparent molar volumes from -20 to 50 °C, and from 0 to 100 wt % of solute, are tabulated for the electrolytes listed in the title and have also been incorporated into the extended aerosol inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) together with densities of the solid salts and hydrates.

Premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions: deprotonation of dye in ion pair micelles.

PubMed

Gohain, Biren; Dutta, Robin K

2008-07-15

The premicellar and micelle formation behavior of dye surfactant ion pairs in aqueous solutions monitored by surface tension and spectroscopic measurements has been described. The measurements have been made for three anionic sulfonephthalein dyes and cationic surfactants of different chain lengths, head groups, and counterions. The observations have been attributed to the formation of closely packed dye surfactant ion pairs which is similar to nonionic surfactants in very dilute concentrations of the surfactant. These ion pairs dominate in the monolayer at the air-water interface of the aqueous dye surfactant solutions below the CMC of the pure surfactant. It has been shown that the dye in the ion pair deprotonates on micelle formation by the ion pair surfactants at near CMC but submicellar surfactant concentrations. The results of an equilibrium study at varying pH agree with the model of deprotonated 1:1 dye-surfactant ion pair formation in the near CMC submicellar solutions. At concentrations above the CMC of the cationic surfactant the dye is solubilized in normal micelles and the monolayer at the air-water interface consists of the cationic surfactant alone even in the presence of the dyes.

L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array

NASA Astrophysics Data System (ADS)

Titus, Charles J.; Baker, Michael L.; Lee, Sang Jun; Cho, Hsiao-Mei; Doriese, William B.; Fowler, Joseph W.; Gaffney, Kelly; Gard, Johnathon D.; Hilton, Gene C.; Kenney, Chris; Knight, Jason; Li, Dale; Marks, Ronald; Minitti, Michael P.; Morgan, Kelsey M.; O'Neil, Galen C.; Reintsema, Carl D.; Schmidt, Daniel R.; Sokaras, Dimosthenis; Swetz, Daniel S.; Ullom, Joel N.; Weng, Tsu-Chien; Williams, Christopher; Young, Betty A.; Irwin, Kent D.; Solomon, Edward I.; Nordlund, Dennis

2017-12-01

We present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100-2000 eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by grating spectrometers. These results show that soft-X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry, and catalysis. In particular, TES spectrometers have a unique ability to characterize frozen solutions of radiation- and temperature-sensitive samples.

Molecular crowding has no effect on the dilution thermodynamics of the biologically relevant cation mixtures.

PubMed

Głogocka, Daria; Przybyło, Magdalena; Langner, Marek

2017-04-01

The ionic composition of intracellular space is rigorously maintained in the expense of high-energy expenditure. It has been recently postulated that the cytoplasmic ionic composition is optimized so the energy cost of the fluctuations of calcium ion concentration is minimized. Specifically, thermodynamic arguments have been produced to show that the presence of potassium ions at concentrations higher than 100 mM reduce extend of the energy dissipation required for the dilution of calcium cations. No such effect has been measured when sodium ions were present in the solution or when the other divalent cation magnesium was diluted. The experimental observation has been interpreted as the indication of the formation of ionic clusters composed of calcium, chloride and potassium. In order to test the possibility that such clusters may be preserved in biological space, the thermodynamics of ionic mixtures dilution in solutions containing albumins and model lipid bilayers have been measured. Obtained thermograms clearly demonstrate that the energetics of calcium/potassium mixture is qualitatively different from calcium/sodium mixture indicating that the presence of the biologically relevant quantities of proteins and membrane hydrophilic surfaces do not interfere with the properties of the intracellular aqueous phase.

Effect of ethanol on the gelation of aqueous solutions of Pluronic F127.

PubMed

Chaibundit, Chiraphon; Ricardo, Nágila M P S; Ricardo, Nádja M P S; Muryn, Christopher A; Madec, Marie-Beatrice; Yeates, Stephen G; Booth, Colin

2010-11-01

In dilute aqueous solution unimers of copolymer F127 (E(98)P(67)E(98)) associate to form micelles, and in more concentrated solution micelles pack to form high-modulus gels. Cosolvents are known to affect these processes, and ethanol/water mixtures have been of particular interest. Dynamic light scattering from dilute solutions was used to confirm micellization, but major attention was directed towards the gels. Visual observation of mobility (tube inversion) was used to detect gel formation, oscillatory rheometry to confirm gel formation and provide values of the elastic moduli over a wide temperature range, and small-angle X-ray scattering to determine gel structure. The solvents were limited to 10, 20 and 30 wt.% ethanol/water. Critical concentrations for gel formation were similar for 10 and 20 wt.% ethanol/water but were significantly increased for 30 wt.% ethanol/water, e.g. at T=45 degrees C from c approximately 15 wt.% to c approximately 28 wt.%. The elastic moduli reached maximum values at T approximately 50 degrees C: e.g. G' approximately 25 kPa for 25 wt.% F127 in 10 and 20 wt.% ethanol/water and a similar value for 30 wt.% F127 in 30 wt.% ethanol/water. Hard gels of 30 and 35 wt.% F127 in ethanol/water at 25 and 40 degrees C had the body-centered cubic (bcc) structure. Copyright 2010 Elsevier Inc. All rights reserved.

Hydrogen bonding in hydrates with one acetic acid molecule.

PubMed

Pu, Liang; Sun, Yueming; Zhang, Zhibing

2010-10-14

Hydrogen bonding (H-bond) interaction significantly influences the separation of acetic acid (HAc) from the HAc/H(2)O mixtures, especially the dilute solution, in distillation processes. It has been examined from the HAc mono-, di-, tri-, and tetrahydrates by analyzing the structures, binding energies, and infrared vibrational frequencies from quantum chemical calculations. For the first coordinate shell the 6-membered head-on ring is surely the most favorable structure because it has (1) the most favorable H-bonding parameters, (2) almost the largest binding energy per H-bond, (3) the biggest wavenumber shifts, and (4) the highest ring distribution (the AIMD simulations). Moreover, the comparison of the calculations with the experiments (the X-ray scattering data and IR frequencies) suggests that the possible structures in dilute aqueous solution are those involving two or more coordinate shells. The H-bonding in these water-surrounded HAc hydrates are the origin of the low-efficiency problem of isolating HAc from the dilute HAc/H(2)O mixtures. It is apparently a tougher work to break the H-bonds among HAc and the surrounded H(2)O molecules with respect to the case of more concentrated solutions, where the dominant structures are HAc or H(2)O aggregates.

Thermodynamic studies of aqueous solutions of 2,2,2-cryptand at 298.15 K: enthalpy-entropy compensation, partial entropies, and complexation with K+ ions.

PubMed

Shaikh, Vasim R; Terdale, Santosh S; Ahamad, Abdul; Gupta, Gaurav R; Dagade, Dilip H; Hundiwale, Dilip G; Patil, Kesharsingh J

2013-12-19

The osmotic coefficient measurements for binary aqueous solutions of 2,2,2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane) in the concentration range of ~0.009 to ~0.24 mol·kg(-1) and in ternary aqueous solutions containing a fixed concentration of 2,2,2-cryptand of ~0.1 mol·kg(-1) with varying concentration of KBr (~0.06 to ~0.16 mol·kg(-1)) have been reported at 298.15 K. The diamine gets hydrolyzed in aqueous solutions and needs proper approach to obtain meaningful thermodynamic properties. The measured osmotic coefficient values are corrected for hydrolysis and are used to determine the solvent activity and mean ionic activity coefficients of solute as a function of concentration. Strong ion-pair formation is observed, and the ion-pair dissociation constant for the species [CrptH](+)[OH(-)] is reported. The excess and mixing thermodynamic properties (Gibbs free energy, enthalpy, and entropy changes) have been obtained using the activity data from this study and the heat data reported in the literature. Further, the data are utilized to compute the partial molal entropies of solvent and solute at finite as well as infinite dilution of 2,2,2-cryptand in water. The concentration dependent non-linear enthalpy-entropy compensation effect has been observed for the studied system, and the compensation temperature along with entropic parameter are reported. Using solute activity coefficient data in ternary solutions, the transfer Gibbs free energies for transfer of the cryptand from water to aqueous KBr as well as transfer of KBr from water to aqueous cryptand were obtained and utilized to obtain the salting constant (ks) and thermodynamic equilibrium constant (log K) values for the complex (2,2,2-cryptand:K(+)) at 298.15 K. The value of log K = 5.8 ± 0.1 obtained in this work is found to be in good agreement with that reported by Lehn and Sauvage. The standard molar entropy for complexation is also estimated for the 2,2,2-cryptand-KBr complex in aqueous medium.

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

PubMed

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

2012-11-16

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

PROCESS FOR THE RECOVERY OF URANIUM

DOEpatents

Morris, G.O.

1955-06-21

This patent relates to a process for the recovery of uranium from impure uranium tetrafluoride. The process consists essentially of the steps of dissolving the impure uranium tetrafluoride in excess dilute sulfuric acid in the presence of excess hydrogen peroxide, precipitating ammonium uranate from the solution so formed by adding an excess of aqueous ammonia, dissolving the precipitate in sulfuric acid and adding hydrogen peroxide to precipitate uranium peroxdde.

Determination of free sulfites (SO3-2) in dried fruits processed with sulfur dioxide by ion chromatography through anion exchange column and conductivity detection.

PubMed

Liao, Benjamin S; Sram, Jacqueline C; Files, Darin J

2013-01-01

A simple and effective anion ion chromatography (IC) method with anion exchange column and conductivity detector has been developed to determine free sulfites (SO3-2) in dried fruits processed with sulfur dioxide. No oxidation agent, such as hydrogen peroxide, is used to convert sulfites to sulfates for IC analysis. In addition, no stabilizing agent, such as formaldehyde, fructose or EDTA, is required during the sample extraction. This method uses aqueous 0.2 N NaOH as the solvent for standard preparation and sample extraction. The sulfites, either prepared from standard sodium sulfite powder or extracted from food samples, are presumed to be unbound SO3-2 in aqueous 0.2 N NaOH (pH > 13), because the bound sulfites in the sample matrix are released at pH > 10. In this study, sulfites in the standard solutions were stable at room temperature (i.e., 15-25 degrees C) for up to 12 days. The lowest standard of the linear calibration curve is set at 1.59 microg/mL SO3-2 (equivalent to 6.36 microg/g sample with no dilution) for analysis of processed dried fruits that would contain high levels (>1000 microg/g) of sulfites. As a consequence, this method typically requires significant dilution of the sample extract. Samples are prepared with a simple procedure of sample compositing, extraction with aqueous 0.2 N NaOH, centrifugation, dilution as needed, and filtration prior to IC. The sulfites in these sample extracts are stable at room temperature for up to 20 h. Using anion IC, the sulfites are eluted under isocratic conditions with 10 mM aqueous sodium carbonate solution as the mobile phase passing through an anion exchange column. The sulfites are easily separated, with an analysis run time of 18 min, regardless of the dried fruit matrix. Recoveries from samples spiked with sodium sulfites were demonstrated to be between 81 and 105% for five different fruit matrixes (apricot, golden grape, white peach, fig, and mango). Overall, this method is simple to perform and effective for the determination of high levels of sulfites in dried fruits.

Increase in Ice Nucleation Efficiency of Feldspars, Kaolinite and Mica in Dilute NH3 and NH4+-containing Solutions

NASA Astrophysics Data System (ADS)

Kumar, A.; Marcolli, C.; Luo, B.; Krieger, U. K.; Peter, T.

2017-12-01

Semivolatile species present in the atmosphere are prone to adhere to mineral dust particle surfaces during long range transport, and could potentially change the particle surface properties and its ice nucleation (IN) efficiency. Immersion freezing experiments were performed with microcline (K-feldspar), known to be highly IN active, suspended in aqueous solutions of ammonia, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl to investigate the effect of solutes on the IN efficiency. Freezing of emulsified droplets investigated with a differential scanning calorimeter (DSC) showed that the heterogeneous ice nucleation temperatures deviate from the water activity-based IN theory, describing heterogeneous ice nucleation temperatures as a function of solution water activity by a constant offset with respect to the ice melting point curve (Zobrist et al. 2008). IN temperatures enhanced up to 4.5 K were observed for very dilute NH3 and NH4+-containing solutions while a decrease was observed as the concentration was further increased. For all solutes with cations other than NH4+, the IN efficiency decreased. An increase of the IN efficiency in very dilute NH3 and NH4+-containing solutions followed by a decrease with increasing concentration was also observed for sanidine (K-feldspar) and andesine (Na/Ca-feldspar). This is an important indication towards specific chemical interactions between solutes and the feldspar surface which is not captured by the water activity-based IN theory. A similar trend is present but less pronounced in case of kaolinite and mica, while quartz is barely affected. We hypothesize that the hydrogen bonding of NH3 molecules with surface -OH groups could be the reason for the enhanced freezing temperatures in dilute ammonia and ammonium containing solutions as they could form an ice-like overlayer providing hydrogen bonding groups for ice to nucleate on top of it. This implies to possibilities of enhanced IN efficiency, especially in mixed-phase cloud regime, of ammonium sulfate coated mineral dust particles in the condensation mode when the coating dilutes during cloud droplet activation.

Passivation of high temperature superconductors

NASA Technical Reports Server (NTRS)

Vasquez, Richard P. (Inventor)

1991-01-01

The surface of high temperature superconductors such as YBa2Cu3O(7-x) are passivated by reacting the native Y, Ba and Cu metal ions with an anion such as sulfate or oxalate to form a surface film that is impervious to water and has a solubility in water of no more than 10(exp -3) M. The passivating treatment is preferably conducted by immersing the surface in dilute aqueous acid solution since more soluble species dissolve into the solution. The treatment does not degrade the superconducting properties of the bulk material.

Pervaporation separation of ethanol-water mixtures using polyacrylic acid composite membranes

DOEpatents

Neidlinger, H.H.

1985-05-07

Synthetic, organic, polymeric membranes were prepared from polyacrylic acid salts for use with pervaporation apparatus in the separation of ehthanol-water mixtures. The polymeric material was prepared in dilute aqueous solution and coated onto a polysulfone support film, from which excess polymeric material was subsequently removed. Cross-links were then generated by limited exposure to toluene-2,4-diisocyanata solution, after which the prepared membrane was heat-cured. The resulting membrane structure showed selectivity in permeating water over a wide range of feed concentrations. 4 tabs.

Pervaporation separation of ethanol-water mixtures using polyethylenimine composite membranes

DOEpatents

Neidlinger, H.H.; Schissel, P.O.; Orth, R.A.

1985-06-19

Synthetic, organic, polymeric membranes were prepared from polyethylenimine for use with pervaporation apparatus in the separation of ethanol-water mixtures. The polymeric material was prepared in dilute aqueous solution and coated onto a polysulfone support film, from which excess polymeric material was subsequently removed. Cross-links were then generated by limited exposure to toluene-2,4-diisocyanate solution, after which the prepared membrane was heat-cured. The resulting membrane structures showed high selectivity in permeating ethanol or water over a wide range of feed concentrations. 2 tabs.

Process for Descaling and Decontaminating Metals

DOEpatents

Baybarz, R. D.

1961-04-25

The oxide scale on the surface of stainless steels and similar metals is removed by contacting the metal under an inert atmosphere with a dilute H/sub 2/ SO/sub 4/ solution containing CrSO/sub 4/. The removed oxide scale is either dissolved or disintegrated into a slurry by the solution. Preferred reagent concentrations are 0.3 to 0.5 M CrSO/sub 4/ and 0.5 to 0.6 M H/sub 2/SO/sub 4/. The process is particularly applicable to decontamination of aqueous homogeneous nuclear reactor systems. (AEC)

L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array

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

Titus, Charles J.; Baker, Michael L.; Lee, Sang Jun

Here, we present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements then demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100–2000 eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by grating spectrometers. These results show that soft-X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry, and catalysis. In particular, TES spectrometers have a unique abilitymore » to characterize frozen solutions of radiation- and temperature-sensitive samples.« less

L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array

DOE PAGES

Titus, Charles J.; Baker, Michael L.; Lee, Sang Jun; ...

2017-12-07

Here, we present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements then demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100–2000 eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by grating spectrometers. These results show that soft-X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry, and catalysis. In particular, TES spectrometers have a unique abilitymore » to characterize frozen solutions of radiation- and temperature-sensitive samples.« less

Surface engineered nanoparticles for improved surface enhanced Raman scattering applications and method for preparing same

DOEpatents

Simmons, Blake A [San Francisco, CA; Talin, Albert Alec [Livermore, CA

2009-11-27

A method for producing metal nanoparticles that when associated with an analyte material will generate an amplified SERS spectrum when the analyte material is illuminated by a light source and a spectrum is recorded. The method for preparing the metal nanoparticles comprises the steps of (i) forming a water-in-oil microemulsion comprising a bulk oil phase, a dilute water phase, and one or more surfactants, wherein the water phase comprises a transition metal ion; (ii) adding an aqueous solution comprising a mild reducing agent to the water-in-oil microemulsion; (iii) stirring the water-in-oil microemulsion and aqueous solution to initiate a reduction reaction resulting in the formation of a fine precipitate dispersed in the water-in-oil microemulsion; and (iv) separating the precipitate from the water-in-oil microemulsion.

Partial molar volume of anionic polyelectrolytes in aqueous solution.

PubMed

Salamanca, Constain; Contreras, Martín; Gamboa, Consuelo

2007-05-15

In this work the partial molar volumes (V) of different anionic polyelectrolytes and hydrophobically modified polyelectrolytes (PHM) were measured. Polymers like polymaleic acid-co-styrene, polymaleic acid-co-1-olefin, polymaleic acid-co-vinyl-2-pyrrolidone, and polyacrylic acid (abbreviated as MAS-n, PA-n-K2, AMVP, and PAA, respectively) were employed. These materials were investigated by density measurements in highly dilute aqueous solutions. The molar volume results allow us to discuss the effect of the carboxylic groups and the contributions from the comonomeric principal chain. The PAA presents the smaller V, while the largest V value was for AMVP. The V of PHM shows a linear relationship with the number of methylene groups in the lateral chain. It is found that the magnitude of the contribution per methylene group decreases as the hydrophobic character of the environment increases.

PROCESSING OF NEUTRON-IRRADIATED URANIUM

DOEpatents

Hopkins, H.H. Jr.

1960-09-01

An improved "Purex" process for separating uranium, plutonium, and fission products from nitric acid solutions of neutron-irradiated uranium is offered. Uranium is first extracted into tributyl phosphate (TBP) away from plutonium and fission products after adjustment of the acidity from 0.3 to 0.5 M and heating from 60 to 70 deg C. Coextracted plutonium, ruthenium, and fission products are fractionally removed from the TBP by three scrubbing steps with a 0.5 M nitric acid solution of ferrous sulfamate (FSA), from 3.5 to 5 M nitric acid, and water, respectively, and the purified uranium is finally recovered from the TBP by precipitation with an aqueous solution of oxalic acid. The plutonium in the 0.3 to 0.5 M acid solution is oxidized to the tetravalent state with sodium nitrite and extracted into TBP containing a small amount of dibutyl phosphate (DBP). Plutonium is then back-extracted from the TBP-DBP mixture with a nitric acid solution of FSA, reoxidized with sodium nitrite in the aqueous strip solution obtained, and once more extracted with TBP alone. Finally the plutonium is stripped from the TBP with dilute acid, and a portion of the strip solution thus obtained is recycled into the TBPDBP for further purification.

COMPLEX RUTHENIUM ACIDO-NITROS COMPOUNDS (in Russian)

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

Zvyagintsev, O.E.; Starostin, S.M.

1961-06-01

The chemical nature of the water in the complex ruthenium acidonitroso compounds is studied by measuring certain acid properties, reactions, and behaviors of the compounds in aqueous solution. The dependence of molecular electrical conductivity on time and dilution, variations of specific electroconductivity, the optical density, and the light absorption of the compounds at 200 to 800 m mu wave range were investigated and the dissociation constants were calculated. (R.V.J.)

METHOD FOR DECONTAMINATION OF REACTOR SOLUTIONS

DOEpatents

Maraman, W.J.; Baxman, H.R.; Baker, R.D.

1959-05-01

A process for U recovery from phosphate fuel solutions is described. To fuel solution drawn from the reactor is added Fe(NO/sub 3/)/sub 3/ which destroys the U complex and forms ferric phosphate complex. The UO/sub 2/(NO/sub 3/)/sub 2/ formed is extracted into TBP-kerosene in a countercurrent column. The TBP contalning UO/sub 2/(NO/sub 3/)/sub 2/ is further purified by an aqueous Al(NO/ sub 3/)/sub 3/ scrub solution. The pregnant solution then goes to an H/sub 3/PO/ sub 4/ stripping and kerosene washing column. The H/sub 3/PO/sub 4/--uranyl phosphate solution is separated at the bottom and boiled to remove HNO/sub 3/ then diluted to fuel solution make-up strength. (T.R.H.)

Rheological characterization of schizophyllan aqueous solutions after denaturation-renaturation treatment.

PubMed

Fang, Yapeng; Takahashi, Rheo; Nishinari, Katsuyoshi

2004-07-01

Schizophyllan (SPG) with a molecular weight of 2.6x10(6), designated SPG-1, is denatured and then renatured at a concentration of 1.8 wt % by alkalization-neutralization. The prepared denatured-renatured samples (DRSPG-1) are diluted to various concentrations and equilibrated for 10 days before rheological and intrinsic viscosity measurements. When concentration (C(p)) is above 0.75 wt %, DRSPG-1 aqueous systems have weak gel-type rheological properties. However, for 0.28 wt %

Eco-friendly synthesis of metal dichalcogenides nanosheets and their environmental remediation potential driven by visible light

PubMed Central

Mishra, Ashish Kumar; Lakshmi, K. V.; Huang, Liping

2015-01-01

Exfoliated transition metal dichalcogenides (TMDs) such as WS2 and MoS2 have shown exciting potential for energy storage, catalysis and optoelectronics. So far, solution based methods for scalable production of few-layer TMDs usually involve the use of organic solvents or dangerous chemicals. Here, we report an eco-friendly method for facile synthesis of few-layer WS2 and MoS2 nanosheets using dilute aqueous solution of household detergent. Short time sonication of varying amount of bulk samples in soapy water was used to scale up the production of nanosheets. Thermal stability, optical absorption and Raman spectra of as-synthesized WS2 and MoS2 nanosheets are in close agreement with those from other synthesis techniques. Efficient photocatalytic activity of TMDs nanosheets was demonstrated by decomposing Brilliant Green dye in aqueous solution under visible light irradiation. Our study shows the great potential of TMDs nanosheets for environmental remediation by degrading toxic industrial chemicals in wastewater using sunlight. PMID:26503125

Eco-friendly synthesis of metal dichalcogenides nanosheets and their environmental remediation potential driven by visible light

NASA Astrophysics Data System (ADS)

Mishra, Ashish Kumar; Lakshmi, K. V.; Huang, Liping

2015-10-01

Exfoliated transition metal dichalcogenides (TMDs) such as WS2 and MoS2 have shown exciting potential for energy storage, catalysis and optoelectronics. So far, solution based methods for scalable production of few-layer TMDs usually involve the use of organic solvents or dangerous chemicals. Here, we report an eco-friendly method for facile synthesis of few-layer WS2 and MoS2 nanosheets using dilute aqueous solution of household detergent. Short time sonication of varying amount of bulk samples in soapy water was used to scale up the production of nanosheets. Thermal stability, optical absorption and Raman spectra of as-synthesized WS2 and MoS2 nanosheets are in close agreement with those from other synthesis techniques. Efficient photocatalytic activity of TMDs nanosheets was demonstrated by decomposing Brilliant Green dye in aqueous solution under visible light irradiation. Our study shows the great potential of TMDs nanosheets for environmental remediation by degrading toxic industrial chemicals in wastewater using sunlight.

A method for measuring enthalpy of volatilization of a compound, Delta(vol)H, from dilute aqueous solution.

PubMed

Wang, Tianshu

2006-01-01

This study has developed a method for measuring the enthalpy of volatilization (Delta(vol)H) of a compound in a dilute solution via ion-molecule reactions and gas-phase analysis using selected ion flow tube mass spectrometry (SIFT-MS). The Delta(vol)H/R value was obtained using an equation with three variant forms either from the headspace concentration of the solution or from individual product ion(s). Under certain experimental conditions, the equation has the simplest form [formula: see text], where R is the gas constant (8.314 J . mol(-1) . K(-1)), i(n) and I are the respective product and precursor ion count rates, and T is the temperature of the solution. As an example, a series of 27.0 micromol/L aqueous solutions of acetone was analyzed over a temperature range of 25-50 degrees C at 5 degrees C intervals using H3O+, NO+ and O2+* precursor ions, producing a mean Delta(vol)H/R value of 4700 +/- 200 K. This corresponds with current literature values and supports the consistency of the new method. Notably, using this method, as long as the concentration of the solution falls into the range of Henry's law, the exact concentration does not have to be known and it can require only one sample at each temperature. Compared with previous methods which involve the measurement of Henry's law constant at each temperature, this method significantly reduces the number of samples required and avoids the labour and difficulties in preparing standard solutions at very low concentrations. Further to this, if the contents of a solution were unknown the measured Delta(vol)H/R from individual product ion(s) can help to identify the origin of the ion(s). Copyright 2006 John Wiley & Sons, Ltd.

Gliadins from wheat grain: an overview, from primary structure to nanostructures of aggregates.

PubMed

Urade, Reiko; Sato, Nobuhiro; Sugiyama, Masaaki

2018-04-01

Gliadins are well-known wheat grain proteins, particularly important in food science. They were studied as early as the 1700s. Despite their long history, it has been difficult to identify their higher-order structure as they aggregate in aqueous solution. Consequently, most studies have been performed by extracting the proteins in 70% ethanol or dilute acidic solutions. The carboxy-terminal half of α- and γ-gliadins have α-helix-rich secondary structures stabilized with intramolecular disulfide bonds, which are present in either aqueous ethanol or pure water. The amino-terminal-repeat region of α- and γ-gliadins has poly-L-proline II and β-reverse-turn structures. ω-Gliadins also have poly-L-proline II and β-reverse-turn structures, but no α-helix structure. The size and shape of gliadin molecules have been determined by assessing a variety of parameters: their sedimentation velocity in the analytical ultracentrifuge, intrinsic viscosity, small-angle X-ray scattering profile, and images of the proteins from scanning probe microscopes such as a tunneling electron microscope and atomic force microscope. Models for gliadins are either rods or prolate ellipsoids whether in aqueous ethanol, dilute acid, or pure water. Recently, gliadins have been shown to be soluble in pure water, and a novel extraction method into pure water has been established. This has made it possible to analyze gliadins in pure water at neutral pH, and permitted the characterization of hydrated gliadins. They formed hierarchical nanoscale structures with internal density fluctuations at high protein concentrations.

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.

Biomolecules from HCN

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Wos, J. D.; Ryan, T. J.; Lobo, A. P.; Donner, D. B.

1974-01-01

It has been suggested by Sanchez et al. (1967) that HCN might have been one of the more important precursors of biological molecules on the primitive earth. Studies were conducted to determine the mechanisms involved in HCN oligomerizations in dilute aqueous solutions and to identify the compounds which are produced in these oligomerization mixtures. Indirect evidence for the formation of cyanate was obtained along with direct evidence for the formation of citrulline, aspartic acid, and orotic acid.

Mineral induced formation of pentose-2,4-bisphosphates

NASA Technical Reports Server (NTRS)

Krishnamurthy, R.; Pitsch, S.; Arrhenius, G.; Bada, J. L. (Principal Investigator)

1999-01-01

Formation of rac.-pentose-2,4-bisphosphates is demonstrated, starting from glycolaldehyde phosphate and glyceraldehyde-2-phosphate, and induced by mixed valence double layer metal hydroxide minerals. The reactions proceed from dilute aqueous reactant solutions (1.5 mM) at near neutral pH. Conditions have been established, where ribose-2,4-bisphosphate is the major product (approximately 48%) among the pentose-2,4-bisphosphates, which are formed with up to 25% yield.

Group additivity calculations of the thermodynamic properties of unfolded proteins in aqueous solution: a critical comparison of peptide-based and HKF models.

PubMed

Hakin, A W; Hedwig, G R

2001-02-15

A recent paper in this journal [Amend and Helgeson, Biophys. Chem. 84 (2000) 105] presented a new group additivity model to calculate various thermodynamic properties of unfolded proteins in aqueous solution. The parameters given for the revised Helgeson-Kirkham-Flowers (HKF) equations of state for all the constituent groups of unfolded proteins can be used, in principle, to calculate the partial molar heat capacity, C(o)p.2, and volume, V2(0), at infinite dilution of any polypeptide. Calculations of the values of C(o)p.2 and V2(0) for several polypeptides have been carried out to test the predictive utility of the HKF group additivity model. The results obtained are in very poor agreement with experimental data, and also with results calculated using a peptide-based group additivity model. A critical assessment of these two additivity models is presented.

Novel colorimetric sensors for cyanide based on azo-hydrazone tautomeric skeletons.

PubMed

Adegoke, Olajire A; Adesuji, Temitope E; Thomas, Olusegun E

2014-07-15

The monoazo dyes, 4-carboxyl-2, 6-dinitrophenylazohydroxynaphthalenes dyes (AZ-01, AZ-03 and AZ-04), were evaluated as a highly selective colorimetric chemosensor for cyanide ion. The recognition of cyanide ion gave an obvious colour change from light yellow to brownish red and upon dilution with acetone produced a purple to lilac colour. Optimum conditions for the reaction between the azo dyes and cyanide ion were established at 30°C for 5 min, and different variables affecting the reaction were carefully studied and optimised. Under the optimum conditions, linear relationships between the CN(-) concentrations and light absorption were established. Using these azo-hydrazone molecular switch entities, excellent selectivity towards the detection of CN(-) in aqueous solution over miscellaneous competitive anions was observed. Such selectivity mainly results from the possibility of nucleophilic attack on the azo-hydrazone chemosensors by cyanide anions in aqueous system, which is not afforded by other competing anions. The cyanide chemosensor method described here should have potential application as a new family probes for detecting cyanide in aqueous solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Standard state thermodynamic properties of Ba2+(aq), Co2+(aq), and Cu2+(aq) up to 598.15 K, and temperature effect on ligand field.

PubMed

Djamali, Essmaiil; Chen, Keith; Murray, Richard C; Turner, Peter J; Cobble, James W

2009-02-26

Integral heat of solution measurements of barium chloride to 619.81 K, copper oxide in an excess of perrhenic acid to 585 K, and cobalt perrhenate in perrhenic acid to 573 K were measured in a high dilution calorimeter (< or =10(-3) m) at psat, from which the high temperature thermodynamic properties of aqueous barium chloride, copper perrhenate, and cobalt perrhenate were obtained. From the known differences between the corresponding properties for aqueous perrhenate and chloride ions, the thermodynamic properties of completely ionized aqueous copper and cobalt chloride were obtained from ionic additivity. The enthalpy and derived heat capacity data at higher temperatures (T > 473.15 K) suggest that the ligand field stabilization energy of Co2+(aq) may be disappearing.

Interlaboratory validation of 1% pluronic l92 surfactant as a suitable, aqueous vehicle for testing pesticide formulations using the murine local lymph node assay.

PubMed

Boverhof, Darrell R; Wiescinski, Connie M; Botham, Phil; Lees, David; Debruyne, Eric; Repetto-Larsay, Marina; Ladics, Gregory; Hoban, Denise; Gamer, Armin; Remmele, Marina; Wang-Fan, Weizheng; Ullmann, Ludwig G; Mehta, Jyotigna; Billington, Richard; Woolhiser, Michael R

2008-09-01

The mouse local lymph node assay (LLNA) has become the preferred test for evaluating the dermal sensitization potential of chemicals and requirements are now emerging for its use in the evaluation of their formulated products, especially in the European Union. However, despite its widespread use and extensive validation, the use of this assay for directly testing mixtures and formulated products has been questioned, which could lead to repeat testing using multiple animal models. As pesticide formulations are typically a specific complex blend of chemicals for use as aqueous-based dilutions, traditional vehicles prescribed for the LLNA may change the properties of these formulations leading to inaccurate test results and hazard identification. The objective of this study was to evaluate the effectiveness of an aqueous solution of Pluronic L92 block copolymer surfactant (L92) as a vehicle in the mouse LLNA across five laboratories. Three chemicals with known sensitization potential and four pesticide formulations for which the sensitization potential in guinea pigs and/or humans had previously been assessed were used. Identical LLNA protocols and test materials were used in the evaluation. Assessment of the positive control chemicals, hexylcinnamaldehyde, formaldehyde, and potassium dichromate revealed positive results when using 1% aqueous L92 as the vehicle. Furthermore, results for these chemicals were reproducible among the five laboratories and demonstrated consistent relative potency determinations. The four pesticide formulations diluted in 1% aqueous L92 also demonstrated reproducible results in the LLNA among the five laboratories. Results for these test materials were also consistent with those generated previously using guinea pigs or from human experience. These data support testing aqueous compatible chemicals or pesticide formulations using the mouse LLNA, and provide additional support for the use of 1% aqueous L92 as a suitable, aqueous-based vehicle.

High-performance liquid chromatographic analysis of methadone hydrochloride oral solution.

PubMed

Beasley, T H; Ziegler, H W

1977-12-01

A direct and rapid high-performance liquid chromatographic assay for methadone hydrochloride in a flavored oral solution dosage form is described. A syrup sample, one part diluted with three parts of water, is introduced onto a column packed with octadecylsilane bonded on 10 micrometer porous silica gel (reversed phase). A formic acid-ammonium formate-buffered mobile phase is linear programmed with acetonitrile. The absorbance is monitored continuously at 280 or 254 nm, using a flow-through, UV, double-beam photometer. An aqueous methadone hydrochloride solution is used for external standardization. The relative standard deviation was not more than 1.0%. Drug recovery from a syrup base was better than 99.8%.

Selective recovery of vanadium and scandium by ion exchange with D201 and solvent extraction using P507 from hydrochloric acid leaching solution of red mud.

PubMed

Zhu, Xiaobo; Li, Wang; Tang, Sen; Zeng, Majian; Bai, Pengyuan; Chen, Lunjian

2017-05-01

D201 resin and P507 extractant diluted with sulfonated kerosene were used to respectively separate vanadium and scandium, and impurity ions from hydrochloric acid leaching solution of red mud. More than 99% of vanadium was selectively adsorbed from the hydrochloric acid leaching solution under the conditions of pH value of 1.8, volume ratio of leaching solution to resin of 10, and flow rate of 3.33 mL/min. Maximum extraction and separation of scandium was observed from the acid leaching solution at an aqueous pH value of 0.2. More than 99% of scandium can be selectively extracted using 15% P507, 5% TBP at the aqueous solution/organic phase (A/O) ratio of 10:1 for 6 min. The loaded organic phase was washed with 0.3 mol/L sulfuric acid, wherein most impurities were removed. After the process of desorption or stripping, precipitation, and roasting, high-purity V 2 O 5 and Sc 2 O 3 were obtained. Finally, a conceptual flow sheet was established to separate and recover vanadium and scandium from red mud hydrochloric acid leaching solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

THE SOLVENT EXTRACTION OF NITROSYLRUTHENIUM BY TRILAURYLAMINE IN NITRATE SYSTEM. Summary Report for the Period, July 1, 1960 to March 31, 1962

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

Skavdahl, R.E.; Mason, E.A.

1962-06-01

An investigation of the solvent extraction characteristics of the nitro and nitrato complexes of nitrosylruthenium in nitric acid- sodium nitrate aqueous media was conducted. As the organic extractant phase, a solution of trilaurylamine (TLA) in toluene was utilized. In addition to the usual process parameter variation tyne of experiment, a rapid dilution type of experiment was used extensively to determine qualitative and semiquantitative results regarding the degree of extractability and concentration of the more extractable species of the nitrato complexes of nitrosylruthenium. It was found that the acids of the tetra-nitrato and pentanitrato complexes were the more extractable species formore » that set of complexes and that the acid of the penta-nitrato complex was the more extractable of the two. It was observed that for freshly prepared solutions, the dinitro complex of nitrosylruthenium was much more extractable than the gross nitrato complexes solutions. Nitro complexes in general, and the dinitro complex in particular, may be the controlling agent in ruthenium decontamination of spent nuclear fuel processed by solvent extraction methods. The experimental results from both sets of complexes could be more meaningfully correlated on the basis of unbound nitric acid concentration in the organic phase than on the basis of nitric acid concentration in the aqueous phase. The extraction of nitric acid by TLA from nitric acid-sodium nitrate aqueous solutions was investigated and the results correlated on the basis of activity of the undissociated nitric acid in the aqueous phase. (auth)« less

Structure and Properties of Polymer Interphases

DTIC Science & Technology

1988-09-30

substrate primed with a dilute aqueous solution of y -aminopropyltriethoxy- silane (’APS), there was little reaction between the primer and adhesive and...of y -aminopropyltriethoxysilane (- Y -APS) at pH 10.4 for one minute, withdrawn, and blown dry with a stream of nitrogen gas. The resulting primer...cm-1 is due to the C= N stretching mode of imine groups formed by oxidation of the amino groups in the primer. The negative peak near 1740 cm𔃻 is due

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

Alenaizi, R.; Radiman, S.; Mohamed, F.

The morphology of vesicles system with defined particle size and shape is one of interest in our technical applications. Here we have used dynamic light scattering technique and transmission electron microscopy for structural characterization of N-dimethylglycine Betaine with 5-cholesten-3β-ol vesicles in aqueous solutions. An isotropic one phase region is found in the very diluted regions depending on Betaine/Cholesterol ratio. The isotropic region was stable for more than 3 months at room temperature, with monodispersed unilamellar vesicles ∼ 300nm.

Polyacrolein microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor)

1983-01-01

Microspheres of acrolein homopolymers and co-polymer with hydrophillic comonomers such as methacrylic acid and/or hydroxyethylmethacrylate are prepared by cobalt gamma irradiation of dilute aqueous solutions of the monomers in presence of suspending agents, especially alkyl sulfates such as sodium dodecyl sulfate. Amine or hydroxyl modification is achieved by forming adducts with diamines or alkanol amines. Carboxyl modification is effected by oxidation with peroxides. Pharmaceuticals or other aldehyde reactive materials can be coupled to the microspheres. The microspheres directly form antibody adducts without agglomeration.

Polyacrolein microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor)

1986-01-01

Microspheres of acrolein homopolymers and copolymer with hydrophillic comonomers such as methacrylic acid and/or hydroxyethylmethacrylate are prepared by cobalt gamma irradiation of dilute aqueous solutions of the monomers in presence of suspending agents, especially alkyl sulfates such as sodium dodecyl sulfate. Amine or hydroxyl modification is achieved by forming adducts with diamines or alkanol amines. Carboxyl modification is effected by oxidation with peroxides. Pharmaceuticals or other aldehyde reactive materials can be coupled to the microspheres. The microspheres directly form antibody adducts without agglomeration.

Polyacrolein microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor)

1987-01-01

Microspheres of acrolein homopolymers and copolymer with hydrophillic comonomers such as methacrylic acid and/or hydroxyethylmethacrylate are prepared by cobalt gamma irradiation of dilute aqueous solutions of the monomers in presence of suspending agents, especially alkyl sulfates such as sodium dodecyl sulfate. Amine or hydroxyl modification is achieved by forming adducts with diamines or alkanol amines. Carboxyl modification is effected by oxidation with peroxides. Pharmaceuticals or other aldehyde reactive materials can be coupled to the microspheres. The microspheres directly form antibody adducts without agglomeration.

Discovery and structure determination of a novel Maillard-derived sweetness enhancer by application of the comparative taste dilution analysis (cTDA).

PubMed

Ottinger, Harald; Soldo, Tomislav; Hofmann, Thomas

2003-02-12

Application of a novel screening procedure, the comparative taste dilution analysis (cTDA), on the non-solvent-extractable reaction products formed in a thermally processed aqueous solution of glucose and l-alanine led to the discovery of the presence of a sweetness-enhancing Maillard reaction product. Isolation, followed by LC-MS and 1D- and 2D-NMR measurements, and synthesis led to its unequivocal identification as N-(1-carboxyethyl)-6-(hydroxymethyl)pyridinium-3-ol inner salt. This so-called alapyridaine, although being tasteless itself, is the first nonvolatile, sweetness-enhancing Maillard reaction product reported in the literature. Depending on the pH value, the detection thresholds of sweet sugars, amino acids, and aspartame, respectively, were found to be significantly decreased when alapyridaine was present; for example, the threshold of glucose decreased by a factor of 16 in an equimolar mixture of glucose and alapyridaine. Studies on the influence of the stereochemistry on taste-enhancing activity revealed that the (+)-(S)-alapyridaine is the physiologically active enantiomer, whereas the (-)-(R)-enantiomer did not affect sweetness perception at all. Thermal processing of aqueous solutions of alapyridaine at 80 degrees C demonstrated a high thermal and hydrolytic stability of that sweetness enhancer; for example, more than 90 or 80% of alapyridaine was recovered when heated for 5 h at pH 7.0, 5.0, or 3.0, respectively.

Achieving accurate compound concentration in cell-based screening: validation of acoustic droplet ejection technology.

PubMed

Grant, Richard John; Roberts, Karen; Pointon, Carly; Hodgson, Clare; Womersley, Lynsey; Jones, Darren Craig; Tang, Eric

2009-06-01

Compound handling is a fundamental and critical step in compound screening throughout the drug discovery process. Although most compound-handling processes within compound management facilities use 100% DMSO solvent, conventional methods of manual or robotic liquid-handling systems in screening workflows often perform dilutions in aqueous solutions to maintain solvent tolerance of the biological assay. However, the use of aqueous media in these applications can lead to suboptimal data quality due to compound carryover or precipitation during the dilution steps. In cell-based assays, this effect is worsened by the unpredictable physical characteristics of compounds and the low DMSO tolerance within the assay. In some cases, the conventional approaches using manual or automated liquid handling resulted in variable IC(50) dose responses. This study examines the cause of this variability and evaluates the accuracy of screening data in these case studies. A number of liquid-handling options have been explored to address the issues and establish a generic compound-handling workflow to support cell-based screening across our screening functions. The authors discuss the validation of the Labcyte Echo reformatter as an effective noncontact solution for generic compound-handling applications against diverse compound classes using triple-quad liquid chromatography/mass spectrometry. The successful validation and implementation challenges of this technology for direct dosing onto cells in cell-based screening is discussed.

Thermal decomposition pathways of hydroxylamine: theoretical investigation on the initial steps.

PubMed

Wang, Qingsheng; Wei, Chunyang; Pérez, Lisa M; Rogers, William J; Hall, Michael B; Mannan, M Sam

2010-09-02

Hydroxylamine (NH(2)OH) is an unstable compound at room temperature, and it has been involved in two tragic industrial incidents. Although experimental studies have been carried out to study the thermal stability of hydroxylamine, the detailed decomposition mechanism is still in debate. In this work, several density functional and ab initio methods were used in conjunction with several basis sets to investigate the initial thermal decomposition steps of hydroxylamine, including both unimolecular and bimolecular reaction pathways. The theoretical investigation shows that simple bond dissociations and unimolecular reactions are unlikely to occur. The energetically favorable initial step of decomposition pathways was determined as a bimolecular isomerization of hydroxylamine into ammonia oxide with an activation barrier of approximately 25 kcal/mol at the MPW1K level of theory. Because hydroxylamine is available only in aqueous solutions, solvent effects on the initial decomposition pathways were also studied using water cluster methods and the polarizable continuum model (PCM). In water, the activation barrier of the bimolecular isomerization reaction decreases to approximately 16 kcal/mol. The results indicate that the bimolecular isomerization pathway of hydroxylamine is more favorable in aqueous solutions. However, the bimolecular nature of this reaction means that more dilute aqueous solution will be more stable.

ATR-FTIR spectroscopy for the determination of Na4EDTA in detergent aqueous solutions.

PubMed

Suárez, Leticia; García, Roberto; Riera, Francisco A; Diez, María A

2013-10-15

Fourier transform infrared spectroscopy in the attenuated total reflectance mode (ATR-FTIR) combined with partial last square (PLS) algorithms was used to design calibration and prediction models for a wide range of tetrasodium ethylenediaminetetraacetate (Na4EDTA) concentrations (0.1 to 28% w/w) in aqueous solutions. The spectra obtained using air and water as a background medium were tested for the best fit. The PLS models designed afforded a sufficient level of precision and accuracy to allow even very small amounts of Na4EDTA to be determined. A root mean square error of nearly 0.37 for the validation set was obtained. Over a concentration range below 5% w/w, the values estimated from a combination of ATR-FTIR spectroscopy and a PLS algorithm model were similar to those obtained from an HPLC analysis of NaFeEDTA complexes and subsequent detection by UV absorbance. However, the lowest detection limit for Na4EDTA concentrations afforded by this spectroscopic/chemometric method was 0.3% w/w. The PLS model was successfully used as a rapid and simple method to quantify Na4EDTA in aqueous solutions of industrial detergents as an alternative to HPLC-UV analysis which involves time-consuming dilution and complexation processes. © 2013 Elsevier B.V. All rights reserved.

Preparation of cuxinygazsen precursor films and powders by electroless deposition

DOEpatents

Bhattacharya, Raghu N.; Batchelor, Wendi Kay; Wiesner, Holm; Ramanathan, Kannan; Noufi, Rommel

1999-01-01

A method for electroless deposition of Cu.sub.x In.sub.y Ga.sub.z Se.sub.n (x=0-2, y=0-2, z=0-2, n=0-3) precursor films and powders onto a metallic substrate comprising: preparing an aqueous bath solution of compounds selected from the group consisting of: I) a copper compound, a selenium compound, an indium compound and gallium compound; II) a copper compound, a selenium compound and an indium compound; III) a selenium compound, and indium compound and a gallium compound; IV) a selenium compound and a indium compound; and V) a copper compound and selenium compound; each compound being present in sufficient quantity to react with each other to produce Cu.sub.x In.sub.y Ga.sub.z Se.sub.n (x=0-2, y=0-2, z=0-2, n=0-3); adjusting the pH of the aqueous bath solution to an acidic value by the addition of a dilute acid; and initiating an electroless reaction with an oxidizing counterelectrode for a sufficient time to cause a deposit of Cu.sub.x In.sub.y Ga.sub.z Se.sub.n (x=0-2, y=0-2, z=0-2, n=0-3) from the aqueous bath solution onto a metallic substrate.

Processing of irradiated, enriched uranium fuels at the Savannah River Plant

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

Hyder, M L; Perkins, W C; Thompson, M C

Uranium fuels containing /sup 235/U at enrichments from 1.1% to 94% are processed and recovered, along with neptunium and plutonium byproducts. The fuels to be processed are dissolved in nitric acid. Aluminum-clad fuels are disssolved using a mercury catalyst to give a solution rich in aluminum. Fuels clad in more resistant materials are dissolved in an electrolytic dissolver. The resulting solutions are subjected to head-end treatment, including clarification and adjustment of acid and uranium concentration before being fed to solvent extraction. Uranium, neptunium, and plutonium are separated from fission products and from one another by multistage countercurrent solvent extraction withmore » dilute tri-n-butyl phosphate in kerosene. Nitric acid is used as the salting agent in addition to aluminum or other metal nitrates present in the feed solution. Nuclear safety is maintained through conservative process design and the use of monitoring devices as secondary controls. The enriched uranium is recovered as a dilute solution and shipped off-site for further processing. Neptunium is concentrated and sent to HB-Line for recovery from solution. The relatively small quantities of plutonium present are normally discarded in aqueous waste, unless the content of /sup 238/Pu is high enough to make its recovery desirable. Most of the /sup 238/Pu can be recovered by batch extraction of the waste solution, purified by counter-current solvent extraction, and converted to oxide in HB-Line. By modifying the flowsheet, /sup 239/Pu can be recovered from low-enriched uranium in the extraction cycle; neptunium is then not recovered. The solvent is subjected to an alkaline wash before reuse to remove degraded solvent and fission products. The aqueous waste is concentrated and partially deacidified by evaporation before being neutralized and sent to the waste tanks; nitric acid from the overheads is recovered for reuse.« less

Single-coil properties and concentration effects for polyelectrolyte-like wormlike micelles: a Monte Carlo study

NASA Astrophysics Data System (ADS)

Cannavacciuolo, Luigi; Skov Pedersen, Jan; Schurtenberger, Peter

2002-03-01

Results of an extensive Monte Carlo (MC) study on both single and many semiflexible charged chains with excluded volume (EV) are summarized. The model employed has been tailored to mimic wormlike micelles in solution. Simulations have been performed at different ionic strengths of added salt, charge densities, chain lengths and volume fractions Φ, covering the dilute to concentrated regime. At infinite dilution the scattering functions can be fitted by the same fitting functions as for uncharged semiflexible chains with EV, provided that an electrostatic contribution bel is added to the bare Kuhn length. The scaling of bel is found to be more complex than the Odijk-Skolnick-Fixman predictions, and qualitatively compatible with more recent variational calculations. Universality in the scaling of the radius of gyration is found if all lengths are rescaled by the total Kuhn length. At finite concentrations, the simple model used is able to reproduce the structural peak in the scattering function S(q) observed in many experiments, as well as other properties of polyelectrolytes (PELs) in solution. Universal behaviour of the forward scattering S(0) is established after a rescaling of Φ. MC data are found to be in very good agreement with experimental scattering measurements with equilibrium PELs, which are giant wormlike micelles formed in mixtures of nonionic and ionic surfactants in dilute aqueous solution, with added salt.

Energy-Efficient Bioalcohol Recovery by Gel Stripping

NASA Astrophysics Data System (ADS)

Godbole, Rutvik; Ma, Lan; Hedden, Ronald

2014-03-01

Design of energy-efficient processes for recovering butanol and ethanol from dilute fermentations is a key challenge facing the biofuels industry due to the high energy consumption of traditional multi-stage distillation processes. Gel stripping is an alternative purification process by which a dilute alcohol is stripped from the fermentation product by passing it through a packed bed containing particles of a selectively absorbent polymeric gel material. The gel must be selective for the alcohol, while swelling to a reasonable degree in dilute alcohol-water mixtures. To accelerate materials optimization, a combinatorial approach is taken to screen a matrix of copolymer gels having orthogonal gradients in crosslinker concentration and hydrophilicity. Using a combination of swelling in pure solvents, the selectivity and distribution coefficients of alcohols in the gels can be predicted based upon multi-component extensions of Flory-Rehner theory. Predictions can be validated by measuring swelling in water/alcohol mixtures and conducting h HPLC analysis of the external liquid. 95% + removal of butanol from dilute aqueous solutions has been demonstrated, and a mathematical model of the unsteady-state gel stripping process has been developed. NSF CMMI Award 1335082.

Static and dynamic light scattering studies on dilute polyrotaxane solutions

NASA Astrophysics Data System (ADS)

Kume, Tetsuya; Araki, Jun; Sakai, Yasuhiro; Mayumi, Koichi; Kidowaki, Masatoshi; Yokoyama, Hideaki; Ito, Kohzo

2009-08-01

Static and dynamic light scattering measurements were performed for dilute polyrotaxane solutions in different types of solvent systems, i.e. dimethylacetamide (DMAc) or dimethylformamide (DMF) containing 1-6 wt% lithium chloride (LiCl), 1 M aqueous sodium hydroxide (NaOH) and dimethylsulfoxide (DMSO). No aggregation of the polyrotaxane in DMF/LiCl was confirmed in the present study. Radius of gyration of the dissolved polyrotaxane was largest in NaOHaq., followed by values in amide solvents/LiCl and that in DMSO, and was probably dominated not by Coulombic repulsion but by the mutual affinity between solvent and polyrotaxane. Ratio of radius of gyration to hydrodynamic radius suggested the flexible random-coiled conformation in DMSO and relatively more extended, semi-flexible ones in amide solvents/LiCl and NaOHaq. The obtained values of second virial coefficient and weight average molecular weight seemed to be affected by a potential change in differential refractive index increments, caused by selective macrocationization or ionization.

Selective monovalent cation association and exchange around Keplerate polyoxometalate macroanions in dilute aqueous solutions.

PubMed

Pigga, Joseph M; Teprovich, Joseph A; Flowers, Robert A; Antonio, Mark R; Liu, Tianbo

2010-06-15

The interaction between water-soluble Keplerate polyoxometalate {Mo(72)Fe(30)} macroions and small countercations is explored by laser light scattering, anomalous small-angle X-ray scattering (ASAXS), and isothermal titration calorimetry (ITC) techniques. The macroions are found to be able to select the type of associated counterions based upon the counterions' valence state and hydrated size, when multiple types of additional cations are present in solution (even among different monovalent cations). The preference goes to the cations with higher valences or smaller hydrated sizes if the valences are identical. This counterion exchange process changes the magnitude of the macroion-counterion interaction and, thus, is reflected in the dimension of the self-assembled {Mo(72)Fe(30)} blackberry supramolecular structures. The hydrophilic macroions exhibit a competitive recognition of various monovalent counterions in dilute solutions. A critical salt concentration (CSC) for each type of cation exists for the blackberry formation of {Mo(72)Fe(30)} macroions, above which the blackberry size increases significantly with the increasing total ionic strength in solution. The CSC values are much smaller for cations with higher valences and also decrease with the cations' hydrated size for various monovalent cations. The change of blackberry size corresponding to the change of ionic strength in solution is reversible.

Rheology and physical-chemical characteristics of the solutions of the medicines

NASA Astrophysics Data System (ADS)

Urakov, A.; Urakova, N.

2015-04-01

In the laboratory studied the dynamics of rheology of water solutions with plasma- inflammatory and antiseptic funds when mixing them with blood, plasma and pus under the influence of the following physical and chemical factors of local interaction: gravity, specific gravity, temperature, relative viscosity, internal pressure, sparkling water, total concentration of the ingredients, surface activity, volume of acid and osmotic activity of medicines. Found that the rheology of biological liquids improve hyperthermic, highly alkaline and highly carbonated solution medicines. For the dilution of pus, dense festering mass of sulfur plugs and tear stones invited to apply heated to +39 - +42°C with aqueous solution of 0.5 - 3% hydrogen peroxide and 0.5 - 10% sodium bicarbonate saturated with carbon dioxide to excess pressure 0.2 ATM.

TREATMENT FOR IMPROVING THE OPERATION OF STRONG BASE ANION EXCHANGE RESINS

DOEpatents

Stevenson, P.C.

1960-11-29

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

Thermal and volumetric properties of complex aqueous electrolyte solutions using the Pitzer formalism - The PhreeSCALE code

NASA Astrophysics Data System (ADS)

Lach, Adeline; Boulahya, Faïza; André, Laurent; Lassin, Arnault; Azaroual, Mohamed; Serin, Jean-Paul; Cézac, Pierre

2016-07-01

The thermal and volumetric properties of complex aqueous solutions are described according to the Pitzer equation, explicitly taking into account the speciation in the aqueous solutions. The thermal properties are the apparent relative molar enthalpy (Lϕ) and the apparent molar heat capacity (Cp,ϕ). The volumetric property is the apparent molar volume (Vϕ). Equations describing these properties are obtained from the temperature or pressure derivatives of the excess Gibbs energy and make it possible to calculate the dilution enthalpy (∆HD), the heat capacity (cp) and the density (ρ) of aqueous solutions up to high concentrations. Their implementation in PHREEQC V.3 (Parkhurst and Appelo, 2013) is described and has led to a new numerical tool, called PhreeSCALE. It was tested first, using a set of parameters (specific interaction parameters and standard properties) from the literature for two binary systems (Na2SO4-H2O and MgSO4-H2O), for the quaternary K-Na-Cl-SO4 system (heat capacity only) and for the Na-K-Ca-Mg-Cl-SO4-HCO3 system (density only). The results obtained with PhreeSCALE are in agreement with the literature data when the same standard solution heat capacity (Cp0) and volume (V0) values are used. For further applications of this improved computation tool, these standard solution properties were calculated independently, using the Helgeson-Kirkham-Flowers (HKF) equations. By using this kind of approach, most of the Pitzer interaction parameters coming from literature become obsolete since they are not coherent with the standard properties calculated according to the HKF formalism. Consequently a new set of interaction parameters must be determined. This approach was successfully applied to the Na2SO4-H2O and MgSO4-H2O binary systems, providing a new set of optimized interaction parameters, consistent with the standard solution properties derived from the HKF equations.

Self-association of caffeine in aqueous solution. Study of dilute solutions by normal and second derivative UV absorption spectroscopy.

NASA Astrophysics Data System (ADS)

Iza, N.; Gil, M.; Montero, J. L.; Morcillo, J.

1988-05-01

The concentration dependence of the spectral parameters of caffeine bands at ˜205 and 273 nm has been studied in aqueous solution by normal and second derivative spectroscopy. The concentration range was 5 x 10 -6 - 5 x 10 -3 M and thirty-five different concentrations were used. Discontinuities in parameter variation of these two bands at ˜7.5 x 10 -5, ˜2 x 10 -4, and ˜1 x 10 -3M were observed as concentration was increased. These "limiting" concentrations define three quite differenciated hyper- or hipochromic effects: the first one can be explained as caffeine-water molecule interaction and the second and third as dimer and (dimer + polymer) stacking, respectively. Apparent self-association constants using the isodesmic model have been obtained K= 160 M -1 (for the second hypochromic effect) and K= 13.6 M -1 (for the third hypochromic effect), for the 273 nm band. It is noteworthy that the three "limiting" concentrations coincide with changes in DNA-caffeine interaction modes (H. Lang , 1976) and biological activity (I.B. Syed , 1976).

Interactions of N,N'-dimethylaminoethanol with steel surfaces in alkaline and chlorine containing solutions

NASA Astrophysics Data System (ADS)

Welle, A.; Liao, J. D.; Kaiser, K.; Grunze, M.; Mäder, U.; Blank, N.

1997-10-01

Formulations based on dilute aqueous solutions of N,N'-dimethylethanolamine (DMEA) are used to protect reinforcement steel bars ('rebar') in concrete from corrosion. In a previous paper we discussed the usefulness of X-ray photoelectron spectroscopy (XPS) to detect DMEA adsorbed from solution and the application of secondary neutral mass spectrometry (SNMS) to study migration of DMEA through a cement matrix. In this report we present XPS data of DMEA adsorbed on steel surfaces from alkaline and chlorine containing solutions of variable concentration range and discuss models for the interaction of DMEA with the oxidized steel surface and the mechanism of corrosion inhibition of DMEA. DMEA is strongly bonded to the steel surface and displaces ionic species from the substrate/solution interface hence protecting the ironoxide surface from ionic attack.

Carbonate dissolution rates in high salinity brines: Implications for post-Noachian chemical weathering on Mars

NASA Astrophysics Data System (ADS)

Phillips-Lander, Charity M.; Parnell, S. R.; McGraw, L. E.; Elwood Madden, M. E.

2018-06-01

A diverse suite of carbonate minerals including calcite (CaCO3) and magnesite (MgCO3) have been observed on the martian surface and in meteorites. Terrestrial carbonates usually form via aqueous processes and often record information about the environment in which they formed, including chemical and textural biosignatures. In addition, terrestrial carbonates are often found in association with evaporite deposits on Earth. Similar high salinity environments and processes were likely active on Mars and some areas may contain active high salinity brines today. In this study, we directly compare calcite and magnesite dissolution in ultrapure water, dilute sulfate and chloride solutions, as well as near-saturated sulfate and chloride brines with known activity of water (aH2O) to determine how dissolution rates vary with mineralogy and aH2O, as well as aqueous cation and anion chemistry to better understand how high salinity fluids may have altered carbonate deposits on Mars. We measured both calcite and magnesite initial dissolution rates at 298 K and near neutral pH (6-8) in unbuffered solutions containing ultrapure water (18 MΩ cm-1 UPW; aH2O = 1), dilute (0.1 mol kg-1; aH2O = 1) and near-saturated Na2SO4 (2.5 mol kg-1, aH2O = 0.92), dilute (0.1 mol kg-1, aH2O = 1) and near-saturated NaCl (5.7 mol kg-1, aH2O = 0.75). Calcite dissolution rates were also measured in dilute and near-saturated MgSO4 (0.1 mol kg-1, aH2O = 1 and 2.7 mol kg-1, aH2O = 0.92, respectively) and MgCl2 (0.1 mol kg-1, aH2O = 1 and 3 mol kg-1, aH2O = 0.73, respectively), while magnesite dissolution rates were measured in dilute and near-saturated CaCl2 (0.1 mol kg-1, aH2O = 1 and 9 mol kg-1, aH2O = 0.35). Initial calcite dissolution rates were fastest in near-saturated MgCl2 brine, while magnesite dissolution rates were fastest in dilute (0.1 mol kg-1) NaCl and CaCl2 solutions. Calcite dissolution rates in near-saturated Na2SO4 were similar to those observed in the dilute solutions (-8.00 ± 0.12 log mol m-2 s-1), while dissolution slowed in both NaCl solutions (0.1 mol kg-1; -8.23 ± 0.10 log mol m-2 s-1 and (5.7 mol kg-1; -8.44 ± 0.11 log mol m-2 s-1), as well as near-saturated MgSO4 brine (2.7 mol kg-1; -8.35 ± 0.05 log mol m-2 s-1). The slowest calcite dissolution rates observed in the near-saturated NaCl brine. Magnesite dissolution rates were ∼5 times faster in the dilute salt solutions relative to UPW, but similar to UPW (-8.47 ± 0.06 log mol m-2 s-1) in near-saturated Na2SO4 brines (-8.41 ± 0.18 log mol m-2 s-1). Magnesite dissolution slowed significantly in near-saturated CaCl2 brine (-9.78 ± 0.10 log mol m-2 s-1), likely due to the significantly lower water activity in these experiments. Overall, magnesite dissolution rates are slower than calcite dissolution rates and follow the trend: All dilute salt solutions >2.5 mol kg-1 Na2SO4 ≈ UPW > 5.7 mol kg-1 NaCl >> 9 mol kg-1 CaCl2. Calcite rates follow the trend 3 mol kg-1 MgCl2 > 2.5 mol kg-1 Na2SO4 ≈ UPW ≈ all dilute salt solutions >2.7 mol kg-1 MgSO4 ≈ 5.7 mol kg-1 NaCl. Magnesite dissolution rates in salt solutions generally decrease with decreasing aH2O in both chloride and sulfate brines, which indicates water molecules act as ligands and participate in the rate-limiting magnesite dissolution step. However, there is no general trend associated with water activity observed in the calcite dissolution rates. Calcite dissolution accelerates in near-saturated MgCl2, but slows in near-saturated NaCl brine despite both brines having similar water activities (aH2O = 0.73 and 0.75, respectively). High Mg calcite was observed as a reaction product in the near-saturated MgCl2, indicating Mg2+ from solution likely substituted for Ca2+ in the initial calcite, releasing additional Ca2+ into solution and increasing the observed calcite dissolution rate. Calcite dissolution rates also increase slightly as Na2SO4 concentration increases, while calcite dissolution rates slow slightly with increasing concentration of MgSO4 and NaCl. However, all of the carbonate rates vary by less than 0.5 log units and are within or near the standard deviation observed for each set of replicate experiments. Carbonate mineral lifetimes in high salinity brines indicate magnesite may be preferentially preserved compared to calcite on Mars. Therefore, Mg-carbonates that have experienced post-depositional aqueous alteration are more likely to preserve paleoenvironmental indicators and potential biosignatures. Rapid weathering of carbonates in circum-neutral pH sulfate brines may provide a potential source of cations for abundant sulfate minerals observed on Mars, Ceres, and other planetary bodies.

Dynamic light scattering study on vesicles of Netaine-Cholesterol system

NASA Astrophysics Data System (ADS)

Alenaizi, R.; Radiman, S.; Mohamed, F.; Rahman, I. Abdul

2014-09-01

The morphology of vesicles system with defined particle size and shape is one of interest in our technical applications. Here we have used dynamic light scattering technique and transmission electron microscopy for structural characterization of N-dimethylglycine Betaine with 5-cholesten-3β-ol vesicles in aqueous solutions. An isotropic one phase region is found in the very diluted regions depending on Betaine/Cholesterol ratio. The isotropic region was stable for more than 3 months at room temperature, with monodispersed unilamellar vesicles ˜ 300nm.

Magnetic particles

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

40 CFR Appendix 5 to Subpart A of... - Determination of Crude Oil Contamination in Non-Aqueous Drilling Fluids by Gas Chromatography...

Code of Federal Regulations, 2011 CFR

2011-07-01

.... 6.2.2Analytical balance—Capable of weighing 0.1 mg. 6.2.3Glassware. 6.2.3.1Disposable pipettes... standard at 62.5 mg/mL in methylene chloride. Prepare a medium concentration SPTM standard at 1.25 mg/mL by transferring 1.0 mL of the 62.5 mg/mL solution into a 50 mL volumetric flask and diluting to the mark with...

The Interaction of Polycrystalline Copper Films with Dilute Aqueous Solutions of Cupric Chloride

DTIC Science & Technology

1989-10-01

to interconnect semiconductor devices and other computer components Electronic circuits are mass / produced to obtain poduct uniformity and lowestx...so one needs to determine what if any pH change is produced by this extraneous oxide film growth. Thus, in order to determine any interference which...diffusion type; bulk diffusion rates would lie between 10 - 1 3 and 6x10-12mol.h- 1cm-2 mixed grain -13 boundary and bulk diffusion would lie between 6x10

Examination of a New Desorption Method for Solid Adsorption Method of Working Environment Measurement －Attempt to Improve Desorption Efficiency of Organic Solvents from a Coconut-Shell-Activated Carbon Using Surfactant Solutions－.

PubMed

Hinoue, Mitsuo; Hori, Hajime

2017-01-01

For a new desorption method development for working environment measurement, desorption efficiency of organic solvent vapors from an activated carbon was examined using desorption solutions that consisted of anionic and nonionic surfactants. Ten μl of an aqueous solution of isopropyl alcohol or methyl ethyl ketone diluted with distilled water was spiked into a 10 ml vial with a coconut-shell-activated carbon (100 mg). The vial was left for 24 h, and 5 ml a desorption solution was added. Afterwards, the vial was put into an incubator at 60°C and left for 24 h, then the desorption efficiency was determined by analyzing the headspace gas in the vial with a gas chromatograph equipped with flame ionization detector. By adding one or four kinds of nonionic surfactants to the aqueous solution containing two kinds of anionic surfactants, the effect adding nonionic surfactant to the desorption efficiency was investigated, but improvement of desorption efficiency was not observed. On the other hand, desorption efficiency varied depending on the production lot of the coconut-shell-activated carbon tube used as the adsorbent.

Temperature invariance of NaCl solubility in water: inferences from salt-water cluster behavior of NaCl, KCl, and NH4Cl.

PubMed

Bharmoria, Pankaj; Gupta, Hariom; Mohandas, V P; Ghosh, Pushpito K; Kumar, Arvind

2012-09-27

The growth and stability of salt-water clusters have been experimentally studied in aqueous solutions of NaCl, KCl, and NH(4)Cl from dilute to near-saturation conditions employing dynamic light scattering and zeta potential measurements. In order to examine cluster stability, the changes in the cluster sizes were monitored as a function of temperature. Compared to the other cases, the average size of NaCl-water clusters remained almost constant over the studied temperature range of 20-70 °C. Information obtained from the temperature-dependent solution compressibility (determined from speed of sound and density measurements), multinuclear NMR ((1)H, (17)O, (35)Cl NMR), and FTIR were utilized to explain the cluster behavior. Comparison of NMR chemical shifts of saturated salt solutions with solid-state NMR data of pure salts, and evaluation of spectral modifications in the OH stretch region of saturated salt solutions as compared to that of pure water, provided important clues on ion pair-water interactions and water structure in the clusters. The high stability and temperature independence of the cluster sizes in aqueous NaCl shed light on the temperature invariance of its solubility.

Thermodynamics of Dilute Solutions.

ERIC Educational Resources Information Center

Jancso, Gabor; Fenby, David V.

1983-01-01

Discusses principles and definitions related to the thermodynamics of dilute solutions. Topics considered include dilute solution, Gibbs-Duhem equation, reference systems (pure gases and gaseous mixtures, liquid mixtures, dilute solutions), real dilute solutions (focusing on solute and solvent), terminology, standard states, and reference systems.…

Methods and apparatuses for deoxygenating biomass-derived pyrolysis oil

DOEpatents

Baird, Lance Awender; Brandvold, Timothy A.

2015-10-20

Embodiments of methods and apparatuses for deoxygenating a biomass-derived pyrolysis oil are provided. In one example, a method comprises the steps of separating a low-oxygen biomass-derived pyrolysis oil effluent into a low-oxygen-pyoil organic phase stream and an aqueous phase stream. Phenolic compounds are removed from the aqueous phase stream to form a phenolic-rich diluent recycle stream. A biomass-derived pyrolysis oil stream is diluted and heated with the phenolic-rich diluent recycle stream to form a heated diluted pyoil feed stream. The heated diluted pyoil feed stream is contacted with a deoxygenating catalyst in the presence of hydrogen to deoxygenate the heated diluted pyoil feed stream.

On the Growth of Ice in Aqueous Solutions Contained in Capillaries

NASA Astrophysics Data System (ADS)

Pruppracher, H. R.

1967-06-01

The growth rate of ice in supercooled water and in dilute aqueous solutions of various salts which dissociate in water into univalent ions was studied. The solutions contained in polyethylene tubes of small bore had concentrations between 10-6 and 10-1 moles liter-1 and were investigated at bath supercoolings between 1° and 15°C. The growth rate of ice which in pure water was found to vary approximately with the square of the bath supercooling was affected in a systematic manner by the type and concentration of the salt in solution. At salt concentrations smaller than 5 × 10-2 moles liter-1 most salts did not affect the growth rate. However, the fluorides were found to increase the growth rate over and above the one in pure water. At concentrations larger than 5 × 10-2 moles liter-1 all the salts reduced the growth rate of ice below the one in pure water. By comparing solutions of salts with common anion it was found that at a particular bath supercooling and salt concentration the growth rate of ice was reduced most in lithium solutions and least in cesium and ammonium solutions. By comparing solutions of salts with common cation it was found that the growth rate of ice was reduced most in fluoride solutions and least in bromide solutions. It was concluded that in solutions with salt concentrations larger than 5 × 10-2 moles liter-1 the rate of dissipation of latent heat which controls the growth rate of ice is affected in a systematic manner by the freezing point lowering effects which result from pure mass transfer conditions prevailing at the ice-solution interface of a stagnant system. Some features of the observed growth rates are discussed in terms of the effect of dissolved salts on the growth forms of ice in aqueous solutions.

Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

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

Simone, Peter M.; Lodge, Timothy P.

2008-08-26

The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior ofmore » the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].« less

Enhancement of both salivary protein-enological tannin interactions and astringency perception by ethanol.

PubMed

Obreque-Slíer, Elías; Peña-Neira, Alvaro; López-Solís, Remigio

2010-03-24

Red wine astringency has been associated with interactions of tannins with salivary proteins. Tannins are active protein precipitants. Not much evidence exists demonstrating contribution of other wine components to astringency. We aimed to investigate an eventual role of ethanol both in astringency and salivary protein-enological tannin interactions. A trained sensory panel scored perceived astringency. Salivary protein-tannin interactions were assessed by observing both tannin-dependent changes in salivary protein diffusion on cellulose membranes and tannin-induced salivary protein precipitation. Proanthocyanidins and gallotannins in aqueous and hydroalcoholic solutions were assayed. A biphasic mode of diffusion on cellulose membranes displayed by salivary proteins was unaffected after dilution with water or enological concentrations of ethanol. At those concentrations ethanol was not astringent. In aqueous solution, tannins provoked both restriction of salivary protein diffusion, protein precipitation, and astringency. Those effects were exacerbated by 13% ethanol. In summary, enological concentrations of ethanol exacerbate astringency and salivary protein-tannin interactions.

Anomalous Micellization of Pluronic Block Copolymers

NASA Astrophysics Data System (ADS)

Leonardi, Amanda; Ryu, Chang Y.

2014-03-01

Poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) (PEO-PPO-PEO) block copolymers, commercially known as Pluronics, are a unique family of amphiphilic triblock polymers, which self-assemble into micelles in aqueous solution. These copolymers have shown promise in therapeutic, biomedical, cosmetic, and nanotech applications. As-received samples of Pluronics contain low molecular weight impurities (introduced during the manufacturing and processing), that are ignored in most applications. It has been observed, however, that in semi-dilute aqueous solutions, at concentrations above 1 wt%, the temperature dependent micellization behavior of the Pluronics is altered. Anomalous behavior includes a shift of the critical micellization temperature and formation of large aggregates at intermediate temperatures before stable sized micelles form. We attribute this behavior to the low molecular weight impurities that are inherent to the Pluronics which interfere with the micellization process. Through the use of Dynamic Light Scattering and HPLC, we compared the anomalous behavior of different Pluronics of different impurity levels to their purified counterparts.

Spinning-disk generation and drying of monodisperse solid aerosols with output concentrations sufficient for single-breath inhalation studies.

PubMed

Byron, P R; Hickey, A J

1987-01-01

The air-driven spinning-disk aerosol generator was modified to allow the production of monodisperse dry spherical aerosols of disodium fluorescein (as model solute) in high output concentrations. Output concentrations were determined by filtration. Optical and aerodynamic size distributions were determined microscopically (after electrostatic precipitation) and by cascade impaction. The generator housing allowed the entrainment of 25-microns primary aqueous solution droplets in a 10-L X min-1 downward flow of dry, filtered air. Internal equipment surfaces were machined flush and polished to minimize aerosol losses. Primary droplets were dried within a stainless steel pipe encased in a tube furnace. Water vapor was removed by diffusion drying. Disk-driven air, satellite droplets, and additional dilution air were vented to waste without using a vacuum. Generator yields were increased by reducing the size of the satellite droplet extraction gap. Aerosols were generated reproducibly by delivering aqueous solutions at a rate of 0.2 mL X min-1 to the center of the disk and spinning at 1000 rps. Dry aerosols, with mass median aerodynamic diameters of 2, 4.9, and 9 microns, were produced in concentrations of 0.89, 5.48, and 54.6 micrograms X L-1 from aqueous solutions containing 0.0374, 0.584, and 3.4% solute by weight. Geometric standard deviations were less than 1.2 in all cases. Concentrations are several times higher than others in the literature and are suitable for single-breath inhalation studies of therapeutic aerosol deposition and effect.

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

Wolery, Thomas J.; Tayne, Andrew; Jove-Colon, Carlos F.

Thermodynamic data are essential for understanding and evaluating geochemical processes, as by speciation-solubility calculations, reaction -path modeling, or reactive transport simulation. These data are required to evaluate both equilibrium states and the kinetic approach to such states (via the affinity term in rate laws). The development of thermodynamic databases for these purposes has a long history in geochemistry (e.g., Garrels and Christ, 1965; Helgeson et al., 1969; Helgeson et al., 1978, Johnson et al., 1992; Robie and Hemingway, 1995), paralleled by related and applicable work in the larger scientific community (e.g., Wagman et al., 1982, 1989; Cox et al., 1989;more » Barin and Platzki, 1995; Binneweis and Milke, 1999). The Yucca Mountain Project developed two qualified thermodynamic databases for to model geochemical processes, including ones involving repository components such as spent fuel. The first of the two (BSC, 2007a) was for systems containing dilute aqueous solutions only, the other (BSC, 2007b) for systems involving concentrated aqueous solutions and incorporating a model for such based on Pitzer’s (1991) equations . A 25°C-only database with similarities to the latter was also developed for WIPP (cf. Xiong, 2005). The YMP dilute systems database is widely used in the geochemistry community for a variety of applications involving rock/water interactions. The purpose of the present task is to improve these databases for work on the Used Fuel Disposition Project and maintain some semblance of order that will support qualification in support of the development of future underground high level nuclear waste disposal.« less

Investigation of chemical modifiers for the direct determination of arsenic in fish oil using high-resolution continuum source graphite furnace atomic absorption spectrometry.

PubMed

Pereira, Éderson R; de Almeida, Tarcísio S; Borges, Daniel L G; Carasek, Eduardo; Welz, Bernhard; Feldmann, Jörg; Campo Menoyo, Javier Del

2016-04-01

High-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) has been applied for the development of a method for the determination of total As in fish oil samples using direct analysis. The method does not use any sample pretreatment, besides dilution with 1-propanole, in order to decrease the oil viscosity. The stability and sensitivity of As were evaluated using ruthenium and iridium as permanent chemical modifiers and palladium added in solution over the sample. The best results were obtained with ruthenium as the permanent modifier and palladium in solution added to samples and standard solutions. Under these conditions, aqueous standard solutions could be used for calibration for the fish oil samples diluted with 1-propanole. The pyrolysis and atomization temperatures were 1400 °C and 2300 °C, respectively, and the limit of detection and characteristic mass were 30 pg and 43 pg, respectively. Accuracy and precision of the method have been evaluated using microwave-assisted acid digestion of the samples with subsequent determination by HR-CS GF AAS and ICP-MS; the results were in agreement (95% confidence level) with those of the proposed method. Copyright © 2015 Elsevier B.V. All rights reserved.

Dehydration induced phase transitions in a microfluidic droplet array for the separation of biomolecules

NASA Astrophysics Data System (ADS)

Nelson, Chris; Anna, Shelley

2013-11-01

Droplet-based strategies for fluid manipulation have seen significant application in microfluidics due to their ability to compartmentalize solutions and facilitate highly parallelized reactions. Functioning as micro-scale reaction vessels, droplets have been used to study protein crystallization, enzyme kinetics, and to encapsulate whole cells. Recently, the mass transport out of droplets has been used to concentrate solutions and induce phase transitions. Here, we show that droplets trapped in a microfluidic array will spontaneously dehydrate over the course of several hours. By loading these devices with an initially dilute aqueous polymer solution, we use this slow dehydration to observe phase transitions and the evolution of droplet morphology in hundreds of droplets simultaneously. As an example, we trap and dehydrate droplets of a model aqueous two-phase system consisting of polyethylene glycol and dextran. Initially the drops are homogenous, then after some time the polymer concentration reaches a critical point and two phases form. As water continues to leave the system, the drops transition from a microemulsion of DEX in PEG to a core-shell configuration. Eventually, changes in interfacial tension, driven by dehydration, cause the DEX core to completely de-wet from the PEG shell. Since aqueous two phase systems are able to selectively separate a variety of biomolecules, this core shedding behavior has the potential to provide selective, on-chip separation and concentration.

Preparation of crosslinked chitosan magnetic membrane for cations sorption from aqueous solution.

PubMed

Khan, Adnan; Begum, Samina; Ali, Nauman; Khan, Sabir; Hussain, Sajjad; Sotomayor, Maria Del Pilar Taboada

2017-05-01

A chitosan magnetic membrane was prepared in order to confer magnetic properties to the membrane, which could be used for the removal of cations from aqueous solution. The crosslinked magnetic membrane was compared with pristine chitosan membrane in term of stability, morphology and cation adsorption capacity. The fabricated magnetic materials are thermally stable as shown by thermogravimetric curves. The membrane containing nickel magnetic particles (CHNiF-G) shows high thermal stability compared to the other membranes. The Fourier transform infrared spectroscopy showed successful preparation of chitosan magnetic membrane. Scanning electron microscopy micrographs showed the rough surface of the membrane with increased porosity. The prepared chitosan membranes were applied to cations of copper, nickel and lead in dilute aqueous solution. The chitosan membrane showed the following adsorption order for metallic cations: Cu 2+ > Ni 2+ > Pb 2+ , while CHNiF-G showed higher capacity, 3.51 mmol g -1 for copper, reflecting the improvement in adsorption capacity, since the amount of copper on pristine chitosan gave 1.40 mmol g -1 . The time required for adsorption to reach to the equilibrium was 6 h for the selected cations using different chitosan membranes. The kinetic study showed that adsorption followed pseudo-second order kinetics. The most commonly used isotherm models, Freundlich, Langmuir and Temkin, were applied to experimental data using linear regression technique. However, The Temkin model fits better to experimental data.

Potentiometric and spectrophotometric study of the stability of magnesium carbonate and bicarbonate ion pairs to 150 °C and aqueous inorganic carbon speciation and magnesite solubility

NASA Astrophysics Data System (ADS)

Stefánsson, Andri; Bénézeth, Pascale; Schott, Jacques

2014-08-01

The formation constants of magnesium bicarbonate and carbonate ion pairs have been experimentally determined in dilute hydrothermal solutions to 150 °C. Two experimental approaches were applied, potentiometric acid-base titrations at 10-60 °C and spectrophotometric pH measurements using two pH indicators, 2-naphthol and 4-nitrophenol, at 25 and 80-150 °C. At a given temperature, the first and second ionization constants of carbonic acid (K1, K2) and the ion pair formation constants for MgHCO3+(aq) (KMgHCO3+) and MgCO3(aq) (KMgCO3) were simultaneously fitted to the data. Results of this study compare well with previously determined values of K1 and K2. The formation constants of MgHCO3+(aq) and MgCO3(aq) ion pairs increased significantly with increasing temperature, with values of logKMgHCO3+ = 1.14 and 1.75 and of logKMgCO3 = 2.86 and 3.48 at 10 °C and 100 °C, respectively. These ion pairs are important aqueous species under neutral to alkaline conditions in moderately dilute to concentrated Mg-containing solutions, with MgCO3(aq) predominating over CO32-(aq) in solutions at pH >8. The predominance of magnesium carbonate over carbonate is dependent on the concentration of dissolved magnesium and the ratio of magnesium over carbonate. With increasing temperature and at alkaline pH, brucite solubility further reduced the magnesium concentration to levels below 1 mmol kg-1, thus limiting availability of Mg2+(aq) for magnesite precipitation.

Synthesis of fast response crosslinked PVA-g-NIPAAm nanohydrogels by very low radiation dose in dilute aqueous solution

NASA Astrophysics Data System (ADS)

Fathi, Marziyeh; Reza Farajollahi, Ali; Akbar Entezami, Ali

2013-05-01

Nanohydrogels of poly(vinyl alcohol)-g-N-isopropylacrylamide (PVA-g-NIPAAm) are synthesized by PVA and NIPAAm dilute aqueous solution using much less radiation dose of 1-20 Gy via intramolecular crosslinking at ambient temperature. The radiation synthesis of nanohydrogels is performed in the presence of tetrakis (hydroxymethyl) phosphonium chloride (THPC) due to its rapid oxygen scavenging abilities and hydrogen peroxide (H2O2) as a source of hydroxyl radicals. The effect of radiation dose, feed composition ratio of PVA and H2O2 is investigated on swelling properties such as temperature and pH dependence of equilibrium swelling ratio as well as deswelling kinetics. Experimental data exhibit high equilibrium swelling ratio and fast response time for the synthesized nanohydrogels. The average molecular weight between crosslinks (Mc) and crosslinking density (ρx) of the obtained nanohydrogels are calculated from swelling data as a function of radiation dose, H2O2 and PVA amount. Fourier transform infrared spectroscopy (FT-IR), elemental analysis of nitrogen content and thermogravimetric analysis (TGA) are used to confirm the grafting reaction. Lower critical solution temperature (LCST) is measured around 33 °C by differential scanning calorimetry (DSC) for PVA-g-NIPAAm nanohydrogels. Dynamic light scattering (DLS) data demonstrate that the increase of radiation dose leads to the decreasing in dimension of nanohydrogels. Also, rheological studies are confirmed an improvement in the mechanical properties of the nanohydrogels with increasing the radiation dose. A cytotoxicity study exhibits a good biocompatibility for the obtained nanohydrogels. The prepared nanohydrogels show fast swelling/deswelling behavior, high swelling ratio, dual sensitivity and good cytocompatibility, which may find potential applications as biomaterial.

Physical properties of aqueous solutions of a thermo-responsive neutral copolymer and an anionic surfactant: turbidity and small-angle neutron scattering studies.

PubMed

Galant, Céline; Kjøniksen, Anna-Lena; Knudsen, Kenneth D; Helgesen, Geir; Lund, Reidar; Laukkanen, Antti; Tenhu, Heikki; Nyström, Bo

2005-08-16

Aqueous mixtures of the anionic sodium dodecyl sulfate (SDS) surfactant and thermo-responsive poly(N-vinylcaprolactam) chains grafted with omega-methoxy poly(ethylene oxide) undecyl alpha-methacrylate (PVCL-g-C11EO42) have been characterized using turbidimetry and small-angle neutron scattering (SANS). Turbidity measurements show that the addition of SDS to a dilute aqueous copolymer solution (1.0 wt %) induces an increase of the cloud point (CP) value and a decrease of the turbidity at high temperatures. In parallel, SANS results show a decrease of both the average distance between chains and the global size of the objects in solution at high temperatures as the SDS concentration is increased. Combination of these findings reveals that the presence of SDS in the PVCL-g-C11EO42 solutions (1.0 wt %) promotes the formation of smaller aggregates and, consequently, leads to a more homogeneous distribution of the chains in solution upon heating of the mixtures. Moreover, the SANS data results show that the internal structure of the formed aggregates becomes more swollen as the SDS concentration increases. On the other hand, the addition of moderate amounts of SDS (up to 4 mm) to a semidilute copolymer solution (5.0 wt %) gives rise to a more pronounced aggregation as the temperature rises; turbidity and SANS studies reveal in this case a decrease of the CP value and an increase of the scattered intensity at low q. The overall picture that emerges from this study is that the degree of aggregation can be accurately tuned by varying parameters such as the temperature, level of surfactant addition, and polymer concentration.

Ice Recrystallization in a Solution of a Cryoprotector and Its Inhibition by a Protein: Synchrotron X-Ray Diffraction Study.

PubMed

Zakharov, Boris; Fisyuk, Alexander; Fitch, Andy; Watier, Yves; Kostyuchenko, Anastasia; Varshney, Dushyant; Sztucki, Michael; Boldyreva, Elena; Shalaev, Evgenyi

2016-07-01

Ice formation and recrystallization is a key phenomenon in freezing and freeze-drying of pharmaceuticals and biopharmaceuticals. In this investigation, high-resolution synchrotron X-ray diffraction is used to quantify the extent of disorder of ice crystals in binary aqueous solutions of a cryoprotectant (sorbitol) and a protein, bovine serum albumin. Ice crystals in more dilute (10 wt%) solutions have lower level of microstrain and larger crystal domain size than these in more concentrated (40 wt%) solutions. Warming the sorbitol-water mixtures from 100 to 228 K resulted in partial ice melting, with simultaneous reduction in the microstrain and increase in crystallite size, that is, recrystallization. In contrast to sorbitol solutions, ice crystals in the BSA solutions preserved both the microstrain and smaller crystallite size on partial melting, demonstrating that BSA inhibits ice recrystallization. The results are consistent with BSA partitioning into quasi-liquid layer on ice crystals but not with a direct protein-ice interaction and protein sorption on ice surface. The study shows for the first time that a common (i.e., not-antifreeze) protein can have a major impact on ice recrystallization and also presents synchrotron X-ray diffraction as a unique tool for quantification of crystallinity and disorder in frozen aqueous systems. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Determination of calcium, magnesium and zinc in lubricating oils by flame atomic absorption spectrometry using a three-component solution.

PubMed

Zmozinski, Ariane V; de Jesus, Alexandre; Vale, Maria G R; Silva, Márcia M

2010-12-15

Lubricating oils are used to decrease wear and friction of movable parts of engines and turbines, being in that way essential for the performance and the increase of that equipment lifespan. The presence of some metals shows the addition of specific additives such as detergents, dispersals and antioxidants that improve the performance of these lubricants. In this work, a method for determination of calcium, magnesium and zinc in lubricating oil by flame atomic absorption spectrometry (F AAS) was developed. The samples were diluted with a small quantity of aviation kerosene (AVK), n-propanol and water to form a three-component solution before its introduction in the F AAS. Aqueous inorganic standards diluted in the same way have been used for calibration. To assess the accuracy of the new method, it was compared with ABNT NBR 14066 standard method, which consists in diluting the sample with AVK and in quantification by F AAS. Two other validating methods have also been used: the acid digestion and the certified reference material NIST (SRM 1084a). The proposed method provides the following advantages in relation to the standard method: significant reduction of the use of AVK, higher stability of the analytes in the medium and application of aqueous inorganic standards for calibration. The limits of detection for calcium, magnesium and zinc were 1.3 μg g(-1), 0.052 μg g(-1) and 0.41 μg g(-1), respectively. Concentrations of calcium, magnesium and zinc in six different samples obtained by the developed method did not differ significantly from the results obtained by the reference methods at the 95% confidence level (Student's t-test and ANOVA). Therefore, the proposed method becomes an efficient alternative for determination of metals in lubricating oil. Copyright © 2010 Elsevier B.V. All rights reserved.

Recovery of acetic acid from dilute aqueous solutions using catalytic dehydrative esterification with ethanol.

PubMed

Yagyu, Daisuke; Ohishi, Tetsuo; Igarashi, Takeshi; Okumura, Yoshikuni; Nakajo, Tetsuo; Mori, Yuichiro; Kobayashi, Shū

2013-03-01

We have developed a direct esterification of aqueous acetic acid with ethanol (molar ratio=1:1) catalyzed by polystyrene-supported or homogeneous sulfonic acids toward the recovery of acetic acid from wastewater in chemical plants. The equilibrium yield was significantly increased by the addition of toluene, which had a high ability to extract ethyl acetate from the aqueous phase. It was shown that low-loading and alkylated polystyrene-supported sulfonic acid efficiently accelerated the reaction. These results suggest that the construction of hydrophobic reaction environments in water was critical in improving the chemical yield. Addition of inorganic salts was also effective for the reaction under not only biphasic conditions (toluene-water) but also toluene-free conditions, because the mutual solubility of ethyl acetate and water was suppressed by the salting-out effect. Among the tested salts, CaCl(2) was found to be the most suitable for this reaction system. Copyright © 2012 Elsevier Ltd. All rights reserved.

Quantum mechanical/molecular mechanical modeling finds Diels-Alder reactions are accelerated less on the surface of water than in water.

PubMed

Thomas, Laura L; Tirado-Rives, Julian; Jorgensen, William L

2010-03-10

Quantum and molecular mechanics calculations for the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the vacuum-water interface and in the gas phase. In conjunction with previous studies of these cycloadditions in dilute solution, a more complete picture of aqueous environmental effects emerges with implications for the origin of observed rate accelerations using heterogeneous aqueous suspensions, "on water" conditions. The pure TIP4P water slab maintains the bulk density and hydrogen-bonding properties in central water layers. The bulk region merges to vacuum over a ca. 5 A band with progressive diminution of the density and hydrogen bonding. The relative free energies of activation and transition structures for the reactions at the interface are found to be intermediate between those calculated in the gas phase and in bulk water; i.e., for the reaction with 1,4-naphthoquinone, the DeltaDeltaG(++) values relative to the gas phase are -3.6 and -7.3 kcal/mol at the interface and in bulk water, respectively. Thus, the results do not support the notion that a water surface is more effective than bulk water for catalysis of such pericyclic reactions. The trend is in qualitative agreement with expectations based on density considerations and estimates of experimental rate constants for the gas phase, a heterogeneous aqueous suspension, and a dilute aqueous solution for the reaction of cyclopentadiene with methyl vinyl ketone. Computed energy pair distributions reveal a uniform loss of 0.5-1.0 hydrogen bond for the reactants and transition states in progressing from bulk water to the vacuum-water interface. Orientational effects are apparent at the surface; e.g., the carbonyl group in the methyl vinyl ketone transition structure is preferentially oriented into the surface. Also, the transition structure for the 1,4-naphthoquinone case is buried more in the surface, and the free energy of activation for this reaction is most similar to the result in bulk water.

Functionalized polyethylene fibers for the selective capture of palladium ions from aqueous solution

NASA Astrophysics Data System (ADS)

Pang, Li-juan; Li, Rong; Hu, Jiang-tao; Zhang, Lin-juan; Zhang, Ming-xing; Yang, Chen-guang; Wu, Guo-zhong

2018-03-01

An innovative ultrahigh molecular weight polyethylene (UHMWPE) fibrous adsorbent was successfully synthesized via radiation grafting and applied to the selective capture of palladium ions from dilute aqueous solutions. The influence of the pH, initial Pd(II) concentration, and temperature on the adsorption performance was examined in a batch adsorption experiment. Pd K-edge extended X-ray absorption fine structure (EXAFS) spectra indicated that Pd(II) was immobilized on the adsorbent surface via a ligand exchange reaction that formed a stable UHMWPE-PMDA-Pd complex. Although the concentrations of coexisting ions (Cu(II), Zn(II), Cr(VI), Fe(III), and Ni(II)) in the solution were much higher than that of Pd(II), the adsorption capacity for Pd(II) of the as-prepared absorbent was significantly greater than that for other metal ions. Kinetic studies showed good correlation with the pseudo-second-order model. The maximum capacity for Pd(II) adsorption was approximately 221.8 mg·g-1 at 298 K. The adsorption behavior conformed to the Langmuir isotherm model. Thermodynamic studies revealed that the adsorption of Pd(II) was a feasible, spontaneous, and endothermic process.

Molecular Dynamics Simulations of Strain-Induced Phase Transition of Poly(ethylene oxide) in Water.

PubMed

Donets, Sergii; Sommer, Jens-Uwe

2018-01-11

We study the dilute aqueous solutions of poly(ethylene oxide) (PEO) oligomers that are subject to an elongating force dipole acting on both chain ends using atomistic molecular dynamics. By increasing the force, liquid-liquid demixing can be observed at room temperature far below the lower critical solution temperature. For forces above 35 pN, fibrillar nanostructures are spontaneously formed related to a decrease in hydrogen bonding between PEO and water. Most notable is a rapid decrease in the bifurcated hydrogen bonds during stretching, which can also be observed for isolated single chains. The phase-segregated structures display signs of chain ordering, but a clear signature of the crystalline order is not obtained during the simulation time, indicating a liquid-liquid phase transition induced by chain stretching. Our results indicate that the solvent quality of the aqueous solution of PEO depends on the conformational state of the chains, which is most likely related to the specific hydrogen-bond-induced solvation of PEO in water. The strain-induced demixing of PEO opens the possibility to obtain polymer fibers with low energy costs because crystallization starts via the strain-induced demixing in the extended state only.

Structural motifs of pre-nucleation clusters.

PubMed

Zhang, Y; Türkmen, I R; Wassermann, B; Erko, A; Rühl, E

2013-10-07

Structural motifs of pre-nucleation clusters prepared in single, optically levitated supersaturated aqueous aerosol microparticles containing CaBr2 as a model system are reported. Cluster formation is identified by means of X-ray absorption in the Br K-edge regime. The salt concentration beyond the saturation point is varied by controlling the humidity in the ambient atmosphere surrounding the 15-30 μm microdroplets. This leads to the formation of metastable supersaturated liquid particles. Distinct spectral shifts in near-edge spectra as a function of salt concentration are observed, in which the energy position of the Br K-edge is red-shifted by up to 7.1 ± 0.4 eV if the dilute solution is compared to the solid. The K-edge positions of supersaturated solutions are found between these limits. The changes in electronic structure are rationalized in terms of the formation of pre-nucleation clusters. This assumption is verified by spectral simulations using first-principle density functional theory and molecular dynamics calculations, in which structural motifs are considered, explaining the experimental results. These consist of solvated CaBr2 moieties, rather than building blocks forming calcium bromide hexahydrates, the crystal system that is formed by drying aqueous CaBr2 solutions.

Inhibition of the solid state transformation of carbamazepine in aqueous solution: impact of polymeric properties.

PubMed

Gift, Alan D; Hettenbaugh, Jacob A; Quandahl, Rachel A; Mapes, Madison

2017-11-06

The effects of polymers on the anhydrate-to-hydrate transformation of carbamazepine (CBZ) was investigated. The three types of polymers studied were polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and substituted celluloses which included hydroxypropyl methylcellulose (HPMC) and methylcellulose (MC). Anhydrous CBZ was added to dilute aqueous polymer solutions and Raman spectroscopy measurements were collected to monitor the kinetics of the solution-mediated transformation to CBZ dihydrate. Polymers exhibiting the greatest inhibition were able to reduce the growth phase of the solution-mediated transformation and change the habit of the hydrate crystal indicating polymer adsorption to the hydrate crystal surface as the mechanism of inhibition. The results of the various polymers showed that short chain substituted celluloses (HPMC and MC) inhibited the CBZ transformation to a much greater extent than longer chains. The same trend was observed for PVP and PVA, but to a lesser extent. These chain length effects were attributed to changes in polymer confirmation when adsorbed on the crystal surface. Additionally, decreasing the percentage of hydroxyl groups on the PVA polymer backbone reduced the ability of the polymer to inhibit the transformation and changing the degree of substitutions of methyl and hydroxypropyl groups on the cellulosic polymer backbone had no effect on the transformation.

Poly(methacrylic acid)-grafted chitosan microspheres via surface-initiated ATRP for enhanced removal of Cd(II) ions from aqueous solution.

PubMed

Huang, Liqiang; Yuan, Shaojun; Lv, Li; Tan, Guangqun; Liang, Bin; Pehkonen, S O

2013-09-01

Cross-linked chitosan (CCS) microspheres tethered with pH-sensitive poly(methacrylic acid) (PMAA) brushes were developed for the efficient removal of Cd(II) ions from aqueous solutions. Functional PMAA brushes containing dense and active carboxyl groups (COOH) were grafted onto the CCS microsphere surface via surface-initiated atom transfer radical polymerization (ATRP). Batch adsorption results showed that solution pH values had a major impact on cadmium adsorption by the PMAA-grafted CCS microspheres with the optimal removal observed above pH 5. The CCS-g-PMAA microsphere was found to achieve the adsorption equilibrium of Cd(II) within 1 h, much faster than about 7 h on the CCS microsphere. At pH 5 and with an initial concentration 0.089-2.49 mmol dm(-3), the maximum adsorption capacity of Cd(II), derived from the Langmuir fitting on the PMAA-grafted microspheres was around 1.3 mmol g(-1). Desorption and adsorption cycle experimental results revealed that the PMAA-grafted CCS microspheres loaded with Cd(II) can be effectively regenerated in a dilute HNO3 solution, and the adsorption capacity remained almost unchanged upon five cycle reuse. Copyright © 2013 Elsevier Inc. All rights reserved.

Hydration shell parameters of aqueous alcohols: THz excess absorption and packing density.

PubMed

Matvejev, V; Zizi, M; Stiens, J

2012-12-06

Solvation in water requires minimizing the perturbations in its hydrogen bonded network. Hence solutes distort water molecular motions in a surrounding domain, forming a molecule-specific hydration shell. The properties of those hydration shells impact the structure and function of the solubilized molecules, both at the single molecule and at higher order levels. The size of the hydration shell and the picoseconds time-scale water dynamics retardation are revealed by terahertz (THz) absorption coefficient measurements. Room-temperature absorption coefficient at f = 0.28 [THz] is measured as a function of alcohol concentration in aqueous methanol, ethanol, 1,2-propanol, and 1-butanol solutions. Highly diluted alcohol measurements and enhanced overall measurement accuracy are achieved with a THz absorption measurement technique of nL-volume liquids in a capillary tube. In the absorption analysis, bulk and interfacial molecular domains of water and alcohol are considered. THz ideal and excess absorption coefficients are defined in accordance with thermodynamics mixing formulations. The parameter extraction method is developed based on a THz excess absorption model and hydrated solute molecule packing density representation. First, the hydration shell size is deduced from the hydrated solute packing densities at two specific THz excess absorption nonlinearity points: at infinite alcohol dilution (IAD) and at the THz excess absorption extremum (EAE). Consequently, interfacial water and alcohol molecular domain absorptions are deduced from the THz excess absorption model. The hydration shell sizes obtained at the THz excess absorption extremum are in excellent agreement with other reports. The hydration shells of methanol, ethanol, 1- and 2-propanol consist of 13.97, 22.94, 22.99, and 31.10 water molecules, respectively. The hydration shell water absorption is on average 0.774 ± 0.028 times the bulk water absorption. The hydration shell parameters might shed light on hydration dynamics of biomolecules.

Rapid recovery of dilute copper from a simulated Cu-SDS solution with low-cost steel wool cathode reactor.

PubMed

Chang, Shih-Hsien; Wang, Kai-Sung; Hu, Pei-I; Lui, I-Chun

2009-04-30

Copper-surfactant wastewaters are often encountered in electroplating, printed circuit boards manufacturing, and metal finishing industries, as well as in retentates from micellar-enhanced ultrafiltration process. A low-cost three-dimensional steel wool cathode reactor was evaluated for electrolytic recovery of Cu ion from dilute copper solution (0.2mM) in the presence of sodium dodecyl sulfate (SDS), octylphenol poly (ethyleneglycol) 9.5 ether (TX), nonylphenol poly (oxyethylene) 9 ether (NP9) and polyoxyethylene (20) sorbitan monooleate (TW) and also mixed surfactants (anionic/nonionic). The reactor showed excellent copper recovery ability in comparison to a parallel-plate reactor. The reactor rapidly recovered copper with a reasonable current efficiency. 93% of copper was recovered at current density of 1 A m(-2) and pH 4 in the presence of 8.5mM SDS. Initial solution pH, cathodic current density, solution mixing condition, SDS concentration, and initial copper concentrations significantly influenced copper recovery. The copper recovery rate increased with an increase in aqueous SDS concentrations between 5 and 8.5mM. The influences of nonionic surfactants on Cu recovery from SDS-Cu solution depended not only on the type of surfactants used, but also on applied concentrations. From the copper recovery perspective, TX at 0.1mM or NP should be selected rather than TW, because they did not inhibit copper recovery from SDS-Cu solution.

Comparison of homeopathic globules prepared from high and ultra-high dilutions of various starting materials by ultraviolet light spectroscopy.

PubMed

Klein, Sabine D; Wolf, Ursula

2016-02-01

Homeopathic globules are commonly used in clinical practice, while research focuses on liquid potencies. Sequential dilution and succussion in their production process has been proposed to change the physico-chemical properties of the solvent(s). It has been reported that aqueous potencies of various starting materials showed significant differences in ultraviolet light transmission compared to controls and between different dilution levels. The aim of the present study was to repeat and expand these experiments to homeopathic globules. Globules were specially produced for this study by Spagyros AG (Gümligen, Switzerland) from 6 starting materials (Aconitum napellus, Atropa belladonna, phosphorus, sulfur, Apis mellifica, quartz) and for 6 dilution levels (6x, 12x, 30c, 200c, 200CF (centesimal discontinuous fluxion), 10,000CF). Native globules and globules impregnated with solvents were used as controls. Globules were dissolved in ultrapure water, and absorbance in the ultraviolet range was measured. The average absorbance from 200 to 340nm was calculated and corrected for differences between measurement days and instrumental drift. Statistically significant differences were found for A. napellus, sulfur, and A. mellifica when normalized average absorbance of the various dilution levels from the same starting material (including control and solvent control globules) was compared. Additionally, absorbance within dilution levels was compared among the various starting materials. Statistically significant differences were found among 30c, 200c and 200CF dilutions. This study has expanded previous findings from aqueous potencies to globules and may indicate that characteristics of aqueous high dilutions may be preserved and detectable in dissolved globules. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Dilution Confusion: Conventions for Defining a Dilution

ERIC Educational Resources Information Center

Fishel, Laurence A.

2010-01-01

Two conventions for preparing dilutions are used in clinical laboratories. The first convention defines an "a:b" dilution as "a" volumes of solution A plus "b" volumes of solution B. The second convention defines an "a:b" dilution as "a" volumes of solution A diluted into a final volume of "b". Use of the incorrect dilution convention could affect…

Development of a syringe pump assisted dynamic headspace sampling technique for needle trap device.

PubMed

Eom, In-Yong; Niri, Vadoud H; Pawliszyn, Janusz

2008-07-04

This paper describes a new approach that combines needle trap devices (NTDs) with a dynamic headspace sampling technique (purge and trap) using a bidirectional syringe pump. The needle trap device is a 22-G stainless steel needle 3.5-in. long packed with divinylbenzene sorbent particles. The same sized needle, without packing, was used for purging purposes. We chose an aqueous mixture of benzene, toluene, ethylbenzene, and p-xylene (BTEX) and developed a sequential purge and trap (SPNT) method, in which sampling (trapping) and purging cycles were performed sequentially by the use of syringe pump with different distribution channels. In this technique, a certain volume (1 mL) of headspace was sequentially sampled using the needle trap; afterwards, the same volume of air was purged into the solution at a high flow rate. The proposed technique showed an effective extraction compared to the continuous purge and trap technique, with a minimal dilution effect. Method evaluation was also performed by obtaining the calibration graphs for aqueous BTEX solutions in the concentration range of 1-250 ng/mL. The developed technique was compared to the headspace solid-phase microextraction method for the analysis of aqueous BTEX samples. Detection limits as low as 1 ng/mL were obtained for BTEX by NTD-SPNT.

Development and validation of a gas chromatography/mass spectrometry procedure for confirmation of para-toluenesulfonamide in edible fish fillet tissue

USGS Publications Warehouse

Idowu, O.R.; Kijak, P.J.; Meinertz, J.R.; Schmidt, L.J.

2004-01-01

Chloramine-T is a disinfectant being developed as a treatment for bacterial gill disease in cultured fish. As part of the drug approval process, a method is required for the confirmation of chloramine-T residues in edible fish tissue. The marker residue that will be used to determine the depletion of chloramine-T residues from the edible tissue of treated fish is para-toluenesulfonamide (p-TSA), a metabolite of chloramine-T. The development and validation of a procedure for the confirmation of p-TSA is described. Homogenized fish tissue is dried by mixing with anhydrous sodium sulfate, and the mixture is extracted with methylene chloride. The extract is passed through a silica gel solid-phase extraction column, from which p-TSA is subsequently eluted with acetonitrile. The acetonitrile extract is evaporated, and the oily residue is dissolved in hexane. The hexane solution is shaken with fresh acetonitrile. The acetonitrile solution is evaporated and the residue is redissolved in dilute potassium hydroxide solution. The aqueous solution is extracted with methylene chloride to further remove more of the fat co-extractive. The aqueous solution is reacted with pentafluorobenzyl bromide in presence of tetrabutylammonium hydrogensulfate. The resulting di-(pentafluorobenzyl) derivative of p-TSA is analyzed by gas chromatography/mass spectrometry. This method permits the confirmation of p-TSA in edible fish tissue at 20 ppb.

Development and validation of a gas chromatography/mass spectrometry procedure for confirmation of para-toluenesulfonamide in edible fish fillet tissue.

PubMed

Idowu, Olutosin R; Kijak, Philip J; Meinertz, Jeffery R; Schmidt, Larry J

2004-01-01

Chloramine-T is a disinfectant being developed as a treatment for bacterial gill disease in cultured fish. As part of the drug approval process, a method is required for the confirmation of chloramine-T residues in edible fish tissue. The marker residue that will be used to determine the depletion of chloramine-T residues from the edible tissue of treated fish is para-toluenesulfonamide (p-TSA), a metabolite of chloramine-T. The development and validation of a procedure for the confirmation of p-TSA is described. Homogenized fish tissue is dried by mixing with anhydrous sodium sulfate, and the mixture is extracted with methylene chloride. The extract is passed through a silica gel solid-phase extraction column, from which p-TSA is subsequently eluted with acetonitrile. The acetonitrile extract is evaporated, and the oily residue is dissolved in hexane. The hexane solution is shaken with fresh acetonitrile. The acetonitrile solution is evaporated and the residue is redissolved in dilute potassium hydroxide solution. The aqueous solution is extracted with methylene chloride to further remove more of the fat co-extractive. The aqueous solution is reacted with pentafluorobenzyl bromide in presence of tetrabutylammonium hydrogensulfate. The resulting di-(pentafluorobenzyl) derivative of p-TSA is analyzed by gas chromatography/mass spectrometry. This method permits the confirmation of p-TSA in edible fish tissue at 20 ppb.

Jarosite dissolution rates in perchlorate brine

NASA Astrophysics Data System (ADS)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures <250 K, and may exist as metastable or stable liquids for extended time periods, even under current Mars surface conditions. Therefore, jarosite-bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

Extraction of Trivalent Actinides and Lanthanides from Californium Campaign Rework Solution Using TODGA-based Solvent Extraction System

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

Benker, Dennis; Delmau, Laetitia Helene; Dryman, Joshua Cory

This report presents the studies carried out to demonstrate the possibility of quantitatively extracting trivalent actinides and lanthanides from highly acidic solutions using a neutral ligand-based solvent extraction system. These studies stemmed from the perceived advantage of such systems over cationexchange- based solvent extraction systems that require an extensive feed adjustment to make a low-acid feed. The targeted feed solutions are highly acidic aqueous phases obtained after the dissolution of curium targets during a californium (Cf) campaign. Results obtained with actual Cf campaign solutions, but highly diluted to be manageable in a glove box, are presented, followed by results ofmore » tests run in the hot cells with Cf campaign rework solutions. It was demonstrated that a solvent extraction system based on the tetraoctyl diglycolamide molecule is capable of quantitatively extracting trivalent actinides from highly acidic solutions. This system was validated using actual feeds from a Cf campaign.« less

Gas chromatography/isotope ratio mass spectrometry: analysis of methanol, ethanol and acetic acid by direct injection of aqueous alcoholic and acetic acid samples.

PubMed

Ai, Guomin; Sun, Tong; Dong, Xiuzhu

2014-08-15

Methanol, ethanol, and acetic acid are not easily extracted from aqueous samples and are susceptible to isotope fractionation in gas chromatography/isotope ratio mass spectrometry (GC/IRMS) analysis. Developing a direct dilution GC/IRMS method for aqueous samples, by adjusting the sample concentrations in common solvents to be similar to each other and using a fixed GC split ratio, is very convenient and important because any linearity effects caused by amount-dependent isotope fractionation can be avoided. The suitability of acetonitrile and acetone solvents for the GC/IRMS analysis of pure methanol, ethanol and acetic acid, and commercial liquor and vinegar samples was evaluated using n-hexane and water as control solvents. All the solvents including water were separated from the analyte on a HP-INNOWAX column and were diverted away from the combustion interface. The influence of liquor matrix on the ethanol GC/IRMS analyses was evaluated by adding pure ethanol to liquor samples. Acetonitrile and acetone gave similar δ(13) C values for pure ethanol and pure acetic acid to those obtained in water and n-hexane, and also gave similar δ(13) C values of ethanol in liquor and acetic acid in white vinegar to that obtained in water. For methanol analysis, acetonitrile and refined acetone gave similar δ(13) C values to that obtained in water, but n-hexane was not a suitable solvent. In addition, isotopic fractionation caused by solvent and solute interactions was observed. We recommend using acetonitrile for the GC/IRMS analysis of aqueous alcoholic samples, and acetone for the analysis of aqueous acetic acid samples. This direct dilution method can provide high accurate and precise GC/IRMS analysis of the relative changes in δ(13) C values of methanol, ethanol, and acetic acid. Copyright © 2014 John Wiley & Sons, Ltd.

Quantitative assessments of the distinct contributions of polypeptide backbone amides versus sidechain groups to chain expansion via chemical denaturation

PubMed Central

Holehouse, Alex S.; Garai, Kanchan; Lyle, Nicholas; Vitalis, Andreas; Pappu, Rohit V.

2015-01-01

In aqueous solutions with high concentrations of chemical denaturants such as urea and guanidinium chloride (GdmCl) proteins expand to populate heterogeneous conformational ensembles. These denaturing environments are thought to be good solvents for generic protein sequences because properties of conformational distributions align with those of canonical random coils. Previous studies showed that water is a poor solvent for polypeptide backbones and therefore backbones form collapsed globular structures in aqueous solvents. Here, we ask if polypeptide backbones can intrinsically undergo the requisite chain expansion in aqueous solutions with high concentrations of urea and GdmCl. We answer this question using a combination of molecular dynamics simulations and fluorescence correlation spectroscopy. We find that the degree of backbone expansion is minimal in aqueous solutions with high concentrations denaturants. Instead, polypeptide backbones sample conformations that are denaturant-specific mixtures of coils and globules, with a persistent preference for globules. Therefore, typical denaturing environments cannot be classified as good solvents for polypeptide backbones. How then do generic protein sequences expand in denaturing environments? To answer this question, we investigated the effects of sidechains using simulations of two archetypal sequences with amino acid compositions that are mixtures of charged, hydrophobic, and polar groups. We find that sidechains lower the effective concentration of backbone amides in water leading to an intrinsic expansion of polypeptide backbones in the absence of denaturants. Additional dilution of the effective concentration of backbone amides is achieved through preferential interactions with denaturants. These effects lead to conformational statistics in denaturing environments that are congruent with those of canonical random coils. Our results highlight the role of sidechain-mediated interactions as determinants of the conformational properties of unfolded states in water and in influencing chain expansion upon denaturation. PMID:25664638

Degradation of artificial sweeteners via direct and indirect photochemical reactions.

PubMed

Perkola, Noora; Vaalgamaa, Sanna; Jernberg, Joonas; Vähätalo, Anssi V

2016-07-01

We studied the direct and indirect photochemical reactivity of artificial sweeteners acesulfame, saccharin, cyclamic acid and sucralose in environm entally relevant dilute aqueous solutions. Aqueous solutions of sweeteners were irradiated with simulated solar radiation (>290 nm; 96 and 168 h) or ultraviolet radiation (UVR; up to 24 h) for assessing photochemical reactions in surface waters or in water treatment, respectively. The sweeteners were dissolved in deionised water for examination of direct photochemical reactions. Direct photochemical reactions degraded all sweeteners under UVR but only acesulfame under simulated solar radiation. Acesulfame was degraded over three orders of magnitude faster than the other sweeteners. For examining indirect photochemical reactions, the sweeteners were dissolved in surface waters with indigenous dissolved organic matter or irradiated with aqueous solutions of nitrate (1 mg N/L) and ferric iron (2.8 mg Fe/L) introduced as sensitizers. Iron enhanced the photodegradation rates but nitrate and dissolved organic matter did not. UVR transformed acesulfame into at least three products: iso-acesulfame, hydroxylated acesulfame and hydroxypropanyl sulfate. Photolytic half-life was one year for acesulfame and more than several years for the other sweeteners in surface waters under solar radiation. Our study shows that the photochemical reactivity of commonly used artificial sweeteners is variable: acesulfame may be sensitive to photodegradation in surface waters, while saccharin, cyclamic acid and sucralose degrade very slowly even under the energetic UVR commonly used in water treatment.

[Determination of the alcohol level of alcoholic beverages with the Technicon thermometric autoanalyser].

PubMed

Dupont, P

1978-01-01

Thermometric analyses consists in measuring the enthalpy variations of chemical reaction. The dilution of an hydroalcoholic solution in a aqueous solution of sodium perchlorate is an endothermal reaction, and the variations of temperature within certains limits are functions of the initial alcohol concentration. The variations are collected, amplified and recorded on a diagram. This has been done in the quality control laboratory of our company with a Technicon apparatus to determine the alcoholic strength of spirits at 45 degrees. In industrial use one needs only to compare the height of the peaks corresponding to the product being analysed with the check sample peaks. This quick and precise process, of a great simplicity of utilisation makes it possible to discard the distillation method.

Mineral catalysis of a potentially prebiotic aldol condensation

NASA Technical Reports Server (NTRS)

De Graaf, R. M.; Visscher, J.; Xu, Y.; Arrhenius, G.; Schwartz, A. W.

1998-01-01

Minerals may have played a significant role in chemical evolution. In the course of investigating the chemistry of phosphonoacetaldehyde (PAL), an analogue of glycolaldehyde phosphate, we have observed a striking case of catalysis by the layered hydroxide mineral hydrotalcite ([Mg2Al(OH)6][Cl.nH2O]). In neutral or moderately basic aqueous solutions, PAL is unreactive even at a concentration of 0.1 M. In the presence of a large excess of NaOH (2 M), the compound undergoes aldol condensation to produce a dimer containing a C3-C4 double-bond. In dilute neutral solutions and in the presence of the mineral, however, condensation takes place rapidly, to produce a dimer which is almost exclusively the C2-C3 unsaturated product.

Effects of glaucoma medications and preservatives on cultured human trabecular meshwork and non-pigmented ciliary epithelial cell lines.

PubMed

Ammar, David A; Kahook, Malik Y

2011-10-01

We investigated the potential cytotoxicity of various topical ophthalmic glaucoma formulations containing different preservatives in cultured human trabecular meshwork (TM) and non-pigmented ciliary epithelial (NPCE) cell lines. We tested 0.004% travoprost preserved with either 0.015% benzalkonium chloride (BAK), sofZia or 0.001% Polyquad (PQ); and 0.005% latanoprost preserved with 0.020% BAK. We also tested a range of BAK concentrations in balanced salt solution (BSS). TM cells were treated for 10 min at 37°C with solutions diluted 1:10 to mimic the reduced penetration of topical preparations to the anterior chamber. Viability was determined by the uptake of the fluorescent vital dye calcein-AM (n = 6). BAK solutions (diluted 1:10) demonstrated a dose-dependent reduction in cell viability in both cell types (TM and NPCE). With a 1:10 dilution of 0.020% BAK, there were significantly more living NPCE cells (89 ± 6%) than TM cells (57 ± 6%; p < 0.001). In TM cells, travoprost + BAK had statistically fewer live cells (83 ± 5%) than both travoprost + sofZia (97 ± 5%) and travoprost + PQ (97 ± 6%; p < 0.05). Compared with BSS-treated NPCE cells, travoprost had statistically fewer live cells (p < 0.05) when preserved with BAK (85 ± 16%), sofZia (91 ± 6%) or PQ (94 ± 2%). These results demonstrate that substitution of BAK from topical ophthalmic drugs results in greater viability of cultured TM cells, the cells involved in the conventional outflow pathway. Cultured NPCE, responsible for aqueous inflow, appear more resilient to BAK.

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

Draganic, Z.D.; Draganic, I.G.; Shushtarian, M.J.

A study was made of the radiolytic behavior of dilute, neutral, oxygen-free aqueous solutions of CH/sub 3/CN and C/sub 2/H/sub 5/CN. Small-molecular products were identified as RCHO, NH/sub 3/, CO/sub 2/, and H/sub 2/. The decomposition of nitrile is followed by high yields of formation of the nonvolatile nitrogen-containing compounds, G(N). The ..gamma..-irradiated solutions exhibit a positive biuret reaction. Several amino acids were identified among radiolytic products, and glycine and alanine were found to be the most abundant for CH/sub 3/CN and C/sub 2/H/sub 5/CH, respectively. Their yields increased after strong acid hydrolysis of the irradiated samples. The free radicalsmore » formed by reactions of RCN with H, OH, and e/sub aq/- were found to be important for the phenomena observed. It is suggested that the positive biuret reaction, ir spectra, and the release of amino acids on acid hydrolysis provide some evidence on the formation of peptidic materials and might be of interest for the evaluation of the role that ionizing radiation might have played in prebiotic chemical evolution in aqueous media.« less

Selective adsorption of Pb(II) from aqueous solution using porous biosilica extracted from marine diatom biomass: Properties and mechanism

NASA Astrophysics Data System (ADS)

Qi, Yarong; Wang, Jingfeng; Wang, Xin; Cheng, Jay Jiayang; Wen, Zhiyou

2017-02-01

Biosilica with a surface area of 143 m2 g-1 derived from marine diatoms was prepared using an easy two-step method involving washing with dilute acid and baking. The extracted biosilica was used to remove divalent lead ions, i.e., Pb(II), from aqueous solution. The effects on Pb(II) adsorption of initial pH, shaking speed, and adsorbent loading were investigated. The adsorption of Pb(II) in the presence of other ions was also investigated. The biosilica showed a high adsorption capacity with high selectivity for Pb(II). The experimental maximum adsorption capacity was 108.2-120.4 mg g-1 at an adsorbent loading of 1 g L-1. The adsorption process was best described by the Langmuir model. The adsorbent selectively adsorbed Pb(II) from binary ion systems in the presence of Cu(II), Cd(II), Ni(II), and Ag(I). The results of this study show that biosilica extracted from fresh marine diatoms is a more efficient and selective adsorbent for Pb(II) than other inorganic adsorbents.

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

PubMed

Peng, Xinsheng; Karan, Santanu; Ichinose, Izumi

2009-08-04

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

Investigation of phase stability of poly(1-oxotrimethylene)-dissolved aqueous solutions containing ZnCl2/CaCl2/LiCl: Influence of boric acid introduction and aging time

NASA Astrophysics Data System (ADS)

Chae, Dong Wook; Jang, Han Beol; Kim, Byoung Chul

2018-02-01

Poly(1-oxotrimethylene) (POTM) was dissolved in aqueous solutions containing ZnCl2, CaCl2, and LiCl, and the effects of boric acid introduction on the phase stability of the POTM solutions over various aging times were investigated. In the absence of boric acid, aging at 70°C for 8 h notably reduced the loss tangent (tanδ) for the 7.0 wt.% POTM solutions. Addition of boric acid into unaged solutions had little effect on tanδ over the frequency range measured, regardless of its content, whereas addition of 0.3-1.0 wt.% of boric acid into aged solutions increased tanδ. The dynamic viscosity of the POTM solutions with 1.0 wt.% boric acid was affected little by aging time. Conversely, the POTM solutions without boric acid exhibited increased dynamic viscosity in the low-frequency range with aging time. In addition, the slope of the solutions in the Cole-Cole plot decreased with increasing aging time in the absence of boric acid, whereas aging time had little effect in the presence of 1.0 wt.% boric acid. For dilute POTM solutions ( i.e., 0.5 g/dL), the reduced viscosity decreased with increasing aging time in the absence of boric acid, while it was affected little in solutions with the addition of 1.0 wt.% boric acid. In the UV-Vis spectra, the aging-time-dependent increase of the absorbance peak at 390 nm was associated with the generation of a chromophoric complex in the POTM solutions. Conversely, the disappearance of the peak due to the addition of boric acid indicated suppression of complex formation.

Pretreatment of Dried Distiller Grains with Solubles by Soaking in Aqueous Ammonia and Subsequent Enzymatic/Dilute Acid Hydrolysis to Produce Fermentable Sugars.

PubMed

Nghiem, Nhuan P; Montanti, Justin; Kim, Tae Hyun

2016-05-01

Dried distillers grains with solubles (DDGS), a co-product of corn ethanol production in the dry-grind process, was pretreated by soaking in aqueous ammonia (SAA) using a 15 % w/w NH4OH solution at a solid/liquid ratio of 1:10. The effect of pretreatment on subsequent enzymatic hydrolysis was studied at two temperatures (40 and 60 °C) and four reaction times (6, 12, 24, and 48 h). Highest glucose yield of 91 % theoretical was obtained for the DDGS pretreated at 60 °C and 24 h. The solubilized hemicellulose in the liquid fraction was further hydrolyzed with dilute H2SO4 to generate fermentable monomeric sugars. The conditions of acid hydrolysis included 1 and 4 wt% acid, 60 and 120 °C, and 0.5 and 1 h. Highest yields of xylose and arabinose were obtained at 4 wt% acid, 120 °C, and 1 h. The fermentability of the hydrolysate obtained by enzymatic hydrolysis of the SAA-pretreated DDGS was demonstrated in ethanol fermentation by Saccharomyces cerevisiae. The fermentability of the hydrolysate obtained by consecutive enzymatic and dilute acid hydrolysis was demonstrated using a succinic acid-producing microorganism, strain Escherichia coli AFP184. Under the fermentation conditions, complete utilization of glucose and arabinose was observed, whereas only 47 % of xylose was used. The succinic acid yield was 0.60 g/g total sugar consumed.

Dispersion of nanosized ceramic powders in aqueous suspensions

NASA Astrophysics Data System (ADS)

Chera, L.; Palcevskis, E.; Berzins, M.; Lipe, A.; Jansone, I.

2007-12-01

Seven commercially available dispersants have been applied to produce high concentrated aqueous suspensions of the nanosized alumina and partially stabilized zirconia powders processed by the plasma technique. Simultaneously, the electrokinetic behaviour of powders has been investigated in diluted suspensions by microelectrophoresis method. Zeta potential measurements are used to estimate the influence of selected dispersants on the electrokinetic properties of the powder surface. On the basis of obtained data the correlation between the surface electrokinetic properties in dilute suspensions and reached maximal suspension concentration is discussed.

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride.

PubMed

Boudrahem, F; Aissani-Benissad, F; Aït-Amar, H

2009-07-01

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions. The influence of impregnation ratio (ZnCl2/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m2/g) and micropore volume (0.772 cm3/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio. Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 degrees C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others. Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl2 is a suitable activating agent for the preparation of high-porosity carbons.

Analysis of experimental heats of dilution of aqueous solutions of NaBPh 4 by use of the mean spherical approximation and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

M'halla, Jalel; M'halla, Sondes; Wipff, Georges

2003-03-01

Calorimetric measurements of heats of dilution: QDC→0 =- nsφL,sexp, of aqueous solutions of NaBPh 4 are determined at 25 °C in the concentration range: 0

Compact Fuel-Cell System Would Consume Neat Methanol

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram; Kindler, Andrew; Valdez, Thomas

2007-01-01

In a proposed direct methanol fuel-cell electric-power-generating system, the fuel cells would consume neat methanol, in contradistinction to the dilute aqueous methanol solutions consumed in prior direct methanol fuel-cell systems. The design concept of the proposed fuel-cell system takes advantage of (1) electro-osmotic drag and diffusion processes to manage the flows of hydrogen and water between the anode and the cathode and (2) evaporative cooling for regulating temperature. The design concept provides for supplying enough water to the anodes to enable the use of neat methanol while ensuring conservation of water for the whole fuel-cell system.

Specific Anion Effects on Na+ Adsorption at the Aqueous Solution-Air Interface: MD Simulations, SESSA Calculations, and Photoelectron Spectroscopy Experiments.

PubMed

Olivieri, Giorgia; Parry, Krista M; D'Auria, Raffaella; Tobias, Douglas J; Brown, Matthew A

2018-01-18

Specific ion effects of the large halide anions have been shown to moderate anion adsorption to the air-water interface (AWI), but little quantitative attention has been paid to the behavior of alkali cations. Here we investigate the concentration and local distribution of sodium (Na + ) at the AWI in dilute (<1 M) aqueous solutions of NaCl, NaBr, and NaI using a combination of molecular dynamics (MD) and SESSA simulations, and liquid jet ambient pressure photoelectron spectroscopy measurements. We use SESSA to simulate Na 2p photoelectron intensities on the basis of the atom density profiles obtained from MD simulations, and we compare the simulation results with photoelectron spectroscopy experiments to evaluate the performance of a nonpolarizable force field model versus that of an induced dipole polarizable one. Our results show that the nonpolarizable force model developed by Horinek and co-workers (Chem. Phys. Lett. 2009, 479, 173-183) accurately predicts the local concentration and distribution of Na + near the AWI for all three electrolytes, whereas the polarizable model does not. To our knowledge, this is the first interface-specific spectroscopic validation of a MD force field. The molecular origins of the unique Na + distributions for the three electrolytes are analyzed on the basis of electrostatic arguments, and shown to arise from an indirect anion effect wherein the identity of the anion affects the strength of the attractive Na + -H 2 O electrostatic interaction. Finally, we use the photoelectron spectroscopy results to constrain the range of inelastic mean free paths (IMFPs) for the three electrolyte solutions used in the SESSA simulations that are able to reproduce the experimental intensities. Our results suggest that earlier estimates of IMFPs for aqueous solutions are likely too high.

Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

USGS Publications Warehouse

Tesoriero, A.J.; Pankow, J.F.

1996-01-01

Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

Removal of Pb(II) ions from aqueous solution by a waste mud from copper mine industry: equilibrium, kinetic and thermodynamic study.

PubMed

Ozdes, Duygu; Gundogdu, Ali; Kemer, Baris; Duran, Celal; Senturk, Hasan Basri; Soylak, Mustafa

2009-07-30

The objective of this study was to assess the adsorption potential of a waste mud (WM) for the removal of lead (Pb(II)) ions from aqueous solutions. The WM was activated with NaOH in order to increase its adsorption capacity. Adsorption studies were conducted in a batch system as a function of solution pH, contact time, initial Pb(II) concentration, activated-waste mud (a-WM) concentration, temperature, etc. Optimum pH was specified as 4.0. The adsorption kinetic studies indicated that the overall adsorption process was best described by pseudo-second-order kinetics. The equilibrium adsorption capacity of a-WM was obtained by using Langmuir and Freundlich isotherm models and both models fitted well. Adsorption capacity for Pb(II) was found to be 24.4 mg g(-1) for 10 g L(-1) of a-WM concentration. Thermodynamic parameters including the Gibbs free energy (Delta G degrees), enthalpy (Delta H degrees), and entropy (DeltaS degrees) indicated that the adsorption of Pb(II) ions on the a-WM was feasible, spontaneous and endothermic, at temperature range of 0-40 degrees C. Desorption studies were carried out successfully with diluted HCl solutions. The results indicate that a-WM can be used as an effective and no-cost adsorbent for the treatment of industrial wastewaters contaminated with Pb(II) ions.

In situ formation of phosphate barriers in soil

DOEpatents

Moore, Robert C.

2002-01-01

Reactive barriers and methods for making reactive barriers in situ in soil for sequestering soil ontaminants including actinides and heavy metals. The barrier includes phosphate, and techniques are disclosed for forming specifically apatite barriers. The method includes injecting dilute reagents into soil in proximity to a contamination plume or source such as a waste drum to achieve complete or partial encapsulation of the waste. Controlled temperature and pH facilitates rapid formation of apatite, for example, where dilute aqueous calcium chloride and dilute aqueous sodium phosphate are the selected reagents. Mixing of reagents to form precipitate is mediated and enhanced through movement of reagents in soil as a result of phenomena including capillary action, movement of groundwater, soil washing and reagent injection pressure.

Structure and Conductivity of Semiconducting Polymer Hydrogels.

PubMed

Huber, Rachel C; Ferreira, Amy S; Aguirre, Jordan C; Kilbride, Daniel; Toso, Daniel B; Mayoral, Kenny; Zhou, Z Hong; Kopidakis, Nikos; Rubin, Yves; Schwartz, Benjamin J; Mason, Thomas G; Tolbert, Sarah H

2016-07-07

Poly(fluorene-alt-thiophene) (PFT) is a conjugated polyelectrolyte that self-assembles into rod-like micelles in water, with the conjugated polymer backbone running along the length of the micelle. At modest concentrations (∼10 mg/mL in aqueous solutions), PFT forms hydrogels, and this work focuses on understanding the structure and intermolecular interactions in those gel networks. The network structure can be directly visualized using cryo electron microscopy. Oscillatory rheology studies further tell us about connectivity within the gel network, and the data are consistent with a picture where polymer chains bridge between micelles to hold the network together. Addition of tetrahydrofuran (THF) to the gels breaks those connections, but once the THF is removed, the gel becomes stronger than it was before, presumably due to the creation of a more interconnected nanoscale architecture. Small polymer oligomers can also passivate the bridging polymer chains, breaking connections between micelles and dramatically weakening the hydrogel network. Fits to solution-phase small-angle X-ray scattering data using a Dammin bead model support the hypothesis of a bridging connection between PFT micelles, even in dilute aqueous solutions. Finally, time-resolved microwave conductivity measurements on dried samples show an increase in carrier mobility after THF annealing of the PFT gel, likely due to increased connectivity within the polymer network.

On-line separation and preconcentration of lead(II) by solid-phase extraction using activated carbon loaded with xylenol orange and its determination by flame atomic absorption spectrometry.

PubMed

Ensafi, Ali A; Shiraz, A Zendegi

2008-02-11

Activated carbon loaded with xylenol orange in a mini-column was used for the highly selective separation and preconcentration of Pb(II) ions. An on-line system for enrichment and the determination of Pb(II) was carried out on flame atomic absorption spectrometry. The conditions of preconcentration and quantitative recovery of Pb(II) from diluted solution, such as pH of aqueous phase, amount of the sorbent, volume of the solutions and flow variables were studied as well as effect of potential interfering ions. Under the optimum conditions, Pb(II) in an aqueous sample was concentrated about 200-fold and the detection limit was 0.4 ng mL(-1) Pb(II). The adsorption capacity of the solid phase was 0.20mg of lead per one gram of the modified activated carbon. The modified activated carbon is stable for several treatments of sample solutions without the need for using any chemical reagent. The recovery of lead(II) from river water, waste water, tap water, and in the following reference materials: SRM 2711 Montana soil and GBW-07605 tea were obtained in the range of 97-104% by the proposed method.

A spectrophotometric study of the formation and deprotonation of thioarsenite species in aqueous solution at 22 °C

NASA Astrophysics Data System (ADS)

Zakaznova-Herzog, Valentina P.; Seward, Terry M.

2012-04-01

The ionization constants of thioarsenous acid have been determined at 22 °C by measuring the ultraviolet and visible spectra of thioarsenite species in dilute, aqueous sulfide solutions having S/As = 4.18, As = 1.1 × 10-4 mol/dm3 and pH ≈ 6-10.4. No oxidized species such as arsenate, thioarsenate or polysulfides were detected in the experimental solutions. The equilibrium constants for the thioarsenous acid ionization reactions were obtained from a principal component analysis treatment of the spectra and are as follows: H3AsS3=H+H2AsS3- for which pKa1=3.77 (±0.15) H2-AsS32-=H+H2AsS3- for which pKa2=6.53 (±0.08) HAsS32-=H+AsS33- for which pKa3=9.29 (±0.08) The pKa’s for the oxythioarsenous ionization reactions have also been estimated by analogy with those for the end member arsenous and thioarsenous acids. The data emphasize the important role of the simple arsenic(III) thioanions in defining the transport and redox chemistry of arsenic in sulfide-containing natural waters.

Heat pipe systems using new working fluids

NASA Technical Reports Server (NTRS)

Chao, David F. (Inventor); Zhang, Nengli (Inventor)

2004-01-01

The performance of a heat pipe system is greatly improved by the use of a dilute aqueous solution of about 0.0005 and about 0.005 moles per liter of a long chain alcohol as the working fluid. The surface tension-temperature gradient of the long-chain alcohol solutions turns positive as the temperature exceeds a certain value, for example about 40.degree. C. for n-heptanol solutions. Consequently, the Marangoni effect does not impede, but rather aids in bubble departure from the heating surface. Thus, the bubble size at departure is substantially reduced at higher frequencies and, therefore, increases the boiling limit of heat pipes. This feature is useful in microgravity conditions. In addition to microgravity applications, the heat pipe system may be used for commercial, residential and vehicular air conditioning systems, micro heat pipes for electronic devices, refrigeration and heat exchangers, and chemistry and cryogenics.

Novel Hydrogels from Telechelic Polymers

NASA Astrophysics Data System (ADS)

Taribagil, Rajiv R.

The last two decades have seen telechelic polymers support an increasing number of applications as stabilizers and flow modifiers in fields as varied as pharmaceutics, paints and oil recovery. Mainly consisting of a long hydrophilic block end-capped with hydrophobic blocks, these polymers form gels at modest concentrations, comprising hydrophobic junctions with hydrophilic blocks bridging these junctions. This thesis examines two different types of telechelic polymer hydrogels: concentrated dispersions of telechelic triblock copolymers and dilute solutions of wormlike micelles cross-linked by hydrophobically end-capped polymers. Aqueous gels of telechelic poly(ethylene oxide) (PEO)-based triblock polymers, with homo and hetero combinations of 1,2-polybutadiene (PB) and poly(perfluoropropylene oxide) (PFPO) as hydrophobic end-blocks, were investigated using a combination of cryogenic scanning electron microscopy and small-angle neutron scattering. The PB-b-PEO-b-PB copolymers formed networks of spherical micelles at all concentrations as expected, albeit with significant spatial heterogeneity that diminished with increasing concentration. The PFPO-b-PEO-b-PFPO copolymers also formed networks by aggregation of the end-blocks, but the PFPO blocks tended to adopt disk-like or even sheet-like structures. This is attributed to the extremely high interfacial tension of PFPO with water and is consistent with the "super-strong" segregation regime behavior. The heterotelechelic PB-b-PEO- b-PFPO terpolymers adopted a quite different structure, namely an intricate bicontinuous open-cell foam, with cells on the order of 500 nm in size and cell walls composed of PFPO disks embedded in PB sheets. These various network structures illustrate the potential of using end-block chemistry to manipulate both the morphology and the physical properties of polymer gels. Dilute aqueous solutions containing 1 wt% cetyltrimethylammonium tosylate, a surfactant well recognized to form wormlike micelles, and low concentrations of hydrophobically end-capped poly(ethylene oxide), were investigated using dynamic mechanical spectroscopy and small-angle neutron scattering. The detailed examination shows that addition of as little as 0.1 wt% of the polymer to the dilute wormlike micelle solution leads to a massive enhancement in its viscoelastic response. This phenomenon raises the possibility of significantly reducing the amount of additive required to achieve a desired rheological profile, with concomitant advantages in both cost and environmental impact.

OH radical induced depolymerization of poly(methacrylic acid)

NASA Astrophysics Data System (ADS)

Ulanski, Piotr; Bothe, Eberhard; von Sonntag, Clemens

1999-05-01

Hydroxyl radicals (generated pulse radiolytically in dilute N 2O-saturated aqueous solutions) react with poly(methacrylic acid) producing two kinds of radicals. The primary radical is converted into a secondary one by H-abstraction ( k=3.5 × 10 2 s -1) as monitored by changes in the UV spectrum. Subsequently, the secondary radicals undergo chain scission ( k=1.8 s -1 at pH 7-9). This process has been followed both by spectrophotometry as well as by conductometry. In competition with the bimolecular decay of the radicals the ensuing end-chain radicals undergo efficient depolymerization resulting in the release of monomer. Since the lifetime of the radicals is much longer at high pH, where the polymer attains a rod-like conformation, depolymerization is most efficient in basic solution.

Meyer-Overton reforged: The origins of alcohol and anesthetic potency in membranes as determined by a new NMR partitioning probe, benzyl alcohol

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

Janes, N.; Ma, L.; Hsu, J.W.

1992-01-01

The Meyer-Overton hypothesis--that anesthesia arises from the nonspecific action of solutes on membrane lipids--is reformulated using colligative thermodynamics. Configurational entropy, the randomness imparted by the solute through the partitioning process, is implicated as the energetic driving force that pertubs cooperative membrane equilibria. A proton NMR partitioning approach based on the anesthetic benzyl alcohol is developed to assess the reformulation. Ring resonances from the partitioned drug are shielded by 0.2 ppm and resolved from the free, aqueous drug. Free alcohol is quantitated in dilute lipid dispersions using an acetate internal standard. Cooperative equilibria in model dipalmitoyl lecithin membranes are examined withmore » changes in temperature and alcohol concentration. The L[sub [beta][prime

Ice nucleation activity of silicates and aluminosilicates in pure water and aqueous solutions - Part 1: The K-feldspar microcline

NASA Astrophysics Data System (ADS)

Kumar, Anand; Marcolli, Claudia; Luo, Beiping; Peter, Thomas

2018-05-01

Potassium-containing feldspars (K-feldspars) have been considered as key mineral dusts for ice nucleation (IN) in mixed-phase clouds. To investigate the effect of solutes on their IN efficiency, we performed immersion freezing experiments with the K-feldspar microcline, which is highly IN active. Freezing of emulsified droplets with microcline suspended in aqueous solutions of NH3, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl, with solute concentrations corresponding to water activities aw = 0.9-1.0, were investigated by means of a differential scanning calorimeter (DSC). The measured heterogeneous IN onset temperatures, Thet(aw), deviate strongly from ThetΔawhet(aw), the values calculated from the water-activity-based approach (where ThetΔawhet(aw) = Tmelt(aw + Δawhet) with a constant offset Δawhet with respect to the ice melting point curve). Surprisingly, for very dilute solutions of NH3 and NH4+ salts (molalities ≲1 mol kg-1 corresponding to aw ≳ 0.96), we find IN temperatures raised by up to 4.5 K above the onset freezing temperature of microcline in pure water (Thet(aw = 1)) and 5.5 K above ThetΔawhet(aw), revealing NH3 and NH4+ to significantly enhance the IN of the microcline surface. Conversely, more concentrated NH3 and NH4+ solutions show a depression of the onset temperature below ThetΔawhet(aw) by as much as 13.5 K caused by a decline in IN ability accompanied with a reduction in the volume fraction of water frozen heterogeneously. All salt solutions not containing NH4+ as cation exhibit nucleation temperatures Thet(aw) < ThetΔawhet(aw) even at very small solute concentrations. In all these cases, the heterogeneous freezing peak displays a decrease as solute concentration increases. This deviation from Δawhet = const. indicates specific chemical interactions between particular solutes and the microcline surface not captured by the water-activity-based approach. One such interaction is the exchange of K+ available on the microcline surface with externally added cations (e.g., NH4+). However, the presence of a similar increase in IN efficiency in dilute ammonia solutions indicates that the cation exchange cannot explain the increase in IN temperatures. Instead, we hypothesize that NH3 molecules hydrogen bonded on the microcline surface form an ice-like overlayer, which provides hydrogen bonding favorable for ice to nucleate on, thus enhancing both the freezing temperatures and the heterogeneously frozen fraction in dilute NH3 and NH4+ solutions. Moreover, we show that aging of microcline in concentrated solutions over several days does not impair IN efficiency permanently in case of near-neutral solutions since most of it recovers when aged particles are resuspended in pure water. In contrast, exposure to severe acidity (pH ≲1.2) or alkalinity (pH ≳11.7) damages the microcline surface, hampering or even destroying the IN efficiency irreversibly. Implications for IN in airborne dust containing microcline might be multifold, ranging from a reduction of immersion freezing when exposed to dry, cold and acidic conditions to a 5 K enhancement during condensation freezing when microcline particles experience high humidity (aw≳0.96) at warm (252-257 K) and NH3/NH4+-rich conditions.

A novel technique to determine cobalt exchangeability in soils using isotope dilution.

PubMed

Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

2008-01-01

The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.

Removal of lead from aqueous solutions using Cassia grandis seed gum-graft-poly(methylmethacrylate).

PubMed

Singh, Vandana; Tiwari, Stuti; Sharma, Ajit Kumar; Sanghi, Rashmi

2007-12-15

Using persulfate/ascorbic acid redox system, a series of Cassia grandis seed gum-graft-poly(methylmethacrylate) samples were synthesized. The copolymer samples were evaluated for lead(II) removal from the aqueous solutions where the sorption capacities were found proportional to the grafting extent. The conditions for the sorption were optimized using copolymer sample of highest percent grafting. The sorption was found pH and concentration dependent, pH 2.0 being the optimum value. Adsorption of lead by the grafted seed gum followed a pseudo-second-order kinetics with a rate constant of 4.64 x 10(-5) g/mg/min. The equilibrium data followed the Langmuir isotherm model with maximum sorption capacity of 126.58 mg/g. The influence of electrolytes NaCl, Na(2)SO(4) on lead uptake was also studied. Desorption with 2 N HCl could elute 76% of the lead ions from the lead-loaded copolymer. The regeneration experiments revealed that the copolymer could be successfully reused for at least four cycles though there was a successive loss in lead sorption capacity with every cycle. The adsorbent was also evaluated for Pb(II) removal from battery waste-water containing 2166 mg/L Pb(II). From 1000 times diluted waste water, 86.1% Pb(II) could be removed using 0.05 g/20 ml adsorbent dose, while 0.5 g/20 ml adsorbent dose was capable of removing 60.29% Pb from 10 times diluted waste water. Optimum Pb(II) binding under highly acidic conditions indicated that there was a significant contribution of nonelectrostatic interactions in the adsorption process. A possible mechanism for the adsorption has been discussed.

Carbonic acid ionization and the stability of sodium bicarbonate and carbonate ion pairs to 200 °C - A potentiometric and spectrophotometric study

NASA Astrophysics Data System (ADS)

Stefánsson, Andri; Bénézeth, Pascale; Schott, Jacques

2013-11-01

Carbonic acid ionization and sodium bicarbonate and carbonate ion pair formation constants have been experimentally determined in dilute hydrothermal solutions to 200 °C. Two experimental approaches were applied, potentiometric acid-base titrations at 10-60 °C and spectrophotometric pH measurements using the pH indicators, 2-napthol and 4-nitrophenol, at 25-200 °C. At a given temperature, the first and second ionization constants of carbonic acid (K1, K2) and the ion pair formation constants for NaHCO(aq)(K) and NaCO3-(aq)(K) were simultaneously fitted to the data. Results of this study compare well with previously determined values of K1 and K2. The NaHCO(aq) and NaCO3-(aq) ion pair formation constants vary between 25 and 200 °C having values of logK=-0.18 to 0.58 and logK=1.01 to 2.21, respectively. These ion pairs are weak at low-temperatures but become increasingly important with increasing temperature under neutral to alkaline conditions in moderately dilute to concentrated NaCl solutions, with NaCO3-(aq) predominating over CO32-(aq) in ⩾0.1 M NaCl solution at temperatures above 100 °C. The results demonstrate that NaCl cannot be considered as an inert (non-complexing) electrolyte in aqueous carbon dioxide containing solutions at elevated temperatures.

Raman Analysis of Dilute Aqueous Samples by Localized Evaporation of Submicroliter Droplets on the Tips of Superhydrophobic Copper Wires.

PubMed

Cheung, Melody; Lee, Wendy W Y; McCracken, John N; Larmour, Iain A; Brennan, Steven; Bell, Steven E J

2016-04-19

Raman analysis of dilute aqueous solutions is normally prevented by their low signal levels. A very general method to increase the concentration to detectable levels is to evaporate droplets of the sample to dryness, creating solid deposits which are then Raman probed. Here, superhydrophobic (SHP) wires with hydrophilic tips have been used as supports for drying droplets, which have the advantage that the residue is automatically deposited at the tip. The SHP wires were readily prepared in minutes using electroless galvanic deposition of Ag onto copper wires followed by modification with a polyfluorothiol (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanethiol, HDFT). Cutting the coated wires with a scalpel revealed hydrophilic tips which could support droplets whose maximum size was determined by the wire diameter. Typically, 230 μm wires were used to support 0.6 μL droplets. Evaporation of dilute melamine droplets gave solid deposits which could be observed by scanning electron microscopy (SEM) and Raman spectroscopy. The limit of detection for melamine using a two stage evaporation procedure was 1 × 10(-6) mol dm(-3). The physical appearance of dried droplets of sucrose and glucose showed that the samples retained significant amounts of water, even under high vacuum. Nonetheless, the Raman detection limits of sucrose and glucose were 5 × 10(-4) and 2.5 × 10(-3) mol dm(-3), respectively, which is similar to the sensitivity reported for surface-enhanced Raman spectroscopy (SERS) detection of glucose. It was also possible to quantify the two sugars in mixtures at concentrations which were similar to those found in human blood through multivariate analysis.

Fundamental studies of chalcogenide nanocrystals, carbonaceous nanoparticles, and chromatographic materials

NASA Astrophysics Data System (ADS)

Baker, Jared Scott

2011-12-01

The development of novel nanomaterials and the understanding of their fundamental physical and chemical properties represent an exciting area of research. These materials are continuously being sought for ever-increasing applications; finding their way into uses that influence mankind on a daily basis. Combining elements from traditional nanoparticle characterization with electrophoretic-based techniques, this dissertation presents the analysis of carbon nanoparticles (CNPs) generated from a novel source (candle soot) as well as a unique perspective on the reactivity and degradation process of magic-sized cadmium chalcogenide nanocrystals. One potential application of CNPs is their use as an alternative fluorophore in a separation-based sensor system. Laser-induced-fluorescence (LIF) is a commonly used manner of detection in this type of platform, but is limited in many cases by problems associated with the fluorophore. Carbon-based nanoparticles have the potential to improve upon traditional fluorophores in applications that make use of LIF as the detection scheme. CNPs were extracted from the carbonaceous material produced by the incomplete combustion of a candle. The soot was submitted to an oxidizing treatment and extraction/filtration procedures rendering watersoluble luminescent species. Electron microscopy was used to identify globular, amorphous structures in the nanometer size-range. An aqueous suspension of CNPs demonstrated excellent stability in terms of its electronic properties, showing little change in absorption and emission spectra upon storage under ambient conditions over a two-year period. Capitalizing on the strengths of capillary electrophoresis (CE) as a characterization technique, we have analyzed the negatively-charged CNPs in terms of charge and size by studying the influence of variable CE conditions on the resulting separation. Separations at different pH revealed a highly complex mixture of CNPs, containing species with large electrophoretic mobilities under a wide range of pH values. The mobility of these nanoparticles as a function of ionic strength was compared to classical electrokinetic theory, suggesting that the species are small, highly charged particles with appreciable zeta potentials, even at low pH. In an attempt to reduce the complexity of the CNP solution, two molecular-weight based fractionation techniques were employed and evaluated. Traditional dialysis and ultracentrifugation filtration techniques were modified to generate multiple CNPs fractions based on size. Analysis of the fractions by absorption and photoluminescence spectroscopy as well as CE revealed specific characteristics for a given sized-fraction. Namely, a strong correlation between the size of the CNPs and their luminescent emission was observed. CE was utilized to characterize each fraction and to ultimately judge the effectiveness of the fractionation techniques. The characterization of the persistence and degradation of magic-sized CdSe nanocrystals (NCs) after their removal from the original reaction mixture and dispersion into basic aqueous solutions was performed by absorption spectroscopy. NCs degraded after dilution into aqueous NaOH, resulting in red-shifted excitonic absorption bands and eventual flocculation. Dilution of NCs into basic aqueous solutions of cysteinate resulted in degradation via a different mechanism with an absence of flocculation; kinetics varied with concentration of cysteinate. The chemical fate of NCs after dilution into basic aqueous solutions containing both Cd2+ and cysteinate varied with the cysteinate-to-Cd 2+ molar ratio, which determined the relative solute mole fractions of various Cd2+-cysteinate complexes. CdSe NCs persisted on long timescales only when dispersed in solutions containing [Cd(cysteinate) 3]4-. Equilibria are presented to account for the observed spectral changes after dilution of CdSe into various basic media. Cadmium(II)-cysteinate complex-formation equilibria influenced the temporal persistence of the nanocrystals; the pathway through which CdSe NCs degraded depended on the concentration of free, uncoordinated cysteinate. These findings indicate that solution-phase chemistry can determine whether NCs remain intact upon removal from their original reaction mixtures. Departing from the analysis of nanomaterials, an additional chapter focuses on the evaluation of a new chromatographic packing material. Two chromatographic columns packed with superficially porous packing material, Kinetex(TM) 1.7 mum and 2.6 mum C18 particles were evaluated in terms of their physical properties and performance characteristics. These columns were compared to a column packed with a sub-2 mum totally porous material and to a Halo(TM) column packed with 2.7 mum C18 superficially porous packing. The columns packed with superficially porous particles displayed a comparably narrower size distribution, which is narrower than the distribution of the totally porous sub-2 mum particles. Physical characteristics of the Kinetex(TM) particles were evaluated in terms of surface area, pore diameter, and specific pore volume. Total, external, internal and shell porosities among the four different columns were evaluated and compared. The specific permeability for the Kinetex columns showed values close to those predicted by the Kozeny-Carman equation. All four columns were evaluated in terms of their chromatographic performance and compared using the Knox equation. The columns packed with the 2.6 mum and 2.7 mum superficially porous materials showed reduced plate heights below 2, while the sub-2 mum particles showed values of 2.2 and above.

Metal Sorbing Vesicles: Light Scattering Characterization and Metal Sorbtion Behavior.

NASA Astrophysics Data System (ADS)

van Zanten, John Hollis

1992-01-01

The research described herein consisted of two parts: light scattering characterization of vesicles and kinetic investigations of metal sorbing vesicles. Static light scattering techniques can be used to determine the geometric size, shape and apparent molecular weight of phosphatidylcholine vesicles in aqueous suspension. A Rayleigh-Gans-Debye (RGD) approximation analysis of multiangle scattered light intensity data yields the size and degree of polydispersity of the vesicles in solution, while the Zimm plot technique provides the radius of gyration and apparent weight-average molecular weight. Together the RGD approximation and Zimm plots can be used to confirm the geometric shape of vesicles and can give a good estimate of the vesicle wall thickness in some cases. Vesicles varying from 40 to 115 nm in diameter have been characterized effectively. The static light scattering measurements indicate that, as expected, phosphatidylcholine vesicles in this size range scatter light as isotropic hollow spheres. Additionally, static and dynamic light scattering measurements have been made and compared with one another. The values for geometric radii determined by static light scattering typically agree with those estimated by dynamic light scattering to within a few percent. Interestingly however, dynamic measurements suggest that there is a significant degree of polydispersity present in the vesicle dispersions, while static measurements indicate near size monodisperse dispersions. Metal sorbing vesicles which harbor ionophores, such as antibiotic A23187 and synthetic carriers, in their bilayer membranes have been produced. These vesicles also encapsulate the chelating compound, nitrilotriacetate, to provide the driving force for metal ion uptake. Very dilute dispersions (on the order of 0.03% w/v) of these metal sorbing vesicles were capable of removing Cd ^{2+} and Pb^{2+ } from dilute aqueous solution (5 ppm and less) and concentrating these metal ions several hundred to more than a thousand fold in the vesicle interior in a few minutes time. Synthetic ionophores were found to preferentially transport Pb^{2+} over Cd^{2+}, thus suggesting that engineered vesicle dispersions can be used as selective separations media. The effect of ionophore concentration, solution pH, solution ionic strength, initial metal ion concentration and vesicle concentration have been investigated.

A new method for multicomponent activity coefficients of electrolytes in aqueous atmospheric aerosols

NASA Astrophysics Data System (ADS)

Zaveri, Rahul A.; Easter, Richard C.; Wexler, Anthony S.

2005-01-01

Three-dimensional models of atmospheric inorganic aerosols need accurate and computationally efficient parameterizations of activity coefficients of various electrolytes in multicomponent aqueous solutions. In this paper, we extend the Taylor's series expansion mixing rule used by C. Wagner in 1952 for estimating activity coefficients in dilute alloy solutions to aqueous electrolyte solutions at any concentration. The resulting method, called the multicomponent Taylor expansion method (MTEM), estimates the mean activity coefficient of an electrolyte in a multicomponent solution on the basis of its values in binary solutions of all the electrolytes present in the mixture at the solution water activity aw, assuming aw is equal to the ambient relative humidity. MTEM is applied here for atmospheric aerosol systems containing H+, NH4+, Na+, Ca2+, SO42-, HSO4-, NO3-, and Cl- ions. The aerosol water content is calculated using the Zdanovskii-Stokes-Robinson (ZSR) method. For self-consistency, most of the MTEM and ZSR parameters are derived using the comprehensive Pitzer-Simonson-Clegg model at 298.15 K and are valid for an aw range of 0.2-0.97. Because CaSO4 is sparingly soluble, it is treated as a solid in the model over the entire aw range. MTEM is evaluated for several multicomponent systems representing various continental and marine aerosols and is contrasted against the mixing rule of C. L. Kusik and H. P. Meissner and of L. A. Bromley and the newer approach of S. Metzger and colleagues. Predictions of MTEM are found to be generally within a factor of 0.8-1.25 of the comprehensive Pitzer-Simonson-Clegg model and are shown to be significantly more accurate than predictions of the other three methods. MTEM also yields a noniterative solution of the bisulfate ion dissociation in sulfate-rich systems: a major computational advantage over other ionic-strength-based methods that require an iterative solution. CPU time requirements of MTEM relative to other methods for sulfate-poor and sulfate-rich systems are also discussed.

Acetanilide mediated reversible assembly and disassembly of Au nanoparticles.

PubMed

Murugadoss, A; Kar, Manoranjan; Chattopadhyay, Arun

2008-08-01

Herein we report the generation of Au nanoparticles (NPs) by sparingly soluble acetanilide in water. We also report the formation of linear chain-like superstructures of self-assembled Au NPs, in the presence of excess acetanilide. This was achieved in two different ways. In the first method, acetanilide was added, with increasing concentration, into aqueous HAuCl(4) to produce Au NPs as well as for the formation of assembly, which varied according to the concentration of acetanilide. The other route involved formation of spherical Au NPs at the lowest concentration of acetanilide, which was followed by the formation of assembly of various lengths upon further addition of variable amount of acetanilide. The assemblies were stable in aqueous solution for days with characteristic UV-vis absorption spectra consisting of two peaks. While the wavelength of the first peak remained the same, the position of the second peak changed to longer wavelength with increasing acetanilide concentration. Interestingly, the linear chain-like arrays could be broken into individual particles by first dilution of the solution concentration followed by treatment with ultrasonic waves. The individual Au NPs again formed linear chain-like arrays upon addition of excess acetanilide.

Molecular Dynamics Simulation of Surface Tension of NaCl Aqueous Solution at 298.15K: from Diluted to Highly Supersaturated Concentrations

NASA Astrophysics Data System (ADS)

Wang, Xiaoxiang; Chen, Chuchu; Poeschl, Ulirch; Su, Hang; Cheng, Yafang

2017-04-01

Sodium chloride (NaCl) is one of the key components of atmospheric aerosol particles. Concentration-depend surface tension of aqueous NaCl solution is essential to determine the equilibrium between droplet NaCl solution and water vapor, which is important in regards to aerosol-cloud interaction and aerosol climate effects. Although supersaturated NaCl droplets can be widely found under atmospheric conditions, the experimental determined concentration dependency of surface tension is limited up to the saturated concentration range due to technical difficulties, i.e., heterogeneous nucleation since nearly all surface tension measurement techniques requires contact of the sensor and solution surface. In this study, the surface tension of NaCl aqueous solution with solute mass fraction from 0 to 1 was calculated using molecular dynamics (MD) simulation. The surface tension increases monotonically and near linearly when mass fraction of NaCl (xNaCl) is lower than 0.265 (saturation point), which follows theoretical predictions (e.g., E-AIM, SP parameterization, and PK parameterization). Once entering into the supersaturated concentration range, the calculated surface tension starts to deviate from the near-linear extrapolation and adopts a slightly higher increasing rate until xNaCl of 0.35. We found that these two increasing phases (xNaCl 0.35) is mainly driven by the increase of excessive surface enthalpy when the solution becomes concentrated. After that, the surface tension remains almost unchanged until xNaCl of 0.52. This phenomenon is supported by the results from experiment based Differential Koehler Analyses. The stable surface tension in this concentration range is attributed to a simultaneous change of surface excess enthalpy and entropy at similar degree. When the NaCl solution is getting more concentrated than xNaCl of 0.52, the simulated surface tension regains an even faster growing momentum and shows the tendency of ultimately approaching the surface tension of molten NaCl at 298.15 K ( 148.4 mN/m by MD simulation). Energetic analyses imply that this fast increase is primarily still an excessive surface enthalpy-driven process, although concurrent fluctuation of excessive surface entropy is also expected but in a much smaller scale. Our results unfold the global landscape of concentration dependence of aqueous NaCl solution and its driven forces: a water surface tension dominated regime (xNaCl from 0 to 0.35), a transition regime (xNaCl from 0.35 to 0.52) and a molten NaCl surface tension dominated regime (xNaCl beyond 0.52).

Metal biosorption-flotation. Application to cadmium removal.

PubMed

Matis, K A; Zouboulis, A I; Grigoriadou, A A; Lazaridis, N K; Ekateriniadou, L V

1996-05-01

Biosorption using suspended non-living biomass, and flotation (for consequent solid/liquid separation of the metal-loaded biomass) have been studied in the laboratory as a possible combined process, for the removal of toxic metals (i.e., cadmium) from dilute aqueous solutions. The various parameters of the process were investigated in depth, including re-use of biosorbent. A filter aid (contained in the biomass industrial waste used) was found not really to interfere. Zeta-potential measurements of the aforementioned system were also carried out. Promising results were obtained during continuous-flow experiments. A flotation residence time of 4 min was achieved. Metal removal and suspended biomass recovery were generally over 95%.

Anti-reflection coatings on large area glass sheets

NASA Technical Reports Server (NTRS)

Pastirik, E.

1980-01-01

Antireflective coatings which may be suitable for use on the covers of photovoltaic solar modules can be easily produced by a dipping process. The coatings are applied to glass by drawing sheets of glass vertically out of dilute aqueous sodium silicate solutions at a constant speed, allowing the adherent liquid film to dry, then exposing the dried film to concentrated sulfuric acid, followed by a water rinse and dry. The process produces coatings of good optical performance (96.7 percent peak transmission at 0.540 mu M wavelength) combined with excellent stain and soil resistance, and good resistance to abrasion. The process is reproduceable and easily controlled.

Separation of compounds with multiple -OH groups from dilute aqueous solutions via complexation with organoboronate

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

Chow, Tina Kuo Fung

1992-05-01

The complexing extractant agent investigated in this work is 3-nitrophenylboronic acid (NPBA) in its anionic form (NPB). NPBA and Aliquat 336 (quaternary amine) is dissolved in 2-ethyl-l-hexanol, and the extractant is contacted with aq. NaOH. Solutes investigated were 1,2-propanediol, glycerol, fructose, sorbitol and lactic acid. Batch extraction experiments were performed at 25°C. Partition coefficients, distribution ratios and loadings are reported for varying concentrations of solute and NPB. All solutes complexed with NPB -, with all complexes containing only one NPB - per complex. The 1:1 complexation constants for the solutes glycerol, fructose and sorbitol follow trends similar to complexation withmore » B(OH) 4 - (aq.), i.e. the complexation constants increase with increasing number of -OH groups available for complexation. Assumption of 1:1 complex is not valid for 1, 2-propanediol, which showed overloading (more than one mole of solute complexed to one mole NPB -) at higher concentrations. The -OH group on the NPB - which is left uncomplexed after one solute molecule had bound to the other two -OH groups may be responsible for the overloading. Overloading is also observed in extraction of tactic acid, but through a different mechanism. It was found that TOMA + can extract lactic acid to an extent comparable to the uptake of lactic acid by NPB -. The complexation is probably through formation of an acid-base ion pair. Losses of NPBA into the aqueous phase could lead to problems, poor economics in industrial separation processes. One way of overcoming this problem would be to incorporate the NPBA onto a solid support.« less

Separation of compounds with multiple -OH groups from dilute aqueous solutions via complexation with organoboronate. [1,2-propanediol

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

Chow, Tina Kuo Fung.

1992-05-01

The complexing extractant agent investigated in this work is 3-nitrophenylboronic acid (NPBA) in its anionic form (NPB). NPBA and Aliquat 336 (quaternary amine) is dissolved in 2-ethyl-l-hexanol, and the extractant is contacted with aq. NaOH. Solutes investigated were 1,2-propanediol, glycerol, fructose, sorbitol and lactic acid. Batch extraction experiments were performed at 25{degree}C. Partition coefficients, distribution ratios and loadings are reported for varying concentrations of solute and NPB. All solutes complexed with NPB{sup {minus}}, with all complexes containing only one NPB{sup {minus}} per complex. The 1:1 complexation constants for the solutes glycerol, fructose and sorbitol follow trends similar to complexation withmore » B(OH){sub 4}{sup {minus}} (aq.), i.e. the complexation constants increase with increasing number of {minus}OH groups available for complexation. Assumption of 1:1 complex is not valid for 1, 2-propanediol, which showed overloading (more than one mole of solute complexed to one mole NPB{sup {minus}}) at higher concentrations. The {minus}OH group on the NPB{sup {minus}} which is left uncomplexed after one solute molecule had bound to the other two {minus}OH groups may be responsible for the overloading. Overloading is also observed in extraction of tactic acid, but through a different mechanism. It was found that TOMA{sup +} can extract lactic acid to an extent comparable to the uptake of lactic acid by NPB{sup {minus}}. The complexation is probably through formation of an acid-base ion pair. Losses of NPBA into the aqueous phase could lead to problems, poor economics in industrial separation processes. One way of overcoming this problem would be to incorporate the NPBA onto a solid support.« less

[Influence of dissolved gases on highly diluted aqueous media].

PubMed

Belovolova, L V; Glushkov, M V; Vinogradov, E A

2014-01-01

In the experiments on redox potential measurement for a series of identical samples of purified and presettled water it was found that the response to ultraviolet irradiation varies appreciably within a few days after treatment, including stepwise changes. In a few hours after exposure, leading to a higher content of reactive oxygen species as compared with the equilibrium values, long-term changes including variations in redox potential and optical system parameters are recorded in water and diluted aqueous media. We propose a heuristic organization model of the water-gas system with an increased content of reactive oxygen species.

Single polymer dynamics in semi-dilute unentangled and entangled solutions: from molecular conformation to normal stress

NASA Astrophysics Data System (ADS)

Schroeder, Charles

Semi-dilute polymer solutions are encountered in a wide array of applications such as advanced 3D printing technologies. Semi-dilute solutions are characterized by large fluctuations in concentration, such that hydrodynamic interactions, excluded volume interactions, and transient chain entanglements may be important, which greatly complicates analytical modeling and theoretical treatment. Despite recent progress, we still lack a complete molecular-level understanding of polymer dynamics in these systems. In this talk, I will discuss three recent projects in my group to study semi-dilute solutions that focus on single molecule studies of linear and ring polymers and a new method to measure normal stresses in microfluidic devices based on the Stokes trap. In the first effort, we use single polymer techniques to investigate the dynamics of semi-dilute unentangled and semi-dilute entangled DNA solutions in extensional flow, including polymer relaxation from high stretch, transient stretching dynamics in step-strain experiments, and steady-state stretching in flow. In the semi-dilute unentangled regime, our results show a power-law scaling of the longest polymer relaxation time that is consistent with scaling arguments based on the double cross-over regime. Upon increasing concentration, we observe a transition region in dynamics to the entangled regime. We also studied the transient and steady-state stretching dynamics in extensional flow using the Stokes trap, and our results show a decrease in transient polymer stretch and a milder coil-to-stretch transition for semi-dilute polymer solutions compared to dilute solutions, which is interpreted in the context of a critical Weissenberg number Wi at the coil-to-stretch transition. Interestingly, we observe a unique set of polymer conformations in semi-dilute unentangled solutions that are highly suggestive of transient topological entanglements in solutions that are nominally unentangled at equilibrium. Taken together, these results suggest that the transient stretching pathways in semi-dilute solution extensional flows are qualitatively different than for both dilute solutions and for semi-dilute solutions in shear flow. In a second effort, we studied the dynamics of ring polymers in background solutions of semi-dilute linear polymers. Interestingly, we observe strikingly large fluctuations in steady-state polymer extension for ring polymers in flow, which occurs due to the interplay between polymer topology and concentration leading to chain `threading' in flow. In a third effort, we developed a new microfluidic method to measure normal stress and extensional viscosity that can be loosely described as passive yet non-linear microrheology. In particular, we incorporated 3-D particle imaging velocimetry (PIV) with the Stokes trap to study extensional flow-induced particle migration in semi-dilute polymer solutions. Experimental results are analyzed using the framework of a second-order-fluid model, which allows for measurement of normal stress and extensional viscosity in semi-dilute polymer solutions, all of which is a first-of-its-kind demonstration. Microfluidic measurements of extensional viscosity are directly compared to the dripping-onto-substrate or DOS method, and good agreement is generally observed. Overall, our work aims to provide a molecular-level understanding of the role of polymer topology and concentration on bulk rheological properties by using single polymer techniques.

Radiolysis of paracetamol in dilute aqueous solution

NASA Astrophysics Data System (ADS)

Szabó, László; Tóth, Tünde; Homlok, Renáta; Takács, Erzsébet; Wojnárovits, László

2012-09-01

Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O2 is c.a. 10%. The efficiency is 2-3 times higher in the presence of O2 due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily.

The rapid formation of functional monolayers on silicon under mild conditions.

PubMed

Ciampi, Simone; Luais, Erwann; James, Michael; Choudhury, Moinul H; Darwish, Nadim A; Gooding, J Justin

2014-05-07

We report on an exceedingly mild chemical functionalization of hydrogen-terminated Si(100) with unactivated and unprotected bifunctional α,ω-dialkynes. Monolayer formation occurs rapidly in the dark, and at room temperature, from dilute solutions of an aromatic-conjugated acetylene. The method addresses the poor reactivity of p-type substrates under mild conditions. We suggest the importance of several factors, including an optimal orientation for electron transfer between the adsorbate and the Si surface, conjugation of the acetylenic function with a π-system, as well as the choice of a solvent system that favors electron transfer and screens Coulombic interactions between surface holes and electrons. The passivated Si(100) electrode is amenable to further functionalization and shown to be a viable model system for redox studies at non-oxide semiconductor electrodes in aqueous solutions.

Aqueous Extracts of Hibiscus sabdariffa Calyces to Control Aichi Virus.

PubMed

D'Souza, Doris H; Dice, Lezlee; Davidson, P Michael

2016-06-01

Aqueous Hibiscus sabdariffa extracts possess antimicrobial properties with limited information available on their antiviral effects. Aichi virus (AiV) is an emerging foodborne pathogen that causes gastroenteritis. Vaccines are currently unavailable to prevent their disease transmission. The objective of this study was to determine the antiviral effects of aqueous H. sabdariffa extracts against AiV. AiV at ~5 log PFU/ml was incubated with undiluted (200 mg/ml), 1:1 (100 mg/ml) or 1:5 (40 mg/ml) diluted aqueous hibiscus extract (pH 3.6), phosphate-buffered saline (pH 7.2 as control), or malic acid (pH 3.0, acid control) at 37 °C over 24 h. Treatments were stopped by serially diluting in cell-culture media containing fetal bovine serum and titers were determined using plaque assays on confluent Vero cells. Each treatment was replicated thrice and assayed in duplicate. AiV did not show any significant reduction with 1:1 (100 mg/ml) or 1:5 (40 mg/ml) diluted aqueous hibiscus extracts or malic acid after 0.5, 1, or 2 h at 37 °C. However, AiV titers were reduced to non-detectable levels after 24 h with all the three tested concentrations, while malic acid showed only 0.93 log PFU/ml reduction after 24 h. AiV was reduced by 0.5 and 0.9 log PFU/ml with undiluted extracts (200 mg/ml) after 2 and 6 h, respectively. AiV treated with 1:1 (100 mg/ml) and 1:5 (40 mg/ml) diluted extracts showed a minimal ~0.3 log PFU/ml reduction after 6 h. These extracts show promise to reduce AiV titers mainly through alteration of virus structure, though higher concentrations may have improved effects.

An Isotopic Dilution Experiment Using Liquid Scintillation: A Simple Two-System, Two-Phase Analysis.

ERIC Educational Resources Information Center

Moehs, Peter J.; Levine, Samuel

1982-01-01

A simple isotonic, dilution analysis whose principles apply to methods of more complex radioanalyses is described. Suitable for clinical and instrumental analysis chemistry students, experimental manipulations are kept to a minimum involving only aqueous extraction before counting. Background information, procedures, and results are discussed.…

Hydrodynamics of the VanA-type VanS histidine kinase: an extended solution conformation and first evidence for interactions with vancomycin

PubMed Central

Phillips-Jones, Mary K.; Channell, Guy; Kelsall, Claire J.; Hughes, Charlotte S.; Ashcroft, Alison E.; Patching, Simon G.; Dinu, Vlad; Gillis, Richard B.; Adams, Gary G.; Harding, Stephen E.

2017-01-01

VanA-type resistance to glycopeptide antibiotics in clinical enterococci is regulated by the VanSARA two-component signal transduction system. The nature of the molecular ligand that is recognised by the VanSA sensory component has not hitherto been identified. Here we employ purified, intact and active VanSA membrane protein (henceforth referred to as VanS) in analytical ultracentrifugation experiments to study VanS oligomeric state and conformation in the absence and presence of vancomycin. A combination of sedimentation velocity and sedimentation equilibrium in the analytical ultracentrifuge (SEDFIT, SEDFIT-MSTAR and MULTISIG analysis) showed that VanS in the absence of the ligand is almost entirely monomeric (molar mass M = 45.7 kDa) in dilute aqueous solution with a trace amount of high molar mass material (M ~ 200 kDa). The sedimentation coefficient s suggests the monomer adopts an extended conformation in aqueous solution with an equivalent aspect ratio of ~(12 ± 2). In the presence of vancomycin over a 33% increase in the sedimentation coefficient is observed with the appearance of additional higher s components, demonstrating an interaction, an observation consistent with our circular dichroism measurements. The two possible causes of this increase in s – either a ligand induced dimerization and/or compaction of the monomer are considered. PMID:28397853

Polymer relaxation and stretching dynamics in semi-dilute DNA solutions: a single molecule study

NASA Astrophysics Data System (ADS)

Hsiao, Kai-Wen; Brockman, Christopher; Schroeder, Charles

2015-03-01

In this work, we study polymer relaxation and stretching dynamics in semi-dilute DNA solutions using single molecule techniques. Using this approach, we uncover a unique scaling relation for longest polymer relaxation time that falls in the crossover regime described by semi-flexible polymer solutions, which is distinct from truly flexible polymer chains. In addition, we performed a series of step-strain experiments on single polymers in semi-dilute solutions in planar extensional flow using an automated microfluidic trap. In this way, we are able to precisely control the flow strength and the amount of strain applied to single polymer chains, thereby enabling direct observation of the full stretching and relaxation process in semi-dilute solutions during transient start-up and flow cessation. Interestingly, we observe polymer individualism in the conformation of single chains in semi-dilute solutions, which to our knowledge has not yet been observed. In addition, we observe the relaxation data can be explained by a multi-exponential decay process after flow cessation in semi-dilute solutions. Overall, our work reports key advance in non-dilute polymer systems from a molecular perspective via direct observation of dynamics in strong flows. DOW fellowship.

Symmetric and asymmetric squarylium dyes as noncovalent protein labels: a study by fluorimetry and capillary electrophoresis.

PubMed

Welder, Frank; Paul, Beverly; Nakazumi, Hiroyuki; Yagi, Shigeyuki; Colyer, Christa L

2003-08-05

Noncovalent interactions between two squarylium dyes and various model proteins have been explored. NN127 and SQ-3 are symmetric and asymmetric squarylium dyes, respectively, the fluorescence emissions of which have been shown to be enhanced upon complexation with proteins such as bovine serum albumin (BSA), human serum albumin (HSA), beta-lactoglobulin A, and trypsinogen. Although these dyes are poorly soluble in aqueous solution, they can be dissolved first in methanol followed by dilution with aqueous buffer without precipitation, and are then suitable for use as fluorescent labels in protein determination studies. The nature of interactions between these dyes and proteins was studied using a variety of buffer systems, and it was found that electrostatic interactions are involved but not dominant. Dye/protein stoichiometries in the noncovalent complexes were found to be 1:1 for SQ-3, although various possible stoichiometries were found for NN127 depending upon pH and protein. Association constants on the order of 10(5) and 10(7) were found for noncovalent complexes of SQ-3 and NN127, respectively, with HSA, indicating stronger interactions of the symmetric dye with proteins. Finally, HSA complexes with NN127 were determined by capillary electrophoresis with laser-induced fluorescence detection (CE-LIF). In particular, NN127 shows promise as a reagent capable of fluorescently labeling analyte proteins for analysis by CE-LIF without itself being significantly fluorescent under the aqueous solution conditions studied herein.

Anti Microbial activity of the various leaf extracts of Vitex negundo Linn.

PubMed Central

Devi, P. Renuka; KokilaVani, R.; Poogotha, S. Gnana

2008-01-01

The antibacterial activity of the leaves of Vitex negundo was tested against three bacteria Viz., Staphylococcus aureus Escherichia coli and Klebsiella Peumoniae, The fresh aqueous, heated aqueous extract, chloroform and methanolic extract of leaves were used for screening their antibacterial potential. The fresh and aqueous extracts of leaves in various dilutions were found to have antibacterial activity against the three bacteria. PMID:22557306

Electrothermal atomic absorption spectrometric determination of arsenic in essential lavender and rose oils.

PubMed

Karadjova, Irina B; Lampugnani, Leonardo; Tsalev, Dimiter L

2005-02-28

Analytical procedures for electrothermal atomic absorption spectrometric (ETAAS) determination of arsenic in essential oils from lavender (Lavendula angustifolia) and rose (Rosa damascena) are described. For direct ETAAS analysis, oil samples are diluted with ethanol or i-propanol for lavender and rose oil, respectively. Leveling off responses of four different arsenic species (arsenite, arsenate, monomethylarsonate and dimethylarsinate) is achieved by using a composite chemical modifier: l-cysteine (0.05gl(-1)) in combination with palladium (2.5mug) and citric acid (100mug). Transverse-heated graphite atomizer (THGA) with longitudinal Zeeman-effect background correction and 'end-capped' graphite tubes with integrated pyrolytic graphite platforms, pre-treated with Zr-Ir for permanent modification are employed as most appropriate atomizer. Calibration with solvent-matched standard solutions of As(III) is used for four- and five-fold diluted samples of lavender and rose oil, respectively. Lower dilution factors required standard addition calibration by using aqueous (for lavender oil) or i-propanol (for rose oil) solutions of As(III). The limits of detection (LOD) for the whole analytical procedure are 4.4 and 4.7ngg(-1) As in levender and rose oil, respectively. The relative standard deviation (R.S.D.) for As at 6-30ngg(-1) levels is between 8 and 17% for both oils. As an alternative, procedure based on low temperature plasma ashing in oxygen with ETAAS, providing LODs of 2.5 and 2.7ngg(-1) As in levender and rose oil, respectively, and R.S.D. within 8-12% for both oils has been elaborated. Results obtained by both procedures are in good agreement.

Chemical heat pump and chemical energy storage system

DOEpatents

Clark, Edward C.; Huxtable, Douglas D.

1985-08-06

A chemical heat pump and storage system employs sulfuric acid and water. In one form, the system includes a generator and condenser, an evaporator and absorber, aqueous acid solution storage and water storage. During a charging cycle, heat is provided to the generator from a heat source to concentrate the acid solution while heat is removed from the condenser to condense the water vapor produced in the generator. Water is then stored in the storage tank. Heat is thus stored in the form of chemical energy in the concentrated acid. The heat removed from the water vapor can be supplied to a heat load of proper temperature or can be rejected. During a discharge cycle, water in the evaporator is supplied with heat to generate water vapor, which is transmitted to the absorber where it is condensed and absorbed into the concentrated acid. Both heats of dilution and condensation of water are removed from the thus diluted acid. During the discharge cycle the system functions as a heat pump in which heat is added to the system at a low temperature and removed from the system at a high temperature. The diluted acid is stored in an acid storage tank or is routed directly to the generator for reconcentration. The generator, condenser, evaporator, and absorber all are operated under pressure conditions specified by the desired temperature levels for a given application. The storage tanks, however, can be maintained at or near ambient pressure conditions. In another form, the heat pump system is employed to provide usable heat from waste process heat by upgrading the temperature of the waste heat.

Synthetic Biology in Aqueous Compartments at the Micro- and Nanoscale

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

Boreyko, Jonathan; Caveney, Patrick M.; Norred, Sarah L.

ABSTRACT Aqueous two-phase systems and related emulsion-based structures defined within micro- and nanoscale environments enable a bottom-up synthetic biological approach to mimicking the dynamic compartmentation of biomaterial that naturally occurs within cells. Model systems we have developed to aid in understanding these phenomena include on-demand generation and triggering of reversible phase transitions in ATPS confined in microscale droplets, morpho-logical changes in networks of femtoliter-volume aqueous droplet interface bilayers (DIBs) formulated in microfluidic channels, and temperature-driven phase transitions in interfacial lipid bilayer systems supported on micro and nanostructured substrates. For each of these cases, the dynamics were intimately linked to changesmore » in the chemical potential of water, which becomes increasingly susceptible to confinement and crowding. At these length scales, where interfacial and surface areas predominate over compartment volumes, both evaporation and osmotic forces become enhanced relative to ideal dilute solutions. Finally, consequences of confinement and crowding in cell-sized microcompartments for increasingly complex scenarios will be discussed, from single-molecule mobility measurements with fluorescence correlation spectroscopy to spatio-temporal modulation of resource sharing in cell-free gene expression bursting.« less

Investigating the Affinities and Persistence of VX Nerve Agent in Environmental Matrices

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

Love, A H; Vance, A L; Reynolds, J G

2004-03-09

Laboratory experiments were conducted to determine environmental variables that affect the affinities and persistence of the nerve agent O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothiolate (VX) at dilute concentrations in environmental matrices. Quantitative analyses of VX and its degradation products were performed using LC-MS. Batch hydrolysis experiments demonstrated an increasing hydrolysis rate as pH increased, as shown in previous studies, but also indicated that dissolved aqueous constituents can cause significant differences in the absolute hydrolysis rate. Adsorption isotherms from batch aqueous experiments revealed that VX has a high affinity for hydrophobic organics, a moderate affinity for montmorillonite clay, and a very low affinity formore » an iron-oxyhydroxide soil mineral, goethite. The adsorption on goethite was increased with the presence of dissolved organic matter in solution. VX degraded rapidly when dried onto goethite, when an inner-sphere complex was forced. No enhanced degradation occurred with goethite in small amounts water. These results suggest that aqueous conditions have important controls on VX adsorption and degradation in the environment and a more mechanistic understanding of these controls is needed in order to enable accurate predictions of its long-term fate and persistence.« less

Synthetic Biology in Aqueous Compartments at the Micro- and Nanoscale

DOE PAGES

Boreyko, Jonathan; Caveney, Patrick M.; Norred, Sarah L.; ...

2017-07-10

ABSTRACT Aqueous two-phase systems and related emulsion-based structures defined within micro- and nanoscale environments enable a bottom-up synthetic biological approach to mimicking the dynamic compartmentation of biomaterial that naturally occurs within cells. Model systems we have developed to aid in understanding these phenomena include on-demand generation and triggering of reversible phase transitions in ATPS confined in microscale droplets, morpho-logical changes in networks of femtoliter-volume aqueous droplet interface bilayers (DIBs) formulated in microfluidic channels, and temperature-driven phase transitions in interfacial lipid bilayer systems supported on micro and nanostructured substrates. For each of these cases, the dynamics were intimately linked to changesmore » in the chemical potential of water, which becomes increasingly susceptible to confinement and crowding. At these length scales, where interfacial and surface areas predominate over compartment volumes, both evaporation and osmotic forces become enhanced relative to ideal dilute solutions. Finally, consequences of confinement and crowding in cell-sized microcompartments for increasingly complex scenarios will be discussed, from single-molecule mobility measurements with fluorescence correlation spectroscopy to spatio-temporal modulation of resource sharing in cell-free gene expression bursting.« less

The characterization of the concentration of the single-walled carbon nanotubes in aqueous dispersion by UV-Vis-NIR absorption spectroscopy.

PubMed

Yang, Bing; Ren, Lingling; Li, Luming; Tao, Xingfu; Shi, Yunhua; Zheng, Yudong

2013-11-07

Current and future applications of single-wall carbon nanotubes (SWCNTs) depend on the dispersion of the SWCNTs in aqueous solution and their quantitation. The concentration of SWCNTs is an important indicator to evaluate the dispersibility of the surfactant-dispersed SWCNTs suspension. Due to the complexity of the SWCNTs suspension, it is necessary to determine both the total concentration of the dispersed SWCNTs and the concentration of individually dispersed SWCNTs in aqueous suspensions, and these were evaluated through the absorbance and the resonance ratios of UV-Vis-NIR absorption spectra, respectively. However, there is no specific and reliable position assigned for either calculation of the absorbance or the resonance ratio of the UV-Vis-NIR absorption spectrum. In this paper, different ranges of wavelengths for these two parameters were studied. From this, we concluded that the wavelength range between 300 nm and 600 nm should be the most suitable for evaluation of the total concentration of dispersed SWCNTs in the suspension; also, wavelengths below 800 nm should be most suitable for evaluation of the concentration of individually dispersed SWCNTs in the suspension. Moreover, these wavelength ranges are verified by accurate dilution experiments.

Single- and double-strand break formation in DNA irradiated in aqueous solution: dependence on dose and OH radical scavenger concentration

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

Siddiqi, M.A.; Bothe, E.

The yields of single- and double-strand breaks (SSB and DSB) in calf thymus DNA, after /sup 60/Co gamma irradiation in dilute aqueous solution, have been determined via molecular weight measurements using a low-angle laser light scattering technique. The irradiations were administered to N/sub 2/O-containing solutions of DNA in the absence and presence of oxygen and with different concentrations of the OH radical scavengers phenol, tertiary butanol, and methanol. OH radicals were found to produce SSB linearly with dose with a G value of 55 nmol J-1 and 54 nmol J-1 in deoxygenated and oxygenated solutions, respectively. DSB were formed accordingmore » to a linear-quadratic dose relationship and the G value of linearly formed DSB were GDSB alpha(r.t.) = 3.5 nmol J-1 in deoxygenated and 3.2 nmol J-1 in oxygenated solution. The ratio of GSSB/GDSB alpha(r.t.) = gamma of 19 +/- 6 was independent of the scavenger concentration in the case of tertiary butanol and methanol-containing solutions. GDSB alpha(r.t.) is interpreted to result from a radical site transferred from a sugar moiety of the cleaved strand to the complementary intact strand. This process of radical transfer and subsequent cleavage of the second strand occurs with a probability of about 6 +/- 2% in the presence of oxygen at all scavenger concentrations studied. These data on scavenging capacity on GDSB alpha(r.t.) suggest that the double-strand breakage produced via radical transfer remains higher than that resulting from direct effect, up to scavenging capacities of about 10(9) s-1.« less

Experimental Thermodynamics of [Na-Mg-Cl-SO4] Aqueous Solutions at GPa Pressure With Application to Icy Worlds.

NASA Astrophysics Data System (ADS)

Brown, J. M.; Bollengier, O.; Vance, S.

2017-12-01

Water competes with silicates as the main constituent of solid bodies in the outer solar system. Ganymede and Titan, the Mercury-sized satellites of Jupiter and Saturn, are made up half of water present as massive hydrospheres where pressure can reach up to 1.5 GPa. Geophysical data and planetary models unequivocally support the existence of global aqueous oceans trapped in these hydrospheres. However, the extent of these oceans and their role in the processes governing the internal structure of these moons remain unresolved. At issue is the poor to non-existent characterization, at the relevant pressures, of the properties of the aqueous fluids of significance to the outer solar system (with notably the Na-Mg-Cl-SO4 salts found in primitive chondrites), forcing current models to rely on pure water only. Our team at the University of Washington has developed an experimental apparatus to acquire the speed of sound of aqueous solutions in the 0 - 0.7 GPa and 250 - 350 K pressure and temperature ranges covering most of the conditions of existence of these extra-terrestrial oceans. Speeds of sound measured over a grid of pressures and temperatures allow calculation of the thermodynamic quantities (G, ρ, μ...) required for planetary science. Early analysis of pure water samples indicates our experimental results are on par with (at lower pressures), or better than, the IAPWS water laboratory standard, with sound speeds determined to 0.02% over our entire pressure range. For the first time at the high pressures of interest for large icy moons, we achieved the exploration of H2O-NaCl, H2O-MgSO4, H2O-Na2SO4 and H2O-MgCl2 solutions, from dilute concentrations to saturation. We are now in the process of acquiring the first data for H2O-NaCl-MgSO4 mixtures. We will briefly present our experimental setup and the underlying sound speed theory, and will then compare our results for the four endmembers, with an emphasis on their different association behavior under pressure as revealed by the sound speed data. We also aim to provide the first insights into the mixing behavior of these ions in solution at high pressure, to be compared with common mixing rules. Finally, we will present an application of the thermodynamics of aqueous solutions to calculate liquid-ice equilibria and assess the role of brine densities in the evolution of icy mantles.

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

NASA Astrophysics Data System (ADS)

Seeman, Jeffrey I.

2005-10-01

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

Ca(OH)2-Catalyzed Condensation of Aldehydes with Methyl ketones in Dilute Aqueous Ethanol: A Comprehensive Access to α,β-Unsaturated Ketones

NASA Astrophysics Data System (ADS)

Yu, Lei; Han, Mengting; Luan, Jie; Xu, Lin; Ding, Yuanhua; Xu, Qing

2016-07-01

Cheap, abundant but seldom-employed Ca(OH)2 was found to be an excellent low-loading (5-10 mol%) catalyst for Claisen-Schmidt condensation of aldehydes with methyl ketones under mild conditions. It was interesting that dilute aqueous ethanol (20 v/v%) was unexpectedly discovered to be the optimal solvent. The reaction was scalable at least to 100 mmol and calcium could be precipitated by CO2 and removed by filtration. Evaporation of solvent directly afforded the product in the excellent 96% yield with high purity, as confirmed by its 1H NMR spectrum.

Method for processing aqueous wastes

DOEpatents

Pickett, John B.; Martin, Hollis L.; Langton, Christine A.; Harley, Willie W.

1993-01-01

A method for treating waste water such as that from an industrial processing facility comprising the separation of the waste water into a dilute waste stream and a concentrated waste stream. The concentrated waste stream is treated chemically to enhance precipitation and then allowed to separate into a sludge and a supernate. The supernate is skimmed or filtered from the sludge and blended with the dilute waste stream to form a second dilute waste stream. The sludge remaining is mixed with cementitious material, rinsed to dissolve soluble components, then pressed to remove excess water and dissolved solids before being allowed to cure. The dilute waste stream is also chemically treated to decompose carbonate complexes and metal ions and then mixed with cationic polymer to cause the precipitated solids to flocculate. Filtration of the flocculant removes sufficient solids to allow the waste water to be discharged to the surface of a stream. The filtered material is added to the sludge of the concentrated waste stream. The method is also applicable to the treatment and removal of soluble uranium from aqueous streams, such that the treated stream may be used as a potable water supply.

Aqueous electrolytes for redox flow battery systems

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

Liu, Tianbiao; Li, Bin; Wei, Xiaoliang

An aqueous redox flow battery system includes an aqueous catholyte and an aqueous anolyte. The aqueous catholyte may comprise (i) an optionally substituted thiourea or a nitroxyl radical compound and (ii) a catholyte aqueous supporting solution. The aqueous anolyte may comprise (i) metal cations or a viologen compound and (ii) an anolyte aqueous supporting solution. The catholyte aqueous supporting solution and the anolyte aqueous supporting solution independently may comprise (i) a proton source, (ii) a halide source, or (iii) a proton source and a halide source.

40 CFR 797.1400 - Fish acute toxicity test.

Code of Federal Regulations, 2011 CFR

2011-07-01

... construction materials, test chambers, and testing apparatus to dilution water or to test solutions prior to... or the leaching of substances from the test facilities into the dilution water or test solution. (5... intermittent passage of test solution or dilution water through a test chamber, or a holding or acclimation...

Anti microbial activity of the various leaf extracts of Vitex negundo Linn.

PubMed Central

Devi, P. Renuka; Kokilavani, R.; Poongothai, S. Gnana

2008-01-01

The antibacterial activity of the leaves of Vitex negundo was tested against three types of bacteria Viz., Staphylococcus aureus, Escherichia coli and Klebsiella Pneumoniae. The fresh, aqueous, heated aqueous extract, chloroform and methanolic extract of leaves were used for screening their antibacterial potential. The fresh and aqueous extracts of leaves in various dilutions were found to have antibacterial activity against the three bacteria. PMID:22557282

Compilation of Henry's law constants (version 4.0) for water as solvent

NASA Astrophysics Data System (ADS)

Sander, R.

2015-04-01

Many atmospheric chemicals occur in the gas phase as well as in liquid cloud droplets and aerosol particles. Therefore, it is necessary to understand the distribution between the phases. According to Henry's law, the equilibrium ratio between the abundances in the gas phase and in the aqueous phase is constant for a dilute solution. Henry's law constants of trace gases of potential importance in environmental chemistry have been collected and converted into a uniform format. The compilation contains 17 350 values of Henry's law constants for 4632 species, collected from 689 references. It is also available at http://www.henrys-law.org.

Compilation of Henry's law constants, version 3.99

NASA Astrophysics Data System (ADS)

Sander, R.

2014-11-01

Many atmospheric chemicals occur in the gas phase as well as in liquid cloud droplets and aerosol particles. Therefore, it is necessary to understand the distribution between the phases. According to Henry's law, the equilibrium ratio between the abundances in the gas phase and in the aqueous phase is constant for a dilute solution. Henry's law constants of trace gases of potential importance in environmental chemistry have been collected and converted into a uniform format. The compilation contains 14775 values of Henry's law constants for 3214 species, collected from 639 references. It is also available on the internet at http://www.henrys-law.org.

Hybrid capacitive deionization with anion-exchange membranes for lithium extraction

NASA Astrophysics Data System (ADS)

Siekierka, Anna; Bryjak, Marek

2017-11-01

Lithium is considered to be a critical material for various industrial fields. We present our studies on extraction lithium from diluted aqueous solution by novel hybrid system based on a membrane capacitive deionization and batteries desalination. Hybrid CDI is comprised by a lithium selective adsorbent, activated carbon electrode and anion-exchange membranes. Here, we demonstrated implication of various type of anion-exchange membranes and influence their properties on effective capacity and energy requirements in charge/discharge steps. We described a configuration with anion-exchange membrane characterized by adsorption capacity of 35 mg/g of Li+ with 0.08Wh/g and removal efficiency of 60 % of lithium ions, using novel selective desalination technique.

Sensing aggregation in highly turbid plasmonic and non-plasmonic colloidal suspensions

NASA Astrophysics Data System (ADS)

Ducay, Rey Nann Mark; Philip, Nathan; Boivin, Jordan; Judge, Patrick; Berberich, Jason; Scaffidi, Jonathan; Bali, Lalit; Bali, Samir

2015-05-01

We demonstrate a method for sensing the presence of aggregation in highly turbid aqueous suspensions of polystyrene and gold nanospheres. Aggregation is induced either by changing the pH or the ionic strength, by adding small, controlled amounts of an acid or base solution. The particle concentrations used are at least two orders of magnitude higher than previously reported. To the best of our knowledge, this is a first observation of aggregation in highly dense colloidal suspensions without any sample dilution or special sample preparation. We gratefully acknowledge support from the American Chemical Society Petroleum Research Fund and Miami University's Interdisciplinary Roundtable Fund. We also gratefully acknowledge experimental help from the Miami University Instrumentation Laboratory.

Using temperature-responsive zwitterionic surfactant to enhance the enzymatic hydrolysis of lignocelluloses and recover cellulase by cooling.

PubMed

Cai, Cheng; Pang, Yuxia; Zhan, Xuejuan; Zeng, Meijun; Lou, Hongming; Qian, Yong; Yang, Dongjie; Qiu, Xueqing

2017-11-01

Some zwitterionic surfactants exhibit upper critical solution temperature (UCST) in aqueous solutions. For the zwitterionic surfactant solution mixed with cellulase, when its temperature is below UCST, the cellulase can be recovered by coprecipitation with zwitterionic surfactant. In this work, 3-(Hexadecyldimethylammonio) propanesulfonate (SB3-16) was selected to enhance the enzymatic hydrolysis of lignocelluloses and recover the cellulase. After adding 2mmol/L of SB3-16, the enzymatic digestibility of eucalyptus pretreated by dilute acid (Eu-DA) and by sulfite (Eu-SPORL) increased from 27.9% and 35.1% to 72.6% and 89.7%, respectively. The results showed that SB3-16 could reduce the non-productive adsorption of cellulase on hydrophobic interface, while it did not significantly inhibit the activity of cellulase. For the solution contained 1wt% SB3-16 and 200mg protein/L CTec2 cellulase, 55.2% of protein could be recovered by cooling. The filter paper activity of the recovered cellulase was 1.93FPU/mg protein, which was 95.8% of its initial activity. Copyright © 2017. Published by Elsevier Ltd.

Nickel solvent extraction from cold purification filter cakes of Angouran mine concentrate using LIX984N

NASA Astrophysics Data System (ADS)

Balesini, A. A.; Zakeri, A.; Razavizadeh, H.; Khani, A.

2013-11-01

Cold purification filter cakes generated in the hydrometallurgical processing of Angouran mine zinc concentrate commonly contain significant amounts of Zn, Cd, and Ni ions and thus are valuable resources for metal recovery. In this research, a nickel containing solution that was obtained from sulfuric acid leaching of the filter cake following cadmium and zinc removal was subjected to solvent extraction experiments using 10vol% LIX984N diluted in kerosene. Under optimum experimental conditions (pH 5.3, volume ratio of organic/aqueous (O:A) = 2:1, and contact time = 5 min), more than 97.1% of nickel was extracted. Nickel was stripped from the loaded organic by contacting with a 200 g/L sulfuric acid solution, from which 77.7% of nickel was recovered in a single contact at the optimum conditions (pH 1-1.5, O:A = 5:1, and contact time = 15 min).

Modification of poly(vinylidene fluoride) ultrafiltration membranes with poly(vinyl alcohol) for fouling control in drinking water treatment.

PubMed

Du, Jennifer R; Peldszus, Sigrid; Huck, Peter M; Feng, Xianshe

2009-10-01

A commercial poly(vinylidene fluoride) flat sheet membrane was modified by surface coating with a dilute poly(vinyl alcohol) (PVA) aqueous solution followed by solid-vapor interfacial crosslinking. The resulting PVA layer increased membrane smoothness and hydrophilicity and resulted in comparable pure water permeation between the modified and unmodified membranes. Fouling tests using a 5 mg/L protein solution showed that a short period of coating and crosslinking improved the anti-fouling performance. After 18 h ultrafiltration of a surface water with a TOC of approximately 7 mg C/L, the flux of the modified membrane was twice as high as that of the unmodified membrane. The improved fouling resistance of the modified membrane was related to the membrane physiochemical properties, which were confirmed by pure water permeation, X-ray photoelectron spectroscopy, and contact angle, zeta potential and roughness measurements.

The benzil-cyanide reaction and its application to the development of a selective cyanide anion indicator.

PubMed

Cho, Dong-Gyu; Kim, Jong Hoon; Sessler, Jonathan L

2008-09-10

The benzil-cyanide reaction is a cyanide-specific reaction that has been exploited to produce a colorimetric indicator for this toxic anion. This was done by producing a pi-extended analogue of benzil, 7, which is soluble in a 70:30 (v/v) mixture of methanol-water. In this medium, dilute solutions of 7 are yellow but produce colorless products when exposed to low concentrations of cyanide anion (> or = 1.7 microM; added as an aqueous NaCN solution), but no other common anions (e.g., OH(-), F(-), N3(-), benzoate(-), and H2PO4(-)). On the basis of these observations and supporting mechanistic analyses, it is concluded that the modified benzil system 7 is a promising cyanide anion indicator that is attractive in terms of its selectivity, ease-of-use, water compatibility, and the low, naked-eye discernible cyanide detection limit it provides.

•OH and e-aq are yet good candidates for demolishing the β-lactam system of a penicillin eliminating the antimicrobial activity

NASA Astrophysics Data System (ADS)

Szabó, László; Tóth, Tünde; Rácz, Gergely; Takács, Erzsébet; Wojnárovits, László

2016-07-01

Tracking the pharmacophore of a drug subjected to advanced oxidation is essential for evaluating the efficiency of the process in terms of wastewater treatment. From this standpoint, the •OH and eaq- induced deactivation mechanism of amoxicillin, a penicillin derivative was investigated in dilute aqueous solution using pulse- and gamma-radiolysis techniques. Based on IR measurements, •OH and eaq- destroys the β-lactam system of amoxicillin with ~55% and ~84% efficiency, respectively. In aerated solution the elimination of the pharmacophore was slightly impaired since the reaction pathway of the ring-opening was disturbed owing to the reactivity of O2 and O2• - toward the intermediates of sulfur oxidation. The high potency of eaq- for β-lactam deactivation is attributed to the enhanced electron deficiency of the carbonyl carbon inside the lactam ring.

Experimental investigation of sulphur isotope partitioning during outgassing of hydrogen sulphide from diluted aqueous solutions and seawater.

PubMed

Baune, Claudia; Bottcher, Michael E

2010-12-01

The diffusion of hydrogen sulphide across the sediment-water interface and subsequent liberation to the atmosphere may occur in iron-deficient coastal marine environments with enhanced microbial activity in surface sediments and corresponding accumulation of dissolved H2S in near-surface pore waters. The involvement of analogue processes in periods of global mass extinctions during Earth's history (e.g. at the Permian-Triassic boundary) is currently in discussion [L.R. Kump, A. Pavlov, and M. Arthur,Massive Release of Hydrogen Sulfide to the Surface Ocean and Atmosphere During Intervals of Oceanic Anoxia, Geology 33, 397 (2005)]. The outgassing of H₂S is associated with a fractionation of the stable sulphur isotopes, which has so far only been investigated experimentally at selected acidic and neutral pH values, and no experiments with seawater had been carried out. In this communication, we report on sulphur isotope fractionation that takes place during the experimental degassing of H₂S from aqueous solution by an inert gas (N₂) at 21 °C. Experiments were conducted in the pH range between 2.6 and 10.8, corresponding to the dominance fields of dissolved hydrogen sulphide (H₂S(aq)), bisulphide (HS-(aq)), and mixtures of both sulphide species. Overall isotope enrichment factors between -1.6 and +3.0‰ were observed, with the residual dissolved sulphide being enriched or depleted in ³⁴S compared to the liberated H₂S at low and high pH values, respectively. The difference in the low and high pH isotope fractionation effects can be explained by isotope exchange between H₂S(aq) and HS-(aq) [B. Fry, H. Gest, and J.M. Hayes, Sulfur Isotope Effects Associated with Protonation of HS- and Volatilization of H₂S, Chem. Geol. (Isot. Geosci. Sec.) 58, 253 (1986); R. Geßler and K. von Gehlen, Investigation of Sulfur Isotope Fractionation Between H2S Gas and Aqueous Solutions, Fresenius J. Anal. Chem. 324, 130 (1986)] followed by the subsequent transfer of H₂S(aq) to the gaseous phase. The assumption of pure physical outgassing of H₂S(aq) at low pH values leads to an isotope enrichment factor of -0.9 ± 0.4‰ (n = 14) which is caused by the combined differences in dehydration and diffusion coefficients of H₂³²S(aq) and H₂³⁴S(aq). In the pH range of natural surface and shallow pore waters, ³⁴S will be equal to or enriched in the gaseous phase compared to the aqueous solution, therefore creating no or a slight enrichment of ³²S in the aqueous solution. Experiments in seawater solution showed no significant influence of increased ionic strength and changed corresponding aqueous speciation on sulphur isotope effects.

A modified Lowry protein test for dilute protein solutions

Treesearch

Garold F. Gregory; Keith F. Jensen

1971-01-01

A modified Lowry protein test for dilute protein solutions modified Lowry protein test was compared with the standard Lowry protein test. The modified test was found to give estimates of protein concentration that were as good as the standard test and has the advange that proteins can be measured in very dilute solutions.

Science Notes: Dilution of a Weak Acid

ERIC Educational Resources Information Center

Talbot, Christopher; Wai, Chooi Khee

2014-01-01

This "Science note" arose out of practical work involving the dilution of ethanoic acid, the measurement of the pH of the diluted solutions and calculation of the acid dissociation constant, K[subscript a], for each diluted solution. The students expected the calculated values of K[subscript a] to be constant but they found that the…

Supercritical Water Mixture (SCWM) Experiment

NASA Technical Reports Server (NTRS)

Hicks, Michael C.; Hegde, Uday G.

2012-01-01

The subject presentation, entitled, Supercritical Water Mixture (SCWM) Experiment, was presented at the International Space Station (ISS) Increment 33/34 Science Symposium. This presentation provides an overview of an international collaboration between NASA and CNES to study the behavior of a dilute aqueous solution of Na2SO4 (5% w) at near-critical conditions. The Supercritical Water Mixture (SCWM) investigation, serves as important precursor work for subsequent Supercritical Water Oxidation (SCWO) experiments. The SCWM investigation will be performed in DECLICs High Temperature Insert (HTI) for the purpose of studying critical fluid phenomena at high temperatures and pressures. The HTI includes a completely sealed and integrated test cell (i.e., Sample Cell Unit SCU) that will contain approximately 0.3 ml of the aqueous test solution. During the sequence of tests, scheduled to be performed in FY13, temperatures and pressures will be elevated to critical conditions (i.e., Tc = 374C and Pc = 22 MPa) in order to observe salt precipitation, precipitate agglomeration and precipitate transport in the presence of a temperature gradient without the influences of gravitational forces. This presentation provides an overview of the motivation for this work, a description of the DECLIC HTI hardware, the proposed test sequences, and a brief discussion of the scientific research objectives.

Protein Stabilization and Enzyme Activation in Ionic Liquids: Specific Ion Effects

PubMed Central

Zhao, Hua

2015-01-01

There are still debates on whether the hydration of ions perturbs the water structure, and what is the degree of such disturbance; therefore, the origin of Hofmeister effect on protein stabilization continues being questioned. For this reason, it is suggested to use the ‘specific ion effect’ instead of other misleading terms such as Hofmeister effect, Hofmeister series, lyotropic effect, and lyotropic series. In this review, we firstly discuss the controversial aspect of inorganic ion effects on water structures, and several possible contributors to the specific ion effect of protein stability. Due to recent overwhelming attraction of ionic liquids (ILs) as benign solvents in many enzymatic reactions, we further evaluate the structural properties and molecular-level interactions in neat ILs and their aqueous solutions. Next, we systematically compare the specific ion effects of ILs on enzyme stability and activity, and conclude that (a) the specificity of many enzymatic systems in diluted aqueous IL solutions is roughly in line with the traditional Hofmeister series albeit some exceptions; (b) however, the specificity follows a different track in concentrated or neat ILs because other factors (such as hydrogen-bond basicity, nucelophilicity, and hydrophobicity, etc) are playing leading roles. In addition, we demonstrate some examples of biocatalytic reactions in IL systems that are guided by the empirical specificity rule. PMID:26949281

Comparisons of SPORL and dilute acid pretreatments for sugar and ethanol productions from aspen

Treesearch

S. Tian; W. Zhu; Roland Gleisner; X.J. Pan; Junyong Zhu

2011-01-01

This study reports comparative evaluations of sugar and ethanol production from a native aspen (Populus tremuloides) between sulfite pretreatment to overcome recalcitrance of lignocelluloses (SPORL) and dilute acid (DA) pretreatments. All aqueous pretreatments were carried out in a laboratory wood pulping digester using wood chips at 170°C with a liquid to...

Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity.

PubMed

Hanford, Kate L; Mitchem, Laura; Reid, Jonathan P; Clegg, Simon L; Topping, David O; McFiggans, Gordon B

2008-10-02

Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered.

Molybdenum-oxide based unique polyprotic nanoacids showing different deprotonations and related assembly processes in solution.

PubMed

Kistler, Melissa L; Liu, Tianbo; Gouzerh, Pierre; Todea, Ana Maria; Müller, Achim

2009-07-14

We report the self-assembly processes in solution of three Keplerate-type molybdenum-oxide based clusters {Mo72V30}, {Mo72Cr30} and {Mo72Fe30} (all with diameters of approximately 2.5 nm). These clusters behave as unique weak polyprotic acids owing to the external water ligands attached to the non-Mo metal centers. Whereas the Cr and Fe clusters have 30 water ligands attached at the 30 M3+ centers pointing outside, {Mo72V30} has 20 water ligands coordinated to vanadium atoms, of which only 10 are pointing outside. The self-assembly processes of the Keplerates leading to supramolecular blackberry-type structures are influenced by the effective charge densities on the cluster surfaces, which can be tuned by the pH values and solvent properties. As expected, {Mo72Cr30} and {Mo72Fe30} behave similarly in aqueous solution due to their analogous structures and in both cases the self-assembly follows the partial deprotonation of the external water ligands attached to the non-Mo metal centers. However, the M-OH2 functionalities differ not only in acidity but also lability, i.e. in different residence times of the H2O ligands. In contrast to {Mo72Cr30} and {Mo72Fe30}, the {Mo72V30} clusters carry a rather large number of negative charges so that their solution properties are different. They exist as discrete macroions in dilute aqueous solution, and form only in mixed water/organic solvent (like acetone) blackberry-type structures whose size increases with acetone content. The comparison of the properties of the clusters allows more general information about the interesting self-assembly phenomenon to be unveiled.

[Formation of oxalate in oxaliplatin injection diluted with infusion solutions].

PubMed

Eto, Seiji; Yamamoto, Kie; Shimazu, Kounosuke; Sugiura, Toshimune; Baba, Kaori; Sato, Ayaka; Goromaru, Takeshi; Hagiwara, Yoshiaki; Hara, Keiko; Shinohara, Yoshitake; Takahashi, Kojiro

2014-01-01

Oxaliplatin use can cause acute peripheral neuropathy characterized by sensory paresthesias, which are markedly exacerbated by exposure to cold temperatures, and is a dose-limiting factor in the treatment of colorectal cancer.Oxalate is eliminated in a series of nonenzymatic conversions of oxaliplatin in infusion solutions or biological fluids.Elimination of oxalate from oxaliplatin has been suggested as one of the reasons for the development of acute neuropathy.In this study, we developed a high-performance liquid chromatography(HPLC)-based method to detect oxalate formation, and investigated the time dependent formation of oxalate in oxaliplatin diluted with infusion solutions.The results obtained showed that the amount of oxalate in the solution corresponded to 1.6% of oxaliplatin 8 h after oxaliplatin dilution with a 5% glucose solution. On the other hand, oxalate formation from oxaliplatin diluted with a saline solution was ten-fold higher than that from oxaliplatin diluted with the 5% glucose solution.Most patients who were intravenously injected with oxaliplatin experienced venous pain.As a preventive measure against venous pain, dexamethasone was added to the oxaliplatin injection.We measured the amount of oxalate formed in the dexamethasone-containing oxaliplatin injection diluted with a 5% glucose solution.The amount of oxalate formed when dexamethasone was added did not differ significantly from that formed when dexamethasone was not added.Thus, there are no clinical problems associated with the stability of oxaliplatin solutions.

The enhancement and suppression of immersion mode heterogeneous ice-nucleation by solutes.

PubMed

Whale, Thomas F; Holden, Mark A; Wilson, Theodore W; O'Sullivan, Daniel; Murray, Benjamin J

2018-05-07

Heterogeneous nucleation of ice from aqueous solutions is an important yet poorly understood process in multiple fields, not least the atmospheric sciences where it impacts the formation and properties of clouds. In the atmosphere ice-nucleating particles are usually, if not always, mixed with soluble material. However, the impact of this soluble material on ice nucleation is poorly understood. In the atmospheric community the current paradigm for freezing under mixed phase cloud conditions is that dilute solutions will not influence heterogeneous freezing. By testing combinations of nucleators and solute molecules we have demonstrated that 0.015 M solutions (predicted melting point depression <0.1 °C) of several ammonium salts can cause suspended particles of feldspars and quartz to nucleate ice up to around 3 °C warmer than they do in pure water. In contrast, dilute solutions of certain alkali metal halides can dramatically depress freezing points for the same nucleators. At 0.015 M, solutes can enhance or deactivate the ice-nucleating ability of a microcline feldspar across a range of more than 10 °C, which corresponds to a change in active site density of more than a factor of 10 5 . This concentration was chosen for a survey across multiple solutes-nucleant combinations since it had a minimal colligative impact on freezing and is relevant for activating cloud droplets. Other nucleators, for instance a silica gel, are unaffected by these 'solute effects', to within experimental uncertainty. This split in response to the presence of solutes indicates that different mechanisms of ice nucleation occur on the different nucleators or that surface modification of relevance to ice nucleation proceeds in different ways for different nucleators. These solute effects on immersion mode ice nucleation may be of importance in the atmosphere as sea salt and ammonium sulphate are common cloud condensation nuclei (CCN) for cloud droplets and are internally mixed with ice-nucleating particles in mixed-phase clouds. In addition, we propose a pathway dependence where activation of CCN at low temperatures might lead to enhanced ice formation relative to pathways where CCN activation occurs at higher temperatures prior to cooling to nucleation temperature.

What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents.

PubMed

Mazzini, Virginia; Craig, Vincent S J

2017-10-01

The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity.

Trapping proton transfer intermediates in the disordered hydrogen-bonded network of cryogenic hydrofluoric acid solutions.

PubMed

Ayotte, Patrick; Plessis, Sylvain; Marchand, Patrick

2008-08-28

A molecular-level description of the structural and dynamical aspects that are responsible for the weak acid behaviour of dilute hydrofluoric acid solutions and their unusual increased acidity at near equimolar concentrations continues to elude us. We address this problem by reporting reflection-absorption infrared spectra (RAIRS) of cryogenic HF-H(2)O binary mixtures at various compositions prepared as nanoscopic films using molecular beam techniques. Optical constants for these cryogenic solutions [n(omega) and k(omega)] are obtained by iteratively solving Fresnel equations for stratified media. Modeling of the experimental RAIRS spectra allow for a quantitative interpretation of the complex interplay between multiple reflections, optical interference and absorption effects. The evolution of the strong absorption features in the intermediate 1000-3000 cm(-1) range with increasing HF concentration reveals the presence of various ionic dissociation intermediates that are trapped in the disordered H-bonded network of cryogenic hydrofluoric acid solutions. Our findings are discussed in light of the conventional interpretation of why hydrofluoric acid is a weak acid revealing molecular-level details of the mechanism for HF ionization that may be relevant to analogous elementary processes involved in the ionization of weak acids in aqueous solutions.

Fabrication of environmentally biodegradable lignin nanoparticles.

PubMed

Frangville, Camille; Rutkevičius, Marius; Richter, Alexander P; Velev, Orlin D; Stoyanov, Simeon D; Paunov, Vesselin N

2012-12-21

We developed a method for the fabrication of novel biodegradable nanoparticles (NPs) from lignin which are apparently non-toxic for microalgae and yeast. We compare two alternative methods for the synthesis of lignin NPs which result in particles of very different stability upon change of pH. The first method is based on precipitation of low-sulfonated lignin from an ethylene glycol solution by using diluted acidic aqueous solutions, which yields lignin NPs that are stable over a wide range of pH. The second approach is based on the acidic precipitation of lignin from a high-pH aqueous solution which produces NPs stable only at low pH. Our study reveals that lignin NPs from the ethylene glycol-based precipitation contain densely packed lignin domains which explain the stability of the NPs even at high pH. We characterised the properties of the produced lignin NPs and determined their loading capacities with hydrophilic actives. The results suggest that these NPs are highly porous and consist of smaller lignin domains. Tests with microalgae like Chlamydomonas reinhardtii and yeast incubated in lignin NP dispersions indicated that these NPs lack measurable effect on the viability of these microorganisms. Such biodegradable and environmentally compatible NPs can find applications as drug delivery vehicles, stabilisers of cosmetic and pharmaceutical formulations, or in other areas where they may replace more expensive and potentially toxic nanomaterials. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rheological Characteristics of 2D Titanium Carbide (MXene) Dispersions: A Guide for Processing MXenes.

PubMed

Akuzum, Bilen; Maleski, Kathleen; Anasori, Babak; Lelyukh, Pavel; Alvarez, Nicolas Javier; Kumbur, E Caglan; Gogotsi, Yury

2018-03-27

Understanding the rheological properties of two-dimensional (2D) materials in suspension is critical for the development of various solution processing and manufacturing techniques. 2D carbides and nitrides (MXenes) constitute one of the largest families of 2D materials with >20 synthesized compositions and applications already ranging from energy storage to medicine to optoelectronics. However, in spite of a report on clay-like behavior, not much is known about their rheological response. In this study, rheological behavior of single- and multilayer Ti 3 C 2 T x in aqueous dispersions was investigated. Viscous and viscoelastic properties of MXene dispersions were studied over a variety of concentrations from colloidal dispersions to high loading slurries, showing that a multilayer MXene suspension with up to 70 wt % can exhibit flowability. Processing guidelines for the fabrication of MXene films, coatings, and fibers have been established based on the rheological properties. Surprisingly, high viscosity was observed at very low concentrations for solutions of single-layer MXene flakes. Single-layer colloidal solutions were found to exhibit partial elasticity even at the lowest tested concentrations (<0.20 mg/mL) due to the presence of strong surface charge and excellent hydrophilicity of MXene, making them amenable to fabrication at dilute concentrations. Overall, the findings of this study provide fundamental insights into the rheological response of this quickly growing 2D family of materials in aqueous environments as well as offer guidelines for processing of MXenes.

Interfacial ion solvation: Obtaining the thermodynamic limit from molecular simulations

NASA Astrophysics Data System (ADS)

Cox, Stephen J.; Geissler, Phillip L.

2018-06-01

Inferring properties of macroscopic solutions from molecular simulations is complicated by the limited size of systems that can be feasibly examined with a computer. When long-ranged electrostatic interactions are involved, the resulting finite size effects can be substantial and may attenuate very slowly with increasing system size, as shown by previous work on dilute ions in bulk aqueous solution. Here we examine corrections for such effects, with an emphasis on solvation near interfaces. Our central assumption follows the perspective of Hünenberger and McCammon [J. Chem. Phys. 110, 1856 (1999)]: Long-wavelength solvent response underlying finite size effects should be well described by reduced models like dielectric continuum theory, whose size dependence can be calculated straightforwardly. Applied to an ion in a periodic slab of liquid coexisting with vapor, this approach yields a finite size correction for solvation free energies that differs in important ways from results previously derived for bulk solution. For a model polar solvent, we show that this new correction quantitatively accounts for the variation of solvation free energy with volume and aspect ratio of the simulation cell. Correcting periodic slab results for an aqueous system requires an additional accounting for the solvent's intrinsic charge asymmetry, which shifts electric potentials in a size-dependent manner. The accuracy of these finite size corrections establishes a simple method for a posteriori extrapolation to the thermodynamic limit and also underscores the realism of dielectric continuum theory down to the nanometer scale.

Removal of Pb(II) from aqueous solutions using waste textiles/poly(acrylic acid) composite synthesized by radical polymerization technique.

PubMed

Zhou, Tao; Xia, Fafa; Deng, Yue; Zhao, Youcai

2018-05-01

Waste textiles (WTs) are the inevitable outcome of human activity and should be separated and recycled in view of sustainable development. In this work, WT was modified through grafting with acrylic acid (AA) via radical polymerization process using ceric ammonium nitrate (CAN) as an initiator and microwave and/or UV irradiation as energy supply. The acrylic acid-grafted waste textiles (WT-g-AA) thus obtained was then used as an adsorbent to remove Pb(II) from Pb(II)-containing wastewater. The effects of pH, initial concentrations of Pb(II) and adsorbent dose were investigated, and around 95% Pb(II) can be removed from the aqueous solution containing 10mg/L at pH6.0-8.0. The experimental adsorption isotherm data was fitted to the Langmuir model with maximum adsorption capacity of 35.7mg Pb/g WT-g-AA. The Pb-absorbed WT-g-AA was stripped using dilute nitric acid solution and the adsorption capacity of Pb-free material decreased from 95.4% (cycle 1) to 91.1% (cycle 3). It was considered that the WT-g-AA adsorption for Pb(II) may be realized through the ion-exchange mechanism between COOH and Pb(II). The promising results manifested that WT-g-AA powder was an efficient, eco-friendly and reusable adsorbent for the removal of Pb(II) from wastewater. Copyright © 2017. Published by Elsevier B.V.

Liquid-liquid microextraction in a multicommuted flow system for direct spectrophotometric determination of iodine value in biodiesel.

PubMed

Pereira, Andréia C; Rocha, Fábio R P

2014-06-04

A flow-based procedure was developed for the direct spectrophotometric determination of the iodine value (IV) in biodiesel. The procedure was based on the microextraction/reaction of unsaturated compounds with triiodide ions in an aqueous medium by inserting the reagent solution between the aliquots of biodiesel without any pretreatment. The interaction occurred through the biodiesel film formed on the inner walls of the hydrophobic tube used as the reactor and at the aqueous/biodiesel interfaces. The spectrophotometric detection was based on the discoloration of the I3(-) reagent in the aqueous phase by using a glass tube coupled to a fiber-optic spectrophotometer as the detection cell. Reference solutions were prepared by dilution of biodiesel samples with previously determined IV in hexane. The analytical response was linear for IV from 13 to 135 g I2/100 g with a detection limit of 5 g I2/100 g. A coefficient of variation of 1.7% (n=10) and a sampling rate of 108 determinations per hour were achieved by consuming 224 μL of the sample and 200 μg of I2 per determination. The slopes of analytical curves obtained with three different biodiesel samples were in agreement (variations in slopes lower than 3.1%), thus indicating an absence of any matrix effects. Results for biodiesel samples from different sources agreed with the volumetric official procedure at the 95% confidence level. The proposed procedure is therefore a simple, fast, and reliable alternative for estimating the iodine value of biodiesel. Copyright © 2014. Published by Elsevier B.V.

Self-assembled nanogels of cholesteryl-modified polysaccharides: effect of the polysaccharide structure on their association characteristics in the dilute and semidilute regimes.

PubMed

Akiyama, Eri; Morimoto, Nobuyuki; Kujawa, Piotr; Ozawa, Yayoi; Winnik, Françoise M; Akiyoshi, Kazunari

2007-08-01

The assembly of cholesteryl derivatives of the highly branched polysaccharide mannan Mw = (5.2 x 104 g/mol) in dilute aqueous solution was investigated by 1H nuclear magnetic resonance (NMR) spectroscopy, size-exclusion chromatography coupled with multiangle laser scattering (SEC-MALLS), dynamic light scattering (DLS), atomic force microscopy (AFM), fluorescence quenching, and fluorescence depolarization measurements. In the dilute regime, cholesteryl-bearing mannans (CHM) containing approximately 1 cholesteryl group per 100 mannopyranose units formed nanogels with a hydrodynamic radius (RH) of approximately 20 nm containing approximately 8 macromolecules held together via hydrophobic nanodomains consisting of approximately 9 cholesteryl groups. Their density Phih ( approximately 0.02) was significantly lower than the density ( approximately 0.16) of nanogels formed by a cholesteryl derivative of the linear polysaccharide pullulan (CHP) of identical molar mass and level of cholesteryl substitution. In the semidilute regime, CHM nanogels formed a macrogel network for concentrations higher than 12.5% w/w, whereas CHP nanogels underwent macrogelation only above a threshold concentration of 8.0% w/w, as revealed by oscillatory and steady-shear viscosity measurements. The differences in the solution properties of CHM and CHP reflect differences in their assembly on the molecular level, in particular, the size and number of hydrophobic nanodomains and the hydration level. They are attributed to differences in the mobility of the cholesteryl groups which, itself, can be traced to the fact that in CHM the cholesteryl groups are predominantly linked to short oligomannopyranose branches, whereas in CHP they are linked to the polymer main chain. Our study provides a novel means to nanoengineer polysaccharide nanogels which may find unique biotechnological applications.

Development and application of molecularly imprinted polymer - Mn-doped ZnS quantum dot fluorescent optosensing for cocaine screening in oral fluid and serum.

PubMed

Chantada-Vázquez, María Pilar; de-Becerra-Sánchez, Carolina; Fernández-Del-Río, Alba; Sánchez-González, Juan; Bermejo, Ana María; Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio

2018-05-01

A molecularly imprinted polymer - Mn-doped ZnS quantum dot-based fluorescence probe for cocaine abuse screening has been prepared and applied to complex samples such as serum and oral fluid. The fluorescent sensing material was prepared by anchoring a selective MIP for COC on the surface of polyethylene glycol (PEG) modified Mn-doped ZnS quantum dots (QDs). Simple and low cost methods have thus been optimized for assessing cocaine abuse in serum and oral fluid by monitoring fluorescence quenching when cocaine (COC) is present (optimized operating conditions with 1.5mL of 200mgL -1 MIP-coated QDs solution, pH 5.5, and 15min before fluorescence scanning). The matrix effect was found to be important when analyzing oral fluid and serum, and several strategies based on centrifugation for oral fluid and solid phase extraction (SPE) for serum were explored. Two analytical methods were developed for oral fluid. The first one (direct method) requires a centrifugation step (6°C, 4000rpm, 20min) to avoid the matrix effect, and allows for cocaine determination by using an aqueous calibration (1:20 dilution). The second method was developed for oral fluid sampled by Salivette devices, and also requires a further centrifugation (6°C, 4000rpm, 20min) of the recovered oral fluid. This method, however, requires the standard addition technique (1:20 dilution) because of the existence of the matrix effect. Regarding serum samples, a direct method (serum dilution) was not possible, and an SPE procedure was needed to avoid the matrix effect (use of aqueous calibration). The limits of detection and quantification when using the Salivette method were 0.035mgL -1 and 0.117mgL -1, respectively; whereas, 0.015mgL -1 (LOD) and 0.050mgL -1 (LOQ) were obtained for serum. Copyright © 2018 Elsevier B.V. All rights reserved.

A theoretical framework for modeling dilution enhancement of non-reactive solutes in heterogeneous porous media.

PubMed

de Barros, F P J; Fiori, A; Boso, F; Bellin, A

2015-01-01

Spatial heterogeneity of the hydraulic properties of geological porous formations leads to erratically shaped solute clouds, thus increasing the edge area of the solute body and augmenting the dilution rate. In this study, we provide a theoretical framework to quantify dilution of a non-reactive solute within a steady state flow as affected by the spatial variability of the hydraulic conductivity. Embracing the Lagrangian concentration framework, we obtain explicit semi-analytical expressions for the dilution index as a function of the structural parameters of the random hydraulic conductivity field, under the assumptions of uniform-in-the-average flow, small injection source and weak-to-mild heterogeneity. Results show how the dilution enhancement of the solute cloud is strongly dependent on both the statistical anisotropy ratio and the heterogeneity level of the porous medium. The explicit semi-analytical solution also captures the temporal evolution of the dilution rate; for the early- and late-time limits, the proposed solution recovers previous results from the literature, while at intermediate times it reflects the increasing interplay between large-scale advection and local-scale dispersion. The performance of the theoretical framework is verified with high resolution numerical results and successfully tested against the Cape Cod field data. Copyright © 2015 Elsevier B.V. All rights reserved.

Method for processing aqueous wastes

DOEpatents

Pickett, J.B.; Martin, H.L.; Langton, C.A.; Harley, W.W.

1993-12-28

A method is presented for treating waste water such as that from an industrial processing facility comprising the separation of the waste water into a dilute waste stream and a concentrated waste stream. The concentrated waste stream is treated chemically to enhance precipitation and then allowed to separate into a sludge and a supernate. The supernate is skimmed or filtered from the sludge and blended with the dilute waste stream to form a second dilute waste stream. The sludge remaining is mixed with cementitious material, rinsed to dissolve soluble components, then pressed to remove excess water and dissolved solids before being allowed to cure. The dilute waste stream is also chemically treated to decompose carbonate complexes and metal ions and then mixed with cationic polymer to cause the precipitated solids to flocculate. Filtration of the flocculant removes sufficient solids to allow the waste water to be discharged to the surface of a stream. The filtered material is added to the sludge of the concentrated waste stream. The method is also applicable to the treatment and removal of soluble uranium from aqueous streams, such that the treated stream may be used as a potable water supply. 4 figures.

Solution rheology of polyelectrolytes and polyelectrolyte-surfactant systems

NASA Astrophysics Data System (ADS)

Plucktaveesak, Nopparat

The fundamental understanding of polyelectrolytes in aqueous solutions is an important branch of polymer research. In this work, the rheological properties of polyelectrolytes and polyelectrolyte/surfactant systems are studied. Various synthetic poly electrolytes are chosen with varied hydrophobicity. We discuss the effects of adding various surfactants to aqueous solutions of poly(ethylene oxide)-b-poly(propylene oxide)- b-polyethylene oxide)-g-poly(acrylic acid) (PEO-PPO-PAA) in the first chapter. Thermogelation in aqueous solutions of PEO-PPO-PAA is due to micellization caused by aggregation of poly(propylene oxide) (PPO) blocks resulting from temperature-induced dehydration of PPO. When nonionic surfactants with hydrophilic-lipophilic balance (HLB) parameter exceeding 11 or Cn alkylsulfates; n-octyl (C8), n-decyl (C 10) and n-dodecyl (C12) sulfates are added, the gelation threshold temperature (Tgel) of 1.0wt% PEO-PPO-PAA in aqueous solutions increases. In contrast, when nonionic surfactants with HLB below 11 are added, the gelation temperature decreases. On the other hand, alkylsulfates with n = 16 or 18 and poly(ethylene oxide) (PEO) do not affect the Tgel. The results imply that both hydrophobicity and tail length of the added surfactant play important roles in the interaction of PEO-PPO-PAA micelles and the surfactant. In the second chapter, the solution behavior of alternating copolymers of maleic acid and hydrophobic monomer is studied. The alternating structure of monomers with two-carboxylic groups and hydrophobic monomers make these copolymers unique. Under appropriate conditions, these carboxylic groups dissociate leaving charges on the chain. The potentiometric titrations of copolymer solutions with added CaCl2 reveal two distinct dissociation processes corresponding to the dissociation of the two adjacent carboxylic acids. The viscosity data as a function of polymer concentration of poly(isobutylene-alt-sodium maleate), poly(styrene-alt-sodium maleate) and poly(diisobutylene- alt-sodium maleate) show the polyelectrolyte behavior as predicted. However, the viscosity as a function of concentration of sodium maleate based copolymers with 1-alkenes; 1-octene (C8), 1-decene (C10), 1-dodecene (C12) and 1-hexene (C14) exhibit an abnormal scaling power, which might be caused by aggregation of the alkene tails to form micelles. In the last chapter, we report the rheological properties of aqueous solutions of poly(acrylic acid) and oppositely charged surfactant, dodecyl trimethylammonium bromide (C12TAB). The solution viscosity decreases as surfactant is added, partly because the polyelectrolyte wraps around the surface of the spherical surfactant micelles, shortening the effective chain length. The effects of polymer molecular weight, polymer concentration, and polymer charge have been studied with no added salt. The results are compared with the predictions of a simple model based on the scaling theory for the viscosity of dilute and unentangled semidilute polyelectrolyte solutions in good solvent. This model takes into account two effects of added surfactant. The effective chain length of the polyelectrolyte is shortened when a significant fraction of the chain wraps around micelles. Another effect is the change of solution ionic strength resulting from surfactant addition that further lowers the viscosity. The parameters used in this model are independently determined, allowing the model to make a quantitative prediction of solution viscosity with no adjustable parameters. The model is also applied to predict the decrease in viscosity of various polyelectrolyte/oppositely charged surfactant systems reported in literature. The results are in good agreement with experimental data, proving that our model applies to all polyelectrolytes mixed with oppositely charged surfactants that form spherical micelles.

The enhancement and suppression of immersion mode heterogeneous ice-nucleation by solutes

PubMed Central

Holden, Mark A.; Wilson, Theodore W.; O'Sullivan, Daniel; Murray, Benjamin J.

2018-01-01

Heterogeneous nucleation of ice from aqueous solutions is an important yet poorly understood process in multiple fields, not least the atmospheric sciences where it impacts the formation and properties of clouds. In the atmosphere ice-nucleating particles are usually, if not always, mixed with soluble material. However, the impact of this soluble material on ice nucleation is poorly understood. In the atmospheric community the current paradigm for freezing under mixed phase cloud conditions is that dilute solutions will not influence heterogeneous freezing. By testing combinations of nucleators and solute molecules we have demonstrated that 0.015 M solutions (predicted melting point depression <0.1 °C) of several ammonium salts can cause suspended particles of feldspars and quartz to nucleate ice up to around 3 °C warmer than they do in pure water. In contrast, dilute solutions of certain alkali metal halides can dramatically depress freezing points for the same nucleators. At 0.015 M, solutes can enhance or deactivate the ice-nucleating ability of a microcline feldspar across a range of more than 10 °C, which corresponds to a change in active site density of more than a factor of 105. This concentration was chosen for a survey across multiple solutes–nucleant combinations since it had a minimal colligative impact on freezing and is relevant for activating cloud droplets. Other nucleators, for instance a silica gel, are unaffected by these ‘solute effects’, to within experimental uncertainty. This split in response to the presence of solutes indicates that different mechanisms of ice nucleation occur on the different nucleators or that surface modification of relevance to ice nucleation proceeds in different ways for different nucleators. These solute effects on immersion mode ice nucleation may be of importance in the atmosphere as sea salt and ammonium sulphate are common cloud condensation nuclei (CCN) for cloud droplets and are internally mixed with ice-nucleating particles in mixed-phase clouds. In addition, we propose a pathway dependence where activation of CCN at low temperatures might lead to enhanced ice formation relative to pathways where CCN activation occurs at higher temperatures prior to cooling to nucleation temperature. PMID:29780544

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

PubMed

Stevens, Amy L; Joshi, Neeraj K; Paige, Matthew F; Steer, Ronald P

2017-12-14

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S 2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S 1 state is the only significant product of the radiationless decay of the S 2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S 1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

PROCESS OF REMOVING PLUTONIUM VALUES FROM SOLUTION WITH GROUP IVB METAL PHOSPHO-SILICATE COMPOSITIONS

DOEpatents

Russell, E.R.; Adamson, A.W.; Schubert, J.; Boyd, G.E.

1957-10-29

A process for separating plutonium values from aqueous solutions which contain the plutonium in minute concentrations is described. These values can be removed from an aqueous solution by taking an aqueous solution containing a salt of zirconium, titanium, hafnium or thorium, adding an aqueous solution of silicate and phosphoric acid anions to the metal salt solution, and separating, washing and drying the precipitate which forms when the two solutions are mixed. The aqueous plutonium containing solution is then acidified and passed over the above described precipi-tate causing the plutonium values to be adsorbed by the precipitate.

Phospholipids-embedded fully dilutable liquid nanostructures. Part 2: The role of sodium diclofenac.

PubMed

Amsalem, Orit; Aserin, Abraham; Garti, Nissim

2010-12-01

Complex pseudo-ternary phase diagrams based on sucrose monolaurate (SE), propylene glycol (PG), and phosphatidylcholine (PC) as the "surfactant phase"; triacetin (TA) and decaglycerol ester (10G1CC) as the "oil phase"; and water as the aqueous phase were constructed, into which we solubilized the water-insoluble drug (sodium diclofenac, Na-DFC). In our previous study we demonstrated that the solubilization of Na-DFC in the oil+surfactant phases (prior to diluting it with water), was 90-fold greater than its dissolution in water, and that the system was pH-dependent. The greatest Na-DFC solubilization capacity was obtained at pH 7.2. In this study we examined the effect of the solubilization of Na-DFC in a phosphatidylcholine system using DLS, viscosity, electrical conductivity, SAXS, SD-NMR, and cryo-TEM measurements. It was found that: (1) the system remains micellar after aqueous dilution but with greater polydispersity and greater variety of shapes. We concluded that the structures in the absence of water (but in the presence of PG) were of direct spherical micelles (∼4 nm) mixed with elongated cylindrical micelles (12-140 nm); (2) the aqueous dilution causes fragmentation of the cylinders into smaller spherical micelles; (3) solubilization of Na-DFC behaving like a kosmotropic agent or "structure maker" yields mostly spherical swollen micelles and more ordered systems than in its absence; and (4) Na-DFC is solubilized at the interface of the micelles without swelling the droplets. Copyright © 2010 Elsevier B.V. All rights reserved.

An Alternative Approach for Preparing and Standardizing Some Common Aqueous Reagents Used in an Undergraduate Laboratory

ERIC Educational Resources Information Center

Melaku, Samuel; Dabke, Rajeev B.

2014-01-01

A guide for instructors and laboratory assistants to prepare some common aqueous reagents used in an undergraduate laboratory is presented. Dilute reagents consisting of H[superscript +](aq), I[subscript 3][superscript-](aq), Ce[superscript 4+](aq), and Ag[superscript+](aq) were prepared by electrolytic oxidation of respective precursors.…

Evaluation of Cytotoxic and Anti-Inflammatory Activities of Extracts and Lectins from Moringa oleifera Seeds

PubMed Central

Araújo, Larissa Cardoso Corrêa; Aguiar, Jaciana Santos; Napoleão, Thiago Henrique; Mota, Fernanda Virgínia Barreto; Barros, André Luiz Souza; Moura, Maiara Celine; Coriolano, Marília Cavalcanti; Coelho, Luana Cassandra Breitenbach Barroso; Silva, Teresinha Gonçalves; Paiva, Patrícia Maria Guedes

2013-01-01

Background The extract from Moringa oleifera seeds is used worldwide, especially in rural areas of developing countries, to treat drinking water. M. oleifera seeds contain the lectins cmol and WSMoL, which are carbohydrate-binding proteins that are able to reduce water turbidity because of their coagulant activity. Studies investigating the ability of natural products to damage normal cells are essential for the safe use of these substances. This study evaluated the cytotoxic and anti-inflammatory properties of the aqueous seed extract, the extract used by population to treat water (named diluted seed extract in this work), and the isolated lectins cmol and WSMoL. Methodology/Principal Findings The data showed that the aqueous seed extract and cmol were potentially cytotoxic to human peripheral blood mononuclear cells, while WSMoL and diluted seed extract were not cytotoxic. The M. oleifera aqueous seed extract and the lectins cmol and WSMoL were weakly/moderately cytotoxic to the NCI-H292, HT-29 and HEp-2 cancer cell lines and were not hemolytic to murine erythrocytes. Evaluation of acute toxicity in mice revealed that the aqueous seed extract (2.000 mg/kg) did not cause systemic toxicity. The aqueous seed extract, cmol and WSMoL (6.25 µg/mL) and diluted seed extract at 50 µg/mL exhibited anti-inflammatory activity on lipopolyssaccharide-stimulated murine macrophages by regulating the production of nitric oxide, TNF-α and IL-1β. The aqueous seed extract reduced leukocyte migration in a mouse model of carrageenan-induced pleurisy; the myeloperoxidase activity and nitric oxide, TNF-α and IL-1β levels were similarly reduced. Histological analysis of the lungs showed that the extract reduced the number of leukocytes. Conclusion/Significance This study shows that the extract prepared according to folk use and WSMoL may be non-toxic to mammalian cells; however, the aqueous seed extract and cmol may be cytotoxic to immune cells which may explain the immunosuppressive potential of the extract. PMID:24349164

Evaluation of Hyaluronic Acid Dilutions at Different Concentrations Using a Quartz Crystal Resonator (QCR) for the Potential Diagnosis of Arthritic Diseases

PubMed Central

Ahumada, Luis Armando Carvajal; González, Marco Xavier Rivera; Sandoval, Oscar Leonardo Herrera; Olmedo, José Javier Serrano

2016-01-01

The main objective of this article is to demonstrate through experimental means the capacity of the quartz crystal resonator (QCR) to characterize biological samples of aqueous dilutions of hyaluronic acid according to their viscosity and how this capacity may be useful in the potential diagnosis of arthritic diseases. The synovial fluid is viscous due to the presence of hyaluronic acid, synthesized by synovial lining cells (type B), and secreted into the synovial fluid thus making the fluid viscous. In consequence, aqueous dilutions of hyaluronic acid may be used as samples to emulate the synovial fluid. Due to the viscoelastic and pseudo-plastic behavior of hyaluronic acid, it is necessary to use the Rouse model in order to obtain viscosity values comparable with viscometer measures. A Fungilab viscometer (rheometer) was used to obtain reference measures of the viscosity in each sample in order to compare them with the QCR prototype measures. PMID:27879675

Method for in situ or ex situ bioremediation of hexavalent chromium contaminated soils and/or groundwater

DOEpatents

Turick, C.E.; Apel, W.W.

1997-10-28

A method of reducing the concentration of Cr(VI) in a liquid aqueous residue comprises the steps of providing anaerobic Cr(VI) reducing bacteria, mixing the liquid aqueous residue with a nutrient medium to form a mixture, and contacting the mixture with the anaerobic Cr(VI) reducing bacteria such that Cr(VI) is reduced to Cr(III). The anaerobic Cr(VI) reducing bacteria appear to be ubiquitous in soil and can be selected by collecting a soil sample, diluting the soil sample with a sterile diluent to form a diluted sample, mixing the diluted sample with an effective amount of a nutrient medium and an effective amount of Cr(VI) to form a mixture, and incubating the mixture in the substantial absence of oxygen such that growth of Cr(VI) sensitive microorganisms is inhibited and growth of the anaerobic Cr(VI) reducing bacteria is stimulated. A method of in situ bioremediation of Cr(VI) contaminated soil and/or groundwater is also disclosed. 10 figs.

Method for in situ or ex situ bioremediation of hexavalent chromium contaminated soils and/or groundwater

DOEpatents

Turick, Charles E.; Apel, William W.

1997-10-28

A method of reducing the concentration of Cr(VI) in a liquid aqueous residue comprises the steps of providing anaerobic Cr(VI) reducing bacteria, mixing the liquid aqueous residue with a nutrient medium to form a mixture, and contacting the mixture with the anaerobic Cr(VI) reducing bacteria such that Cr(VI) is reduced to Cr(III). The anaerobic Cr(VI) reducing bacteria appear to be ubiquitous in soil and can be selected by collecting a soil sample, diluting the soil sample with a sterile diluent to form a diluted sample, mixing the diluted sample with an effective amount of a nutrient medium and an effective amount of Cr(VI) to form a mixture, and incubating the mixture in the substantial absence of oxygen such that growth of Cr(VI) sensitive microorganisms is inhibited and growth of the anaerobic Cr(VI) reducing bacteria is stimulated. A method of in situ bioremediation of Cr(VI) contaminated soil and/or groundwater is also disclosed.

Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

USGS Publications Warehouse

Marion, G.M.; Catling, D.C.; Kargel, J.S.

2003-01-01

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 ??C to 25 ??C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars. Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl2??4H2O, FeCl2??6H2O, FeSO4??H2O, FeSO4??7H2O, FeCO3, and Fe(OH)3] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO4, Fe-HCO3, H-Fe-Cl, and H-Fe-SO4. We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO3), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification. What began as a dilute Mg-Fe-HCO3 dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO4-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O2(g)], but later caused oxidation of iron [high O2(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses. ?? 2003 Elsevier Ltd.

The Chemical Behavior of Fluids Released during Deep Subduction Based on Fluid Inclusions

NASA Astrophysics Data System (ADS)

Frezzotti, M. L.; Ferrando, S.

2014-12-01

We present a review of current research on fluid inclusions in (HP-) UHP metamorphic rocks that, combined with existing experimental research and thermodynamic models, allow us to investigate the chemical and physical properties of fluids released during deep subduction, their solvent and element transport capacity, and the subsequent implications for the element recycling in the mantle wedge. An impressive number of fluid inclusion studies indicate three main populations of fluid inclusions in HP and UHP metamorphic rocks: i) aqueous and/or non-polar gaseous fluid inclusions (FI), ii) multiphase solid inclusions (MSI), and iii) melt inclusions (MI). Chemical data from preserved fluid inclusions in rocks match with and implement "model" fluids by experiments and thermodynamics, revealing a continuity behind the extreme variations of physico-chemical properties of subduction-zone fluids. From fore-arc to sub-arc depths, fluids released by progressive devolatilization reactions from slab lithologies change from relatively diluted chloride-bearing aqueous solutions (± N2), mainly influenced by halide ligands, to (alkali) aluminosilicate-rich aqueous fluids, in which polymerization probably governs the solubility and transport of major (e.g., Si and Al) and trace elements (including C). Fluid inclusion data implement the petrological models explaining deep volatile liberation in subduction zones, and their flux into the mantle wedge.

Physicochemical factors affecting ethanol adsorption by activated carbon.

PubMed

Bradley, K J; Hamdy, M K; Toledo, R T

1987-03-01

Powder and granular activated charcoal were evaluated for ethanol adsorptivity from aqueous mixtures using an adsorption isotherm. Ethanol adsorption capacity was more pronounced at 25 degrees C as compared to 5, 15, and 40 degrees C. When pH of the ethanol-buffer mixture (0.09 ionic strength) was changed from acidic (2.3) to neutral and then to alkaline (11.2), ethanol adsorption was decreased. Increasing ionic strength of the ethanol-buffer mixtures from 0.05 to 0.09 enhanced ethanol adsorption but a further increase to 0.14 showed no significant effect. Ethanol adsorption was more efficient from an aqueous ethanol mixture as compared to semidefined and nondefined fermentation worts, respectively. Heating granular charcoal to 400 degrees C for 1 h and 600 degrees C for 3 h in N(2) increased ethanol adsorptivity and heating to 1000 degrees C (1 h) in CO(2) decreased it when ethanol was removed from dilute solutions by simple pass adsorption in a carbon packed column. Granular charcoal was superior to powdered charcoal and an inverse relationship was noted between the weight of the granular carbon bed in the column and ethanol adsorbed/g carbon. Decreasing the column feed flow rate from 7.5 to 2.0 L aqueous ethanol/min increased the adsorption rate.

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.

Heparin-binding epidermal growth factor expression in KATO-III cells after Helicobacter pylori stimulation under the influence of strychnos Nux vomica and Calendula officinalis.

PubMed

Hofbauer, Roland; Pasching, Eva; Moser, Doris; Frass, Michael

2010-07-01

Previous studies have shown the stimulating effect of Helicobacter pylori on the gene expression of heparin-binding epidermal growth factor (HB-EGF) using the gastric epithelial cell line KATO-III. Strychnos Nux vomica (Nux vomica) and Calendula officinalis are used in highly diluted form in homeopathic medicine to treat patients suffering from gastritis and gastric ulcers. To investigate the influence of Nux vomica and Calendula officinalis on HB-EGF-like growth factor gene expression in KATO-III cells under the stimulation of H. pylori strain N6 using real-time PCR with and without addition of Nux vomica and Calendula officinalis as a 10c or 12c potency. Baseline expression and stimulation were similar to previous experiments, addition of Nux vomica 10c and Calendula officinalis 10c in a 43% ethanolic solution led to a significant reduction of H. pylori induced increase in gene expression of HB-EGF (reduced to 53.12+/-0.95% and 75.32+/-1.16% vs. control; p<0.05), respectively. Nux vomica 12c reduced HB-EGF gene expression even in dilutions beyond Avogadro's number (55.77+/-1.09%; p<0.05). Nux vomica 12c in a 21.5% ethanol showed a smaller effect (71.80+/-3.91%, p<0.05). This effect was only be observed when the drugs were primarily prepared in ethanol, not in aqueous solutions. The data suggest that both drugs prepared in ethanolic solution are potent inhibitors of H. pylori induced gene expression. 2010 Elsevier Ltd. All rights reserved.

Role of Metal Oxides in Chemical Evolution: Interaction of Ribose Nucleotides with Alumina

NASA Astrophysics Data System (ADS)

Arora, Avnish Kumar; Kamaluddin

2009-03-01

Interaction of ribonucleotides—namely, 5‧-AMP, 5‧-GMP, 5‧-CMP, and 5‧-UMP—with acidic, neutral, and basic alumina has been studied. Purine nucleotides showed higher adsorption on alumina in comparison with pyrimidine nucleotides under acidic conditions. Adsorption data obtained followed Langmuir adsorption isotherm, and Xm and KL values were calculated. On the basis of infrared spectral studies of ribonucleotides, alumina, and ribonucleotide-alumina adducts, we propose that the nitrogen base and phosphate moiety of the ribonucleotides interact with the positive charge surface of alumina. Results of the present study may indicate the importance of alumina in concentrating organic molecules from dilute aqueous solutions in primeval seas in the course of chemical evolution on Earth.

Respirable form of crystals of cromoglycic acid.

PubMed

Chan, H K; Gonda, I

1989-02-01

Respirable crystals of cromoglycic acid (CA) were prepared by precipitation of CA with hydrochloric acid from aqueous solutions of cromolyn sodium and subsequent recrystallization from hot water or mixtures of dimethyl sulphoxide and water. The properties of the materials were established by melting point measurements, UV, IR, and NMR spectroscopy, and X-ray diffraction. Aerosols of CA were generated by nebulization of dilute CA suspensions and drying. The aerodynamic size distribution of CA in the dried aerosols was found by cascade impaction, and could be characterized by a logarithmic normal function with a mass median aerodynamic diameter (MMAD) of 0.7 micron and geometric standard deviation (sigma g) of 1.9. The likely advantages and problems of CA aerosols in the prevention of asthma are discussed.

Ficts and facts of epinephrine and norepinephrine stability in injectable solutions.

PubMed

Hoellein, Ludwig; Holzgrabe, Ulrike

2012-09-15

Epinephrine (EPI) and norepinephrine (NE) play an important role in emergency medicine and acute treatment of hypotension and shocks in the intensive care unit. Injectable solutions can either be provided as proprietary medicinal products or as individually prepared dilutions. Due to the chemical structure of EPI and NE, the stability of the corresponding solutions is limited. Thus, most manufacturers of EPI and NE injectable solutions use sulfites and nitrogen for stabilization, Nevertheless, storage conditions such as temperature and light have to be considered, but are often neglected in the daily hospital routine. In addition, hospital pharmacies prepare EPI and NE solutions and dilute commercially available solutions for individual therapy, especially on ICUs. Since the influence of dilution and the presence of excipients and other preservatives are not systematically explored, we collected published data and investigations on stability on the potency of EPI and NE injectable solutions in order to deduce storage recommendations for diluted EPI and NE solutions of different concentration. Copyright © 2012 Elsevier B.V. All rights reserved.

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers

PubMed Central

2016-01-01

RAFT solution polymerization of N-(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA63–PNMEPx diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in Mn with increasing PNMEP DP. A gradual increase in Mw/Mn was also observed when targeting higher DPs. However, this problem could be minimized (Mw/Mn < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA63–PNMEPx particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA85–PNMEPx diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses. PMID:27375300

RAFT Aqueous Dispersion Polymerization of N-(2-(Methacryloyloxy)ethyl)pyrrolidone: A Convenient Low Viscosity Route to High Molecular Weight Water-Soluble Copolymers.

PubMed

Cunningham, Victoria J; Derry, Matthew J; Fielding, Lee A; Musa, Osama M; Armes, Steven P

2016-06-28

RAFT solution polymerization of N -(2-(methacryoyloxy)ethyl)pyrrolidone (NMEP) in ethanol at 70 °C was conducted to produce a series of PNMEP homopolymers with mean degrees of polymerization (DP) varying from 31 to 467. Turbidimetry was used to assess their inverse temperature solubility behavior in dilute aqueous solution, with an LCST of approximately 55 °C being observed in the high molecular weight limit. Then a poly(glycerol monomethacylate) (PGMA) macro-CTA with a mean DP of 63 was chain-extended with NMEP using a RAFT aqueous dispersion polymerization formulation at 70 °C. The target PNMEP DP was systematically varied from 100 up to 6000 to generate a series of PGMA 63 -PNMEP x diblock copolymers. High conversions (≥92%) could be achieved when targeting up to x = 5000. GPC analysis confirmed high blocking efficiencies and a linear evolution in M n with increasing PNMEP DP. A gradual increase in M w / M n was also observed when targeting higher DPs. However, this problem could be minimized ( M w / M n < 1.50) by utilizing a higher purity grade of NMEP (98% vs 96%). This suggests that the broader molecular weight distributions observed at higher DPs are simply the result of a dimethacrylate impurity causing light branching, rather than an intrinsic side reaction such as chain transfer to polymer. Kinetic studies confirmed that the RAFT aqueous dispersion polymerization of NMEP was approximately four times faster than the RAFT solution polymerization of NMEP in ethanol when targeting the same DP in each case. This is perhaps surprising because both 1 H NMR and SAXS studies indicate that the core-forming PNMEP chains remain relatively solvated at 70 °C in the latter formulation. Moreover, dissolution of the initial PGMA 63 -PNMEP x particles occurs on cooling from 70 to 20 °C as the PNMEP block passes through its LCST. Hence this RAFT aqueous dispersion polymerization formulation offers an efficient route to a high molecular weight water-soluble polymer in a rather convenient low-viscosity form. Finally, the relatively expensive PGMA macro-CTA was replaced with a poly(methacrylic acid) (PMAA) macro-CTA. High conversions were also achieved for PMAA 85 -PNMEP x diblock copolymers prepared via RAFT aqueous dispersion polymerization for x ≤ 4000. Again, better control was achieved when using the 98% purity NMEP monomer in such syntheses.

Colloidal properties and stability of aqueous suspensions of few-layer graphene: Importance of graphene concentration

PubMed Central

Su, Yu; Yang, Guoqing; Lu, Kun; Petersen, Elijah J.; Mao, Liang

2017-01-01

Understanding the colloidal stability of graphene is essential for predicting its transport and ecological risks in aquatic environments. We investigated the agglomeration of 14C-labeled few-layer graphene (FLG) at concentrations spanning nearly four orders of magnitude (2 μg/L to 10 mg/L) using dynamic light scattering and sedimentation measurements. FLG agglomerates formed rapidly in deionized water at concentrations > 3 mg/L. From 1 mg/L to 3 mg/L, salt-induced agglomeration was decreased with dilution of FLG suspensions; the critical coagulation concentration of the more concentrated suspension (3 mg/L) was significantly lower than the dilute suspension (1 mg/L) in the presence of NaCl (1.6 mmol/L and 10 mmol/L, respectively). In contrast, FLG underwent slow agglomeration and settling at concentrations ≤ 0.1 mg/L in NaCl solutions and ambient waters with low ionic strength (< 10 mmol/L). Although salt-induced agglomeration led to 67 % reduction in number of small FLG (25 nm to 50 nm) according to atomic force microscopy characterization, transition from concentrated to dilute suspension retarded the removal of the small FLG. Additionally, the small FLG exhibited greater bioaccumulation in zebrafish embryo and stronger chorion penetration ability than larger ones. These findings suggest that FLG at more environmentally relevant concentration is relatively stable and may have implications for exposure of small FLG to ecological receptors. PMID:27720543

Preparation of novel alginate based anion exchanger from Ulva japonica and its application for the removal of trace concentrations of fluoride from water.

PubMed

Paudyal, Hari; Pangeni, Bimala; Inoue, Katsutoshi; Kawakita, Hidetaka; Ohto, Keisuke; Ghimire, Kedar Nath; Alam, Shafiq

2013-11-01

A green seaweed, Ulva japonica, was modified by loading multivalent metal ions such as Zr(IV) and La(III) after CaCl2 cross-linking to produce metal loaded cross-linked seaweed (M-CSW) adsorbents, which were characterized by elemental analysis, functional groups identification, and metal content determination. Maximum sorption potential for fluoride was drastically increased after La(III) and Zr(IV) loading, which were evaluated as 0.58 and 0.95 mmol/g, respectively. Loaded fluoride was quantitatively desorbed by using dilute alkaline solution for its regeneration. Mechanism of fluoride adsorption was inferred in terms of ligand exchange reaction between hydroxyl ion on co-ordination sphere of the loaded metal ions of M-CSW and fluoride ion in aqueous solution. Application of M-CSW for the treatment of actual waste plating solution exhibited successful removal of fluoride to clear the effluent and environmental standards in Japan, suggesting high possibility of its application for the treatment of fluoride rich waste water. Copyright © 2013 Elsevier Ltd. All rights reserved.

Optimization of Aqueous Ammonia Soaking of manure fibers by Response Surface Methodology for unlocking the methane potential of swine manure.

PubMed

Lymperatou, Anna; Gavala, Hariklia N; Skiadas, Ioannis V

2017-11-01

Swine manure mono-digestion often results to economically non-feasible processes, due to the high dilution and ammonia concentration together with the low degradation rates it presents. The effects of different parameters of Aqueous Ammonia Soaking (AAS) as a pretreatment for improving the digestion of manure fibers when coupled to an ammonia removal step were investigated in this study. Response Surface Methodology was followed and the influence and interactions of the following AAS parameters were studied: NH 3 concentration, duration and solid-to-liquid ratio. The mild conditions found to be optimal (7%w/w NH 3 , 96h, and 0.16kg/L) in combination to a significant increase of the short term CH 4 yield (244% in 17days), make this pretreatment a promising solution for improving swine manure mono-digestion. Furthermore, compositional analysis of the manure fibers revealed significant solubilization of hemicellulose, while no lignin removal or loss of cellulose occurred under optimal conditions. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Examination of an aloe vera galacturonate polysaccharide capable of in situ gelation for the controlled release of protein therapeutics

NASA Astrophysics Data System (ADS)

McConaughy, Shawn David

A therapeutic delivery platform has been investigated with the ultimate goal of designing a sustained protein release matrix utilizing an in-situ gelling, acidic polysaccharide derived from the Aloe vera plant. The Aloe vera polysaccharide (AvP) has been examined in order to determine how chemical composition, structure, molecular weight and solution behavior affect gelation and protein/peptide delivery. Correlations are drawn between structural characteristics and solution behavior in order to determine the impact of polymer conformation and solvation on gel formation under conditions designed to simulate nasal applications. Steady state and dynamic rheology, classic and dynamic light scattering, zeta potential, pulse field gradient nuclear magnetic resonance and fluorescence spectroscopy have been employed to gain insight into the effects of galacturonic acid content, degree of methylation, entanglement and ionic strength on both solution behavior and the hydrogel state which ultimately governs protein/peptide release. This dissertation is divided into two sections. In the first section, a series of Aloe vera polysaccharides (AvP), from the pectin family have been structurally characterized indicating high galacturonic acid (GalA) content, low degree of methylester substitution (DM), low numbers of rhamnose residues and high molecular weight with respect to pectins extracted from traditional sources. The behavior of AvP was examined utilizing dilute solution, low-shear rheological techniques for specific molecular weight samples at selected conditions of ionic strength. From these dilute aqueous solution studies, the Mark-Houwink-Sakurada (MHS) constants (K and alpha), persistence length (Lp) and inherent chain stiffness (B parameter) were determined, indicating an expanded random coil in aqueous salt solutions. The critical concentration for transition from dilute to concentrated solution, C e, was determined by measuring both the zero shear viscosity and fluorescence emission of the probe molecule 1,8-anilino-1-naphthalene sulphonic acid (1,8-ANS) as a function of polymer concentration. Correlations are drawn between viscosity experiments and measurement of zeta potential. Increased degrees of intermolecular interactions are responsible for a shift of Ce to lower polymer concentrations with increasing ionic strength. Additionally, dynamic rheology data are presented highlighting the ability of AvP to form gels at low polymer and calcium ion concentrations, exemplifying the technological potential of this polysaccharide for in-situ drug delivery. In the second section, properties of Aloe vera galacturonate hydrogels formed via Ca2+ crosslinking have been studied in regard to key parameters influencing gel formation including molecular weight, ionic strength and molar ratio of Ca2+ to COO- functionality. Dynamic oscillatory rheology and pulsed field gradient NMR (PFG-NMR) studies have been conducted on hydrogels formed at specified Ca2+ concentrations in the presence and absence of Na+ and K+ ions, in order to assess the feasibility of in situ gelation for controlled delivery of therapeutics. Aqueous Ca2+ concentrations similar to those present in nasal and subcutaneous fluids induce the formation of elastic Aloe vera polysaccharide (AvP) hydrogel networks. By altering the ratio of Ca2+ to COO- functionality, networks may be tailored to provide elastic modulus (G') values between 20 and 20,000 Pa. The Aloe vera polysaccharide exhibits time dependent phase separation in the presence of monovalent electrolytes. Thus the relative rates of calcium induced gelation and phase separation become major considerations when designing a system for in situ delivery applications where both monovalent (Na+, K+) and divalent (Ca2+) ions are present. PFG-NMR and fluorescence microscopy confirm that distinctly different morphologies are present in gels formed in the presence and absence 0.15 M NaCl. Curve fitting of theoretical models to experimental release profiles of fluorescein labeled dextrans indicate diffusion rates are related to hydrogel morphology. These studies suggest that for efficient in situ release of therapeutic agents, polymer concentrations should be maintained above the critical entanglement concentration (Ce, 0.60 wt%) when [Ca2+]/[COO -] ratios are less than 1. Additionally, the monovalent electrolyte concentration in AvP solutions should not exceed 0.10 M prior to Ca 2+ crosslinking.

Steady-state voltammetry of hydroxide ion oxidation in aqueous solutions containing ammonia.

PubMed

Daniele, Salvatore; Baldo, M Antonietta; Bragato, Carlo; Abdelsalam, Mamdouh Elsayed; Denuault, Guy

2002-07-15

An oxidation process observed in dilute aqueous solutions of ammonia was investigated under steady-state conditions with gold microelectrodes with radii in the range 2.5-30 microm. Over the ammonia concentration range 0.1-10 mM, a well-defined voltammetric wave was observed at approximately 1.4 V versus Ag/AgCl. It was attributed to the oxidation of hydroxide ions that arise from the dissociation of the weak base. The steady-state limiting current was found to depend on the concentration of supporting electrolyte, and in solution with low electrolyte, it was enhanced by migration contribution, as expected for a negatively charged species that oxidizes on a positively charged electrode. In addition, the steady-state limiting current was proportional to both the ammonia concentration and the electrode radius. The overall electrode process was analyzed in terms of a CE mechanism (homogeneous chemical reaction preceding the heterogeneous electron transfer) with a fast chemical reaction when measurements were carried out in solutions containing NH3 at < or = 5 mM and with electrodes having a radius of > or = 5 microm. This was ascertained by comparing experimental and theoretical data obtained by simulation. The formation of the soluble complex species Au(NH3)2+ was also considered as a possible alternative to explain the presence of the oxidation wave. This process however was ruled out, as the experimental data did not fit theoretical predictions in any of the conditions employed in the investigation. Instead, the direct oxidation of NH3, probably to N2O, was invoked to explain the anomalous currents found when the CE process was strongly kinetically hindered. Throughout this study, a parallel was made between the CE mechanism investigated here and that known to occur during the hydrogen evolution reaction from weak acids.

The use of synthesized aqueous solutions for determining strontium sorption isotherms

USGS Publications Warehouse

Liszewski, M.J.; Bunde, R.L.; Hemming, C.; Rosentreter, J.; Welhan, J.

1998-01-01

The use of synthesized aqueous solutions for determining experimentally derived strontium sorption isotherms of sediment was investigated as part of a study accessing strontium chemical transport properties. Batch experimental techniques were used to determine strontium sorption isotherms using synthesized aqueous solutions designed to chemically represent water from a natural aquifer with respect to major ionic character and pH. A strontium sorption isotherm for a sediment derived using a synthesized aqueous solution was found to be most comparable to an isotherm derived using natural water when the synthesized aqueous solution contained similar concentrations of calcium and magnesium. However, it is difficult to match compositions exactly due to the effects of disequilibrium between the solution and the sediment. Strong linear relations between sorbed strontium and solution concentrations of calcium and magnesium confirm that these cations are important co-constituents in these synthesized aqueous solutions. Conversely, weak linear relations between sorbed strontium and solution concentrations of sodium and potassium indicate that these constituents do not affect sorption of strontium. The addition of silica to the synthesized aqueous solution does not appreciably affect the resulting strontium sorption isotherm.

Activity of water in aqueous systems; a frequently neglected property.

PubMed

Blandamer, Mike J; Engberts, Jan B F N; Gleeson, Peter T; Reis, Joao Carlos R

2005-05-01

In this critical review, the significance of the term 'activity' is examined in the context of the properties of aqueous solutions. The dependence of the activity of water(l) at ambient pressure and 298.15 K on solute molality is examined for aqueous solutions containing neutral solutes, mixtures of neutral solutes and salts. Addition of a solute to water(l) always lowers its thermodynamic activity. For some solutes the stabilisation of water(l) is less than and for others more than in the case where the thermodynamic properties of the aqueous solution are ideal. In one approach this pattern is accounted for in terms of hydrate formation. Alternatively the pattern is analysed in terms of the dependence of practical osmotic coefficients on the composition of the aqueous solution and then in terms of solute-solute interactions. For salt solutions the dependence of the activity of water on salt molalities is compared with that predicted by the Debye-Hückel limiting law. The analysis is extended to consideration of the activities of water in binary aqueous mixtures. The dependence on mole fraction composition of the activity of water in binary aqueous mixtures is examined. Different experimental methods for determining the activity of water in aqueous solutions are critically reviewed. The role of water activity is noted in a biochemical context, with reference to the quality, stability and safety of food and finally with regard to health science.

Comparison of the in vitro effects of saline, hypertonic hydroxyethyl starch, hypertonic saline, and two forms of hydroxyethyl starch on whole blood coagulation and platelet function in dogs.

PubMed

Wurlod, Virginie A; Howard, Judith; Francey, Thierry; Schweighauser, Ariane; Adamik, Katja N

2015-01-01

To compare the in vitro effects of hypertonic solutions and colloids to saline on coagulation in dogs. In vitro experimental study. Veterinary teaching hospital. Twenty-one adult dogs. Blood samples were diluted with saline, 7.2% hypertonic saline solution with 6% hydroxyethylstarch with an average molecular weight of 200 kDa and a molar substitution of 0.4 (HH), 7.2% hypertonic saline (HTS), hydroxyethyl starch (HES) 130/0.4 or hydroxyethyl starch 600/0.75 at ratios of 1:22 and 1:9, and with saline and HES at a ratio of 1:3. Whole blood coagulation was analyzed using rotational thromboelastometry (extrinsic thromboelastometry-cloting time (ExTEM-CT), maximal clot firmness (MCF) and clot formation time (CFT) and fibrinogen function TEM-CT (FibTEM-CT) and MCF) and platelet function was analyzed using a platelet function analyzer (closure time, CTPFA ). All parameters measured were impaired by saline dilution. The CTPFA was prolonged by 7.2% hypertonic saline solution with 6% hydroxyethylstarch with an average molecular weight of 200 kDa and a molar substitution of 0.4 (HH) and HTS but not by HES solutions. At clinical dilutions equivalent to those generally administered for shock (saline 1:3, HES 1:9, and hypertonic solutions 1:22), CTPFA was more prolonged by HH and HTS than other solutions but more by saline than HES. No difference was found between the HES solutions or the hypertonic solutions. ExTEM-CFT and MCF were impaired by HH and HTS but only mildly by HES solutions. At clinically relevant dilutions, no difference was found in ExTEM-CFT between HTS and saline or in ExTEM-MCF between HH and saline. No consistent difference was found between the 2 HES solutions but HH impaired ExTEM-CFT and MCF more than HTS. At high dilutions, FibTEM-CT and -MCF and ExTEM-CT were impaired by HES. Hypertonic solutions affect platelet function and whole blood coagulation to a greater extent than saline and HES. At clinically relevant dilutions, only CTPFA was markedly more affected by hypertonic solutions than by saline. At high dilutions, HES significantly affects coagulation but to no greater extent than saline at clinically relevant dilutions. © Veterinary Emergency and Critical Care Society 2015.

PLUTONIUM PURIFICATION PROCESS EMPLOYING THORIUM PYROPHOSPHATE CARRIER

DOEpatents

King, E.L.

1959-04-28

The separation and purification of plutonium from the radioactive elements of lower atomic weight is described. The process of this invention comprises forming a 0.5 to 2 M aqueous acidffc solution containing plutonium fons in the tetravalent state and elements with which it is normally contaminated in neutron irradiated uranium, treating the solution with a double thorium compound and a soluble pyrophosphate compound (Na/sub 4/P/sub 2/O/sub 7/) whereby a carrier precipitate of thorium A method is presented of reducing neptunium and - trite is advantageous since it destroys any hydrazine f so that they can be removed from solutions in which they are contained is described. In the carrier precipitation process for the separation of plutonium from uranium and fission products including zirconium and columbium, the precipitated blsmuth phosphate carries some zirconium, columbium, and uranium impurities. According to the invention such impurities can be complexed and removed by dissolving the contaminated carrier precipitate in 10M nitric acid, followed by addition of fluosilicic acid to about 1M, diluting the solution to about 1M in nitric acid, and then adding phosphoric acid to re-precipitate bismuth phosphate carrying plutonium.

TBARs distillation method: revision to minimize the interference from yellow pigments in meat products.

PubMed

Díaz, P; Linares, M B; Egea, M; Auqui, S M; Garrido, M D

2014-12-01

The aim was to study the effect of the incubation method and TBA reagent (concentration/solvent) on yellow pigment interference in meat products. Distillates from red sausage, sucrose, malondialdehyde and a mixture of sucrose-malondialdehyde were reacted with four different TBA solutions at five different temperature/time relations. Two TBA solutions were prepared at 20mM using 90% glacial acetic acid or 3.86% perchloric acid. In addition, an 80mM TBA solution was prepared using distilled water adjusted to pH4 and another using 0.8% TBA in distilled water. The temperature/time relations were: (1) 35min in a boiling water bath; (2) 70°C/30min; (3) 40°C/90min; (4) room temperature (r.t.) (24°C) in dark conditions for 20h; and (5) 60min in a boiling water bath. The results showed that aqueous or diluted acid solutions of TBA reagent and the application of 100°C for less than 1h provided the best conditions to minimize the presence of yellow pigments and maximize pink pigment formation in meat products. Copyright © 2014 Elsevier Ltd. All rights reserved.

A new solution to emulsion liquid membrane problems by non-Newtonian conversion

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

Skelland, A.H.P.; Meng, X.

1996-02-01

Surfactant-stabilized emulsion liquid membrane processes constitute an emerging separation technology that has repeatedly been shown to be highly suited for such diverse separation processes as metal recovery or removal from dilute aqueous solutions; separations in the food industry; removal of organic bases and acids from water; and separation of hydrocarbons. Emulsion liquid membrane separation processes remain excessively vulnerable to one or more of four major problems. Difficulties lie in developing liquid membranes that combine high levels of both stability and permeability with acceptably low levels of swelling and ease of subsequent demulsification for membrane and solute recovery. This article providesmore » a new technique for simultaneously overcoming the first three problems, while identifying physical indications that the proposed solution may have little adverse effect on the fourth problem (demulsification) and may even alleviate it. Numerous benefits of optimized conversion of the membrane phase into suitable non-Newtonian form are identified, their mechanisms outlined, and experimental verifications provided. These include increased stability, retained (or enhanced) permeability, reduced swelling, increased internal phase volume, and increased stirrer speeds. The highly favorable responsiveness of both aliphatic and aromatic membranes to the new technique is demonstrated.« less

Forced intrusion of water and aqueous solutions in microporous materials: from fundamental thermodynamics to energy storage devices.

PubMed

Fraux, Guillaume; Coudert, François-Xavier; Boutin, Anne; Fuchs, Alain H

2017-12-07

We review the high pressure forced intrusion studies of water in hydrophobic microporous materials such as zeolites and MOFs, a field of research that has emerged some 15 years ago and is now very active. Many of these studies are aimed at investigating the possibility of using these systems as energy storage devices. A series of all-silica zeolites (zeosil) frameworks were found suitable for reversible energy storage because of their stability with respect to hydrolysis after several water intrusion-extrusion cycles. Several microporous hydrophobic zeolite imidazolate frameworks (ZIFs) also happen to be quite stable and resistant towards hydrolysis and thus seem very promising for energy storage applications. Replacing pure water by electrolyte aqueous solutions enables to increase the stored energy by a factor close to 3, on account of the high pressure shift of the intrusion transition. In addition to the fact that aqueous solutions and microporous silica materials are environmental friendly, these systems are thus becoming increasingly interesting for the design of new energy storage devices. This review also addresses the theoretical approaches and molecular simulations performed in order to better understand the experimental behavior of nano-confined water. Molecular simulation studies showed that water condensation takes place through a genuine first-order phase transition, provided that the interconnected pores structure is 3-dimensional and sufficiently open. In an extreme confinement situations such as in ferrierite zeosil, condensation seem to take place through a continuous supercritical crossing from a diluted to a dense fluid, on account of the fact that the first-order transition line is shifted to higher pressure, and the confined water critical point is correlatively shifted to lower temperature. These molecular simulation studies suggest that the most important features of the intrusion/extrusion process can be understood in terms of equilibrium thermodynamics considerations.

Antibacterial Effect of Curcuma longa (Turmeric) Against Staphylococcus aureus and Escherichia coli.

PubMed

Afrose, R; Saha, S K; Banu, L A; Ahmed, A U; Shahidullah, A S; Gani, A; Sultana, S; Kabir, M R; Ali, M Y

2015-07-01

This observational study was conducted during the period from July 2010 to June 2011 in the Department of Pharmacology in the collaboration of Department of Microbiology, Mymensingh Medical College, Mymensingh to determine the profile of antibacterial effect of Crude Turmeric paste aqueous turmeric extract, and standard antibiotic Amikacin against Staphylococcus aureus and Escherichia coli. Three separate experiments were done e.g. (Expt- I) Inhibitory effect of Crude Turmeric paste incorporated into nutrient agar (NA) media, (Expt- II) Minimum inhibitory concentration of (a) Aqueous Turmeric extract and (b) Amikacin by broth dilution technique and (Expt-III) their subculture study in nutrient agar (NA) media for confirmation of respective results of previous experiments. Inhibitory effects were observed against the growth of Staph Aureus and Esch coli at 10% and 30% respectively of Crude Turmeric paste incorporated into NA media. The broth dilution technique was followed to determine the MIC of Aqueous Turmeric extract and Amikacin. The MIC of Aqueous Turmeric extract was 800 μg/ml against Staph aureus and that against Esch coli was 2000 μg/ml and the MIC of Amikacin was 10 μg/ml for both the bacteria. The MIC of Amikacin was the lowest in comparison to MIC of Aqueous Turmeric extract for complete inhibition of growth of Staph aureus and Esch coli. The subculture study showed similar results with that of previous experiments in terms of inhibitory effects of Crude Turmeric paste and MIC of Aqueous Turmeric extract and Amikacin against all of the organisms studied.

Solubility and modeling acid-base properties of adrenaline in NaCl aqueous solutions at different ionic strengths and temperatures.

PubMed

Bretti, Clemente; Cigala, Rosalia Maria; Crea, Francesco; De Stefano, Concetta; Vianelli, Giuseppina

2015-10-12

Solubility and acid-base properties of adrenaline were studied in NaCl aqueous solutions at different ionic strengths (0