Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes.

PubMed

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-15

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

Detection limits for nanoparticles in solution with classical turbidity spectra

NASA Astrophysics Data System (ADS)

Le Blevennec, G.

2013-09-01

Detection of nanoparticles in solution is required to manage safety and environmental problems. Spectral transmission turbidity method has now been known for a long time. It is derived from the Mie Theory and can be applied to any number of spheres, randomly distributed and separated by large distance compared to wavelength. Here, we describe a method for determination of size, distribution and concentration of nanoparticles in solution using UV-Vis transmission measurements. The method combines Mie and Beer Lambert computation integrated in a best fit approximation. In a first step, a validation of the approach is completed on silver nanoparticles solution. Verification of results is realized with Transmission Electronic Microscopy measurements for size distribution and an Inductively Coupled Plasma Mass Spectrometry for concentration. In view of the good agreement obtained, a second step of work focuses on how to manage the concentration to be the most accurate on the size distribution. Those efficient conditions are determined by simple computation. As we are dealing with nanoparticles, one of the key points is to know what the size limits reachable are with that kind of approach based on classical electromagnetism. In taking into account the transmission spectrometer accuracy limit we determine for several types of materials, metals, dielectrics, semiconductors the particle size limit detectable by such a turbidity method. These surprising results are situated at the quantum physics frontier.

A simple high performance liquid chromatography method for analyzing paraquat in soil solution samples.

PubMed

Ouyang, Ying; Mansell, Robert S; Nkedi-Kizza, Peter

2004-01-01

A high performance liquid chromatography (HPLC) method with UV detection was developed to analyze paraquat (1,1'-dimethyl-4,4'-dipyridinium dichloride) herbicide content in soil solution samples. The analytical method was compared with the liquid scintillation counting (LSC) method using 14C-paraquat. Agreement obtained between the two methods was reasonable. However, the detection limit for paraquat analysis was 0.5 mg L(-1) by the HPLC method and 0.05 mg L(-1) by the LSC method. The LSC method was, therefore, 10 times more precise than the HPLC method for solution concentrations less than 1 mg L(-1). In spite of the high detection limit, the UC (nonradioactive) HPLC method provides an inexpensive and environmentally safe means for determining paraquat concentration in soil solution compared with the 14C-LSC method.

Technical note: Simultaneous carotenoid and vitamin analysis of milk from total mixed ration-fed cows optimized for xanthophyll detection.

PubMed

Stout, M A; Benoist, D M; Drake, M A

2018-06-01

Concentrations of retinol, α-tocopherol, and major carotenoids in dairy products are often determined simultaneously by liquid chromatography. These compounds have different polarity and solubility; thus, extracting them simultaneously can be difficult and inefficient. In milks with low carotenoid concentrations, the xanthophylls lutein and zeaxanthin may not be completely resolved using common extraction techniques. A simplified method was developed to optimize extraction efficiency and the limit of detection and limit of quantification (LoQ) of lutein and zeaxanthin in bovine milk without decreasing sensitivity to other vitamins or carotenoids. The developed method evaluates lutein, zeaxanthin, β-carotene, retinol, and α-tocopherol simultaneously by ultra-high performance liquid chromatography-photodiode array detection. Common saponification temperatures (40-60°C) and concentrations of KOH in water (10-50% KOH wt/vol) were evaluated. Multiple solvents were evaluated for optimal xanthophyll extraction (diethyl ether, dichloromethane, hexane, and tetrahydrofuran) following saponification. The limit of detection and LoQ were defined as 3:1 and 10:1 signal-to-noise ratio, respectively. All experiments were performed in triplicate. The optimal saponification procedure was a concentration of 25% KOH at either 40 or 50°C. Saponified extracts solubilized in solutions containing diethyl ether had greater concentrations of lutein- than hexane- or tetrahydrofuran-based solutions, with peak areas above LoQ values. The solution containing diethyl ether solubilized similar concentrations of retinol, α-tocopherol, and β-carotene when compared with other solutions. The proposed optimized method allows for the simultaneous determination of carotenoids from milk with increased lutein and zeaxanthin sensitivity without sacrificing recovery of retinol, α-tocopherol, and β-carotene. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Mechanistic insights from DGT and soil solution measurements on the uptake of Ni and Cd by radish.

PubMed

Luo, Jun; Cheng, Hao; Ren, Jinghua; Davison, William; Zhang, Hao

2014-07-01

This work tests the previously proposed hypothesis that plant uptake of metals is determined dominantly by diffusional controlled or plant limiting uptake mechanisms at, respectively, low and high metal concentrations. Radish (Raphanus sativus) was grown in 13 soils spiked with Ni (10 and 100 mg kg(-1)) and Cd (0.5 and 4 mg kg(-1)) for 4 weeks to investigate the mechanisms affecting plant uptake. Soil solution concentrations, Css, of Ni and Cd were measured, along with the DGT interfacial concentration, CDGT, and the derived effective concentration in soil solution, CE. Free ion activities, aNi(2+) and aCd(2+), were obtained using WHAM 6. Although there was a poor relationship between Ni in radish roots and either Css or aNi(2+) in unamended soils, the distribution of data could be rationalized in terms of the extent of release of Ni from the soil solid phase, as identified by DGT and soil solution measurements. By contrast Ni in radish was linearly related to CE, demonstrating diffusion limited uptake. For soils amended with high concentrations of Ni, linear relationships were obtained for Ni in radish plotted against, Css, aNi(2+), and CE, consistent with the plant controlling uptake. For Ni the hypothesis concerning dominant diffusional and plant limiting uptake mechanisms was demonstrated. Poor relationships between Cd in radish and Css, aCd(2+), and CE, irrespective of amendment by Cd, showed the importance of factors other than diffusional supply, such as rhizosphere and inhibitory processes, and that fulfilment of this hypothesis is plant and metal specific.

Establishing the traceability of a uranyl nitrate solution to a standard reference material

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

Jackson, C.H.; Clark, J.P.

1978-01-01

A uranyl nitrate solution for use as a Working Calibration and Test Material (WCTM) was characterized, using a statistically designed procedure to document traceability to National Bureau of Standards Reference Material (SPM-960). A Reference Calibration and Test Material (PCTM) was prepared from SRM-960 uranium metal to approximate the acid and uranium concentration of the WCTM. This solution was used in the characterization procedure. Details of preparing, handling, and packaging these solutions are covered. Two outside laboratories, each having measurement expertise using a different analytical method, were selected to measure both solutions according to the procedure for characterizing the WCTM. Twomore » different methods were also used for the in-house characterization work. All analytical results were tested for statistical agreement before the WCTM concentration and limit of error values were calculated. A concentration value was determined with a relative limit of error (RLE) of approximately 0.03% which was better than the target RLE of 0.08%. The use of this working material eliminates the expense of using SRMs to fulfill traceability requirements for uranium measurements on this type material. Several years' supply of uranyl nitrate solution with NBS traceability was produced. The cost of this material was less than 10% of an equal quantity of SRM-960 uranium metal.« less

Influence of an americium solid phase on americium concentrations in solutions

NASA Astrophysics Data System (ADS)

Rai, Dhanpat; Strickert, R. G.; Moore, D. A.; Serne, R. J.

1981-11-01

Americium-241 concentrations in solutions contacting contaminated sediments for up to 2 yr were measured as a function of pH. Steady-state concentrations were reached within a few days. The solubility-limited Am concentration was found to decrease approximately 10-fold with one unit increase in pH. The log equilibrium constant for the solubility of Am (soil) solid [Am (soil) + H + ⇌ Am (aq complex)+] was found to be -4.12. The predictions based upon thermodynamic data suggest that Am (aq complex)+ is likely to be Am(OH) 2+. Although the chemical formula of Am (soil) was not determined, it does not appear to be Am(OH) 3(a). Published data on sorption coefficients of Am by different rocks, soils, and minerals were critically evaluated. Final Am solution concentrations calculated from the sorption coefficients of a variety of earth materials with several solutions agreed well with the concentrations predicted from the solubility of Am (soil) solid, indicating that the sorption coefficient data are controlled by Am precipitation.

Long-term stability study of clofarabine injection concentrate and diluted clofarabine infusion solutions.

PubMed

Kaiser, Jeanette; Krämer, Irene

2012-06-01

The aim of this study was to investigate the physicochemical stability of clofarabine (CAFdA) injection concentrate and ready-to-use CAFdA infusion solutions over a prolonged period of 28 days. To determine the stability of CAFdA infusion solutions, the injection concentrate (Evoltra®, 1 mg/mL, Genzyme) was diluted either with 0.9% sodium chloride or 5% glucose infusion solution. The resulting concentrations of 0.2 mg/mL or 0.6 mg/mL, respectively, were chosen to represent the lower and upper limit of the ordinary concentration range. Test solutions were stored under refrigeration (2-8°C) or at room temperature either light protected or exposed to light. CAFdA concentrations and pH values were determined at different time intervals throughout a 28-day storage period. Compatibility of diluted CAFdA infusion solutions (0.1-0.4 mg/mL) with different container materials (polyvinyl chloride (PVC), glass, and polypropylene/polyethylene (PP/PE)) was tested over a 48-h storage period. CAFdA concentrations were measured by a stability-indicating reversed phase high-performance liquid chromatography (HPLC) assay with ultraviolet detection. CAFdA injection concentrate and CAFdA infusion solutions remained physicochemically stable (>90% CAFdA) for 4 weeks. Results are independent of storage conditions, drug concentrations (0.2, 0.6, and 1.0 mg/mL) and diluents (0.9% sodium chloride, 5% glucose infusion solution). Adsorption of CAFdA to container material can be excluded. CAFdA injection concentrate and diluted infusion solutions in commonly used vehicles are stable for at least 28 days either refrigerated or at room temperature. Physicochemical stability favors pharmacy-based centralized preparation. Due to microbiological reasons, strict aseptic handling and storage of the products under refrigeration is recommended.

Humidity-insensitive water evaporation from molecular complex fluids.

PubMed

Salmon, Jean-Baptiste; Doumenc, Frédéric; Guerrier, Béatrice

2017-09-01

We investigated theoretically water evaporation from concentrated supramolecular mixtures, such as solutions of polymers or amphiphilic molecules, using numerical resolutions of a one-dimensional model based on mass transport equations. Solvent evaporation leads to the formation of a concentrated solute layer at the drying interface, which slows down evaporation in a long-time-scale regime. In this regime, often referred to as the falling rate period, evaporation is dominated by diffusive mass transport within the solution, as already known. However, we demonstrate that, in this regime, the rate of evaporation does not also depend on the ambient humidity for many molecular complex fluids. Using analytical solutions in some limiting cases, we first demonstrate that a sharp decrease of the water chemical activity at high solute concentration leads to evaporation rates which depend weakly on the humidity, as the solute concentration at the drying interface slightly depends on the humidity. However, we also show that a strong decrease of the mutual diffusion coefficient of the solution enhances considerably this effect, leading to nearly independent evaporation rates over a wide range of humidity. The decrease of the mutual diffusion coefficient indeed induces strong concentration gradients at the drying interface, which shield the concentration profiles from humidity variations, except in a very thin region close to the drying interface.

Does water chemistry limit the distribution of New Zealand mud snails in Redwood National Park?

USGS Publications Warehouse

Vazquez, Ryan; Ward, Darren M.; Sepulveda, Adam

2016-01-01

New Zealand mud snails (NZMS) are exotic mollusks present in many waterways of the western United States. In 2009, NZMS were detected in Redwood Creek in Redwood National Park, CA. Although NZMS are noted for their ability to rapidly increase in abundance and colonize new areas, after more than 5 years in Redwood Creek, their distribution remains limited to a ca. 300 m reach. Recent literature suggests that low specific conductivity and environmental calcium can limit NZMS distribution. We conducted laboratory experiments, exposing NZMS collected from Redwood Creek to both natural waters and artificial treatment solutions, to determine if low conductivity and calcium concentration limit the distribution of NZMS in Redwood National Park. For natural water exposures, we held NZMS in water from their source location (conductivity 135 μS/cm, calcium 13 mg/L) or water from four other locations in the Redwood Creek watershed encompassing a range of conductivity (77–158 μS/cm) and calcium concentration (<5–13 mg/L). For exposures in treatment solutions, we manipulated both conductivity (range 20–200 μS/cm) and calcium concentration (range <5–17.5 mg/L) in a factorial design. Response variables measured included mortality and reproductive output. Adult NZMS survived for long periods (>4 months) in the lowest conductivity waters from Redwood Creek and all but the lowest-conductivity treatment solutions, regardless of calcium concentration. However, reproductive output was very low in all natural waters and all low-calcium treatment solutions. Our results suggest that water chemistry may inhibit the spread of NZMS in Redwood National Park by reducing their reproductive output.

A simple method for determination of carmine in food samples based on cloud point extraction and spectrophotometric detection.

PubMed

Heydari, Rouhollah; Hosseini, Mohammad; Zarabi, Sanaz

2015-01-01

In this paper, a simple and cost effective method was developed for extraction and pre-concentration of carmine in food samples by using cloud point extraction (CPE) prior to its spectrophotometric determination. Carmine was extracted from aqueous solution using Triton X-100 as extracting solvent. The effects of main parameters such as solution pH, surfactant and salt concentrations, incubation time and temperature were investigated and optimized. Calibration graph was linear in the range of 0.04-5.0 μg mL(-1) of carmine in the initial solution with regression coefficient of 0.9995. The limit of detection (LOD) and limit of quantification were 0.012 and 0.04 μg mL(-1), respectively. Relative standard deviation (RSD) at low concentration level (0.05 μg mL(-1)) of carmine was 4.8% (n=7). Recovery values in different concentration levels were in the range of 93.7-105.8%. The obtained results demonstrate the proposed method can be applied satisfactory to determine the carmine in food samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Ultrasound degradation of xanthan polymer in aqueous solution: Its scission mechanism and the effect of NaCl incorporation.

PubMed

Saleh, H M; Annuar, M S M; Simarani, K

2017-11-01

Degradation of xanthan polymer in aqueous solution by ultrasonic irradiation was investigated. The effects of selected variables i.e. sonication intensity, irradiation time, concentration of xanthan gum and molar concentration of NaCl in solution were studied. Combined approach of full factorial design and conventional one-factor-at-a-time was applied to obtain optimum degradation at sonication power intensity of 11.5Wcm -2 , irradiation time 120min and 0.1gL -1 xanthan in a salt-free solution. Molecular weight reduction of xanthan gum under sonication was described by an exponential decay function with higher rate constant for polymer degradation in the salt free solution. The limiting molecular weight where fragments no longer undergo scission was determined from the function. The incorporation of NaCl in xanthan solution resulted in a lower limiting molecular weight. The ultrasound-mediated degradation of aqueous xanthan polymer chain agreed with a random scission model. Side chain of xanthan polymer is proposed to be the primary site of scission action. Copyright © 2017 Elsevier B.V. All rights reserved.

Nano porous silicon microcavity sensor for determination organic solvents and pesticide in water

NASA Astrophysics Data System (ADS)

Pham, Van Hoi; Van Nguyen, Thuy; Nguyen, The Anh; Pham, Van Dai; Bui, Huy

2014-12-01

In this paper we present a sensing method using nano-porous silicon microcavity sensor, which was developed in order to obtain simultaneous determination of two volatile substances with different solvent concentrations as well as very low pesticide concentration in water. The temperature of the solution and the velocity of the air stream flowing through the solution have been used to control the response of the sensor for different solvent solutions. We study the dependence of the cavity-resonant wavelength shift on solvent concentration, velocity of the airflow and solution temperature. The wavelength shift depends linearly on concentration and increases with solution temperature and velocity of the airflow. The dependence of the wavelength shift on the solution temperature in the measurement contains properties of the temperature dependence of the solvent vapor pressure, which characterizes each solvent. As a result, the dependence of the wavelength shift on the solution temperature discriminates between solutions of ethanol and acetone with different concentrations. This suggests a possibility for the simultaneous determination of the volatile substances and their concentrations. On the other hand, this method is able to detect the presence of atrazine pesticide by the shift of the resonant wavelength, with good sensitivity (0.3 nm pg-1 ml) and limit of detection (LOD) (0.8-1.4 pg ml-1), that we tested for concentrations in the range from 2.15 to 21.5 pg ml-1, which is the range useful for monitoring acceptable water for human consumption.

Relationships between CO 2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

DOE PAGES

Winnick, Matthew J.; Maher, Kate

2018-01-27

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO 2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO 2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. Here, we test this theoretical scaling relationship against reactive transport simulations of chemical weathering profilesmore » under open-and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO 2(y =kx n)where nis dependent on reaction stoichiometry and kis dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO 2 at low values and approach open-system scaling at high pCO 2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO 2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO 2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.« less

Relationships between CO 2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

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

Winnick, Matthew J.; Maher, Kate

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO 2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO 2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. Here, we test this theoretical scaling relationship against reactive transport simulations of chemical weathering profilesmore » under open-and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO 2(y =kx n)where nis dependent on reaction stoichiometry and kis dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO 2 at low values and approach open-system scaling at high pCO 2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO 2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO 2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.« less

Relationships between CO2, thermodynamic limits on silicate weathering, and the strength of the silicate weathering feedback

NASA Astrophysics Data System (ADS)

Winnick, Matthew J.; Maher, Kate

2018-03-01

Recent studies have suggested that thermodynamic limitations on chemical weathering rates exert a first-order control on riverine solute fluxes and by extension, global chemical weathering rates. As such, these limitations may play a prominent role in the regulation of carbon dioxide levels (pCO2) over geologic timescales by constraining the maximum global weathering flux. In this study, we develop a theoretical scaling relationship between equilibrium solute concentrations and pCO2 based on equilibrium constants and reaction stoichiometry relating primary mineral dissolution and secondary mineral precipitation. We test this theoretical scaling relationship against reactive transport simulations of chemical weathering profiles under open- and closed-system conditions, representing partially and fully water-saturated regolith, respectively. Under open-system conditions, equilibrium bicarbonate concentrations vary as a power-law function of pCO2 (y = kxn) where n is dependent on reaction stoichiometry and k is dependent on both reaction stoichiometry and the equilibrium constant. Under closed-system conditions, bicarbonate concentrations vary linearly with pCO2 at low values and approach open-system scaling at high pCO2. To describe the potential role of thermodynamic limitations in the global silicate weathering feedback, we develop a new mathematical framework to assess weathering feedback strength in terms of both (1) steady-state atmospheric pCO2 concentrations, and (2) susceptibility to secular changes in degassing rates and transient carbon cycle perturbations, which we term 1st and 2nd order feedback strength, respectively. Finally, we discuss the implications of these results for the effects of vascular land plant evolution on feedback strength, the potential role of vegetation in controlling modern solute fluxes, and the application of these frameworks to a more complete functional description of the silicate weathering feedback. Most notably, the dependence of equilibrium solute concentrations on pCO2 may represent a direct weathering feedback largely independent of climate and modulated by belowground organic carbon respiration.

An iPhone-based digital image colorimeter for detecting tetracycline in milk.

PubMed

Masawat, Prinya; Harfield, Antony; Namwong, Anan

2015-10-01

An iPhone-based digital image colorimeter (DIC) was fabricated as a portable tool for monitoring tetracycline (TC) in bovine milk. An application named ColorConc was developed for the iPhone that utilizes an image matching algorithm to determine the TC concentration in a solution. The color values; red (R), green (G), blue (B), hue (H), saturation (S), brightness (V), and gray (Gr) were measured from each pictures of the TC standard solutions. TC solution extracted from milk samples using solid phase extraction (SPE) was captured and the concentration was predicted by comparing color values with those collected in a database. The amount of TC could be determined in the concentration range of 0.5-10 μg mL(-1). The proposed DIC-iPhone is able to provide a limit of detection (LOD) of 0.5 μg mL(-1) and limit of quantitation (LOQ) of 1.5 μg mL(-1). The enrichment factor was 70 and color of the extracted milk sample was a strong yellow solution after SPE. Therefore, the SPE-DIC-iPhone could be used for the assay of TC residues in milk at the concentration lower than LOD and LOQ of the proposed technique. Copyright © 2015 Elsevier Ltd. All rights reserved.

Prediction the concentration of graphite direct exfoliation by liquid solution with solubility parameters map

NASA Astrophysics Data System (ADS)

Liang, Ko-Yuan; Yang, Wein-Duo

2018-01-01

This study is to discuss solvent selection with graphene dispersion concentration of directly exfoliation graphite. That limiting boundaries of fractional cohesion parameters will be draw on the triangular diagram to prediction and estimate. It is based on the literature of data and check with experimental or other literature results, include organic solution, aqueous solution and ionic liquid. In this work, we found that estimated the graphene dispersion concentration by distance (Ra) of Hansen solubility parameters (HSP) between graphene and solvent, the lower Ra; the higher concentration, some case the lower Ra; the lower dispersion concentration (such as acetone). It is compatible with the graphene dispersion concentration on the Hansen space or Triangular fractional cohesion parameters dispersion diagram. From Triangular fractional cohesion parameters dispersion diagram, 2D maps are more convenient for researchers than 3D maps of Hansen space and quickly to find the appropriate combination of solvents for different application.

Response of oxidative enzyme activities to nitrogen deposition affects soil concentrations of dissolved organic carbon

USGS Publications Warehouse

Waldrop, M.P.; Zak, D.R.

2006-01-01

Recent evidence suggests that atmospheric nitrate (NO3- ) deposition can alter soil carbon (C) storage by directly affecting the activity of lignin-degrading soil fungi. In a laboratory experiment, we studied the direct influence of increasing soil NO 3- concentration on microbial C cycling in three different ecosystems: black oak-white oak (BOWO), sugar maple-red oak (SMRO), and sugar maple-basswood (SMBW). These ecosystems span a broad range of litter biochemistry and recalcitrance; the BOWO ecosystem contains the highest litter lignin content, SMRO had intermediate lignin content, and SMBW leaf litter has the lowest lignin content. We hypothesized that increasing soil solution NO 3- would reduce lignolytic activity in the BOWO ecosystem, due to a high abundance of white-rot fungi and lignin-rich leaf litter. Due to the low lignin content of litter in the SMBW, we further reasoned that the NO3- repression of lignolytic activity would be less dramatic due to a lower relative abundance of white-rot basidiomycetes; the response in the SMRO ecosystem should be intermediate. We increased soil solution NO3- concentrations in a 73-day laboratory incubation and measured microbial respiration and soil solution dissolved organic carbon (DOC) and phenolics concentrations. At the end of the incubation, we measured the activity of ??-glucosidase, N-acetyl-glucosaminidase, phenol oxidase, and peroxidase, which are extracellular enzymes involved with cellulose and lignin degradation. We quantified the fungal biomass, and we also used fungal ribosomal intergenic spacer analysis (RISA) to gain insight into fungal community composition. In the BOWO ecosystem, increasing NO 3- significantly decreased oxidative enzyme activities (-30% to -54%) and increased DOC (+32% upper limit) and phenolic (+77% upper limit) concentrations. In the SMRO ecosystem, we observed a significant decrease in phenol oxidase activity (-73% lower limit) and an increase in soluble phenolic concentrations (+57% upper limit) in response to increasing NO 3- in soil solution, but there was no significant change in DOC concentration. In contrast to these patterns, increasing soil solution NO3- in the SMBW soil resulted in significantly greater phenol oxidase activity (+700% upper limit) and a trend toward lower DOC production (-52% lower limit). Nitrate concentration had no effect on microbial respiration or ??-glucosidase or N-acetyl-glucosaminidase activities. Fungal abundance and basidiomycete diversity tended to be highest in the BOWO soil and lowest in the SMBW, but neither displayed a consistent response to NO 3- additions. Taken together, our results demonstrate that oxidative enzyme production by microbial communities responds directly to NO3- deposition, controlling extracellular enzyme activity and DOC flux. The regulation of oxidative enzymes by different microbial communities in response to NO3- deposition highlights the fact that the composition and function of soil microbial communities directly control ecosystem-level responses to environmental change. ?? 2006 Springer Science+Business Media, Inc.

Determination of chlorine in atmosphere by kinetic spectrophotometry.

PubMed

Meng, Jian-Xin; Wang, Xiao-Bo; Ruan, Ge-Lan; Li, Guo-Qiang; Deng, Zhao-Xia

2005-03-01

A kinetic method for determination of chlorine in air was described in the present work. The method based on fading of methyl orange (MO) containing solution in air absorption process. A determination limit of 2.64 microg L(-1) was found. With the present method, chlorine concentration could be determined in several minutes with convenient manipulation. As concentration variation of methyl orange in the absorption solution did not affect the experimental results, fabrication and preservation of the stock absorption is also convenient. The present method is promising in monitoring chlorine concentration in atmosphere.

Determination of chlorine in atmosphere by kinetic spectrophotometry

NASA Astrophysics Data System (ADS)

Meng, Jian-Xin; Wang, Xiao-Bo; Ruan, Ge-Lan; Li, Guo-Qiang; Deng, Zhao-Xia

2005-03-01

A kinetic method for determination of chlorine in air was described in the present work. The method based on fading of methyl orange (MO) containing solution in air absorption process. A determination limit of 2.64 μg L -1 was found. With the present method, chlorine concentration could be determined in several minutes with convenient manipulation. As concentration variation of methyl orange in the absorption solution did not affect the experimental results, fabrication and preservation of the stock absorption is also convenient. The present method is promising in monitoring chlorine concentration in atmosphere.

Theory of the formation of the electric double layer at the ion exchange membrane-solution interface.

PubMed

Moya, A A

2015-02-21

This work aims to extend the study of the formation of the electric double layer at the interface defined by a solution and an ion-exchange membrane on the basis of the Nernst-Planck and Poisson equations, including different values of the counter-ion diffusion coefficient and the dielectric constant in the solution and membrane phases. The network simulation method is used to obtain the time evolution of the electric potential, the displacement electric vector, the electric charge density and the ionic concentrations at the interface between a binary electrolyte solution and a cation-exchange membrane with total co-ion exclusion. The numerical results for the temporal evolution of the interfacial electric potential and the surface electric charge are compared with analytical solutions derived in the limit of the shortest times by considering the Poisson equation for a simple cationic diffusion process. The steady-state results are justified from the Gouy-Chapman theory for the diffuse double layer in the limits of similar and high bathing ionic concentrations with respect to the fixed-charge concentration inside the membrane. Interesting new physical insights arise from the interpretation of the process of the formation of the electric double layer at the ion exchange membrane-solution interface on the basis of a membrane model with total co-ion exclusion.

Influence of external factors on the self-assembly of two structurally related antidepressant drugs: a thermodynamic study

NASA Astrophysics Data System (ADS)

Gutiérrez-Pichel, Manuel; Attwood, David; Taboada, Pablo; Mosquera, Víctor

Apparent molal volumes and adiabatic compressibilities of aqueous solutions of the amphiphilic antidepressant drugs imipramine and desipramine hydrochlorides have been determined from density and ultrasound velocity measurements in the temperature range 288.15-313.15 K in buffered solution of pH 3.0 and 5.5. Critical concentrations for aggregation of these drugs were obtained from inflections on the plots of the sound velocity against drug concentration. Positive deviation from the Debye-Hückel limiting law of the apparent molal volume of imipramine provides evidence of limited association at concentrations below the critical concentration over the temperature range studied. Apparent molal adiabatic compressibilities of the aggregates formed by the drugs, calculated by combining the ultrasound velocity and density data, were typical of those for a stacked aggregate. The critical concentration and energy involved in the aggregation process of these drugs have been evaluated using isothermal titration calorimetry. The solvent-aggregate interactions have been discussed from compressibility and calorimetry data.

A path-independent integral for the characterization of solute concentration and flux at biofilm detachments

USGS Publications Warehouse

Moran, B.; Kulkarni, S.S.; Reeves, H.W.

2007-01-01

A path-independent (conservation) integral is developed for the characterization of solute concentration and flux in a biofilm in the vicinity of a detachment or other flux limiting boundary condition. Steady state conditions of solute diffusion are considered and biofilm kinetics are described by an uptake term which can be expressed in terms of a potential (Michaelis-Menten kinetics). An asymptotic solution for solute concentration at the tip of the detachment is obtained and shown to be analogous to that of antiplane crack problems in linear elasticity. It is shown that the amplitude of the asymptotic solution can be calculated by evaluating a path-independent integral. The special case of a semi-infinite detachment in an infinite strip is considered and the amplitude of the asymptotic field is related to the boundary conditions and problem parameters in closed form for zeroth and first order kinetics and numerically for Michaelis-Menten kinetics. ?? Springer Science+Business Media, Inc. 2007.

Z-scan and optical limiting properties of Hibiscus Sabdariffa dye

NASA Astrophysics Data System (ADS)

Diallo, A.; Zongo, S.; Mthunzi, P.; Rehman, S.; Alqaradawi, S. Y.; Soboyejo, W.; Maaza, M.

2014-12-01

The intensity-dependent refractive index n 2 and the nonlinear susceptibility χ (3) of Hibiscus Sabdariffa dye solutions in the nanosecond regime at 532 nm are reported. More presicely, the variation of n 2, β, and real and imaginary parts of χ (3) versus the natural dye extract concentration has been carried out by z-scan and optical limiting techniques. The third-order nonlinearity of the Hibiscus Sabdariffa dye solutions was found to be dominated by nonlinear refraction, which leads to strong optical limiting of laser.

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

DOE PAGES

Swift, T. Dallas; Nguyen, Hannah; Anderko, Andrzej; ...

2015-07-25

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl 3–HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl 3 concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl 3 concentration. This is attributed to the interactions between HCl and CrCl 3 speciation in solution that leadsmore » to HMF yield being maximized at moderate HCl concentrations for each CrCl 3 concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.« less

Tandem Lewis/Brønsted homogeneous acid catalysis: conversion of glucose to 5-hydoxymethylfurfural in an aqueous chromium(iii) chloride and hydrochloric acid solution

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

Swift, T. Dallas; Nguyen, Hannah; Anderko, Andrzej

Here, a kinetic model for the tandem conversion of glucose to 5-hydroxymethylfurfural (HMF) through fructose in aqueous CrCl 3–HCl solution was developed by analyzing experimental data. We show that the coupling of Lewis and Brønsted acids in a single pot overcomes equilibrium limitations of the glucose–fructose isomerization leading to high glucose conversions and identify conditions that maximize HMF yield. Adjusting the HCl/CrCl 3 concentration has a more pronounced effect on HMF yield at constant glucose conversion than that of temperature or CrCl 3 concentration. This is attributed to the interactions between HCl and CrCl 3 speciation in solution that leadsmore » to HMF yield being maximized at moderate HCl concentrations for each CrCl 3 concentration. This volcano-like behavior is accompanied with a change in the rate-limiting step from fructose dehydration to glucose isomerization as the concentration of the Brønsted acid increases. The maximum HMF yield in a single aqueous phase is only modest and appears independent of catalysts’ concentrations as long as they are appropriately balanced. However, it can be further maximized in a biphasic system. Our findings are consistent with recent studies in other tandem reactions catalyzed by different catalysts.« less

Use of nonwettable membranes for water transfer

NASA Technical Reports Server (NTRS)

Hausch, H. G.

1970-01-01

Transfer of water through nonwettable vinyl fluoride membranes has two unique features - /1/ very low water transfer rates can be held constant by holding temperature and solute concentrations constant, /2/ the pressure gradient against which water is transported is limited only by solution breakthrough or membrane strength.

[Stability study of oxaliplatin and doxorubicin for intraperitoneal administration with hyperthermia].

PubMed

Escudero-Ortiz, V; Duart-Duart, M J; Pérez-Ruixo, C; Pérez-Ruixo, J J; Valenzuela, B

2014-05-01

To evaluate the in vitro physicochemical stability of oxaliplatin and doxorubicin when the in vivo hyperthermic intraperitoneal conditions are reproduced. Three solutions were prepared, A (oxaliplatin 200 mg/L), B(doxorubicin 15 mg/L) and C (oxaliplatin 200 mg/L with doxorubicin 15mg/L) in glucose 5%. The three solutions were subjected to the maximum temperature reached in vivo (49° C) for two hours. Physical stability was focused on visual control of particles or precipitates in solutions, discharge of gases, odor and color. Samples were taken every 15 minutes and the chemical stability was evaluated by determining the concentration of oxaliplatin and doxorubicin remaining in the samples. Oxaliplatin concentrations were determined by atomic absorption graphite chamber while doxorubicin was determined by high performance liquid chromatography.The chemical stability criteria selected was the one described by the American Pharmacopoeia, which sets a permissible variation range between the 90-110% of the initial concentration. During the assay there was no appearance of particles, precipitates in the samples, discharge of gases, nor colour changes in the solutions. The samples showed a remaining concentration of oxaliplatin and doxorubicin within the 90-110% limit. The stability of the samples that follow to two cycles of freeze-thaw after hyperthermia was also found within the specified limits. A, B and c solutions in 5% glucose, are physically and chemically stable at 49° C for two hours. Under these conditions, these solutions could be used with guarantees of stability in patients with peritoneal carcinomatosis subsidiary of intraperitoneal hyperthermic chemotherapy based in these antineoplastic agents. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.

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

NASA Astrophysics Data System (ADS)

Svoboda, Martin; Lísal, Martin

2018-06-01

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

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

PubMed

Svoboda, Martin; Lísal, Martin

2018-06-14

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

Development of apple chips technology

NASA Astrophysics Data System (ADS)

Kowalska, Hanna; Marzec, Agata; Kowalska, Jolanta; Samborska, Kinga; Tywonek, Małgorzata; Lenart, Andrzej

2018-05-01

For develop of apple chips technology without chemical preservation osmotic dehydration in cherry or apple juice concentrates or fructooligosaccharide solutions and convection drying were used. Studies included the effect of dehydration on the mass transfer in apples and the quality of the final product. The temperature, type of osmotic solution and its concentration were changeable. The fruit were tested on mass transfer indicators, stability (water activity), texture (breaking test) and nutritional value (polyphenol content, acidity). Sensory evaluation was also performed. On this basis, the verification of all options was made and the most acceptable samples were selected. Concentration of osmotic solutions at 25°Brix limited solids gain in apples. Under these conditions, the phenomenon of osmosis caused 8-10 times greater water loss than solids gain. Increasing the concentration of solutions up to 50°Brix had a significantly greater impact on mass exchange in apples, compared to increasing the temperature from 40 to 60 °C. Osmotic dehydration before drying did not significantly affect the water activity but increase of the temperature negatively affected on breaking force of the chips. Chips obtained by osmotic dehydration of apples in a cherry concentrate solution contained significantly more polyphenols, and were characterized by a higher acidity than the variants obtained by dehydration in concentrated apple juice. Furthermore, they were marked by red color which has been thought as part of the attractiveness of the product. The least sensory acceptable chips were prepared using osmotic pre-treatment in cherry concentrated juice solution with the addition of fructooligosaccharide.

Solution electrostatic levitator for measuring surface properties and bulk structures of an extremely supersaturated solution drop above metastable zone width limit.

PubMed

Lee, Sooheyong; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Lee, Geun Woo

2017-05-01

We report on the first integrated apparatus for measuring surface and thermophysical properties and bulk structures of a highly supersaturated solution by combining electrostatic levitation with real-time laser/x-ray scattering. Even today, a proper characterization of supersaturated solutions far above their solubility limits is extremely challenging because heterogeneous nucleation sites such as container walls or impurities readily initiate crystallization before the measurements can be performed. In this work, we demonstrate simultaneous measurements of drying kinetics and surface tension of a potassium dihydrogen phosphate (KH 2 PO 4 ) aqueous solution droplet and its bulk structural evolution beyond the metastable zone width limit. Our experimental finding shows that the noticeable changes of the surface properties are accompanied by polymerizations of hydrated monomer clusters. The novel electrostatic levitation apparatus presented here provides an effective means for studying a wide range of highly concentrated solutions and liquids in deep metastable states.

Investigation of absolute and relative response for three different liquid chromatography/tandem mass spectrometry systems; the impact of ionization and detection saturation.

PubMed

Nilsson, Lars B; Skansen, Patrik

2012-06-30

The investigations in this article were triggered by two observations in the laboratory; for some liquid chromatography/tandem mass spectrometry (LC/MS/MS) systems it was possible to obtain linear calibration curves for extreme concentration ranges and for some systems seemingly linear calibration curves gave good accuracy at low concentrations only when using a quadratic regression function. The absolute and relative responses were tested for three different LC/MS/MS systems by injecting solutions of a model compound and a stable isotope labeled internal standard. The analyte concentration range for the solutions was 0.00391 to 500 μM (128,000×), giving overload of the chromatographic column at the highest concentrations. The stable isotope labeled internal standard concentration was 0.667 μM in all samples. The absolute response per concentration unit decreased rapidly as higher concentrations were injected. The relative response, the ratio for the analyte peak area to the internal standard peak area, per concentration unit was calculated. For system 1, the ionization process was found to limit the response and the relative response per concentration unit was constant. For systems 2 and 3, the ion detection process was the limiting factor resulting in decreasing relative response at increasing concentrations. For systems behaving like system 1, simple linear regression can be used for any concentration range while, for systems behaving like systems 2 and 3, non-linear regression is recommended for all concentration ranges. Another consequence is that the ionization capacity limited systems will be insensitive to matrix ion suppression when an ideal internal standard is used while the detection capacity limited systems are at risk of giving erroneous results at high concentrations if the matrix ion suppression varies for different samples in a run. Copyright © 2012 John Wiley & Sons, Ltd.

Study of Separation and Fouling of Reverse Osmosis Membranes during Model Hydrolysate Solution Filtration.

PubMed

Ajao, Olumoye; Rahni, Mohamed; Marinova, Mariya; Chadjaa, Hassan; Savadogo, Oumarou

2017-12-15

Prehydrolysate, a dilute solution consisting mainly of pentoses, hexoses, and lesser quantities of organic acids, furfural and phenolics, is generated in the Kraft dissolving pulp process. An obstacle facing the valorization of the solution in hemicellulose biorefineries, by conversion of the sugars into bioproducts such as furfural, is the low sugar concentration. Membrane filtration is typically proposed in several hemicellulose based biorefineries for concentrating the solution, although they are usually generated using different wood species, pretreatment methods, and operating conditions. However, the chemical composition of the solutions is generally not considered. Also, the combined effect of composition and operating conditions is rarely investigated for biorefinery applications. The purpose of this work was to determine the impact of the prehydrolysate composition and operating parameters on the component separation and permeate flux during membrane filtration. Using model prehydrolysate solutions, two commercial reverse osmosis (RO) membranes were screened, and one was selected for use, based on its higher sugar and acetic acid retention. A Taguchi L18 experimental design array was then applied to determine the dominant parameters and limiting factors. Results showed that the feed pressure and temperature have the highest impact on permeate flux, but the least effect on sugar retention. Further experiments to quantify flux decline, due to fouling and osmotic pressure, showed that furfural has the highest membrane fouling tendency, and can limit the lifetime of the membrane. Regeneration of the membrane by cleaning with a sodium hydroxide solution is also effective for reversing fouling. It has been demonstrated that RO can efficiently and sustainably concentrate wood prehydrolysate.

Study of Separation and Fouling of Reverse Osmosis Membranes during Model Hydrolysate Solution Filtration

PubMed Central

Rahni, Mohamed; Marinova, Mariya; Chadjaa, Hassan; Savadogo, Oumarou

2017-01-01

Prehydrolysate, a dilute solution consisting mainly of pentoses, hexoses, and lesser quantities of organic acids, furfural and phenolics, is generated in the Kraft dissolving pulp process. An obstacle facing the valorization of the solution in hemicellulose biorefineries, by conversion of the sugars into bioproducts such as furfural, is the low sugar concentration. Membrane filtration is typically proposed in several hemicellulose based biorefineries for concentrating the solution, although they are usually generated using different wood species, pretreatment methods, and operating conditions. However, the chemical composition of the solutions is generally not considered. Also, the combined effect of composition and operating conditions is rarely investigated for biorefinery applications. The purpose of this work was to determine the impact of the prehydrolysate composition and operating parameters on the component separation and permeate flux during membrane filtration. Using model prehydrolysate solutions, two commercial reverse osmosis (RO) membranes were screened, and one was selected for use, based on its higher sugar and acetic acid retention. A Taguchi L18 experimental design array was then applied to determine the dominant parameters and limiting factors. Results showed that the feed pressure and temperature have the highest impact on permeate flux, but the least effect on sugar retention. Further experiments to quantify flux decline, due to fouling and osmotic pressure, showed that furfural has the highest membrane fouling tendency, and can limit the lifetime of the membrane. Regeneration of the membrane by cleaning with a sodium hydroxide solution is also effective for reversing fouling. It has been demonstrated that RO can efficiently and sustainably concentrate wood prehydrolysate. PMID:29244761

Electrodialytic in-line preconcentration for ionic solute analysis.

PubMed

Ohira, Shin-Ichi; Yamasaki, Takayuki; Koda, Takumi; Kodama, Yuko; Toda, Kei

2018-04-01

Preconcentration is an effective way to improve analytical sensitivity. Many types of methods are used for enrichment of ionic solute analytes. However, current methods are batchwise and include procedures such as trapping and elution. In this manuscript, we propose in-line electrodialytic enrichment of ionic solutes. The method can enrich ionic solutes within seconds by quantitative transfer of analytes from the sample solution to the acceptor solution under an electric field. Because of quantitative ion transfer, the enrichment factor (the ratio of the concentration in the sample and to that in the obtained acceptor solution) only depends on the flow rate ratio of the sample solution to the acceptor solution. The ratios of the concentrations and flow rates are equal for ratios up to 70, 20, and 70 for the tested ionic solutes of inorganic cations, inorganic anions, and heavy metal ions, respectively. The sensitivity of ionic solute determinations is also improved based on the enrichment factor. The method can also simultaneously achieve matrix isolation and enrichment. The method was successively applied to determine the concentrations of trace amounts of chloroacetic acids in tap water. The regulated concentration levels cannot be determined by conventional high-performance liquid chromatography with ultraviolet detection (HPLC-UV) without enrichment. However, enrichment with the present method is effective for determination of tap water quality by improving the limits of detection of HPLC-UV. The standard addition test with real tap water samples shows good recoveries (94.9-109.6%). Copyright © 2017 Elsevier B.V. All rights reserved.

Variational extension of the mean spherical approximation to arbitrary dimensions

NASA Astrophysics Data System (ADS)

Velázquez, Esov S.; Blum, Lesser; Frisch, Harry L.

1997-10-01

We generalize a variational principle for the mean spherical approximation for a system of charged hard spheres in 3D to arbitrary dimensions. We first construct a free energy variational trial function from the Debye-Hückel excess charging internal energy at a finite concentration and an entropy obtained at the zero-concentration limit by thermodynamic integration. In three dimensions the minimization of this expression with respect to the screening parameter leads to the mean spherical approximation, usually obtained by solution of the Ornstein-Zernike equation. This procedure, which interpolates naturally between the zero concentration/coupling limit and the high-concentration/ coupling limit, is extended to arbitrary dimensions. We conjecture that this result is also equivalent to the MSA as originally defined, although a technical proof of this point is left for the future. The Onsager limit T ΔS MSA / ΔE MSA → 0 for infinite concentration/coupling is satisfied for all d ≠ 2, while for d=2 this limit is 1.

Purfication kinetics of beryllium during vacuum induction melting

NASA Technical Reports Server (NTRS)

Mukherjee, J. L.; Gupta, K. P.; Li, C. H.

1972-01-01

The kinetics of evaporation in binary alloys were quantitatively treated. The formalism so developed works well for several systems studied. The kinetics of purification of beryllium was studied through evaporation data actually acquired during vacuum induction melting. Normal evaporation equations are shown to be generally valid and useful for understanding the kinetics of beryllium purification. The normal evaporation analysis has been extended to cover cases of limited liquid diffusion. It was shown that under steady-state evaporation, the solute concentration near the surface may be up to six orders of magnitude different from the bulk concentration. Corrections for limited liquid diffusion are definitely needed for the highly evaporative solute elements, such as Zn, Mg, and Na, for which the computed evaporation times are improved by five orders of magnitude. The commonly observed logarithmic relation between evaporation time and final concentration further supports the validity of the normal evaporation equations.

Multiple scattering in chiral media: border effects, reduced depolarization, and sensitivity limit

NASA Astrophysics Data System (ADS)

Delplancke, Francoise; Badoz, Jacques P.; Boccara, A. Claude

1997-10-01

Suspensions of polystyrene latex beads in chiral solutions were investigated. The rotatory power, induced by solubilized sucrose, in near-forward scattering was measured via a method using polarization modulation by photo-elastic modulator. The sensitivity of the measurement was enhanced and optimized in order to measure sucrose concentrations as low as 5 mg/ml in a cell 5 mm thick only. Different concentrations and diameters of latex particles were used in combination with different sucrose concentrations going from 1 mg/ml up to saturation. The experiments showed that the apparent rotatory power is enhanced by multiple scattering, that depolarization effects are less important with highly concentrated sucrose solutions and that attention has to be paid to cell border effects in order to avoid important artifacts, in case of highly scattering suspensions. Qualitative and theoretical explanations of those observations are presented. One possible application of this method is to measure the sugar content in human blood, in vivo, non-invasively, through the skin. The concentration to be evaluated is at the sensitivity limit. So any artifact has to be removed carefully, e.g. skin cell birefringence or chirality.

Novel second-stage solar concentrator for parabolic troughs

NASA Astrophysics Data System (ADS)

Collares-Pereira, Manuel; Mendes, Joao F.

1995-08-01

Conventional parabolic troughs can be combined with second stage concentrators (SSC), to increase temperature and pressure inside the absorber, making possible the direct production of steam, improving substantially the overall system efficiency and leading to a new generation of distributed solar power plants. To attain this objective, research is needed at the optical, thermodynamic, system control, and engineering levels. In what concerns the receiver of such a system, different practical solutions have been proposed recently and in the past for the geometry of the second stage concentrator: CPC type and others. In this work we discuss these solutions and we propose a new one, 100% efficient in energy collection while reaching a total concentration ratio which is almost 65% of the thermodynamic limit. This SSC has an asymmetric elliptical geometry, rendering possible a smooth solution for the reflectors while maintaining a reasonable size for the receiver.

Influence of physical and chemical properties of HTSXT-FTIR samples on the quality of prediction models developed to determine absolute concentrations of total proteins, carbohydrates and triglycerides: a preliminary study on the determination of their absolute concentrations in fresh microalgal biomass.

PubMed

Serrano León, Esteban; Coat, Rémy; Moutel, Benjamin; Pruvost, Jérémy; Legrand, Jack; Gonçalves, Olivier

2014-11-01

Absolute concentrations of total macromolecules (triglycerides, proteins and carbohydrates) in microorganisms can be rapidly measured by FTIR spectroscopy, but caution is needed to avoid non-specific experimental bias. Here, we assess the limits within which this approach can be used on model solutions of macromolecules of interest. We used the Bruker HTSXT-FTIR system. Our results show that the solid deposits obtained after the sampling procedure present physical and chemical properties that influence the quality of the absolute concentration prediction models (univariate and multivariate). The accuracy of the models was degraded by a factor of 2 or 3 outside the recommended concentration interval of 0.5-35 µg spot(-1). Change occurred notably in the sample hydrogen bond network, which could, however, be controlled using an internal probe (pseudohalide anion). We also demonstrate that for aqueous solutions, accurate prediction of total carbohydrate quantities (in glucose equivalent) could not be made unless a constant amount of protein was added to the model solution (BSA). The results of the prediction model for more complex solutions, here with two components: glucose and BSA, were very encouraging, suggesting that this FTIR approach could be used as a rapid quantification method for mixtures of molecules of interest, provided the limits of use of the HTSXT-FTIR method are precisely known and respected. This last finding opens the way to direct quantification of total molecules of interest in more complex matrices.

Evaluation of Shiryaev-Roberts Procedure for On-line Environmental Radiation Monitoring

NASA Astrophysics Data System (ADS)

Watson, Mara Mae

An on-line radiation monitoring system that simultaneously concentrates and detects radioactivity is needed to detect an accidental leakage from a nuclear waste disposal facility or clandestine nuclear activity. Previous studies have shown that classical control chart methods can be applied to on-line radiation monitoring data to quickly detect these events as they occur; however, Bayesian control chart methods were not included in these studies. This work will evaluate the performance of a Bayesian control chart method, the Shiryaev-Roberts (SR) procedure, compared to classical control chart methods, Shewhart 3-sigma and cumulative sum (CUSUM), for use in on-line radiation monitoring of 99Tc in water using extractive scintillating resin. Measurements were collected by pumping solutions containing 0.1-5 Bq/L of 99Tc, as 99T cO4-, through a flow cell packed with extractive scintillating resin coupled to a Beta-RAM Model 5 HPLC detector. While 99T cO4- accumulated on the resin, simultaneous measurements were acquired in 10-s intervals and then re-binned to 100-s intervals. The Bayesian statistical method, Shiryaev-Roberts procedure, and classical control chart methods, Shewhart 3-sigma and cumulative sum (CUSUM), were applied to the data using statistical algorithms developed in MATLAB RTM. Two SR control charts were constructed using Poisson distributions and Gaussian distributions to estimate the likelihood ratio, and are referred to as Poisson SR and Gaussian SR to indicate the distribution used to calculate the statistic. The Poisson and Gaussian SR methods required as little as 28.9 mL less solution at 5 Bq/L and as much as 170 mL less solution at 0.5 Bq/L to exceed the control limit than the Shewhart 3-sigma method. The Poisson SR method needed as little as 6.20 mL less solution at 5 Bq/L and up to 125 mL less solution at 0.5 Bq/L to exceed the control limit than the CUSUM method. The Gaussian SR and CUSUM method required comparable solution volumes for test solutions containing at least 1.5 Bq/L of 99T c. For activity concentrations less than 1.5 Bq/L, the Gaussian SR method required as much as 40.8 mL less solution at 0.5 Bq/L to exceed the control limit than the CUSUM method. Both SR methods were able to consistently detect test solutions containing 0.1 Bq/L, unlike the Shewhart 3-sigma and CUSUM methods. Although the Poisson SR method required as much as 178 mL less solution to exceed the control limit than the Gaussian SR method, the Gaussian SR false positive of 0% was much lower than the Poisson SR false positive rate of 1.14%. A lower false positive rate made it easier to differentiate between a false positive and an increase in mean count rate caused by activity accumulating on the resin. The SR procedure is thus the ideal tool for low-level on-line radiation monitoring using extractive scintillating resin, because it needed less volume in most cases to detect an upward shift in the mean count rate than the Shewhart 3-sigma and CUSUM methods and consistently detected lower activity concentrations. The desired results for the monitoring scheme, however, need to be considered prior to choosing between the Poisson and Gaussian distribution to estimate the likelihood ratio, because each was advantageous under different circumstances. Once the control limit was exceeded, activity concentrations were estimated from the SR control chart using the slope of the control chart on a semi-logarithmic plot. Five of nine test solutions for the Poisson SR control chart produced concentration estimates within 30% of the actual value, but the worst case was 263.2% different than the actual value. The estimations for the Gaussian SR control chart were much more precise, with six of eight solutions producing estimates within 30%. Although the activity concentrations estimations were only mediocre for the Poisson SR control chart and satisfactory for the Gaussian SR control chart, these results demonstrate that a relationship exists between activity concentration and the SR control chart magnitude that can be exploited to determine the activity concentration from the SR control chart. More complex methods should be investigated to improve activity concentration estimations from the SR control charts.

Concentration history during pumping from a leaky aquifer with stratified initial concentration

USGS Publications Warehouse

Goode, Daniel J.; Hsieh, Paul A.; Shapiro, Allen M.; Wood, Warren W.; Kraemer, Thomas F.

1993-01-01

Analytical and numerical solutions are employed to examine the concentration history of a dissolved substance in water pumped from a leaky aquifer. Many aquifer systems are characterized by stratification, for example, a sandy layer overlain by a clay layer. To obtain information about separate hydrogeologic units, aquifer pumping tests are often conducted with a well penetrating only one of the layers. When the initial concentration distribution is also stratified (the concentration varies with elevation only), the concentration breakthrough in the pumped well may be interpreted to provide information on aquifer hydraulic and transport properties. To facilitate this interpretation, we present some simple analytical and numerical solutions for limiting cases and illustrate their application to a fractured bedrock/glacial drift aquifer system where the solute of interest is dissolved radon gas. In addition to qualitative information on water source, this method may yield estimates of effective porosity and saturated thickness (or fracture transport aperture) from a single-hole test. Little information about dispersivity is obtained because the measured concentration is not significantly affected by dispersion in the aquifer.

The effect of topography and rock type on soil cation contents and stream solute and phosphorus concentrations of streams in the southwestern Brazilian Amazon basin.

NASA Astrophysics Data System (ADS)

Biggs, T. W.; Dunne, T.; Holmes, K.; Martinelli, L. A.

2001-12-01

Topography plays an important role in determining soil properties, stream solute concentrations and landscape denudation rates. Stallard (1985) suggested that catchment denudation rates should depend on soil thickness. Areas with low slopes are limited by the rate of transport of sediment, and typically contain thick soils that prevent interaction of stream waters with underlying bedrock [Stallard 1985]. Steep areas typically have thin soils, but a lower hydrologic residence time that may prevent soil water from coming into thermodynamic equilibrium with the soil-rock complex. In a survey of streams in the Brazilian Amazon basin, Biggs et al. (2001) found that stream solute concentrations correlate with soil cation contents in the humid tropics, but the mechanism underlying the correlation has not been determined. We combine chemical analyses of water samples from ~40 different streams with soil surveys, geology maps, and a 100m resolution DEM to examine the relationship between topography, rock type, soil cation contents, and stream solute concentrations in the Brazilian Amazon state of Rondônia. The basins are all more than 60% forested at the time of stream sampling and lie on granite-gneiss rocks, tertiary sediments, or sandstone. The catchment-averaged slope correlates positively with both soil cation contents and stream concentrations of P, Na, Ca, Mg, K, Si, ANC, and pH. Though we have no data about the relationship between soil depth and average slope, we assume an inverse correlation, so the data demonstrates that thick soils yield lower solute concentrations. Stream concentrations of Ca, Mg, ANC and pH reach a maximum at intermediate average slopes (3 degrees), suggesting that denudation rates may increase with slope up to a maximum, when the catchment becomes limited by the weathering rate of the basement rock. Catchments on mica-schists or mafic rocks have low average slopes and higher concentrations of Ca, Mg, Si, ANC, and pH than catchments on granite-gneiss, tertiary sediments or sandstone.

Uremic Solutes in Chronic Kidney Disease and Their Role in Progression.

PubMed

van den Brand, Jan A J G; Mutsaers, Henricus A M; van Zuilen, Arjan D; Blankestijn, Peter J; van den Broek, Petra H; Russel, Frans G M; Masereeuw, Rosalinde; Wetzels, Jack F M

2016-01-01

To date, over 150 possible uremic solutes have been listed, but their role in the progression of CKD is largely unknown. Here, the association between a selected panel of uremic solutes and progression in CKD patients was investigated. Patients from the MASTERPLAN study, a randomized controlled trial in CKD patients with a creatinine clearance between 20 and 70 ml/min per 1.73m2, were selected based on their rate of eGFR decline during the first five years of follow-up. They were categorized as rapid (decline >5 ml/min per year) or slow progressors. Concentrations of eleven uremic solutes were obtained at baseline and after one year of follow-up. Logistic regression was used to compare the odds for rapid to slow progression by uremic solute concentrations at baseline. Variability in uremic solute levels was assessed using scatter plots, and limits of variability were calculated. In total, 40 rapidly and 40 slowly progressing patients were included. Uremic solutes were elevated in all patients compared to reference values for healthy persons. The serum levels of uremic solutes were not associated with rapid progression. Moreover, we observed substantial variability in solute levels over time. Elevated concentrations of uremic solutes measured in this study did not explain differences in rate of eGFR decline in CKD patients, possibly due to lack of power as a result of the small sample size, substantial between patient variability, and variability in solute concentrations over time. The etiology of intra-individual variation in uremic solute levels remains to be elucidated.

Evaluation of metal biouptake from the analysis of bulk metal depletion kinetics at various cell concentrations: theory and application.

PubMed

Rotureau, Elise; Billard, Patrick; Duval, Jérôme F L

2015-01-20

Bioavailability of trace metals is a key parameter for assessment of toxicity on living organisms. Proper evaluation of metal bioavailability requires monitoring the various interfacial processes that control metal partitioning dynamics at the biointerface, which includes metal transport from solution to cell membrane, adsorption at the biosurface, internalization, and possible excretion. In this work, a methodology is proposed to quantitatively describe the dynamics of Cd(II) uptake by Pseudomonas putida. The analysis is based on the kinetic measurement of Cd(II) depletion from bulk solution at various initial cell concentrations using electroanalytical probes. On the basis of a recent formalism on the dynamics of metal uptake by complex biointerphases, the cell concentration-dependent depletion time scales and plateau values reached by metal concentrations at long exposure times (>3 h) are successfully rationalized in terms of limiting metal uptake flux, rate of excretion, and metal affinity to internalization sites. The analysis shows the limits of approximate depletion models valid in the extremes of high and weak metal affinities. The contribution of conductive diffusion transfer of metals from the solution to the cell membrane in governing the rate of Cd(II) uptake is further discussed on the basis of estimated resistances for metal membrane transfer and extracellular mass transport.

Middle infrared optoelectronic absorption systems for monitoring physiological glucose solutions

NASA Astrophysics Data System (ADS)

Martin, W. Blake

Tight monitoring of the glucose levels for diabetic individuals is essential to control long-term complications. A definitive diabetes management system has yet to be developed for the diabetic. This research investigates the application of middle infrared absorption frequencies for monitoring glucose levels in biological solutions. Three frequencies were identified using a Fourier transform infrared spectrometer and correlated to changes in glucose concentrations. The 1035 +/- 1 cm-1 frequency was determined to be the best representative frequency. Other biological molecules contributed no significant interference to monitoring glucose absorption. A second frequency at 1193 cm-1 was suggested as a representative background absorption frequency, which could be used for more accurate glucose absorption values. Next, a quantum cascade laser optoelectronic absorption system was designed and developed to monitor glucose. After careful alignment and design, the system was used to monitor physiological glucose concentrations. Correlation at 1036 cm-1 with glucose changes was comparable to the previous results. The use of the background absorption frequency was verified. This frequency essentially acts as a calibrating frequency to adjust in real-time to any changes in the background absorption that may alter the accuracy of the predicted glucose value. An evanescent wave cavity ring-down spectroscopy technique was explored to monitor molecules in a biological solution. Visible light at 425 nm was used to monitor hemoglobin in control urine samples. An adsorption isotherm for hemoglobin was detectable to limit of 5.8 nM. Evanescent wave cavity ring-down spectroscopy would be useful for a glucose solution. Given an equivalent system designed for the middle infrared, the molar extinction coefficient of glucose allows for a detectable limit of 45 mg/dl for a free-floating glucose solution, which is below normal physiological concentrations. The future use of a hydrophobic coating could limit the adsorption of glucose to the surface but still allow physiological monitoring. Three middle infrared optoelectronic absorption systems have been designed for monitoring glucose in a physiological solution. The systems are applicable for the monitoring of glucose. These systems may lead to a useful monitoring device for the diabetic so that the universal complications associated with the disease may be limited.

Conductometry of electrolyte solutions

NASA Astrophysics Data System (ADS)

Safonova, Lyubov P.; Kolker, Arkadii M.

1992-09-01

A review is given of the theories of the electrical conductance of electrolyte solutions of different ionic strengths and concentrations, and of the models of ion association. An analysis is made of the methods for mathematical processing of experimental conductometric data. An account is provided of various theories describing the dependence of the limiting value of the ionic electrical conductance on the properties of the solute and solvent. The bibliography includes 115 references.

Solution of non-steady-state substrate concentration in the action of biosensor response at mixed enzyme kinetics

NASA Astrophysics Data System (ADS)

Senthamarai, R.; Jana Ranjani, R.

2018-04-01

In this paper, a mathematical model of an amperometric biosensor at mixed enzyme kinetics and diffusion limitation in the case of substrate inhibition has been developed. The model is based on time dependent reaction diffusion equation containing a non -linear term related to non -Michaelis - Menten kinetics of the enzymatic reaction. Solution for the concentration of the substrate has been derived for all values of parameters using the homotopy perturbation method. All the approximate analytic expressions of substrate concentration are compared with simulation results using Scilab/Matlab program. Finally, we have given a satisfactory agreement between them.

Effect of silicate ions on electrode overvoltage

NASA Technical Reports Server (NTRS)

Gras, J. M.; Seite, C.

1979-01-01

The influence of the addition of a silicate to a caustic solution (KOH) is studied in order to determine the degree to which silicates inhibit the corrosion of chrysotile under conditions of electrolysis at working temperatures of 100 C and above. In an alkaline solution containing various silicate concentrations, current density was increased and electrode overvoltage was measured. Results show that silicate ion concentrations in the electrolyte increase with temperature without effecting electrochemical performance up to 115 C at 700 MA/sqcm. At this point the concentration is about 0.5 g Si/100 g KOH. Beyond this limit, electrolytic performance rapidly degenerates due to severe oxidation of the electrodes.

Stress concentration in a cylindrical shell containing a circular hole.

NASA Technical Reports Server (NTRS)

Adams, N. J. I.

1971-01-01

The state of stress in a cylindrical shell containing a circular cutout was determined for axial tension, torsion, and internal pressure loading. The solution was obtained for the shallow shell equations by a variational method. The results were expressed in terms of a nondimensional curvature parameter which was a function of shell radius, shell thickness, and hole radius. The function chosen for the solution was such that when the radius of the cylindrical shell approaches infinity, the flat-plate solution was obtained. The results are compared with solutions obtained by more rigorous analytical methods, and with some experimental results. For small values of the curvature parameter, the agreement is good. For higher values of the curvature parameter, the present solutions indicate a limiting value of stress concentration, which is in contrast to previous results.

Influence of pH, temperature, and concentration on stabilization of aqueous hornet silk solution and fabrication of salt-free materials.

PubMed

Kameda, Tsunenori

2015-01-01

We found that an aqueous solution of silk from cocoons produced by hornet larvae (hornet silk) can be obtained when the solution is adjusted to basic conditions of pH > 9.2. It is known that native hornet cocoons can be dissolved in concentrated aqueous solution of salts, such as lithium bromide (LiBr) and calcium chloride (CaCl2). Upon the removal of these salts from solution by dialysis, solidification, gelation, or sedimentation of hornet silk is known to occur. In the present study, under basic conditions, however, no such solidification occurred, even after salt removal. In this study, ammonia was used for alkalization of solution because it is volatilized during the casting process and pure hornet silk materials can be obtained after drying. The effects of the concentrations of hornet silk and ammonia, as well as dialysis temperature, on preventing gelation during dialysis were investigated. Dialysis conditions that limit the degradation of hornet silk by hydrolysis in alkali solution were identified. Moreover, casting conditions to prepare flexible and transparent hornet silk film from aqueous ammonia solution were optimized. Molecular structural analysis of hornet silk in aqueous ammonia solution and cast film indicated the formation of α-helix conformations. © 2014 Wiley Periodicals, Inc.

Diffusion Limitations in Root Uptake of Cadmium and Zinc, But Not Nickel, and Resulting Bias in the Michaelis Constant1[W][OA

PubMed Central

Degryse, Fien; Shahbazi, Afsaneh; Verheyen, Liesbeth; Smolders, Erik

2012-01-01

It has long been recognized that diffusive boundary layers affect the determination of active transport parameters, but this has been largely overlooked in plant physiological research. We studied the short-term uptake of cadmium (Cd), zinc (Zn), and nickel (Ni) by spinach (Spinacia oleracea) and tomato (Lycopersicon esculentum) in solutions with or without metal complexes. At same free ion concentration, the presence of complexes, which enhance the diffusion flux, increased the uptake of Cd and Zn, whereas Ni uptake was unaffected. Competition effects of protons on Cd and Zn uptake were observed only at a very large degree of buffering, while competition of magnesium ions on Ni uptake was observed even in unbuffered solutions. These results strongly suggest that uptake of Cd and Zn is limited by diffusion of the free ion to the roots, except at very high degree of solution buffering, whereas Ni uptake is generally internalization limited. All results could be well described by a model that combined a diffusion equation with a competitive Michaelis-Menten equation. Direct uptake of the complex was estimated to be a major contribution only at millimolar concentrations of the complex or at very large ratios of complex to free ion concentration. The true Km for uptake of Cd2+ and Zn2+ was estimated at <5 nm, three orders of magnitude smaller than the Km measured in unbuffered solutions. Published Michaelis constants for plant uptake of Cd and Zn likely strongly overestimate physiological ones and should not be interpreted as an indicator of transporter affinity. PMID:22864584

Arsenic in the rhizosphere soil solution of ferns.

PubMed

Wei, Chaoyang; Zheng, Huan; Yu, Jiangping

2012-12-01

The aim of this study was to explore the evidence of arsenic hyperaccumulation in plant rhizosphere solutions. Six common fern plants were selected and grown in three types of substrate: arsenic (As) -tailings, As-spiked soil, and soil-As-tailing composites. A rhizobox was designed with an in-situ collection of soil solutions to analyze changes in the As concentration and valence as well as the pH, dissolved organic carbon (DOC) and total nitrogen (TN). Arsenite composed less than 20% of the total As, and As depletion was consistent with N depletion in the rhizosphere solutions of the various treatments. The As concentrations in the rhizosphere and non-rhizosphere solutions in the presence of plants were lower than in the respective controls without plants, except for in the As-spiked soils. The DOC concentrations were invariably higher in the rhizosphere versus non-rhizosphere solutions from the various plants; however, no significant increase in the DOC content was observed in Pteris vittata, in which only a slight decrease in pH appeared in the rhizosphere compared to non-rhizosphere solutions. The results showed that As reduction by plant roots was limited, acidification-induced solubilization was not the mechanism for As hyperaccumulation.

Nanoscale volume confinement and fluorescence enhancement with double nanohole aperture

PubMed Central

Regmi, Raju; Al Balushi, Ahmed A.; Rigneault, Hervé; Gordon, Reuven; Wenger, Jérôme

2015-01-01

Diffraction ultimately limits the fluorescence collected from a single molecule, and sets an upper limit to the maximum concentration to isolate a single molecule in the detection volume. To overcome these limitations, we introduce here the use of a double nanohole structure with 25 nm gap, and report enhanced detection of single fluorescent molecules in concentrated solutions exceeding 20 micromolar. The nanometer gap concentrates the light into an apex volume down to 70 zeptoliter (10−21 L), 7000-fold below the diffraction-limited confocal volume. Using fluorescence correlation spectroscopy and time-correlated photon counting, we measure fluorescence enhancement up to 100-fold, together with local density of optical states (LDOS) enhancement of 30-fold. The distinctive features of double nanoholes combining high local field enhancement, efficient background screening and relative nanofabrication simplicity offer new strategies for real time investigation of biochemical events with single molecule resolution at high concentrations. PMID:26511149

Organic Carbon Release from Groundwater Sediments under Changing Geochemical Conditions

NASA Astrophysics Data System (ADS)

Tinnacher, R. M.; Bhattacharyya, A.; Fox, P. M.; Nico, P. S.

2016-12-01

Due to climate change, local weather patterns are expected to change, especially with respect to precipitation, the frequency of extreme storm water events, and `drought-like' conditions. This in turn, may affect groundwater recharge, the geochemical conditions in natural groundwater systems, and the chemical and microbiological processes involved in organic matter degradation. Besides the complexity of organic matter structures and local limitations in nutrients, the association of organic carbon with sediment minerals can strongly limit organic matter bioaccessability and degradability. In this study, we investigate how variations in groundwater chemistry, e.g. with respect to dissolved CO2 concentrations, may potentially affect the release of natural organic carbon from groundwater sediments, and render organic matter more bioaccessible. In lab-scale experiments under anaerobic conditions, aquifer sediments from the floodplain of the Colorado River (Rifle, USA) were brought into contact with fresh, organic-carbon free groundwater solutions, at natural or reduced CO2 concentration levels. During the repeated exchange of solutions at two temperature settings (room-temperature and 4 °C), supernatant solutions were characterized in terms of pH, dissolved metal and organic carbon (OC) concentrations, and potential changes in released OC characteristics. Sediment samples were evaluated for possible differences in Fe-speciation before and after the experiment based on EXAFS (bulk Fe K-edge). Preliminary results for 20 exchanges of groundwater solutions show a repeated release of low OC concentrations ( 0.5-2 mg OC/g sediment; 0.05-0.2% of sediment-associated OC) without any apparent depletion in the overall source term over 50 days. After 14 days, room-temperature samples released slightly higher OC concentrations than samples kept at 4 °C. An increase in solution pH, after switching to a `CO2-free' groundwater solution, did not trigger a higher OC release. Last, specific UV absorbance measurements for room-temperature samples suggest changes in released OC characteristics due to repeated solution exchanges. Additional sample characterization is ongoing, with the goal to elucidate potential changes in released OC characteristics over the course of the experiment.

Simulating contaminant attenuation, double-porosity exchange, and water age in aquifers using MOC3D

USGS Publications Warehouse

Goode, Daniel J.

1999-01-01

MOC3D is a general-purpose computer model developed by the U.S. Geological Survey (USGS) for simulation of three-dimensional solute transport in ground water (Konikow and others, 1996). The model is an update to the widely used USGS two-dimensional solute-transport model (MOC) and is implemented as an optional “package” for the ground-water flow model MODFLOW (Harbaugh and McDonald, 1996). Directly coupling the time-tested MOC transport algorithms with the widely used MODFLOW program makes MOC3D a powerful tool for simulation of solute transport in ground water in many hydrogeologic settings. The model simulates transport processes that include:Advection - Transport of dissolved solutes at the same rate as the average ground-water flow velocity.Diffusion - Spreading of solute from areas of high concentration to areas of low concentration, caused by “random” molecular motionDispersion - Diffusion-like spreading of solute that is caused primarily by spatial variability in aquifer properties, which results in spatial variability in transport velocity.Retardation - Reduction in the apparent solute velocity, compared to the ground-water velocity, caused by linear equilibrium sorption on aquifer materials.Decay - Disappearance of solute caused by reactions such as radioactive decay or biodegradation that are proportional to concentration.Growth - Creation (or disappearance) of solute mass caused by reactions that proceed independent of the solute concentration, such as some cases of biodegradationDouble-porosity exchange - rate-limited exchange of solute mass between mobile and immobile zones; for example, between fractures and the rock matrix.

Effect of flow rate and concentration difference on reverse electrodialysis system

NASA Astrophysics Data System (ADS)

Kwon, Kilsugn; Han, Jaesuk; Kim, Daejoong

2013-11-01

Various energy conversion technologies have been developed to reduce dependency on limited fossil fuels, including wind power, solar power, hydropower, ocean power, and geothermal power. Among them, reverse electrodialysis (RED), which is one type of salinity gradient power (SGP), has received much attention due to high reliability and simplicity without moving parts. Here, we experimentally evaluated the RED performance with several parameters like flow rate of concentrated and dilute solution, concentration difference, and temperature. RED was composed of endplates, electrodes, spacers, anion exchange membrane, and cation exchange membrane. Endplates are made by a polypropylene. It included the electrodes, flow field for the electrode rinse solution, and path to supply a concentrated and dilute solution. Titanium coated by iridium and ruthenium was used as the electrode. The electrode rinse solution based on hexacyanoferrate system is used to reduce the power loss generated by conversion process form ionic current to electric current. Maximum power monotonously increases as increasing flow rate and concentration difference. Net power has optimal point because pumping power consumption increases with flow rate. This work was supported by Basic Science Research Program (Grat No. NRF-2011-0009993) through the National Research Foundation of Korea.

Can oral rehydration solution be safely flavored at home?

PubMed

Nijssen-Jordan, C

1997-12-01

To determine the concentration of sodium, potassium, glucose, and osmolality of oral rehydration solutions (ORS) which have been flavored with varying amounts of unsweetened Kool-Aid powder, Jell-O powder, apple juice, or orange juice. Descriptive. Alberta Children's Hospital Chemistry Laboratory. None. Addition of varying amounts of flavoring easily available in all households to commercially available unsweetened ORS. Concentrations of electrolytes, glucose, and osmolality. Addition of fruit juices or flavor powders to commercially produced ORS does alter the electrolyte content and osmolality. When limited amounts of flavoring or juice is added, the osmolality of the solution approaches iso-osmolality. Small amounts of unsweetened Kool-Aid powder, Jell-O powder, and apple or orange juice can be added to oral rehydration solutions without significantly altering electrolyte composition and osmolality.

Preferential Solvation of an Asymmetric Redox Molecule

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

Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.

2016-12-15

The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ionmore » pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.« less

Relationship between height and width of resonance peaks in a whispering gallery mode resonator immersed in water and sucrose solutions

NASA Astrophysics Data System (ADS)

Teraoka, Iwao; Yao, Haibei; Huiyi Luo, Natalie

2017-06-01

We employed a recently developed whispering gallery mode (WGM) dip sensor made of silica to obtain spectra for many resonance peaks in water and solutions of sucrose at different concentrations and thus having different refractive indices (RI). The apparent Q factor was estimated by fitting each peak profile in the busy resonance spectrum by a Lorentzian or a sum of Lorentzians. A plot of the Q factor as a function the peak height for all the peaks analyzed indicates a straight line with a negative slope as the upper limit, for each of water and the solutions. A coupling model for a resonator and a pair of fiber tapers to feed and pick up light, developed here, supports the presence of the upper limit. We also found that the round-trip attenuation of WGM was greater than the one estimated from light absorption by water, and the difference increased with the concentration of sucrose.

A liquid-phase microextraction method, combining a dual gauge microsyringe with a hollow fiber membrane, for the determination of organochlorine pesticides in aqueous solution by gas chromatography/ion trap mass spectrometry.

PubMed

Yan, Chih-Hao; Wu, Hui-Fen

2004-01-01

A liquid-phase microextraction (LPME) method has been demonstrated for the extraction and determination of organochlorine pesticides (OCPs) in aqueous solution. The method combines a dual gauge microsyringe with a hollow fiber membrane (LPME/DGM-HF) followed by detection by gas chromatography/ion trap mass spectrometry (GC/ITMS). The advantages include speed, low solvent and sample consumption, simplicity and ease of use. The extraction time, solvent selection, salt concentration and sample stirring rate have been investigated in order to optimize extraction efficiency. The viability is evaluated by measuring the linearity and detection limit of the five OCPs in aqueous solution. Detection linearity for the OCPs has been achieved over a range of concentrations between 1 and 500 microg/L (r2 > 0.930), with a detection limit of 0.1 microg/L for each OCP. Copyright 2004 John Wiley & Sons, Ltd.

A new method of auxiliary purification for motor vehicle exhaust.

PubMed

Li, Dingqi

2018-07-01

As a result of the limitations of current purification technologies, purification efficiency is relatively low, particularly during startup or in the case of other abnormal automobile exhaust. Therefore, a new method of auxiliary purification is proposed in this paper. The acidic solution of potassium permanganate can oxidize carbon monoxide, nitrogen oxides and sulfur dioxide at relatively high temperatures and the alkaline solution of potassium permanganate can selectively absorb nitrogen oxide and sulfur dioxide. Therefore, we carried out the experiment using a solution of potassium permanganate and sulfuric acid as well as a solution of sodium carbonate and potassium permanganate, which served as the reagents for the auxiliary purification. The results of the test showed that after auxiliary purification by the acidic solution of potassium permanganate and the alkaline solution of potassium permanganate, the concentrations of carbon monoxide, hydrocarbons, nitrogen oxides and solid particles in the emissions were considerably lower than the concentrations prior to purification. It is possible to reduce the motor vehicle exhaust by the auxiliary purification of the solutions.

Development of a Distributed Source Contaminant Transport Model for ARAMS

DTIC Science & Technology

2005-09-01

runoff as a result of rainfall. The transfer of dissolved chemicals from the soil solution to overland flow is a rate-limited process ERDC/EL TN-ECMI...boundary layer that separates the stagnant soil solution and the moving overland flow (Wallach et al. 1988, 1989). Dissolution. Some chemicals may...layer (L/T) The mass transfer coefficient relates solute flux across the soil surface interface to the difference in concentration between the soil

Applied spectrophotometry: analysis of a biochemical mixture.

PubMed

Trumbo, Toni A; Schultz, Emeric; Borland, Michael G; Pugh, Michael Eugene

2013-01-01

Spectrophotometric analysis is essential for determining biomolecule concentration of a solution and is employed ubiquitously in biochemistry and molecular biology. The application of the Beer-Lambert-Bouguer Lawis routinely used to determine the concentration of DNA, RNA or protein. There is however a significant difference in determining the concentration of a given species (RNA, DNA, protein) in isolation (a contrived circumstance) as opposed to determining that concentration in the presence of other species (a more realistic situation). To present the student with a more realistic laboratory experience and also to fill a hole that we believe exists in student experience prior to reaching a biochemistry course, we have devised a three week laboratory experience designed so that students learn to: connect laboratory practice with theory, apply the Beer-Lambert-Bougert Law to biochemical analyses, demonstrate the utility and limitations of example quantitative colorimetric assays, demonstrate the utility and limitations of UV analyses for biomolecules, develop strategies for analysis of a solution of unknown biomolecular composition, use digital micropipettors to make accurate and precise measurements, and apply graphing software. Copyright © 2013 Wiley Periodicals, Inc.

A highly sensitive and temporal visualization system for gaseous ethanol with chemiluminescence enhancer.

PubMed

Arakawa, Takahiro; Ando, Eri; Wang, Xin; Kumiko, Miyajima; Kudo, Hiroyuki; Saito, Hirokazu; Mitani, Tomoyo; Takahashi, Mitsuo; Mitsubayashi, Kohji

2012-01-01

A two-dimensional gaseous ethanol visualization system has been developed and demonstrated using a horseradish peroxidase-luminol-hydrogen peroxide system with high-purity luminol solution and a chemiluminescence (CL) enhancer. This system measures ethanol concentrations as intensities of CL via the luminol reaction. CL was emitted when the gaseous ethanol was injected onto an enzyme-immobilized membrane, which was employed as a screen for two-dimensional gas visualization. The average intensity of CL on the substrate was linearly related to the concentration of standard ethanol gas. These results were compared with the CL intensity of the CCD camera recording image in the visualization system. This system is available for gas components not only for spatial but also for temporal analysis in real time. A high-purity sodium salt HG solution (L-HG) instead of standard luminol solution and an enhancer, eosin Y (EY) solution, were adapted for improvement of CL intensity of the system. The visualization of gaseous ethanol was achieved at a detection limit of 3 ppm at optimized concentrations of L-HG solution and EY. Copyright © 2011 John Wiley & Sons, Ltd.

Nature of the Renal Concentrating Defect in Sickle Cell Disease*

PubMed Central

Hatch, Fred E.; Culbertson, James W.; Diggs, Lemuel W.

1967-01-01

Free water reabsorption (TcH2O) measured during 10% mannitol diuresis and subsequently during 3% saline diuresis was compared in patients with sickle cell anemia and in normal subjects. During mannitol infusion, TcH2O progressively rose with increasing osmolar clearance (Cosm) and reached a maximal level in both groups studied. During hypertonic saline diuresis, TcH2O progressively rose in the normal subjects and exceeded the maximal levels attained during mannitol diuresis, with no evidence of a maximal TcH2O level appearing. In contrast, none of the saline curves significantly exceeded the mannitol curves in the sickle cell patients but tended to parallel the mannitol curves at comparable rates of solute clearance. Since TcH2O is an index of both solute (sodium) transport from the loop of Henle and solute accumulation in the hypertonic medullary interstitium, tubular sodium handling was examined in both sickle cell patients and control subjects alike. No difference in the tubular transport of sodium could be demonstrated either under conditions of sodium loading or under conditions in which the tubular sodium load was low (water diuresis). These data support the conclusion that the defect in urinary concentration in sickle cell patients is caused by a limitation in maintaining a high concentration of solute in the medullary interstitium, thus limiting the rate of TcH2O from the collecting duct. PMID:6023770

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

PubMed

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

2013-01-01

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

A mixture theory model of fluid and solute transport in the microvasculature of normal and malignant tissues. I. Theory.

PubMed

Schuff, M M; Gore, J P; Nauman, E A

2013-05-01

In order to better understand the mechanisms governing transport of drugs, nanoparticle-based treatments, and therapeutic biomolecules, and the role of the various physiological parameters, a number of mathematical models have previously been proposed. The limitations of the existing transport models indicate the need for a comprehensive model that includes transport in the vessel lumen, the vessel wall, and the interstitial space and considers the effects of the solute concentration on fluid flow. In this study, a general model to describe the transient distribution of fluid and multiple solutes at the microvascular level was developed using mixture theory. The model captures the experimentally observed dependence of the hydraulic permeability coefficient of the capillary wall on the concentration of solutes present in the capillary wall and the surrounding tissue. Additionally, the model demonstrates that transport phenomena across the capillary wall and in the interstitium are related to the solute concentration as well as the hydrostatic pressure. The model is used in a companion paper to examine fluid and solute transport for the simplified case of an axisymmetric geometry with no solid deformation or interconversion of mass.

Detection of colloidal silver chloride near solubility limit

NASA Astrophysics Data System (ADS)

Putri, K. Y.; Adawiah, R.

2018-03-01

Detection of nanoparticles in solution has been made possible by several means; one of them is laser-induced breakdown detection (LIBD). LIBD is able to distinguish colloids of various sizes and concentrations. This technique has been used in several solubility studies. In this study, the formation of colloids in a mixed system of silver nitrate and sodium chloride was observed by acoustic LIBD. Silver chloride has low solubility limit, therefore LIBD measurement is appropriate. Silver and chloride solutions with equal concentrations, set at below and above the solubility of silver chloride as the expected solid product, were mixed and the resulting colloids were observed. The result of LIBD measurement showed that larger particles were present as more silver and chloride introduced. However, once the concentrations exceeded the solubility limit of silver chloride, the detected particle size seemed to be decreasing, hence suggested the occurrence of coprecipitation process. This phenomenon indicated that the ability of LIBD to detect even small changes in colloid amounts might be a useful tool in study on formation and stability of colloids, i.e. to confirm whether nanoparticles synthesis has been successfully performed and whether the system is stable or not.

Kinetics and mechanisms of the conversion of silicate (45S5), borate, and borosilicate glasses to hydroxyapatite in dilute phosphate solutions.

PubMed

Huang, Wenhai; Day, Delbert E; Kittiratanapiboon, Kanisa; Rahaman, Mohamed N

2006-07-01

Bioactive glasses with controllable conversion rates to hydroxyapatite (HA) may provide a novel class of scaffold materials for bone tissue engineering. The objective of the present work was to comprehensively characterize the conversion of a silicate bioactive glass (45S5), a borate glass, and two intermediate borosilicate glass compositions to HA in a dilute phosphate solution at 37 degrees Celsius. The borate glass and the borosilicate glasses were derived from the 45S5 glass by fully or partially replacing the SiO(2) with B(2)O(3). Higher B(2)O(3) content produced a more rapid conversion of the glass to HA and a lower pH value of the phosphate solution. Whereas the borate glass was fully converted to HA in less than 4 days, the silicate (45S5) and borosilicate compositions were only partially converted even after 70 days, and contained residual SiO(2) in a Na-depleted core. The concentration of Na(+) in the phosphate solution increased with reaction time whereas the PO(4) (3-) concentration decreased, both reaching final limiting values at a rate that increased with the B(2)O(3) content of the glass. However, the Ca(2+) concentration in the solution remained low, below the detection limit of atomic absorption, throughout the reaction. Immersion of the glasses in a mixed solution of K(2)HPO(4) and K(2)CO(3) produced a carbonate-substituted HA but the presence of the K(2)CO(3) had little effect on the kinetics of conversion to HA. The kinetics and mechanisms of the conversion process of the four glasses to HA are compared and used to develop a model for the process.

Laboratory study of polymer solutions used for mobility control during in situ NAPL recovery

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

Martel, K.E.; Martel, R.; Lefebvre, R.

1998-12-31

The use of surfactant solutions for the in situ recovery of residual NAPL in aquifers is increasingly considered as a viable remediation technique. The injection of a few pore volumes of high-concentration surfactant solutions can mobilize or solubilize most of the residual NAPL contacted by the solutions. However, the washing solutions` physico-chemical properties (low density and high viscosity), combined with the natural porous media heterogeneity, can prevent a good sweep of the entire contaminated volume. The objective of this laboratory study is first to select and characterize polymers that would be suitable for aquifer restoration. Their experiments showed that amongmore » several polymers, xanthan gum is the most suitable for aquifer remediation. An evaluation of xanthan gum solution rheology was made in order to predict shear rates, xanthan gum concentrations, salinity, and temperature effects on solution viscosity. The second set of experiments were made with a sand box which was designed to reproduce a simple heterogeneous media consisting of layers of sand with different permeability. These tests illustrate the xanthan gum solution`s ability to increase surfactant solution`s sweep efficiency and limit viscous fingering.« less

Production of nattokinase by high cell density fed-batch culture of Bacillus subtilis.

PubMed

Kwon, Eun-Yeong; Kim, Kyung Mi; Kim, Mi Kyoung; Lee, In Young; Kim, Beom Soo

2011-09-01

Bacillus subtilis was cultivated to high cell density for nattokinase production by pH-stat fed-batch culture. A concentrated mixture solution of glucose and peptone was automatically added by acid-supplying pump when culture pH rose above high limit. Effect of the ratio of glucose to peptone in feeding solution was investigated on cell growth and nattokinase production by changing the ratio from 0.2 to 5 g glucose/g peptone. The highest cell concentration was 77 g/L when the ratio was 0.2 g glucose/g peptone. Cell concentration decreased with increasing the ratio of glucose to peptone in feeding solution, while the optimum condition existed for nattokinase production. The highest nattokinase activity was 14,500 unit/mL at a ratio of 0.33 g glucose/g peptone, which was 4.3 times higher than that in batch culture.

Solute-mediated interactions between active droplets

NASA Astrophysics Data System (ADS)

Moerman, Pepijn G.; Moyses, Henrique W.; van der Wee, Ernest B.; Grier, David G.; van Blaaderen, Alfons; Kegel, Willem K.; Groenewold, Jan; Brujic, Jasna

2017-09-01

Concentration gradients play a critical role in embryogenesis, bacterial locomotion, as well as the motility of active particles. Particles develop concentration profiles around them by dissolution, adsorption, or the reactivity of surface species. These gradients change the surface energy of the particles, driving both their self-propulsion and governing their interactions. Here, we uncover a regime in which solute gradients mediate interactions between slowly dissolving droplets without causing autophoresis. This decoupling allows us to directly measure the steady-state, repulsive force, which scales with interparticle distance as F ˜1 /r2 . Our results show that the dissolution process is diffusion rather than reaction rate limited, and the theoretical model captures the dependence of the interactions on droplet size and solute concentration, using a single fit parameter, l =16 ±3 nm , which corresponds to the length scale of a swollen micelle. Our results shed light on the out-of-equilibrium behavior of particles with surface reactivity.

Accumulation of Colloidal Particles in Flow Junctions Induced by Fluid Flow and Diffusiophoresis

NASA Astrophysics Data System (ADS)

Shin, Sangwoo; Ault, Jesse T.; Warren, Patrick B.; Stone, Howard A.

2017-10-01

The flow of solutions containing solutes and colloidal particles in porous media is widely found in systems including underground aquifers, hydraulic fractures, estuarine or coastal habitats, water filtration systems, etc. In such systems, solute gradients occur when there is a local change in the solute concentration. While the effects of solute gradients have been found to be important for many applications, we observe an unexpected colloidal behavior in porous media driven by the combination of solute gradients and the fluid flow. When two flows with different solute concentrations are in contact near a junction, a sharp solute gradient is formed at the interface, which may allow strong diffusiophoresis of the particles directed against the flow. Consequently, the particles accumulate near the pore entrance, rapidly approaching the packing limit. These colloidal dynamics have important implications for the clogging of a porous medium, where particles that are orders of magnitude smaller than the pore width can accumulate and block the pores within a short period of time. We also show that this effect can be exploited as a useful tool for preconcentrating biomolecules for rapid bioassays.

Thermodynamic modeling of solid solutions between monosulfate and monochromate 3CaO Bullet Al{sub 2}O{sub 3} Bullet Ca[(CrO{sub 4}){sub x}(SO{sub 4}){sub 1-x}] Bullet nH{sub 2}O

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

Leisinger, Sabine M., E-mail: sabine.leisinger@eawag.ch; Institute of Biogeochemistry and Pollutant Dynamics, ETH, CH-8092 Zurich; Lothenbach, Barbara

2012-01-15

In hydrated cement paste AFm-phases are regarded to play an important role in the binding of the toxic contaminant chromate through isomorphic substitution with sulfate. Solid solutions formation can lower the solubility of the solids, thus reducing chromate leaching concentrations. Solid solutions between monosulfate and monochromate were synthesized and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Based on the measured ion concentrations in solution total solubility products of the solid solution series were determined. For pure monochromate a logK = - 28.4more » {+-} 0.7 was determined. Results from solid and solution analysis showed that limited solid solutions exist. Based on XRD diffractograms a solid solution with a miscibility gap 0.15 < Crx < 0.85 with a dimensionless Guggenheim parameter of 2.43 was proposed.« less

On the modeling of irradiation-induced homogeneous precipitation in proton-bombarded Ni-Si solid solutions

NASA Astrophysics Data System (ADS)

Lam, Nghi Q.; Janghorban, K.; Ardell, A. J.

1981-10-01

Irradiation-induced solute redistribution leading to precipitation of coherent γ' particles in undersaturated Ni-based solid solutions containing 6 and 8 at.% Si during 400-keV proton bombardment was modeled, based on the concept of solute segregation in concentrated alloys under spatially-dependent defect production conditions. The combined effects of (i) an extremely large difference between the defect production rates in the peak-damage and mid-range regions during irradiation and (ii) a preferential coupling between the interstitial and solute fluxes generate a net transient flux of Si atoms into the mid-range region, which is much larger than the solute flux out of this location. As a result, the Si concentration exceeds the solubility limit and homogeneous precipitation of the γ' phase occurs in this particular region of the irradiated samples. The spatial, compositional and temperature dependences of irradiation-induced homogeneous precipitation derived from the present theoretical calculations are in good qualitative agreement with experimental observations

Novel three-stage kinetic model for aqueous benzene adsorption on activated carbon.

PubMed

Choi, Jae-Woo; Choi, Nag-Choul; Lee, Soon-Jae; Kim, Dong-Ju

2007-10-15

We propose a novel kinetic model for adsorption of aqueous benzene onto both granular activated carbon (GAC) and powdered activated carbon (PAC). The model is based on mass conservation of benzene coupled with three-stage adsorption: (1) the first portion for an instantaneous stage or external surface adsorption, (2) the second portion for a gradual stage with rate-limiting intraparticle diffusion, and (3) the third portion for a constant stage in which the aqueous phase no longer interacts with activated carbon. An analytical solution of the kinetic model was validated with the kinetic data obtained from aqueous benzene adsorption onto GAC and PAC in batch experiments with two different solution concentrations (C(0)=300 mg L(-1), 600 mg L(-1)). Experimental results revealed that benzene adsorption for the two concentrations followed three distinct stages for PAC but two stages for GAC. The analytical solution could successfully describe the kinetic adsorption of aqueous benzene in the batch reaction system, showing a fast instantaneous adsorption followed by a slow rate-limiting adsorption and a final long constant adsorption. Use of the two-stage model gave incorrect values of adsorption coefficients in the analytical solution due to inability to describe the third stage.

Chemical Sensors Based on IR Spectroscopy and Surface-Modified Waveguides

NASA Technical Reports Server (NTRS)

Lopez, Gabriel P.; Niemczyk, Thomas

1999-01-01

Sol-gel processing techniques have been used to apply thin porous films to the surfaces of planar infrared (IR) waveguides to produce widely useful chemical sensors. The thin- film coating serves to diminish the concentration of water and increase the concentration of the analyte in the region probed by the evanescent IR wave. These porous films are composed of silica, and therefore, conventional silica surface modification techniques can be used to give the surface a specific functional character. The sol-gel film was surface-modified to make the film highly hydrophobic. These sensors were shown to be capable of detecting non-polar organic analytes, such as benzonitrile, in aqueous solution with detection limits in the ppb range. Further, these porous sol-gel structures allow the analytes to diffuse into and out of the films rapidly, thus reaching equilibrium in less than ten seconds. These sensors are unique because of the fact that their operation is based on the measurement of an IR absorption spectrum. Thus, these sensors are able to identify the analytes as well as measure concentration with high sensitivity. These developments have been documented in previous reports and publications. Recently, we have also targeted detection of the polar organic molecules acetone and isopropanol in aqueous solution. Polar organics are widely used in industrial and chemical processes, hence it is of interest to monitor their presence in effluents or decontamination process flows. Although large improvements in detection limits were expected with non-polar organic molecules in aqueous solutions using very hydrophobic porous sol-gel films on silicon attenuated total reflectance (Si ATR) waveguides, it was not as clear what the detection enhancements might be for polar organic molecules. This report describes the use of modified sol-gel-coated Si ATR sensors for trace detection and quantitation of small polar organic molecules in aqueous solutions. The detection of both acetone and isopropanol molecules in aqueous solution has been previously reported for chalcogenide fiber optic sensors. The sol-gel film was produced using a mixture of ethyltriethoxysilane and tetraethoxysilane and the surface modification was carried out using trimethylchlorosilane. We have demonstrated that this film concentrates the target polar analytes from aqueous solution in the region probed by the evanescent wave to improve detection limits by as much as a factor of 450.

Contribution of extracellular ice formation and the solution effects to the freezing injury of PC-3 cells suspended in NaCl solutions.

PubMed

Takamatsu, Hiroshi; Zawlodzka, Sylwia

2006-08-01

The mechanism of cell injury during slow freezing was examined using PC-3 human prostate adenocarcinoma cells suspended in NaCl solutions. The objective was to evaluate contribution of extracellular ice and the 'solution effects' to freezing injury separately. The solution effects that designate the influence of elevated concentration were evaluated from a pseudo-freezing experiment, where cells were subjected to the milieu that simulated a freeze-thaw process by changing the NaCl concentration and the temperature at the same time. The effect of extracellular ice formation on cell injury was then estimated from the difference in cell survival between the pseudo-freezing experiment and a corresponding freezing experiment. When cells were frozen to a relatively higher freezing temperature at -10 degrees C, about 30% of cells were damaged mostly due to extracellular ice formation, because the concentration increase without ice formation to 2.5-M NaCl, i.e., the equilibrium concentration at -10 degrees C, had no effect on cell survival. In contrast, in the case of the lower freezing temperature at -20 degrees C, about 90% of cells were injured by both effects, particularly 60-80% by the solution effects among them. The present results suggested that the solution effects become more crucial to cell damage during slow freezing at lower temperatures, while the effect of ice is limited to some extent.

Coupling a Reactive Transport Code with a Global Land Surface Model for Mechanistic Biogeochemistry Representation: 1. Addressing the Challenge of Nonnegativity

DOE PAGES

Tang, Guoping; Yuan, Fengming; Bisht, Gautam; ...

2016-01-01

Reactive transport codes (e.g., PFLOTRAN) are increasingly used to improve the representation of biogeochemical processes in terrestrial ecosystem models (e.g., the Community Land Model, CLM). As CLM and PFLOTRAN use explicit and implicit time stepping, implementation of CLM biogeochemical reactions in PFLOTRAN can result in negative concentration, which is not physical and can cause numerical instability and errors. The objective of this work is to address the nonnegativity challenge to obtain accurate, efficient, and robust solutions. We illustrate the implementation of a reaction network with the CLM-CN decomposition, nitrification, denitrification, and plant nitrogen uptake reactions and test the implementation atmore » arctic, temperate, and tropical sites. We examine use of scaling back the update during each iteration (SU), log transformation (LT), and downregulating the reaction rate to account for reactant availability limitation to enforce nonnegativity. Both SU and LT guarantee nonnegativity but with implications. When a very small scaling factor occurs due to either consumption or numerical overshoot, and the iterations are deemed converged because of too small an update, SU can introduce excessive numerical error. LT involves multiplication of the Jacobian matrix by the concentration vector, which increases the condition number, decreases the time step size, and increases the computational cost. Neither SU nor SE prevents zero concentration. When the concentration is close to machine precision or 0, a small positive update stops all reactions for SU, and LT can fail due to a singular Jacobian matrix. The consumption rate has to be downregulated such that the solution to the mathematical representation is positive. A first-order rate downregulates consumption and is nonnegative, and adding a residual concentration makes it positive. For zero-order rate or when the reaction rate is not a function of a reactant, representing the availability limitation of each reactant with a Monod substrate limiting function provides a smooth transition between a zero-order rate when the reactant is abundant and first-order rate when the reactant becomes limiting. When the half saturation is small, marching through the transition may require small time step sizes to resolve the sharp change within a small range of concentration values. Our results from simple tests and CLM-PFLOTRAN simulations caution against use of SU and indicate that accurate, stable, and relatively efficient solutions can be achieved with LT and downregulation with Monod substrate limiting function and residual concentration.« less

A pilot-scale forward osmosis membrane system for concentrating low-strength municipal wastewater: performance and implications

PubMed Central

Wang, Zhiwei; Zheng, Junjian; Tang, Jixu; Wang, Xinhua; Wu, Zhichao

2016-01-01

Recovery of nutrients and energy from municipal wastewater has attracted much attention in recent years; however, its efficiency is significantly limited by the low-strength properties of municipal wastewater. Herein, we report a pilot-scale forward osmosis (FO) system using a spiral-wound membrane module to concentrate real municipal wastewater. Under active layer facing feed solution mode, the critical concentration factor (CCF) of this FO system was determined to be 8 with 0.5 M NaCl as draw solution. During long-term operation at a concentration factor of 5, (99.8 ± 0.6)% of chemical oxygen demand and (99.7 ± 0.5)% of total phosphorus rejection rates could be achieved at a flux of 6 L/(m2 h) on average. In comparison, only (48.1 ± 10.5)% and (67.8 ± 7.3)% rejection of ammonium and total nitrogen were observed. Cake enhanced concentration polarization is a major contributor to the decrease of water fluxes. The fouling also led to the occurrence of a cake reduced concentration polarization effect, improving ammonium rejection rate with the increase of operation time in each cycle. This work demonstrates the applicability of using FO process for wastewater concentrating and also limitations in ammonium recovery that need further improvement in future. PMID:26898640

HPLC separation post-column reaction, UV-visible and fluorescence detection of trace UO/sub 2//sup 2 +//U/sup 4 +/ species in aqueous solutions

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

Karimi, A.R.

In this study a method for the measurement of uranium in natural waters at sub-ppB concentration levels by the separation and determination of U/sup 4 +/ and UO/sub 2//sup 2 +/ species is proposed. Reversed phase high performance liquid chromatography, followed by a post-column reaction and a sensitive UV-visible detection system was the method of choice to determine qualitatively and quantitatively the two uranium species. Also a cation-exchange and fluorescence detection system was studied for separation and determination of UO/sub 2//sup 2 +/ ions. Uranyl ion was selectively complexed with L-phenylalanine moetie in the sample solution containing U/sup 4 +/more » ions. Uranium (IV)/U(VI)-ligand was separated on a C/sub 18/ column with acetate buffer. Hexanesulfonate was found to be the choice for ion-pair reagent. The separation was best done with the acetate buffer at .01 M concentration and pH of 3.5. Absorption of the two species were measured after a post-column reaction with Arsenazo-III. Chromatographic parameters were calculated and a calibration curves were constructed. The detection limit for the procedure was 0.7 ..mu..g/mo and 1.2..mu..g/ml for U(IV) and U(VI) respectively. When U(VI) was separated on the cation-exchange column the limit of detection was calculated to be 1 ..mu..g/ml. The direct fluorometric method for U(VI) measurement results in a detection limit of 2 ppB and upper concentration limit of 2 ppM. The effect of interfering ions in the direct method of determination could be eliminated by dilution of sample solution.« less

Evaluation of a Compartmental Model for Prediction of Nitrate Leaching Losses,

DTIC Science & Technology

1981-12-01

model results limit their utility, the calculated total dissolved solids (TDS) of the soil solution (7146 mg L-1) and the measured TDS of tile...measured values of plant uptake, residual inorganic N and average annual In eq 1, the term on the left-hand side represents soil solution N concentrations...Research Applied to National the soil solution below which the uptake efficiency Needs, decreases sharply. 11 Table 3. Summary of water input data (cm of H2

Determination of aliphatic amines in mineral flotation liquors and reagents by high-performance liquid chromatography after derivatization with 4-chloro-7-nitrobenzofurazan.

PubMed

Hao, F; Lwin, T; Bruckard, W J; Woodcock, J T

2004-11-05

The method described here fulfils the need for a suitable analytical method to determine the concentrations of single and mixed aliphatic amines in the range from hexylamine (C6) to octadecylamine (C18) in flotation test solutions and in commercial flotation collectors. Amines do not have a UV-vis spectrum in aqueous solution but by reacting an amine-containing solution with 4-chloro-7-nitrobenzofurazan solution (chloro-NBD), derivatized products (amino-NBDs) are formed which have absorbance maxima at 470nm. Excess chloro-NBD and the amino-NBDs can be separated from each other by high-performance liquid chromatography (HPLC) and their concentrations measured with a UV-vis detector. Important variables in the derivatization stage are pH, temperature, chloro-NBD concentration, and reaction time, all of which interact with each other. A three-stage statistical procedure was used to determine the optimum conditions. In each stage, an 8-test design was used in which a high and low limit was set for each variable, and the chromatogram peak area of the derived amino-NBD was measured. The optimum derivatization conditions established were pH 8.9, chloro-NBD concentration 0.20% (w/v), temperature 70 degrees C, and reaction time 60 min. Optimum elution conditions for chromatography were an eluent containing 80% (v/v) acetonitrile in aqueous solution containing 40mM acetic acid at pH 4.5. With a flow rate of 2.0 ml/min, dodecylamine had a retention time of about 3 min, whereas octadecylamine had a retention time of 44 min. Straight-line calibration curves were obtained up to at least 200 ppm of amine in solution. The lower limit of detection was estimated to be 0.05 microM (10ppb) with a signal to noise ratio of 3. No interfering substances were found. The method was successfully applied to the analysis of solutions from an actual flotation test and to a solid commercial amine.

Role of Transport and Kinetics in Growth of Renal Stones

NASA Technical Reports Server (NTRS)

Kassemi, Mohammad; Iskovitz, Ilana

2012-01-01

Renal stone disease is not only a concern on earth but could conceivably pose as a serious risk to the astronauts health and safety in Space. In this paper, a combined transport-kinetics model for growth of calcium oxalate crystals is presented. The model is used to parametrically investigate the growth of renal calculi in urine with a focus on the coupled effects of transport and surface reaction on the ionic concentrations at the surface of the crystal and their impact on the resulting growth rates. It is shown that under nominal conditions of low solution supersaturation and low Damkohler number that typically exist on Earth, the surface concentrations of calcium and oxalate approach their bulk solution values in the urine and the growth rate is most likely limited by the surface reaction kinetics. But for higher solution supersaturations and larger Damkohler numbers that may be prevalent in the microgravity environment of Space, the calcium and oxalate surface concentrations tend to shift more towards their equilibrium or saturation values and thus the growth process may be limited by the transport through the medium. Furthermore, parametric numerical studies suggest that changes to the renal biochemistry of astronauts due in space may promote development of renal calculi during long duration space expeditions.

The kinetics of nucleated polymerizations at high concentrations: amyloid fibril formation near and above the "supercritical concentration".

PubMed

Powers, Evan T; Powers, David L

2006-07-01

The formation of amyloid and other types of protein fibrils is thought to proceed by a nucleated polymerization mechanism. One of the most important features commonly associated with nucleated polymerizations is a strong dependence of the rate on the concentration. However, the dependence of fibril formation rates on concentration can weaken and nearly disappear as the concentration increases. Using numerical solutions to the rate equations for nucleated polymerization and analytical solutions to some limiting cases, we examine this phenomenon and show that it is caused by the concentration approaching and then exceeding the equilibrium constant for dissociation of monomers from species smaller than the nucleus, a quantity we have named the "supercritical concentration". When the concentration exceeds the supercritical concentration, the monomer, not the nucleus, is the highest-energy species on the fibril formation pathway, and the fibril formation reaction behaves initially like an irreversible polymerization. We also derive a relation that can be used in a straightforward method for determining the nucleus size and the supercritical concentration from experimental measurements of fibril formation rates.

Direct identification and analysis of heavy metals in solution (Hg, Cu, Pb, Zn, Ni) by use of in situ electrochemical X-ray fluorescence.

PubMed

O'Neil, Glen D; Newton, Mark E; Macpherson, Julie V

2015-01-01

The development and application of a new methodology, in situ electrochemical X-ray fluorescence (EC-XRF), is described that enables direct identification and quantification of heavy metals in solution. A freestanding film of boron-doped diamond serves as both an X-ray window and the electrode material. The electrode is biased at a suitable driving potential to electroplate metals from solution onto the electrode surface. Simultaneously, X-rays that pass through the back side of the electrode interrogate the time-dependent electrodeposition process by virtue of the XRF signals, which are unique to each metal. In this way it is possible to unambiguously identify which metals are in solution and relate the XRF signal intensity to a concentration of metal species in solution. To increase detection sensitivity and reduce detection times, solution is flown over the electrode surface by use of a wall-jet configuration. Initial studies focused on the in situ detection of Pb(2+), where concentration detection limits of 99 nM were established in this proof-of-concept study (although significantly lower values are anticipated with system refinement). This is more than 3 orders of magnitude lower than that achievable by XRF alone in a flowing solution (0.68 mM). In situ EC-XRF measurements were also carried out on a multimetal solution containing Hg(2+), Pb(2+), Cu(2+), Ni(2+), Zn(2+), and Fe(3+) (all at 10 μM concentration). Identification of five of these metals was possible in one simple measurement. In contrast, while anodic stripping voltammetry (ASV) also revealed five peaks, peak identification was not straightforward, requiring further experiments and prior knowledge of the metals in solution. Time-dependent EC-XRF nucleation data for the five metals, recorded simultaneously, demonstrated similar deposition rates. Studies are now underway to lower detection limits and provide a quantitative understanding of EC-XRF responses in real, multimetal solutions. Finally, the production of custom-designed portable in situ EC-XRF instrumentation will make heavy metal analysis at the source a very realistic possibility.

iron phase control during pressure leaching at elevated temperature

NASA Astrophysics Data System (ADS)

Fleuriault, Camille

Iron is a common contaminant encountered in most metal recovery operations, and particularly hydrometallurgical processes. For example, the Hematite Process uses autoclaves to precipitate iron oxide out of the leaching solution, while other metals are solubilized for further hydrometallurgical processing. In some cases, Basic Iron Sulfate (BIS) forms in place of hematite. The presence of BIS is unwanted in the autoclave discharge because it diminishes recovery and causes environmental matters. The focus of this master thesis is on the various iron phases forming during the pressure oxidation of sulfates. Artificial leaching solutions were produced from CuSO4, FeSO4 and H2SO4 in an attempt to recreate the matrix composition and conditions used for copper sulfides autoclaving. The following factors were investigated in order to determine which conditions hinder the formation of BIS: initial free acidity (5 -- 98 g/L), initial copper concentration (12.7 -- 63.5 g/L), initial iron concentration (16.7 -- 30.7 g/L) and initial iron oxidation state. There were three solid species formed in the autoclave: hematite, BIS and hydronium jarosite. The results show that free acid is the main factor influencing the composition of the residue. At an initial concentration of 22.3 g/L iron and no copper added, the upper limit for iron oxide formation is 41 g/L H2SO4. The increase of BIS content in the residue is not gradual and occurs over a change of a few grams per liter around the aforementioned limit. Increasing copper sulfate concentration in the solution hinders the formation of BIS. At 63.5g/L copper, the upper free acidity limit is increased to 61g/L. This effect seems to be related to the buffering action of copper sulfate, decreasing the overall acid concentration and thus extending the stability range of hematite. The effect of varying iron concentration on the precipitate chemistry is unclear. At high iron levels, the only noticeable effect was the inhibition of jarosite. The results were reported within a Cu-Fe-S ternary system and modeled. The modeling confirmed the experimental observations with the exception that increasing iron concentrations seem to promote BIS stability.

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

NASA Technical Reports Server (NTRS)

Pusey, Marc L.; Forsythe, Elizabeth; Sumida, John; Maxwell, Daniel; Gorti, Sridhar; Curreri, Peter A. (Technical Monitor)

2002-01-01

Experimental evidence indicates a dominant role of solution phase interactions in nucleating and growing tetragonal lysozyme crystals. These interactions are extensive, even at saturation, and may be a primary cause of misoriented regions in crystals grown on Earth. Microgravity, by limiting interfacial concentrations to diffusion-controlled levels, may benefit crystal quality by also reducing the extent of associated species present at the interface.

Relationship between metal speciation in soil solution and metal adsorption at the root surface of ryegrass.

PubMed

Kalis, Erwin J J; Temminghoff, Erwin J M; Town, Raewyn M; Unsworth, Emily R; van Riemsdijk, Willem H

2008-01-01

The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.

The relationship between pH and concentrations of antioxidants and vasoconstrictors in local anesthetic solutions.

PubMed

Hondrum, S O; Ezell, J H

1996-01-01

pH affects the efficacy of local anesthetics by determining the percentage of the lipid-soluble base form of the anesthetic available for diffusion and penetration of the nerve sheath. The purpose of this study was to determine the relationship between pH and the concentrations of antioxidant and vasoconstrictor in dental local anesthetic solutions over real-time and after accelerated aging. Several batches of lidocaine and mepivacaine with vasoconstrictors were tested. Results showed that, immediately upon receipt from the manufacturers, three batches were below the USP pH limit (pH 3.3), and two batches contained less than the minimum limit of vasoconstrictors (90%). Real-time tests on batches that were within normal limits revealed that solutions were stable past 4 yr. Accelerated aging tests revealed a strong correlation between a decrease in pH and loss of antioxidants and vasoconstrictors. In conclusion, a quality batch of local anesthetic should remain efficacious long past the manufacturer's stated shelf life; a batch that is less than optimal, or one that is exposed to environmental stresses, will degrade rapidly, and efficacy may be affected by decreases in pH and loss of vasoconstrictor. pH may be an inexpensive, readily available screening test for efficacy of local anesthetics.

The relationship between pH and concentrations of antioxidants and vasoconstrictors in local anesthetic solutions.

PubMed Central

Hondrum, S. O.; Ezell, J. H.

1996-01-01

pH affects the efficacy of local anesthetics by determining the percentage of the lipid-soluble base form of the anesthetic available for diffusion and penetration of the nerve sheath. The purpose of this study was to determine the relationship between pH and the concentrations of antioxidant and vasoconstrictor in dental local anesthetic solutions over real-time and after accelerated aging. Several batches of lidocaine and mepivacaine with vasoconstrictors were tested. Results showed that, immediately upon receipt from the manufacturers, three batches were below the USP pH limit (pH 3.3), and two batches contained less than the minimum limit of vasoconstrictors (90%). Real-time tests on batches that were within normal limits revealed that solutions were stable past 4 yr. Accelerated aging tests revealed a strong correlation between a decrease in pH and loss of antioxidants and vasoconstrictors. In conclusion, a quality batch of local anesthetic should remain efficacious long past the manufacturer's stated shelf life; a batch that is less than optimal, or one that is exposed to environmental stresses, will degrade rapidly, and efficacy may be affected by decreases in pH and loss of vasoconstrictor. pH may be an inexpensive, readily available screening test for efficacy of local anesthetics. PMID:10323112

Evaluation of Shiryaev-Roberts procedure for on-line environmental radiation monitoring.

PubMed

Watson, Mara M; Seliman, Ayman F; Bliznyuk, Valery N; DeVol, Timothy A

2018-04-30

Water can become contaminated as a result of a leak from a nuclear facility, such as a waste facility, or from clandestine nuclear activity. Low-level on-line radiation monitoring is needed to detect these events in real time. A Bayesian control chart method, Shiryaev-Roberts (SR) procedure, was compared with classical methods, 3-σ and cumulative sum (CUSUM), for quantifying an accumulating signal from an extractive scintillating resin flow-cell detection system. Solutions containing 0.10-5.0 Bq/L of 99 Tc, as T99cO 4 - were pumped through a flow cell packed with extractive scintillating resin used in conjunction with a Beta-RAM Model 5 HPLC detector. While T99cO 4 - accumulated on the resin, time series data were collected. Control chart methods were applied to the data using statistical algorithms developed in MATLAB. SR charts were constructed using Poisson (Poisson SR) and Gaussian (Gaussian SR) probability distributions of count data to estimate the likelihood ratio. Poisson and Gaussian SR charts required less volume of radioactive solution at a fixed concentration to exceed the control limit in most cases than 3-σ and CUSUM control charts, particularly solutions with lower activity. SR is thus the ideal control chart for low-level on-line radiation monitoring. Once the control limit was exceeded, activity concentrations were estimated from the SR control chart using the control chart slope on a semi-logarithmic plot. A linear regression fit was applied to averaged slope data for five activity concentration groupings for Poisson and Gaussian SR control charts. A correlation coefficient (R 2 ) of 0.77 for Poisson SR and 0.90 for Gaussian SR suggest this method will adequately estimate activity concentration for an unknown solution. Copyright © 2018 Elsevier Ltd. All rights reserved.

Imidacloprid movement in soils and impacts on soil microarthropods in southern Appalachian eastern hemlock stands.

PubMed

Knoepp, Jennifer D; Vose, James M; Michael, Jerry L; Reynolds, Barbara C

2012-01-01

Imidacloprid is a systemic insecticide effective in controlling the exotic pest (hemlock woolly adelgid) in eastern hemlock () trees. Concerns over imidacloprid impacts on nontarget species have limited its application in southern Appalachian ecosystems. We quantified the movement and adsorption of imidacloprid in forest soils after soil injection in two sites at Coweeta Hydrologic Laboratory in western North Carolina. Soils differed in profile depth, total carbon and nitrogen content, and effective cation exchange capacity. We injected imidacloprid 5 cm into mineral soil, 1.5 m from infested trees, using a Kioritz soil injector. We tracked the horizontal and vertical movement of imidacloprid by collecting soil solution and soil samples at 1 m, 2 m, and at the drip line from each tree periodically for 1 yr. Soil solution was collected 20 cm below the surface and just above the saprolite, and acetonitrile-extractable imidacloprid was determined through the profile. Soil solution and extractable imidacloprid concentrations were determined by high-performance liquid chromatography. Soil solution and extractable imidacloprid concentrations were greater in the site with greater soil organic matter. Imidacloprid moved vertically and horizontally in both sites; concentrations generally declined downward in the soil profile, but preferential flow paths allowed rapid vertical movement. Horizontal movement was limited, and imidacloprid did not move to the tree drip line. We found a negative relationship between adsorbed imidacloprid concentrations and soil microarthropod populations largely in the low-organic-matter site; however, population counts were similar to other studies at Coweeta. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Suppression of vacancy cluster growth in concentrated solid solution alloys

DOE PAGES

Zhao, Shijun; Velisa, Gihan; Xue, Haizhou; ...

2016-12-13

Large vacancy clusters, such as stacking-fault tetrahedra, are detrimental vacancy-type defects in ion-irradiated structural alloys. Suppression of vacancy cluster formation and growth is highly desirable to improve the irradiation tolerance of these materials. In this paper, we demonstrate that vacancy cluster growth can be inhibited in concentrated solid solution alloys by modifying cluster migration pathways and diffusion kinetics. The alloying effects of Fe and Cr on the migration of vacancy clusters in Ni concentrated alloys are investigated by molecular dynamics simulations and ion irradiation experiment. While the diffusion coefficients of small vacancy clusters in Ni-based binary and ternary solid solutionmore » alloys are higher than in pure Ni, they become lower for large clusters. This observation suggests that large clusters can easily migrate and grow to very large sizes in pure Ni. In contrast, cluster growth is suppressed in solid solution alloys owing to the limited mobility of large vacancy clusters. Finally, the differences in cluster sizes and mobilities in Ni and in solid solution alloys are consistent with the results from ion irradiation experiments.« less

Detox{sup SM} wet oxidation system studies for engineering scale up

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

Robertson, D.T.; Moslander, J.E.; Zigmond, J.A.

1995-12-31

Catalyzed wet oxidation utilizing iron(III) has been shown to have promise for treating many hazardous and mixed wastes. The reaction occurs at the surface of contact between an aqueous iron(III) solution and organic material. Studies with liquid- and vapor-phase organic waste surrogates have established reaction kinetics and the limits of reaction rate based on organic concentration and iron(III) diffusion. Continuing engineering studies have concentrated on reaction vessel agitator and solids feed configurations, an improved bench scale reflux condenser and reflux condenser calculations, sparging of organic compounds from the process condensate water, filtration of solids from the process solution, and flammabilitymore » limits for volatile organic compounds in the headspace of the reaction vessel under the reaction conditions. Detailed engineering design and fabrication of a demonstration unit for treatment of mixed waste is in progress.« less

Interferometric measurements of a dendritic growth front solutal diffusion layer

NASA Technical Reports Server (NTRS)

Hopkins, John A.; Mccay, T. D.; Mccay, Mary H.

1991-01-01

An experimental study was undertaken to measure solutal distributions in the diffusion layer produced during the vertical directional solidification (VDS) of an ammonium chloride - water (NH4Cl-H2O) solution. Interferometry was used to obtain concentration measurements in the 1-2 millimeter region defining the diffusion layer. These measurements were fitted to an exponential form to extract the characteristic diffusion parameter for various times after the start of solidification. The diffusion parameters are within the limits predicted by steady state theory and suggest that the effective solutal diffusivity is increasing as solidification progresses.

Roles of conformational stability and colloidal stability in the aggregation of recombinant human granulocyte colony-stimulating factor

PubMed Central

Chi, Eva Y.; Krishnan, Sampathkumar; Kendrick, Brent S.; Chang, Byeong S.; Carpenter, John F.; Randolph, Theodore W.

2003-01-01

We studied the non-native aggregation of recombinant human granulocyte stimulating factor (rhGCSF) in solution conditions where native rhGCSF is both conformationally stable compared to its unfolded state and at concentrations well below its solubility limit. Aggregation of rhGCSF first involves the perturbation of its native structure to form a structurally expanded transition state, followed by assembly process to form an irreversible aggregate. The energy barriers of the two steps are reflected in the experimentally measured values of free energy of unfolding (ΔGunf) and osmotic second virial coefficient (B22), respectively. Under solution conditions where rhGCSF conformational stability dominates (i.e., large ΔGunf and negative B22), the first step is rate-limiting, and increasing ΔGunf (e.g., by the addition of sucrose) decreases aggregation. In solutions where colloidal stability is high (i.e., large and positive B22 values) the second step is rate-limiting, and solution conditions (e.g., low pH and low ionic strength) that increase repulsive interactions between protein molecules are effective at reducing aggregation. rhGCSF aggregation is thus controlled by both conformational stability and colloidal stability, and depending on the solution conditions, either could be rate-limiting. PMID:12717013

Applicability of refractometry for fast routine checking of hospital preparations.

PubMed

Hendrickx, Stijn; Verón, Aurora Monteagudo; Van Schepdael, Ann; Adams, Erwin

2016-04-30

Quality control of hospital pharmacy formulations is of the utmost importance to ensure constant quality and to avoid potential mistakes before administration to the patient. In this study we investigated the applicability of refractometry as a fast, inexpensive and easy-to-use quality control measurement. Refractive indices (RI) of a multitude of different hospital formulations with varying concentrations of active compound were measured. The samples consisted of a number of binary aqueous solutions (one compound in water), complex aqueous solutions (multiple compounds in water or in a constant matrix), two suspensions and one emulsion. For all these formulations, linear regression analysis was performed, quality control limits determined and accuracy and repeatability were checked. Subsequently, actual hospital pharmacy samples were analyzed to check whether they were within the specified limits. For both binary and complex aqueous formulations, repeatability was good and a linear correlation for all samples could be observed on condition that the concentration of the active compound was sufficiently high. The refractometer was not sensitive enough for solutions of folic acid and levothyroxine, which had too low a concentration of active compound. Due to lack of homogeneity and light scattering, emulsions and suspensions do not seem suitable for quality control by refractometry. A mathematical equation was generated to predict the refractive index of an aqueous solution containing clonidine HCl as active compound. Values calculated from the equation were compared with measured values and deviations of all samples were found to be lower than 1.3%. In order to use refractometry in a hospital pharmacy for quality control of multicomponent samples, additional intermediate measurements would be required, to overcome the fact that refractometry is not compound specific. In conclusion, we found that refractometry could potentially be useful for daily, fast quality measurements of relatively concentrated binary and more complex aqueous solutions in the hospital pharmacy. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of inoculum type and bulk dissolved oxygen concentration on achieving partial nitrification by entrapped-cell-based reactors.

PubMed

Rongsayamanont, Chaiwat; Limpiyakorn, Tawan; Khan, Eakalak

2014-07-01

An entrapment of nitrifiers into gel matrix is employed as a tool to fulfill partial nitrification under non-limiting dissolved oxygen (DO) concentrations in bulk solutions. This study aims to clarify which of these two attributes, inoculum type and DO concentration in bulk solutions, is the decisive factor for partial nitrification in an entrapped-cell based system. Four polyvinyl alcohol entrapped inocula were prepared to have different proportions of nitrite-oxidizing bacteria (NOB) and nitrite-oxidizing activity. At a DO concentration of 3 mg l(-1), the number of active NOB cells in an inoculum was the decisive factor for partial nitrification enhancement. However, when the DO concentration was reduced to 2 mg l(-1), all entrapped cell inocula showed similar degrees of partial nitrification. The results suggested that with the lower bulk DO concentration, the preparation of entrapped cell inocula is not useful as the DO level becomes the decisive factor for achieving partial nitrification. Copyright © 2014 Elsevier Ltd. All rights reserved.

An approximate stationary solution for multi-allele neutral diffusion with low mutation rates.

PubMed

Burden, Conrad J; Tang, Yurong

2016-12-01

We address the problem of determining the stationary distribution of the multi-allelic, neutral-evolution Wright-Fisher model in the diffusion limit. A full solution to this problem for an arbitrary K×K mutation rate matrix involves solving for the stationary solution of a forward Kolmogorov equation over a (K-1)-dimensional simplex, and remains intractable. In most practical situations mutations rates are slow on the scale of the diffusion limit and the solution is heavily concentrated on the corners and edges of the simplex. In this paper we present a practical approximate solution for slow mutation rates in the form of a set of line densities along the edges of the simplex. The method of solution relies on parameterising the general non-reversible rate matrix as the sum of a reversible part and a set of (K-1)(K-2)/2 independent terms corresponding to fluxes of probability along closed paths around faces of the simplex. The solution is potentially a first step in estimating non-reversible evolutionary rate matrices from observed allele frequency spectra. Copyright © 2016 Elsevier Inc. All rights reserved.

Study of solvent sublation for concentration of trace phthalate esters in plastic beverage packaging and analysis by gas chromatography-mass spectrometry.

PubMed

Chang, Lin; Bi, Pengyu; Li, Xiaochen; Wei, Yun

2015-06-15

A novel trace analytical method based on solvent sublation (SS) and gas chromatography-mass spectrometry (GC-MS) was developed for the trace determination of twenty-two phthalate esters (PAEs) from plastic beverage packaging. In the solvent sublation section, the effects of solution pH, NaCl concentration, nitrogen flow rate, and sublation time on the sublation efficiency were investigated in detail, and the optimal conditions were obtained. The trace PAEs migrated from plastic beverage packaging to food simulants were separated and concentrated by solvent sublation, and then the trace target compounds in the concentrated solution were analyzed by GC-MS. According to the European Union Regulation, the food simulants including distilled water for the normal beverages and acetic acid solution (3%) for the acetic beverage of yogurt were prepared for migration tests. The trace analysis method showed good linearity, low limits of detection (LODs) of 1.6-183.5 ng/L, and satisfied recoveries (67.3-113.7%). Copyright © 2015 Elsevier Ltd. All rights reserved.

Fabrication of Polyvinylpyrrolidone Fibers by Means of Rotary Forcespinning Method

NASA Astrophysics Data System (ADS)

Andjani, D.; Sriyanti, I.; Fauzi, A.; Edikresnha, D.; Munir, M. M.; Khairurrijal

2018-05-01

Fibers made from polymer materials have been widely developed as a carrier medium of active ingredients in drug delivery systems. In this research, PVP polymer was chosen because of its wide and safe use in the medical field. The purpose of this study was to produce PVP fibers that can later be applied as a carrier of active ingredients in drug delivery systems. The rotary forcespinning (RFS) method was chosen to shorten the time of production and to overcome the limitations of electrospinning method such as the use of high voltage and dielectric solutions. The PVP solution was varied in several concentrations (8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, and 18 wt%) to achieve the best fibers morphology. The morphology and the diameter of fibers were analyzed using a digital microscope. From the microscope images, it can be shown that beaded fibers were formed when the concentration of polymer in the precursor solution was low. The number of beads decreased as the concentration of polymer increased. Beads-free fibers were fully formed at above certain polymer concentration.

Negative Transference Numbers in Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Timachova, Ksenia; Balsara, Nitash

Energy density and safety of conventional lithium-ion batteries is limited by the use of flammable organic liquids as a solvent for lithium salts. Polymer electrolytes have the potential to address both limitations. The poor performance of batteries with polymer electrolytes is generally attributed to low ionic conductivity. The purpose of our work is to show that another transport property, the cation transference number, t +, of polymer electrolytes is fundamentally different from that of conventional electrolytes. Our experimental approach, based on concentrated solution theory, indicates that t + of mixtures of poly(ethylene oxide) and LiTFSI salt are negative over most of the accessible concentration window. In contrast, approaches based on dilute solution theory suggest that t + in the same system is positive. In addition to presenting a new approach for determining t +, we also present data obtained from the steady-state current method, pulsed-field-gradient NMR, and the current-interrupt method. Discrepancies between different approaches are resolved. Our work implies that in the absence of concentration gradients, the net fluxes of both cations and anions are directed toward the positive electrode. Conventional liquid electrolytes do not suffer from this constraint.

Tunable Assembly of Gold Nanorods in Polymer Solutions To Generate Controlled Nanostructured Materials

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

Poling-Skutvik, Ryan; Lee, Jonghun; Narayanan, Suresh

In this study, gold nanorods grafted with short chain polymers are assembled into controlled open structures using polymer-induced depletion interactions and structurally characterized using small angle x-ray scattering. When the nanorod diameter is smaller than the radius of gyration of the depletant polymer, the depletion interaction depends solely on the correlation length of the polymer solution and not directly on the polymer molecular weight. As the polymer concentration increases, the stronger depletion interactions increasingly compress the grafted chains and push the gold nanorods closer together. By contrast, other structural characteristics such as the number of nearest neighbors and fractal dimensionmore » exhibit a non-monotonic dependence on polymer concentration. These parameters are maximal at intermediate concentrations, which are attributed to a crossover from reaction-limited to diffusion-limited aggregation. Finally, the control over structural properties of anisotropic nanoscale building blocks demonstrated here will be beneficial to designing and producing materials in situ with specific direction-dependent nanoscale properties and provides a crucial route for advances in additive manufacturing.« less

Tunable Assembly of Gold Nanorods in Polymer Solutions To Generate Controlled Nanostructured Materials

DOE PAGES

Poling-Skutvik, Ryan; Lee, Jonghun; Narayanan, Suresh; ...

2018-01-17

In this study, gold nanorods grafted with short chain polymers are assembled into controlled open structures using polymer-induced depletion interactions and structurally characterized using small angle x-ray scattering. When the nanorod diameter is smaller than the radius of gyration of the depletant polymer, the depletion interaction depends solely on the correlation length of the polymer solution and not directly on the polymer molecular weight. As the polymer concentration increases, the stronger depletion interactions increasingly compress the grafted chains and push the gold nanorods closer together. By contrast, other structural characteristics such as the number of nearest neighbors and fractal dimensionmore » exhibit a non-monotonic dependence on polymer concentration. These parameters are maximal at intermediate concentrations, which are attributed to a crossover from reaction-limited to diffusion-limited aggregation. Finally, the control over structural properties of anisotropic nanoscale building blocks demonstrated here will be beneficial to designing and producing materials in situ with specific direction-dependent nanoscale properties and provides a crucial route for advances in additive manufacturing.« less

Simple detection of residual enrofloxacin in meat products using microparticles and biochips.

PubMed

Ha, Mi-Sun; Chung, Myung-Sub; Bae, Dong-Ho

2016-05-01

A simple and sensitive method for detecting enrofloxacin, a major veterinary fluoroquinolone, was developed. Monoclonal antibody specific for enrofloxacin was immobilised on a chip and fluorescent dye-labelled microparticles were covalently bound to the enrofloxacin molecules. Enrofloxacin in solution competes with the microparticle-immobilised enrofloxacin (enroMPs) to bind to the antibody on the chip. The presence of enrofloxacin was verified by detecting the fluorescence of enrofloxacin-bound microparticles. Under optimum conditions, a high dynamic range was achieved at enrofloxacin concentrations ranging from 1 to 1000 μg kg(-1). The limits of detection and quantification for standard solutions were 5 and 20 μg kg(-1) respectively, which are markedly lower than the maximum residue limit. Using simple extraction methods, recoveries from fortified beef, pork and chicken samples were 43.4-62.3%. This novel method also enabled approximate quantification of enrofloxacin concentration: the enroMP signal intensity decreased with increasing enrofloxacin concentration. Because of its sensitivity, specificity, simplicity and rapidity, the method described herein will facilitate the detection and approximate quantification of enrofloxacin residues in foods in a high-throughput manner.

Limits to anaerobic energy and cytosolic concentration in the living cell.

PubMed

Paglietti, A

2015-01-01

For many physical systems at any given temperature, the set of all states where the system's free energy reaches its largest value can be determined from the system's constitutive equations of internal energy and entropy, once a state of that set is known. Such an approach is fraught with complications when applied to a living cell, because the cell's cytosol contains thousands of solutes, and thus thousands of state variables, which makes determination of its state impractical. We show here that, when looking for the maximum energy that the cytosol can store and release, detailed information on cytosol composition is redundant. Compatibility with cell's life requires that a single variable that represents the overall concentration of cytosol solutes must fall between defined limits, which can be determined by dehydrating and overhydrating the cell to its maximum capacity. The same limits are shown to determine, in particular, the maximum amount of free energy that a cell can supply in fast anaerobic processes, starting from any given initial state. For a typical skeletal muscle in normal physiological conditions this energy, i.e., the maximum anaerobic capacity to do work, is calculated to be about 960 J per kg of muscular mass. Such energy decreases as the overall concentration of solutes in the cytosol is increased. Similar results apply to any kind of cell. They provide an essential tool to understand and control the macroscopic response of single cells and multicellular cellular tissues alike. The applications include sport physiology, cell aging, disease produced cell damage, drug absorption capacity, to mention the most obvious ones.

Limits to anaerobic energy and cytosolic concentration in the living cell

NASA Astrophysics Data System (ADS)

Paglietti, A.

2015-11-01

For many physical systems at any given temperature, the set of all states where the system's free energy reaches its largest value can be determined from the system's constitutive equations of internal energy and entropy, once a state of that set is known. Such an approach is fraught with complications when applied to a living cell, because the cell's cytosol contains thousands of solutes, and thus thousands of state variables, which makes determination of its state impractical. We show here that, when looking for the maximum energy that the cytosol can store and release, detailed information on cytosol composition is redundant. Compatibility with cell's life requires that a single variable that represents the overall concentration of cytosol solutes must fall between defined limits, which can be determined by dehydrating and overhydrating the cell to its maximum capacity. The same limits are shown to determine, in particular, the maximum amount of free energy that a cell can supply in fast anaerobic processes, starting from any given initial state. For a typical skeletal muscle in normal physiological conditions this energy, i.e., the maximum anaerobic capacity to do work, is calculated to be about 960 J per kg of muscular mass. Such energy decreases as the overall concentration of solutes in the cytosol is increased. Similar results apply to any kind of cell. They provide an essential tool to understand and control the macroscopic response of single cells and multicellular cellular tissues alike. The applications include sport physiology, cell aging, disease produced cell damage, drug absorption capacity, to mention the most obvious ones.

Analyzing the effects of instillation volume on intravesical delivery using biphasic solute transport in a deformable geometry.

PubMed

Smith, Sean G; Griffith, Boyce E; Zaharoff, David A

2018-04-05

Ailments of the bladder are often treated via intravesical delivery-direct application of therapeutic into the bladder through a catheter. This technique is employed hundreds of thousands of times every year, but protocol development has largely been limited to empirical determination. Furthermore, the numerical analyses of intravesical delivery performed to date have been restricted to static geometries and have not accounted for bladder deformation. This study uses a finite element analysis approach with biphasic solute transport to investigate several parameters pertinent to intravesical delivery including solute concentration, solute transport properties and instillation volume. The volume of instillation was found to have a substantial impact on the exposure of solute to the deeper muscle layers of the bladder, which are typically more difficult to reach. Indeed, increasing the instillation volume from 50-100 ml raised the muscle solute exposure as a percentage of overall bladder exposure from 60-70% with higher levels achieved for larger instillation volumes. Similar increases were not seen for changes in solute concentration or solute transport properties. These results indicate the role that instillation volume may play in targeting particular layers of the bladder during an intravesical delivery.

Accumulation of Colloidal Particles in Flow Junctions Induced by Fluid Flow and Diffusiophoresis

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

Shin, Sangwoo; Ault, Jesse T.; Warren, Patrick B.

The flow of solutions containing solutes and colloidal particles in porous media is widely found in systems including underground aquifers, hydraulic fractures, estuarine or coastal habitats, water filtration systems, etc. In such systems, solute gradients occur when there is a local change in the solute concentration. While the effects of solute gradients have been found to be important for many applications, we observe an unexpected colloidal behavior in porous media driven by the combination of solute gradients and the fluid flow. When two flows with different solute concentrations are in contact near a junction, a sharp solute gradient is formedmore » at the interface, which may allow strong diffusiophoresis of the particles directed against the flow. Consequently, the particles accumulate near the pore entrance, rapidly approaching the packing limit. These colloidal dynamics have important implications for the clogging of a porous medium, where particles that are orders of magnitude smaller than the pore width can accumulate and block the pores within a short period of time. As a result, we also show that this effect can be exploited as a useful tool for preconcentrating biomolecules for rapid bioassays.« less

Accumulation of Colloidal Particles in Flow Junctions Induced by Fluid Flow and Diffusiophoresis

DOE PAGES

Shin, Sangwoo; Ault, Jesse T.; Warren, Patrick B.; ...

2017-11-16

The flow of solutions containing solutes and colloidal particles in porous media is widely found in systems including underground aquifers, hydraulic fractures, estuarine or coastal habitats, water filtration systems, etc. In such systems, solute gradients occur when there is a local change in the solute concentration. While the effects of solute gradients have been found to be important for many applications, we observe an unexpected colloidal behavior in porous media driven by the combination of solute gradients and the fluid flow. When two flows with different solute concentrations are in contact near a junction, a sharp solute gradient is formedmore » at the interface, which may allow strong diffusiophoresis of the particles directed against the flow. Consequently, the particles accumulate near the pore entrance, rapidly approaching the packing limit. These colloidal dynamics have important implications for the clogging of a porous medium, where particles that are orders of magnitude smaller than the pore width can accumulate and block the pores within a short period of time. As a result, we also show that this effect can be exploited as a useful tool for preconcentrating biomolecules for rapid bioassays.« less

Assessment of electrochemical properties of a biogalvanic system for tissue characterisation

PubMed Central

Chandler, J.H.; Culmer, P.R.; Jayne, D.G.; Neville, A.

2015-01-01

Biogalvanic characterisation is a promising method for obtaining health-specific tissue information. However, there is a dearth of understanding in the literature regarding the underlying galvanic cell, electrode reactions and their controlling factors which limits the application of the technique. This work presents a parametric electrochemical investigation into a zinc–copper galvanic system using salt (NaCl) solution analogues at physiologically-relevant concentrations (1.71, 17.1 & 154 mM). The potential difference at open cell, closed cell maximum current and the internal resistance (based on published characterisation methods) were measured. Additionally, independent and relative polarisation scans of the electrodes were performed to improve understanding of the system. Our findings suggest that the prominent reaction at the cathode is that of oxygen-reduction, not hydrogen-evolution. Results indicate that cell potentials are influenced by the concentration of dissolved oxygen at low currents and maximum closed cell currents are limited by the rate of oxygen diffusion to the cathode. Characterised internal resistance values for the salt solutions did not correspond to theoretical values at the extremes of concentration (1.71 and 154 mM) due to electrode resistance and current limitation. Existing biogalvanic models do not consider these phenomena and should be improved to advance the technique and its practical application. PMID:25460609

Rotaxane liquid crystals with variable length: The effect of switching efficiency on the isotropic-nematic transition

NASA Astrophysics Data System (ADS)

He, Hao; Sevick, Edith M.; Williams, David R. M.

2018-04-01

We examine a solution of non-adaptive two-state rotaxane molecules which can switch from a short state of length L to a long state of length qL, using statistical thermodynamics. This molecular switching is externally driven and can result in an isotropic-nematic phase transition without altering temperature and concentration. Here we concentrate on the limitation imposed by switching inefficiency, i.e., on the case where molecular switching is not quantitative, leading to a solution of rotaxanes in different states. We present switching diagrams that can guide in the design of rotaxanes which affect a macroscopic phase change.

The Kinetics of Nucleated Polymerizations at High Concentrations: Amyloid Fibril Formation Near and Above the “Supercritical Concentration”

PubMed Central

Powers, Evan T.; Powers, David L.

2006-01-01

The formation of amyloid and other types of protein fibrils is thought to proceed by a nucleated polymerization mechanism. One of the most important features commonly associated with nucleated polymerizations is a strong dependence of the rate on the concentration. However, the dependence of fibril formation rates on concentration can weaken and nearly disappear as the concentration increases. Using numerical solutions to the rate equations for nucleated polymerization and analytical solutions to some limiting cases, we examine this phenomenon and show that it is caused by the concentration approaching and then exceeding the equilibrium constant for dissociation of monomers from species smaller than the nucleus, a quantity we have named the “supercritical concentration”. When the concentration exceeds the supercritical concentration, the monomer, not the nucleus, is the highest-energy species on the fibril formation pathway, and the fibril formation reaction behaves initially like an irreversible polymerization. We also derive a relation that can be used in a straightforward method for determining the nucleus size and the supercritical concentration from experimental measurements of fibril formation rates. PMID:16603497

Catchment chemostasis revisited: water quality responds differently to variations in weather and climate

NASA Astrophysics Data System (ADS)

Godsey, Sarah; Kirchner, James

2017-04-01

Solute concentrations in streamflow typically vary systematically with stream discharge, and the resulting concentration-discharge relationships are important signatures of catchment (bio)geochemical processes. Solutes derived from mineral weathering often exhibit decreasing concentrations with increasing flows, suggesting dilution of a kinetically limited weathering flux by a variable flux of water. However, Godsey et al. (2009) showed that concentration-discharge relationships of weathering-derived solutes in 59 headwater catchments were much flatter than this simple dilution model would predict. Instead, their analysis showed that these catchments behaved almost like chemostats, with rates of solute production and/or mobilization that were nearly proportional to water fluxes, on both event and inter-annual time scales. Here we re-examine these findings using data from roughly 1000 catchments, ranging from ˜10 to >1,000,000 km2 in drainage area, and spanning a wide range of lithologic and climatic settings. Concentration-discharge relationships among this much larger set of much larger catchments are broadly consistent with the chemostatic behavior described by Godsey et al. (2009). Among these same catchments, however, site-to-site variations in mean concentrations are strongly (negatively) correlated with long-term average precipitation and discharge, suggesting strong dilution of stream concentrations under long-term leaching of the critical zone. The picture that emerges is one in which, on event and inter-annual time scales, stream solute concentrations are chemostatically buffered by groundwater storage and fast chemical reactions (such as ion exchange), but on much longer time scales, the catchment's chemostatic "set point" is determined by climatically driven critical zone evolution. Examples illustrating the different influences of (short-term) weather and (long-term) climate on water quality will be presented, and their implications will be discussed. Godsey, S.E., J.W. Kirchner and D.W. Clow, Concentration-discharge relationships reflect chemostatic characteristics of US catchments, Hydrological Processes, 23, 1844-1864, 2009.

Cation exchange concentraion of the Americium product from TRUEX

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

Barney, G.S.; Cooper, T.D.; Fisher, F.D.

1991-06-01

A transuranic extraction (TRUEX) process has been developed to separate and recover plutonium, americium, and other transuranic (TRU) elements from acid wastes. The main objective of the process is to reduce the effluent to below the TRU limit for actinide concentrations (<100 nCi/g of material) so it can be disposed of inexpensively. The process yields a dilute nitric acid stream containing low concentrations of the extracted americium product. This solution also contains residual plutonium and trace amounts of iron. The americium will be absorbed into a cation exchange resin bed to concentrate it for disposal or for future use. Themore » overall objective of these laboratory tests was to determine the performance of the cation exchange process under expected conditions of the TRUEX process. Effects of acid, iron, and americium concentrations on americium absorption on the resin were determined. Distribution coefficients for americium absorption from acide solutions on the resin were measured using batch equilibrations. Batch equilibrations were also used to measure americium absorption in the presence of complexants. This data will be used to identify complexants and solution conditions that can be used to elute the americium from the columns. The rate of absorption was measured by passing solutions containing americium through small columns of resin, varying the flowrates, and measuring the concentrations of americium in the effluent. The rate data will be used to estimate the minimum bed size of the columns required to concentrate the americium product. 11 refs. , 10 figs., 2 tabs.« less

Influence of calcium ions on the crystallization of sodium bicarbonate

NASA Astrophysics Data System (ADS)

Zhu, Yi; Demilie, Paul; Davoine, Perrine; Cartage, Thierry; Delplancke-Ogletree, Marie-Paule

2005-02-01

In industrial crystallization of sodium bicarbonate (sodium hydrogenocarbonate), the presence of calcium ions in solutions is unavoidable due to the production process. The understanding of the Ca 2+ role in NaHCO 3 crystallization would be helpful for improving the quality of the final products. The influence of calcium ions on NaHCO 3 crystallization was investigated in a 5-l mixed suspension mixed product removal crystallizer under controlled conditions. A density meter was used for continuous supersaturation monitoring. After a steady state had been reached, different CaCl 2 amounts were added at a constant flow rate. It was found that limited calcium ion levels in the system reduce drastically the nucleation frequency of NaHCO 3 and has a limited influence on crystal growth rate. The supersaturation measurements and other methods confirmed this phenomenon. The relationship between the Ca 2+ influence on NaHCO 3 crystallization, the calcium carbonate solubility and its metastable zone in concentrated NaHCO 3 solution was established. In fact, Ca 2+ has a maximum effect on NaHCO 3 crystallization kinetics when the saturation of calcium carbonate in NaHCO 3 solution has been reached, and the effect is constant in the metastable zone. The excess of Ca 2+ precipitates in NaHCO 3 solution as CaCO 3, as observed by energy dispersive X-ray and X-ray diffraction. This explained why an increasing Ca 2+ concentration in the solution has a limited influence on NaHCO 3 crystal size distribution and habit, but decreases the crystal purity. It is also confirmed that an impurity as Ca 2+ has no influence on the equilibrium NaHCO 3-Na 2CO 3.

Probing mass-transport and binding inhomogeneity in macromolecular interactions by molecular interferometric imaging

NASA Astrophysics Data System (ADS)

Zhao, Ming; Wang, Xuefeng; Nolte, David

2009-02-01

In solid-support immunoassays, the transport of target analyte in sample solution to capture molecules on the sensor surface controls the detected binding signal. Depletion of the target analyte in the sample solution adjacent to the sensor surface leads to deviations from ideal association, and causes inhomogeneity of surface binding as analyte concentration varies spatially across the sensor surface. In the field of label-free optical biosensing, studies of mass-transport-limited reaction kinetics have focused on the average response on the sensor surface, but have not addressed binding inhomogeneities caused by mass-transport limitations. In this paper, we employ Molecular Interferometric Imaging (MI2) to study mass-transport-induced inhomogeneity of analyte binding within a single protein spot. Rabbit IgG binding to immobilized protein A/G was imaged at various concentrations and under different flow rates. In the mass-transport-limited regime, enhanced binding at the edges of the protein spots was caused by depletion of analyte towards the center of the protein spots. The magnitude of the inhomogeneous response was a function of analyte reaction rate and sample flow rate.

Water chemistry and electrical conductivity database for rivers in Yellowstone National Park, Wyoming

USGS Publications Warehouse

Clor, Laura E.; McCleskey, R. Blaine; Huebner, Mark A.; Lowenstern, Jacob B.; Heasler, Henry P.; Mahony, Dan L.; Maloney, Tim; Evans, William C.

2012-01-01

This study aims to quantify relations between solute concentrations (especially chloride) and electrical conductivity for several rivers in Yellowstone National Park (YNP), by using automated samplers and conductivity meters. Norton and Friedman (1985) found that chloride concentrations and electrical conductivity have a good correlation in the Falls, Snake, Madison, and Yellowstone Rivers. However, their results are based on limited sampling and hydrologic conditions and their relation with other solutes was not determined. Once the correlations are established, conductivity measurements can then be used as a proxy for chloride concentrations, thereby enabling continuous heat-flow estimation on a much finer timescale and at lower cost than is currently possible with direct sampling. This publication serves as a repository for all data collected during the course of the study from May 2010 through July 2011, but it does not include correlations between solutes and conductivity or recommendations for quantification of chloride through continuous electrical conductivity measurements. This will be the object of a future document.

Investigation of Termination in Free Radical Polymerization by Use of >Diffusion-Limited Interactions in Polymer Solutions

NASA Astrophysics Data System (ADS)

Wisnudel, Marc; Torkelson, John

1997-03-01

Termination between radicals has been simulated by use of phosphorescence quenching interactions, showing that segmental diffusion plays a strong role in the origin of autoacceleration or the gel effect. Quenching rate constants (k_q) were measured between benzil-labeled polymer as a function of anthracene-labeled polymer in polystyrene or polymethylmethacrylate solutions. Values of kq were obtained for interactions involving end- or center-labeled chains as a function of polymer MW and concentration. A large effect of label location was observed as interactions between center-labeled chains resulted in values of kq that were more MW-dependent and smaller in magnitude than those for interactions between end-labeled chains. For interactions between end-labeled chains at concentrations between 0 and 600 g/L, data show only very weak dependencies of kq on MW and concentration dependencies similar to that of segmental mobility. In addition, comparisons of kq data for interactions in PMMA-toluene solutions with termination rate constant (k_t) data for MMA polymerizations, showing weaker concentration dependencies for both kq and kt than translational diffusion coefficients in similar solutions, also indicate that segmental diffusion is important in termination.

Improved detection limits for electrospray ionization on a magnetic sector mass spectrometer by using an array detector.

PubMed

Cody, R B; Tamura, J; Finch, J W; Musselman, B D

1994-03-01

Array detection was compared with point detection for solutions of hen egg-white lysozyme, equine myoglobin, and ubiquitin analyzed by electrospray ionization with a magnetic sector mass spectrometer. The detection limits for samples analyzed by using the array detector system were at least 10 times lower than could be achieved by using a point detector on the same mass spectrometer. The minimum detectable quantity of protein corresponded to a signal-to-background ratio of approximately 2∶1 for a 500 amol/μL solution of hen egg-white lysozyme. However, the ultimate practical sample concentrations appeared to be in the 10-100 fmol/μL range for the analysis of dilute solutions of relatively pure proteins or simple mixtures.

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).

Comparison and extension of free dendritic growth models through application to silver-15 mass percent copper alloy

NASA Astrophysics Data System (ADS)

Onel, Selis

Modeling free dendritic growth in supercooled alloys is a critical requirement in controlling the microstructure of materials during rapid solidification processing of materials. Recent models developed to predict the growth of a dendrite in a highly supercooled melt adopt modifications that account for the interface kinetics and thermodynamics at high interface velocities, but the assumptions necessary to simplify the mathematical problem impose inherent restrictions. The assumption of straight phase boundaries adopted in early models often loses validity at high supercoolings, where phase boundaries are often curved. The use of equations with Henrian restrictions, such as the Baker-Cahn equation for the interfacial driving force and the Aziz equation for solute trapping confine these models to dilute solutions. Turnbull's collision-limited linear kinetic equation for interface growth may not apply to large interfacial driving forces. Therefore, a useful application and modification of free dendritic growth models require a thorough understanding of their limitations in producing consistent results. One of the objectives of this research is to numerically compare the free dendritic growth models derived from the earlier LGK model developed by Lipton et al. The subsequent LKT model by Lipton et al., the TLK model by Trivedi et al., and the BCT model by Boettinger et al., together with a modification of the TLK model, and the DA model by DiVenuti and Ando are compared through application to an Ag-15 mass % Cu alloy. In addition, a new model to extend the DA model is developed by incorporating a thermodynamic solution model for the calculation of the interfacial driving force, thereby eliminating the Baker-Cahn equation that limits the use of the correct BCT and DA models to dilute solutions. Direct computation of the interfacial driving force by calculating a metastable phase diagram for the Ag-Cu system using a temperature dependent subregular solution model is carried out. Comparison of the results of the new model with the DA model confirms that the Baker-Cahn equation is applicable at low solute concentrations. As a future research direction, the new model can be extended to apply to higher concentration alloys by using a new solute trapping equation to further eliminate the dilute solution limitations.

Stability of Levothyroxine in Sodium Chloride for IV Administration.

PubMed

Strong, Dawn K; Decarie, Diane; Ensom, Mary H H

2010-11-01

Levothyroxine by IV administration is often prescribed in the intensive care unit for the management of potential solid organ donors, following declaration of brain death and provision of consent for organ donation. Published data on the stability of levothyroxine in IV solutions are limited. To evaluate the physical compatibility and chemical stability, over a 24-h period, of 2 concentrations of levothyroxine in 0.9% sodium chloride with storage at room temperature and with exposure to or protection from light. Levothyroxine solutions (0.4 μg/mL and 2.0 μg/mL) were prepared in 50-mL minibags of 0.9% NaCl and stored at room temperature (25°C) with exposure to or protection from light. Samples were collected from each minibag at time 0 and after 0.5, 1.0, 1.5, 2.0, 3.0, 4.0, 8.0, 12.0, and 24.0 h. The samples were analyzed in triplicate with a validated stability-indicating high-performance liquid chromatography method using ultraviolet detection. A solution was considered stable if it maintained 90% of its initial concentration of levothyroxine. Changes in colour, clarity, and pH were assessed to determine the physical compatibility of the solutions. All samples remained clear, colourless, and free of precipitate throughout the study, and there were no significant changes in pH. Based on the 95% confidence interval of the slope of the curve relating concentration to time determined by linear regression, solutions of levothyroxine with concentration 0.4 μg/mL would maintain at least 90% of the initial concentration for 16.9 h with exposure to light and for 18.0 h if kept in the dark. Solutions of levothyroxine with concentration 2.0 μg/mL would maintain at least 90% of the initial concentration for 6.5 h with exposure to light and for 12.0 h if kept in the dark, with 95% confidence. Extemporaneously prepared solutions of levothyroxine in 0.9% NaCl can be expected to remain stable for at least 6.5 h if stored without protection from light and at least 12 h if stored in the dark. Stability is related to concentration, with more dilute solutions having greater stability.

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

Microwave enhanced electroanalysis of formulations: processes in micellar media at glassy carbon and at platinum electrodes.

PubMed

Ghanem, Mohamed A; Compton, Richard G; Coles, Barry A; Canals, Antonio; Marken, Frank

2005-10-01

The direct electroanalysis of complex formulations containing alpha-tocopherol (vitamin E) is possible in micellar solution and employing microwave-enhanced voltammetry. In the presence of microwave radiation substantial heating and current enhancement effects have been observed at 330 microm diameter glassy carbon electrodes placed into a micellar aqueous solution and both hydrophilic and highly hydrophobic redox systems are detected. For the water soluble Fe(CN)(6)(3-/4-) redox system in micellar aqueous solutions of 0.1 M NaCl and 0.1 M sodium dodecylsulfate (SDS) at low to intermediate microwave power, thermal effects and convection effects are observed. At higher microwave power, thermal cavitation is induced and dominates the mass transport at the electrode surface. For the micelle-soluble redox systems tert-butylferrocene and 2,5-di-tert-butyl-1,4-benzoquinone, strong and concentration dependent current responses are observed only in the presence of microwave radiation. For the oxidation of micelle-soluble alpha-tocopherol current responses at glassy carbon electrodes are affected by adsorption and desorption processes whereas at platinum electrodes, analytical limiting currents are obtained over a wide range of alpha-tocopherol concentrations. However, for the determination of alpha-tocopherol in a commercial formulation interference from proteins is observed at platinum electrodes and direct measurements are possible only over a limited concentration range and at glassy carbon electrodes.

Analysis of Ag(I) Biocide in Water Samples Using Anodic Stripping Voltammetry with a Boron-Doped Diamond Disk Electrode.

PubMed

Maldonado, Vanessa Y; Espinoza-Montero, Patricio J; Rusinek, Cory A; Swain, Greg M

2018-06-05

The electroanalytical performance of a new commercial boron-doped diamond disk and a traditional nanocrystalline thin-film electrode were compared for the anodic stripping voltammetric determination of Ag(I). The diamond disk electrode is more flexible than the planar film as the former is compatible with most electrochemical cell designs including those incorporating magnetic stirring. Additionally, mechanical polishing and surface cleaning are simpler to execute. Differential pulse anodic stripping voltammetry (DPASV) was used to detect Ag(I) in standard solutions after optimization of the deposition potential, deposition time and scan rate. The optimized conditions were used to determine the concentration of Ag(I) in a NASA simulated potable water sample and a NIST standard reference solution. The electrochemical results were validated by ICP-OES measurements of the same solutions. The detection figures of merit for the disk electrode were as good or superior to those for the thin-film electrode. Detection limits were ≤5 μg L -1 (S/N = 3) for a 120 s deposition period, and response variabilities were <5% RSD. The polished disk electrode presented a more limited linear dynamic range presumably because of the reduced surface area available for metal phase formation. The concentrations of Ag(I) in the two water samples, as determined by DPASV, were in good agreement with the concentrations determined by ICP-OES.

Moving beyond the limits of mass transport in liquid absorbent microfilms through the implementation of surface-induced vortices

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

Bigham, S; Yu, DZ; Chugh, D

2014-02-01

The slow diffusion of an absorbate molecule into an absorbent often makes the absorption process a rate-limiting step in many applications. In cases involving an absorbate with a high heat of phase change, such as water absorption into a LiBr (lithium bromide) solution, the absorption rate is further slowed due to significant heating of the absorbent. Recently, it has been demonstrated that constraining a LiBr solution film by a hydrophobic porous structure enables manipulation of the solution flow thermohydraulic characteristics. Here, it is shown that mass transport mode in a constrained laminar solution flow can be changed from diffusive tomore » advective. This change in mode is accomplished through stretching and folding the laminar streamlines within the solution film via the implementation of micro-scale features on the flow channel surface. The process induces vortices within the solution film, which continuously bring concentrated solution from the bottom and middle of the solution channel to its interface with the vapor phase, thus leading to a significant enhancement in the absorption rate. The detailed physics of the involved transport processes is elucidated using the LBM (Lattice Boltzmann Method). Published by Elsevier Ltd.« less

Limiting solubilizing capacity of some nonionic surfactants

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

Wan, L.S.C.

1980-12-01

This report gives an account of the attempts to solubilize corn oil. A fixed quantity of corn oil or oily dispersion containing corn oil and a sorbitan ester was added to a series of 25 ml of polysorbate solutions of increasing concentration. This investigation showed that corn oil is not solubilized by either aqueous solutions of polyoxyethylene sorbitan esters or by a combination of these surfactants with sorbitan esters. The findings suggest that nonionic surfactants of the polyoxyethylene sorbitan ester type as well as the sorbitan esters have limiting capacities to solubilize extremely hydrophobic substances such as corn oil. 19more » references.« less

Long-term stability of dexamethasone and alizapride or ondansetron in sodium chloride 0.9% polyolefin bag at 5±3°C.

PubMed

Simar, J; Godet, M; Hecq, J-D; Closset, M; Gillet, P; Langhendries, C; Bihin, B; Jamart, J; Galanti, L

2017-01-01

The aim of the study was to investigate the long-term stability of dexamethasone 10mg associated with alizapride 100mg or ondansetron 8mg in 100mL of 0.9% sodium chloride solution stored at 5±3°C. Solutions of 0.9% sodium chloride 100mL in polyolefin bags (n=5) containing approximately dexamethasone (DEX) 10mg associated with alizapride (ALI) 100mg or ondansetron (OND) 8mg were prepared under aseptic conditions and stored about 30 days at 5±3°C. ALI, DEX and OND concentrations were measured by high-performance liquid chromatography (HPLC). Optic density measurement at different wavelengths, pH measurement and optic microscope observations were performed periodically during the storage. A forced degradation test with HCL 5M and NaOH 5M before and after heating at 100°C was also performed. Solutions were considered stable if the 95% one-sided lower confidence limit of the concentration remains superior to 90% of the initial concentration or 95% of the initial concentration when any signs of physical instability exist as recently recommend. The calibration was linear over the following range from 20 to 1.25mg/100mL for DEX, from 200 to 12.5mg/100mL for ALI and from 20 to 1.25mg/100mL for OND with a calculated correlation coefficient (r 2 ) of 0.998, 0.999 and 0.999, respectively. The inter- and intra-assay precision was below 10% for both mixtures. All formulations were physically stable during the storage. The lower confidence limit of the concentration for these solutions remains superior to 90% of the initial concentration at this date as recommended by the Food and Drug Administration (FDA) until 30 days. The HPLC method is specific and reproducible and can easily be adopted for monitoring the quality control in the production of DEX-ALI and DEX-OND bags. Solutions of DEX-ALI and DEX-OND were physically and chemically stable for 30 days in polyolefin bags stored at 5±3°C and could therefore be prepared in advance. Copyright © 2016 Académie Nationale de Pharmacie. Published by Elsevier Masson SAS. All rights reserved.

Nonparabolic solar concentrators matching the parabola.

PubMed

Cooper, Thomas; Schmitz, Max; Good, Philipp; Ambrosetti, Gianluca; Pedretti, Andrea; Steinfeld, Aldo

2014-08-01

We consider the limit of geometric concentration for a focusing concave mirror, e.g., a parabolic trough or dish, designed to collect all radiation within a finite acceptance angle and direct it to a receiver with a flat or circular cross-section. While a concentrator with a parabolic cross-section indeed achieves this limit, it is not the only geometry capable of doing so. We demonstrate that there are infinitely many solutions. The significance of this finding is that geometries which can be more easily constructed than the parabola can be utilized without loss of concentration, thus presenting new avenues for reducing the cost of solar collectors. In particular, we investigate a low-cost trough mirror profile which can be constructed by inflating a stack of thin polymer membranes and show how it can always be designed to match the geometric concentration of a parabola of similar form.

Efficient ensemble system based on the copper binding motif for highly sensitive and selective detection of cyanide ions in 100% aqueous solutions by fluorescent and colorimetric changes.

PubMed

Jung, Kwan Ho; Lee, Keun-Hyeung

2015-09-15

A peptide-based ensemble for the detection of cyanide ions in 100% aqueous solutions was designed on the basis of the copper binding motif. 7-Nitro-2,1,3-benzoxadiazole-labeled tripeptide (NBD-SSH, NBD-SerSerHis) formed the ensemble with Cu(2+), leading to a change in the color of the solution from yellow to orange and a complete decrease of fluorescence emission. The ensemble (NBD-SSH-Cu(2+)) sensitively and selectively detected a low concentration of cyanide ions in 100% aqueous solutions by a colorimetric change as well as a fluorescent change. The addition of cyanide ions instantly removed Cu(2+) from the ensemble (NBD-SSH-Cu(2+)) in 100% aqueous solutions, resulting in a color change of the solution from orange to yellow and a "turn-on" fluorescent response. The detection limits for cyanide ions were lower than the maximum allowable level of cyanide ions in drinking water set by the World Health Organization. The peptide-based ensemble system is expected to be a potential and practical way for the detection of submicromolar concentrations of cyanide ions in 100% aqueous solutions.

Differences of cadmium absorption and accumulation in selected vegetable crops.

PubMed

Ni, Wu-Zhong; Yang, Xiao-E; Long, Xin-Xian

2002-07-01

A pot experiment and a sandy culture experiment grown with three vegetable crops of Chinese cabbage (B. chinensis L., cv. Zao-Shu 5), winter greens (B. var. rosularis Tsen et Lee, cv. Shang-Hai-Qing) and celery (A. graveolens L. var. dulce DC., cv. Qing-Qin) were conducted, respectively. The initial soil and four incubated soils with different extractable Cd (0.15, 0.89, 1.38, 1.84 and 2.30 mg Cd/kg soil) were used for the pot experiment. Five treatments were designed (0, 0.0625, 0.125, 0.250 and 0.500 mg Cd/L) in nutrient solution in the sandy culture experiment. Each treatment in pot and sandy culture experiments was trireplicated. The objectives of the study were to examine Cd accumulation in edible parts of selected vegetable crops, its correlation with Cd concentrations in vegetable garden soil or in nutrient solution, and evaluate the criteria of Cd pollution in vegetable garden soil and in nutrient solution based on the hygienic limit of Cd in vegetables. Cadmium concentrations in edible parts of the three selected vegetable crops were as follows: 0.01-0.15 mg/kg fresh weight for Chinese cabbage, 0.02-0.17 mg/kg fresh weight for winter greens, and 0.02-0.24 mg/kg fresh weight for celery in the pot experiment, and 0.1-0.4 mg/kg fresh weight for Chinese cabbage, 0.1-1.4 mg/kg fresh weight for winter greens, and 0.05-0.5 mg/kg fresh weight for celery in the pot experiment (except no-Cd treatment). The order of the three test vegetable crops for cadmium accumulation in the edible parts was celery > winter greens > Chinese cabbage in both the pot experiment and the sandy culture experiment. Cadmium accumulation in edible parts or roots of the vegetable crops increased with increasing of cadmium concentration in the medium (soil or nutrient solution). And cadmium concentrations in edible parts of the test vegetable crops were significantly linearly related to the Cd levels in the growth media (soil and nutrient solution). Based on the regression equations established and the limit of cadmium concentration in vegetable products, the thresholds of Cd concentration in the growth medium evaluated was as follows: 0.5 mg/kg soil of extractable Cd for soil and 0.02 mg/L for nutrient solution. The high capacity for cadmium accumulation in the edible parts of different vegetable crops together with the absence of visual symptoms implies a potential danger for humans.

Osmotic Transport across Cell Membranes in Nondilute Solutions: A New Nondilute Solute Transport Equation

PubMed Central

Elmoazzen, Heidi Y.; Elliott, Janet A.W.; McGann, Locksley E.

2009-01-01

The fundamental physical mechanisms of water and solute transport across cell membranes have long been studied in the field of cell membrane biophysics. Cryobiology is a discipline that requires an understanding of osmotic transport across cell membranes under nondilute solution conditions, yet many of the currently-used transport formalisms make limiting dilute solution assumptions. While dilute solution assumptions are often appropriate under physiological conditions, they are rarely appropriate in cryobiology. The first objective of this article is to review commonly-used transport equations, and the explicit and implicit assumptions made when using the two-parameter and the Kedem-Katchalsky formalisms. The second objective of this article is to describe a set of transport equations that do not make the previous dilute solution or near-equilibrium assumptions. Specifically, a new nondilute solute transport equation is presented. Such nondilute equations are applicable to many fields including cryobiology where dilute solution conditions are not often met. An illustrative example is provided. Utilizing suitable transport equations that fit for two permeability coefficients, fits were as good as with the previous three-parameter model (which includes the reflection coefficient, σ). There is less unexpected concentration dependence with the nondilute transport equations, suggesting that some of the unexpected concentration dependence of permeability is due to the use of inappropriate transport equations. PMID:19348741

Hydrogen peroxide concentration by pervaporation of a ternary liquid solution in microfluidics.

PubMed

Ziemecka, Iwona; Haut, Benoît; Scheid, Benoit

2015-01-21

Pervaporation in a microfluidic device is performed on liquid ternary solutions of hydrogen peroxide-water-methanol in order to concentrate hydrogen peroxide (H2O2) by removing methanol. The quantitative analysis of the pervaporation of solutions with different initial compositions is performed, varying the operating temperature of the microfluidic device. Experimental results together with a mathematical model of the separation process are used to understand the effect of the operating conditions on the microfluidic device efficiency. The parameters influencing significantly the performance of pervaporation in the microfluidic device are determined and the limitations of the process are discussed. For the analysed system, the operating temperature of the chip has to be below the temperature at which H2O2 decomposes. Therefore, the choice of an adequate reduced operating pressure is required, depending on the expected separation efficiency.

Voluntary ethanol consumption differs in adolescent and adult male rats using a modified sucrose-fading paradigm.

PubMed

Maldonado, Antoniette M; Finkbeiner, Lauren M; Alipour, Kent K; Kirstein, Cheryl L

2008-09-01

Initiation of alcohol consumption during adolescence is high, which usually begins with consumption of highly concentrated sweetened alcoholic beverages in adolescent humans. Enhanced voluntary ethanol (EtOH) intake has been observed previously in adolescent relative to adult rats under continuous access conditions using sweetened EtOH solutions. The present set of experiments investigated patterns of voluntary EtOH intake in adolescent and adult rats using sweetened EtOH solutions in a limited access paradigm. Rats were trained with modified sucrose-substitution protocols that ended at either 5% sucrose-20% EtOH (5S/20E) (Exp. 1) or 5% sucrose-10% EtOH (5S/10E) (Exp. 2). Voluntary EtOH consumption differences between the 2 age groups were apparent at higher (i.e., 10 and 20%), but not lower (i.e., 2 and 5%) EtOH concentrations. Adolescent rats consumed more EtOH on a g/kg basis only at 20% EtOH (Exp. 1). Adolescent rats voluntarily consumed more EtOH than adults when maintained at 5S/10E (Exp. 2). To assess whether these age-related differences in voluntary EtOH intake were concentration dependent, rats were trained with 5S/20E and subsequently trained with decreasing EtOH concentrations (i.e., 5S/10E and 5S/5E). Adolescents consumed more EtOH when initially presented with the 5S/10E and 5S/20E EtOH concentrations, and subsequently at the lower 5S/5E EtOH concentration (Exp. 3). There were no differences in preference for the sucrose-only solution, however adolescents tended to consume more sucrose at the 5S sucrose concentration (Exp. 4). Given that adolescents consumed more EtOH at the 5S/10E and 5S/20E, but not at the 5S/5E EtOH concentrations, preference for sucrose does not solely explain the age differences in voluntary EtOH intake observed. Overall, results replicate previous work, demonstrating adolescent rats consume more EtOH relative to adults. However, the present results were observed using sweetened EtOH solutions in a limited access paradigm. The present modified sucrose-substitution paradigm may serve as a valid model of human adolescent drinking behavior.

Chemiluminescent imaging of transpired ethanol from the palm for evaluation of alcohol metabolism.

PubMed

Arakawa, Takahiro; Kita, Kazutaka; Wang, Xin; Miyajima, Kumiko; Toma, Koji; Mitsubayashi, Kohji

2015-05-15

A 2-dimensional imaging system was constructed and applied in measurements of gaseous ethanol emissions from the human palm. This imaging system measures gaseous ethanol concentrations as intensities of chemiluminescence by luminol reaction induced by alcohol oxidase and luminol-hydrogen peroxide-horseradish peroxidase system. Conversions of ethanol distributions and concentrations to 2-dimensional chemiluminescence were conducted on an enzyme-immobilized mesh substrate in a dark box, which contained a luminol solution. In order to visualize ethanol emissions from human palm skin, we developed highly sensitive and selective imaging system for transpired gaseous ethanol at sub ppm-levels. Thus, a mixture of a high-purity luminol solution of luminol sodium salt HG solution instead of standard luminol solution and an enhancer of eosin Y solution was adapted to refine the chemiluminescent intensity of the imaging system, and improved the detection limit to 3 ppm gaseous ethanol. The highly sensitive imaging allows us to successfully visualize the emissions dynamics of transdermal gaseous ethanol. The intensity of each site on the palm shows the reflection of ethanol concentrations distributions corresponding to the amount of alcohol metabolized upon consumption. This imaging system is significant and useful for the assessment of ethanol measurement of the palmar skin. Copyright © 2014 Elsevier B.V. All rights reserved.

Evaluation of experimental parameters for growth of homogeneous solid solutions

NASA Astrophysics Data System (ADS)

Scheel, Hans J.; Swendsen, Robert H.

2001-12-01

In this paper, we discuss the experimental conditions required to grow large two-component crystals from homogeneous solid solutions. Building on the work of Burton, Prim, and Slichter and that of Van Erk, we are able to establish that the concentration fluctuations for diffusion-limited growth are rather insensitive to hydrodynamic fluctuations. This enables a crystal grower to take advantage of forced convection to optimize growth rates without aggravating the striation problem.

Impact of small-scale saline tracer heterogeneity on electrical resistivity monitoring in fully and partially saturated porous media: Insights from geoelectrical milli-fluidic experiments

NASA Astrophysics Data System (ADS)

Jougnot, Damien; Jiménez-Martínez, Joaquín; Legendre, Raphaël; Le Borgne, Tanguy; Méheust, Yves; Linde, Niklas

2018-03-01

Time-lapse electrical resistivity tomography (ERT) is a geophysical method widely used to remotely monitor the migration of electrically-conductive tracers and contaminant plumes in the subsurface. Interpretations of time-lapse ERT inversion results are generally based on the assumption of a homogeneous solute concentration below the resolution limits of the tomogram depicting inferred electrical conductivity variations. We suggest that ignoring small-scale solute concentration variability (i.e., at the sub-resolution scale) is a major reason for the often-observed apparent loss of solute mass in ERT tracer studies. To demonstrate this, we developed a geoelectrical milli-fluidic setup where the bulk electric conductivity of a 2D analogous porous medium, consisting of cylindrical grains positioned randomly inside a Hele-Shaw cell, is monitored continuously in time while saline tracer tests are performed through the medium under fully and partially saturated conditions. High resolution images of the porous medium are recorded with a camera at regular time intervals, and provide both the spatial distribution of the fluid phases (aqueous solution and air), and the saline solute concentration field (where the solute consists of a mixture of salt and fluorescein, the latter being used as a proxy for the salt concentration). Effective bulk electrical conductivities computed numerically from the measured solute concentration field and the spatial distributions of fluid phases agree well with the measured bulk conductivities. We find that the effective bulk electrical conductivity is highly influenced by the connectivity of high electrical conductivity regions. The spatial distribution of air, saline tracer fingering, and mixing phenomena drive temporal changes in the effective bulk electrical conductivity by creating preferential paths or barriers for electrical current at the pore-scale. The resulting heterogeneities in the solute concentrations lead to strong anisotropy of the effective bulk electrical conductivity, especially for partially saturated conditions. We highlight how these phenomena contribute to the typically large apparent mass loss observed when conducting field-scale time-lapse ERT.

Redox polymer mediation for enzymatic biofuel cells

NASA Astrophysics Data System (ADS)

Gallaway, Joshua

Mediated biocatalytic cathodes prepared from the oxygen-reducing enzyme laccase and redox-conducting osmium hydrogels were characterized for use as cathodes in enzymatic biofuel cells. A series of osmium-based redox polymers was synthesized with redox potentials spanning the range from 0.11 V to 0.85 V (SHE), and the resulting biocatalytic electrodes were modeled to determine reaction kinetic constants using the current response, measured osmium concentration, and measured apparent electron diffusion. As in solution-phase systems, the bimolecular rate constant for mediation was found to vary greatly with mediator potential---from 250 s-1M-1 when mediator and enzyme were close in potential to 9.4 x 10 4 s-1M-1 when this overpotential was large. Optimum mediator potential for a cell operating with a non-limiting platinum anode and having no mass transport limitation from bulk solution was found to be 0.66 V (SHE). Redox polymers were synthesized under different concentrations, producing osmium variation. An increase from 6.6% to 7.2% osmium increased current response from 1.2 to 2.1 mA/cm2 for a planar film in 40°C oxygen-saturated pH 4 buffer, rotating at 900 rpm. These results translated to high surface area electrodes, nearly doubling current density to 13 mA/cm2, the highest to date for such an electrode. The typical fungal laccase from Trametes versicolor was replaced by a bacterially-expressed small laccase from Streptomyces coelicolor, resulting in biocatalytic films that reduced oxygen at increased pH, with full functionality at pH 7, producing 1.5 mA/cm 2 in planar configuration. Current response was biphasic with pH, matching the activity profile of the free enzyme in solution. The mediated enzyme electrode system was modeled with respect to apparent electron diffusion, mediator concentration, and transport of oxygen from bulk solution, all of which are to some extent controlled by design. Each factor was found to limit performance in certain circumstances. In systems relying on stagnant solution, oxygen transport was found to dominate. However, if mass transport was efficient, differences in mediator design greatly affected performance.

Applicability of direct total reflection X-ray fluorescence analysis for selenium determination in solutions related to environmental and geochemical studies

NASA Astrophysics Data System (ADS)

Marguí, E.; Floor, G. H.; Hidalgo, M.; Kregsamer, P.; Roman-Ross, G.; Streli, C.; Queralt, I.

2010-12-01

A significant amount of environmental studies related to selenium determination in different environmental compartments have been published in the last years due to the narrow range between the Se nutritious requirement as essential element and toxic effects upon exposure. However, the direct analysis of complex liquid samples like natural waters and extraction solutions presents significant problems related to the low Se concentrations and the complicated matrix of this type of samples. The goal of the present research was to study the applicability of direct TXRF analysis of different type of solutions commonly used in environmental and geochemical studies, confirm the absence or presence of matrix effects and evaluate the limits of detection and accuracy for Se determination in the different matrices. Good analytical results were obtained for the direct analysis of ground and rain water samples with limits of detection for Se two orders of magnitude lower than the permissible Se concentration in drinking waters ([Se] = 10 μg/L) according to the WHO. However, the Se detection limits for more complex liquid samples such as thermal waters and extraction solutions were in the μg/L range due to the presence of high contents of other elements present in the matrix (i.e., Br, Fe, Zn) or the high background of the TXRF spectrum that hamper the Se determination at trace levels. Our results give insight into the possibilities and drawbacks of direct TXRF analysis and to a certain extent the potential applications in the environmental and geochemical field.

A combination turbidity and supernatant microplate assay to rank-order the supersaturation limits of early drug candidates.

PubMed

Morrison, John S; Nophsker, Michelle J; Haskell, Roy J

2014-10-01

A unique opportunity exists at the drug discovery stage to overcome inherently poor solubility by selecting drug candidates with superior supersaturation propensity. Existing supersaturation assays compare either precipitation-resistant or precipitation-inhibiting excipients, or higher-energy polymorphic forms, but not multiple compounds or multiple concentrations. Furthermore, these assays lack sufficient throughput and compound conservation necessary for implementation in the discovery environment. A microplate-based combination turbidity and supernatant concentration assay was therefore developed to determine the extent to which different compounds remain in solution as a function of applied concentration in biorelevant media over a specific period of time. Dimethyl sulfoxide stock solutions at multiple concentrations of four poorly soluble, weak base compounds (Dipyridamole, Ketoconazole, Albendazole, and Cinnarizine) were diluted with pH 6.5 buffer as well as FaSSIF. All samples were monitored for precipitation by turbidity at 600 nm over 1 h and the final supernatant concentrations were measured. The maximum supersaturation ratio was calculated from the supersaturation limit and the equilibrium solubility in each media. Compounds were rank-ordered by supersaturation ratio: Ketoconazole > Dipyridamole > Cinnarizine ∼ Albendazole. These in vitro results correlated well with oral AUC ratios from published in vivo pH effect studies, thereby confirming the validity of this approach. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Formation and rupture of Ca(2+) induced pectin biopolymer gels.

PubMed

Basak, Rajib; Bandyopadhyay, Ranjini

2014-10-07

When calcium salts are added to an aqueous solution of polysaccharide pectin, ionic cross-links form between pectin chains, giving rise to a gel network in dilute solution. In this work, dynamic light scattering (DLS) is employed to study the microscopic dynamics of the fractal aggregates (flocs) that constitute the gels, while rheological measurements are carried out to study the process of gel rupture. As the calcium salt concentration is increased, DLS experiments reveal that the polydispersity of the flocs increase simultaneously with the characteristic relaxation times of the gel network. Above a critical salt concentration, the flocs become interlinked to form a reaction-limited fractal gel network. Rheological studies demonstrate that the limits of the linear rheological response and the critical stresses required to rupture these networks both decrease with the increase in salt concentration. These features indicate that the ion-mediated pectin gels studied here lie in a 'strong link' regime that is characterised by inter-floc links that are stronger than intra-floc links. A scaling analysis of the experimental data presented here demonstrates that the elasticities of the individual fractal flocs exhibit power-law dependences on the added salt concentration. We conclude that when both pectin and salt concentrations are increased, the number of fractal flocs of pectin increases simultaneously with the density of crosslinks, giving rise to very large values of the bulk elastic modulus.

Effects of ethanol addition on micellar solubilization and plume migration during surfactant enhanced recovery of tetrachloroethene.

PubMed

Taylor, Tammy P; Rathfelder, Klaus M; Pennell, Kurt D; Abriola, Linda M

2004-03-01

Alcohol addition has been suggested for use in combination with surfactant flushing to enhance solubilization kinetics and permit density control of dense non-aqueous phase liquid (DNAPL)-laden surfactant plumes. This study examined the effects of adding ethanol (EtOH) to a 4% Tween 80 (polyoxyethylene (20) sorbitan monooleate) solution used to flush tetrachloroethene (PCE)-contaminated porous media. The influence of EtOH concentration, subsurface layering and scale on flushing solution delivery and PCE recovery was investigated through a combination of experimental and mathematical modeling studies. Results of batch experiments demonstrated that the addition of 2.5%, 5% and 10% (wt.) EtOH incrementally increased the PCE solubilization capacity and viscosity of the surfactant solution, while reducing solution density from 1.002 to 0.986 g/cm3. Effluent concentration data obtained from one-dimensional (1-D) column experiments were used to characterize rate-limited micellar solubilization of residual PCE, which was strongly dependent upon flow velocity and weakly dependent upon EtOH concentration. Two-dimensional (2-D) box studies illustrated that minor differences (0.008 g/cm3) between flushing and resident solution density can strongly influence surfactant front propagation. A two-dimensional multiphase simulator, MISER, was used to model the influence of EtOH composition on the aqueous flow field and PCE mass recovery. The ability of the numerical simulator to predict effluent concentrations and front propagation was demonstrated for both 1-D columns and 2-D boxes flushed with EtOH-amended Tween 80 solutions. Results of this study quantify the potential influence of alcohol addition on surfactant solution properties and solubilization capacity, and demonstrate the importance of considering small density variations in remedial design.

Scaling of physical constraints at the root-soil interface to macroscopic patterns of nutrient retention in ecosystems.

PubMed

Gerber, Stefan; Brookshire, E N Jack

2014-03-01

Nutrient limitation in terrestrial ecosystems is often accompanied with maintaining a nearly closed vegetation-soil nutrient cycle. The ability to retain nutrients in an ecosystem requires the capacity of the plant-soil system to draw down nutrient levels in soils effectually such that export concentrations in soil solutions remain low. Here we address the physical constraints of plant nutrient uptake that may be limited by the diffusive movement of nutrients in soils, by the uptake at the root/mycorrhizal surface, and from interactions with soil water flow. We derive an analytical framework of soil nutrient transport and uptake and predict levels of plant available nutrient concentration and residence time. Our results, which we evaluate for nitrogen, show that the physical environment permits plants to lower soil solute concentration substantially. Our analysis confirms that plant uptake capacities in soils are considerable, such that water movement in soils is generally too small to significantly erode dissolved plant-available nitrogen. Inorganic nitrogen concentrations in headwater streams are congruent with the prediction of our theoretical framework. Our framework offers a physical-based parameterization of nutrient uptake in ecosystem models and has the potential to serve as an important tool toward scaling biogeochemical cycles from individual roots to landscapes.

Kirkwood–Buff integrals for ideal solutions

PubMed Central

Ploetz, Elizabeth A.; Bentenitis, Nikolaos; Smith, Paul E.

2010-01-01

The Kirkwood–Buff (KB) theory of solutions is a rigorous theory of solution mixtures which relates the molecular distributions between the solution components to the thermodynamic properties of the mixture. Ideal solutions represent a useful reference for understanding the properties of real solutions. Here, we derive expressions for the KB integrals, the central components of KB theory, in ideal solutions of any number of components corresponding to the three main concentration scales. The results are illustrated by use of molecular dynamics simulations for two binary solutions mixtures, benzene with toluene, and methanethiol with dimethylsulfide, which closely approach ideal behavior, and a binary mixture of benzene and methanol which is nonideal. Simulations of a quaternary mixture containing benzene, toluene, methanethiol, and dimethylsulfide suggest this system displays ideal behavior and that ideal behavior is not limited to mixtures containing a small number of components. PMID:20441282

The effect of calcium hydroxide, alkali dilution and calcium concentration in mitigating the alkali silica reaction using palm oil fuel ash

NASA Astrophysics Data System (ADS)

Asrah, Hidayati; Mirasa, Abdul Karim; Bolong, Nurmin

2018-02-01

This study investigated the mechanism of how POFA mitigated the ASR expansion. Two types of POFA; the UPOFA and GPOFA with different fineness were used to replace the cement at 20% and 40% and their effects on the mortar bar expansion, calcium hydroxide, alkali dilution, and calcium concentration were investigated. The results showed that UPOFA has a significant ability to mitigate the ASR, even at a lower level of replacement (20%) compared to GPOFA. The mechanism of UPOFA in mitigating the ASR expansion was through a reduction in the calcium hydroxide content, which produced low calcium concentration within the mortar pore solution. Low pore solution alkalinity signified that UPOFA had good alkali dilution effect. Meanwhile, a higher dosage of GPOFA was required to mitigate the ASR expansion. An increase in the pore solution alkalinity of GPOFA mortar indicated higher penetration of alkalis from the NaOH solution, which reduced the alkali dilution effect. However, this was compensated by the increase in the cement dilution effect at higher GPOFA replacement, which controlled the mortar bar expansion below the ASTM limit.

Application of a data assimilation method via an ensemble Kalman filter to reactive urea hydrolysis transport modeling

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

Juxiu Tong; Bill X. Hu; Hai Huang

2014-03-01

With growing importance of water resources in the world, remediations of anthropogenic contaminations due to reactive solute transport become even more important. A good understanding of reactive rate parameters such as kinetic parameters is the key to accurately predicting reactive solute transport processes and designing corresponding remediation schemes. For modeling reactive solute transport, it is very difficult to estimate chemical reaction rate parameters due to complex processes of chemical reactions and limited available data. To find a method to get the reactive rate parameters for the reactive urea hydrolysis transport modeling and obtain more accurate prediction for the chemical concentrations,more » we developed a data assimilation method based on an ensemble Kalman filter (EnKF) method to calibrate reactive rate parameters for modeling urea hydrolysis transport in a synthetic one-dimensional column at laboratory scale and to update modeling prediction. We applied a constrained EnKF method to pose constraints to the updated reactive rate parameters and the predicted solute concentrations based on their physical meanings after the data assimilation calibration. From the study results we concluded that we could efficiently improve the chemical reactive rate parameters with the data assimilation method via the EnKF, and at the same time we could improve solute concentration prediction. The more data we assimilated, the more accurate the reactive rate parameters and concentration prediction. The filter divergence problem was also solved in this study.« less

Breakdown of Burton Prim Slichter approach and lateral solute segregation in radially converging flows

NASA Astrophysics Data System (ADS)

Priede, J.; Gerbeth, G.

2005-11-01

A theoretical study is presented of the effect of a radially converging melt flow, which is directed away from the solidification front, on the radial solute segregation in simple solidification models. We show that the classical Burton-Prim-Slichter (BPS) solution describing the effect of a diverging flow on the solute incorporation into the solidifying material breaks down for the flows converging along the solidification front. The breakdown is caused by a divergence of the integral defining the effective boundary layer thickness which is the basic concept of the BPS theory. Although such a divergence can formally be avoided by restricting the axial extension of the melt to a layer of finite height, radially uniform solute distributions are possible only for weak melt flows with an axial velocity away from the solidification front comparable to the growth rate. There is a critical melt velocity for each growth rate at which the solution passes through a singularity and becomes physically inconsistent for stronger melt flows. To resolve these inconsistencies we consider a solidification front presented by a disk of finite radius R0 subject to a strong converging melt flow and obtain an analytic solution showing that the radial solute concentration depends on the radius r as ˜ln(R0/r) and ˜ln(R0/r) close to the rim and at large distances from it. The logarithmic increase of concentration is limited in the vicinity of the symmetry axis by the diffusion becoming effective at a distance comparable to the characteristic thickness of the solute boundary layer. The converging flow causes a solute pile-up forming a logarithmic concentration peak at the symmetry axis which might be an undesirable feature for crystal growth processes.

Modeling reactive transport with particle tracking and kernel estimators

NASA Astrophysics Data System (ADS)

Rahbaralam, Maryam; Fernandez-Garcia, Daniel; Sanchez-Vila, Xavier

2015-04-01

Groundwater reactive transport models are useful to assess and quantify the fate and transport of contaminants in subsurface media and are an essential tool for the analysis of coupled physical, chemical, and biological processes in Earth Systems. Particle Tracking Method (PTM) provides a computationally efficient and adaptable approach to solve the solute transport partial differential equation. On a molecular level, chemical reactions are the result of collisions, combinations, and/or decay of different species. For a well-mixed system, the chem- ical reactions are controlled by the classical thermodynamic rate coefficient. Each of these actions occurs with some probability that is a function of solute concentrations. PTM is based on considering that each particle actually represents a group of molecules. To properly simulate this system, an infinite number of particles is required, which is computationally unfeasible. On the other hand, a finite number of particles lead to a poor-mixed system which is limited by diffusion. Recent works have used this effect to actually model incomplete mix- ing in naturally occurring porous media. In this work, we demonstrate that this effect in most cases should be attributed to a defficient estimation of the concentrations and not to the occurrence of true incomplete mixing processes in porous media. To illustrate this, we show that a Kernel Density Estimation (KDE) of the concentrations can approach the well-mixed solution with a limited number of particles. KDEs provide weighting functions of each particle mass that expands its region of influence, hence providing a wider region for chemical reactions with time. Simulation results show that KDEs are powerful tools to improve state-of-the-art simulations of chemical reactions and indicates that incomplete mixing in diluted systems should be modeled based on alternative conceptual models and not on a limited number of particles.

Prebiotic chemistry in eutectic solutions at the water-ice matrix.

PubMed

Menor-Salván, César; Marín-Yaseli, Margarita R

2012-08-21

A crystalline ice matrix at subzero temperatures can maintain a liquid phase where organic solutes and salts concentrate to form eutectic solutions. This concentration effect converts the confined reactant solutions in the ice matrix, sometimes making condensation and polymerisation reactions occur more favourably. These reactions occur at significantly high rates from a prebiotic chemistry standpoint, and the labile products can be protected from degradation. The experimental study of the synthesis of nitrogen heterocycles at the ice-water system showed the efficiency of this scenario and could explain the origin of nucleobases in the inner Solar System bodies, including meteorites and extra-terrestrial ices, and on the early Earth. The same conditions can also favour the condensation of monomers to form ribonucleic acid and peptides. Together with the synthesis of these monomers, the ice world (i.e., the chemical evolution in the range between the freezing point of water and the limit of stability of liquid brines, 273 to 210 K) is an under-explored experimental model in prebiotic chemistry.

Development of new UV-vis spectroscopic microwave-assisted method for determination of glucose in pharmaceutical samples

NASA Astrophysics Data System (ADS)

Mabood, Fazal; Hussain, Z.; Haq, H.; Arian, M. B.; Boqué, R.; Khan, K. M.; Hussain, K.; Jabeen, F.; Hussain, J.; Ahmed, M.; Alharasi, A.; Naureen, Z.; Hussain, H.; Khan, A.; Perveen, S.

2016-01-01

A new UV-Visible spectroscopic method assisted with microwave for the determination of glucose in pharmaceutical formulations was developed. In this study glucose solutions were oxidized by ammonium molybdate in the presence of microwave energy and reacted with aniline to produce a colored solution. Optimum conditions of the reaction including wavelength, temperature, and pH of the medium and relative concentration ratio of the reactants were investigated. It was found that the optimal wavelength for the reaction is 610 nm, the optimal reaction time is 80 s, the optimal reaction temperature is 160 °C, the optimal reaction pH is 4, and the optimal concentration ratio aniline/ammonium molybdate solution was found to be 1:1. The limits of detection and quantification of the method are 0.82 and 2.75 ppm for glucose solution, respectively. The use of microwaves improved the speed of the method while the use of aniline improved the sensitivity of the method by shifting the wavelength.

Surfactant-enhanced remediation of a trichloroethene-contaminated aquifer. 2. Transport of TCE

USGS Publications Warehouse

Sahoo, D.; Smith, J.A.; Imbrigiotta, T.E.; Mclellan, H.M.

1998-01-01

Field studies were conducted under an induced gradient in a trichloroethene (TCE)-contaminated aquifer at Picatinny Arsenal, NJ, to study (a) the rate-limited desorption of TCE from aquifer sediments to water and (b) the effect of a surfactant (Triton X-100) on the desorption and transport of TCE. Clean water was injected into the contaminated aquifer for 206 day. Triton X-100 was added for a 36-day period (days 36-71 from the start of clean water injection). The effect of Triton X-100 on the desorption and transport of TCE in the field was examined by observing the concentrations of these two solutes in four monitoring wells 3-9 m from the injection wells. These data show a small but discernible increase in the TCE concentration in two of the wells corresponding approximately to the time when surfactant reaches the wells; in the other two monitoring wells, the increase in TCE concentration is negligible. A solute transport model that assumes local sorption equilibrium and used a laboratory-derived distribution coefficient could not adequately describe TCE desorption and transport observed in the aquifer. Two model formulations that accounted for rate-limited sorption - two-site and multisite models - fit the data well. TCE concentrations after surfactant injection were underpredicted by the models unless mass transfer rate was increased to account for the effect of surfactant on the rate of TCE desorption. The concentration data from the two wells and the model analysis suggest that the rate of TCE desorption is increased (by approximately 30%) as a result of Triton X-100 injection.Field studies were conducted under an induced gradient in a trichloroethene (TCE)-contaminated aquifer at Picatinny Arsenal, NJ, to study (a) the rate-limited desorption of TCE from aquifer sediments to water and (b) the effect of a surfactant (Triton X-100) on the desorption and transport of TCE. Clean water was injected into the contaminated aquifer for 206 day. Triton X-100 was added for a 36-day period (days 36-71 from the start of clean water injection). The effect of Triton X-100 on the desorption and transport of TCE in the field was examined by observing the concentrations of these two solutes in four monitoring wells 3-9 m from the injection wells. These data show a small but discernible increase in the TCE concentration in two of the wells corresponding approximately to the time when surfactant reaches the wells; in the other two monitoring wells, the increase in TCE concentration is negligible. A solute transport model that assumes local sorption equilibrium and used a laboratory-derived distribution coefficient could not adequately describe TCE desorption and transport observed in the aquifer. Two model formulations that accounted for rate-limited sorption - two-site and multisite models - fit the data well. TCE concentrations after surfactant injection were underpredicted by the models unless mass transfer rate was increased to account for the effect of surfactant on the rate of TCE desorption. The concentration data from the two wells and the model analysis suggest that the rate of TCE desorption is increased (by approximately 30%) as a result of Triton X-100 injection.

Optimal conditions for peripheral nerve storage in green tea polyphenol: an experimental study in animals.

PubMed

Matsumoto, Taiichi; Kakinoki, Ryosuke; Ikeguchi, Ryosuke; Hyon, Suong-Hyu; Nakamura, Takashi

2005-06-30

Our previous study demonstrated successful peripheral nerve storage for 1 month using polyphenol solution. We here report two studies to solve residual problems in using polyphenols as a storage solution for peripheral nerves. Study 1 was designed to determine the optimal concentration of the polyphenol solution and the optimal immersion period for nerve storage. Rat sciatic nerve segments were immersed in polyphenol solution at three different concentrations (2.5, 1.0, and 0.5 mg/ml) for three different periods (1, 7, and 26 days). Electrophysiological and morphological studies demonstrated that nerve regeneration from nerve segments that had been immersed in 1mg/ml polyphenol solution for 1 week and in Dulbecco's modified Eagle's medium (DMEM) for the subsequent 3 weeks was superior to the regeneration in other treatment groups. In study 2, the permeability of nerve tissue to polyphenol solution was investigated using canine sciatic nerve segments stored in 1.0mg/ml polyphenol solution for 1 week and in DMEM for the subsequent 3 weeks. Electron microscopy revealed that the Schwann cell structure within 500-700 microm of the perineurium was preserved, but cells deeper than 500-700 microm were badly damaged or had disappeared. The infiltration limit for polyphenol solution into neural tissue is inferred to be 500-700 microm.

Quantification of protein concentration using UV absorbance and Coomassie dyes.

PubMed

Noble, James E

2014-01-01

The measurement of a solubilized protein concentration in solution is an important assay in biochemistry research and development labs for applications ranging from enzymatic studies to providing data for biopharmaceutical lot release. Spectrophotometric protein quantification assays are methods that use UV and visible spectroscopy to rapidly determine the concentration of protein, relative to a standard, or using an assigned extinction coefficient. Where multiple samples need measurement, and/or the sample volume and concentration is limited, preparations of the Coomassie dye commonly known as the Bradford assay can be used. © 2014 Elsevier Inc. All rights reserved.

Improved radiation dose efficiency in solution SAXS using a sheath flow sample environment

PubMed Central

Kirby, Nigel; Cowieson, Nathan; Hawley, Adrian M.; Mudie, Stephen T.; McGillivray, Duncan J.; Kusel, Michael; Samardzic-Boban, Vesna; Ryan, Timothy M.

2016-01-01

Radiation damage is a major limitation to synchrotron small-angle X-ray scattering analysis of biomacromolecules. Flowing the sample during exposure helps to reduce the problem, but its effectiveness in the laminar-flow regime is limited by slow flow velocity at the walls of sample cells. To overcome this limitation, the coflow method was developed, where the sample flows through the centre of its cell surrounded by a flow of matched buffer. The method permits an order-of-magnitude increase of X-ray incident flux before sample damage, improves measurement statistics and maintains low sample concentration limits. The method also efficiently handles sample volumes of a few microlitres, can increase sample throughput, is intrinsically resistant to capillary fouling by sample and is suited to static samples and size-exclusion chromatography applications. The method unlocks further potential of third-generation synchrotron beamlines to facilitate new and challenging applications in solution scattering. PMID:27917826

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.

Advanced linear Fresnel optics for solar thermal energy (STE) production (Conference Presentation)

NASA Astrophysics Data System (ADS)

Collares-Pereira, Manuel

2016-09-01

One path towards low electricity cost is the use of ever higher concentration values, since that, in turn, will provide less thermal losses at higher temperatures and high temperature operation means higher thermodynamic efficiency in the conversion of heat into electricity. However concentration has an added value, since it is associated with larger primaries (see below) and thus with a reduction of collector rows in any given collector field. That, in turn, will reduce receiver length, connecting pipe lengths, number of components, thermal losses in pipes, heat transfer fluid mass, pumping power required (thus less parasitics), OM necessary, and all of that will contribute towards a lower electricity production cost. Conventional PT and LFR concentrators are, essentially, focusing optics solutions and thus very far from the concentration limits set by Non Imaging Optics. However if a conventional PT optics is designed to accommodate a second stage concentrator (or, even better, if a parabolic like primary is designed in an optimal way with a secondary concentrator for a given receiver) the result will have a much higher concentration, but also, as a consequence, a much larger size, since available evacuated tubular receivers come in basically one (standard) size : 70mm diameter. Thus from a typical aperture size of 6m and a concentration value of 26, to double the concentration value with n.i.o., would bring the aperture close to 12m, a value which is not practical for manufacture, transportation, field installation and operation (think about wind loads, for instance) . But with LFR technology this size limitation is not there at all, and low concentration values can now be substituted by much higher ones, and primaries between 20 and 30 m can be produced for the same tube. Some LFRs on the market do have second stage concentration and offer primaries of about 12m total mirror width when designed for those evacuated tubes. These correspond to a CPC type second stage combined with the conventional primary. But is possible to go much further in concentration ( or better yet, to go much further in CAP value - CAP= C*sinθ) by adopting Advanced LFR configurations which achieve the highest concentration possible for any given θ and do so by simultaneously conserve etendue as much as possible. This talk will present and some of these solutions and discuss their merits for the application in view. It will show that all things considered, Advanced LFR solutions, with Molten Salts operating at 565°C , have a much higher final solar to electricity conversion efficiency than the conventional solutions and thus LFR technology seems to have a future market potential (given its inherently low cost) much beyond its present very low market share.

Effect of solvent polarity on the spectroscopic properties of an alkynyl gold(i) gelator. The particular case of water.

PubMed

Gavara, Raquel; Lima, João Carlos; Rodríguez, Laura

2016-05-11

The spectroscopic properties of aggregates obtained from the hydrogelator [Au(4-pyridylethynyl)(PTA)] were studied in solvents of different polarities. Inspection of the absorption and emission spectra of diluted solutions showed that the singlet ground state of the monomeric species is sensitive to polarity and is stabilized in more polar solvents whereas the triplet excited state is rather insensitive to changes in polarity. The study of relatively concentrated solutions revealed the presence of new emission and excitation bands at 77 K that was attributed to the presence of different kinds of aggregates. Particularly interesting behaviour was revealed in water where aggregation is observed to be more efficient. For this, absorption, emission quantum yields and luminescence lifetimes of aqueous solutions at different concentrations were investigated in more detail. These data permitted one to correlate the increase of non-radiative and radiative rate constants of the low lying triplet emissive state with concentration, and therefore with the low limit concentration for aggregation, due to the shortening of the AuAu average distances in the aggregates and consequent enhancement of the spin-orbit coupling in the system.

Zeta potential of microfluidic substrates: 1. Theory, experimental techniques, and effects on separations.

PubMed

Kirby, Brian J; Hasselbrink, Ernest F

2004-01-01

This paper summarizes theory, experimental techniques, and the reported data pertaining to the zeta potential of silica and silicon with attention to use as microfluidic substrate materials, particularly for microchip chemical separations. Dependence on cation concentration, buffer and cation type, pH, cation valency, and temperature are discussed. The Debye-Hückel limit, which is often correctly treated as a good approximation for describing the ion concentration in the double layer, can lead to serious errors if it is extended to predict the dependence of zeta potential on the counterion concentration. For indifferent univalent electrolytes (e.g., sodium and potassium), two simple scalings for the dependence of zeta potential on counterion concentration can be derived in high- and low-zeta limits of the nonlinear Poisson-Boltzman equation solution in the double layer. It is shown that for most situations relevant to microchip separations, the high-zeta limit is most applicable, leading to the conclusion that the zeta potential on silica substrates is approximately proportional to the logarithm of the molar counterion concentration. The zeta vs. pH dependence measurements from several experiments are compared by normalizing the zeta based on concentration.

Functional lignocellulosic material for the remediation of copper(II) ions from water: Towards the design of a wood filter.

PubMed

Vitas, Selin; Keplinger, Tobias; Reichholf, Nico; Figi, Renato; Cabane, Etienne

2018-05-09

In this study, the chemical modification of bulk beech wood is described along with its utilization as biosorbent for the remediation of copper from water. The material was prepared by esterification using anhydrides, and reaction conditions were optimized to propose a greener process, in particular by reducing the amount of solvent. This modification yields a lignocellulosic material whose native structure is preserved, with an increased amount of carboxylic groups (up to 3 mmol/g). We demonstrate that the material can remove up to 95% of copper from low concentration solutions (100- 500 ppm). The adsorption efficiency decreases with concentrated copper solutions, and we show that a limited number of -COOH groups participate in copper binding (ca. 0.1 Cu/-COOH). This result suggests a limited accessibility of -COOH groups in the wood scaffold. This was demonstrated by the characterization of -COOH and copper distributions inside wood. Raman and EDX imaging confirmed that most -COOH groups are located inside the wood cell walls, thereby limiting interactions with copper. According to this study, critical limitations of bulk wood as a biosorbent were identified, and the results will be used to improve the material and design an efficient wood filter for heavy metal remediation. Copyright © 2018 Elsevier B.V. All rights reserved.

REMOVAL OF 137Cs FROM DISSOLVED HANFORD TANK SALTCAKE BY TREATMENT WITH IONSIV IE-911

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

Rapko, Brian M.; Sinkov, Serguei I.; Levitskaia, Tatiana G.

2005-03-01

This paper describes the preparation of a 137Cs-depleted form of dissolved Hanford tank saltcake. A composite feed solution was treated with IONSIV{reg_sign} IE-911, which effectively reduced the concentration of 137Cs. This allowed for subsequent testing of waste immobilization without significant radiological hazard. Limited characterization of the initial feed solution and a more extensive characterization of the 137Cs-depleted material also are provided.

Stability of suxamethonium in pharmaceutical solution for injection by validated stability-indicating chromatographic method.

PubMed

Beck, William; Kabiche, Sofiane; Balde, Issa-Bella; Carret, Sandra; Fontan, Jean-Eudes; Cisternino, Salvatore; Schlatter, Joël

2016-12-01

To assess the stability of pharmaceutical suxamethonium (succinylcholine) solution for injection by validated stability-indicating chromatographic method in vials stored at room temperature. The chromatographic assay was achieved by using a detector wavelength set at 218 nm, a C18 column, and an isocratic mobile phase (100% of water) at a flow rate of 0.6 mL/min for 5 minutes. The method was validated according to the International Conference on Harmonization guidelines with respect to the stability-indicating capacity of the method including linearity, limits of detection and quantitation, precision, accuracy, system suitability, robustness, and forced degradations. Linearity was achieved in the concentration range of 5 to 40 mg/mL with a correlation coefficient higher than 0.999. The limits of detection and quantification were 0.8 and 0.9 mg/mL, respectively. The percentage relative standard deviation for intraday (1.3-1.7) and interday (0.1-2.0) precision was found to be less than 2.1%. Accuracy was assessed by the recovery test of suxamethonium from solution for injection (99.5%-101.2%). Storage of suxamethonium solution for injection vials at ambient temperature (22°C-26°C) for 17 days demonstrated that at least 95% of original suxamethonium concentration remained stable. Copyright © 2016 Elsevier Inc. All rights reserved.

Development of low-level liquid-waste-treatment systems, October 1981 - March 1982

NASA Astrophysics Data System (ADS)

Williams, M. K.; Colvin, C. M.

1982-05-01

A plant design for a reverse osmosis (RO) membrane unit was completed. The design includes a conceptual diagram, specifications for a RO unit producing 40 gal/min of permeated product, a list of radioisotopes tested on RO units and the rejections achieved, a discussion of the principle of RO, a discussion of the upper limits of cation and anion concentrations (there are no lower limits), a discussion of membrane configurations and porosities, a discussion of factors affecting membranes, a section on calculating the membrane area needed for a particular application, and capital and operating cost calculations. The three factors found to affect the adsorption of cobalt on ion exchange resins were investigated in an interaction effects design experiment. These factors are solution pH, and sulfite and ammonium concentrations. Greater than 99% of the cobalt can usually be removed from solutions at a pH between 3 and 6. A design for an ion-exchange pilot plant was completed.

Ultrasensitive molecular detection using thermal conductance of a hydrophobic gold-water interface.

PubMed

Green, Andrew J; Alaulamie, Arwa A; Baral, Susil; Richardson, Hugh H

2013-09-11

The thermal conductance from a hydrophobic gold aqueous interface is measured with increasing solute concentration. A small amount of aqueous solute molecules (1 solute molecule in 550 water molecules) dramatically increases the heat dissipation into the surrounding liquid. This result is consistent with a thermal conductance that is limited by an interface interaction where minority aqueous components significantly alter the surface properties and heat transport through the interface. The increase in heat dissipation can be used to make an extremely sensitive molecular detector that can be scaled to give single molecule detection without amplification or utilizing fluorescence labels.

A field experiment with variable-suction multi-compartment samplers to measure the spatio-temporal distribution of solute leaching in an agricultural soil.

PubMed

Bloem, E; Hogervorst, F A N; de Rooij, G H

2009-04-01

Solutes spread out in time and space as they move downwards from the soil surface with infiltrating water. Solute monitoring in the field is often limited to observations of resident concentrations, while flux concentrations govern the movement of solutes in soils. A recently developed multi-compartment sampler is capable of measuring fluxes at a high spatial resolution with minimal disturbance of the local pressure head field. The objective of this paper is to use this sampler to quantify the spatial and temporal variation of solute leaching below the root zone in an agricultural field under natural rainfall in winter and spring. We placed two samplers at 31 and 25 cm depth in an agricultural field, leaving the soil above undisturbed. Each sampler contained 100 separate cells of 31x31 mm. Water fluxes were measured every 5 min for each cell. We monitored leaching of a chloride pulse under natural rainfall by frequently extracting the collected leachate while leaving the samplers buried in situ. This experiment was followed by a dye tracer experiment. This setting yielded information that widely surpassed the information that can be provided by separate anionic and dye tracer trials, and solute transport monitoring by coring or suction cups. The detailed information provided by the samplers showed that percolation at the sampling depth started much faster (approximately 3 h after the start of rainfall) in initially wet soil (pressure head above -65 cm) than in drier soil (more than 14 h at pressure heads below -80 cm). At any time, 25% of the drainage passed through 5-6% of the sampled area, reflecting the effect of heterogeneity on the flow paths. The amount of solute carried by individual cells varied over four orders of magnitude. The lateral concentration differences were limited though. This suggests a convective-dispersive regime despite the short vertical travel distance. On the other hand, the dilution index indicates a slight tendency towards stochastic-convective transport at this depth. There was no evidence in the observed drainage patterns and dye stained profiles of significant disturbance of the flow field by the samplers.

Influence of dissolved organic carbon content on modelling natural organic matter acid-base properties.

PubMed

Garnier, Cédric; Mounier, Stéphane; Benaïm, Jean Yves

2004-10-01

Natural organic matter (NOM) behaviour towards proton is an important parameter to understand NOM fate in the environment. Moreover, it is necessary to determine NOM acid-base properties before investigating trace metals complexation by natural organic matter. This work focuses on the possibility to determine these acid-base properties by accurate and simple titrations, even at low organic matter concentrations. So, the experiments were conducted on concentrated and diluted solutions of extracted humic and fulvic acid from Laurentian River, on concentrated and diluted model solutions of well-known simple molecules (acetic and phenolic acids), and on natural samples from the Seine river (France) which are not pre-concentrated. Titration experiments were modelled by a 6 acidic-sites discrete model, except for the model solutions. The modelling software used, called PROSECE (Programme d'Optimisation et de SpEciation Chimique dans l'Environnement), has been developed in our laboratory, is based on the mass balance equilibrium resolution. The results obtained on extracted organic matter and model solutions point out a threshold value for a confident determination of the studied organic matter acid-base properties. They also show an aberrant decreasing carboxylic/phenolic ratio with increasing sample dilution. This shift is neither due to any conformational effect, since it is also observed on model solutions, nor to ionic strength variations which is controlled during all experiments. On the other hand, it could be the result of an electrode troubleshooting occurring at basic pH values, which effect is amplified at low total concentration of acidic sites. So, in our conditions, the limit for a correct modelling of NOM acid-base properties is defined as 0.04 meq of total analysed acidic sites concentration. As for the analysed natural samples, due to their high acidic sites content, it is possible to model their behaviour despite the low organic carbon concentration.

Microelectrode Geochemical Observatory for In Situ Monitoring of Metals Concentration and Mobility in Contaminated Sediments

DTIC Science & Technology

2013-09-01

SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON a. REPORT b. ABSTRACT c . THIS PAGE 19b. TELEPHONE...Report Microelectrode Geochemcial Observatory for In Situ Monitoring of Metals Concentration and Mobility in Contaminated Sediments N62583-11- C -0524...Representative Poor Electrochemical Scans APPENDIX B: Standard Solution Test Data APPENDIX C : Bremerton Porewater Test Data APPENDIX D: Porewater

On the refractive index of sodium iodide solutions for index matching in PIV

NASA Astrophysics Data System (ADS)

Bai, Kunlun; Katz, Joseph

2014-04-01

Refractive index matching has become a popular technique for facilitating applications of modern optical diagnostic techniques, such as particle image velocimetry, in complex systems. By matching the refractive index of solid boundaries with that of the liquid, unobstructed optical paths can be achieved for illumination and image acquisition. In this research note, we extend previously provided data for the refractive index of aqueous solutions of sodium iodide (NaI) for concentrations reaching the temperature-dependent solubility limit. Results are fitted onto a quadratic empirical expression relating the concentration to the refractive index. Temperature effects are also measured. The present range of indices, 1.333-1.51, covers that of typical transparent solids, from silicone elastomers to several recently introduced materials that could be manufactured using rapid prototyping. We also review briefly previous measurements of the refractive index, viscosity, and density of NaI solutions, as well as prior research that has utilized this fluid.

Charging and Screening in Nonpolar Solutions of Nonionizable Surfactants

NASA Astrophysics Data System (ADS)

Behrens, Sven

2010-03-01

Nonpolar liquids do not easily accommodate electric charges, but surfactant additives are often found to dramatically increase the solution conductivity and promote surface charging of suspended colloid particles. Such surfactant-mediated electrostatic effects have been associated with equilibrium charge fluctuations among reverse surfactant micelles and in some cases with the statistically rare ionization of individual surfactant molecules. Here we present experimental evidence that even surfactants without any ionizable group can mediate charging and charge screening in nonpolar oils, and that they can do so at surfactant concentrations well below the critical micelle concentration (cmc). Precision conductometry, light scattering, and Karl-Fischer titration of sorbitan oleate solutions in hexane, paired with electrophoretic mobility measurements on suspended polymer particles, reveal a distinctly electrostatic action of the surfactant. We interpret our observations in terms of a charge fluctuation model and argue that the observed charging processes are likely facilitated, but not limited, by the presence of ionizable impurities.

Normal evaporation of binary alloys

NASA Technical Reports Server (NTRS)

Li, C. H.

1972-01-01

In the study of normal evaporation, it is assumed that the evaporating alloy is homogeneous, that the vapor is instantly removed, and that the alloy follows Raoult's law. The differential equation of normal evaporation relating the evaporating time to the final solute concentration is given and solved for several important special cases. Uses of the derived equations are exemplified with a Ni-Al alloy and some binary iron alloys. The accuracy of the predicted results are checked by analyses of actual experimental data on Fe-Ni and Ni-Cr alloys evaporated at 1600 C, and also on the vacuum purification of beryllium. These analyses suggest that the normal evaporation equations presented here give satisfactory results that are accurate to within an order of magnitude of the correct values, even for some highly concentrated solutions. Limited diffusion and the resultant surface solute depletion or enrichment appear important in the extension of this normal evaporation approach.

Disappearance kinetics of solutes from synovial fluid after intra-articular injection.

PubMed Central

Owen, S G; Francis, H W; Roberts, M S

1994-01-01

1. Five rheumatoid patients with a knee joint effusion participated in the study. An aqueous solution (0.1 to 0.2 ml) containing paracetamol, salicylate, diclofenac and [125I]-albumin was injected into a given joint to yield target concentrations of approximately 20 micrograms ml-1 for diclofenac, salicylate and paracetamol and 10(8) counts ml-1 for [125I]-albumin. 2. Paracetamol, salicylate and diclofenac were analysed in synovial fluid by h.p.l.c. [125I]-albumin was analysed using gamma counting. 3. The clearances (+/- s.d.) obtained for the solutes were [125I]-albumin (0.0053 +/- 0.0019 l h-1), diclofenac (0.0096 +/- 0.0061 l h-1), salicylate (0.024 +/- 0.022 l h-1) and paracetamol (0.055 +/- 0.041 l h-1). The corresponding fractions unbound of these solutes in synovial fluid were 0.0, < or = 0.01, 0.34 +/- 0.09 and 0.85 +/- 0.10, respectively. 4. Diffusion of unbound solute through the synovium is estimated to account for (+/- s.d.) 0.52 +/- 0.08, 0.87 +/- 0.06 and 0.99 +/- 0.01 of the total clearance of diclofenac, salicylate and paracetamol from the joint space, respectively. The remaining proportion of clearance is accounted for by efflux of solute bound to albumin. 5. An expression for the ratio of synovial fluid to total plasma concentrations after systemic administration was developed to include both diffusion of unbound solute and albumin flux. Most solutes appear to satisfy the conditions in which this expression reduces to the limiting case where the unbound concentration of the solute is identical in the synovial fluid and plasma under steady state conditions. PMID:7833225

An approximate analytical methodology for the concentration CDF and corresponding adverse health effects in 3D heterogeneous aquifers

NASA Astrophysics Data System (ADS)

Zarlenga, Antonio; de Barros, Felipe; Fiori, Aldo

2017-04-01

Predicting solutes displacement in ecosystems is a complex task because of heterogeneity of hydrogeological properties and limited financial resources for characterization. As a consequence, solute transport model predictions are subject to uncertainty and probabilistic methods are invoked. Despite the significant theoretical advances in subsurface hydrology, there is a compelling need to transfer those specialized know-hows into an easy-to-use practical tool. The deterministic approach is able to capture some features of the transport behavior but its adoption in practical applications (e.g. remediation strategies or health risk assessment) is often inadequate because of its inability to accurately model the phenomena triggered by the spatial heterogeneity. The rigorous evaluation of the local contaminant concentration in natural aquifers requires an accurate estimate of the domain properties and huge computational times; those aspects limit the adoption of fully 3D numerical models. In this presentation, we illustrate a physically-based methodology to analytically estimate of the statistics of the solute concentration in natural aquifers and the related health risk. Our methodology aims to provide a simple tool for a quick assessment of the contamination level in aquifers, as function of a few relevant, physically based parameters such as the log conductivity variance, the mean flow velocity, the Péclet number. Solutions of the 3D analytical model adopt the results of previous works: transport model is based on the solutions proposed by Zarlenga and Fiori (2013, 2014) where semi-analytical relations for the statics of local contaminant concentration are carry out through a Lagrangian first-order model. As suggested in de Barros and Fiori (2014), the Beta distribution is assumed for the concentration cumulative density function (CDF). We illustrate the use of the closed-form equations for the probability of local contaminant concentration and health risk in a series of problems of practical relevance. The basic scenario is constituted by a steady state plume in a 3D heterogeneous formation. In this case the non-reactive transport is ruled by interplay of the spreading (lateral and vertical) and dilution. The second scenario considers two different dynamics of degradation in aerobic and anaerobic conditions which allows the contaminant abatement. The final example links the environmental concentration with adverse health effects. For this case, additional information on toxicological and behavioral parameters are required. Despite the simplifying assumptions adopted, the proposed solutions are appealing in applications due to their simplicity and the fact that they allow to easily propagate the uncertainty from different sources in the final risk endpoint. de Barros, F.P., Fiori, A., 2014. First-order based cumulative distribution function for solute concentration in heterogeneous aquifers: theoretical analysis and implications for human health risk assessment. Water Resour. Res. 50, 4018-4037. Zarlenga, A., Fiori, A., 2013. Steady plumes in heterogeneous porous formations: a stochastic lagrangian approach. Water Resour. Res. 49, 864-873. Zarlenga, A., Fiori, A., 2014. Stochastic analytical modeling of the biodegradation of steady plumes. J. Contam. Hydrol. 157, 106-116.

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.

Response of Periphyton to Seasonal Changes in Nutrient Concentrations in Central Illinois Agricultural Streams

NASA Astrophysics Data System (ADS)

Kirkham, K. G.; Perry, W. L.

2005-05-01

Headwater streams in central Illinois have been dredged and channelized to drain surrounding agricultural fields and has led to extensive erosion and eutrophication. Restoration of these systems through farmer implementation of Best Management Practices (BMPs) may be one solution. Examination of algal population dynamics may be useful in assessment of BMP effectiveness. We have monitored two small headwater streams, Bray Creek and Frog Alley, for a suite of physicochemical parameters focusing on dissolved oxygen, nitrogen, and phosphorus for three years. Nutrient concentrations suggested potential nutrient limitation by nitrates during late summer and phosphorus limitation in early summer. To determine seasonal algal dynamics with seasonally varying nutrient limitation in agricultural headwater streams, we used nutrient diffusing substrata (NDS). NDS with agar (controls) or amended with either nitrogen, phosphorus, or both were deployed for 21-24 days in both streams each month for a year. Slight nutrient limitation was observed in Bray Creek during August and November while phosphorus was limiting in September (P<0.05). We suggest agricultural streams are more dynamic than previously thought and algal populations may be seasonally nutrient limited and with consequent effects on dissolved oxygen concentrations.

Validation of uranium determination in urine by ICP-MS.

PubMed

Bouvier-Capely, C; Baglan, N; Montègue, A; Ritt, J; Cossonnet, C

2003-08-01

A rapid procedure--dilution of urine+ICP-MS measurement--for the determination of uranium in urine was validated. Large ranges of concentration and isotopic composition were studied on urine samples excreted by occupationally exposed workers. The results were consistent with those obtained by fluorimetry and by alpha spectrometry after a purification procedure, two currently used techniques. However, the proposed procedure is limited for determination of the minor isotope 234U. Thus for worker monitoring, the conversion of 234U mass concentration into activity concentration can lead to an erroneous value of the effective dose, in particular for a contamination at very low level with highly enriched uranium. A solution to avoid this hazard is to perform a chemical purification prior to ICP-MS measurement to lower uncertainty and detection limit for 234U.

Multiplicity of solutions for the noncooperative Schrödinger-Kirchhoff system involving the fractional p-Laplacian in R^N

NASA Astrophysics Data System (ADS)

Liang, Sihua; Zhang, Jihui

2017-06-01

In this paper, we investigate the existence of solutions for the noncooperative Schrödinger-Kirchhoff-type system involving the fractional p-Laplacian and critical nonlinearities in RN. By applying the Limit Index Theory due to Li (Nonlinear Anal 25:1371-1389, 1995) and the fractional version of concentration-compactness principle, we obtain the existence and multiplicity of solutions for the above systems under some suitable assumptions. To our best knowledge, it seems that this is the first time to exploit the existence of solutions for the noncooperative Schrödinger-Kirchhoff-type system involving the fractional p-Laplacian and critical nonlinearity in RN.

Super-resolution study of polymer mobility fluctuations near c*.

PubMed

King, John T; Yu, Changqian; Wilson, William L; Granick, Steve

2014-09-23

Nanoscale dynamic heterogeneities in synthetic polymer solutions are detected using super-resolution optical microscopy. To this end, we map concentration fluctuations in polystyrene-toluene solutions with spatial resolution below the diffraction limit, focusing on critical fluctuations near the polymer overlap concentration, c*. Two-photon super-resolution microscopy was adapted to be applicable in an organic solvent, and a home-built STED-FCS system with stimulated emission depletion (STED) was used to perform fluorescence correlation spectroscopy (FCS). The polystyrene serving as the tracer probe (670 kg mol(-1), radius of gyration RG ≈ 35 nm, end-labeled with a bodipy derivative chromophore) was dissolved in toluene at room temperature (good solvent) and mixed with matrix polystyrene (3,840 kg mol(-1), RG ≈ 97 nm, Mw/Mn = 1.04) whose concentration was varied from dilute to more than 10c*. Whereas for dilute solutions the intensity-intensity correlation function follows a single diffusion process, it splits starting at c* to imply an additional relaxation process provided that the experimental focal area does not greatly exceed the polymer blob size. We identify the slower mode as self-diffusion and the increasingly rapid mode as correlated segment fluctuations that reflect the cooperative diffusion coefficient, Dcoop. These real-space measurements find quantitative agreement between correlation lengths inferred from dynamic measurements and those from determining the limit below which diffusion coefficients are independent of spot size. This study is considered to illustrate the potential of importing into polymer science the techniques of super-resolution imaging.

Density of Gadolinium Nitrate Solutions for the High Flux Isotope Reactor

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

Taylor, Paul Allen; Lee, Denise L

2009-05-01

In late 1992, the High Flux Isotope Reactor (HFIR) was planning to switch the solution contained in the poison injection tank from cadmium nitrate to gadolinium nitrate. The poison injection system is an emergency system used to shut down the reactor by adding a neutron poison to the cooling water. This system must be able to supply a minimum of 69 pounds of gadolinium to the reactor coolant system in order to guarantee that the reactor would become subcritical. A graph of the density of gadolinium nitrate solutions over a concentration range of 5 to 30 wt% and a temperaturemore » range of 15 to 40{sup o}C was prepared. Routine density measurements of the solution in the poison injection tank are made by HFIR personnel, and an adaptation of the original graph is used to determine the gadolinium nitrate concentration. In late 2008, HFIR personnel decided that the heat tracing that was present on the piping for the poison injection system could be removed without any danger of freezing the solution; however, the gadolinium nitrate solution might get as cold as 5{sup o}C. This was outside the range of the current density-concentration correlation, so the range needed to be expanded. This report supplies a new density-concentration correlation that covers the extended temperature range. The correlation is given in new units, which greatly simplifies the calculation that is required to determine the pounds of gadolinium in the tank solution. The procedure for calculating the amount of gadolinium in the HFIR poison injection system is as follows: (1) Calculate the usable volume in the system; (2) Measure the density of the solution; (3) Calculate the gadolinium concentration using the following equation: Gd(lb/ft{sup 3}) = measured density (g/mL) x 34.681 - 34.785; (4) Calculate the amount of gadolinium in the system using the following equation: Amount of Gd(lb) = Gd concentration (lb/ft{sup 3}) x usable volume (ft{sup 3}). The equation in step 3 is exact for a temperature of 5{sup o}C, and overestimates the gadolinium concentration at all higher temperatures. This guarantees that the calculation is conservative, in that the actual concentration will be at least as high as that calculated. If an additional safety factor is desired, it is recommended that an administrative control limit be set that is higher than the required minimum amount of gadolinium.« less

Effect of deodorant and antiperspirant use and presence or absence of axillary hair on absorption of testosterone 2% solution applied to men's axillae.

PubMed

Small, David S; Ni, Xiao; Polzer, Paula; Vart, Richard; Satonin, Darlene K; Mitchell, Malcolm I

2014-11-01

Testosterone 2% solution is applied to axillae and is indicated for testosterone replacement therapy in males deficient in endogenous testosterone. This open-label crossover study evaluated the effect of deodorant/antiperspirant use and presence or absence of axillary hair on absorption of testosterone solution. Healthy males (N = 30; ≥50 years of age with baseline testosterone <400 ng/dL) were randomized to one of four treatment sequences involving six treatments. Each treatment consisted of one 1.5-mL dose of testosterone 2% solution (30 mg of testosterone) applied to each axilla. Axillae were unshaved or shaved, and were untreated or pretreated with deodorant/antiperspirant. Blood samples were taken over 72 hours after each dose for measuring serum testosterone concentrations. Profiles of mean testosterone concentrations were similar across treatments. For all treatments, area under the concentration-time curve through 24 hours (AUC[0-24] ) and 72 hours (AUC[0-72] ), and maximum total testosterone concentration (Cmax ) were similar except for 15% lower Cmax when treatment was applied after deodorant/antiperspirant to shaved vs. unshaved axillae (least squares mean, 531 ng/dL vs. 626 ng/dL, respectively; P = 0.011). This difference is not considered clinically significant. The 95% confidence intervals for AUC(0-24) , AUC(0-72) , and Cmax fell within the traditional bioequivalence limits of 0.8 to 1.25. Incidence of treatment-emergent adverse events (TEAEs) was low (<15%) in each treatment arm, and most TEAEs were mild. Absorption of testosterone 2% solution was unaffected by use of deodorant/antiperspirant or by the presence or absence of axillary hair. Testosterone solution was generally well tolerated. © 2014 International Society for Sexual Medicine.

Analytical solutions for a soil vapor extraction model that incorporates gas phase dispersion and molecular diffusion

NASA Astrophysics Data System (ADS)

Huang, Junqi; Goltz, Mark N.

2017-06-01

To greatly simplify their solution, the equations describing radial advective/dispersive transport to an extraction well in a porous medium typically neglect molecular diffusion. While this simplification is appropriate to simulate transport in the saturated zone, it can result in significant errors when modeling gas phase transport in the vadose zone, as might be applied when simulating a soil vapor extraction (SVE) system to remediate vadose zone contamination. A new analytical solution for the equations describing radial gas phase transport of a sorbing contaminant to an extraction well is presented. The equations model advection, dispersion (including both mechanical dispersion and molecular diffusion), and rate-limited mass transfer of dissolved, separate phase, and sorbed contaminants into the gas phase. The model equations are analytically solved by using the Laplace transform with respect to time. The solutions are represented by confluent hypergeometric functions in the Laplace domain. The Laplace domain solutions are then evaluated using a numerical Laplace inversion algorithm. The solutions can be used to simulate the spatial distribution and the temporal evolution of contaminant concentrations during operation of a soil vapor extraction well. Results of model simulations show that the effect of gas phase molecular diffusion upon concentrations at the extraction well is relatively small, although the effect upon the distribution of concentrations in space is significant. This study provides a tool that can be useful in designing SVE remediation strategies, as well as verifying numerical models used to simulate SVE system performance.

Do Clustering Monoclonal Antibody Solutions Really Have a Concentration Dependence of Viscosity?

PubMed Central

Pathak, Jai A.; Sologuren, Rumi R.; Narwal, Rojaramani

2013-01-01

Protein solution rheology data in the biophysics literature have incompletely identified factors that govern hydrodynamics. Whereas spontaneous protein adsorption at the air/water (A/W) interface increases the apparent viscosity of surfactant-free globular protein solutions, it is demonstrated here that irreversible clusters also increase system viscosity in the zero shear limit. Solution rheology measured with double gap geometry in a stress-controlled rheometer on a surfactant-free Immunoglobulin solution demonstrated that both irreversible clusters and the A/W interface increased the apparent low shear rate viscosity. Interfacial shear rheology data showed that the A/W interface yields, i.e., shows solid-like behavior. The A/W interface contribution was smaller, yet nonnegligible, in double gap compared to cone-plate geometry. Apparent nonmonotonic composition dependence of viscosity at low shear rates due to irreversible (nonequilibrium) clusters was resolved by filtration to recover a monotonically increasing viscosity-concentration curve, as expected. Although smaller equilibrium clusters also existed, their size and effective volume fraction were unaffected by filtration, rendering their contribution to viscosity invariant. Surfactant-free antibody systems containing clusters have complex hydrodynamic response, reflecting distinct bulk and interface-adsorbed protein as well as irreversible cluster contributions. Literature models for solution viscosity lack the appropriate physics to describe the bulk shear viscosity of unstable surfactant-free antibody solutions. PMID:23442970

Flower-like ZnO decorated polyaniline/reduced graphene oxide nanocomposites for simultaneous determination of dopamine and uric acid.

PubMed

Ghanbari, Kh; Moloudi, M

2016-11-01

A novel sensor was fabricated by electrochemical deposition of ZnO flower-like/polyaniline nanofiber/reduced graphene oxide nanocomposite (ZnO/PANI/RGO) on glassy carbon electrode (GCE) for direct detection of dopamine (DA) and uric acid (UA) in the presence of fixed concentration of ascorbic acid (AA). Surface morphology and characterization of the modified electrodes were confirmed by field emission scanning microscopy (FE-SEM), X-ray diffraction (XRD), Raman and FT-IR spectroscopies. For individual detection, the linear responses were in the two concentration ranges of 0.001-1 μM and 1-1000 μM with detection limit 0.8 nM (S/N = 3) for DA, and also 0.1-100 μM and 100-1000 μM with detection limit 0.042 μM (S/N = 3) for UA. Simultaneous determination of these species in their mixture solution showed the linear responses in the two concentration ranges of 0.1-90 μM and 90-1000 μM with detection limit 0.017 μM (S/N = 3) for DA and also showed two linear range of 0.5-90 μM and 100-1000 μM with detection limit 0.12 μM (S/N = 3) for UA, with coexistence of 1000 μM AA. The applicability of sensor for the analysis of DA, and UA in dopamine injection solution, human serum and human urine samples was successfully demonstrated. Copyright © 2016 Elsevier Inc. All rights reserved.

Selective concentration of aromatic bases from water with a resin adsorbent

USGS Publications Warehouse

Stuber, H.A.; Leenheer, J.A.

1983-01-01

Aromatic bases are concentrated from water on columns of a resin adsorbent and recovered by aqueous-acid elution. The degree of concentration attainable depends on the ratio of the capacity factor (k) of the neutral form of the amine to that of the ionized form. Capacity factors of ionic forms of amines on XAD-8 resin (a methylacrylic ester polymer) are greater than zero, ranging from 20 to 250 times lower than those of their neutral forms; they increase with increasing hydrophobicity of the amine. Thus, desorption by acid is an edition (k during desorption >0) rather than a displacement (k during desorption = 0) process. The degree of concentration attainable on XAD-8 resin varies with the hydrophobicity of the amine, being limited for hydrophilic solutes (for example, pyridine) by small neutral-form k's, reaching a maximum for amines of intermediate hydrophobicity (for example, quinoline), and decreasing for more hydrophobc solutes (for example, acridine) because of their large ionic-form k's.

Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

DOE PAGES

Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; ...

2014-12-04

We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na 2 35SO 4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na 2SO 4(L1) 2(H 2O) 4 capsules. We foundmore » that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. Moreover, this corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.« less

Optimising concentrations of antimicrobial agents in pharmaceutical preparations: Case of an oral solution of glycerol and an ophthalmic solution containing cysteamine.

PubMed

Chan Hew Wai, A; Becasse, P; Tworski, S; Pradeau, D; Planas, V

2014-11-01

In the context of current distrust of antimicrobial preservatives, the quantities of these substances in two pharmaceutical formulas were studied: an ophthalmic solution of cysteamine preserved benzalkonium chloride at 1mg/5mL and Glycerotone(®) preserved with sorbic acid at 0.1g/100g. The purpose of this work was to verify that a reduction of the quantities of preservative continues to fulfil the requirements for antimicrobial preservation. The Test of efficacy of antimicrobial preservation, section 5.1.3 of the 8th edition of the European Pharmacopoeia, was carried out on each formulation prepared with decreasing quantities of preservative. The results show that formulations whose preservative concentration was reduced by a factor of four remained compliant with standards. It is to be noted that in formulas without preservative, fungal growth was observed in both the solution of Glycerotone(®) and the ophthalmic solution containing cysteamine. Although there is no question that an antimicrobial preservative is necessary, the quantity of preservative can be reduced without deteriorating the quality of the pharmaceutical product but the minimal effective concentration remains to be determined. The formulations of many pharmaceutical products should therefore be examined in order to limit the quantities of preservative while continuing to guarantee patient's safety. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Adsorption interactions of humic acids with biocides

NASA Astrophysics Data System (ADS)

Mal'Tseva, E. V.; Ivanov, A. A.; Yudina, N. V.

2009-11-01

The chemical composition of humic acids from brown coal (Aldrich) was determined by element analysis, 13C NMR spectroscopy, and potentiometric titration. The adsorption ability of humic acids with different biocides (cyproconasol, propiconasol, tebuconasol, irgarol 1051, and DCOIT) was studied. The adsorption ability of a mixture of biocides in aqueous solutions was higher than that of the individual components. The limiting concentration of humic acids at which adsorption of biocides was maximum was determined. Adsorption constants were calculated by the Freundlich equation for each biocide in aqueous solution.

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.

C-H oxidation and chelation of a dipyrromethane mediated rapid colorimetric naked-eye Cu(ii) chemosensor.

PubMed

Rajmohan, Rajamani; Ayaz Ahmed, Khan Behlol; Sangeetha, Sampathkumar; Anbazhagan, Veerappan; Vairaprakash, Pothiappan

2017-09-08

Copper(ii) ion mediated C-H oxidation of dipyrromethanes (DPMs) to the corresponding dipyrrins followed by complexation invoked the selective sensing of copper(ii) ions in aqueous solutions. On the addition of copper, the colour of the DPM solution instantaneously changes from yellow to pink with the detection limit of 0.104 μM measured by absorption spectroscopy, whereas visible colour changes could be observed by the naked eye for concentrations as low as 3 μM.

Quantitative relationship between the octanol/water partition coefficient and the diffusion limitation of the exchange between adipose and blood

PubMed Central

2010-01-01

Background The goal of physiologically based pharmacokinetics (PBPK) is to predict drug kinetics from an understanding of the organ/blood exchange. The standard approach is to assume that the organ is "flow limited" which means that the venous blood leaving the organ equilibrates with the well-stirred tissue compartment. Although this assumption is valid for most solutes, it has been shown to be incorrect for several very highly fat soluble compounds which appear to be "diffusion limited". This paper describes the physical basis of this adipose diffusion limitation and its quantitative dependence on the blood/water (Kbld-wat) and octanol/water (Kow) partition coefficient. Methods Experimental measurements of the time dependent rat blood and adipose concentration following either intravenous or oral input were used to estimate the "apparent" adipose perfusion rate (FA) assuming that the tissue is flow limited. It is shown that the ratio of FA to the anatomic perfusion rate (F) provides a measure of the diffusion limitation. A quantitative relationship between this diffusion limitation and Kbld-wat and Kow is derived. This analysis was applied to previously published data, including the Oberg et. al. measurements of the rat plasma and adipose tissue concentration following an oral dose of a mixture of 13 different polychlorinated biphenyls. Results Solutes become diffusion limited at values of log Kow greater than about 5.6, with the adipose-blood exchange rate reduced by a factor of about 30 for a solute with a log Kow of 7.36. Quantitatively, a plot of FA/F versus Kow is well described assuming an adipose permeability-surface area product (PS) of 750/min. This PS corresponds to a 0.14 micron aqueous layer separating the well-stirred blood from the adipose lipid. This is approximately equal to the thickness of the rat adipose capillary endothelium. Conclusions These results can be used to quantitate the adipose-blood diffusion limitation as a function of Kow. This is especially important for the highly fat soluble persistent organic chemicals (e.g. polychlorinated biphenyls, dioxins) whose pharmacokinetics are primarily determined by the adipose-blood exchange kinetics. PMID:20055995

Quantitative relationship between the octanol/water partition coefficient and the diffusion limitation of the exchange between adipose and blood.

PubMed

Levitt, David G

2010-01-07

The goal of physiologically based pharmacokinetics (PBPK) is to predict drug kinetics from an understanding of the organ/blood exchange. The standard approach is to assume that the organ is "flow limited" which means that the venous blood leaving the organ equilibrates with the well-stirred tissue compartment. Although this assumption is valid for most solutes, it has been shown to be incorrect for several very highly fat soluble compounds which appear to be "diffusion limited". This paper describes the physical basis of this adipose diffusion limitation and its quantitative dependence on the blood/water (Kbld-wat) and octanol/water (Kow) partition coefficient. Experimental measurements of the time dependent rat blood and adipose concentration following either intravenous or oral input were used to estimate the "apparent" adipose perfusion rate (FA) assuming that the tissue is flow limited. It is shown that the ratio of FA to the anatomic perfusion rate (F) provides a measure of the diffusion limitation. A quantitative relationship between this diffusion limitation and Kbld-wat and Kow is derived. This analysis was applied to previously published data, including the Oberg et. al. measurements of the rat plasma and adipose tissue concentration following an oral dose of a mixture of 13 different polychlorinated biphenyls. Solutes become diffusion limited at values of log Kow greater than about 5.6, with the adipose-blood exchange rate reduced by a factor of about 30 for a solute with a log Kow of 7.36. Quantitatively, a plot of FA/F versus Kow is well described assuming an adipose permeability-surface area product (PS) of 750/min. This PS corresponds to a 0.14 micron aqueous layer separating the well-stirred blood from the adipose lipid. This is approximately equal to the thickness of the rat adipose capillary endothelium. These results can be used to quantitate the adipose-blood diffusion limitation as a function of Kow. This is especially important for the highly fat soluble persistent organic chemicals (e.g. polychlorinated biphenyls, dioxins) whose pharmacokinetics are primarily determined by the adipose-blood exchange kinetics.

Coalescence Kinetics of Lipid Based Bicelles

NASA Astrophysics Data System (ADS)

Hu, Andrew; Fan, Tai-Hsi; Katsaras, John; Xia, Yan; Li, Ming; Nieh, Mu-Ping

2014-03-01

Uniform nanodisc can be self-assembled from lipid mixtures of dimyristoyl phosphatidylcholine (DMPC), dimyristoyl phosphatidylglycerol (DMPG), and dihexanoyl phosphatidylcholine (DHPC). This study focuses on the theoretical and experimental growth kinetics of phospholipid based nanodiscs. Motivation for this project comes from the nanodisc's small size and their potential use as a carrier for drug delivery. It was observed that at high total lipid concentration the nanodiscs are stable at approximately 10 nm. However, growth of these nanodiscs is observed at relatively low total lipid concentrations. Dynamic light scattering (DLS) is used to monitor the size and growth rate of these nanodiscs at different solution conditions. The growth at low concentrations is caused by to the transfer of charged lipid (DMPG) from the discs to the solution, reducing the Columbic interaction. The growth of nanodisc as a function of size and surface potential is modeled using the Smoluchowski transport equation with transport-limited boundary conditions.

Reversible thrombin detection by aptamer functionalized STING sensors

PubMed Central

Actis, Paolo; Rogers, Adam; Nivala, Jeff; Vilozny, Boaz; Seger, R. Adam; Jejelowo, Olufisayo; Pourmand, Nader

2011-01-01

Signal Transduction by Ion NanoGating (STING) is a label-free technology based on functionalized quartz nanopipettes. The nanopipette pore can be decorated with a variety of recognition elements and the molecular interaction is transduced via a simple electrochemical system. A STING sensor can be easily and reproducibly fabricated and tailored at the bench starting from inexpensive quartz capillaries. The analytical application of this new biosensing platform, however, was limited due to the difficult correlation between the measured ionic current and the analyte concentration in solution. Here we show that STING sensors functionalized with aptamers allow the quantitative detection of thrombin. The binding of thrombin generates a signal that can be directly correlated to its concentration in the bulk solution. PMID:21636261

Mathematical analysis of thermal diffusion shock waves

NASA Astrophysics Data System (ADS)

Gusev, Vitalyi; Craig, Walter; Livoti, Roberto; Danworaphong, Sorasak; Diebold, Gerald J.

2005-10-01

Thermal diffusion, also known as the Ludwig-Soret effect, refers to the separation of mixtures in a temperature gradient. For a binary mixture the time dependence of the change in concentration of each species is governed by a nonlinear partial differential equation in space and time. Here, an exact solution of the Ludwig-Soret equation without mass diffusion for a sinusoidal temperature field is given. The solution shows that counterpropagating shock waves are produced which slow and eventually come to a halt. Expressions are found for the shock time for two limiting values of the starting density fraction. The effects of diffusion on the development of the concentration profile in time and space are found by numerical integration of the nonlinear differential equation.

Kinetic-limited etching of magnesium doping nitrogen polar GaN in potassium hydroxide solution

NASA Astrophysics Data System (ADS)

Jiang, Junyan; Zhang, Yuantao; Chi, Chen; Yang, Fan; Li, Pengchong; Zhao, Degang; Zhang, Baolin; Du, Guotong

2016-01-01

KOH based wet etchings were performed on both undoped and Mg-doped N-polar GaN films grown by metal-organic chemical vapor deposition. It is found that the etching rate for Mg-doped N-polar GaN gets slow obviously compared with undoped N-polar GaN. X-ray photoelectron spectroscopy analysis proved that Mg oxide formed on N-polar GaN surface is insoluble in KOH solution so that kinetic-limited etching occurs as the etching process goes on. The etching process model of Mg-doped N-polar GaN in KOH solution is tentatively purposed using a simplified ideal atomic configuration. Raman spectroscopy analysis reveals that Mg doping can induce tensile strain in N-polar GaN films. Meanwhile, p-type N-polar GaN film with a hole concentration of 2.4 ÿ 1017 cm⿿3 was obtained by optimizing bis-cyclopentadienyl magnesium flow rates.

A hollow-fiber membrane extraction process for recovery and separation of lactic acid from aqueous solution.

PubMed

Huang, Hanjing; Yang, Shang-Tian; Ramey, David E

2004-01-01

An energy-efficient hollow-fiber membrane extraction process was successfully developed to separate and recover lactic acid produced in fermentation. Although many fermentation processes have been developed for lactic acid production, an economical method for lactic acid recovery from the fermentation broth is still needed. Continuous extraction of lactic acid from a simulated aqueous stream was achieved by using Alamine 336 in 2-octanol contained in a hollow-fiber membrane extractor. In this process, the extractant was simultaneously regenerated by stripping with NaOH in a second membrane extractor, and the final product is a concentrated lactate salt solution. The extraction rate increased linearly with an increase in the Alamine 336 content in the solvent (from 5 to 40%). Increasing the concentration of the undissociated lactic acid in the feed solution by either increasing the lactate concentration (from 5 to 40 g/L) or decreasing the solution pH (from 5.0 to 4.0) also increased the extraction rate. Based on these observations, a reactive extraction model with a first-order reaction mechanism for both lactic acid and amine concentrations was proposed. The extraction rate also increased with an increase in the feed flow rate, but not the flow rates of solvent and the stripping solution, suggesting that the process was not limited by diffusion in the liquid films or membrane pores. A mathematical model considering both diffusion and chemical reaction in the extractor and back extractor was developed to simulate the process. The model fits the experimental data well and can be used in scale up design of the process.

Impedance Analysis of Colloidal Gold Nanoparticles in Chromatography Paper for Quantitation of an Immunochromatographic Assay.

PubMed

Hori, Fumitaka; Harada, Yuji; Kuretake, Tatsumi; Uno, Shigeyasu

2016-01-01

A detection method of gold nanoparticles in chromatography paper has been developed for a simple, cost-effective and reliable quantitation of immunochromatographic strip test. The time courses of the solution resistance in chromatography paper with the gold nanoparticles solution are electrochemically measured by chrono-impedimetry. The dependence of the solution resistance on the concentration of gold nanoparticles has been successfully observed. The main factor to increase the solution resistance may be obstruction of the ion transport due to the presence of gold nanoparticles. The existence of gold nanoparticles with 1.92 × 10(9) particles/mL in an indistinctly-colored chromatography paper is also identified by a solution resistance measurement. This indicates that the solution resistance assay has the potential to lower the detection limit of the conventional qualitative assay.

THE QUANTIFICATION OF AQUEOUS TRACERS IN LABORATORY AQUIFER MODELS USING LIGHT TRANSMISSION VISUALIZATION METHOD

EPA Science Inventory

The quantification of solute concentrations in laboratory aquifer models has been largely limited to the use of sampling ports, from which samples are collected for external analysis. One of the drawbacks to this method is that the act of sampling may disturb plume dynamics and ...

Scaling Relative Incentive Value in Anticipatory Behavior

ERIC Educational Resources Information Center

Pellegrini, Santiago; Papini, Mauricio R.

2007-01-01

Papini and Pellegrini (Papini, M. R., & Pellegrini, S. "Scaling relative incentive value in consummatory behavior." "Learning and Motivation", in press) observed that, within limits, the level of consummatory responding of rats exposed to incentive downshifts in the concentration of sucrose solutions was similar when the ratio of test/training…

Sample Introduction Using the Hildebrand Grid Nebulizer for Plasma Spectrometry

DTIC Science & Technology

1988-01-01

linear dynamic ranges, precision, and peak width were de- termined for elements in methanol and acetonitrile solutions. , (1)> The grid nebulizer was...FIA) with ICP-OES detection were evaluated. Detec- tion limits, linear dynamic ranges, precision, and peak width were de- termined for elements in...Concentration vs. Log Peak Area for Mn, 59 Cd, Zn, Au, Ni in Methanol (CMSC) 3-28 Log Concentration vs. Log Peak Area for Mn, 60 Cd, Au, Ni in

Thermodynamic Cconstraints on Coupled Carbonate-Pyrite Weathering Dynamics and Carbon Fluxes

NASA Astrophysics Data System (ADS)

Winnick, M.; Maher, K.

2017-12-01

Chemical weathering within the critical zone regulates global biogeochemical cycles, atmospheric composition, and the supply of key nutrients to terrestrial and aquatic ecosystems. Recent studies suggest that thermodynamic limits on solute production act as a first-order control on global chemical weathering rates; however, few studies have addressed the factors that set these thermodynamic limits in natural systems. In this presentation, we investigate the effects of soil CO2 concentrations and pyrite oxidation rates on carbonate dissolution and associated carbon fluxes in the East River watershed in Colorado, using concentration-discharge relationships and thermodynamic constraints. Within the shallow subsurface, soil respiration rates and moisture content determine the extent of carbonic acid-promoted carbonate dissolution through their modulation of soil pCO2 and the balance of open- v. closed-system weathering processes. At greater depths, pyrite oxidation generates sulfuric acid, which alters the approach to equilibrium of infiltrating waters. Through comparisons of concentration-discharge data and reactive transport model simulations, we explore the conditions that determine whether sulfuric acid reacts to dissolve additional carbonate mineral or instead reacts with alkalinity already in solution - the balance of which determines watershed carbon flux budgets. Our study highlights the importance of interactions between the chemical structure of the critical zone and the hydrologic regulation of flowpaths in determining concentration-discharge relationships and overall carbon fluxes.

Atomic-absorption determination of rhodium in chromite concentrates

USGS Publications Warehouse

Schnepfe, M.M.; Grimaldi, F.S.

1969-01-01

Rhodium is determined in chromite concentrates by atomic absorption after concentration either by co-precipitation with tellurium formed by the reduction of tellurite with tin(II) chloride or by fire assay into a gold bead. Interelement interferences in the atomic-absorption determination are removed by buffering the solutions with lanthanum sulphate (lanthanum concentration 1%). Substantial amounts of Ag, Al, Au, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ho, Hg, K, La, Mg, Mn, Mo, Na, Ni, Pb, Te, Ti, V, Y, Zn and platinum metals can be tolerated. A lower limit of approximately 0.07 ppm Rh can be determined in a 3-g sample. ?? 1969.

Stability of Melphalan in 0.9% Sodium Chloride Solutions Prepared in Polyvinyl Chloride Bags for Intravenous Injection.

PubMed

Desmaris, Romain-Pacôme; Mercier, Lionel; Paci, Angelo

2015-09-01

Melphalan is an alkylating agent frequently used in an intravenous formulation to treat hematologic malignancies and solid tumors in both adults and children. According to the manufacturer, melphalan is stable in sterile 0.9% sodium chloride for 90 min at room temperature (RT). Several authors have studied the stability of different concentrations of melphalan; however, most were not adapted to the current manufacturing process applied in pharmaceutical centralized units. This study was conducted to determine the stability of melphalan in 0.9% sodium chloride solutions at concentrations used for intravenous injection in practice. Melphalan is commonly prepared in diluted solutions ranging from 2 to 4 mg/ml for the treatment of adult patients and at lower concentrations (down to 0.5 mg/ml) for pediatric use. Accordingly, these were the three concentrations chosen for this study. Melphalan concentrations were measured with high-performance thin-layer chromatography (HPTLC). At RT, admixtures prepared at 4 mg/ml were stable for up to 8 h without protection from light; however, at lower concentrations, such as 0.5 and 2 mg/ml, stability did not exceed 2 h. When refrigerated, melphalan was stable for 24 h at 2 mg/ml; however, at 0.5 and 4 mg/ml, the drug was not stable. Melphalan solutions present with limited stability at 0.5, 2, and 4 mg/ml and are not adapted for delayed administration in pharmaceutical centralized units. However, at 4 mg/ml and at RT, a stability of 8 h is very interesting in practice and allows sufficient time for preparation, pharmaceutical control, transport, and administration.

Novel high-pressure windows made of glass-like carbon for x-ray analysis.

PubMed

Testemale, Denis; Prat, Alain; Lahera, Eric; Hazemann, Jean-Louis

2016-07-01

Original high-pressure glass-like carbon windows developed for x-ray spectroscopy applications are presented. The scientific and technological background of this new technical development is exposed, in particular the limitations of our existing beryllium windows in the context of x-ray absorption spectroscopy (XAS) measurements of solutions with very low solute concentrations at hydrothermal conditions (0.1-200 MPa, 30-600 °C). The benefits of glass-like carbon are exposed, notably its non-crystalline character, the absence of impurities which has been verified by micro-fluorescence laboratory measurements, and its non-toxicity which makes its machining safer. Finite elements mechanical calculations and experimental pressure tests were conducted to determine the pressure limits of windows with two different geometries: cylindrical (thickness 0.5 mm) and inversed-dome shape (thickness 0.5 mm at the tip of the dome). The former break at 150 MPa and the latter show no sign of rupture at 400 MPa. Recent XAS measurements conducted with the new dome shaped windows are presented to show the advantages of the design that allow for the detection of very low concentrations in the transmission mode (down to 30 ppm) and the acquisition of fluorescence XAS spectra in diluted solutions at high pressure. Eventually the perspectives of this original development are discussed.

Effect of sodium chloride concentration on elemental analysis of brines by laser-induced breakdown spectroscopy (LIBS).

PubMed

Goueguel, Christian; Singh, Jagdish P; McIntyre, Dustin L; Jain, Jinesh; Karamalidis, Athanasios K

2014-01-01

Leakage of injected carbon dioxide (CO2) or resident fluids, such as brine, is a major concern associated with the injection of large volumes of CO2 into deep saline formations. Migration of brine could contaminate drinking water resources by increasing their salinity or endanger vegetation and animal life as well as human health. The main objective of this study was to investigate the effect of sodium chloride (NaCl) concentration on the detection of calcium and potassium in brine samples using laser-induced breakdown spectroscopy (LIBS). The ultimate goals were to determine the suitability of the LIBS technique for in situ measurements of metal ion concentrations in NaCl-rich solution and to develop a chemical sensor that can provide the early detection of brine intrusion into formations used for domestic or agricultural water production. Several brine samples of NaCl-CaCl2 and NaCl-KCl were prepared at NaCl concentrations between 0.0 and 3.0 M. The effect of NaCl concentration on the signal-to-background ratio (SBR) and signal-to-noise ratio (SNR) for calcium (422.67 nm) and potassium (769.49 nm) emission lines was evaluated. Results show that, for a delay time of 300 ns and a gate width of 3 μs, the presence of and changes in NaCl concentration significantly affect the SBR and SNR for both emission lines. An increase in NaCl concentration from 0.0 to 3.0 M produced an increase in the SNR, whereas the SBR dropped continuously. The detection limits obtained for both elements were in the milligrams per liter range, suggesting that a NaCl-rich solution does not severely limit the ability of LIBS to detect trace amount of metal ions.

Location-allocation models and new solution methodologies in telecommunication networks

NASA Astrophysics Data System (ADS)

Dinu, S.; Ciucur, V.

2016-08-01

When designing a telecommunications network topology, three types of interdependent decisions are combined: location, allocation and routing, which are expressed by the following design considerations: how many interconnection devices - consolidation points/concentrators should be used and where should they be located; how to allocate terminal nodes to concentrators; how should the voice, video or data traffic be routed and what transmission links (capacitated or not) should be built into the network. Including these three components of the decision into a single model generates a problem whose complexity makes it difficult to solve. A first method to address the overall problem is the sequential one, whereby the first step deals with the location-allocation problem and based on this solution the subsequent sub-problem (routing the network traffic) shall be solved. The issue of location and allocation in a telecommunications network, called "The capacitated concentrator location- allocation - CCLA problem" is based on one of the general location models on a network in which clients/demand nodes are the terminals and facilities are the concentrators. Like in a location model, each client node has a demand traffic, which must be served, and the facilities can serve these demands within their capacity limit. In this study, the CCLA problem is modeled as a single-source capacitated location-allocation model whose optimization objective is to determine the minimum network cost consisting of fixed costs for establishing the locations of concentrators, costs for operating concentrators and costs for allocating terminals to concentrators. The problem is known as a difficult combinatorial optimization problem for which powerful algorithms are required. Our approach proposes a Fuzzy Genetic Algorithm combined with a local search procedure to calculate the optimal values of the location and allocation variables. To confirm the efficiency of the proposed algorithm with respect to the quality of solutions, significant size test problems were considered: up to 100 terminal nodes and 50 concentrators on a 100 × 100 square grid. The performance of this hybrid intelligent algorithm was evaluated by measuring the quality of its solutions with respect to the following statistics: the standard deviation and the ratio of the best solution obtained.

Determination of Minor and Trace Metals in Aluminum and Aluminum Alloys by ICP-AES; Evaluation of the Uncertainty and Limit of Quantitation from Interlaboratory Testing.

PubMed

Uemoto, Michihisa; Makino, Masanori; Ota, Yuji; Sakaguchi, Hiromi; Shimizu, Yukari; Sato, Kazuhiro

2018-01-01

Minor and trace metals in aluminum and aluminum alloys have been determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) as an interlaboratory testing toward standardization. The trueness of the measured data was successfully investigated to improve the analytical protocols, using certified reference materials of aluminum. Their precision could also be evaluated, feasible to estimate the uncertainties separately. The accuracy (trueness and precision) of the data were finally in good agreement with the certified values and assigned uncertainties. Repeated measurements of aluminum solutions with different concentrations of the analytes revealed the relative standard deviations of the measurements with concentrations, thus enabling their limits of quantitation. They differed separately and also showed slightly higher values with an aluminum matrix than those without one. In addition, the upper limit of the detectable concentration of silicon with simple acid digestion was estimated to be 0.03 % in the mass fraction.

Positional stability as the light emission limit in sonoluminescence with sulfuric acid.

PubMed

Urteaga, Raúl; Dellavale, Damián H; Puente, Gabriela F; Bonetto, Fabián J

2007-11-01

We studied a single bubble sonoluminescence system consisting of an argon bubble in a sulfuric acid aq. solution. We experimentally determined the relevant variables of the system. We also measured the bubble position, extent of the bubble orbits, and light intensity as a function of acoustic pressure for different argon concentrations. We find that the Bjerknes force is responsible for the bubble mean position and this imposes a limitation in the maximum acoustic pressure that can be applied to the bubble. The Rayleigh-Taylor instability does not play a role in this system and, at a given gas concentration, the SL intensity depends more on the bubble time of collapse than any other investigated parameter.

Investigation of factors affecting in vitro doxorubicin release from PEGylated liposomal doxorubicin for the development of in vitro release testing conditions.

PubMed

Shibata, Hiroko; Izutsu, Ken-Ichi; Yomota, Chikako; Okuda, Haruhiro; Goda, Yukihiro

2015-01-01

Establishing appropriate drug release testing methods of liposomal products for assuring quality and performance requires the determination of factors affecting in vitro drug release. In this study, we investigated the effects of test conditions (human plasma lot, pH/salt concentration in the test media, dilution factor, temperature, ultrasound irradiation, etc.), and liposomal preparation conditions (pH/concentration of ammonium sulfate solution), on doxorubicin (DXR) release from PEGylated liposomal DXR. Higher temperature and lower pH significantly increased DXR release. The evaluation of DXR solubility indicated that the high DXR release induced by low pH may be attributed to the high solubility of DXR at low pH. Ultrasound irradiation induced rapid DXR release in an amplitude-dependent manner. The salt concentration in the test solution, human plasma lot, and dilution factor had a limited impact on DXR-release. Variations in the ammonium sulfate concentration used in solutions for the formation/hydration of liposomes significantly affected DXR release behavior, whereas differences in pH did not. In addition, heating condition in phosphate-buffered saline at lower pH (<6.5) exhibited higher discriminative ability for the release profiles from various liposomes with different concentrations of ammonium sulfate than did ultrasound irradiation. These results are expected to be helpful in the process of establishing appropriate drug release testing methods for PEGylated liposomal DXR.

How do bubbles grow in a weakly supersaturated solution?

NASA Astrophysics Data System (ADS)

Enriquez, Oscar; Sun, Chao; Lohse, Detlef; Prosperetti, Andrea; van der Meer, Devaraj

2013-11-01

Beer, champagne and soft-drinks are water-based solutions which owe their ``bubbliness'' to a moderate degree of carbon dioxide supersaturation. Bubbles grow sequentially from nucleation sites due to solute concentration gradients and detach due to buoyancy. The leading mass transfer mechanism is diffusion, but the advection caused by the moving surface also plays an important role. Now, what happens at the limit of very weak supersaturation? We take an experimental look at CO2 bubbles growing in water under such a condition. Nucleation sites are provided by hydrophobic micro-cavities on a silicon chip, therefore controlling the number and position of bubbles. Although advection is negligible, measured growth rates for an isolated bubble differ noticeably from a purely diffusive theoretical solution. We can explain the differences as effects of the concentration boundary layer around the bubble. Initially, its interaction with the surface on which the bubble grows slows the process down. Later on, the growth rate is enhanced by buoyancy effects caused by the depletion of the solute in the surroundings of the bubble. When neighboring bubbles are brought into play they interact through their boundary layers, further slowing down their growth rates.

Contrasts in Flushing Patterns Among Solutes

NASA Astrophysics Data System (ADS)

Shanley, J. B.; Sebestyen, S. D.; Boyer, E. W.; Ross, D. S.

2005-12-01

High-frequency sampling since 1991 at the 41-ha forested W-9 catchment at Sleepers River, Vermont provides a wealth of data to evaluate catchment flushing responses. Snowmelt and rain-on-snow account for about half the annual flow at Sleepers River during a 6-week period in early spring. Summer and fall storms produce frequent high-flows of short duration. Flushing of weathering products (Ca, Mg, Na, K, SO4 ANC, Si) is generally supply-limited, and is masked by rapid dilution with meteoric and soil water during events. In contrast, flushing dominates the stream dynamics of atmospheric and pedogenic solutes (NO3, DOC, Hg), causing concentration increases with increasing flow. During snowmelt, NO3 peaks well before the peak in discharge, whereas DOC tracks discharge closely and peaks concurrently. These patterns suggest that NO3 is supply-limited and DOC is transport-limited; W-9 is not N saturated and the available NO3 supply is readily leached from the soil, whereas stream DOC progressively increases as rising water tables and expanding saturated areas connect with new source areas. In summer storms, DOC and NO3 both peak simultaneously with discharge. Unlike DOC, however, NO3 concentrations are attenuated with subsequent storms that follow within a few days, consistent with a depletion of the NO3 pool available for flushing as observed during snowmelt. Sleepers River contrasts with the Snake River in Colorado, where NO3 and DOC reverse roles; DOC peaks early in snowmelt and may be supply-limited due to the paucity of organic matter. An ample supply of NO3 is available due to N saturation and N fixation, but NO3 may be transport-limited due to primary N sources in talus deposits far from the stream. Hg is an atmospheric solute that accumulates in soils because of its affinity for organic matter, and is flushed by high flows, mostly in association with suspended sediment. The concept of flushing provides a useful context for understanding the variable responses of solutes to the expansion of catchment saturation during high flow events.

Acoustically levitated droplets: a contactless sampling method for fluorescence studies.

PubMed

Leiterer, Jork; Grabolle, Markus; Rurack, Knut; Resch-Genger, Ute; Ziegler, Jan; Nann, Thomas; Panne, Ulrich

2008-01-01

Acoustic levitation is used as a new tool to study concentration-dependent processes in fluorescence spectroscopy. With this technique, small amounts of liquid and solid samples can be measured without the need for sample supports or containers, which often limits signal acquisition and can even alter sample properties due to interactions with the support material. We demonstrate that, because of the small sample volume, fluorescence measurements at high concentrations of an organic dye are possible without the limitation of inner-filter effects, which hamper such experiments in conventional, cuvette-based measurements. Furthermore, we show that acoustic levitation of liquid samples provides an experimentally simple way to study distance-dependent fluorescence modulations in semiconductor nanocrystals. The evaporation of the solvent during levitation leads to a continuous increase of solute concentration and can easily be monitored by laser-induced fluorescence.

High-resolution surface plasmon resonance biosensing system for glucose concentration detecting

NASA Astrophysics Data System (ADS)

Huang, Xian; Li, Dachao; Yu, Haixia; Huang, Fuxiang; Hu, Xiaotang; Xu, Kexin

2007-02-01

Glucose is one of the most important substances widely contained in organism and food, thus people pay much attention in researching and improving the way for the detection of glucose. Traditional ways, although precise and reliable when in high concentration and large amount of sample, have unconvincing performance in detecting mixture and solution with low concentration and micro-volume. As far as the ideal way is concerned, it should not only specifically detect the glucose and exclude other components in solution, but also meet the need of micro-sample (approximately 5μL) and low concentration. We introduced D-galactose/D-glucose Binding Protein (GGBP) - a kind of protein which has the ability to absorb the glucose specifically, to construct a novel surface plasmon resonance measuring system. By immobilizing GGBP onto the surface of the SPR sensor, we develop a new detecting system for glucose testing in mixed solution. The experimental result indicates that compared with 0.1g/L before immobilization of GGBP, the detecting limit or the resolution of glucose testing rises to 1mg/L after the immobilization, the system succeeds in distinguishing glucose from other components in mixture, which reveals a bright future to apply SPR in the minimally invasive diabetes testing and food quality control.

Hydroxyl Radical Formation in Solutions of Fe(III) and Hydrogen Peroxide - Impact of Freezing and Thawing Process

NASA Astrophysics Data System (ADS)

Arakaki, T.; Kinjo, M.; Shiroma, K.; Shibata, M.; Miyake, T.; Hirakawa, T.; Sakugawa, H.

2003-12-01

Hydroxyl radical formation was studied by detecting concentration of formate in solutions of hydrated formaldehyde, HOOH, and Fe(III) or Cu(II). Oxidation of hydrated formaldehyde by OH radical is known to form formate. Formate formation increased by about 4 times when the solution underwent freezing and thawing. Although the reaction mechanisms are not clearly understood, we believe that the concentration effect of freezing enhanced the catalytic reactions between HOOH and Fe(III) or Cu(II) and the reduction of transition metals, i.e., Fe(III) to Fe(II) and Cu(II) to Cu(I). The concentration effect also enhanced reactions between Fe(II) and HOOH or Cu(I) and HOOH, which generated OH radical (freeze-Fenton reaction). Study of the effects of pH showed that formate formation was the highest at pH = 4.0, indicating that the speciation of Fe(III) affected the formation of formate. Concentration-dependent experiments demonstrated that Fe is probably the limiting agent under typical atmospheric conditions. Our results suggested that the freezing process could be an important source of hydroxyl radical in high cloud, winter fog, rime ice and freezing acidic rain, and more importantly, a potentially additional oxidation mechanism in the atmosphere.

Recent Mascon Solutions from GRACE

NASA Technical Reports Server (NTRS)

Yuan, Dah-Ning; Watkins, M. M.

2006-01-01

Mascon (mass concentration) solutions computed for entire land area of Earth with several variants from Jul. 2003 through Dec. 2005 Automated scripts developed, "pipeline" now in place. Solutions generally consistent with harmonics for large features but appear able to resolve and localize smaller features more cleanly. Greenland solutions generally consistent with areas of max ice mass loss in South, but mascons seem to clearly identify sub-regions of ice mass growth. May be amplified by mascon sensitivity and ground tracks. Irregular coverage, errors due to tides in Arctic or other leakage from nearby sources? Although mascons are technically 30+ years old, gravity/geodesy community has vastly more experience with harmonics and thus we are still learning the full advantages, limitations, and idiosyncrasies of mascons.

On N. Park's Analytical solution for steady state density- and mixing regime—dependent solute transport in a vertical soil column

NASA Astrophysics Data System (ADS)

Thiele, Michael

1998-04-01

Recently, Park [1996] presented an analytical solution for stationary one-dimensional solute transport in a variable-density fluid flow through a vertical soil column. He used the widespread Bear-Scheidegger dispersion model describing solute mixing as a sum of molecular diffusion and velocity-proportional mechanical dispersion effects. His closed-form implicit concentration and pressure distributions thus allow for a discussion of the combined impact of molecular diffusion and mechanical dispersion in a variable-density environment. Whereas Park only considered the example of vanishing molecular diffusion in detail, both phenomena are taken into account simultaneously in the present study in order to elucidate their different influences on concentration distribution characteristics. The boundary value problem dealt with herein is based on an upward inflow of high-density fluid of constant solute concentration and corresponding outflow of a lower constant concentration fluid at the upper end of the column when dispersivity does not change along the flow path. The thickness of the transition zone between the two fluids appeared to strongly depend on the prevailing share of the molecular diffusion and mechanical dispersion mechanisms. The latter can be characterized by a molecular Peclet number Pe, which here is defined as the ratio of the column outflow velocity multiplied by a characteristic pore size and the molecular diffusion coefficient. For very small values of Pe, when molecular diffusion represents the exclusive mixing process, density differences have no impact on transition zone thicknesses. A relative density-;dependent thickness increases with flow velocities (increasing Pe values) very rapidly compared to the density-independent case, and after having passed a maximum decreases asymptotically to a constant value for the large Peclet number limit when mechanical dispersion is the only mixing mechanism. Hence the special transport problem analyzed gives further evidence for the importance of simultaneously considering molecular diffusion and mechanical dispersion in gravity-affected solute transport in porous media.

Features of the complexation of octadecane-2,4-dione and lanthanide ions in Langmuir monolayers

NASA Astrophysics Data System (ADS)

Sokolov, M. E.; Repina, I. N.; Raitman, O. A.; Kolokolov, F. A.; Panyushkin, V. T.

2016-05-01

Monolayers of octadecane-2,4-dione on the surfaces of EuCl3 and TbCl3 solutions in the concentration range of 1 × 10-4 to 5 × 10-3 M at pH 5.8 are studied. It is found that the limiting area of octadecane-2,4-dione molecule in a monolayer dependence on Eu3+ and Tb3+ concentration is of extreme nature. The formation of complex compounds in the ligand monolayer is postulated, and structures are proposed for these compounds at different concentrations of metal ions.

Effects of dilute substitutional solutes on interstitial carbon in α-Fe: Interactions and associated carbon diffusion from first-principles calculations

NASA Astrophysics Data System (ADS)

Liu, Peitao; Xing, Weiwei; Cheng, Xiyue; Li, Dianzhong; Li, Yiyi; Chen, Xing-Qiu

2014-07-01

By means of first-principles calculations coupled with the kinetic Monte Carlo simulations, we have systematically investigated the effects of dilute substitutional solutes on the behaviors of carbon in α-Fe. Our results uncover the following. (i) Without the Fe vacancy the interactions between most solutes and carbon are repulsive due to the strain relief, whereas Mn has a weak attractive interaction with its nearest-neighbor carbon due to the local ferromagnetic coupling effect. (ii) The presence of the Fe vacancy results in attractive interactions of all the solutes with carbon. In particular, the Mn-vacancy pair shows an exceptionally large binding energy of -0.81 eV with carbon. (iii) The alloying addition significantly impacts the atomic-scale concentration distributions and chemical potential of carbon in the Fe matrix. Among them, Mn and Cr increase the carbon chemical potential, whereas Al and Si reduce it. (iv) Within the dilute scale of the alloying solution, the solute concentration- and temperature-dependent carbon diffusivities demonstrate that Mn has a little impact on the carbon diffusion, whereas Cr (Al or Si) remarkably retards the carbon diffusion. Our results provide a certain implication for better understanding the experimental observations related with the carbon solubility limit, carbon microsegregation, and carbide precipitations in the ferritic steels.

A New Technique for Measuring Concentration Dependence of Self and Collective Diffusivity by using a Single Sample

NASA Astrophysics Data System (ADS)

Sirorattanakul, Krittanon; Shen, Chong; Ou-Yang, Daniel

Diffusivity governs the dynamics of interacting particles suspended in a solvent. At high particle concentration, the interactions between particles become non-negligible, making the values of self and collective diffusivity diverge and concentration-dependent. Conventional methods for measuring this dependency, such as forced Rayleigh scattering, fluorescence correlation spectroscopy (FCS), and dynamic light scattering (DLS) require preparation of multiple samples. We present a new technique to measure this dependency by using only a single sample. Dielectrophoresis (DEP) is used to create concentration gradient in the solution. Across this concentration distribution, we use FCS to measure the concentration-dependent self diffusivity. Then, we switch off DEP to allow the particles to diffuse back to equilibrium. We obtain the time series of concentration distribution from fluorescence microscopy and use them to determine the concentration-dependent collective diffusivity. We compare the experimental results with computer simulations to verify the validity of this technique. Time and spatial resolution limits of FCS and imaging are also analyzed to estimate the limitation of the proposed technique. NSF DMR-0923299, Lehigh College of Arts and Sciences Undergraduate Research Grant, Lehigh Department of Physics, Emulsion Polymers Institute.

Colorimetric detection of copper ions in sub-micromolar concentrations using a triarylamine-linked resin bead.

PubMed

Thomas, Tony George; Sreenath, Kesavapillai; Gopidas, Karical R

2012-11-21

The triarylamine derivative ETPA reacts with Cu(2+) to give deeply colored, stable radical cations in acetonitrile solution. ETPA was immobilized on to a tentagel resin bead which was then used for the fabrication of a simple device capable of the colorimetric detection of submicromolar concentrations of Cu(2+) ions in water. The naked eye detection limit reported here for Cu(2+) is one of the lowest ever reported for small molecule sensors.

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

Goltz, M.N.; Oxley, M.E.

Aquifer cleanup efforts at contaminated sites frequently involve operation of a system of extraction wells. It has been found that contaminant load discharged by extraction wells typically declines with time, asymptotically approaching a residual level. Such behavior could be due to rate-limited desorption of an organic contaminant from aquifer solids. An analytical model is presented which accounts for rate-limited desorption of an organic solute during cleanup of a contaminated site. Model equations are presented which describe transport of a sorbing contaminant in a converging radial flow field, with sorption described by (1) equilibrium, (2) first-order rate, and (3) Fickian diffusionmore » expressions. The model equations are solved in the Laplace domain and numerically inverted to simulate contaminant concentrations at an extraction well. A Laplace domain solution for the total contaminant mass remaining in the aquifer is also derived. It is shown that rate-limited sorption can have a significant impact upon aquifer remediation. Approximate equivalence among the various rate-limited models is also demonstrated.« less

Determination of dissolved aluminum in water samples

USGS Publications Warehouse

Afifi, A.A.

1983-01-01

A technique has been modified for determination of a wide range of concentrations of dissolved aluminum (Al) in water and has been tested. In this technique, aluminum is complexed with 8-hydroxyquinoline at pH 8.3 to minimize interferences, then extracted with methyl isobutyl ketone (MIBK). The extract is analyzed colorimetrically at 395 nm. This technique is used to analyze two forms of monomeric Al, nonlabile (organic complexes) and labile (free, Al, Al sulfate, fluoride and hydroxide complexes). A detection limit 2 ug/L is possible with 25-ml samples and 10-ml extracts. The detection limit can be decreased by increasing the volume of the sample and (or) decreasing the volume of the methyl isobutyl ketone extract. The analytical uncertainty of this method is approximately + or - 5 percent. The standard addition technique provides a recovery test for this technique and ensures precision in samples of low Al concentrations. The average percentage recovery of the added Al plus the amount originally present was 99 percent. Data obtained from analyses of filtered standard solutions indicated that Al is adsorbed on various types of filters. However, the relationship between Al concentrations and adsorption remains linear. A test on standard solutions also indicated that Al is not adsorbed on nitric acid-washed polyethylene and polypropylene bottle wells. (USGS)

The thermodynamic and hydrodynamic properties of macromolecules that influence the hydrodynamics of porous systems.

PubMed

Comper, W D

1994-06-21

The water flow across porous, semipermeable membranes associated with osmosis and filtration under a variety of conditions is analysed and compared to macromolecular diffusion across free-liquid boundaries, diffusion and sedimentation in the ultracentrifuge, and tracer diffusion of water. This study establishes that osmosis can be explained in terms of the irreversible thermodynamics of diffusion. For macromolecular osmotically active solutes in the semidilute concentration regime the water flows across semipermeable porous membranes are interpreted in terms of a rate-limiting solute-solvent exchange layer that exists on the solution side of the membrane adjacent to the membrane pore; both osmosis and filtration will be governed by these exchange layers. These exchange layers also yield unique properties of their constituent molecules in systems where there is osmotic equilibration between solutions of different solutes. This study also establishes the need to consider the internal osmotic pressure of membranes in the pressure balance associated with the flow across the membrane. The complex situation of partially permeable membranes is analysed for the simple case where there are no mechanical gradients and there is only one osmotically active solution that creates a rate-limiting exchange layer. This treatment predicts that the flow will be governed primarily by the osmotic pressure difference associated with the partitioning of the solute at the membrane-solution interface.

A compartmentalized solute transport model for redox zones in contaminated aquifers: 1. Theory and development

USGS Publications Warehouse

Abrams , Robert H.; Loague, Keith

2000-01-01

This paper, the first of two parts [see Abrams and Loague, this issue], takes the compartmentalized approach for the geochemical evolution of redox zones presented by Abrams et al. [1998] and embeds it within a solute transport framework. In this paper the compartmentalized approach is generalized to facilitate the description of its incorporation into a solute transport simulator. An equivalent formulation is developed which removes any discontinuities that may occur when switching compartments. Rate‐limited redox reactions are modeled with a modified Monod relationship that allows either the organic substrate or the electron acceptor to be the rate‐limiting reactant. Thermodynamic constraints are used to inhibit lower‐energy redox reactions from occurring under infeasible geochemical conditions without imposing equilibrium on the lower‐energy reactions. The procedure used allows any redox reaction to be simulated as being kinetically limited or thermodynamically limited, depending on local geochemical conditions. Empirical reaction inhibition methods are not needed. The sequential iteration approach (SIA), a technique which allows the number of solute transport equations to be reduced, is adopted to solve the coupled geochemical/solute transport problem. When the compartmentalized approach is embedded within the SIA, with the total analytical concentration of each component as the dependent variable in the transport equation, it is possible to reduce the number of transport equations even further than with the unmodified SIA. A one‐dimensional, coupled geochemical/solute transport simulation is presented in which redox zones evolve dynamically in time and space. The compartmentalized solute transport (COMPTRAN) model described in this paper enables the development of redox zones to be simulated under both kinetic and thermodynamic constraints. The modular design of COMPTRAN facilitates the use of many different, preexisting solute transport and geochemical codes. The companion paper [Abrams and Loague, this issue] presents examples of the application of COMPTRAN to field‐scale problems.

Reducing the risk of fatal and disabling hypoglycaemia: a comparison of arterial blood sampling systems.

PubMed

Brennan, K A; Eapen, G; Turnbull, D

2010-04-01

In 2008, the National Patient Safety Agency (NPSA) published a report after 42 incidents and two deaths where glucose-containing flush solutions were attached to the arterial line. The molar concentration of 5% glucose is 277 mmol litre(-1). Only a tiny amount of sample contamination will lead to an artificially high glucose. As the NPSA sought a solution, a bench model was constructed to compare the performance of three open and three closed arterial line systems in limiting sample contamination. All arterial line systems were set up in a standard manner and pressurized to 300 mm Hg with 5% glucose used as the flush solution. This was connected to the 'radial artery' using an 18 G needle representing the radial cannula. The radial artery was simulated using a wide-bore extension set with 'blood' flow at 60 ml min(-1). Blood was simulated by the addition of red dye to Hartmann's solution. Increasing multiples of arterial line dead space were aspirated and discarded. Blood samples were then obtained and glucose concentration was measured. Significant glucose contamination (3 mmol litre(-1) +/-3.4) was detected in all open arterial line systems up to an aspiration volume of five times the dead space. No samples from the closed systems recorded glucose concentration >1 mmol litre(-1). Recommended minimal discard volumes are inadequate in the presence of glucose as the flush solution and can lead to high blood glucose readings, inappropriate insulin use, and iatrogenic neuroglycopaenia. Our study demonstrates that the closed-loop arterial sampling system could be the universal solution sought by the NPSA.

Quantitative HPLC Analysis of an Analgesic/Caffeine Formulation: Determination of Caffeine

NASA Astrophysics Data System (ADS)

Ferguson, Glenda K.

1998-04-01

A modern high performance liquid chromatography (HPLC) laboratory experiment which entails the separation of acetaminophen, aspirin, and caffeine and the quantitative assay of caffeine in commercial mixtures of these compounds has been developed. Our HPLC protocol resolves these compounds in only three minutes with a straightforward chromatographic apparatus which consists of a C-18 column, an isocratic mobile phase, UV detection at 254 nm, and an integrator; an expensive, sophisticated system is not required. The separation is both repeatable and rapid. Moreover, the experiment can be completed in a single three-hour period. The experiment is appropriate for any chemistry student who has completed a minimum of one year of general chemistry and is ideal for an analytical or instrumental analysis course. The experiment detailed herein involves the determination of caffeine in Goody's Extra Strength Headache Powders, a commercially available medication which contains acetaminophen, aspirin, and caffeine as active ingredients. However, the separation scheme is not limited to this brand of medication nor is it limited to caffeine as the analyte. With only minor procedural modifications, students can simultaneously quantitate all of these compounds in a commercial mixture. In our procedure, students prepare a series of four caffeine standard solutions as well as a solution from a pharmaceutical analgesic/caffeine mixture, chromatographically analyze each solution in quadruplicate, and plot relative average caffeine standard peak area versus concentration. From the mathematical relationship that results, the concentration of caffeine in the commercial formulation is obtained. Finally, the absolute standard deviation of the mean concentration is calculated.

Practical implications of some recent studies in electrospray ionization fundamentals.

PubMed

Cech, N B; Enke, C G

2001-01-01

In accomplishing successful electrospray ionization analyses, it is imperative to have an understanding of the effects of variables such as analyte structure, instrumental parameters, and solution composition. Here, we review some fundamental studies of the ESI process that are relevant to these issues. We discuss how analyte chargeability and surface activity are related to ESI response, and how accessible parameters such as nonpolar surface area and reversed phase HPLC retention time can be used to predict relative ESI response. Also presented is a description of how derivitizing agents can be used to maximize or enable ESI response by improving the chargeability or hydrophobicity of ESI analytes. Limiting factors in the ESI calibration curve are discussed. At high concentrations, these factors include droplet surface area and excess charge concentration, whereas at low concentrations ion transmission becomes an issue, and chemical interference can also be limiting. Stable and reproducible non-pneumatic ESI operation depends on the ability to balance a number of parameters, including applied voltage and solution surface tension, flow rate, and conductivity. We discuss how changing these parameters can shift the mode of ESI operation from stable to unstable, and how current-voltage curves can be used to characterize the mode of ESI operation. Finally, the characteristics of the ideal ESI solvent, including surface tension and conductivity requirements, are discussed. Analysis in the positive ion mode can be accomplished with acidified methanol/water solutions, but negative ion mode analysis necessitates special constituents that suppress corona discharge and facilitate the production of stable negative ions. Copyright 2002 Wiley Periodicals, Inc.

Explicit continuous charge-based compact model for long channel heavily doped surrounding-gate MOSFETs incorporating interface traps and quantum effects

NASA Astrophysics Data System (ADS)

Hamzah, Afiq; Hamid, Fatimah A.; Ismail, Razali

2016-12-01

An explicit solution for long-channel surrounding-gate (SRG) MOSFETs is presented from intrinsic to heavily doped body including the effects of interface traps and fixed oxide charges. The solution is based on the core SRGMOSFETs model of the Unified Charge Control Model (UCCM) for heavily doped conditions. The UCCM model of highly doped SRGMOSFETs is derived to obtain the exact equivalent expression as in the undoped case. Taking advantage of the undoped explicit charge-based expression, the asymptotic limits for below threshold and above threshold have been redefined to include the effect of trap states for heavily doped cases. After solving the asymptotic limits, an explicit mobile charge expression is obtained which includes the trap state effects. The explicit mobile charge model shows very good agreement with respect to numerical simulation over practical terminal voltages, doping concentration, geometry effects, and trap state effects due to the fixed oxide charges and interface traps. Then, the drain current is obtained using the Pao-Sah's dual integral, which is expressed as a function of inversion charge densities at the source/drain ends. The drain current agreed well with the implicit solution and numerical simulation for all regions of operation without employing any empirical parameters. A comparison with previous explicit models has been conducted to verify the competency of the proposed model with the doping concentration of 1× {10}19 {{cm}}-3, as the proposed model has better advantages in terms of its simplicity and accuracy at a higher doping concentration.

Challenges in Determining Intrinsic Viscosity Under Low Ionic Strength Solution Conditions.

PubMed

Pindrus, Mariya A; Shire, Steven J; Yadav, Sandeep; Kalonia, Devendra S

2017-04-01

To determine the intrinsic viscosity of several monoclonal antibodies (mAbs) under varying pH and ionic strength solution conditions. An online viscosity detector attached to HPLC (Viscotek®) was used to determine the intrinsic viscosity of mAbs. The Ross and Minton equation was used for viscosity prediction at high protein concentrations. Bulk viscosity was determined by a Cambridge viscometer. At 15 mM ionic strength, intrinsic viscosity of the mAbs determined by the single-point approach varied from 5.6 to 6.4 mL/g with changes in pH. High ionic strength did not significantly alter intrinsic viscosity, while a significant increase (up to 24.0 mL/g) was observed near zero mM. No difference in bulk viscosity of mAb3 was observed around pH 6 as a function of ionic strength. Data analysis revealed that near zero mM ionic strength limitations of the single-point technique result in erroneously high intrinsic viscosity. Intrinsic viscosity is a valuable tool that can be used to model baseline viscosity at higher protein concentrations. However, it is not predictive of solution non-ideality at higher protein concentrations. Furthermore, breakdown of numerous assumptions limits the applicability of experimental techniques near zero mM ionic strength conditions. For molecules and conditions studied, the single-point approach produced reliable intrinsic viscosity results at 15 mM. However, this approach must be used with caution near zero mM ionic strength. Data analysis can be used to reveal whether determined intrinsic viscosity is reliable or erroneously high.

Determination of trace amounts of chemical warfare agent degradation products in decontamination solutions with NMR spectroscopy.

PubMed

Koskela, Harri; Rapinoja, Marja-Leena; Kuitunen, Marja-Leena; Vanninen, Paula

2007-12-01

Decontamination solutions are used for an efficient detoxification of chemical warfare agents (CWAs). As these solutions can be composed of strong alkaline chemicals with hydrolyzing and oxidizing properties, the analysis of CWA degradation products in trace levels from these solutions imposes a challenge for any analytical technique. Here, we present results of application of nuclear magnetic resonance spectroscopy for analysis of trace amounts of CWA degradation products in several untreated decontamination solutions. Degradation products of the nerve agents sarin, soman, and VX were selectively monitored with substantially reduced interference of background signals by 1D 1H-31P heteronuclear single quantum coherence (HSQC) spectrometry. The detection limit of the chemicals was at the low part-per-million level (2-10 microg/mL) in all studied solutions. In addition, the concentration of the degradation products was obtained with sufficient confidence with external standards.

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...

THE QUANTIFICATION OF AQUEOUS TRACERS IN LABORATORY AQUIFER MODELS USING A LIGHT TRANSMISSION VISUALIZATION METHOD - 3

EPA Science Inventory

The quantification of solute concentrations in laboratory aquifer models has been largely limited to the use of sampling ports, from which samples are collected for external analysis. One of the drawbacks to this method is that the act of sampling may disturb plume dynamics and ...

THE QUANTIFICATION OF AQUEOUS TRACERS IN LABORATORY AQUIFER MODELS USING A LIGHT TRANSMISSION VISUALIZATION METHOD - 2

EPA Science Inventory

The quantification of solute concentrations in laboratory aquifer models has been largely limited to the use of sampling ports, from which samples are collected for external analysis. One of the drawbacks to this method is that the act of sampling may disturb plume dynamics and ...

THE QUANTIFICATION OF AQUEOUS TRACERS IN LABORATORY AQUIFER MODELS USING A LIGHT TRANSMISSION VISUALIZATION METHOD - 1

EPA Science Inventory

The quantification of solute concentrations in laboratory aquifer models has been largely limited to the use of sampling ports, from which samples are collected for external analysis. One of the drawbacks to this method is that the act of sampling may disturb plume dynamics and ...

Compatibility of amino acids in ice Ih and high-pressure phases: implications for the origin of life

NASA Astrophysics Data System (ADS)

Hao, J.; Giovenco, E.; Pedreira-Segade, U.; Montagnac, G.; Daniel, I.

2017-12-01

Icy environments may have been common on the early Earth due to the faint young sun. Previous studies have proposed that the formation of large icy bodies in the early ocean could concentrate the building blocks of life in eutectic fluids and therefore facilitate the polymerization of monomers. This hypothesis is based on the untested assumption that organic molecules are virtually incompatible in ice Ih. In this study, we conducted freezing experiments to explore the partitioning behavior of selected amino acids (glycine, L-alanine, L-proline, and L-phenylalanine) between ice Ih and aqueous solutions analogous to seawater. We let ice crystals grow slowly from a few seeds in equilibrium with the solution and used Raman spectroscopy to analyze in situ the relative concentrations of amino acids in the ice and aqueous solution. During freezing, there was no precipitation of amino acid crystals, indicating that the concentrations in solution never reached their solubility limit, even when the droplet was mostly frozen. Analyses of the Raman spectra of ice and eutectic solution showed that considerable amounts of amino acids existed in the ice phase with partition coefficients ranging between 0.2 and 0.5. This study also explored the partitioning of amino acids between other phases of ice (ice VI and ice VII) and solutions at high pressures and observed similar results. These observations implied little incompatibility of amino acids in ice during the freezing of the solutions, rendering the hypothesis of a cold origin of life unwarranted. However, incorporation into ice could significantly improve the efficiency of extraterrestrial transport of small organics. Therefore, this study supports the hypothesis of extraterrestrial delivery of organic molecules in the icy comets and asteroids to the primitive Earth as suggested by an increasing number of independent observations.

Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

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

Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita

To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of themore » Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.« less

Design and application of fiber optic evanescent wave biosensor

NASA Astrophysics Data System (ADS)

Huang, Huijie; Zhai, Junhui; Zhao, Yongkai; Yang, Ruifu; Ren, Bingqiang; Cheng, Zhaogu; Du, Longlong; Lu, Dunwu

2003-12-01

A fiber-optic biosensor is developed based on the principle of evanescent wave while light propagates in optical fiber. The biosensor uses a red laser diode at 636.85 nm for exciting Cy5 fluorescent dye. Sensitivity limit of 0.01 nnmol/l is obtained from the detection of serial Cy5 solutions with various concentrations. In log-to-log plot, excellent linear response characteristic is seen in the Cy5 concentrations ranging from 0.01 nmlo/l to 100 nmol/l. And a good result of signal-to-noise ratio of 4.61 is obtained when the biosensor is used to measure Legionella pneumophila solution of 0.01 μmol/l. All the results are comparable with those that are obtained by a commercial biochip scanner GeneTAC 1000.

Reversible thrombin detection by aptamer functionalized STING sensors.

PubMed

Actis, Paolo; Rogers, Adam; Nivala, Jeff; Vilozny, Boaz; Seger, R Adam; Jejelowo, Olufisayo; Pourmand, Nader

2011-07-15

Signal Transduction by Ion NanoGating (STING) is a label-free technology based on functionalized quartz nanopipettes. The nanopipette pore can be decorated with a variety of recognition elements and the molecular interaction is transduced via a simple electrochemical system. A STING sensor can be easily and reproducibly fabricated and tailored at the bench starting from inexpensive quartz capillaries. The analytical application of this new biosensing platform, however, was limited due to the difficult correlation between the measured ionic current and the analyte concentration in solution. Here we show that STING sensors functionalized with aptamers allow the quantitative detection of thrombin. The binding of thrombin generates a signal that can be directly correlated to its concentration in the bulk solution. Copyright © 2011 Elsevier B.V. All rights reserved.

Transient finite element analysis of electric double layer using Nernst-Planck-Poisson equations with a modified Stern layer.

PubMed

Lim, Jongil; Whitcomb, John; Boyd, James; Varghese, Julian

2007-01-01

A finite element implementation of the transient nonlinear Nernst-Planck-Poisson (NPP) and Nernst-Planck-Poisson-modified Stern (NPPMS) models is presented. The NPPMS model uses multipoint constraints to account for finite ion size, resulting in realistic ion concentrations even at high surface potential. The Poisson-Boltzmann equation is used to provide a limited check of the transient models for low surface potential and dilute bulk solutions. The effects of the surface potential and bulk molarity on the electric potential and ion concentrations as functions of space and time are studied. The ability of the models to predict realistic energy storage capacity is investigated. The predicted energy is much more sensitive to surface potential than to bulk solution molarity.

The influence of solution environment on the nucleation kinetics and crystallisability of para-aminobenzoic acid.

PubMed

Turner, T D; Corzo, D M C; Toroz, D; Curtis, A; Dos Santos, M M; Hammond, R B; Lai, X; Roberts, K J

2016-10-05

The influence of solvent type on the solution thermodynamics, nucleation-kinetics and crystal growth of alpha para-aminobenzoic acid (PABA) crystallising from supersaturated ethanol, acetonitrile and water solutions, is examined using poly-thermal analysis of the metastable zone width. Application of a recently proposed model for analysis of crystallisation kinetics (J. Cryst. Growth, 2010, 312, 698-704) indicates a solvent and concentration dependence of the nucleation mechanism and key nucleation parameters for the alpha form of PABA. The mechanism of nucleation is found to change from instantaneous to progressive with decreasing concentration and also when changing the solvent from ethanol to acetonitrile to water. The dependence of the nucleation mechanism is correlated to the kinetic component of the nucleation rate through calculated values of instantaneously nucleated crystallites, which increase from 1.40 × 10 9 m -3 in ethanol to 1.08 × 10 10 m -3 in acetonitrile to 2.58 × 10 10 m -3 in water. This in combination with low calculated number concentrations of interfacial tension between 1.13 and 2.71 mJ m -2 , supports the conclusion that the kinetic component of the nucleation rate is more limiting when crystallising PABA from ethanol solutions in comparison to water solutions. This finding is further supported by molecular dynamics simulations of the solvation free energy of PABA, which is found to be greatest in water, -42.4 kJ mol -1 and lowest in ethanol, -58.5 kJ mol -1 .

A New Approach to Look at the Electrical Conductivity of Streamflow: Decomposing a Bulk Signal to Recover Individual Solute Concentrations at High-Frequency

NASA Astrophysics Data System (ADS)

Benettin, P.; Van Breukelen, B. M.

2017-12-01

The ability to evaluate stream hydrochemistry is often constrained by the capacity to sample streamwater at an adequate frequency. While technology is no longer a limiting factor, economic and management efforts can still be a barrier to high-resolution water quality instrumentation. We propose a new framework to investigate the electrical conductivity (EC) of streamwater, which can be measured continuously through inexpensive sensors. We show that EC embeds information on ion content which can be isolated to retrieve solute concentrations at high resolution. The approach can already be applied to a number of datasets worldwide where water quality campaigns are conducted, provided continuous EC measurements can be collected. The essence of the approach is the decomposition of the EC signal into its "harmonics", i.e. the specific contributions of the major ions which conduct current in water. The ion contribution is used to explore water quality patterns and to develop algorithms that reconstruct solute concentrations during periods where solute measurements are not available. The approach is validated on a hydrochemical dataset from Plynlimon, Wales. Results show that the decomposition of EC is feasible and for at least two major elements the methodology provided improved estimates of high-frequency solute dynamics. Our results support the installation of EC probes to complement water quality campaigns and suggest that the potential of EC measurements in rivers is currently far from being fully exploited.

The Effect of Valinomycin on the Electrical Properties of Solutions of Red Cell Lipids in n-Decane

PubMed Central

Andreoli, Thomas E.; Tosteson, Daniel C.

1971-01-01

This paper reports the electrical properties of thick lipid membranes in the absence and presence of valinomycin. The thick lipid membranes were formed by placing a solution of sheep red cell lipids in decane between two cellophane partitions which formed the interfaces between the membrane and the two aqueous bathing solutions. The DC electrical resistance of these structures was found to be directly proportional to the reciprocal of the concentration of lipids in the decane (CL). The limiting resistance, as (CL -1) approached zero, was 3 x 108 ohm-cm2. Resistance was also found to be linearly related to membrane thickness. The limiting resistance at zero thickness was again 1–3 x 108 ohm-cm2. These data are interpreted to indicate that the DC resistance of thick lipid membranes comprises two surface resistances (RS) at each interface with the aqueous bathing solutions, and a bulk resistance (RB) of the lipid-decane solution, arranged in series. Measurements of the effect of variations of area on resistance were consistent with this interpretation. Valinomycin reduced RS but had no effect on RB. Under certain conditions, thick lipid membranes containing valinomycin behaved like highly selective K+ electrodes. PMID:5553100

Thermal analysis of a growing crystal in an aqueous solution

NASA Astrophysics Data System (ADS)

Shiomi, Yuji; Kuroda, Toshio; Ogawa, Tomoya

1980-10-01

The temperature profiles around growing crystals in aqueous solutions of Rochelle salt were measured with accuracy of 0.005°C in a two-dimensional cell which was used for elimination of thermal convection current in the cell. The temperature distribution became stationary after 2 h from injection of the mother liquid, but the concentration distribution did not become stationary because the diffusion constant of solute in the solution was much smaller than the thermal diffusivity of the solution. The growth rate was linearly proportional to the temperature gradient at every growing interface. Since crystal growth is a typical interaction process between thermal and material flow, the experimental results were analysed by such an interaction model. The analysis confirms that the material flow is limited by diffusion within a layer width of about a few hundreds micrometers on the growing interface.

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.

Quantifying solute transport processes: are chemically "conservative" tracers electrically conservative?

USGS Publications Warehouse

Singha, Kamini; Li, Li; Day-Lewis, Frederick D.; Regberg, Aaron B.

2012-01-01

The concept of a nonreactive or conservative tracer, commonly invoked in investigations of solute transport, requires additional study in the context of electrical geophysical monitoring. Tracers that are commonly considered conservative may undergo reactive processes, such as ion exchange, thus changing the aqueous composition of the system. As a result, the measured electrical conductivity may reflect not only solute transport but also reactive processes. We have evaluated the impacts of ion exchange reactions, rate-limited mass transfer, and surface conduction on quantifying tracer mass, mean arrival time, and temporal variance in laboratory-scale column experiments. Numerical examples showed that (1) ion exchange can lead to resistivity-estimated tracer mass, velocity, and dispersivity that may be inaccurate; (2) mass transfer leads to an overestimate in the mobile tracer mass and an underestimate in velocity when using electrical methods; and (3) surface conductance does not notably affect estimated moments when high-concentration tracers are used, although this phenomenon may be important at low concentrations or in sediments with high and/or spatially variable cation-exchange capacity. In all cases, colocated groundwater concentration measurements are of high importance for interpreting geophysical data with respect to the controlling transport processes of interest.

Inorganic Carbon Source for Photosynthesis in the Seagrass Thalassia hemprichii (Ehrenb.) Aschers.

PubMed

Abel, K M

1984-11-01

Photosynthetic carbon uptake of the tropical seagrass Thalassia hemprichii (Ehrenb.) Aschers was studied by several methods. Photosynthesis in buffered seawater in media in the range of pH 6 to pH 9 showed an exponentially increasing rate with decreasing pH, thus indicating that free CO(2) was a photosynthetic substrate. However, these experiments were unable to determine whether photosynthesis at alkaline pH also contained some component due to HCO(3) (-) uptake. This aspect was further investigated by studying photosynthetic rates in a number of media of varying pH (7.8-8.61) and total inorganic carbon (0.75-13.17 millimolar). In these media, photosynthetic rate was correlated with free CO(2) concentration and was independent of the HCO(3) (-) concentration in the medium. Short time-course experiments were conducted during equilibration of free CO(2) and HCO(3) (-) after injection of (14)C labeled solution at acid or alkaline pH. High initial photosynthetic rates were observed when acidic solutions (largely free CO(2)) were used but not with alkaline solutions. The concentration of free CO(2) was found to be a limiting factor for photosynthesis in this plant.

Temporal variability and annual budget of inorganic dissolved matter in Andean Pacific Rivers located along a climate gradient from northern Ecuador to southern Peru

NASA Astrophysics Data System (ADS)

Moquet, Jean-Sébastien; Guyot, Jean-Loup; Morera, Sergio; Crave, Alain; Rau, Pedro; Vauchel, Philippe; Lagane, Christelle; Sondag, Francis; Lavado, Casimiro Waldo; Pombosa, Rodrigo; Martinez, Jean-Michel

2018-01-01

In Ecuador and Peru, geochemical information from Pacific coastal rivers is limited and scarce. Here, we present an unedited database of major element concentrations from five HYBAM observatory stations monitored monthly between 4 and 10 years, and the discrete sampling of 23 Andean rivers distributed along the climate gradient of the Ecuadorian and Peruvian Pacific coasts. Concentration (C) vs. discharge (Q) relationships of the five monitored basins exhibit a clear dilution behavior for evaporites and/or pyrite solutes, while the solute concentrations delivered by other endmembers are less variable. Spatially, the annual specific fluxes for total dissolved solids (TDS), Ca2+, HCO3-, K+, Mg2+, and SiO2 are controlled on the first order by runoff variability, while Cl-, Na+ and SO42- are controlled by the occurrence of evaporites and/or pyrite. The entire Pacific basin in Ecuador and Peru exported 30 Mt TDS·yr-1, according to a specific flux of ∼70 t·km-2·yr-1. This show that, even under low rainfall conditions, this orogenic context is more active, in terms of solute production, than the global average.

Review: Water recovery from brines and salt-saturated solutions: operability and thermodynamic efficiency considerations for desalination technologies

PubMed Central

Vane, Leland M.

2017-01-01

BACKGROUND When water is recovered from a saline source, a brine concentrate stream is produced. Management of the brine stream can be problematic, particularly in inland regions. An alternative to brine disposal is recovery of water and possibly salts from the concentrate. RESULTS This review provides an overview of desalination technologies and discusses the thermodynamic efficiencies and operational issues associated with the various technologies particularly with regard to high salinity streams. CONCLUSION Due to the high osmotic pressures of the brine concentrates, reverse osmosis, the most common desalination technology, is impractical. Mechanical vapor compression which, like reverse osmosis, utilizes mechanical work to operate, is reported to have the highest thermodynamic efficiency of the desalination technologies for treatment of salt-saturated brines. Thermally-driven processes, such as flash evaporation and distillation, are technically able to process saturated salt solutions, but suffer from low thermodynamic efficiencies. This inefficiency could be offset if an inexpensive source of waste or renewable heat could be used. Overarching issues posed by high salinity solutions include corrosion and the formation of scales/precipitates. These issues limit the materials, conditions, and unit operation designs that can be used. PMID:29225395

Review: Water recovery from brines and salt-saturated solutions: operability and thermodynamic efficiency considerations for desalination technologies.

PubMed

Vane, Leland M

2017-03-08

When water is recovered from a saline source, a brine concentrate stream is produced. Management of the brine stream can be problematic, particularly in inland regions. An alternative to brine disposal is recovery of water and possibly salts from the concentrate. This review provides an overview of desalination technologies and discusses the thermodynamic efficiencies and operational issues associated with the various technologies particularly with regard to high salinity streams. Due to the high osmotic pressures of the brine concentrates, reverse osmosis, the most common desalination technology, is impractical. Mechanical vapor compression which, like reverse osmosis, utilizes mechanical work to operate, is reported to have the highest thermodynamic efficiency of the desalination technologies for treatment of salt-saturated brines. Thermally-driven processes, such as flash evaporation and distillation, are technically able to process saturated salt solutions, but suffer from low thermodynamic efficiencies. This inefficiency could be offset if an inexpensive source of waste or renewable heat could be used. Overarching issues posed by high salinity solutions include corrosion and the formation of scales/precipitates. These issues limit the materials, conditions, and unit operation designs that can be used.

Drug Loading Capacity of Environmentally Sensitive Polymeric Microgels

NASA Astrophysics Data System (ADS)

McDonough, Ryan; Streletzky, Kiril; Bayachou, Mekki; Peiris, Pubudu

2009-10-01

Microgel nanoparticles consisting of cross-linked polymer hydroxypropyl cellulose chains have a temperature dependent volume phase transition, prompting the use of microgels for controlled drug transport. Drug particles aggregate in the slightly hydrophobic interior of microgels. Microgels are stored in equilibrium until the critical temperature (Tv) is reached and the volume phase transition limits available space, thus expelling the drugs. Our study was designed to test this property of microgels using amperometric electrochemical methods. A critical assumption was that small molecules inside microgels would not interact via diffusion with the electrode surface and thus total current would be decreased across the electrodes in a microgel sample. A room temperature (Troom) flow amperometric measurement comparing microgel/tylenol solution with control tylenol samples yielded about 20% tylenol concentration reduction of the microgel sample. Results from the steady state electrochemical experiment confirm the presence of about 20% tylenol concentration drop of the microgel sample compared to control sample at Troom. Using the steady-state experiment with a cyclic temperature ramp from Troom to beyond Tv showed that the tylenol concentration change between the temperature extremes was greater for the microgel solution than for the control solution.

Environmental Quality Research: Fish and Aufwuchs Bioassay

DTIC Science & Technology

1977-11-01

WSF) of JP-8 and the solution was renewed each day. Acute toxicity as assessed by the 96-hr LC 50 values was not significantly different over the pH...The 96-hr LC 50 of hydrazine to three-spine sticklebacks was 3.4 mg/i (nominal initial concentration) using 24 hr solution renewal, but the estimated...34spill," i.e., static bioassay with no hydrazine renewal, the 96-hr LC 50 to sticklebacks was 6.6 mg/k (95% confidence limits of 5.0 to 8.8 mg/k) based

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.

A flow injection chemiluminescence system for the determination of isoniazid.

PubMed

Huang, Y; Zhang, Z; Zhang, D; Lv, J

2000-10-01

A chemiluminescence (CL) flow system is described for the determination of isoniazid based on its enhancement on the chemiluminescence (CL) emission produced upon mixing a hexacyanoferrate(III) solution with an alkaline luminol solution. The system responds linearly to isoniazid concentration in the range 0-1 mg/L with a detection limit (3sigma) of 0.03 microg/L, relative standard deviation (RSD) of 1.2% for 0.1 mg/L isoniazid (n = 11). The system has been successfully applied to the determination of isoniazid in pharmaceutical preparations.

Use of cellulose-based wastes for adsorption of dyes from aqueous solutions.

PubMed

Annadurai, Gurusamy; Juang, Ruey-Shin; Lee, Duu-Jong

2002-06-10

Low-cost banana and orange peels were prepared as adsorbents for the adsorption of dyes from aqueous solutions. Dye concentration and pH were varied. The adsorption capacities for both peels decreased in the order methyl orange (MO) > methylene blue (MB) > Rhodamine B (RB) > Congo red (CR) > methyl violet (MV) > amido black 10B (AB). The isotherm data could be well described by the Freundlich and Langmuir equations in the concentration range of 10-120 mg/l. An alkaline pH was favorable for the adsorption of dyes. Based on the adsorption capacity, it was shown that banana peel was more effective than orange peel. Kinetic parameters of adsorption such as the Langergren rate constant and the intraparticle diffusion rate constant were determined. For the present adsorption process intraparticle diffusion of dyes within the particle was identified to be rate limiting. Both peel wastes were shown to be promising materials for adsorption removal of dyes from aqueous solutions.

[Determination of ru, rh and Pd in 30% trialkyl phosphine oxide (TRPO)-kerosene by inductively coupled plasma-atomic emission spectrum (ICP-AES)].

PubMed

Wang, Jian-Chen; Zhang, Lin

2013-07-01

The determination method of Ru, Rh and Pd in 30% TRPO-kerosene ICP-AES was studied by using aqueous calibration reference solution and choosing ethanol as diluent. The effects of the contents of 30% TRPO-kerosene and aqueous solution and the concentration of HNO3 in 30% TRPO-kerosene on the intensities of Ru, Rh and Pd were described. The optimized condition for preparing samples and calibration solutions was chosen as follows: The contents of 30% TRPO-kerosene and aqueous phase were 10% (V/V) and 5% (V/V) respectively and the concentration of HNO3 30% TRPO-kerosene was 0.20 mol x L(-1). The determination method of Au, Ru and Pd was set up according to the above condition. The detection limit, precision and recovery ratio of Ru, Rh and Pd are well. The method is not only used in determination of Au, Ru and Pd in 30% TRPO-kerosene, but also used in other organic phases.

Competitive sorption of organic contaminants in chalk.

PubMed

Graber, E R; Borisover, M

2003-12-01

In the Negev desert, Israel, a chemical industrial complex is located over fractured Eocene chalk formations where transfer of water and solutes between fracture voids and matrix pores affects migration of contaminants in the fractures due to diffusion into the chalk matrix. This study tests sorption and sorption competition between contaminants in the chalk matrix to make it possible to evaluate the potential for contaminant attenuation during transport in fractures. Single solute sorption isotherms on chalk matrix material for five common contaminants (m-xylene, ametryn, 1,2-dichloroethane, phenanthrene, and 2,4,6-tribromophenol) were found to be nonlinear, as confirmed in plots of Kd versus initial solution concentration. Over the studied concentration ranges, m-xylene Kd varied by more than a factor of 100, ametryn Kd by a factor of 4, 1,2-dichloroethane Kd by more than a factor of 3, phenanthrene Kd by about a factor of 2, and 2,4,6-tribromophenol Kd by a factor of 10. It was earlier found that sorption is to the organic matter component of the chalk matrix and not to the mineral phases (Chemosphere 44 (2001) 1121). Nonlinear sorption isotherms indicate that there is at least some finite sorption domain. Bi-solute competition experiments with 2,4,6-tribromophenol as the competitor were designed to explore the nature of the finite sorption domain. All of the isotherms in the bi-solute experiments are more linear than in the single solute experiments, as confirmed by smaller variations in Kd as a function of initial solution concentration. For both m-xylene and ametryn, there is a small nonlinear component or domain that was apparently not susceptible to competition by 2,4,6-tribromophenol. The nonlinear sorption domain(s) is best expressed at low solution concentrations. Inert-solvent-normalized single and bi-solute sorption isotherms demonstrate that ametryn undergoes specific force interactions with the chalk sorbent. The volume percent of phenanthrene sorbed at the liquid solubility limit is calculated to be 13% v:v in both the single and bi-solute experiments. This value exceeds what may be reasonably interpreted as partitioning of phenanthrene into organic matter, despite the relative linearity of the phenanthrene sorption isotherm (compared with other compounds) in both single and bi-solute systems.

MC ICP-MS δ(34)S(VCDT) measurement of dissolved sulfate in environmental aqueous samples after matrix separation by means of an anion exchange membrane.

PubMed

Hanousek, Ondrej; Berger, Torsten W; Prohaska, Thomas

2016-01-01

Analysis of (34)S/(32)S of sulfate in rainwater and soil solutions can be seen as a powerful tool for the study of the sulfur cycle. Therefore, it is considered as a useful means, e.g., for amelioration and calibration of ecological or biogeochemical models. Due to several analytical limitations, mainly caused by low sulfate concentration in rainwater, complex matrix of soil solutions, limited sample volume, and high number of samples in ecosystem studies, a straightforward analytical protocol is required to provide accurate S isotopic data on a large set of diverse samples. Therefore, sulfate separation by anion exchange membrane was combined with precise isotopic measurement by multicollector inductively coupled plasma mass spectrometry (MC ICP-MS). The separation method proved to be able to remove quantitatively sulfate from matrix cations (Ca, K, Na, or Li) which is a precondition in order to avoid a matrix-induced analytical bias in the mass spectrometer. Moreover, sulfate exchange on the resin is capable of preconcentrating sulfate from low concentrated solutions (to factor 3 in our protocol). No significant sulfur isotope fractionation was observed during separation and preconcentration. MC ICP-MS operated at edge mass resolution has enabled the direct (34)S/(32)S analysis of sulfate eluted from the membrane, with an expanded uncertainty U (k = 2) down to 0.3 ‰ (a single measurement). The protocol was optimized and validated using different sulfate solutions and different matrix compositions. The optimized method was applied in a study on solute samples retrieved in a beech (Fagus sylvatica) forest in the Vienna Woods. Both rainwater (precipitation and tree throughfall) and soil solution δ (34)SVCDT ranged between 4 and 6 ‰, the ratio in soil solution being slightly lower. The lower ratio indicates that a considerable portion of the atmospherically deposited sulfate is cycled through the organic S pool before being released to the soil solution. Nearly the same trends and variations were observed in soil solution and rainwater δ (34)SVCDT values showing that sulfate adsorption/desorption are not important processes in the studied soil.

Surfactant-enhanced remediation of a trichloroethene-contaminated aquifer. 1. Transport of triton X-100

USGS Publications Warehouse

Smith, J.A.; Sahoo, D.; Mclellan, H.M.; Imbrigiotta, T.E.

1997-01-01

Transport of a nonionic surfactant (Triton X-100) at aqueous concentrations less than 400 mg/L through a trichloroethene-contaminated sand-and-gravel aquifer at Picatinny Arsenal, NJ, has been studied through a series of laboratory and field experiments. In the laboratory, batch and column experiments were conducted to quantify the rate and amount of Triton X-100 sorption to the aquifer sediments. In the field, a 400 mg/L aqueous Triton X-100 solution was injected into the aquifer at a rate of 26.5 L/min for a 35-d period. The transport of Triton X-100 was monitored by sampling and analysis of groundwater at six locations surrounding the injection well. Equilibrium batch sorption experiments showed that Triton X-100 sorbs strongly and nonlinearly to the field soil with the sharpest inflection point of the isotherm occurring at an equilibrium aqueous Triton X-100 concentration close to critical micelle concentration. Batch, soil column, and field experimental data were analyzed with zero-, one-, and two- dimensional (respectively) transient solute transport models with either equilibrium or rate-limited sorption. These analyses reveal that Triton X- 100 sorption to the aquifer solids is slow relative to advective and dispersive transport and that an equilibrium sorption model cannot simulate accurately the observed soil column and field data. Comparison of kinetic sorption parameters from batch, column, and field transport data indicate that both physical heterogeneities and Triton X-100 mass transfer between water and soil contribute to the kinetic transport effects.Transport of a nonionic surfactant (Triton X-100) at aqueous concentrations less than 400 mg/L through a trichloroethene-contaminated sand-and-gravel aquifer was studied. Equilibrium batch sorption experiments showed that Triton X-100 sorbs strongly and nonlinearly to the field soil with the sharpest inflection point of the isotherm occurring at an equilibrium aqueous Triton X-100 concentration close to critical micelle concentration. Batch, soil column, and field experimental data were analyzed with zero-, one-, and two-dimensional transient solute transport models with either equilibrium or rate-limited sorption. These analyses revealed that Triton X-100 sorption to the aquifer solids was slow relative to advective and dispersive transport.

Influence of Concentration and Salinity on the Biodegradability of Organic Additives in Hydraulic Fracturing Fluid

NASA Astrophysics Data System (ADS)

Mouser, P. J.; Kekacs, D.

2014-12-01

One of the risks associated with the use of hydraulic fracturing technologies for energy development is the potential release of hydraulic fracturing-related fluids into surface waters or shallow aquifers. Many of the organic additives used in hydraulic fracturing fluids are individually biodegradable, but little is know on how they will attenuate within a complex organic fluid in the natural environment. We developed a synthetic hydraulic fracturing fluid based on disclosed recipes used by Marcellus shale operators to evaluate the biodegradation potential of organic additives across a concentration (25 to 200 mg/L DOC) and salinity gradient (0 to 60 g/L) similar to Marcellus shale injected fluids. In aerobic aqueous solutions, microorganisms removed 91% of bulk DOC from low SFF solutions and 57% DOC in solutions having field-used SFF concentrations within 7 days. Under high SFF concentrations, salinity in excess of 20 g/L inhibited organic compound biodegradation for several weeks, after which time the majority (57% to 75%) of DOC remained in solution. After SFF amendment, the initially biodiverse lake or sludge microbial communities were quickly dominated (>79%) by Pseudomonas spp. Approximately 20% of added carbon was converted to biomass while the remainder was respired to CO2 or other metabolites. Two alcohols, isopropanol and octanol, together accounted for 2-4% of the initial DOC, with both compounds decreasing to below detection limits within 7 days. Alcohol degradation was associated with an increase in acetone at mg/L concentrations. These data help to constrain the biodegradation potential of organic additives in hydraulic fracturing fluids and guide our understanding of the microbial communities that may contribute to attenuation in surface waters.

Concentration-Induced Association in a Protein System Caused by a Highly Directional Patch Attraction.

PubMed

Li, Weimin; Persson, Björn A; Lund, Mikael; Bergenholtz, Johan; Zackrisson Oskolkova, Malin

2016-09-01

Self-association of the protein lactoferrin is studied in solution using small-angle X-ray scattering techniques. Effective static structure factors have been shown to exhibit either a monotonic or a nonmonotonic dependence on protein concentration in the small wavevector limit, depending on salt concentration. The behavior correlates with a nonmonotonic dependence of the second virial coefficient on salt concentration, such that a maximum appears in the structure factor at a low protein concentration when the second virial coefficient is negative and close to a minimum. The results are interpreted in terms of an integral equation theory with explicit dimers, formulated by Wertheim, which provides a consistent framework able to explain the behavior in terms of a monomer-dimer equilibrium that appears because of a highly directional patch attraction. Short attraction ranges preclude trimer formation, which explains why the protein system behaves as if it were subject to a concentration-dependent isotropic protein-protein attraction. Superimposing an isotropic interaction, comprising screened Coulomb repulsion and van der Waals attraction, on the patch attraction allows for a semiquantitative modeling of the complete transition pathway from monomers in the dilute limit to monomer-dimer systems at somewhat higher protein concentrations.

Analytical solutions of one-dimensional multispecies reactive transport in a permeable reactive barrier-aquifer system

NASA Astrophysics Data System (ADS)

Mieles, John; Zhan, Hongbin

2012-06-01

The permeable reactive barrier (PRB) remediation technology has proven to be more cost-effective than conventional pump-and-treat systems, and has demonstrated the ability to rapidly reduce the concentrations of specific chemicals of concern (COCs) by up to several orders of magnitude in some scenarios. This study derives new steady-state analytical solutions to multispecies reactive transport in a PRB-aquifer (dual domain) system. The advantage of the dual domain model is that it can account for the potential existence of natural degradation in the aquifer, when designing the required PRB thickness. The study focuses primarily on the steady-state analytical solutions of the tetrachloroethene (PCE) serial degradation pathway and secondly on the analytical solutions of the parallel degradation pathway. The solutions in this study can also be applied to other types of dual domain systems with distinct flow and transport properties. The steady-state analytical solutions are shown to be accurate and the numerical program RT3D is selected for comparison. The results of this study are novel in that the solutions provide improved modeling flexibility including: 1) every species can have unique first-order reaction rates and unique retardation factors, and 2) daughter species can be modeled with their individual input concentrations or solely as byproducts of the parent species. The steady-state analytical solutions exhibit a limitation that occurs when interspecies reaction rate factors equal each other, which result in undefined solutions. Excel spreadsheet programs were created to facilitate prompt application of the steady-state analytical solutions, for both the serial and parallel degradation pathways.

Sorption behavior of microamounts of zinc on titanium oxide from aqueous solutions

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

Hasany, S.M.; Ghaffar, A.; Chughtai, F.A.

1991-08-01

To correlate soil response toward zinc, it is necessary to study its adsorption in detail on soils or on their constituents. The adsorption of microamounts of zinc on titanium oxide, prepared and characterized in this laboratory, has been studied in detail. Zinc adsorption has been found to be dependent on the pH of the aqueous solution, amount of oxide, and zinc concentration. Maximum adsorption is from pH 10 buffer. EDTA and cyanide ions inhibit adsorption significantly. The adsorption of other elements under optimal conditions has also been measured on this oxide. Sc(III) and Cs(I) show almost negligible adsorption. Zinc adsorptionmore » follows the linear form of the Freundlich adsorption isotherm: log C{sub Ads} = log A + (1/n) log C{sub Bulk} with A = 0.48 mol/g and n = 1. Except at a very low bulk concentration (3 {times} 10{sup {minus}5} mol/dm{sup 3}), Langmuir adsorption isotherm is also linear for the entire zinc concentration investigated. The limiting adsorbed concentration is estimated to be 0.18 mol/g.« less

Anodic stripping voltammetry enhancement by redox magnetohydrodynamics.

PubMed

Clark, Emily A; Fritsch, Ingrid

2004-04-15

The effect of an external magnetic field on linear scan anodic stripping voltammetry (ASV) in solutions of 10(-6)-10(-7) M concentrations of lead, cadmium, and copper at mercury films on glassy carbon electrodes has been investigated. A high concentration of Hg(2+) was added to the analyte solution to induce a large cathodic current during the deposition step. Therefore, a large Lorentz force from the net flux of charge through the magnetic field resulted in convection due to magnetohydrodynamics. The faster delivery of analytes to the mercury film electrode during deposition caused an increase in the anodic stripping peaks. The effect of varying Hg(2+) concentrations (0-60 mM) and magnetic field strengths (0-1.77 T) on the enhancement of the stripping peaks was investigated. Enhancements as large as 129% for peak currents and 167% for peak areas were observed. An enhancement of approximately 100% was observed when 60 mM Fe(3+) replaced high concentrations of Hg(2+). This method of convection exhibits promise for small-volume ASV analysis with possible improved limits of detection and decreased preconcentration times.

Cloud water composition during HCCT-2010: Scavenging efficiencies, solute concentrations, and droplet size dependence of inorganic ions and dissolved organic carbon

NASA Astrophysics Data System (ADS)

van Pinxteren, Dominik; Wadinga Fomba, Khanneh; Mertes, Stephan; Müller, Konrad; Spindler, Gerald; Schneider, Johannes; Lee, Taehyoung; Collett, Jeffrey L.; Herrmann, Hartmut

2016-03-01

Cloud water samples were taken in September/October 2010 at Mt. Schmücke in a rural, forested area in Germany during the Lagrange-type Hill Cap Cloud Thuringia 2010 (HCCT-2010) cloud experiment. Besides bulk collectors, a three-stage and a five-stage collector were applied and samples were analysed for inorganic ions (SO42-,NO3-, NH4+, Cl-, Na+, Mg2+, Ca2+, K+), H2O2 (aq), S(IV), and dissolved organic carbon (DOC). Campaign volume-weighted mean concentrations were 191, 142, and 39 µmol L-1 for ammonium, nitrate, and sulfate respectively, between 4 and 27 µmol L-1 for minor ions, 5.4 µmol L-1 for H2O2 (aq), 1.9 µmol L-1 for S(IV), and 3.9 mgC L-1 for DOC. The concentrations compare well to more recent European cloud water data from similar sites. On a mass basis, organic material (as DOC × 1.8) contributed 20-40 % (event means) to total solute concentrations and was found to have non-negligible impact on cloud water acidity. Relative standard deviations of major ions were 60-66 % for solute concentrations and 52-80 % for cloud water loadings (CWLs). The similar variability of solute concentrations and CWLs together with the results of back-trajectory analysis and principal component analysis, suggests that concentrations in incoming air masses (i.e. air mass history), rather than cloud liquid water content (LWC), were the main factor controlling bulk solute concentrations for the cloud studied. Droplet effective radius was found to be a somewhat better predictor for cloud water total ionic content (TIC) than LWC, even though no single explanatory variable can fully describe TIC (or solute concentration) variations in a simple functional relation due to the complex processes involved. Bulk concentrations typically agreed within a factor of 2 with co-located measurements of residual particle concentrations sampled by a counterflow virtual impactor (CVI) and analysed by an aerosol mass spectrometer (AMS), with the deviations being mainly caused by systematic differences and limitations of the approaches (such as outgassing of dissolved gases during residual particle sampling). Scavenging efficiencies (SEs) of aerosol constituents were 0.56-0.94, 0.79-0.99, 0.71-98, and 0.67-0.92 for SO42-, NO3-, NH4+, and DOC respectively when calculated as event means with in-cloud data only. SEs estimated using data from an upwind site were substantially different in many cases, revealing the impact of gas-phase uptake (for volatile constituents) and mass losses across Mt. Schmücke likely due to physical processes such as droplet scavenging by trees and/or entrainment. Drop size-resolved cloud water concentrations of major ions SO42-, NO3-, and NH4+ revealed two main profiles: decreasing concentrations with increasing droplet size and "U" shapes. In contrast, profiles of typical coarse particle mode minor ions were often increasing with increasing drop size, highlighting the importance of a species' particle concentration size distribution for the development of size-resolved solute concentration patterns. Concentration differences between droplet size classes were typically < 2 for major ions from the three-stage collector and somewhat more pronounced from the five-stage collector, while they were much larger for minor ions. Due to a better separation of droplet populations, the five-stage collector was capable of resolving some features of solute size dependencies not seen in the three-stage data, especially sharp concentration increases (up to a factor of 5-10) in the smallest droplets for many solutes.

Cloud water composition during HCCT-2010: Scavenging efficiencies, solute concentrations, and droplet size dependence of inorganic ions and dissolved organic carbon

NASA Astrophysics Data System (ADS)

van Pinxteren, D.; Fomba, K. W.; Mertes, S.; Müller, K.; Spindler, G.; Schneider, J.; Lee, T.; Collett, J.; Herrmann, H.

2015-09-01

Cloud water samples were taken in September/October 2010 at Mt. Schmücke in a rural, forested area in Germany during the Lagrange-type Hill Cap Cloud Thuringia 2010 (HCCT-2010) cloud experiment. Besides bulk collectors, a 3-stage and a 5-stage collector were applied and samples were analysed for inorganic ions (SO42-, NO3-, NH4+, Cl-, Na+, Mg2+, Ca2+, K+), H2O2 (aq), S(IV), and dissolved organic carbon (DOC). Campaign volume-weighted mean concentrations were 191, 142, and 39 μmol L-1 for ammonium, nitrate, and sulfate, respectively, between 4 and 27 μmol L-1 for minor ions, 5.4 μmol L-1 for H2O2 (aq), 1.9 μmol L-1 for S(IV), and 3.9 mgC L-1 for DOC. The concentrations compare well to more recent European cloud water data from similar sites. On a mass basis, organic material (as DOC · 1.8) contributed 20-40 % (event means) to total solute concentrations and was found to have non-negligible impact on cloud water acidity. Relative standard deviations of major ions were 60-66 % for solute concentrations and 52-80 % for cloud water loadings (CWLs). Contrary to some earlier suggestions, the similar variability of solute concentrations and CWLs together with the results of back trajectory analysis and principal component analysis, suggests that concentrations in incoming air masses (i.e. air mass history), rather than cloud liquid water content (LWC) was the main factor controlling bulk solute concentrations at Mt. Schmücke. Droplet effective radius was found to be a somewhat better predictor for cloud water total ionic content (TIC) than LWC, even though no single explanatory variable can fully describe TIC (or solute concentration) variations in a simple functional relation due to the complex processes involved. Bulk concentrations typically agreed within a factor of 2 with co-located measurements of residual particle concentrations sampled by a counterflow virtual impactor (CV) and analysed by an aerosol mass spectrometer (AMS), with the deviations being mainly caused by systematic differences and limitations of the approaches (such as outgassing of dissolved gases during residual particle sampling). Scavenging efficiencies (SEs) of aerosol constituents were 0.56-0.94, 0.79-0.99, 0.71-98, and 0.67-0.92 for SO42-, NO3-, NH4+, and DOC, respectively, when calculated as event means with in-cloud data only. SEs estimated using data from an upwind site were substantially different in many cases, revealing the impact of gas-phase uptake (for volatile constituents) and mass losses across Mt. Schmücke likely due to physical processes such as droplet scavenging by trees and/or entrainment. Drop size-resolved cloud water concentrations of major ions SO42-, NO3-, and NH4+ revealed two main profiles: decreasing concentrations with increasing droplet size and "U"-shapes. In contrast, profiles of typical coarse particle mode minor ions were often increasing with increasing drop size, highlighting the importance of a species' particle concentration size distribution for the development of size-resolved solute concentration patterns. Concentration differences between droplet size classes were typically < 2 for major ions from the 3-stage collector and somewhat more pronounced from the 5-stage collector, while they were much larger for minor ions. Due to a better separation of droplet populations, the 5-stage collector was capable of resolving some features of solute size dependencies not seen in the 3-stage data, especially sharp concentration increases (up to a factor of 5-10) in the smallest droplets for many solutes.

Use of Artificial Neural Networks to Examine Parameters Affecting the Immobilization of Streptokinase in Chitosan

PubMed Central

Modaresi, Seyed Mohamad Sadegh; Faramarzi, Mohammad Ali; Soltani, Arash; Baharifar, Hadi; Amani, Amir

2014-01-01

Streptokinase is a potent fibrinolytic agent which is widely used in treatment of deep vein thrombosis (DVT), pulmonary embolism (PE) and acute myocardial infarction (MI). Major limitation of this enzyme is its short biological half-life in the blood stream. Our previous report showed that complexing streptokinase with chitosan could be a solution to overcome this limitation. The aim of this research was to establish an artificial neural networks (ANNs) model for identifying main factors influencing the loading efficiency of streptokinase, as an essential parameter determining efficacy of the enzyme. Three variables, namely, chitosan concentration, buffer pH and enzyme concentration were considered as input values and the loading efficiency was used as output. Subsequently, the experimental data were modeled and the model was validated against a set of unseen data. The developed model indicated chitosan concentration as probably the most important factor, having reverse effect on the loading efficiency. PMID:25587327

Electrical conductivity of solutions of copper(II) nitrate crystalohydrate in dimethyl sulfoxide

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul K.; Mamitova, A. D.; Mamyrbekova, Aizhan K.

2016-06-01

Conductometry is used to investigate the electric conductivity of Cu(NO3)2 ṡ 3H2O solutions in dimethyl sulfoxide in the 0.01-2.82 M range of concentrations and at temperatures of 288-318 K. The limiting molar conductivity of the electrolyte and the mobility of Cu2+ and NO 3 - ions, the effective coefficients of diffusion of copper(II) ions and nitrate ions, and the degree and constant of electrolytic dissociation are calculated for different temperatures from the experimental results. It is established that solutions containing 0.1-0.6 M copper nitrate trihydrate in DMSO having low viscosity and high electrical conductivity can be used in electrochemical deposition.

Targeted Analyte Detection by Standard Addition Improves Detection Limits in MALDI Mass Spectrometry

PubMed Central

Eshghi, Shadi Toghi; Li, Xingde; Zhang, Hui

2014-01-01

Matrix-assisted laser desorption/ionization has proven an effective tool for fast and accurate determination of many molecules. However, the detector sensitivity and chemical noise compromise the detection of many invaluable low-abundance molecules from biological and clinical samples. To challenge this limitation, we developed a targeted analyte detection (TAD) technique. In TAD, the target analyte is selectively elevated by spiking a known amount of that analyte into the sample, thereby raising its concentration above the noise level, where we take advantage of the improved sensitivity to detect the presence of the endogenous analyte in the sample. We assessed TAD on three peptides in simple and complex background solutions with various exogenous analyte concentrations in two MALDI matrices. TAD successfully improved the limit of detection (LOD) of target analytes when the target peptides were added to the sample in a concentration close to optimum concentration. The optimum exogenous concentration was estimated through a quantitative method to be approximately equal to the original LOD for each target. Also, we showed that TAD could achieve LOD improvements on an average of 3-fold in a simple and 2-fold in a complex sample. TAD provides a straightforward assay to improve the LOD of generic target analytes without the need for costly hardware modifications. PMID:22877355

Targeted analyte detection by standard addition improves detection limits in matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Toghi Eshghi, Shadi; Li, Xingde; Zhang, Hui

2012-09-18

Matrix-assisted laser desorption/ionization (MALDI) has proven an effective tool for fast and accurate determination of many molecules. However, the detector sensitivity and chemical noise compromise the detection of many invaluable low-abundance molecules from biological and clinical samples. To challenge this limitation, we developed a targeted analyte detection (TAD) technique. In TAD, the target analyte is selectively elevated by spiking a known amount of that analyte into the sample, thereby raising its concentration above the noise level, where we take advantage of the improved sensitivity to detect the presence of the endogenous analyte in the sample. We assessed TAD on three peptides in simple and complex background solutions with various exogenous analyte concentrations in two MALDI matrices. TAD successfully improved the limit of detection (LOD) of target analytes when the target peptides were added to the sample in a concentration close to optimum concentration. The optimum exogenous concentration was estimated through a quantitative method to be approximately equal to the original LOD for each target. Also, we showed that TAD could achieve LOD improvements on an average of 3-fold in a simple and 2-fold in a complex sample. TAD provides a straightforward assay to improve the LOD of generic target analytes without the need for costly hardware modifications.

Solid Solutions of Rare Earth Cations in Mesoporous Anatase Beads and Their Performances in Dye-Sensitized Solar Cells

PubMed Central

Cavallo, Carmen; Salleo, Alberto; Gozzi, Daniele; Di Pascasio, Francesco; Quaranta, Simone; Panetta, Riccardo; Latini, Alessandro

2015-01-01

Solid solutions of the rare earth (RE) cations Pr3+, Nd3+, Sm3+, Gd3+, Er3+ and Yb3+ in anatase TiO2 have been synthesized as mesoporous beads in the concentration range 0.1–0.3% of metal atoms. The solid solutions were have been characterized by XRD, SEM, diffuse reflectance UV-Vis spectroscopy, BET and BJH surface analysis. All the solid solutions possess high specific surface areas, up to more than 100 m2/g. The amount of adsorbed dye in each photoanode has been determined spectrophotometrically. All the samples were tested as photoanodes in dye-sensitized solar cells (DSSCs) using N719 as dye and a nonvolatile, benzonitrile based electrolyte. All the cells were have been tested by conversion efficiency (J–V), quantum efficiency (IPCE), electrochemical impedance spectroscopy (EIS) and dark current measurements. While lighter RE cations (Pr3+, Nd3+) limit the performance of DSSCs compared to pure anatase mesoporous beads, cations from Sm3+ onwards enhance the performance of the devices. A maximum conversion efficiency of 8.7% for Er3+ at a concentration of 0.2% has been achieved. This is a remarkable efficiency value for a DSSC employing N719 dye without co-adsorbents and a nonvolatile electrolyte. For each RE cation the maximum performances are obtained for a concentration of 0.2% metal atoms. PMID:26577287

Do centrally pre-prepared solutions achieve more reliable drug concentrations than solutions prepared on the ward?

PubMed

Dehmel, Carola; Braune, Stephan A; Kreymann, Georg; Baehr, Michael; Langebrake, Claudia; Hilgarth, Heike; Nierhaus, Axel; Dartsch, Dorothee C; Kluge, Stefan

2011-08-01

To compare the concentration conformity of infusion solutions manually prepared on intensive care units (ICU) with solutions from pharmacy-based, automated production. A prospective observational study conducted in a university hospital in Germany. Drug concentrations of 100 standardised infusion solutions manually prepared in the ICU and 100 matching solutions from automated production containing amiodarone, noradrenaline or hydrocortisone were measured by high-performance liquid chromatography analysis. Deviations from stated concentrations were calculated, and the quality of achieved concentration conformity of the two production methods was compared. Actual concentrations of 53% of the manually prepared and 16% of the machine-made solutions deviated by >5% above or below the stated concentration. A deviation of >10% was measured in 22% of the manually prepared samples and in 5% of samples from automated production. Of the manually prepared solutions, 15% deviated by >15% above or below the intended concentration. The mean concentration of the manually prepared solutions was 97.2% (SD 12.7%, range 45-129%) and of the machine-made solutions was 101.1% (SD 4.3%, range 90-114%) of the target concentration (p < 0.01). In this preliminary study, ward-based, manually prepared infusion solutions showed clinically relevant deviations in concentration conformity significantly more often than pharmacy-prepared, machine-made solutions. Centralised, automated preparation of standardised infusion solutions may be an effective means to reduce this type of medication error. Further confirmatory studies in larger settings and under conditions of routine automated production are required.

Low-level (PPB) determination of cisplatin in cleaning validation (rinse water) samples. II. A high-performance liquid chromatographic method.

PubMed

Raghavan, R; Burchett, M; Loffredo, D; Mulligan, J A

2000-04-01

A high-performance liquid chromatographic (HPLC) method is described for the determination of residual levels of cisplatin from extracts of surfaces with very low surface area; from extracts of surfaces of coupons made of Teflon (polytetrafluoroethylene, PTFE), stainless steel, and glass; and in aqueous solution collected after rinsing equipment and parts. Initially, the method was developed to determine cisplatin at concentrations ranging from 20 to 200 ng/ml by direct injection. Retaining the same method conditions, the scope of the method was expanded by the addition of a sample preconcentration step, allowing analyses at levels ranging from 0.5 ng to 20 ng/ml. Preconcentration is necessary for the determination of cisplatin in rinse waters at a quantifiable concentration of about 2 PPB. Under these conditions, the detection limit is about 0.2 to 0.3 ng/ml. Residual cisplatin on different types of surfaces, including surfaces with very low surface area, can be determined by swabbing each test surface with a derivatizing solution. The cisplatin recovered in the swabbing solution can be analyzed by HPLC using direct injection or preconcentration, depending on the expected level of cisplatin in the sample. Initial methods were developed to quantitate at a cisplatin concentration of about 100 PPB or higher in solution extracted from surfaces. However, when surface areas are limited because of the size of the parts, solution concentration becomes very low as a result of the minimum volume required for extraction. To support the application of swabbing techniques to surface analysis, stainless steel, Teflon, and glass surfaces were spiked with cisplatin at 2.5 to 20 ng/cm2. Satisfactory overall recoveries of 90% +/- 10% were obtained from all surfaces. Cisplatin has no ultraviolet/visible (UV/Vis) spectral-active functional group that can be used to detect low levels of cisplatin. Hence, diethyldithiocarbamate (DDTC) was used as a derivatizing agent to increase sensitivity to UV absorption at 340 nm. Diethyldithiocarbamate forms complexes with the platinum in cisplatin to yield a platinum-DDTC (Pt-DDTC) complex with a high molar-extinction coefficient. The Pt(DDTC)2 complex thus formed was chromatographically separated and the quantitated by comparison of its detector response to that of a similarly derivatized standard preparation. DDTC also has application as a cleaning agent for cisplatin (e.g., for production equipment cleaning, spill cleanup). Destruction of cisplatin can be affected by the reaction of cisplatin with this cleaning agent. Derivatization of cisplatin will convert active cisplatin to platinum-DDTC on surfaces or in solution. Final cleaning can be accomplished using a water-for-injection rinse. After such a cleaning process, the rinse water, when collected and analyzed, showed levels of free cisplatin less than the detection concentration of 0.2 PPB and a total platinum concentration less than 10 PPB as Pt-DDTC complex.

Exploring the limits of crop productivity: A model to evaluate progress

NASA Technical Reports Server (NTRS)

Bugbee, Bruce

1990-01-01

The goal was to determine the limits of crop productivity when all environmental constraints were removed. Researchers define productivity as food output per unit of input. Researchers evaluated cultivars of wheat with reduced leaf size and number to decrease the leaf area index at high plant densities. These cultivars may also have an improved harvest index. Hydroponic studies indicate that 1 mM nitrate in solution is adequate to support maximum growth in these systems, provided iron nutrition is adequate. Wheat does not accumulate nitrate in leaves even when the solution nitrate concentration is 15 mM. Long-term photosynthetic efficiency (g mol (exp -1) of photons) and harvest index were not altered by photoperiod (16, 20, or 24 hours). Wheat does not need, nor benefit from, a diurnal dark period.

Revisiting the Fundamental Analytical Solutions of Heat and Mass Transfer: The Kernel of Multirate and Multidimensional Diffusion

NASA Astrophysics Data System (ADS)

Zhou, Quanlin; Oldenburg, Curtis M.; Rutqvist, Jonny; Birkholzer, Jens T.

2017-11-01

There are two types of analytical solutions of temperature/concentration in and heat/mass transfer through boundaries of regularly shaped 1-D, 2-D, and 3-D blocks. These infinite-series solutions with either error functions or exponentials exhibit highly irregular but complementary convergence at different dimensionless times, td. In this paper, approximate solutions were developed by combining the error-function-series solutions for early times and the exponential-series solutions for late times and by using time partitioning at the switchover time, td0. The combined solutions contain either the leading term of both series for normal-accuracy approximations (with less than 0.003 relative error) or the first two terms for high-accuracy approximations (with less than 10-7 relative error) for 1-D isotropic (spheres, cylinders, slabs) and 2-D/3-D rectangular blocks (squares, cubes, rectangles, and rectangular parallelepipeds). This rapid and uniform convergence for rectangular blocks was achieved by employing the same time partitioning with individual dimensionless times for different directions and the product of their combined 1-D slab solutions. The switchover dimensionless time was determined to minimize the maximum approximation errors. Furthermore, the analytical solutions of first-order heat/mass flux for 2-D/3-D rectangular blocks were derived for normal-accuracy approximations. These flux equations contain the early-time solution with a three-term polynomial in √td and the late-time solution with the limited-term exponentials for rectangular blocks. The heat/mass flux equations and the combined temperature/concentration solutions form the ultimate kernel for fast simulations of multirate and multidimensional heat/mass transfer in porous/fractured media with millions of low-permeability blocks of varying shapes and sizes.

Revisiting the Fundamental Analytical Solutions of Heat and Mass Transfer: The Kernel of Multirate and Multidimensional Diffusion

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

Zhou, Quanlin; Oldenburg, Curtis M.; Rutqvist, Jonny

There are two types of analytical solutions of temperature/concentration in and heat/mass transfer through boundaries of regularly shaped 1D, 2D, and 3D blocks. These infinite-series solutions with either error functions or exponentials exhibit highly irregular but complementary convergence at different dimensionless times, t d0. In this paper, approximate solutions were developed by combining the error-function-series solutions for early times and the exponential-series solutions for late times and by using time partitioning at the switchover time, t d0. The combined solutions contain either the leading term of both series for normal-accuracy approximations (with less than 0.003 relative error) or the firstmore » two terms for high-accuracy approximations (with less than 10-7 relative error) for 1D isotropic (spheres, cylinders, slabs) and 2D/3D rectangular blocks (squares, cubes, rectangles, and rectangular parallelepipeds). This rapid and uniform convergence for rectangular blocks was achieved by employing the same time partitioning with individual dimensionless times for different directions and the product of their combined 1D slab solutions. The switchover dimensionless time was determined to minimize the maximum approximation errors. Furthermore, the analytical solutions of first-order heat/mass flux for 2D/3D rectangular blocks were derived for normal-accuracy approximations. These flux equations contain the early-time solution with a three-term polynomial in √td and the late-time solution with the limited-term exponentials for rectangular blocks. The heat/mass flux equations and the combined temperature/concentration solutions form the ultimate kernel for fast simulations of multirate and multidimensional heat/mass transfer in porous/fractured media with millions of low-permeability blocks of varying shapes and sizes.« less

Revisiting the Fundamental Analytical Solutions of Heat and Mass Transfer: The Kernel of Multirate and Multidimensional Diffusion

DOE PAGES

Zhou, Quanlin; Oldenburg, Curtis M.; Rutqvist, Jonny; ...

2017-10-24

There are two types of analytical solutions of temperature/concentration in and heat/mass transfer through boundaries of regularly shaped 1D, 2D, and 3D blocks. These infinite-series solutions with either error functions or exponentials exhibit highly irregular but complementary convergence at different dimensionless times, t d0. In this paper, approximate solutions were developed by combining the error-function-series solutions for early times and the exponential-series solutions for late times and by using time partitioning at the switchover time, t d0. The combined solutions contain either the leading term of both series for normal-accuracy approximations (with less than 0.003 relative error) or the firstmore » two terms for high-accuracy approximations (with less than 10-7 relative error) for 1D isotropic (spheres, cylinders, slabs) and 2D/3D rectangular blocks (squares, cubes, rectangles, and rectangular parallelepipeds). This rapid and uniform convergence for rectangular blocks was achieved by employing the same time partitioning with individual dimensionless times for different directions and the product of their combined 1D slab solutions. The switchover dimensionless time was determined to minimize the maximum approximation errors. Furthermore, the analytical solutions of first-order heat/mass flux for 2D/3D rectangular blocks were derived for normal-accuracy approximations. These flux equations contain the early-time solution with a three-term polynomial in √td and the late-time solution with the limited-term exponentials for rectangular blocks. The heat/mass flux equations and the combined temperature/concentration solutions form the ultimate kernel for fast simulations of multirate and multidimensional heat/mass transfer in porous/fractured media with millions of low-permeability blocks of varying shapes and sizes.« less

Hydroponics as a valid tool to assess arsenic availability in mine soils.

PubMed

Moreno-Jiménez, E; Esteban, E; Fresno, T; de Egea, C López; Peñalosa, J M

2010-04-01

The low solubility of As in mine soils limits its phytoavailability. This makes the extrapolation of data obtained under hydroponic conditions unrealistic because the concentration in nutrient solution frequently overexposes plants to this metalloid. This work evaluates whether As supply in hydroponics resembles, to some extent, the As phytoavailable fraction in soils and the implications for phytoremediation. Phytotoxicity of As, in terms of biomass production, chlorophyll levels, and As concentrations in plants, was estimated and compared in both soils and hydroponics. In order for hydroponic conditions to be compared to soil conditions, plant exposure levels were measured in both cultures. Hydroponic As concentration ranging from 2-8microM equated to the same plant organ concentrations from soils with 700-3000mgkg(-1). Total and extractable As fractions exceeded those values, but As concentrations in pore water were bellow them. According to our results (i) hydroponics should include doses in the range 0-10microM As to allow the extrapolation of the results to As-polluted soils, and (ii) phytoextraction of As in mining sites will be limited by low As phytoavailability.

A potential for overestimating the absolute magnitudes of second virial coefficients by small-angle X-ray scattering.

PubMed

Scott, David J; Patel, Trushar R; Winzor, Donald J

2013-04-15

Theoretical consideration is given to the effect of cosolutes (including buffer and electrolyte components) on the determination of second virial coefficients for proteins by small-angle X-ray scattering (SAXS)-a factor overlooked in current analyses in terms of expressions for a two-component system. A potential deficiency of existing practices is illustrated by reassessment of published results on the effect of polyethylene glycol concentration on the second virial coefficient for urate oxidase. This error reflects the substitution of I(0,c3,0), the scattering intensity in the limit of zero scattering angle and solute concentration, for I(0,0,0), the corresponding parameter in the limit of zero cosolute concentration (c3) as well. Published static light scattering results on the dependence of the apparent molecular weight of ovalbumin on buffer concentration are extrapolated to zero concentration to obtain the true value (M2) and thereby establish the feasibility of obtaining the analogous SAXS parameter, I(0,0,0), experimentally. Copyright © 2013 Elsevier Inc. All rights reserved.

Cell culture media impact on drug product solution stability.

PubMed

Purdie, Jennifer L; Kowle, Ronald L; Langland, Amie L; Patel, Chetan N; Ouyang, Anli; Olson, Donald J

2016-07-08

To enable subcutaneous administration of monoclonal antibodies, drug product solutions are often needed at high concentrations. A significant risk associated with high drug product concentrations is an increase in aggregate level over the shelf-life dating period. While much work has been done to understand the impact of drug product formulation on aggregation, there is limited understanding of the link between cell culture process conditions and soluble aggregate growth in drug product. During cell culture process development, soluble aggregates are often measured at harvest using cell-free material purified by Protein A chromatography. In the work reported here, cell culture media components were evaluated with respect to their impact on aggregate levels in high concentration solution drug product during accelerated stability studies. Two components, cysteine and ferric ammonium citrate, were found to impact aggregate growth rates in our current media (version 1) leading to the development of new chemically defined media and concentrated feed formulations. The new version of media and associated concentrated feeds (version 2) were evaluated across four cell lines producing recombinant IgG4 monoclonal antibodies and a bispecific antibody. In all four cell lines, the version 2 media reduced aggregate growth over the course of a 12 week accelerated stability study compared with the version 1 media, although the degree to which aggregate growth decreased was cell line dependent. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:998-1008, 2016. © 2016 American Institute of Chemical Engineers.

EDTA: a synthetic draw solute for forward osmosis.

PubMed

Lutchmiah, Kerusha; Post, Jan W; Rietveld, Luuk C; Cornelissen, Emile R

2014-01-01

The draw solution is the driving force of the forward osmosis (FO) process; however, the solute loss of the draw solute to the feed side is a general, financial limitation for most applications. The anthropogenic amino acid ethylenediaminetetraacetic acid (EDTA) was investigated as a draw solution for FO. At concentrations of approximately 1.0 osmol/kg, EDTA demonstrated comparable water fluxes (Jv = 5.29 L/m(2) h) to the commonly used salt, NaCl (Jv = 4.86 L/m(2) h), and both produced better water fluxes than glucose (Jv = 3.46 L/m(2) h). EDTA showed the lowest solute loss with Js (reverse solute loss or solute leakage) = 0.54 g/m(2) h. The molecular weight, degree of ionisation and charge of EDTA played a major role in this efficiency and EDTA was therefore well rejected by the membrane, showing a low Js/Jv ratio of 0.10 g/L. Owing to the low solute loss of EDTA and its resistance to biodegradation, this compound has the potential to be used as a draw solute for FO during long periods without requiring much replenishment.

Chemical Composition and Evaluation of Nicotine, Tobacco Alkaloids, pH and Selected Flavors in e-Cigarette Cartridges and Refill Solutions

PubMed Central

Lisko, Joseph G.; Tran, Hang; Stanfill, Stephen B.; Blount, Benjamin C.; Watson, Clifford H.

2015-01-01

Introduction Electronic cigarette (e-cigarette) use is increasing dramatically in developed countries, but little is known about these rapidly evolving products. This study analyzed and evaluated the chemical composition including nicotine, tobacco alkaloids, pH and flavors in 36 e-liquids brands from four manufacturers. Methods We determined the concentrations of nicotine, alkaloids, and select flavors and measured pH in solutions used in e-cigarettes. E-cigarette products were chosen based upon favorable consumer approval ratings from online review websites. Quantitative analyses were performed using strict quality assurance/quality control (QC) validated methods previously established by our lab for the measurement of nicotine, alkaloids, pH and flavors. Results Three-quarters of the products contained lower measured nicotine levels than the stated label values (6% - 42% by concentration). The pH for e-liquids ranged from 5.1 – 9.1. Minor tobacco alkaloids were found in all samples containing nicotine, and their relative concentrations varied widely among manufacturers. A number of common flavor compounds were analyzed in all e-liquids. Conclusions Free nicotine levels calculated from the measurement of pH correlated with total nicotine content. The direct correlation between the total nicotine concentration and pH suggests that the alkalinity of nicotine drives the pH of e-cigarette solutions. A higher percentage of nicotine exists in the more absorbable free form as total nicotine concentration increases. A number of products contained tobacco alkaloids at concentrations that exceed U.S. Pharmacopeia limits for impurities in nicotine used in pharmaceutical and food products. PMID:25636907

Bio fuel ash in a road construction: impact on soil solution chemistry.

PubMed

Thurdin, R T; van Hees, P A W; Bylund, D; Lundström, U S

2006-01-01

Limited natural resources and landfill space, as well as increasing amounts of ash produced from incineration of bio fuel and municipal solid waste, have created a demand for useful applications of ash, of which road construction is one application. Along national road 90, situated about 20 km west of Sollefteå in the middle of Sweden, an experiment road was constructed with a 40 cm bio fuel ash layer. The environmental impact of the ash layer was evaluated from soil solutions obtained by centrifugation of soil samples taken on four occasions during 2001-2003. Soil samples were taken in the ash layer, below the ash layer at two depths in the road and in the ditch. In the soil solutions, pH, conductivity, dissolved organic carbon (DOC) and the total concentration of cations (metals) and anions were determined. Two years after the application of the ash layers in the test road, the concentrations in the ash layer of K, SO4, Zn, and Hg had increased significantly while the concentration of Se, Mo and Cd had decreased significantly. Below the ash layer in the road an initial increase of pH was observed and the concentrations of K, SO4, Se, Mo and Cd increased significantly, while the concentrations of Cu and Hg decreased significantly in the road and also in the ditch. Cd was the element showing a potential risk of contamination of the groundwater. The concentrations of Ca in the ash layer indicated an ongoing hardening, which is important for the leaching rate and the strength of the road construction.

The electrokinetic behavior of calcium oxalate monohydrate in macromolecular solutions

NASA Technical Reports Server (NTRS)

Curreri, P. A.; Onoda, G. Y., Jr.; Finlayson, B.

1988-01-01

Electrophoretic mobilities were measured for calcium oxalate monohydrate (COM) in solutions containing macromolecules. Two mucopolysaccharides (sodium heparin and chrondroitin sulfate) and two proteins (positively charged lysozyme and negatively charged bovine serum albumin) were studied as adsorbates. The effects of pH, calcium oxalate surface charge (varied by calcium or oxalate ion activity), and citrate concentration were investigated. All four macromolecules showed evidence for chemical adsorption. The macromolecule concentrations needed for reversing the surface charge indicated that the mucopopolysacchrides have greater affinity for the COM surface than the proteins. The amount of proteins that can chemically adsorb appears to be limited to approximately one monomolecular layer. When the surface charge is high, an insufficient number of proteins can chemically adsorb to neutralize or reverse the surface charge. The remaining surface charge is balanced by proteins held near the surface by longer range electrostatic forces only. Citrate ions at high concentrations appear to compete effectively with the negative protein for surface sites but show no evidence for competing with the positively charged protein.

The Energy Measure for the Euler and Navier-Stokes Equations

NASA Astrophysics Data System (ADS)

Leslie, Trevor M.; Shvydkoy, Roman

2018-04-01

The potential failure of energy equality for a solution u of the Euler or Navier-Stokes equations can be quantified using a so-called `energy measure': the weak-* limit of the measures {|u(t)|^2dx} as t approaches the first possible blowup time. We show that membership of u in certain (weak or strong) {L^q L^p} classes gives a uniform lower bound on the lower local dimension of E ; more precisely, it implies uniform boundedness of a certain upper s-density of E . We also define and give lower bounds on the `concentration dimension' associated to E , which is the Hausdorff dimension of the smallest set on which energy can concentrate. Both the lower local dimension and the concentration dimension of E measure the departure from energy equality. As an application of our estimates, we prove that any solution to the 3-dimensional Navier-Stokes Equations which is Type-I in time must satisfy the energy equality at the first blowup time.

Kinetics of Substrate Biodegradation under the Cumulative Effects of Bioavailability and Self-Inhibition.

PubMed

Gharasoo, Mehdi; Centler, Florian; Van Cappellen, Philippe; Wick, Lukas Y; Thullner, Martin

2015-05-05

Microbial degradation is an important process in many environments controlling for instance the cycling of nutrients or the biodegradation of contaminants. At high substrate concentrations toxic effects may inhibit the degradation process. Bioavailability limitations of a degradable substrate can therefore either improve the overall dynamics of degradation by softening the contaminant toxicity effects to microorganisms, or slow down the biodegradation by reducing the microbial access to the substrate. Many studies on biodegradation kinetics of a self-inhibitive substrate have mainly focused on physiological responses of the bacteria to substrate concentration levels without considering the substrate bioavailability limitations rising from different geophysical and geochemical dynamics at pore-scale. In this regard, the role of bioavailability effects on the kinetics of self-inhibiting substrates is poorly understood. In this study, we theoretically analyze this role and assess the interactions between self-inhibition and mass transfer-limitations using analytical/numerical solutions, and show the findings practical relevance for a simple model scenario. Although individually self-inhibition and mass-transfer limitations negatively impact biodegradation, their combined effect may enhance biodegradation rates above a concentration threshold. To our knowledge, this is the first theoretical study describing the cumulative effects of the two mechanisms together.

Novel high-pressure windows made of glass-like carbon for x-ray analysis

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

Testemale, Denis; Prat, Alain; Lahera, Eric

Original high-pressure glass-like carbon windows developed for x-ray spectroscopy applications are presented. The scientific and technological background of this new technical development is exposed, in particular the limitations of our existing beryllium windows in the context of x-ray absorption spectroscopy (XAS) measurements of solutions with very low solute concentrations at hydrothermal conditions (0.1-200 MPa, 30-600 °C). The benefits of glass-like carbon are exposed, notably its non-crystalline character, the absence of impurities which has been verified by micro-fluorescence laboratory measurements, and its non-toxicity which makes its machining safer. Finite elements mechanical calculations and experimental pressure tests were conducted to determine the pressuremore » limits of windows with two different geometries: cylindrical (thickness 0.5 mm) and inversed-dome shape (thickness 0.5 mm at the tip of the dome). The former break at 150 MPa and the latter show no sign of rupture at 400 MPa. Recent XAS measurements conducted with the new dome shaped windows are presented to show the advantages of the design that allow for the detection of very low concentrations in the transmission mode (down to 30 ppm) and the acquisition of fluorescence XAS spectra in diluted solutions at high pressure. Eventually the perspectives of this original development are discussed.« less

Stability of 10 mg/mL cefuroxime solution for intracameral injection in commonly used polypropylene syringes and new ready-to-use cyclic olefin copolymer sterile vials using the LC-UV stability-indicating method.

PubMed

Feutry, Frédéric; Simon, Nicolas; Genay, Stéphanie; Lannoy, Damien; Barthélémy, Christine; Décaudin, Bertrand; Labalette, Pierre; Odou, Pascal

2016-01-01

Injecting intracameral cefuroxime has been found beneficial in reducing the risk of postoperative endophthalmitis but its use has been limited through a lack of approved marketing and of ready-to-use single-units as well as the problem of aseptic compounding. Our aim was to assess a new automated primary packaging system which should ensure a higher level of sterility, thanks to its closed, sterile, ready-to-use polymer vial called "Crystal® vial". The chemical stability of a 10 mg/mL cefuroxime solution was compared in 1 mL Crystal® vials and 1 mL Luer-lock polypropylene syringes (actual reference) to eliminate any potential and specific interactions with its cyclic olefin copolymer (COC) body and elastomer stopper. Cefuroxime solution was introduced into vials and syringes and stored at -20 °C, +5 °C and +25°C/60% Relative Humidity. Cefuroxime concentration and the relative amount of the main degradation product (descarbamoyl-cefuroxime) were both determined by an HPLC/UV method indicating stability. Solutions were considered steady if the concentration remained at over 90% of the initial value. In the adapted storage conditions, the evolution of osmolality, pH and sterility was assessed. Stability profiles were identical between vials and syringes in all storage and temperature conditions. The solution was stable (cefuroxime concentration, pH and osmolality) and still sterile for 365 days at -20°C. The concentration fell below 90% after 21 days at +5 °C and after 16 h at +25°C/60%s relative humidity. The COC and thermoplastic elastomer of the vials had no impact on the degradation process confirming its possible use for a ready-to-use cefuroxime solution single-unit dose.

Diffusion Influenced Adsorption Kinetics.

PubMed

Miura, Toshiaki; Seki, Kazuhiko

2015-08-27

When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.

Space-charge-limited currents for cathodes with electric field enhanced geometry

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

Lai, Dingguo, E-mail: laidingguo@nint.ac.cn; Qiu, Mengtong; Xu, Qifu

This paper presents the approximate analytic solutions of current density for annulus and circle cathodes. The current densities of annulus and circle cathodes are derived approximately from first principles, which are in agreement with simulation results. The large scaling laws can predict current densities of high current vacuum diodes including annulus and circle cathodes in practical applications. In order to discuss the relationship between current density and electric field on cathode surface, the existing analytical solutions of currents for concentric cylinder and sphere diodes are fitted from existing solutions relating with electric field enhancement factors. It is found that themore » space-charge-limited current density for the cathode with electric-field enhanced geometry can be written in a general form of J = g(β{sub E}){sup 2}J{sub 0}, where J{sub 0} is the classical (1D) Child-Langmuir current density, β{sub E} is the electric field enhancement factor, and g is the geometrical correction factor depending on the cathode geometry.« less

Cournot games with network effects for electric power markets

NASA Astrophysics Data System (ADS)

Spezia, Carl John

The electric utility industry is moving from regulated monopolies with protected service areas to an open market with many wholesale suppliers competing for consumer load. This market is typically modeled by a Cournot game oligopoly where suppliers compete by selecting profit maximizing quantities. The classical Cournot model can produce multiple solutions when the problem includes typical power system constraints. This work presents a mathematical programming formulation of oligopoly that produces unique solutions when constraints limit the supplier outputs. The formulation casts the game as a supply maximization problem with power system physical limits and supplier incremental profit functions as constraints. The formulation gives Cournot solutions identical to other commonly used algorithms when suppliers operate within the constraints. Numerical examples demonstrate the feasibility of the theory. The results show that the maximization formulation will give system operators more transmission capacity when compared to the actions of suppliers in a classical constrained Cournot game. The results also show that the profitability of suppliers in constrained networks depends on their location relative to the consumers' load concentration.

Chemical analysis of freshly prepared and stored capsaicin solutions: implications for tussigenic challenges.

PubMed

Kopec, Scott E; DeBellis, Ronald J; Irwin, Richard S

2002-01-01

The purpose of this study was to assess the stability of stored capsaicin solutions and the actual concentrations of prepared solutions. Capsaicin solutions ranging in concentration from 0.5 to 128 microM were mixed and analyzed using high performance liquid chromatography. Samples of varying concentrations were then stored under 4 environmental conditions: 4 degrees C and protected from light, room temperature (RT) exposed to light, RT protected from light, and -20 degrees C and protected from light. The concentrations were measured every other month for 1 year. Actual concentrations of freshly prepared solutions were on average 88.3% of predicted. For solutions stored at 4 degrees C, there was a decrease only in the lower concentrations (0.5, 1, and 2 microM) after 2 months (P=0.003). Solutions stored at RT exposed to light decreased in concentration after 6 months (P=0.020), and solutions stored at RT protected from light decreased in concentration after 4 months (P=0.026). The group stored at -20 degrees C decreased in concentration after 1 year (P=0.033). We conclude that the actual concentration of capsaicin solution is less than predicted, and solutions of 4 microM or higher concentration are stable for 1 year if stored at 4 degrees C protected from light.

Compatible solute influence on nucleic acids: Many questions but few answers

PubMed Central

Kurz, Matthias

2008-01-01

Compatible solutes are small organic osmolytes including but not limited to sugars, polyols, amino acids, and their derivatives. They are compatible with cell metabolism even at molar concentrations. A variety of organisms synthesize or take up compatible solutes for adaptation to extreme environments. In addition to their protective action on whole cells, compatible solutes display significant effects on biomolecules in vitro. These include stabilization of native protein and nucleic acid structures. They are used as additives in polymerase chain reactions to increase product yield and specificity, but also in other nucleic acid and protein applications. Interactions of compatible solutes with nucleic acids and protein-nucleic acid complexes are much less understood than the corresponding interactions of compatible solutes with proteins. Although we may begin to understand solute/nucleic acid interactions there are only few answers to the many questions we have. I summarize here the current state of knowledge and discuss possible molecular mechanisms and thermodynamics. PMID:18522725

76 FR 72719 - Certain Stilbenic Optical Brightening Agents From China and Taiwan; Scheduling of the Final Phase...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-25

... whether an industry in the United States is materially injured or threatened with material injury, or the... any state (including but not limited to powder, slurry, or solution), of any concentrations of active... that are not certain stilbenic OBAs) and in any type of packaging.'' [[Page 72720

77 FR 17027 - Certain Stilbenic Optical Brightening Agents From Taiwan: Final Determination of Sales at Less...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-03-23

... limited to powder, slurry, or solution), of any concentrations of active certain stilbenic OBA ingredient... OBAs), and in any type of packaging. \\3\\ Id. These stilbenic OBAs are classifiable under subheading... which the material terms of sale are established. TFM reported its sales using shipment date as the date...

Short-Time Glassy Dynamics in Viscous Protein Solutions with Competing Interactions

DOE PAGES

Godfrin, P. Douglas; Hudson, Steven; Hong, Kunlun; ...

2015-11-24

Although there have been numerous investigations of the glass transition for colloidal dispersions with only a short-ranged attraction, less is understood for systems interacting with a long-ranged repulsion in addition to this attraction, which is ubiquitous in aqueous protein solutions at low ionic strength. Highly puri ed concentrated lysozyme solutions are used as a model system and investigated over a large range of protein concentrations at very low ionic strength. Newtonian liquid behavior is observed at all concentrations, even up to 480 mg/mL, where the zero shear viscosity increases by more than three orders of magnitude with increasing concentration. Remarkably,more » despite this macroscopic liquid-like behavior, the measurements of the dynamics in the short-time limit shows features typical of glassy colloidal systems. Investigation of the inter-protein structure indicates that the reduced short-time mobility of the protein is caused by localized regions of high density within a heterogeneous density distribution. This structural heterogeneity occurs on intermediate range length scale, driven by the competing potential features, and is distinct from commonly studied colloidal gel systems in which a heterogeneous density distribution tends to extend to the whole system. The presence of long-ranged repulsion also allows for more mobility over large length and long time scales resulting in the macroscopic relaxation of the structure. The experimental results provide evidence for the need to explicitly include intermediate range order in theories for the macroscopic properties of protein solutions interacting via competing potential features.« less

Direct evidence of ionic fluxes across ion-selective membranes: a scanning electrochemical microscopic and potentiometric study.

PubMed

Gyurcsányi, R E; Pergel, E; Nagy, R; Kapui, I; Lan, B T; Tóth, K; Bitter, I; Lindner, E

2001-05-01

Scanning electrochemical microscopy (SECM) supplemented with potentiometric measurements was used to follow the time-dependent buildup of a steady-state diffusion layer at the aqueous-phase boundary of lead ion-selective electrodes (ISEs). Differential pulse voltammetry is adapted to SECM for probing the local concentration profiles at the sample side of solvent polymeric membranes. Major factors affecting the membrane transport-related surface concentrations were identified from SECM data and the potentiometric transients obtained under different experimental conditions (inner filling solution composition, membrane thickness, surface pretreatment). The amperometrically determined surface concentrations correlated well with the lower detection limits of the lead ion-selective electrodes.

Influence of ion sterics on diffusiophoresis and electrophoresis in concentrated electrolytes

NASA Astrophysics Data System (ADS)

Stout, Robert F.; Khair, Aditya S.

2017-01-01

We quantify the diffusiophoresis and electrophoresis of a uniformly charged, spherical colloid in a binary electrolyte using modified Poisson-Nernst-Planck equations that account for steric repulsion between finite sized ions. Specifically, we utilize the Bikerman (Bik) lattice gas model and the Carnahan-Starling (CS) and Boublik-Mansoori-Carnahan-Starling-Leland (BMCSL) equations of state for monodisperse and polydisperse, respectively, hard spheres. We compute the phoretic mobility for weak applied fields using an asymptotic approach for thin diffuse layers, where ion steric effects are expected to be most prevalent. The thin diffuse layer limit requires λD/R →0 , where λD is the Debye screening length and R is the particle radius; this limit is readily attained for micron-sized colloids in concentrated electrolytic solutions. It is well known that the classic Poisson-Boltzmann (PB) model for pointlike, noninteracting ions leads to a prediction of a maximum in both the diffusiophoretic and electrophoretic mobilities with increasing particle zeta potential (at fixed λD/R ). In contrast, we find that ion sterics essentially eliminate this maximum (for reasonably attainable zeta potentials) and increase the mobility relative to PB. Next, we consider the more experimentally relevant case of a particle with a constant surface charge density and vary the electrolyte concentration, neglecting charge regulation on surface active sites. Rather surprisingly, there is little difference between the predictions of the four models (PB, Bik, CS, and BMCSL) for electrophoretic mobility in concentrated solutions, at reasonable surface charge densities (˜1 -10 μ C /cm2 ). This is because as the concentration increases, the zeta potential is reduced (to below the thermal voltage for concentrations above about 1 M) and therefore the diffuse layer structure is largely unaffected by ion sterics. For gradients of symmetric electrolytes (equal diffusivities, charge, and size) diffusiophoresis is also essentially unaffected by ion sterics, with a mobility that approaches zero with increasing concentration, just as in electrophoresis. For gradients of asymmetric electrolytes, the difference in diffusivities of the cation and anions leads to an induced electric field that acts on the charged particle. Importantly, we show that ion sterics leads to an excess contribution to the induced electric field, which increases rapidly with concentration. This increase overwhelms the accompanying decrease in zeta potential. The result is the diffusiophoretic mobility increases with concentration, rather than approaching zero. Therefore, diffusiophoresis could be an appealing alternative transport mechanism to electrophoresis in concentrated electrolyte solutions.

Large-scale and highly efficient synthesis of micro- and nano-fibers with controlled fiber morphology by centrifugal jet spinning for tissue regeneration

NASA Astrophysics Data System (ADS)

Ren, Liyun; Pandit, Vaibhav; Elkin, Joshua; Denman, Tyler; Cooper, James A.; Kotha, Shiva P.

2013-02-01

PLLA fibrous tissue scaffolds with controlled fiber nanoscale surface roughness are fabricated with a novel centrifugal jet spinning process. The centrifugal jet spinning technique is a highly efficient synthesis method for micron- to nano-sized fibers with a production rate up to 0.5 g min-1. During the centrifugal jet spinning process, a polymer solution jet is stretched by the centrifugal force of a rotating chamber. By engineering the rheological properties of the polymer solution, solvent evaporation rate and centrifugal force that are applied on the solution jet, polyvinylpyrrolidone (PVP) and poly(l-lactic acid) (PLLA) composite fibers with various diameters are fabricated. Viscosity measurements of polymer solutions allowed us to determine critical polymer chain entanglement limits that allow the generation of continuous fiber as opposed to beads or beaded fibers. Above a critical concentration at which polymer chains are partially or fully entangled, lower polymer concentrations and higher centrifugal forces resulted in thinner fibers. Etching of PVP from the PLLA-PVP composite fibers doped with increasing PVP concentrations yielded PLLA fibers with increasing nano-scale surface roughness and porosity, which increased the fiber hydrophilicity dramatically. Scanning electron micrographs of the etched composite fibers suggest that PVP and PLLA were co-contiguously phase separated within the composite fibers during spinning and nano-scale roughness features were created after the partial etching of PVP. To study the tissue regeneration efficacy of the engineered PLLA fiber matrix, human dermal fibroblasts are used to simulate partial skin graft. Fibers with increased PLLA surface roughness and porosity demonstrated a trend towards higher cell attachment and proliferation.PLLA fibrous tissue scaffolds with controlled fiber nanoscale surface roughness are fabricated with a novel centrifugal jet spinning process. The centrifugal jet spinning technique is a highly efficient synthesis method for micron- to nano-sized fibers with a production rate up to 0.5 g min-1. During the centrifugal jet spinning process, a polymer solution jet is stretched by the centrifugal force of a rotating chamber. By engineering the rheological properties of the polymer solution, solvent evaporation rate and centrifugal force that are applied on the solution jet, polyvinylpyrrolidone (PVP) and poly(l-lactic acid) (PLLA) composite fibers with various diameters are fabricated. Viscosity measurements of polymer solutions allowed us to determine critical polymer chain entanglement limits that allow the generation of continuous fiber as opposed to beads or beaded fibers. Above a critical concentration at which polymer chains are partially or fully entangled, lower polymer concentrations and higher centrifugal forces resulted in thinner fibers. Etching of PVP from the PLLA-PVP composite fibers doped with increasing PVP concentrations yielded PLLA fibers with increasing nano-scale surface roughness and porosity, which increased the fiber hydrophilicity dramatically. Scanning electron micrographs of the etched composite fibers suggest that PVP and PLLA were co-contiguously phase separated within the composite fibers during spinning and nano-scale roughness features were created after the partial etching of PVP. To study the tissue regeneration efficacy of the engineered PLLA fiber matrix, human dermal fibroblasts are used to simulate partial skin graft. Fibers with increased PLLA surface roughness and porosity demonstrated a trend towards higher cell attachment and proliferation. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr33423f

Removal of chromium (VI) from aqueous solution using walnut hull.

PubMed

Wang, Xue Song; Li, Zhi Zhong; Tao, Sheng Rong

2009-02-01

In this study, removal of chromium (VI) from aqueous solution by walnut hull (a local low-cost adsorbent) was studied. The extent of adsorption was investigated as a function of solution pH, contact time, adsorbent and adsorbate concentration, reaction temperature and supporting electrolyte (sodium chloride). The Cr (VI) removal was pH-dependent, reaching a maximum (97.3%) at pH 1.0. The kinetic experimental data were fitted to the first-order, modified Freundlich, intraparticle diffusion and Elovich models and the corresponding parameters were obtained. A 102.78 kJ/mol Ea (activation energy) for the reaction of chromium (VI) adsorption onto walnut indicated that the rate-limiting step in this case might be a chemically controlled process. Both the Langmuir and Freundlich isotherms were suitable for describing the biosorption of chromium (VI) onto walnut hull. The uptake of chromium (VI) per weight of adsorbent increased with increasing initial chromium (VI) concentration up to 240-480 mg/L, and decreased sharply with increasing adsorbent concentration ranging from 1.0 to 5.0 g/L. An increase in sodium chloride (as supporting electrolyte) concentration was found to induce a negative effect while an increase in temperature was found to give rise to a positive effect on the chromium (VI) adsorption process. Compared to the various other adsorbents reported in the literature, the walnut hull in this study shows very good promise for practical applicability.

High-Sensitivity Surface-Enhanced Raman Scattering (SERS) Substrate Based on a Gold Colloid Solution with a pH Change for Detection of Trace-Level Polycyclic Aromatic Hydrocarbons in Aqueous Solution.

PubMed

Shi, Xiaofeng; Liu, Shu; Han, Xiaohong; Ma, Jun; Jiang, Yongchao; Yu, Guifeng

2015-05-01

In this study, a gold colloid solution whose parameters were optimized, and without any surfactants, was developed as a surface-enhanced Raman scattering (SERS) substrate for the detection of trace-level polycyclic aromatic hydrocarbons (PAHs). A gold colloid solution with 57 nm gold particles and pH 13 was prepared to be the SERS substrate. It had impressive enhancement that was two orders of magnitude higher than that of a gold colloid solution with 57 nm gold particles and without pH change (pH 6). Even with a compact field-based Raman spectrometer, naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene were detected, with limits of detection at 6.8 nM, 3.4 nM, 1.8 nM, 0.68 nM (680 pM), and 0.44 nM (440 pM), respectively. The significant enhancement was ascribed to an electromagnetic mechanism and a charge-transfer mechanism. Quantitative analyses for these five PAHs in water were also performed. The SERS intensities of PAHs were found to have good linear dependence relations with the concentrations in low concentration. This high-sensitivity, easily prepared substrate offers a promising technology for the quantitative detection of trace-level PAHs.

Streamlined system for purifying and quantifying a diverse library of compounds and the effect of compound concentration measurements on the accurate interpretation of biological assay results.

PubMed

Popa-Burke, Ioana G; Issakova, Olga; Arroway, James D; Bernasconi, Paul; Chen, Min; Coudurier, Louis; Galasinski, Scott; Jadhav, Ajit P; Janzen, William P; Lagasca, Dennis; Liu, Darren; Lewis, Roderic S; Mohney, Robert P; Sepetov, Nikolai; Sparkman, Darren A; Hodge, C Nicholas

2004-12-15

As part of an overall systems approach to generating highly accurate screening data across large numbers of compounds and biological targets, we have developed and implemented streamlined methods for purifying and quantitating compounds at various stages of the screening process, coupled with automated "traditional" storage methods (DMSO, -20 degrees C). Specifically, all of the compounds in our druglike library are purified by LC/MS/UV and are then controlled for identity and concentration in their respective DMSO stock solutions by chemiluminescent nitrogen detection (CLND)/evaporative light scattering detection (ELSD) and MS/UV. In addition, the compound-buffer solutions used in the various biological assays are quantitated by LC/UV/CLND to determine the concentration of compound actually present during screening. Our results show that LC/UV/CLND/ELSD/MS is a widely applicable method that can be used to purify, quantitate, and identify most small organic molecules from compound libraries. The LC/UV/CLND technique is a simple and sensitive method that can be easily and cost-effectively employed to rapidly determine the concentrations of even small amounts of any N-containing compound in aqueous solution. We present data to establish error limits for concentration determination that are well within the overall variability of the screening process. This study demonstrates that there is a significant difference between the predicted amount of soluble compound from stock DMSO solutions following dilution into assay buffer and the actual amount present in assay buffer solutions, even at the low concentrations employed for the assays. We also demonstrate that knowledge of the concentrations of compounds to which the biological target is exposed is critical for accurate potency determinations. Accurate potency values are in turn particularly important for drug discovery, for understanding structure-activity relationships, and for building useful empirical models of protein-ligand interactions. Our new understanding of relative solubility demonstrates that most, if not all, decisions that are made in early discovery are based upon missing or inaccurate information. Finally, we demonstrate that careful control of compound handling and concentration, coupled with accurate assay methods, allows the use of both positive and negative data in analyzing screening data sets for structure-activity relationships that determine potency and selectivity.

Partial Molar Volumes of 15-Crown-5 Ether in Mixtures of N,N-Dimethylformamide with Water.

PubMed

Tyczyńska, Magdalena; Jóźwiak, Małgorzata

2014-01-01

The density of 15-crown-5 ether (15C5) solutions in the mixtures of N,N -dimethylformamide (DMF) and water (H 2 O) was measured within the temperature range 293.15-308.15 K using an Anton Paar oscillatory U-tube densimeter. The results were used to calculate the apparent molar volumes ( V Φ ) of 15C5 in the mixtures of DMF + H 2 O over the whole concentration range. Using the apparent molar volumes and Redlich and Mayer equation, the standard partial molar volumes of 15-crown-5 were calculated at infinite dilution ([Formula: see text]). The limiting apparent molar expansibilities ( α ) were also calculated. The data are discussed from the point of view of the effect of concentration changes on interactions in solution.

Longitudinal dispersion coefficients for numerical modeling of groundwater solute transport in heterogeneous formations

NASA Astrophysics Data System (ADS)

Lee, Jonghyun; Rolle, Massimo; Kitanidis, Peter K.

2018-05-01

Most recent research on hydrodynamic dispersion in porous media has focused on whole-domain dispersion while other research is largely on laboratory-scale dispersion. This work focuses on the contribution of a single block in a numerical model to dispersion. Variability of fluid velocity and concentration within a block is not resolved and the combined spreading effect is approximated using resolved quantities and macroscopic parameters. This applies whether the formation is modeled as homogeneous or discretized into homogeneous blocks but the emphasis here being on the latter. The process of dispersion is typically described through the Fickian model, i.e., the dispersive flux is proportional to the gradient of the resolved concentration, commonly with the Scheidegger parameterization, which is a particular way to compute the dispersion coefficients utilizing dispersivity coefficients. Although such parameterization is by far the most commonly used in solute transport applications, its validity has been questioned. Here, our goal is to investigate the effects of heterogeneity and mass transfer limitations on block-scale longitudinal dispersion and to evaluate under which conditions the Scheidegger parameterization is valid. We compute the relaxation time or memory of the system; changes in time with periods larger than the relaxation time are gradually leading to a condition of local equilibrium under which dispersion is Fickian. The method we use requires the solution of a steady-state advection-dispersion equation, and thus is computationally efficient, and applicable to any heterogeneous hydraulic conductivity K field without requiring statistical or structural assumptions. The method was validated by comparing with other approaches such as the moment analysis and the first order perturbation method. We investigate the impact of heterogeneity, both in degree and structure, on the longitudinal dispersion coefficient and then discuss the role of local dispersion and mass transfer limitations, i.e., the exchange of mass between the permeable matrix and the low permeability inclusions. We illustrate the physical meaning of the method and we show how the block longitudinal dispersivity approaches, under certain conditions, the Scheidegger limit at large Péclet numbers. Lastly, we discuss the potential and limitations of the method to accurately describe dispersion in solute transport applications in heterogeneous aquifers.

Graphene decorated with mu-opioid receptor: the ionic screening effect and detection of enkephalin

NASA Astrophysics Data System (ADS)

Ping, Jinglei; Johnson, A. T. Charlie; Liu, Renyu; A. T. Charlie Johnson Team; Renyu Liu Collaboration

2015-03-01

We investigated the properties of graphene field effect transistors (GFETs) decorated with a computaionally redesigned, water-soluble variant of the human mu-opioid receptor (wsMOR) in physiological buffer solution. The shift of the Fermi level in the GFETs is quantitatively described by chemical-gating effect of charges on the wsMOR that are screened by the ionic solution. Our results suggest that sensitivity to the molecular target is lost when the Debye screening length of the solution is shorter than the distance from the graphene to the wsMOR; thus de-salting may be necessary when wsMOR decorated GFETs are used as biosensors in solution. We used this insight to detect DAMGO, a synthetic analog to the endogenous opioid peptide encephalin, at a concentration of 10 pM (5.1 pg/mL) in artificial cerebrospinal fluid (aCSF) diluted to 5% of its normal salt concentration. When the sensors were measured in a dry state, the limit of detection for DAGMO was 1 pM (0.5 pg/mL), one-third of the baseline in human body.Funding for this work was provided by DARPA.

Finite element analysis of the effect of a non-planar solid-liquid interface on the lateral solute segregation during unidirectional solidification

NASA Technical Reports Server (NTRS)

Carlson, F. M.; Chin, L.-Y.; Fripp, A. L.; Crouch, R. K.

1982-01-01

The effect of solid-liquid interface shape on lateral solute segregation during steady-state unidirectional solidification of a binary mixture is calculated under the assumption of no convection in the liquid. A finite element technique is employed to compute the concentration field in the liquid and the lateral segregation in the solid with a curved boundary between the liquid and solid phases. The computational model is constructed assuming knowledge of the solid-liquid interface shape; no attempt is made to relate this shape to the thermal field. The influence of interface curvature on the lateral compositional variation is investigated over a range of system parameters including diffusivity, growth speed, distribution coefficient, and geometric factors of the system. In the limiting case of a slightly nonplanar interface, numerical results from the finite element technique are in good agreement with the analytical solutions of Coriell and Sekerka obtained by using linear theory. For the general case of highly non-planar interface shapes, the linear theory fails and the concentration field in the liquid as well as the lateral solute segregation in the solid can be calculated by using the finite element method.

Determination of palladium and platinum by atomic absorption

USGS Publications Warehouse

Schnepfe, M.M.; Grimaldi, F.S.

1969-01-01

Palladium and platinum are determined by atomic absorption after fire-assay concentration into a gold bead. The limit of determination is ~0??06 ppm in a 20-g sample. Serious depressive interelement interferences are removed by buffering the solutions with a mixture of cadmium and copper sulphates with cadmium and copper concentrations each at 0??5%. Substantial amounts of Ag, Al, Au, Bi, Ca, Co, Cr, Fe, Hg, K, La, Mg, Mn, Mo, Na, Ni, Pb, Te, Ti, V, Y, Zn, and the platinum metals do not interfere in the atomic-absorption determination. ?? 1969.

Data on snow chemistry of the Cascade-Sierra Nevada Mountains

USGS Publications Warehouse

Laird, L.B.; Taylor, Howard E.; Lombard, R.E.

1986-01-01

Snow chemistry data were measured for solutes found in snow core samples collected from the Cascade-Sierra Nevada Mountains from late February to mid-March 1983. The data are part of a study to assess geographic variations in atmospheric deposition in Washington, Oregon, and California. The constituents and properties include pH and concentrations of hydrogen ion, calcium, magnesium, sodium, potassium, chloride, sulfate, nitrate, fluoride, phosphate, ammonium, iron, aluminum, manganese, copper, cadmium, lead, and dissolved organic carbon. Concentrations of arsenic and bromide were below the detection limit. (USGS)

[Determination of Arsenic in Food Package Aluminum by Ultrasound Assisted Solid Phase Extraction/ICP-AES].

PubMed

Qin, Wen-xia; Gong, Qi; Li, Min; Deng, Li-xin; Mo, Li-shu; Li, Yan-lin

2015-04-01

Determination of arsenic in pure aluminum by inductively coupled plasma atomic emission spectrometry was interfered by aluminum matrix. The experiment showed that when the mass concentration of Al was greater than or equal to 5 000 times the As in the test solution, the measurement error was greater than 5%. In order to eliminate the interference, strong acid cation exchange fiber (SACEF) was used as solid phase extraction agent to adsorb Al(3+). The extraction conditions included amount of SACEF, extraction time, temperature and pH were investigated. The optimal extraction conditions were that 0.9000 g SACEF was used to extract the aluminum from the sample solution of pH 2.0 at 55 °C for 5 min with the ultrasonic assist, and in this case, the arsenic in the form of arsenic acid was not extracted and left in the solution for the determination. The results showed that after treating 10. 00 mL test solution containing 1.00 µg arsenic and 20.0 mg aluminum, arsenic did not lose. The mass concentration of residual aluminum in the raffinate was about 2,000 times the As, which had not interfered the determination of arsenic. The detection limit (3 s) was 0.027 µg · mL(-1) and quantification limit (10 s) was 0.0091 µg · mL(-1). The proposed method was successfully applied to the separation and determination of arsenic in the synthetic samples, the aluminum cans and the barbecue aluminum foil. Recovery was in the range of 98.3%-105% and RSD (n = 3) was in the range of 0.1%-4.3%. The results showed that the content of arsenic in the aluminum cans and the aluminum barbecue foil was below the limited value of national standard (GB/T 3190-2008).

A bioequivalence study of levothyroxine tablets versus an oral levothyroxine solution in healthy volunteers.

PubMed

Yannovits, N; Zintzaras, E; Pouli, A; Koukoulis, G; Lyberi, S; Savari, E; Potamianos, S; Triposkiadis, F; Stefanidis, I; Zartaloudis, E; Benakis, A

2006-01-01

Probably for genetic reasons a substantial part of the Greek population requires Levothyroxine treatment. Since commercially available Levothyroxine was first marketed, the manufacture and storage of the drug in tablet form has been complicated and difficult; and as cases of therapeutic failure have frequently been reported following treatment with this medicinal agent, quality control is an essential factor. Due to the unreliability of Levothyroxine-based commercial products, in the present study we decided to follow the Food and Drug Administration (FDA) guidelines*, and use a Levothyroxine solution as reference product. The bioavailability of the Levothyroxine sodium tablet formulation THYROHORMONE/Ni-The Ltd (0.2 mg/tab) and that of a reference oral solution (0.3 mg/100 ml) under fasting conditions were compared in an open, randomized, single-dose two-way crossover study. Twenty four healthy Caucasian volunteers (M/F=15/9, mean age=32.9+/-7.4yr) participated in the study. Bioavailability was assessed by pharmacokinetic parameters such as the area under plasma concentration-time curve from time zero up to the measurable last time point (AUC(last)) and the maximum plasma concentration (Cmax). Heparinized venous blood samples were collected pre-dose and up to a 48-hour period post-dose. Levothyroxine sodium in plasma samples was assayed by a validated electrochemiluninescent immunoassay technique. Statistical analysis showed that the post-dose thyrotropin-stimulating hormone (TSH) levels decreased significantly (p<0.05). Regarding Levothyroxine (T4), the point estimate of the test formulation to the reference formulation ratios (T/R) for AUC(last) and Cmax was 0.92 with 90% confidence limits (0.90, 0.94) and 0.93 with 90% confidence limits (0.91, 0.94), respectively. Regarding triiodo-L-thyronine (T3), the point estimate for the T/R ratios of AUC(last) and Cmax was 0.92 with 90% confidence limits (0.90, 0.95) and 0.94 with 90% confidence limits (0.92, 0.95), respectively. The 90% confidence limits for the pharmacokinetic parameters AUC(last) and Cmax lie within the acceptance limits for bioequivalence (0.80, 1.25), for both T3 and T4.

Effect of Immersion Solutions Containing Enterocin AS-48 on Listeria monocytogenes in Vegetable Foods

PubMed Central

Cobo Molinos, Antonio; Abriouel, Hikmate; Ben Omar, Nabil; Valdivia, Eva; Lucas López, Rosario; Maqueda, Mercedes; Cañamero, Magdalena Martínez; Gálvez, Antonio

2005-01-01

The effect of immersion solutions containing enterocin AS-48 alone or in combination with chemical preservatives on survival and proliferation of Listeria monocytogenes CECT 4032 inoculated on fresh alfalfa sprouts, soybean sprouts, and green asparagus was tested. Immersion treatments (5 min at room temperature) with AS-48 solutions (25 μg/ml) reduced listeria counts of artificially contaminated alfalfa and soybean sprouts by approximately 2.0 to 2.4 log CFU/g compared to a control immersion treatment in distilled water. The same bacteriocin immersion treatment applied on green asparagus had a very limited effect. During storage of vegetable samples treated with immersion solutions of 12.5 and 25 μg of AS-48/ml, viable listeria counts were reduced below detection limits at days 1 to 7 for alfalfa and soybean sprouts at 6 and 15°C, as well as green asparagus at 15°C. Only a limited inhibition of listeria proliferation was detected during storage of bacteriocin-treated alfalfa sprouts and green asparagus at 22°C. Treatment with solutions containing AS-48 plus lactic acid, sodium lactate, sodium nitrite, sodium nitrate, trisodium phosphate, trisodium trimetaphosphate, sodium thiosulphate, n-propyl p-hydroxybenzoate, p-hydoxybenzoic acid methyl ester, hexadecylpyridinium chloride, peracetic acid, or sodium hypochlorite reduced viable counts of listeria below detection limits (by approximately 2.6 to 2.7 log CFU/g) upon application of the immersion treatment and/or further storage for 24 h, depending of the chemical preservative concentration. Significant increases of antimicrobial activity were also detected for AS-48 plus potassium permanganate and in some combinations with acetic acid, citric acid, sodium propionate, and potassium sorbate. PMID:16332751

Effect of parenteral serum plant sterols on liver enzymes and cholesterol metabolism in a patient with short bowel syndrome.

PubMed

Hallikainen, Maarit; Huikko, Laura; Kontra, Kirsi; Nissinen, Markku; Piironen, Vieno; Miettinen, Tatu; Gylling, Helena

2008-01-01

Hepatobiliary complications are common during parenteral nutrition. Lipid moiety in commercially available solutions contains plant sterols. It is not known whether plant sterols in parenteral nutrition interfere with hepatic function in adults. We detected how different amounts of plant sterols in parenteral nutrition solution affected serum plant sterol concentrations and liver enzymes during a 1.5-year follow-up in a patient with short bowel syndrome. Serum lipid, plant sterol, and liver enzyme levels were measured regularly during the transition from Intralipid (100% soy-based intravenous fat emulsion) to ClinOleic (an olive oil-based intravenous fat emulsion with 80% olive oil, 20% soy oil and lower plant sterols); the lipid supply was also gradually increased from 20 to 35 g/d. Plant sterols in parenteral nutrition solution and serum were measured with gas-liquid chromatography. During infusion of soy-based intravenous fat emulsion (30 g/d, total plant sterols 87 mg/d), the concentrations of sitosterol, campesterol, and stigmasterol were 4361, 1387, and 378 microg/dL, respectively, and serum liver enzyme values were >or= 2.5 times above upper limit of normal. After changing to olive oil-based intravenous fat emulsion (20-35 g/d, plant sterols 37-65 mg/d), concentrations decreased to 2148 to 2251 microg/dL for sitosterol, 569-297 microg/dL for campesterol, and 95-55 microg/dL for stigmasterol. Concomitantly, liver enzyme values decreased to 1.4 to 1.8 times above upper limit of normal at the end of follow-up. The nutrition status of the patient improved. The amount of plant sterols in lipid emulsion affects serum liver enzyme levels more than the amount of lipid.

Impact of Solubilizing Additives on Supersaturation and Membrane Transport of Drugs.

PubMed

Raina, Shweta A; Zhang, Geoff G Z; Alonzo, David E; Wu, Jianwei; Zhu, Donghua; Catron, Nathaniel D; Gao, Yi; Taylor, Lynne S

2015-10-01

Many enabling formulations give rise to supersaturated solutions wherein the solute possesses higher thermodynamic activity gradients than the solute in a saturated solution. Since flux across a membrane is driven by solute activity rather than concentration, understanding how solute thermodynamic activity varies with solution composition, particularly in the presence of solubilizing additives, is important in the context of passive absorption. In this study, a side-by-side diffusion cell was used to evaluate solute flux for solutions of nifedipine and felodipine in the absence and presence of different solubilizing additives at various solute concentrations. At a given solute concentration above the equilibrium solubility, it was observed that the solubilizing additives could reduce the membrane flux, indicating that the extent of supersaturation can be reduced. However, the flux could be increased back to the same maximum value (which was determined by the concentration where liquid-liquid phase separation (LLPS) occurred) by increasing the total solute concentration. Qualitatively, the shape of the curves of solute flux through membrane as a function of total solute concentration is the same in the absence and presence of solubilizing additives. Quantitatively, however, LLPS occurs at higher solute concentrations in the presence of solubilizing additives. Moreover, the ratios of the LLPS onset concentration and equilibrium solubility vary significantly in the absence and presence of additives. These findings clearly point out the flaws in using solute concentration in estimating solute activity or supersaturation, and reaffirm the use of flux measurements to understand supersaturated systems. Clear differentiation between solubilization and supersaturation, as well as thorough understanding of their respective impacts on membrane transport kinetics is important for the rational design of enabling formulations for poorly soluble compounds.

Preparation and evaluation of HPMC-based pirfenidone solution in vivo.

PubMed

Yang, Mei; Yang, Yang-Fan; Lei, Ming; Ye, Cheng-Tian; Zhao, Chun-Shun; Xu, Jian-Gang; Wu, Kai-Li; Yu, Min-Bin

2017-01-01

Pirfenidone (PFD) has exhibited therapeutic potential in the treatment of cell proliferative disorders. The previously developed 0.5% water-based PFD eye drops by our team exhibited antiscarring effectiveness and ocular safety but with a limit of short half-life and poor bioavailability. To increase bioavailability of the water-based PFD eye drops, we prepared a viscous solution by adding hydroxypropyl methylcellulose (HPMC, F4M), which acted as a viscosity-enhancer. Subsequently, we compared the HPMC-based PFD solution with the water-based PFD eye drops. PFD solution with 1% HPMC (w/v) was prepared, and the viscosities at different shear rates were measured to investigate its rheology. PFD concentrations in the tear, aqueous humor, conjunctiva, cornea, and sclerae of New Zealand rabbits were detected at different time points with high-performance liquid chromatography (HPLC) following single instillation of the 0.5% PFD (w/v) water-based eye drops or HPMC-based solution. Compared with the 0.5% water-based PFD eye drops, the HPMC-based solution increased the PFD levels in tears and prolonged the residence time from 10 to more than 20 min (p < .01). Consequently, the concentrations of PFD in aqueous humor, conjunctiva, cornea, and sclera were elevated to varying degrees until 90 min after topical administration. The developed formulation possesses a same readily administration and simple preparation as the PFD eye drops; however, the HPMC-based solution exhibited the higher bioavailability.

Nature and consequences of protein-protein interactions in high protein concentration solutions.

PubMed

Saluja, Atul; Kalonia, Devendra S

2008-06-24

High protein concentration solutions are becoming increasingly important in the pharmaceutical industry. The solution behavior of proteins at high concentrations can markedly differ from that predicted based on dilute solution analysis due to thermodynamic non-ideality in these solutions. The non-ideality observed in these systems is related to the protein-protein interactions (PPI). Different types of forces play a key role in determining the overall nature and extent of these PPI and their relative contributions are affected by solute and solvent properties. However, individual contributions of these forces to the solution properties of concentrated protein solutions are not fully understood. The role of PPI, driven by these intermolecular forces, in governing solution rheology and physical stability of high protein concentration solutions is discussed from the point of view of pharmaceutical product development. Investigation of protein self-association and aggregation in concentrated protein solutions is crucial for ensuring the safety and efficacy of the final product for the duration of the desired product shelf life. Understanding rheology of high concentration protein solutions is critical for addressing issues during product manufacture and administration of final formulation to the patient. To this end, analysis of solution viscoelastic character can also provide an insight into the nature of PPI affecting solution rheology.

An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems to high concentration and temperature

NASA Astrophysics Data System (ADS)

Christov, Christomir

2007-07-01

The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H 2O (from 0.745 to 5.953 mol kg -1) and KBr-H 2O (from 0.741 to 5.683 mol kg -1) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral's solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO 4-H 2O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO 4-H 2O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br - pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H 2O (cr), NaBr (cr) and KBr (cr).

Global classical solvability and stabilization in a two-dimensional chemotaxis-Navier-Stokes system modeling coral fertilization

NASA Astrophysics Data System (ADS)

Espejo, Elio; Winkler, Michael

2018-04-01

The interplay of chemotaxis, convection and reaction terms is studied in the particular framework of a refined model for coral broadcast spawning, consisting of three equations describing the population densities of unfertilized sperms and eggs and the concentration of a chemical released by the latter, coupled to the incompressible Navier-Stokes equations. Under mild assumptions on the initial data, global existence of classical solutions to an associated initial-boundary value problem in bounded planar domains is established. Moreover, all these solutions are shown to approach a spatially homogeneous equilibrium in the large time limit.

7/5nm logic manufacturing capabilities and requirements of metrology

NASA Astrophysics Data System (ADS)

Bunday, Benjamin; Bello, A. F.; Solecky, Eric; Vaid, Alok

2018-03-01

This paper will provide an update to previous works [2][4][9] to our view of the future for in-line high volume manufacturing (HVM) metrology for the semiconductor industry, concentrating on logic technology for foundries. First, we will review of the needs of patterned defect, critical dimensional (CD/3D), overlay and films metrology, and present the extensive list of applications for which metrology solutions are needed. We will then update the industry's progress towards addressing gating technical limits of the most important of these metrology solutions, highlighting key metrology technology gaps requiring industry attention and investment.

Controlled drug delivery to the lung: Influence of hyaluronic acid solution conformation on its adsorption to hydrophobic drug particles.

PubMed

Rouse, J J; Whateley, T L; Thomas, M; Eccleston, G M

2007-02-07

This work reports investigations into the interaction and adsorption of the hydrophilic polymer hyaluronic acid (HA) onto the surface of the hydrophobic corticosteroid drug fluticasone propionate (FP). The eventual aim is to formulate a bioadhesive pulmonary drug delivery system with prolonged action that avoids rapid clearance from the lungs by the mucociliary escalator. Adsorption isotherms detailing the adsorption of HA from aqueous HA solution concentrations ranging from 0.14 to 0.0008% (w/v) to a fixed FP particle concentration of 0.1% (w/v) were investigated. The method of preparing FP particles with HA molecules adsorbed on their surfaces (FP/HA particles) involved suspension of the FP either in hydrated HA solution or in water followed by addition of solid HA, centrifugation of the solids to form a pellet, washing the pellet several times with water until no HA was found in the supernatant and then freeze drying the suspension obtained by dispersing the final pellet. The freeze dried powder was then analysed for adsorbed HA using a Stains-all assay. The influence of order of addition of HA to FP, time for the adsorption process, and temperature of preparation on the adsorption isotherms was investigated. The non-equilibrium adsorption isotherms produced generally followed the same trend, in that as the HA solution concentration increased, the amount of HA adsorbed increased to a maximum at a solution concentration of approximately 0.1% (w/v) and then decreased. The maxima in the adsorption isotherms were close to the change from secondary to tertiary conformation in the HA solutions. Below the maxima, adsorption occurred via interaction of FP with the hydrophobic patches along the HA chains in the secondary structures. Above the maxima, secondary HA molecules aggregate in solution to form tertiary network structures. Adsorption from tertiary structure was reduced because strong interactions between the HA molecules limited the availability of hydrophobic patches for adsorption of HA onto FP. The influence of preparation variables on adsorption was also related to the availability of hydrophobic patches for adsorption.

Electron and hole transport in the organic small molecule α-NPD

NASA Astrophysics Data System (ADS)

Rohloff, R.; Kotadiya, N. B.; Crǎciun, N. I.; Blom, P. W. M.; Wetzelaer, G. A. H.

2017-02-01

Electron and hole transport properties of the organic small molecule N,N'-Di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine are investigated by space-charge-limited current measurements. The hole transport shows trap-free behavior with a mobility of 2.3 × 10-8 m2/Vs at vanishing carrier density and electric field. The electron transport, on the other hand, shows heavily trap-limited behavior, which leads to highly unbalanced transport. A trap concentration of 1.3 × 1024 m-3 was found by modeling the electron currents, similar to the universal trap concentration found in conjugated polymers. This indicates that electron trapping is a generic property of organic semiconductors, ranging from vacuum-deposited small-molecules to solution-processed conjugated polymers.

Ion aggregation in high salt solutions. VII. The effect of cations on the structures of ion aggregates and water hydrogen-bonding network

NASA Astrophysics Data System (ADS)

Choi, Jun-Ho; Choi, Hyung Ran; Jeon, Jonggu; Cho, Minhaeng

2017-10-01

Ions in high salt solutions have a strong propensity to form polydisperse ion aggregates with broad size and shape distributions. In a series of previous comparative investigations using femtosecond IR pump-probe spectroscopy, molecular dynamics simulation, and graph theoretical analysis, we have shown that there exists a morphological difference in the structures of ion aggregates formed in various salt solutions. As salt concentration increases, the ions in high salt solutions form either cluster-like structures excluding water molecules or network-like structures entwined with water hydrogen-bonding networks. Interestingly, such morphological characteristics of the ion aggregates have been found to be in correlation with the solubility limits of salts. An important question that still remains unexplored is why certain salts with different cations have notably different solubility limits in water. Here, carrying out a series of molecular dynamics simulations of aqueous salt solutions and analyzing the distributions and connectivity patterns of ion aggregates with a spectral graph analysis method, we establish the relationship between the salt solubility and the ion aggregate morphology with a special emphasis on the cationic effects on water structures and ion aggregation. We anticipate that the understanding of large scale ion aggregate structures revealed in this study will be critical for elucidating the specific ion effects on the solubility and conformational stability of co-solute molecules such as proteins in water.

Correlation of Solubility with the Metastable Limit of Nucleation Using Gauge-Cell Monte Carlo Simulations.

PubMed

Clark, Michael D; Morris, Kenneth R; Tomassone, Maria Silvina

2017-09-12

We present a novel simulation-based investigation of the nucleation of nanodroplets from solution and from vapor. Nucleation is difficult to measure or model accurately, and predicting when nucleation should occur remains an open problem. Of specific interest is the "metastable limit", the observed concentration at which nucleation occurs spontaneously, which cannot currently be estimated a priori. To investigate the nucleation process, we employ gauge-cell Monte Carlo simulations to target spontaneous nucleation and measure thermodynamic properties of the system at nucleation. Our results reveal a widespread correlation over 5 orders of magnitude of solubilities, in which the metastable limit depends exclusively on solubility and the number density of generated nuclei. This three-way correlation is independent of other parameters, including intermolecular interactions, temperature, molecular structure, system composition, and the structure of the formed nuclei. Our results have great potential to further the prediction of nucleation events using easily measurable solute properties alone and to open new doors for further investigation.

Redox-Phen solution: A water equivalent dosimeter for UVA, UVB and X-rays radiation

NASA Astrophysics Data System (ADS)

Marini, A.; Ciribolla, C.; Lazzeri, L.; d'Errico, F.

2018-06-01

Polysulphone films are the only type of UV passive dosimeters that are widely adopted for research and personal monitoring. Even though many studies concentrated on the development and characterization of these films, they still present some shortcomings. The more important limitations of them are that they can measure only UVB radiations and that they change color at 330 nm, requiring special equipment to read them. To overcome these limitations we developed an aqueous dosimeter that is sensitive to UVA, UVB and X-rays named Redox-Phen solution. This dosimeter is inexpensive and water equivalent, being made of more than 99 wt% of water. It changes color in the visible region upon irradiation, thus it can be measured via simple optical method, and an evaluation of the exposition can be made also by naked eyes.

Dense CO2 as a Solute, Co-Solute or Co-Solvent in Particle Formation Processes: A Review

PubMed Central

Nunes, Ana V. M.; Duarte, Catarina M. M.

2011-01-01

The application of dense gases in particle formation processes has attracted great attention due to documented advantages over conventional technologies. In particular, the use of dense CO2 in the process has been subject of many works and explored in a variety of different techniques. This article presents a review of the current available techniques in use in particle formation processes, focusing exclusively on those employing dense CO2 as a solute, co-solute or co-solvent during the process, such as PGSS (Particles from gas-saturated solutions®), CPF (Concentrated Powder Form®), CPCSP (Continuous Powder Coating Spraying Process), CAN-BD (Carbon dioxide Assisted Nebulization with a Bubble Dryer®), SEA (Supercritical Enhanced Atomization), SAA (Supercritical Fluid-Assisted Atomization), PGSS-Drying and DELOS (Depressurization of an Expanded Liquid Organic Solution). Special emphasis is given to modifications introduced in the different techniques, as well as the limitations that have been overcome. PMID:28824121

Radio Frequency Detection and Characterization of Water-Ethanol Solution through Spiral-Coupled Passive Micro-Resonator Sensor.

PubMed

Koirala, Gyan Raj; Dhakal, Rajendra; Kim, Eun-Seong; Yao, Zhao; Kim, Nam-Young

2018-04-03

We present a microfabricated spiral-coupled passive resonator sensor realized through integrated passive device (IPD) technology for the sensitive detection and characterization of water-ethanol solutions. In order to validate the performance of the proposed device, we explicitly measured and analyzed the radio frequency (RF) characteristics of various water-ethanol solution compositions. The measured results showed a drift in the resonance frequency from 1.16 GHz for deionized (DI) water to 1.68 GHz for the solution containing 50% ethanol, whereas the rejection level given by the reflection coefficient decreased from -29.74 dB to -14.81 dB. The obtained limit of detection was 3.82% volume composition of ethanol in solution. The derived loaded capacitance was 21.76 pF for DI water, which gradually decreased to 8.70 pF for the 50% ethanol solution, and the corresponding relative permittivity of the solution decreased from 80.14 to 47.79. The dissipation factor increased with the concentration of ethanol in the solution. We demonstrated the reproducibility of the proposed sensor through iterative measures of the samples and the study of surface morphology. Successive measurement of different samples had no overlapping and had very minimum bias between RF characteristics for each measured sample. The surface profile for bare sensors was retained after the sample test, resulting a root mean square (RMS) value of 11.416 nm as compared to 10.902 nm for the bare test. The proposed sensor was shown to be a viable alternative to existing sensors for highly sensitive water-ethanol concentration detection.

Ionic Liquid Fuels for Chemical Propulsion

DTIC Science & Technology

2014-11-20

researchers seeking hypergolic fuels have limited themselves to the extremely toxic and corrosive nitric acid solutions. While important questions remain...storable oxidizer (N204 , nitric acid ) have been synthesized and demonstrated. The bipropellant fuels are based upon salts containing dicyanamide or...20-30% nanoparticle loading but decreases between 10-20%, perhaps indicating an optimal loading concentration for these nanoparticles between 10-20

Portable Low-Volume Therapy for Severe Blood Loss

DTIC Science & Technology

2014-06-01

experiments are described in this Annual Report for Year 3. In summary we made the following conclusions: 1.) Melatonin provides therapeutic effects at...very low concentrations. This was shown by the low histopathological score observed when administering a solution containing melatonin at a...hydroxybutyrate, melatonin 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON

75 FR 36701 - Issuance of Environmental Assessment and Finding of No Significant Impact for Modification of...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-28

... in the form of highly water soluble uranyl fluoride. EnergySolutions also proposed the addition of...; the concentration of residual uranyl fluoride in the K-25 piping waste in the railcars would likely... soluble uranyl fluoride in quantities in excess of the limits in Condition 4 of the 2006 Order (i.e., up...

Determination of thiopental in urine sample with high-performance liquid chromatography using iodine-azide reaction as a postcolumn detection system.

PubMed

Zakrzewski, Robert; Ciesielski, Witold

2005-09-25

The reaction between iodine and azide ions induced by thiopental was utilized as a postcolumn reaction for chromatographic determination of thiopental. The method is based on the separation of thiopental on an Nova-Pak CN HP column with an acetonitrile-aqueous solution of sodium azide as a mobile phase, followed by spectrophotometric measurement of the residual iodine (lambda=350 nm) from the postcolumn iodine-azide reaction induced by thiopental after mixing an iodine solution containing iodide ions with the column effluent containing azide ions and thiopental. Chromatograms obtained for thiopental showed negative peaks as a result of the decrease in background absorbance. The detection limit (defined as S/N=3) was 20 nM (0.4 pmol injected amount) for thiopental. Calibration graphs, plotted as peak area versus concentrations, were linear from 40 nM. The elaborated method was applied to determine thiopental in urine samples. The detection limit (defined as S/N=3) was 0.025 nmol/ml urine. Calibration graphs, plotted as peak area versus concentrations, were linear from 0.05 nmol/ml urine. Authentic urine samples were analyzed, thiopental was determined at nmol/ml urine level.

Albumin adsorption onto surfaces of urine collection and analysis containers☆

PubMed Central

Robinson, Mary K.; Caudill, Samuel P.; Koch, David D.; Ritchie, James; Hortin, Glen; Eckfeldt, John H.; Sandberg, Sverre; Williams, Desmond; Myers, Gary; Miller, W. Greg

2017-01-01

Background Adsorption of albumin onto urine collection and analysis containers may cause falsely low concentrations. Methods We added 125I-labeled human serum albumin to urine and to phosphate buffered solutions, incubated them with 22 plastic container materials and measured adsorption by liquid scintillation counting. Results Adsorption of urine albumin (UA) at 5–6 mg/l was <0.9%; and at 90 mg/l was <0.4%. Adsorption was generally less at pH 8 than pH 5 but only 3 cases had p <0.05. Adsorption from 11 unaltered urine samples with albumin 5–333 mg/l was <0.8%. Albumin adsorption for the material with greatest binding was extrapolated to the surface areas of 100 ml and 2 l collection containers, and to instrument sample cups and showed <1% change in concentration at 5 mg/l and <0.5% change at 20 mg/l or higher concentrations. Adsorption of albumin from phosphate buffered solutions (2–28%) was larger than that from urine. Conclusions Albumin adsorption differed among urine samples and plastic materials, but the total influence of adsorption was <1% for all materials and urine samples tested. Adsorption of albumin from phosphate buffered solutions was larger than that from urine and could be a limitation for preparations used as calibrators. PMID:24513540

Albumin adsorption onto surfaces of urine collection and analysis containers.

PubMed

Robinson, Mary K; Caudill, Samuel P; Koch, David D; Ritchie, James; Hortin, Glen; Eckfeldt, John H; Sandberg, Sverre; Williams, Desmond; Myers, Gary; Miller, W Greg

2014-04-20

Adsorption of albumin onto urine collection and analysis containers may cause falsely low concentrations. We added (125)I-labeled human serum albumin to urine and to phosphate buffered solutions, incubated them with 22 plastic container materials and measured adsorption by liquid scintillation counting. Adsorption of urine albumin (UA) at 5-6 mg/l was <0.9%; and at 90 mg/l was <0.4%. Adsorption was generally less at pH8 than pH5 but only 3 cases had p<0.05. Adsorption from 11 unaltered urine samples with albumin 5-333 mg/l was <0.8%. Albumin adsorption for the material with greatest binding was extrapolated to the surface areas of 100 ml and 2l collection containers, and to instrument sample cups and showed <1% change in concentration at 5 mg/l and <0.5% change at 20 mg/l or higher concentrations. Adsorption of albumin from phosphate buffered solutions (2-28%) was larger than that from urine. Albumin adsorption differed among urine samples and plastic materials, but the total influence of adsorption was <1% for all materials and urine samples tested. Adsorption of albumin from phosphate buffered solutions was larger than that from urine and could be a limitation for preparations used as calibrators. Copyright © 2014 Elsevier B.V. All rights reserved.

Slow-release Permanganate Gel (SRP-G) for Groundwater Remediation: Spreading, Gelation, and Release in Porous and Low-Permeability Media

NASA Astrophysics Data System (ADS)

Lee, E. S.; Hastings, J.; Kim, Y.

2015-12-01

Dense nonaqueous phase liquids (DNAPLs) like trichloroethylene (TCE) serve as the most common form of groundwater pollution in the world. Pore-plugging by the solid oxidation product MnO2 and limited lateral dispersion of the oxidant are two common problems with existing in-situ chemical oxidation (ISCO) schemes that could be alleviated through the development of a delayed gelation method for oxidant delivery. The objective of the current study was to further develop and optimize slow-release permanganate gel (SRP-G), a solution comprising colloidal silica and KMnO4, as a novel low-cost treatment option for large and dilute TCE plumes in groundwater. Batch tests showed that gelation could be delayed through manipulation of KMnO4 concentration, pH, and silica particle size of the SRP-G solution. In flow-through columns and flow-tanks filled with saturated sands, silica concentration had little effect on the gelation lag stage and release rate, but increasing silica concentration was associated with increasing release duration. When compared to a pure KMnO4 solution, visual observations and [MnO4-] measurements from flow tank tests demonstrated that the SRP-G prolonged the release duration and enhanced lateral spreading of the oxidant.

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.

Potentiometric determination of trypsin using a polymeric membrane polycation-sensitive electrode based on current-controlled reagent delivery.

PubMed

Chen, Yan; Ding, Jiawang; Qin, Wei

2012-12-01

A potentiometric biosensor for the determination of trypsin is described based on current-controlled reagent delivery. A polymeric membrane protamine-sensitive electrode with dinonylnaphthalene sulfonate as cation exchanger is used for in situ generation of protamine. Diffusion of protamine across the polymeric membrane can be controlled precisely by applying an external current. The hydrolysis catalyzed with trypsin in sample solution decreases the concentration of free protamine released at the sample-membrane interface and facilitates the stripping of protamine out of the membrane surface via the ion-exchange process with sodium ions from the sample solution, thus decreasing the membrane potential, by which the protease can be sensed potentiometrically. The influences of anodic current amplitude, current pulse duration and protamine concentration in the inner filling solution on the membrane potential response have been studied. Under optimum conditions, the proposed protamine-sensitive electrode is useful for continuous and reversible detection of trypsin over the concentration range of 0.5-5UmL(-1) with a detection limit of 0.3UmL(-1). The proposed detection strategy provides a rapid and reagentless way for the detection of protease activities and offers great potential in the homogeneous immunoassays using proteases as labels. Copyright © 2012 Elsevier B.V. All rights reserved.

Modelling the effect of intervillous flow on solute transfer based on 3D imaging of the human placental microstructure.

PubMed

Perazzolo, S; Lewis, R M; Sengers, B G

2017-12-01

A healthy pregnancy depends on placental transfer from mother to fetus. Placental transfer takes place at the micro scale across the placental villi. Solutes from the maternal blood are taken up by placental villi and enter the fetal capillaries. This study investigated the effect of maternal blood flow on solute uptake at the micro scale. A 3D image based modelling approach of the placental microstructures was undertaken. Solute transport in the intervillous space was modelled explicitly and solute uptake with respect to different maternal blood flow rates was estimated. Fetal capillary flow was not modelled and treated as a perfect sink. For a freely diffusing small solute, the flow of maternal blood through the intervillous space was found to be limiting the transfer. Ignoring the effects of maternal flow resulted in a 2.4 ± 0.4 fold over-prediction of transfer by simple diffusion, in absence of binding. Villous morphology affected the efficiency of solute transfer due to concentration depleted zones. Interestingly, less dense microvilli had lower surface area available for uptake which was compensated by increased flow due to their higher permeability. At super-physiological pressures, maternal flow was not limiting, however the efficiency of uptake decreased. This study suggests that the interplay between maternal flow and villous structure affects the efficiency of placental transfer but predicted that flow rate will be the major determinant of transfer. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preparation of chitosan/tripolyphosphate nanoparticles with highly tunable size and low polydispersity.

PubMed

Sawtarie, Nader; Cai, Yuhang; Lapitsky, Yakov

2017-09-01

Nanoparticles prepared through the ionotropic gelation of chitosan with tripolyphosphate (TPP) have been extensively studied as vehicles for drug and gene delivery. Though a number of these works have focused on preparing particles with narrow size distributions, the monodisperse particles produced by these methods have been limited to narrow size ranges (where the average particle size was not varied by more than twofold). Here we show how, by tuning the NaCl concentration in the parent chitosan and TPP solutions, low-polydispersity particles with z-average diameters ranging between roughly 100 and 900nm can be prepared. Further, we explore how the size of these particles depends on the method by which the TPP is mixed into the chitosan solution, specifically comparing: (1) single-shot mixing; (2) dropwise addition; and (3) a dilution technique, where chitosan and TPP are codissolved at a high (gelation-inhibiting) ionic strength and then diluted to lower ionic strengths to trigger gelation. Though the particle size increases sigmoidally with the NaCl concentration for all three mixing methods, the dilution method delivers the most uniform/gradual size increase - i.e., it provides the most precise control. Also investigated are the effects of mixture composition and mixing procedure on the particle yield. These reveal the particle yield to increase with the chitosan/TPP concentration, decrease with the NaCl concentration, and vary only weakly with the mixing protocol; thus, at elevated NaCl concentrations, it may be beneficial to increase chitosan and TPP concentrations to ensure high particle yields. Finally, possible pitfalls of the salt-assisted size control strategy (and their solutions) are discussed. Taken together, these findings provide a simple and reliable method for extensively tuning chitosan/TPP particle size while maintaining narrow size distributions. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical Composition and Evaluation of Nicotine, Tobacco Alkaloids, pH, and Selected Flavors in E-Cigarette Cartridges and Refill Solutions.

PubMed

Lisko, Joseph G; Tran, Hang; Stanfill, Stephen B; Blount, Benjamin C; Watson, Clifford H

2015-10-01

Electronic cigarette (e-cigarette) use is increasing dramatically in developed countries, but little is known about these rapidly evolving products. This study analyzed and evaluated the chemical composition including nicotine, tobacco alkaloids, pH, and flavors in 36 e-liquids brands from 4 manufacturers. We determined the concentrations of nicotine, alkaloids, and select flavors and measured pH in solutions used in e-cigarettes. E-cigarette products were chosen based upon favorable consumer approval ratings from online review websites. Quantitative analyses were performed using strict quality assurance/quality control validated methods previously established by our lab for the measurement of nicotine, alkaloids, pH, and flavors. Three-quarters of the products contained lower measured nicotine levels than the stated label values (6%-42% by concentration). The pH for e-liquids ranged from 5.1-9.1. Minor tobacco alkaloids were found in all samples containing nicotine, and their relative concentrations varied widely among manufacturers. A number of common flavor compounds were analyzed in all e-liquids. Free nicotine levels calculated from the measurement of pH correlated with total nicotine content. The direct correlation between the total nicotine concentration and pH suggests that the alkalinity of nicotine drives the pH of e-cigarette solutions. A higher percentage of nicotine exists in the more absorbable free form as total nicotine concentration increases. A number of products contained tobacco alkaloids at concentrations that exceed U.S. pharmacopeia limits for impurities in nicotine used in pharmaceutical and food products. © Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco 2015. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Fractal binding and dissociation kinetics of lecithin cholesterol acyl transferase (LCAT), a heart-related compound, on biosensor surfaces

NASA Astrophysics Data System (ADS)

Doke, Atul M.; Sadana, Ajit

2006-05-01

A fractal analysis is presented for the binding and dissociation of different heart-related compounds in solution to receptors immobilized on biosensor surfaces. The data analyzed include LCAT (lecithin cholesterol acyl transferase) concentrations in solution to egg-white apoA-I rHDL immobilized on a biosensor chip surface.1 Single- and dual- fractal models were employed to fit the data. Values of the binding and the dissociation rate coefficient(s), affinity values, and the fractal dimensions were obtained from the regression analysis provided by Corel Quattro Pro 8.0 (Corel Corporation Limited).2 The binding rate coefficients are quite sensitive to the degree of heterogeneity on the sensor chip surface. Predictive equations are developed for the binding rate coefficient as a function of the degree of heterogeneity present on the sensor chip surface and on the LCAT concentration in solution, and for the affinity as a function of the ratio of fractal dimensions present in the binding and the dissociation phases. The analysis presented provided physical insights into these analyte-receptor reactions occurring on different biosensor surfaces.

The effect of Fe 3+ doping in Potassium Hydrogen Phthalate single crystals on structural and optical properties

NASA Astrophysics Data System (ADS)

Kumar, R. Ashok; Sivakumar, N.; Vizhi, R. Ezhil; Babu, D. Rajan

2011-02-01

This work investigates the influence of iron doping on Potassium Hydrogen Phthalate (KHP) single crystals by the slow evaporation solution growth technique. Factors such as evaporation rate, solution pH, solute concentration, super saturation limit, etc. are very important in order to have optically transparent single crystals. As part of the work, the effects of metallic salt FeCl 3 in different concentrations were analyzed with pure KHP. Powder X-ray diffraction suggests that the grown crystals are crystallized in the orthorhombic structure. The functional groups and the effect of moisture on the doped crystals can be analyzed with the help of a FTIR spectrum. The pure and doped KHP single crystal shows good transparency in the entire visible region, which is suitable for optical device applications. The refractive indices along b axis of pure and doped KHP single crystals were analyzed by the prism coupling technique. The emission of green light with the use of a Nd:YAG laser ( λ=1064 nm) confirmed the second harmonic generation properties of the grown crystals.

A novel luminol chemiluminescent method catalyzed by silver/gold alloy nanoparticles for determination of anticancer drug flutamide.

PubMed

Chaichi, Mohammad Javad; Azizi, Seyed Naser; Heidarpour, Maryam

2013-12-01

It was found that silver/gold alloy nanoparticles enhance the chemiluminescence (CL) of the luminol-H2O2 system in alkaline solution. The studies of UV-Vis spectra, CL spectra, effects of concentrations luminol, hydrogen peroxide and silver/gold alloy nanoparticles solutions were carried out to explore the CL enhancement mechanism. Flutamide was found to quench the CL signals of the luminol-H2O2 reaction catalyzed by silver/gold alloy nanoparticles, which made it applicable for the determination of flutamide. Under the optimum conditions, the CL intensity is proportional to the concentration of the flutamide in solution over the range 5.0 × 10(-7) to 1.0 × 10(-4)mol L(-1). Detection limit was obtained 1.2 × 10(-8)mol L(-1)and the relative standard deviation (RSD) γ5%. This work is introduced as a new method for the determination of flutamide in commercial tablets. Box-Behnken experimental design is applied to investigate and validate the CL measurement parameters. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of wall couple stress in MHD flow of a micropolar fluid in a porous medium with energy and concentration transfer

NASA Astrophysics Data System (ADS)

Khalid, Asma; Khan, Ilyas; Khan, Arshad; Shafie, Sharidan

2018-06-01

The intention here is to investigate the effects of wall couple stress with energy and concentration transfer in magnetohydrodynamic (MHD) flow of a micropolar fluid embedded in a porous medium. The mathematical model contains the set of linear conservation forms of partial differential equations. Laplace transforms and convolution technique are used for computation of exact solutions of velocity, microrotations, temperature and concentration equations. Numerical values of skin friction, couple wall stress, Nusselt and Sherwood numbers are also computed. Characteristics for the significant variables on the physical quantities are graphically discussed. Comparison with previously published work in limiting sense shows an excellent agreement.

Solution-processed organic thermoelectric materials exhibiting doping-concentration-dependent polarity.

PubMed

Hwang, Sunbin; Potscavage, William J; Yang, Yu Seok; Park, In Seob; Matsushima, Toshinori; Adachi, Chihaya

2016-10-26

Recent progress in conducting polymer-based organic thermoelectric generators (OTEGs) has resulted in high performance due to high Seebeck coefficient, high electrical conductivity (σ), and low thermal conductivity obtained by chemically controlling the materials's redox levels. In addition to improving the properties of individual OTEGs to obtain high performance, the development of solution processes for the fabrication of OTEG modules is necessary to realize large thermoelectric voltage and low-cost mass production. However, the scarcity of good candidates for soluble organic n-type materials limits the use of π-leg module structures consisting of complementary elements of p- and n-type materials because of unbalanced transport coefficients that lead to power losses. In particular, the extremely low σ of n-type materials compared with that of p-type materials is a serious challenge. In this study, poly(pyridinium phenylene) (P(PymPh)) was tested as an n-type semiconductor in solution-processed OTEGs, and the carrier density was controlled by a solution-based chemical doping process using the dopant sodium naphthalenide, a well-known reductant. The electronic structures and doping mechanism of P(PymPh) were explored based on the changes in UV-Vis-IR absorption, ultraviolet photoelectron, and X-ray photoelectron spectra. By controlling the dopant concentration, we demonstrate a maximum n-type power factor of 0.81 μW m -1 K -2 with high σ, and at higher doping concentrations, a switch from n-type to p-type TE operation. This is one of the first cases of a switch in polarity just by increasing the concentration of the reductant and may open a new route for simplified fabrication of complementary organic layers.

Preventing Precipitation in the ISS Urine Processor

NASA Technical Reports Server (NTRS)

Muirhead, Dean; Carter, Layne; Williamson, Jill; Chambers, Antja

2017-01-01

The ISS Urine Processor Assembly (UPA) was initially designed to achieve 85% recovery of water from pretreated urine on ISS. Pretreated urine is comprised of crew urine treated with flush water, an oxidant (chromium trioxide), and an inorganic acid (sulfuric acid) to control microbial growth and inhibit precipitation. Unfortunately, initial operation of the UPA on ISS resulted in the precipitation of calcium sulfate at 85% recovery. This occurred because the calcium concentration in the crew urine was elevated in microgravity due to bone loss. The higher calcium concentration precipitated with sulfate from the pretreatment acid, resulting in a failure of the UPA due to the accumulation of solids in the Distillation Assembly. Since this failure, the UPA has been limited to a reduced recovery of water from urine to prevent calcium sulfate from reaching the solubility limit. NASA personnel have worked to identify a solution that would allow the UPA to return to a nominal recovery rate of 85%. This effort has culminated with the development of a pretreatment based on phosphoric acid instead of sulfuric acid. By eliminating the sulfate associated with the pretreatment, the brine can be concentrated to a much higher concentration before calcium sulfate reach the solubility limit. This paper summarizes the development of this pretreatment and the testing performed to verify its implementation on ISS.

Inhibition Of Washed Sludge With Sodium Nitrite

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

Congdon, J. W.; Lozier, J. S.

2012-09-25

This report describes the results of electrochemical tests used to determine the relationship between the concentration of the aggressive anions in washed sludge and the minimum effective inhibitor concentration. Sodium nitrate was added as the inhibitor because of its compatibility with the DWPF process. A minimum of 0.05M nitrite is required to inhibit the washed sludge simulant solution used in this study. When the worst case compositions and safety margins are considered, it is expected that a minimum operating limit of nearly 0.1M nitrite will be specified. The validity of this limit is dependent on the accuracy of the concentrationsmore » and solubility splits previously reported. Sodium nitrite additions to obtain 0.1M nitrite concentrations in washed sludge will necessitate the additional washing of washed precipitate in order to decrease its sodium nitrite inhibitor requirements sufficiently to remain below the sodium limits in the feed to the DWPF. Nitrite will be the controlling anion in "fresh" washed sludge unless the soluble chloride concentration is about ten times higher than predicted by the solubility splits. Inhibition of "aged" washed sludge will not be a problem unless significant chloride dissolution occurs during storage. It will be very important tomonitor the composition of washed sludge during processing and storage.« less

Stability study of PbSe semiconductor nanocrystals over concentration, size, atmosphere, and light exposure.

PubMed

Dai, Quanqin; Wang, Yingnan; Zhang, Yu; Li, Xinbi; Li, Ruowang; Zou, Bo; Seo, JaeTae; Wang, Yiding; Liu, Manhong; Yu, William W

2009-10-20

Infrared-emitting PbSe nanocrystals are of increasing interest in both fundamental research and technical application. However, the practical applications are greatly limited by their poor stability. In this work, absorption and photoluminescence spectra of PbSe nanocrystals were utilized to observe the stability of PbSe nanocrystals over several conventional factors, that is, particle concentration, particle size, temperature, light exposure, contacting atmosphere, and storage forms (solution or solid powder). Both absorption and luminescence spectra of PbSe nanocrystals exposed to air showed dependence on particle concentration, size, and light exposure, which caused large and quick blue-shifts in the optical spectra. This air-contacted instability arising from the destructive oxidation and subsequent collision-induced decomposition was kinetically dominated and differed from the traditional thought that smaller particles with lower concentrations shrank fast. The photoluminescence emission intensity of the PbSe nanocrystal solution under ultraviolet (UV) exposure in air increased first and then decreased slowly; without UV irradiation, the emission intensity monotonously decreased over time. However, if stored under nitrogen, no obvious changes in absorption and photoluminescence spectra of the PbSe nanocrystals were observed even under UV exposure or upon being heated up to 100 degrees C.

Ruthenium in komatiitic chromite

NASA Astrophysics Data System (ADS)

Locmelis, Marek; Pearson, Norman J.; Barnes, Stephen J.; Fiorentini, Marco L.

2011-07-01

The distinction between Ru in solid solution and Ru-bearing inclusions is essential for the predictive modeling of platinum-group element (PGE) geochemistry in applications such as the lithogeochemical exploration for magmatic sulfide deposits in komatiites. This study investigates the role of chromite in the fractionation of Ru in ultramafic melts by analyzing chromite grains from sulfide-undersaturated komatiites and a komatiitic basalt from the Yilgarn Craton in Western Australia. In situ analysis using laser ablation ICP-MS yields uniform Ru concentrations in chromites both within-grain and on a sample scale, with concentrations between 220 and 540 ppb. All other platinum-group elements are below the detection limit of the laser ablation ICP-MS analysis. Carius tube digestion isotope dilution ICP-MS analysis of chromite concentrates confirms the accuracy of the in-situ method. Time resolved laser ablation ICP-MS analyses have identified the presence of sub-micron Ir-bearing inclusions in some chromite grains from the komatiitic basalt. However, Ru-bearing inclusions have not been recognized in the analyzed chromites and this combined with the in situ data suggests that Ru exists in solid solution in the crystal lattice of chromite. These results show that chromite can control the fractionation and concentration of Ru in ultramafic systems.

Magnetohydrodynamic Flow by a Stretching Cylinder with Newtonian Heating and Homogeneous-Heterogeneous Reactions

PubMed Central

Hayat, T.; Hussain, Zakir; Alsaedi, A.; Farooq, M.

2016-01-01

This article examines the effects of homogeneous-heterogeneous reactions and Newtonian heating in magnetohydrodynamic (MHD) flow of Powell-Eyring fluid by a stretching cylinder. The nonlinear partial differential equations of momentum, energy and concentration are reduced to the nonlinear ordinary differential equations. Convergent solutions of momentum, energy and reaction equations are developed by using homotopy analysis method (HAM). This method is very efficient for development of series solutions of highly nonlinear differential equations. It does not depend on any small or large parameter like the other methods i. e., perturbation method, δ—perturbation expansion method etc. We get more accurate result as we increase the order of approximations. Effects of different parameters on the velocity, temperature and concentration distributions are sketched and discussed. Comparison of present study with the previous published work is also made in the limiting sense. Numerical values of skin friction coefficient and Nusselt number are also computed and analyzed. It is noticed that the flow accelerates for large values of Powell-Eyring fluid parameter. Further temperature profile decreases and concentration profile increases when Powell-Eyring fluid parameter enhances. Concentration distribution is decreasing function of homogeneous reaction parameter while opposite influence of heterogeneous reaction parameter appears. PMID:27280883

Towards operating direct methanol fuel cells with highly concentrated fuel

NASA Astrophysics Data System (ADS)

Zhao, T. S.; Yang, W. W.; Chen, R.; Wu, Q. X.

A significant advantage of direct methanol fuel cells (DMFCs) is the high specific energy of the liquid fuel, making it particularly suitable for portable and mobile applications. Nevertheless, conventional DMFCs have to be operated with excessively diluted methanol solutions to limit methanol crossover and the detrimental consequences. Operation with diluted methanol solutions significantly reduces the specific energy of the power pack and thereby prevents it from competing with advanced batteries. In view of this fact, there exists a need to improve conventional DMFC system designs, including membrane electrode assemblies and the subsystems for supplying/removing reactants/products, so that both the cell performance and the specific energy can be simultaneously maximized. This article provides a comprehensive review of past efforts on the optimization of DMFC systems that operate with concentrated methanol. Based on the discussion of the key issues associated with transport of the reactants/products, the strategies to manage the supply/removal of the reactants/products in DMFC operating with highly concentrated methanol are identified. With these strategies, the possible approaches to achieving the goal of concentrated fuel operation are then proposed. Past efforts in the management of the reactants/products for implementing each of the approaches are also summarized and reviewed.

Magnetohydrodynamic Flow by a Stretching Cylinder with Newtonian Heating and Homogeneous-Heterogeneous Reactions.

PubMed

Hayat, T; Hussain, Zakir; Alsaedi, A; Farooq, M

2016-01-01

This article examines the effects of homogeneous-heterogeneous reactions and Newtonian heating in magnetohydrodynamic (MHD) flow of Powell-Eyring fluid by a stretching cylinder. The nonlinear partial differential equations of momentum, energy and concentration are reduced to the nonlinear ordinary differential equations. Convergent solutions of momentum, energy and reaction equations are developed by using homotopy analysis method (HAM). This method is very efficient for development of series solutions of highly nonlinear differential equations. It does not depend on any small or large parameter like the other methods i. e., perturbation method, δ-perturbation expansion method etc. We get more accurate result as we increase the order of approximations. Effects of different parameters on the velocity, temperature and concentration distributions are sketched and discussed. Comparison of present study with the previous published work is also made in the limiting sense. Numerical values of skin friction coefficient and Nusselt number are also computed and analyzed. It is noticed that the flow accelerates for large values of Powell-Eyring fluid parameter. Further temperature profile decreases and concentration profile increases when Powell-Eyring fluid parameter enhances. Concentration distribution is decreasing function of homogeneous reaction parameter while opposite influence of heterogeneous reaction parameter appears.

Structure-Function Study of Tertiary Amines as Switchable Polarity Solvents

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

Aaron D. Wilson; Frederick F. Stewart

2014-02-01

A series of tertiary amines have been screened for their function as switchable polarity solvents (SPS). The relative ratios of tertiary amine and carbonate species as well as maximum possible concentration were determined through quantitative 1H and 13C NMR spectroscopy. The viscosities of the polar SPS solutions were measured and ranged from near water in dilute systems through to gel formation at high concentrations. The van't Hoff indices for SPS solutions were measured through freezing point depression studies as a proxy for osmotic pressures. A new form of SPS with an amine : carbonate ratio significantly greater than unity hasmore » been identified. Tertiary amines that function as SPS at ambient pressures appear to be limited to molecules with fewer than 12 carbons. The N,N-dimethyl-n-alkylamine structure has been identified as important to the function of an SPS.« less

Molecular Simulations of Graphene-Based Electric Double-Layer Capacitors

NASA Astrophysics Data System (ADS)

Kalluri, Raja K.; Konatham, Deepthi; Striolo, Alberto

2011-03-01

Towards deploying renewable energy sources it is crucial to develop efficient and cost-effective technologies to store electricity. Traditional batteries are plagued by a number of practical problems that at present limit their widespread applicability. One possible solution is represented by electric double-layer capacitors (EDLCs). To deploy EDLCs at the large scale it is necessary to better understand how electrolytes pack and diffuse within narrow charged pores. We present here simulation results for the concentrated aqueous solutions of NaCl, CsCl, and NaI confined within charged graphene-based porous materials. We discuss how the structure of confined water, the salt concentration, the ions size, and the surface charge density determine the accumulation of electrolytes within the porous network. Our results, compared to data available for bulk systems, are critical for relating macroscopic observations to molecular-level properties of the confined working fluids. Research supported by the Department of Energy.

Dynamic response of gold nanoparticle chemiresistors to organic analytes in aqueous solution.

PubMed

Müller, Karl-Heinz; Chow, Edith; Wieczorek, Lech; Raguse, Burkhard; Cooper, James S; Hubble, Lee J

2011-10-28

We investigate the response dynamics of 1-hexanethiol-functionalized gold nanoparticle chemiresistors exposed to the analyte octane in aqueous solution. The dynamic response is studied as a function of the analyte-water flow velocity, the thickness of the gold nanoparticle film and the analyte concentration. A theoretical model for analyte limited mass-transport is used to model the analyte diffusion into the film, the partitioning of the analyte into the 1-hexanethiol capping layers and the subsequent swelling of the film. The degree of swelling is then used to calculate the increase of the electron tunnel resistance between adjacent nanoparticles which determines the resistance change of the film. In particular, the effect of the nonlinear relationship between resistance and swelling on the dynamic response is investigated at high analyte concentration. Good agreement between experiment and the theoretical model is achieved. This journal is © the Owner Societies 2011

Reducing background contributions in fluorescence fluctuation time-traces for single-molecule measurements in solution.

PubMed

Földes-Papp, Zeno; Liao, Shih-Chu Jeff; You, Tiefeng; Barbieri, Beniamino

2009-08-01

We first report on the development of new microscope means that reduce background contributions in fluorescence fluctuation methods: i) excitation shutter, ii) electronic switches, and iii) early and late time-gating. The elements allow for measuring molecules at low analyte concentrations. We first found conditions of early and late time-gating with time-correlated single-photon counting that made the fluorescence signal as bright as possible compared with the fluctuations in the background count rate in a diffraction-limited optical set-up. We measured about a 140-fold increase in the amplitude of autocorrelated fluorescence fluctuations at the lowest analyte concentration of about 15 pM, which gave a signal-to-background advantage of more than two-orders of magnitude. The results of this original article pave the way for single-molecule detection in solution and in live cells without immobilization or hydrodynamic/electrokinetic focusing at longer observation times than are currently available.

The effect of solute concentration on hindered gradient diffusion in polymeric gels

NASA Astrophysics Data System (ADS)

Buck, Kristan K. S.; Dungan, Stephanie R.; Phillips, Ronald J.

1999-10-01

The effect of solute concentration on hindered diffusion of sphere-like colloidal solutes in stiff polymer hydrogels is examined theoretically and experimentally. In the theoretical development, it is shown that the presence of the gel fibres enhances the effect of concentration on the thermodynamic driving force for gradient diffusion, while simultaneously reducing the effect of concentration on the hydrodynamic drag. The result is that gradient diffusion depends more strongly on solute concentration in gels than it does in pure solution, by an amount that depends on the partition coefficient and hydraulic permeability of the gel solute system. Quantitative calculations are made to determine the concentration-dependent diffusivity correct to first order in solute concentration. In order to compare the theoretical predictions with experimental data, rates of diffusion have been measured for nonionic micelles and globular proteins in solution and agarose hydrogels at two gel concentrations. The measurements were performed by using holographic interferometry, through which one monitors changes in refractive index as gradient diffusion takes place within a transparent gel. If the solutes are modelled as spheres with short-range repulsive interactions, then the experimentally measured concentration dependence of the diffusivities of both the protein and micelles is in good agreement with the theoretical predictions.

Study on rheological properties of CMC/Eu-Tb solutions with different concentrations

NASA Astrophysics Data System (ADS)

Fu, Z. C.; Ye, J.; Xiong, J.

2018-05-01

The rheological properties of polymer solution are sensitive to variations in the polymer structure. Carboxymethyl cellulose (CMC) aqueous solution has been used in many fields, such as food, medicine and paper industry. In this paper, the effects of different concentrations (2% - 6%) of CMC/Eu-Tb on their rheological properties were investigeted, including steady-state flow and viscoelastic response. The results show that, the viscosity of CMC/Eu-Tb is lower than that of CMC, at the same concentrations; the products solutions present a nearly Newtonian behavior at the low concentrations (2% - 3%); while at the higher concentrations (4% - 6%), the products solutions present a pseudoplastic behavior; shear-thinning behavior is due to the polymer chains unravel under the action of flow and the molecular chains are oriented in the flow direction. The results also show that the viscosity of the solutions decreases with increasing temperature. Dynamic rheological tests show that CMC/Eu-Tb has viscoelasticity in the concentrations of 2% - 6%. At lower concentrations, the elastic modulus G‧ is slightly higher than the viscous modulus G″, and as the concentrations increase, the elastic modulus G‧ is significantly higher than the viscous modulus G″. It means that at the lower solution concentrations, the solutions tend to be less elastic and easier to flow. Most of the energies are lost through the viscous flow. As the solution concentrations increase, the solutions tend to be more elastic, and the system tends to form a gel.

Probing the rate-limiting step for intramolecular transfer of a transcription factor between specific sites on the same DNA molecule by (15)Nz-exchange NMR spectroscopy.

PubMed

Ryu, Kyoung-Seok; Tugarinov, Vitali; Clore, G Marius

2014-10-15

The kinetics of translocation of the homeodomain transcription factor HoxD9 between specific sites of the same or opposite polarities on the same DNA molecule have been studied by (15)Nz-exchange NMR spectroscopy. We show that exchange occurs by two facilitated diffusion mechanisms: a second-order intermolecular exchange reaction between specific sites located on different DNA molecules without the protein dissociating into free solution that predominates at high concentrations of free DNA, and a first-order intramolecular process involving direct transfer between specific sites located on the same DNA molecule. Control experiments using a mixture of two DNA molecules, each possessing only a single specific site, indicate that transfer between specific sites by full dissociation of HoxD9 into solution followed by reassociation is too slow to measure by z-exchange spectroscopy. Intramolecular transfer with comparable rate constants occurs between sites of the same and opposing polarity, indicating that both rotation-coupled sliding and hopping/flipping (analogous to geminate recombination) occur. The half-life for intramolecular transfer (0.5-1 s) is many orders of magnitude larger than the calculated transfer time (1-100 μs) by sliding, leading us to conclude that the intramolecular transfer rates measured by z-exchange spectroscopy represent the rate-limiting step for a one-base-pair shift from the specific site to the immediately adjacent nonspecific site. At zero concentration of added salt, the intramolecular transfer rate constants between sites of opposing polarity are smaller than those between sites of the same polarity, suggesting that hopping/flipping may become rate-limiting at very low salt concentrations.

A large-scale superhydrophobic surface-enhanced Raman scattering (SERS) platform fabricated via capillary force lithography and assembly of Ag nanocubes for ultratrace molecular sensing.

PubMed

Tan, Joel Ming Rui; Ruan, Justina Jiexin; Lee, Hiang Kwee; Phang, In Yee; Ling, Xing Yi

2014-12-28

An analytical platform with an ultratrace detection limit in the atto-molar (aM) concentration range is vital for forensic, industrial and environmental sectors that handle scarce/highly toxic samples. Superhydrophobic surface-enhanced Raman scattering (SERS) platforms serve as ideal platforms to enhance detection sensitivity by reducing the random spreading of aqueous solution. However, the fabrication of superhydrophobic SERS platforms is generally limited due to the use of sophisticated and expensive protocols and/or suffers structural and signal inconsistency. Herein, we demonstrate a high-throughput fabrication of a stable and uniform superhydrophobic SERS platform for ultratrace molecular sensing. Large-area box-like micropatterns of the polymeric surface are first fabricated using capillary force lithography (CFL). Subsequently, plasmonic properties are incorporated into the patterned surfaces by decorating with Ag nanocubes using the Langmuir-Schaefer technique. To create a stable superhydrophobic SERS platform, an additional 25 nm Ag film is coated over the Ag nanocube-decorated patterned template followed by chemical functionalization with perfluorodecanethiol. Our resulting superhydrophobic SERS platform demonstrates excellent water-repellency with a static contact angle of 165° ± 9° and a consequent analyte concentration factor of 59-fold, as compared to its hydrophilic counterpart. By combining the analyte concentration effect of superhydrophobic surfaces with the intense electromagnetic "hot spots" of Ag nanocubes, our superhydrophobic SERS platform achieves an ultra-low detection limit of 10(-17) M (10 aM) for rhodamine 6G using just 4 μL of analyte solutions, corresponding to an analytical SERS enhancement factor of 10(13). Our fabrication protocol demonstrates a simple, cost- and time-effective approach for the large-scale fabrication of a superhydrophobic SERS platform for ultratrace molecular detection.

Freezing point depression in model Lennard-Jones solutions

NASA Astrophysics Data System (ADS)

Koschke, Konstantin; Jörg Limbach, Hans; Kremer, Kurt; Donadio, Davide

2015-09-01

Crystallisation of liquid solutions is of uttermost importance in a wide variety of processes in materials, atmospheric and food science. Depending on the type and concentration of solutes the freezing point shifts, thus allowing control on the thermodynamics of complex fluids. Here we investigate the basic principles of solute-induced freezing point depression by computing the melting temperature of a Lennard-Jones fluid with low concentrations of solutes, by means of equilibrium molecular dynamics simulations. The effect of solvophilic and weakly solvophobic solutes at low concentrations is analysed, scanning systematically the size and the concentration. We identify the range of parameters that produce deviations from the linear dependence of the freezing point on the molal concentration of solutes, expected for ideal solutions. Our simulations allow us also to link the shifts in coexistence temperature to the microscopic structure of the solutions.

Mechanistic study of the electrodeposition of nanoporous self-assembled ZnO/Eosin Y hybrid thin films: effect of eosin concentration.

PubMed

Goux, Aurélie; Pauporté, Thierry; Yoshida, Tsukasa; Lincot, Daniel

2006-12-05

ZnO films prepared by one-step electrodeposition in the presence of dissolved eosin molecules present an internal nanoporous hybrid structure resulting from self-assembling processes occurring in solution between ZnO and eosin components. This study aims to better understand the underlying growth mechanism, which is still unexplained. The films were deposited by cathodic electrodeposition from an oxygen-saturated aqueous zinc chloride solution. The effects of the addition of 10 to 100 micromol.L(-1) eosin Y, as a sodium salt, on the growth rate and film properties, were systematically studied while all other parameters remained constant (concentrations of zinc salt and supporting electrolyte, applied potential of -1.4 V versus the mercurous sulfate electrode (MSE), temperature of 70 degrees C, rotating disk electrode at 300 rotations per min, and a glass-coated tin oxide electrode). It is shown that the addition of eosin provokes the formation of a nanoporous "cauliflower" structure whose nodule size and composition depend on the eosin concentration in the bath. The growth rate of the hybrid films increases markedly with the eosin concentration. The ZnO and eosin contents of the films are determined for each concentration by chemical analysis. Comparing with thickness determinations, it is shown that the total porosity increases up to 60-65% in volume fraction toward an eosin concentration of 100 micromol.L(-1). The empty pore volume fraction increases up to about 30% at an eosin concentration of about 20 micromol.L(-1) and then decreases. These correlations have been precisely established for the first time. It is shown that the global composition is fixed by the relative rate of deposition for zinc oxide, which is constant, and for the relative rate of eosin inclusion, which is proportional to the concentration in solution. This is explained on the basis of different steps in the growth mechanism, in particular, a diffusion effect limitation for both oxygen and eosin. This variation explains part of the increase in the growth rate. Another contribution is related by the structural effect on the nanoscale leading to the formation of the interpenetrated porous network. Competition between empty and eosin-filled parts of the pore network is evidenced. The formation of the porous network structure could be governed by a diffusion-limited aggregation mechanism. The system may represent a reference case of competing reactions in the electrochemical self-assembly of hybrid nanostructures.

Soil nutrient bioavailability and nutrient content of pine trees (Pinus thunbergii) in areas impacted by acid deposition in Korea.

PubMed

Yang, Jae E; Lee, Wi-Young; Ok, Yong Sik; Skousen, Jeffrey

2009-10-01

Acid deposition has caused detrimental effects on tree growth near industrial areas of the world. Preliminary work has indicated that concentrations of NO(3-), SO(4)(2-), F( - ) and Al in soil solutions were 2 to 33 times higher in industrial areas compared to non-industrial areas in Korea. This study evaluated soil nutrient bioavailability and nutrient contents of red pine (Pinus thunbergii) needles in forest soils of industrial and non-industrial areas of Korea. Results confirm that forest soils of industrial areas have been acidified mainly by deposition of sulfate, resulting in increases of Al, Fe and Mn and decreases of Ca, Mg and K concentrations in soils and soil solutions. In soils of industrial areas, the molar ratios of Ca/Al and Mg/Al in forest soils were <2, which can lead to lower levels and availability of nutrients for tree growth. The Ca/Al molar ratio of Pinus thunbergii needles on non-industrial sites was 15, while that of industrial areas was 10. Magnesium concentrations in needles of Pinus thunbergii were lower in soils of industrial areas and the high levels of acid cations such as Al and Mn in these soils may have antagonized the uptake of base cations like Mg. Continued acidification can further reduce uptake of base cations by trees. Results show that Mg deficiency and high concentrations of Al and Mn in soil solution can be limiting factors for Pinus thunbergii growth in industrial areas of Korea.

Chemiluminescence from an oxidation reaction of rhodamine B with cerium(IV) in a reversed micellar medium of cetyltrimethylammonium chloride in 1-hexanol-cyclohexane/water.

PubMed

Hasanin, Tamer H A; Tsunemine, Yusuke; Tsukahara, Satoshi; Okamoto, Yasuaki; Fujiwara, Terufumi

2011-01-01

The chemiluminescence (CL) emission, observed when rhodamine B (RB) in 1-hexanol-cyclohexane was mixed with cerium(IV) sulfate in sulfuric acid dispersed in a reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water, was investigated using a flow-injection system. The CL emission from the oxidation reaction of RB with Ce(IV) was found to be stronger in the CTAC reversed micellar solution compared with an aqueous solution. Bearing on the enhancement effect of the CTAC reverse micelles on the RB-Ce(IV) CL, several studies including stopped-flow, fluorescence and electron spin resonance (ESR) spectrometries were performed. Rapid spectral changes of an intermediate in the RB-Ce(IV) reaction in the aqueous and reversed micellar solutions were successfully observed using a stopped-flow method. The effect of the experimental variables, i.e., oxidant concentration, sulfuric acid concentration, the mole fraction of 1-hexanol, water-to-surfactant molar concentration ratio, flow rate, upon the CL intensity was evaluated. Under the experimental conditions optimized for a flow-injection determination of RB based on the new reversed micellar-mediated CL reaction with Ce(IV), a detection limit of 0.08 µmol dm(-3) RB was achieved, and a linear calibration graph was obtained with a dynamic range from 0.5 to 20 µmol dm(-3). The relative standard deviation (n = 6) obtained at an RB concentration of 3 µmol dm(-3) was 3%.

A facile synthesis of mesoporous Pdsbnd ZnO nanocomposites as efficient chemical sensor

NASA Astrophysics Data System (ADS)

Ismail, Adel A.; Harraz, Farid A.; Faisal, M.; El-Toni, Ahmed Mohamed; Al-Hajry, A.; Al-Assiri, M. S.

2016-07-01

Mesoporous ZnO was synthesized through the sol-gel method in the presence of triblock co-polymer Pluronic (F-127) template as the structure directing agent. Palladium nanoparticles were photochemically reduced and deposited onto mesoporous ZnO to obtain 1 wt.% Pd/ZnO nanocomposite. Structural and morphological analysis revealed high homogeneity and monodispersity of Pd nanoclusters with small particle sizes ∼ 2-5 nm onto mesoporous ZnO. The electrochemical detection of ethanol in aqueous solutions was conducted at the newly developed Pd/ZnO modified glassy carbon electrode (GCE) by the current-potential (IV) and cyclic voltammetry (CV) techniques and compared with bare GCE or pure ZnO. The presence of Pd dopant greatly enhances the sensitivity of ZnO, and the obtained mesoporous Pd/ZnO sensor has an excellent performance for precision detection of ethanol in aqueous solution with low concentration. The sensitivity was found to be 33.08 μAcm-2 mM-1 at lower concentration zone (0.05-0.8 mM) and 2.13 μAcm-2 mM-1 at higher concentration zone (0.8-12 mM), with a limit of detection (LOD) 19.2 μM. The kinetics study of ethanol oxidation revealed a characteristic feature for a mixed surface and diffusion-controlled process. These excellent sensing characteristics make the mesoporous Pd/ZnO nanocomposite a good candidate for the production of high-performance electrochemical sensors at low ethanol concentration in aqueous solution.

Fmoc-phenylalanine displays antibacterial activity against Gram-positive bacteria in gel and solution phases.

PubMed

Gahane, Avinash Y; Ranjan, Pritish; Singh, Virender; Sharma, Raj K; Sinha, Neeraj; Sharma, Mandeep; Chaudhry, Rama; Thakur, Ashwani K

2018-03-28

In the quest for new antimicrobial materials, hydrogels of Fmoc-protected peptides and amino acids have gained momentum due to their ease of synthesis and cost effectiveness; however, their repertoire is currently limited, and the mechanistic details of their function are not well understood. Herein, we report the antibacterial activity of the hydrogel and solution phases of Fmoc-phenylalanine (Fmoc-F) against a variety of Gram-positive bacteria including methicillin-resistant Staphylococcus aureus (MRSA). Fmoc-F, a small molecule hydrogelator, reduces the bacterial load both in vitro and in the skin wound infections of mice. The antibacterial activity of Fmoc-F is predominantly due to its release from the hydrogel. Fmoc-F shows surfactant-like properties with critical micelle concentration nearly equivalent to its minimum bactericidal concentration. Similar to Fmoc-F, some Fmoc-conjugated amino acids (Fmoc-AA) have also shown antibacterial effects that are linearly correlated with their surfactant properties. At low concentrations, where Fmoc-F does not form micelles, it inhibits bacterial growth by entering the cell and reducing the glutathione levels. However, at higher concentrations, Fmoc-F triggers oxidative and osmotic stress and, alters the membrane permeabilization and integrity, which kills Gram-positive bacteria. Herein, we proposed the use of the Fmoc-F hydrogel and its solution for several biomedical applications. This study will open up new avenues to enhance the repertoire of Fmoc-AA to act as antimicrobial agents and improve their structure-activity relationship.

Colloid transport in porous media: impact of hyper-saline solutions.

PubMed

Magal, Einat; Weisbrod, Noam; Yechieli, Yoseph; Walker, Sharon L; Yakirevich, Alexander

2011-05-01

The transport of colloids suspended in natural saline solutions with a wide range of ionic strengths, up to that of Dead Sea brines (10(0.9) M) was explored. Migration of microspheres through saturated sand columns of different sizes was studied in laboratory experiments and simulated with mathematical models. Colloid transport was found to be related to the solution salinity as expected. The relative concentration of colloids at the columns outlet decreased (after 2-3 pore volumes) as the solution ionic strength increased until a critical value was reached (ionic strength > 10(-1.8) M) and then remained constant above this level of salinity. The colloids were found to be mobile even in the extremely saline brines of the Dead Sea. At such high ionic strength no energetic barrier to colloid attachment was presumed to exist and colloid deposition was expected to be a favorable process. However, even at these salinity levels, colloid attachment was not complete and the transport of ∼ 30% of the colloids through the 30-cm long columns was detected. To further explore the deposition of colloids on sand surfaces in Dead Sea brines, transport was studied using 7-cm long columns through which hundreds of pore volumes were introduced. The resulting breakthrough curves exhibited a bimodal shape whereby the relative concentration (C/C(0)) of colloids at the outlet rose to a value of 0.8, and it remained relatively constant (for the ∼ 18 pore volumes during which the colloid suspension was flushed through the column) and then the relative concentration increased to a value of one. The bimodal nature of the breakthrough suggests different rates of colloid attachment. Colloid transport processes were successfully modeled using the limited entrapment model, which assumes that the colloid attachment rate is dependent on the concentration of the attached colloids. Application of this model provided confirmation of the colloid aggregation and their accelerated attachment during transport through soil in high salinity solution. Copyright © 2011 Elsevier Ltd. All rights reserved.

Final Report: Exudation by Poplar Ectomycorrhizas: Qualitative and Quantitative Assessment of C Sequestration

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

Cumming, J R

Study 1. We compared mycorrhizal Populus tremuloides inoculated with Laccaria bicolor and nonmycorrhizal (NM) P. tremuloides seedlings grown under different levels of P nutrition. Decreasing concentrations of P significantly increased the activity of reactive oxygen scavenging enzymes. In addition, phosphoenolpyruvate carboxylase activity increased under P limitation. P deficiency also increased organic acid exudation and total organic carbon exudation. Colonization by L. bicolor reduced the P concentration thresholds where these physiological changes occurred. Study 2. We assessed the influences of ectomycorrhizal colonization on phosphate limitation responses of trembling aspen. Photosynthetic CO2 uptake was reduced in NM poplar, but not in plantsmore » colonized by L. bicolor or P. involutus. Reductions in shoot and root biomass in NM plants were substantially greater than reductions in plants colonized by either ectomycorrhizal fungi. Leaf starch and sugar concentrations declined with Pi limitation across mycorrhizal treatments, but were higher in plants colonized by L. bicolor and P. involutus. In roots, starch concentrations were greater in NM plants with Pi limitation. In roots, sugars were significantly higher in NM plants compared to mycorrhizal plants and increased significantly in NM plants under Pi limitation. Concentrations were unaffected by Pi limitation in plants colonized by L. bicolor or P. involutus. Study 3. We analyzed proteins that were differentially expressed during the mycorrhizal association. A comparison of global protein expression elucidated broad differences in protein profiles between NM plants and plants colonized by ectomycorrhizal (ECM) or arbuscular mycorrhizal (AM) fungi as well as differences between the ECM fungi L. bicolor and P. involutus. Plants colonized by P. involutus and G. intraradices exhibited unique patterns of up/down-regulated proteins compared to NM plants, whereas plants colonized by L. bicolor exhibited patterns of protein expression more aligned with NM plants. The greatest change in protein expression was in the areas of energy production and the TCA cycle. Among these proteins, fructose-bisphosphate and glyceraldehyde-3-phosphate dedydrogenase were notably up-regulated due to mycorrhizal colonization of aspen by L. bicolor. Pyruvate dehydrogenase, aldehyde dehydrogenase, and aconitate hydratase were up-regulated due to mycorrhizal colonized by P. involutus. Malate dehydrogenase, cinnamyl-alcohol dehydrogenase, and NADH-ubiquinone oxidoreductase proteins were up-regulated due to mycorrhizal colonization of aspen by G. intraradices. Study 4. Eight hybrid crosses of P. trichocarpa, P. deltoides and P. nigra were exposed to Al in solution culture. Resistance to Al varied by genotype and hybrid cross, with P. trichocarpa P. deltoides crosses being most resistant, P. trichocarpa P. nigra being intermediate and P. deltoides P. nigra being most sensitive to Al. Total root Al accumulation was not a good indicator of Al resistance/sensitivity. However, differences in sensitivity among genotypes were associated with Al uptake into the symplasm. Aluminum treatment increased callose and pectin concentrations of root tips more prominently in Al sensitive genotypes/hybrids. In Al sensitive genotypes, higher levels of symplastic Al accumulation correlated with elevated concentrations of citrate, malate, succinate or formate in root tips, whereas organic acid accumulation was not as pronounced in Al resistant genotypes. These findings suggest that exclusion of Al from the symplast is associated with Al resistance. Study 5. We assessed patterns of exudation in Al-resistant and Al-sensitive Populus hybrid crosses. Exposure to Al in solution induced the exudation of citrate and malate from the roots of both hybrid genotypes and altered the contributions of other organic acids to the exudation profiles. Citrate exudation was about 8-times greater in DTAC-7 (resistant) than OP-367 (sensitive). The analysis of total and cationic Al in solution indicated that the amount of bound Al in solution was three-times higher in solutions from DTAC-7 compared to OP-367 plants over both Al treatments. Study 6. We explored the growth, comparative physiology and transcriptional changes of poplar origin that were associated with ECM and/or AM colonization with low Pi availability. Microarray analysis revealed that the symbiosis-associated transcriptome of Populus involves a set of highly conserved genes that overlaps expressed ion other species. Pi-dependent changes in transcript levels involved the down-regulation of symbiosis-responsive genes encoding phosphate transporter proteins, pathogenesis-related proteins, and certain proteases. The up-regulation of genes encoding enzymes involved in carotenoid and apocarotenoid biosynthesis in AM colonized roots indicates that these pathways are specific to AM activation.« less

Biogeochemical responses of arctic hillslopes to storms and seasonal thaw

NASA Astrophysics Data System (ADS)

Harms, T.

2015-12-01

Resilience of watersheds includes maintenance of biogeochemical functions, including retention and transport of solutes, following perturbations. In the arctic, important perturbations that may result in departure from the current state of watersheds include gradual or catastrophic loss of permafrost, increasing temperature, and increased intensity of storms. However, these long-term changes are occurring against the backdrop of variation introduced by seasonality and storms. Thus, establishing baselines that capture temporal patterns is an essential step in predicting vulnerability of arctic watersheds to climate-induced change. We have documented temporal patterns in solute concentrations of six water tracks, zero-order channels that drain arctic hillslopes. Temporal patterns were typically site-specific, underscoring the value of watershed monitoring for predicting responses to perturbations. In some catchments, peak export of organic carbon, nitrogen, and phosphorus occurred during snowmelt, whereas in others, flushing during storms yielded greater export. Concentrations of non-limiting inorganic solutes (e.g., sulfate, calcium) increased through the thaw period in some catchments, suggesting that these solutes may serve as indicators of degrading permafrost. We observed a decrease in the magnitude of flushing of biolabile solutes (e.g., ammonium, organic carbon) during storms through the thaw season, reflecting hydrologic disconnection of upper, organic soils as thaw depth increases and flowpaths deepen. The observed patterns establish a template of temporal variation against which future observations may be assessed to evaluate departures from a stable state.

Assessment of factors limiting algal growth in acidic pit lakes--a case study from Western Australia, Australia.

PubMed

Kumar, R Naresh; McCullough, Clint D; Lund, Mark A; Larranaga, Santiago A

2016-03-01

Open-cut mining operations can form pit lakes on mine closure. These new water bodies typically have low nutrient concentrations and may have acidic and metal-contaminated waters from acid mine drainage (AMD) causing low algal biomass and algal biodiversity. A preliminary study was carried out on an acidic coal pit lake, Lake Kepwari, in Western Australia to determine which factors limited algal biomass. Water quality was monitored to obtain baseline data. pH ranged between 3.7 and 4.1, and solute concentrations were slightly elevated to levels of brackish water. Concentrations of N were highly relative to natural lakes, although concentrations of FRP (<0.01 mg/L) and C (total C 0.7-3.7 and DOC 0.7-3.5 mg/L) were very low, and as a result, algal growth was also extremely low. Microcosm experiment was conducted to test the hypothesis that nutrient enrichment will be able to stimulate algal growth regardless of water quality. Microcosms of Lake Kepwari water were amended with N, P and C nutrients with and without sediment. Nutrient amendments under microcosm conditions could not show any significant phytoplankton growth but was able to promote benthic algal growth. P amendments without sediment showed a statistically higher mean algal biomass concentration than controls or microcosms amended with phosphorus but with sediment did. Results indicated that algal biomass in acidic pit lake (Lake Kepwari) may be limited primarily by low nutrient concentrations (especially phosphorus) and not by low pH or elevated metal concentrations. Furthermore, sediment processes may also reduce the nutrient availability.

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

PubMed

Tas, A Cuneyt

2014-05-01

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

Viscosities encountered during the cryopreservation of dimethyl sulphoxide systems.

PubMed

Kilbride, P; Morris, G J

2017-06-01

This study determined the viscous conditions experienced by cells in the unfrozen freeze concentrated channels between ice crystals in slow cooling protocols. This was examined for both the binary Me 2 SO-water and the ternary Me 2 SO-NaCl-water systems. Viscosity increases from 6.9 ± 0.1 mPa s at -14.4 ± 0.3 °C to 958 ± 27 mPa s at -64.3 ± 0.4 °C in the binary system, and up to 55387 ± 1068 mPa s at -75 ± 0.5 °C in the ternary (10% Me 2 SO, 0.9% NaCl by weight) solution were seen. This increase in viscosity limits molecular diffusion, reducing adsorption onto the crystal plane. These viscosities are significantly lower than observed in glycerol based systems and so cells in freeze concentrated channels cooled to between -60 °C and -75 °C will reside in a thick fluid not a near-solid state as is often assumed. In addition, the viscosities experienced during cooling of various Me 2 SO based vitrification solutions is determined to below -70 °C, as is the impact which additional solutes exert on viscosity. These data show that additional solutes in a cryopreservation system cause disproportionate increases in viscosity. This in turn impacts diffusion rates and mixing abilities of high concentrations of cryoprotectants, and have applications to understanding the fundamental cooling responses of cells to Me 2 SO based cryopreservation solutions. Copyright © 2017 Elsevier Inc. All rights reserved.

Ammonium citrate as enhancement for electrodialytic soil remediation and investigation of soil solution during the process.

PubMed

Dias-Ferreira, Celia; Kirkelund, Gunvor M; Ottosen, Lisbeth M

2015-01-01

Seven electrodialytic experiments were conducted using ammonium citrate as enhancing agent to remediate copper and chromium-contaminated soil from a wood-preservation site. The purpose was to investigate the effect of current density (0.2, 1.0 and 1.5 mA cm(-2)), concentration of enhancing agent (0.25, 0.5 and 1.0 M) and remediation times (21, 42 and 117 d) for the removal of Cu and Cr from a calcareous soil. To gain insight on metal behavior, soil solution was periodically collected using suction cups. It was seen that current densities higher than 1.0 mA cm(-2) did not increase removal and thus using too high current densities can be a waste of energy. Desorption rate is important and both remediation time and ammonium citrate concentration are relevant parameters. It was possible to collect soil solution samples following an adaptation of the experimental set-up to ensure continuous supply of ammonium citrate to the soil in order to keep it saturated during the remediation. Monitoring soil solution gives valuable information on the evolution of remediation and helps deciding when the soil is remediated. Final concentrations in the soil ranged from 220 to 360 mg Cu kg(-1) (removals: 78-86%) and 440-590 mg Cr kg(-1) (removals: 35-51%), being within the 500 mg kg(-1) limit for a clean soil only for Cu. While further optimization is still required for Cr, the removal percentages are the highest achieved so far, for a real Cu and Cr-contaminated, calcareous soil. The results highlight EDR potential to remediate metal polluted soils at neutral to alkaline pH by choosing a good enhancement solution. Copyright © 2014 Elsevier Ltd. All rights reserved.

Metal Complexation in Xylem Fluid 1

PubMed Central

White, Michael C.; Decker, A. Morris; Chaney, Rufus L.

1981-01-01

Xylem fluid was analyzed for numerous solutes to characterize chemically the sap as a medium for forming and transporting metal complexes. The stem exudate was collected hourly for 8 hours from topped 31-day-old soybean (Glycine max L. Merr.) and 46-day-old tomato (Lycopersicon esculentum Mill.) plants grown in normal (0.5 micromolar) and Za-phytotoxic nutrient solutions. Soybean plants were grown in the normal and high-Zn solutions for 24 days; tomato plants were grown for 32 days. The exudate was analyzed for seven organic acids, 22 amino acids, eight inorganic solutes, apparent ionic strength, and pH. Significant changes in many solutes occurred over the 8-hour sampling period. These fluctuations depended on plant species, individual solute, and Zn treatment, and demonstrated that extrapolation of xylem-fluid analyses to whole-plant xylem sap is valid only for sap samples collected shortly after topping a plant. Exudate pH decreased over the 8-hour period for both species; exudate ionic strength increased for tomato and decreased for soybean. At the normal-Zn treatment (0 to 1 hour), the highest acid micromolar concentrations in soybean exudate were: asparagine, 2,583; citric, 1,706; malic, 890; and malonic, 264. Under the same conditions, the highest acid micromolar concentrations in tomato exudate were: maleic, 1,206; malic, 628; glutamine, 522; citric, 301; and asparagine, 242. Cysteine and methionine were above detection limits only in soybean exudate. Zinc phytotoxicity caused significant changes in many solutes. The analyses reported here provide a comprehensive data base for further studies on metal-complex equilibria in xylem fluid. PMID:16661664

Trends in bromide wet deposition concentrations in the contiguous United States, 2001-2016.

PubMed

Wetherbee, Gregory A; Lehmann, Christopher M B; Kerschner, Brian M; Ludtke, Amy S; Green, Lee A; Rhodes, Mark F

2018-02-01

Bromide (Br - ) and other solute concentration data from wet deposition samples collected and analyzed by the National Atmospheric Deposition Program (NADP) from 2001 to 2016, were statistically analyzed for trends both geographically and temporally by precipitation type. Analysis was limited to NADP sites in the contiguous 48 United States. The Br - concentrations for this time period had a high number of values censored at the detection limits with greater than 86 percent of sample concentrations below analytical detection. Bromide was more frequently detected at NADP sites in coastal regions. Analysis using specialized statistical techniques for censored data revealed that Br - concentrations varied by precipitation type with higher concentrations usually observed in liquid versus precipitation containing snow. Negative temporal trends in Br - wet deposition concentrations were observed at a majority of NADP sites; approximately 25 percent of these trend values were statistically significant at less than 0.05 to 0.10 significance levels. Potential causes for the negative trends were explored, including annual and seasonal changes in precipitation depth, reduced emissions of methyl bromide (CH 3 Br) from coastal wetlands, and declining industrial use of bromine compounds. The results indicate that Br - in non-coastal wet-deposition comes mainly from long-range transport, not local sources. Correlations between Br - , chloride, and nitrate concentrations also were evaluated. Published by Elsevier Ltd.

[Effect of Acetonitrile and n-hexane on the Immunoassay of Environmental Representative Pollutants].

PubMed

Lou, Xue-ning; Zhou, Li-ping; Song, Dan; Yang, Rong; Long, Feng

2016-01-15

Based on indirect competitive immunoassay mechanism, bisphenol A (BPA) was detected by the evanescent wave all-fiber immunosensor previously developed with the detection limit of 0.2 microg x L(-1) and the linear detection range of 0.3-33.4 microg x L(-1). The effects of two commonly used organic solvents, including acetonitrile and n-hexane, on the immunosensing assay of BPA were investigated. The influence mechanism of organic solvents on immunosensing assay was discussed. The experimental results showed that the effect of n-hexane on immunosensing assay was negligible even at a high concentration of up to 10%, whereas the effect of acetonitrile on the immunosensing assay was relatively great. BPA could be detected in solutions containing a low concentration of acetonitrile. However, the specific binding reaction between antibody and antigen in homogeneous solution was completely inhibited by high concentrations of acetonitrile, and the quantitative analysis of BPA was not achieved. This might result from the changes of antibody conformation or binding capability between antibody and antigen because acetonitrile replaced a part of the water molecules on the antibody surface.

Human serum albumin crystals and method of preparation

NASA Technical Reports Server (NTRS)

Carter, Daniel C. (Inventor)

1989-01-01

Human serum albumin (HSA) crystals are provided in the form of tetragonal plates having the space groups P42(sub 1)2, the crystals being grown to sizes in excess of 0.5 mm in two dimensions and a thickness of 0.1 mm. Growth of the crystals is carried out by a hanging drop method wherein a precipitant solution containing polyethylene glycol (PEG) and a phosphate buffer is mixed with an HSA solution, and a droplet of mixed solution is suspended over a well of precipitant solution. Crystals grow to the desired size in 3 to 7 days. Concentration of reagents, pH and other parameters are controlled within prescribed limits. The resulting crystals exhibit a size and quality such as to allow performance of x ray diffraction studies and enable the conduct of drug binding studies as well as genetic engineering studies.

Ion-Conserving Modified Poisson-Boltzmann Theory Considering a Steric Effect in an Electrolyte

NASA Astrophysics Data System (ADS)

Sugioka, Hideyuki

2016-12-01

The modified Poisson-Nernst-Planck (MPNP) and modified Poisson-Boltzmann (MPB) equations are well known as fundamental equations that consider a steric effect, which prevents unphysical ion concentrations. However, it is unclear whether they are equivalent or not. To clarify this problem, we propose an improved free energy formulation that considers a steric limit with an ion-conserving condition and successfully derive the ion-conserving modified Poisson-Boltzmann (IC-MPB) equations that are equivalent to the MPNP equations. Furthermore, we numerically examine the equivalence by comparing between the IC-MPB solutions obtained by the Newton method and the steady MPNP solutions obtained by the finite-element finite-volume method. A surprising aspect of our finding is that the MPB solutions are much different from the MPNP (IC-MPB) solutions in a confined space. We consider that our findings will significantly contribute to understanding the surface science between solids and liquids.

Solid Phase Luminescence of Several Rare Earth Ions on Ion-Exchange Films

NASA Technical Reports Server (NTRS)

Tanner, Stephen P.; Street, Kenneth W., Jr.

1999-01-01

The development and characterization of a novel ion-exchange film for solid-phase fluorometry and phosphorimetry is reported. This new cation-exchange material is suitable for spectroscopic applications in the ultraviolet and visible regions. It is advantageous because it, as a single entity, is easily recovered from solution and mounted in the spectrofluorometers. After preconcentration on the film, the luminescence intensity of lanthanide ions is several orders of magnitude greater than that of the corresponding solution, depending on the volume of solution and the amount of film. This procedure allows emission spectral measurements and determination of lanthanide ions at solution concentrations of < 5 (micro)g/L. The film may be stored for subsequent reuse or as a permanent record of the analysis. The major drawback to the use of the film is slow uptake of analyte due to diffusion limitations.

Organic N cycling in Arctic ecosystems: Quantifying root uptake kinetics and temporal variability of soil amino acids.

NASA Astrophysics Data System (ADS)

Homyak, P. M.; Iverson, S. L.; Slessarev, E.; Marchus, K.; Schimel, J.

2017-12-01

Arctic ecosystems are undergoing shifts in plant community composition with increased warming. How these changes may alter ecosystem function is not well constrained, owing in part to uncertainties on how plant-soil feedbacks influence nutrient cycling. For nitrogen (N), in particular, understanding how these feedbacks may alter cycling rates is challenging because i) Arctic plants take up organic N (i.e., amino acids; AA) when inorganic N is limiting, yet ii) it has never been quantified, for any plant species growing in the wild, how much of its N demand is actually met by taking up AA. To advance fundamental understanding of plant-soil feedbacks as the Arctic warms, we are integrating field measurements of AA availability in N-limited tussock tundra (E. vaginatum) and a comparably less N-limited birch shrub tundra (Betula nana and Salix spp.) with a root uptake model. We used soil microdialysis to determine available AA concentrations in the soil solution and potential rates of AA diffusion and mass flow to roots at the Toolik Field Station in Alaska. These measurements are being combined with AA root uptake kinetic experiments using E. vaginatum to establish actual AA root uptake rates. We found that in the early growing season (June), total AA concentrations in the soil solution averaged 104 µg N L-1 and were similar to NH4+ across sites. In the late growing season (August), AA were the dominant form of N averaging 75 µg N L-1 while NH4+ decreased to 13 µg N L-1. In the early growing season AA diffusion rates in the soil averaged 200 ng N cm-2 s-1 and declined to 150 ng N cm-2 s-1 in the late growing season. Lysine, serine, and arginine were the most abundant AA and differences in the N status of sites did not affect total AA concentrations. Amino acids made up at least half of the N diffusing through the soil solution, suggesting they can subsidize the N demand of arctic plants. Ongoing field experiments at Toolik will be used to constrain actual AA root uptake rates.

Effect of number and washing solutions on functional properties of surimi-like material from duck meat.

PubMed

Ramadhan, Kurnia; Huda, Nurul; Ahmad, Ruzita

2014-02-01

Duck meat is less utilized than other meats in processed products because of limitations of its functional properties, including lower water holding capacity, emulsion stability, and higher cooking loss compared with chicken meat. These limitations could be improved using surimi technology, which consists of washing and concentrating myofibrillar protein. In this study, surimi-like materials were made from duck meat using two or three washings with different solutions (tap water, sodium chloride, sodium bicarbonate, and sodium phosphate buffer). Better improvement of the meat's functional properties was obtained with three washings versus two washings. Washing with tap water achieved the highest gel strength; moderate elevation of water holding capacity, pH, lightness, and whiteness; and left a small amount of fat. Washing with sodium bicarbonate solution generated the highest water holding capacity and pH and high lightness and whiteness values, but it resulted in the lowest gel strength. Processing duck meat into surimi-like material improves its functional properties, thereby making it possible to use duck meat in processed products.

Sensitive determination of cadmium using solidified floating organic drop microextraction-slotted quartz tube-flame atomic absorption spectroscopy.

PubMed

Akkaya, Erhan; Chormey, Dotse Selali; Bakırdere, Sezgin

2017-09-20

In this study, solidified floating organic drop microextraction (SFODME) by 1-undecanol was combined with slotted quartz tube flame atomic absorption spectrometry (SQT-FAAS) for the determination of cadmium at trace levels. Formation of a complex with 4,4'-dimethyl-2,2'-bipyridine facilitated the extraction of cadmium from aqueous solutions. Several chemical variables were optimized in order to obtain high extraction outputs. Parameters such as concentration of the ligand, pH, and amount of buffer solution were optimized to enhance the formation of cadmium complex. The SFODME method was assisted by dispersion of extractor solvent into aqueous solutions using 2-propanol. Under the optimum extraction and instrumental conditions, the limit of detection and limit of quantitation values obtained for cadmium using the combined methods (SFODME-SQT-FAAS) were found to be 0.4 and 1.3 μg L -1 , respectively. Matrix effects on the method were also examined for tap water and wastewater, and spiked recovery results were found to be very satisfactory. Graphical Abstract SFODME-SQT-FAAS system for sensitive determination of cadmium.

Identification of a triplet pair intermediate in singlet exciton fission in solution

PubMed Central

Stern, Hannah L.; Musser, Andrew J.; Gelinas, Simon; Parkinson, Patrick; Herz, Laura M.; Bruzek, Matthew J.; Anthony, John; Friend, Richard H.; Walker, Brian J.

2015-01-01

Singlet exciton fission is the spin-conserving transformation of one spin-singlet exciton into two spin-triplet excitons. This exciton multiplication mechanism offers an attractive route to solar cells that circumvent the single-junction Shockley–Queisser limit. Most theoretical descriptions of singlet fission invoke an intermediate state of a pair of spin-triplet excitons coupled into an overall spin-singlet configuration, but such a state has never been optically observed. In solution, we show that the dynamics of fission are diffusion limited and enable the isolation of an intermediate species. In concentrated solutions of bis(triisopropylsilylethynyl)[TIPS]—tetracene we find rapid (<100 ps) formation of excimers and a slower (∼10 ns) break up of the excimer to two triplet exciton-bearing free molecules. These excimers are spectroscopically distinct from singlet and triplet excitons, yet possess both singlet and triplet characteristics, enabling identification as a triplet pair state. We find that this triplet pair state is significantly stabilized relative to free triplet excitons, and that it plays a critical role in the efficient endothermic singlet fission process. PMID:26060309

Thermal properties and surface reactivity in simulated body fluid of new strontium ion-containing phosphate glasses.

PubMed

Massera, J; Petit, L; Cardinal, T; Videau, J J; Hupa, M; Hupa, L

2013-06-01

In this paper, we investigate the effect of SrO substitution for CaO in 50P₂O₅-10Na₂-(40-x)CaO-xSrO glass system (x from 0 to 40) on the thermal and structural properties and also on the glass reactivity in simulated body fluid (SBF) in order to find new glass candidates for biomedical glass fibers. The addition of SrO at the expense of CaO seems to restrain the leaching of phosphate ions in the solution limiting the reduction of the solution pH. We observed the formation of an apatite layer at the surface of the glasses when in contact with SBF. SrO and MgO were found in the apatite layer of the strontium ion-containing glasses, the concentration of which increases with an increase of SrO content. We think that it is the presence of MgO and SrO in the layer which limits the leaching of phosphate in the solution and thus the glass dissolution in SBF.

Observation of small cluster formation in concentrated monoclonal antibody solutions and its implications to solution viscosity.

PubMed

Yearley, Eric J; Godfrin, Paul D; Perevozchikova, Tatiana; Zhang, Hailiang; Falus, Peter; Porcar, Lionel; Nagao, Michihiro; Curtis, Joseph E; Gawande, Pradad; Taing, Rosalynn; Zarraga, Isidro E; Wagner, Norman J; Liu, Yun

2014-04-15

Monoclonal antibodies (mAbs) are a major class of biopharmaceuticals. It is hypothesized that some concentrated mAb solutions exhibit formation of a solution phase consisting of reversibly self-associated aggregates (or reversible clusters), which is speculated to be responsible for their distinct solution properties. Here, we report direct observation of reversible clusters in concentrated solutions of mAbs using neutron spin echo. Specifically, a stable mAb solution is studied across a transition from dispersed monomers in dilute solution to clustered states at more concentrated conditions, where clusters of a preferred size are observed. Once mAb clusters have formed, their size, in contrast to that observed in typical globular protein solutions, is observed to remain nearly constant over a wide range of concentrations. Our results not only conclusively establish a clear relationship between the undesirable high viscosity of some mAb solutions and the formation of reversible clusters with extended open structures, but also directly observe self-assembled mAb protein clusters of preferred small finite size similar to that in micelle formation that dominate the properties of concentrated mAb solutions. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Iodine uptake by spinach (Spinacia oleracea L.) plants grown in solution culture: effects of iodine species and solution concentrations.

PubMed

Zhu, Y-G; Huang, Y-Z; Hu, Y; Liu, Y-X

2003-04-01

A hydroponic experiment was carried out to investigate the effects of iodine species and solution concentrations on iodine uptake by spinach (Spinacia oleracea L.). Five iodine concentrations (0, 1, 10, 50 and 100 microM) for iodate (IO(3)(-)) and iodide (I(-)) were used. Results show that higher concentrations of I(-) (> or =10 microM) had some detrimental effect on plant growth, while IO(3)(-) had little effect on the biomass production of spinach plants. Increases in iodine concentration in the growth solution significantly enhanced I concentrations in plant tissues. The detrimental effect of I(-) on plant growth was probably due to the excessively high accumulation of I in plant tissues. The solution-to-spinach leaf transfer factors (TF(leaf), fresh weight basis) for plants treated with iodide were between 14.2 and 20.7 at different solution concentrations of iodide; TF(leaf) for plants treated with iodate decreased gradually from 23.7 to 2.2 with increasing solution concentrations of iodate. The distribution coefficients (DCs) of I between leaves and roots were constantly higher for plants treated with iodate than those treated with iodide. DCs for plants treated with iodide increased with increasing solution concentrations of iodide, while DCs for plants treated with iodate (around 5.5) were similar across the range of solution concentrations of iodate used in this experiment. The implications of iodine accumulation in leafy vegetables in human iodine nutrition are also discussed. Copyright 2002 Elsevier Science Ltd.

High sensitive analysis of steroids in doping control using gas chromatography/time-of-flight mass-spectrometry.

PubMed

Revelsky, A I; Samokhin, A S; Virus, E D; Rodchenkov, G M; Revelsky, I A

2011-04-01

The method of high sensitive gas chromatographic/time-of-flight mass-spectrometric (GC/TOF-MS) analysis of steroids was developed. Low-resolution TOF-MS instrument (with fast spectral acquisition rate) was used. This method is based on the formation of the silyl derivatives of steroids; exchange of the reagent mixture (pyridine and N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA)) for tert-butylmethylether; offline large sample volume injection of this solution based on sorption concentration of the respective derivatives from the vapour-gas mixture flow formed from the solution and inert gas flows; and entire analytes solvent-free concentrate transfer into the injector of the gas chromatograph. Detection limits for 100 µl sample solution volume were 0.5-2 pg/µl (depending on the component). Application of TOF-MS model 'TruTOF' (Leco, St Joseph, MO, USA) coupled with gas chromatograph and ChromaTOF software (Leco, St Joseph, MO, USA) allowed extraction of the full mass spectra and resolving coeluted peaks. Due to use of the proposed method (10 µl sample aliquot) and GC/TOF-MS, two times more steroid-like compounds were registered in the urine extract in comparison with the injection of 1 µl of the same sample solution. Copyright © 2010 John Wiley & Sons, Ltd.

Cloud point extraction of vanadium in pharmaceutical formulations, dialysate and parenteral solutions using 8-hydroxyquinoline and nonionic surfactant.

PubMed

Khan, Sumaira; Kazi, Tasneem G; Baig, Jameel A; Kolachi, Nida F; Afridi, Hassan I; Wadhwa, Sham Kumar; Shah, Abdul Q; Kandhro, Ghulam A; Shah, Faheem

2010-10-15

A cloud point extraction (CPE) method has been developed for the determination of trace quantity of vanadium ions in pharmaceutical formulations (PF), dialysate (DS) and parenteral solutions (PS). The CPE of vanadium (V) using 8-hydroxyquinoline (oxine) as complexing reagent and mediated by nonionic surfactant (Triton X-114) was investigated. The parameters that affect the extraction efficiency of CPE, such as pH of sample solution, concentration of oxine and Triton X-114, equilibration temperature and time period for shaking were investigated in detail. The validity of CPE of V was checked by standard addition method in real samples. The extracted surfactant-rich phase was diluted with nitric acid in ethanol, prior to subjecting electrothermal atomic absorption spectrometry. Under these conditions, the preconcentration of 50 mL sample solutions, allowed raising an enrichment factor of 125-fold. The lower limit of detection obtained under the optimal conditions was 42 ng/L. The proposed method has been successfully applied to the determination of trace quantity of V in various pharmaceutical preparations with satisfactory results. The concentration ranges of V in PF, DS and PS samples were found in the range of 10.5-15.2, 0.65-1.32 and 1.76-6.93 microg/L, respectively. 2010 Elsevier B.V. All rights reserved.

Kinetics of radiation-induced precipitation at the alloy surface

NASA Astrophysics Data System (ADS)

Lam, N. Q.; Nguyen, T.; Leaf, G. K.; Yip, S.

1988-05-01

Radiation-induced precipitation of a new phase at the surface of an alloy during irradiation at elevated temperatures was studied with the aid of a kinetic model of segregation. The preferential coupling of solute atoms with the defect fluxes gives rise to a strong solute enrichment at the surface, which, if surpassing the solute solubility limit, leads to the formation of a precipitate layer. The moving precipitate/matrix interface was accommodated by means of a mathematical scheme that transforms spatial coordinates into a reference frame in which the boundaries are immobile. Sample calculations were performed for precipitation of the γ'-Ni 3Si layer on Ni-Si alloys undergoing electron irradiation. The dependences of the precipitation kinetics on the defect-production rate, irradiation temperature, internal defect sink concentration and alloy composition were investigated systematically.

Real-time monitoring of the solution concentration variation during the crystallization process of protein-lysozyme by using digital holographic interferometry.

PubMed

Zhang, Yanyan; Zhao, Jianlin; Di, Jianglei; Jiang, Hongzhen; Wang, Qian; Wang, Jun; Guo, Yunzhu; Yin, Dachuan

2012-07-30

We report a real-time measurement method of the solution concentration variation during the growth of protein-lysozyme crystals based on digital holographic interferometry. A series of holograms containing the information of the solution concentration variation in the whole crystallization process is recorded by CCD. Based on the principle of double-exposure holographic interferometry and the relationship between the phase difference of the reconstructed object wave and the solution concentration, the solution concentration variation with time for arbitrary point in the solution can be obtained, and then the two-dimensional concentration distribution of the solution during crystallization process can also be figured out under the precondition which the refractive index is constant through the light propagation direction. The experimental results turns out that it is feasible to in situ, full-field and real-time monitor the crystal growth process by using this method.

Stable, concentrated solutions of polyaniline using amines as gel inhibitors

DOEpatents

Wang, Hsing-Lin; Mattes, Benjamin R.

2002-01-01

Stable, concentrated solutions of high-molecular weight polyaniline using amines as gel inhibitors. Certain amine compounds (gel inhibitors) are used to form highly concentrated, stable solutions of the emeraldine base form of polyaniline in numerous organic solvents from which coatings, films and fibers are readily prepared without problems associated with rapid gelation which occurs when concentrated solutions are attempted without the use of the gel inhibitors of the present invention. Tertiary amines are used to solubilize low-molecular weight fractions (M.sub.w <120,000, M.sub.n <30,000) of the pernigraniline, emeraldine, and leucoemeraldine oxidation states of polyaniline as concentrated (>20 wt. %) polyaniline solutions, while primary and secondary amines are used to produce solutions having 15-40 wt % of high-molecular weight polyaniline [M.sub.w.gtoreq.120,000, M.sub.n.gtoreq.30,000]. Concentrated solutions of polyaniline co-polymers or ring and/or nitrogen-substituted polyanilines may also be prepared.

The role of fluid mobility in the development of shale weathering profiles: Direct observations from a vadose zone monitoring system

NASA Astrophysics Data System (ADS)

Druhan, J. L.; Wang, J.; Cargill, S.; Murphy, C.; Tune, A. K.; Dietrich, W. E.; Rempe, D.

2017-12-01

Extensive effort has focused on resolving the contribution of weathering reactions to the transfer of mass over scales ranging from individual hillslope weathering profiles, across local watersheds, to continental drainage networks. A persistent limitation in quantifying these fluxes is the variability in fluid flowpaths through the subsurface, which may alter the extent of chemical weathering relative to that expected from idealized homogenous conditions. In the past decade, the consequence of fluid travel time on solute flux has been recognized as a key complexity in the interpretation of solute concentrations, particularly in upland watersheds characterized by fracture flowpaths, as is typical of shale-dominated landscapes. Though recent studies have suggested a variety of models for solute generation in such dual (matrix and fracture flow) domain systems, a central impediment to advancing prediction is the lack of direct observations. Here, we report solute chemistry as a function of depth across an 18 m thick vadose zone of weathered argillite (shale) in the Eel River Critical Zone Observatory (ERCZO) using novel sub-horizontal distributed samplers (Vadose Zone Monitoring System). We contrast a year of major and trace ion chemistry obtained from water samples collected approximately biweekly using two complementary sampling systems, one applying active pressure to extract matrix-bound pore fluid, and the other using a passive collection method to extract freely draining water. Precipitation falling during the winter rainy season passes through this vadose zone, causing increased rock moisture that is subsequently depleted by transpiring trees. Solute concentrations reflect these seasonal changes, and, surprisingly, normalized ion ratios span the full range of values reported for the world's largest rivers. Notably, for some major cations, freely draining water is consistently less concentrated than matrix-bound water, and the composition of vadose zone water is consistently more variable than the underlying groundwater. Dual domain 1D reactive transport simulations demonstrate that even a simplified scoping model for solute concentrations across fractured shale systems requires a non-uniform fluid travel time to reasonably reproduce observations.

Partitioning of lysolipids, fatty acids and their mixtures in aqueous lipid bilayers: solute concentration/composition effects.

PubMed

Singh, Jasmeet; Lai, Amy Jo; Alaee, Yasmin; Ranganathan, Radha

2014-01-01

Distributions of lysopalmitoylphosphatidylcholine (LPPC), palmitic acid (PA) and their 1:1 mixtures between water and dipalmitoylphosphatidylcholine (DPPC) bilayer were determined using a fluorescence probe that selectively detects only the solutes in water. Water solute concentrations were obtained at each of several lipid concentrations. Dynamic Light Scattering experiments confirmed that the lipid/solute aggregates were vesicles in the concentration range investigated. Lipid concentration dependence of the solute component in water was fit to a thermodynamic model of solute distribution between two coexisting solvents. Water/bilayer partition coefficient and the free energy of transfer, for each of these solutes were determined from the fit. Main findings are: (1) Water/bilayer partition coefficient of solute is greater for 2 to 10% solute mole fraction than for 0 to 2%, signaling solute induced bilayer perturbation that increases bilayer solubility, beginning at 2% solute mole fraction. (2) Partition coefficients are in the order LPPC

Partitioning of Lysolipids, Fatty Acids and Their Mixtures in Aqueous Lipid Bilayers: Solute Concentration / Composition Effects

PubMed Central

Singh, Jasmeet; Lai, Amy Jo; Alaee, Yasmin; Ranganathan, Radha

2013-01-01

Distribution of lysopalmitoylphosphatidylcholine (LPPC), Palmitic acid (PA) and their 1:1 mixtures between water and dipalmitoylphosphatidylcholine (DPPC) bilayer were determined using a fluorescence probe that selectively detects only the solutes in water. Water solute concentrations were obtained at each of several lipid concentrations. Dynamic Light Scattering experiments confirmed that the lipid/solute aggregates were vesicles in the concentration range investigated. Lipid concentration dependence of the solute component in water was fit to a thermodynamic model of solute distribution between two coexisting solvents. Water/bilayer partition coefficient and the free energy of transfer, for each of these solutes were determined from the fit. Main findings are: (1) Water/bilayer partition coefficient of solute is greater for 2 to 10 % solute mole fraction than for 0 to 2 %, signaling solute induced bilayer perturbation that increases bilayer solubility, beginning at 2 % solute mole fraction. (2) Partition coefficients are in the order LPPC

On the global existence of hairy black holes and solitons in anti-de Sitter Einstein-Yang-Mills theories with compact semisimple gauge groups

NASA Astrophysics Data System (ADS)

Baxter, J. Erik

2016-10-01

We investigate the existence of black hole and soliton solutions to four dimensional, anti-de Sitter (adS), Einstein-Yang-Mills theories with general semisimple connected and simply connected gauge groups, concentrating on the so-called regular case. We here generalise results for the asymptotically flat case, and compare our system with similar results from the well-researched adS {mathfrak {su}}(N) system. We find the analysis differs from the asymptotically flat case in some important ways: the biggest difference is that for Λ <0, solutions are much less constrained as r→ infty , making it possible to prove the existence of global solutions to the field equations in some neighbourhood of existing trivial solutions, and in the limit of |Λ |→ infty . In particular, we can identify non-trivial solutions where the gauge field functions have no zeroes, which in the {mathfrak {su}}(N) case proved important to stability.

Dissolution mechanism of aluminum hydroxides in acid media

NASA Astrophysics Data System (ADS)

Lainer, Yu. A.; Gorichev, I. G.; Tuzhilin, A. S.; Gololobova, E. G.

2008-08-01

The effects of the concentration, temperature, and potential at the hydroxide/electrolyte interface on the aluminum hydroxide dissolution in sulfuric, hydrochloric, and perchloric acids are studied. The limiting stage of the aluminum hydroxide dissolution in the acids is found to be the transition of the complexes that form on the aluminum hydroxide surface from the solid phase into the solution. The results of the calculation of the acid-base equilibrium constants at the oxide (hydroxide)/solution interface using the experimental data on the potentiometric titration of Al2O3 and AlOOH suspensions are analyzed. A mechanism is proposed for the dissolution of aluminum hydroxides in acid media.

Determination of dextrose in peritoneal dialysis solution by localized surface plasmon resonance technique based on silver nanoparticles formation

NASA Astrophysics Data System (ADS)

Masrournia, Mahboube; Montazarolmahdi, Maliheh; Sani, Faramarz Aliasghari

2017-07-01

Determination of dextrose in peritoneal dialysis with a method based on silver nanoparticles (AgNPs) formation was investigated. In a green chemistry method, silver nanoparticles (AgNPs) were synthesized in the natural polymeric matrix of gelatin. The nanoparticles were characterized with UV-Vis spectroscopy and transmission electron microscopy (TEM). Absorbance signal of AgNPs could be applied to determine the various concentrations of dextrose solutions. Drop wise and ultrasonic methods were used and compared with each other. The dynamic range of methods with limit of detection and relative standard deviations were obtained. Results for real sample (peritoneal dialysis) were satisfied.

Integrating nanohybrid membranes of reduced graphene oxide: chitosan: silica sol gel with fiber optic SPR for caffeine detection

NASA Astrophysics Data System (ADS)

Kant, Ravi; Tabassum, Rana; Gupta, Banshi D.

2017-05-01

Caffeine is the most popular psychoactive drug consumed in the world for improving alertness and enhancing wakefulness. However, caffeine consumption beyond limits can result in lot of physiological complications in human beings. In this work, we report a novel detection scheme for caffeine integrating nanohybrid membranes of reduced graphene oxide (rGO) in chitosan modified silica sol gel (rGO: chitosan: silica sol gel) with fiber optic surface plasmon resonance. The chemically synthesized nanohybrid membrane forming the sensing route has been dip coated over silver coated unclad central portion of an optical fiber. The sensor works on the mechanism of modification of dielectric function of sensing layer on exposure to analyte solution which is manifested in terms of red shift in resonance wavelength. The concentration of rGO in polymer network of chitosan and silica sol gel and dipping time of the silver coated probe in the solution of nanohybrid membrane have been optimized to extricate the supreme performance of the sensor. The optimized sensing probe possesses a reasonably good sensitivity and follows an exponentially declining trend within the entire investigating range of caffeine concentration. The sensor boasts of an unparalleled limit of detection value of 1.994 nM and works well in concentration range of 0-500 nM with a response time of 16 s. The impeccable sensor methodology adopted in this work combining fiber optic SPR with nanotechnology furnishes a novel perspective for caffeine determination in commercial foodstuffs and biological fluids.

Stability of nitrate-ion concentrations in simulated deposition samples used for quality-assurance activities by the U.S. Geological Survey

USGS Publications Warehouse

Willoughby, T.C.; See, R.B.; Schroder, L.J.

1989-01-01

Three experiments were conducted to determine the stability of nitrate-ion concentrations in simulated deposition samples. In the four experiment-A solutions, nitric acid provided nitrate-ion concentrations ranging from 0.6 to 10.0 mg/L and that had pH values ranging from 3.8 to 5.0. In the five experiment-B solutions, sodium nitrate provided nitrate-ion concentrations ranging from 0.5 to 3.0 mg/L. The pH was adjusted to about 4.5 for each of the solutions by addition of sulfuric acid. In the four experiment-C solutions, nitric acid provided nitrate-ion concentrations ranging from 0.5 to 3.0 mg/L. Major cation and anion concentrations were added to each solution to simulate natural deposition. Aliquots were removed from the 13 original solutions and analyzed by ion chromatography about once a week for 100 days to determine if any changes occurred in nitrate-ion concentrations throughout the study period. No substantial changes were observed in the nitrate-ion concentrations in solutions that had initial concentrations below 4.0 mg/L in experiments A and B, although most of the measured nitrate-ion concentrations for the 100-day study were below the initial concentrations. In experiment C, changes in nitrate-ion concentrations were much more pronounced; the measured nitrate-ion concentrations for the study period were less than the initial concentrations for 62 of the 67 analyses. (USGS)

Dissolved metals and associated constituents in abandoned coal-mine discharges, Pennsylvania, USA. Part 2: Geochemical controls on constituent concentrations

USGS Publications Warehouse

Cravotta, C.A.

2008-01-01

Water-quality data for discharges from 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania reveal complex relations among the pH and dissolved solute concentrations that can be explained with geochemical equilibrium models. Observed values of pH ranged from 2.7 to 7.3 in the coal-mine discharges (CMD). Generally, flow rates were smaller and solute concentrations were greater for low-pH CMD samples; pH typically increased with flow rate. Although the frequency distribution of pH was similar for the anthracite and bituminous discharges, the bituminous discharges had smaller median flow rates; greater concentrations of SO4, Fe, Al, As, Cd, Cu, Ni and Sr; comparable concentrations of Mn, Cd, Zn and Se; and smaller concentrations of Ba and Pb than anthracite discharges with the same pH values. The observed relations between the pH and constituent concentrations can be attributed to (1) dilution of acidic water by near-neutral or alkaline ground water; (2) solubility control of Al, Fe, Mn, Ba and Sr by hydroxide, sulfate, and/or carbonate minerals; and (3) aqueous SO4-complexation and surface-complexation (adsorption) reactions. The formation of AlSO4+ and AlHSO42 + complexes adds to the total dissolved Al concentration at equilibrium with Al(OH)3 and/or Al hydroxysulfate phases and can account for 10-20 times greater concentrations of dissolved Al in SO4-laden bituminous discharges compared to anthracite discharges at pH of 5. Sulfate complexation can also account for 10-30 times greater concentrations of dissolved FeIII concentrations at equilibrium with Fe(OH)3 and/or schwertmannite (Fe8O8(OH)4.5(SO4)1.75) at pH of 3-5. In contrast, lower Ba concentrations in bituminous discharges indicate that elevated SO4 concentrations in these CMD sources could limit Ba concentrations by the precipitation of barite (BaSO4). Coprecipitation of Sr with barite could limit concentrations of this element. However, concentrations of dissolved Pb, Cu, Cd, Zn, and most other trace cations in CMD samples were orders of magnitude less than equilibrium with sulfate, carbonate, and/or hydroxide minerals. Surface complexation (adsorption) by hydrous ferric oxides (HFO) could account for the decreased concentrations of these divalent cations with increased pH. In contrast, increased concentrations of As and, to a lesser extent, Se with increased pH could result from the adsorption of these oxyanions by HFO at low pH and desorption at near-neutral pH. Hence, the solute concentrations in CMD and the purity of associated "ochres" formed in CMD settings are expected to vary with pH and aqueous SO4 concentration, with potential for elevated SO4, As and Se in ochres formed at low pH and elevated Cu, Cd, Pb and Zn in ochres formed at near-neutral pH. Elevated SO4 content of ochres could enhance the adsorption of cations at low pH, but decrease the adsorption of anions such as As. Such information on environmental processes that control element concentrations in aqueous samples and associated precipitates could be useful in the design of systems to reduce dissolved contaminant concentrations and/or to recover potentially valuable constituents in mine effluents.

Seasonal dynamics of meltwater chemistry on the Tibetan Plateau and insights into the hydrologic and hydrochemical process coupling and sampling strategy

NASA Astrophysics Data System (ADS)

Li, X.; Ding, Y.; He, X.; Han, T.

2017-12-01

Meltwater chemistry was examined at the Dongkemadi Glacier (DG) basin on the Tibetan Plateau (TP) over a full melt season of 2013. Results showed that concentrations of most solutes (e.g. Li, B, Sc, Fe, Rb, Sr, Mo, Ba and U) (Group 1) exhibit pronounced seasonal variations, but some (e.g. NH4+, F-, Al, Cr, Mn, Co, Cu, Zn, Y, Cd, Sn, Pb, Bi and Th) (Group 2) show a random change. Concentration-discharge for Group 1 was dominated by a well-defined power law relation, with the magnitude of exponent (-0.79 to -0.24) and R2 values (p<0.001) lower on rising than falling limbs. This has important implications for efforts to estimate daily concentrations for Group 1 from glaciers where only glacial discharge is available. Although concentrations of some solutes are not related to discharge, fluxes of almost all solutes, except for NH4+, Cu, Zn, Cd, Sn, are positively correlated to discharge, exhibiting a good power law relation (0.27

Chemical evaluation of soil-solution in acid forest soils

USGS Publications Warehouse

Lawrence, G.B.; David, M.B.

1996-01-01

Soil-solution chemistry is commonly studied in forests through the use of soil lysimeters.This approach is impractical for regional survey studies, however, because lysimeter installation and operation is expensive and time consuming. To address these problems, a new technique was developed to compare soil-solution chemistry among red spruce stands in New York, Vermont, New Hampshire, Maine. Soil solutions were expelled by positive air pressure from soil that had been placed in a sealed cylinder. Before the air pressure was applied, a solution chemically similar to throughfall was added to the soil to bring it to approximate field capacity. After the solution sample was expelled, the soil was removed from the cylinder and chemically analyzed. The method was tested with homogenized Oa and Bs horizon soils collected from a red spruce stand in the Adirondack Mountains of New York, a red spruce stand in east-central Vermont, and a mixed hardwood stand in the Catskill Mountains of New York. Reproducibility, effects of varying the reaction time between adding throughfall and expelling soil solution (5-65 minutes) and effects of varying the chemical composition of added throughfall, were evaluated. In general, results showed that (i) the method was reproducible (coefficients of variation were generally < 15%), (ii) variations in the length of reaction-time did not affect expelled solution concentrations, and (iii) adding and expelling solution did not cause detectable changes in soil exchange chemistry. Concentrations of expelled solutions varied with the concentrations of added throughfall; the lower the CEC, the more sensitive expelled solution concentrations were to the chemical concentrations of added throughfall. Addition of a tracer (NaBr) showed that the expelled solution was a mixture of added solution and solution that preexisted in the soil. Comparisons of expelled solution concentrations with concentrations of soil solutions collected by zero-tension and tension lysimetry indicated that expelled solution concentrations were higher than those obtained with either type of lysimeter, although there was less difference with tension lysimeters than zero-tension lysimeters. The method used for collection of soil solution should be taken into consideration whenever soil solution data are being interpreted.

Impact of heat treatment on the physical properties of noncrystalline multisolute systems concentrated in frozen aqueous solutions.

PubMed

Izutsu, Ken-ichi; Yomota, Chikako; Kawanishi, Toru

2011-12-01

The purpose of this study was to elucidate the effect of heat treatment on the miscibility of multiple concentrated solutes that mimic biopharmaceutical formulations in frozen solutions. The first heating thermal analysis of frozen solutions containing either a low-molecular-weight saccharide (e.g., sucrose, trehalose, and glucose) or a polymer (e.g., polyvinylpyrrolidone and dextran) and their mixtures from -70°C showed a single transition at glass transition temperature of maximally freeze-concentrated solution (T(g) ') that indicated mixing of the freeze-concentrated multiple solutes. The heat treatment of single-solute and various polymer-rich mixture frozen solutions at temperatures far above their T(g) ' induced additional ice crystallization that shifted the transitions upward in the following scan. Contrarily, the heat treatment of frozen disaccharide-rich solutions induced two-step heat flow changes (T(g) ' splitting) that suggested separation of the solutes into multiple concentrated noncrystalline phases, different in the solute compositions. The extent of the T(g) ' splitting depended on the heat treatment temperature and time. Two-step glass transition was observed in some sucrose and dextran mixture solids, lyophilized after the heat treatment. Increasing mobility of solute molecules during the heat treatment should allow spatial reordering of some concentrated solute mixtures into thermodynamically favorable multiple phases. Copyright © 2011 Wiley-Liss, Inc.

A New Look at Factors Affecting Microbial Silicification: Effects of Microbe to Solution Ratio, Al and Fe on Silica Accumulation on B. subtilis Surfaces

NASA Astrophysics Data System (ADS)

Tenesch, A. C.; Hinman, N. W.; Blank, C. E.

2006-12-01

In this investigation, we aim to constrain the geochemical conditions that favor siliceous microfossil formation. This work will provide a framework for assessing the biogenic origin of putative microfossils in siliceous hydrothermal deposits on early Earth, and potentially, on Mars. Previous work on silicification of microbial cells has been done under unnatural conditions or when cells were physiological stressed. Here, we attempt to reduce the amount reduce the amount of physiological stress on the organisms and to better emulate the natural environment. Silicification experiments involving the gram-positive bacterium, Bacillus subtilis, have been conducted under different experimental conditions to provide insight into the processes that affect silicification of microorganisms. Experiments were conducted with silica stock solution at an initial pH of 8, and with and without added Al and Fe, in two different experimental designs. The first experimental design represented a silica-limited environment in which the ratio of exponentially growing culture (O.D.600 = 0.2) to silica-rich stock solution was very high (1:1 v/v). Silica concentrations declined likely due to nucleation and precipitation mediated by microbial surfaces, and the pH dropped from 8.0 to 6.5. The presence of Fe and Al resulted in lower dissolved silica concentrations, suggesting additional effects of these ions on nucleation and precipitation. The second experimental design used a lower ratio of exponentially growing culture (O.D.600 = .2) to silica-rich stock solution (0.004:1 v/v) resulting in a stable concentration of silica, which was also accompanied by a slight decline in pH. This latter design is more similar to the cell:silica ratios found in natural environments. B. subtilis cells were examined using scanning electron microscopy (SEM) accompanied by energy dispersive spectrometry (EDS). Cells exhibited silica crystallites under SEM and yet continued to undergo cell division in an environment of limited resources. Silicification in the low-ratio experiments appeared to be more efficient as cells were more encrusted with Si than cells in the high-ratio experiments. Further, sporulation was more efficient in the low-ratio experiments.

The effect of natural and anthropogenic factors on sorption of copper in chernozem

NASA Astrophysics Data System (ADS)

Bauer, Tatiana; Minkina, Tatiana; Mandzhieva, Saglara; Pinskii, David; Linnik, Vitaly; Sushkova, Svetlana

2016-04-01

The aim of this work was to study the effect of the attendant anions and particle-size distribution on the adsorption of copper by ordinary chernozem. Solutions of HM nitrates, acetates, chlorides, and sulfates were used to study the effect of the chemical composition of added copper salts on the adsorption of copper by an ordinary chernozem. Samples of the soil sieved through a 1-mm sieve in the natural ionic form and soil fraction with different particle size (clay - the particle with size < 1μm and physical clay < 10 μm) were treated with solutions of the corresponding copper salts at a soil : solution ratio of 1:10. The concentrations of the initial copper solutions were 0.02, 0.05, 0.08, 0.1, 0.3, 0.5, and 1.0 mM/L. The range of Cu2+ concentrations in the studied system covers different geochemical situations corresponding to the actual levels of soil contamination with the metal under study. The suspensions were shaken for 1 h, left to stand for 24 h, and then filtered. The contents of the HM in the filtrates were determined by atomic absorption spectrometry (AAS). The contents of the adsorbed copper cations were calculated from the difference between the metal concentrations in the initial and equilibrium solutions. The isotherms of copper adsorption from the metal nitrate, chloride, and sulfate solutions have near linear shapes and, hence, can be satisfactorily described by a Henry or Freundlich equation: Cads = KH •Ceq.(1) Cads = KF •Ceqn,(2) where Cadsis the content of the adsorbed cations, mM/kg soil;Ceq is the concentration of copper in the equilibrium solution, mM/L; KH and KF denote the Henry and Freundlich adsorption coefficients, respectively, kg/L. The isotherm of Cu2+ adsorption by ordinary chernozem from acetate solutions is described by the Langmuir equation: Cads = C∞ÊLC / (1 + ÊLC), (3) where Cadsis the content of the adsorbed cations, mM/kg soil;C∞ is the maximum adsorption of the HM, mM/kg soil; ÊL is the affinity constant, L/mM; C is the concentration of the HM in the equilibrium solution, mM/L. According to the values of KH, the binding strength of the copper cations adsorbed from different salt solutions decreases in the series: Cu(Ac)2(1880,5± 76,2) > CuCl2(1442,8±113,5) > Cu(NO3)2(911,4 ± 31,1) >> CuSO4(165,3 ± 12,9). Thus, copper is most strongly adsorbed from the acetate solution and least strongly from the sulfate solution. The adsorption of copper by clay and physical clay fractions from the ordinary chernozem was of limited character and followed the (3) equation. In the particle-size fractions separated from the soils, the concentrations of copper decreased with the decreasing particle size. The values of ÊL and C∞characterizing the HM adsorption by the chernozem and its particle-size fractions formed the following sequence: clay (80,20±20,29 and 28,45±0,46 > physical clay (58,20±14,54 and 22,15±1,22) > entire soil (38,80±12,33 and 17,58±3,038). This work was supported by the Russian Ministry of Education and Science, project no. 5.885.2014/K, Russian Foundation for Basic Research, projects no. 14-05-00586 À

Batch Fabrication of Ultrasensitive Carbon Nanotube Hydrogen Sensors with Sub-ppm Detection Limit.

PubMed

Xiao, Mengmeng; Liang, Shibo; Han, Jie; Zhong, Donglai; Liu, Jingxia; Zhang, Zhiyong; Peng, Lianmao

2018-04-27

Carbon nanotube (CNT) has been considered as an ideal channel material for building highly sensitive gas sensors. However, the reported H 2 sensors based on CNT always suffered from the low sensitivity or low production. We developed the technology to massively fabricate ultra-highly sensitive H 2 sensors based on solution derived CNT network through comprehensive optimization of the CNT material, device structure, and fabrication process. In the H 2 sensors, high semiconducting purity solution-derived CNT film sorted by poly[9-(1-octylonoyl)-9 H-carbazole-2,7-diyl](PCz) is used as the main channel, which is decorated with Pd nanoparticles as functionalization for capturing H 2 . Meanwhile, Ti contacts are used to form a Schottky barrier for enhancing transferred charge-induced resistance change, and then a response of resistance change by 3 orders of magnitude is achieved at room temperature under the concentration of ∼311 ppm with a very fast response time of approximately 7 s and a detection limit of 890 ppb, which is the highest response to date for CNT H 2 sensors and the very first time to show the sub-ppm detection for H 2 at room temperature. Furthermore, the detection limit concentration can be improved to 89 ppb at 100 °C. The batch fabrication of CNT film H 2 sensors with ultra-high sensitivity and high uniformity is ready to promote CNT devices to application for the first time in some specialized field.

Quantitative determination of insulin entrapment efficiency in triblock copolymeric nanoparticles by high-performance liquid chromatography.

PubMed

Xu, Xiongliang; Fu, Yao; Hu, Haiyan; Duan, Yourong; Zhang, Zhirong

2006-04-11

A rapid and effective isocratic chromatographic procedure was described in this paper for the determination of insulin entrapment efficiency (EE) in triblock copolymeric nanoparticles using reversed-phase high-performance liquid chromatography (RP-HPLC) with an ultraviolet/visible detector at low flow rate. The method has been developed on a Shimadzu Shim-pack VP-ODS column (150 mm x 4.6 mm, 5 microm, Chiyoda-Ku, Tokyo, Japan) using a mixture of 0.2 M sodium sulfate anhydrous solution adjusted to pH 2.3 with phosphoric acid and acetonitrile (73:27, v/v) as mobile phase at the flow rate of 0.8 ml min(-1) and a 214 nm detection. The method was validated in terms of selectivity, linearity, precision, accuracy, solution stability, limit of detection (LOD) and limit of quantification (LOQ). The calibration curve was linear in the concentration range of 2.0-500.0 microg ml(-1), and the limits of detection and quantitation were 8 and 20 ng, respectively. The mean recovery of insulin from spiked samples, in a concentration range of 8-100 microg ml(-1), was 98.96% (R.S.D.= 2.51%, n = 9). The intra- and inter-assay coefficients of variation were less than 2.24%. The proposed method has the advantages of simple pretreatment, rapid isolation, high specificity and precision, which can be used for direct analysis of insulin in commercially available raw materials, formulations of nanoparticles, and drug release as well as stability studies.

Degradation alternatives for a commercial fungicide in water: biological, photo-Fenton, and coupled biological photo-Fenton processes.

PubMed

López-Loveira, Elsa; Ariganello, Federico; Medina, María Sara; Centrón, Daniela; Candal, Roberto; Curutchet, Gustavo

2017-11-01

Imazalil (IMZ) is a widely used fungicide for the post-harvest treatment of citrus, classified as "likely to be carcinogenic in humans" for EPA, that can be only partially removed by conventional biological treatment. Consequently, specific or combined processes should be applied to prevent its release to the environment. Biological treatment with adapted microorganism consortium, photo-Fenton, and coupled biological photo-Fenton processes were tested as alternatives for the purification of water containing high concentration of the fungicide and the coadjutants present in the commercial formulation. IMZ-resistant consortium with the capacity to degrade IMZ in the presence of a C-rich co-substrate was isolated from sludge coming from a fruit packaging company wastewater treatment plant. This consortium was adapted to resist and degrade the organics present in photo-Fenton-oxidized IMZ water solution. Bacteria colonies from the consortia were isolated and identified. The effect of H 2 O 2 initial concentration and dosage on IMZ degradation rate, average oxidation state (AOS), organic acid concentration, oxidation, and mineralization percentage after photo-Fenton process was determined. The application of biological treatment to the oxidized solutions notably decreased the total organic carbon (TOC) in solution. The effect of the oxidation degree, limited by H 2 O 2 concentration and dosage, on the percentage of mineralization obtained after the biological treatment was determined and explained in terms of changes in AOS. The concentration of H 2 O 2 necessary to eliminate IMZ by photo-Fenton and to reduce TOC and chemical oxygen demand (COD) by biological treatment, in order to allow the release of the effluents to rivers with different flows, was estimated.

PhreeqcRM: A reaction module for transport simulators based on the geochemical model PHREEQC

USGS Publications Warehouse

Parkhurst, David L.; Wissmeier, Laurin

2015-01-01

PhreeqcRM is a geochemical reaction module designed specifically to perform equilibrium and kinetic reaction calculations for reactive transport simulators that use an operator-splitting approach. The basic function of the reaction module is to take component concentrations from the model cells of the transport simulator, run geochemical reactions, and return updated component concentrations to the transport simulator. If multicomponent diffusion is modeled (e.g., Nernst–Planck equation), then aqueous species concentrations can be used instead of component concentrations. The reaction capabilities are a complete implementation of the reaction capabilities of PHREEQC. In each cell, the reaction module maintains the composition of all of the reactants, which may include minerals, exchangers, surface complexers, gas phases, solid solutions, and user-defined kinetic reactants.PhreeqcRM assigns initial and boundary conditions for model cells based on standard PHREEQC input definitions (files or strings) of chemical compositions of solutions and reactants. Additional PhreeqcRM capabilities include methods to eliminate reaction calculations for inactive parts of a model domain, transfer concentrations and other model properties, and retrieve selected results. The module demonstrates good scalability for parallel processing by using multiprocessing with MPI (message passing interface) on distributed memory systems, and limited scalability using multithreading with OpenMP on shared memory systems. PhreeqcRM is written in C++, but interfaces allow methods to be called from C or Fortran. By using the PhreeqcRM reaction module, an existing multicomponent transport simulator can be extended to simulate a wide range of geochemical reactions. Results of the implementation of PhreeqcRM as the reaction engine for transport simulators PHAST and FEFLOW are shown by using an analytical solution and the reactive transport benchmark of MoMaS.

Pilot-scale field study for ammonia removal from lagoon biogas using an acid wet scrubber.

PubMed

Lin, Hongjian; Wu, Xiao; Miller, Curtis; Zhu, Jun; Hadlocon, Lara Jane; Manuzon, Roderick; Zhao, Lingying

2014-01-01

The anaerobic activities in swine slurry storage and treatment generate biogas containing gaseous ammonia component which is a chemical agent that can cause adverse environmental impacts when released to the atmosphere. The aim of this pilot plant study was to remove ammonia from biogas generated in a covered lagoon, using a sulfuric acid wet scrubber. The data showed that, on average, the biogas contained 43.7 ppm of ammonia and its concentration was found to be exponentially related to the air temperature inside the lagoon. When the air temperature rose to 35°C and the biogas ammonia concentration reached 90 ppm, the mass transfer of ammonia/ammonium from the deeper liquid body to the interface between the air and liquid became a limiting factor. The biogas velocity was critical in affecting ammonia removal efficiency of the wet scrubber. A biogas flow velocity of 8 to 12 mm s(-1) was recommended to achieve a removal efficiency of greater than 60%. Stepwise regression revealed that the biogas velocity and air temperature, not the inlet ammonia concentration in biogas, affected the ammonia removal efficiency. Overall, when 73 g L(-1) (or 0.75 M) sulfuric acid solution was used as the scrubber solution, removal efficiencies varied from 0% to 100% with an average of 55% over a 40-d measurement period. Mass balance calculation based on ammonium-nitrogen concentration in final scrubber liquid showed that about 21.3 g of ammonia was collected from a total volume of 1169 m(3) of biogas, while the scrubber solution should still maintain its ammonia absorbing ability until its concentration reaches up to 1 M. These results showed promising use of sulfuric acid wet scrubber for ammonia removal in the digester biogas.

Effect of molecular structure on the hydration of structurally related antidepressant drugs

NASA Astrophysics Data System (ADS)

Cheema, M. A.; Taboada, P.; Barbosa, S.; Siddiq, M.; Mosquera, V.

Apparent molal volumes and adiabatic compressibilities of aqueous solutions of the amphiphilic cationic antidepressant drugs butriptyline and doxepin hydrochlorides have been determined from density and ultrasound velocity measurements in the temperature range 20-50°C. Critical concentrations for aggregation of these drugs were obtained from ultrasound velocity measurements. Negative deviations from the Debye-Hückel limiting law of the apparent molal volume were obtained from both drugs in all temperature ranges, except for doxepin at 50°C, which provides evidence of no pre-association at concentrations below the critical concentration. Apparent molal adiabatic compressibilities of the aggregates formed by these drugs were typical of those corresponding for an aggregate formed by a stacking process.

A Novel Tri-Enzyme System in Combination with Laser-Driven NMR Enables Efficient Nuclear Polarization of Biomolecules in Solution

PubMed Central

Lee, Jung Ho; Cavagnero, Silvia

2013-01-01

NMR is an extremely powerful, yet insensitive technique. Many available nuclear polarization methods that address sensitivity are not directly applicable to low-concentration biomolecules in liquids and are often too invasive. Photochemically induced dynamic nuclear polarization (photo-CIDNP) is no exception. It needs high-power laser irradiation, which often leads to sample degradation, and photosensitizer reduction. Here, we introduce a novel tri-enzyme system that significantly overcomes the above challenges rendering photo-CIDNP a practically applicable technique for NMR sensitivity enhancement in solution. The specificity of the nitrate reductase (NR) enzyme is exploited to selectively in situ re-oxidize the reduced photo-CIDNP dye FMNH2. At the same time, the oxygen-scavenging ability of glucose oxidase (GO) and catalase (CAT) is synergistically employed to prevent sample photodegradation. The resulting tri-enzyme system (NR-GO-CAT) enables prolonged sensitivity-enhanced data collection in 1D and 2D heteronuclear NMR, leading to the highest photo-CIDNP sensitivity enhancement (48-fold relative to SE-HSQC) achieved to date for amino acids and polypeptides in solution. NR-GO-CAT extends the concentration limit of photo-CIDNP NMR down to the low micromolar range. In addition, sensitivity (relative to the reference SE-HSQC) is found to be inversely proportional to sample concentration, paving the way to the future analysis of even more diluted samples. PMID:23560683

Response surface modeling of boron adsorption from aqueous solution by vermiculite using different adsorption agents: Box-Behnken experimental design.

PubMed

Demirçivi, Pelin; Saygılı, Gülhayat Nasün

2017-07-01

In this study, a different method was applied for boron removal by using vermiculite as the adsorbent. Vermiculite, which was used in the experiments, was not modified with adsorption agents before boron adsorption using a separate process. Hexadecyltrimethylammonium bromide (HDTMA) and Gallic acid (GA) were used as adsorption agents for vermiculite by maintaining the solid/liquid ratio at 12.5 g/L. HDTMA/GA concentration, contact time, pH, initial boron concentration, inert electrolyte and temperature effects on boron adsorption were analyzed. A three-factor, three-level Box-Behnken design model combined with response surface method (RSM) was employed to examine and optimize process variables for boron adsorption from aqueous solution by vermiculite using HDTMA and GA. Solution pH (2-12), temperature (25-60 °C) and initial boron concentration (50-8,000 mg/L) were chosen as independent variables and coded x 1 , x 2 and x 3 at three levels (-1, 0 and 1). Analysis of variance was used to test the significance of variables and their interactions with 95% confidence limit (α = 0.05). According to the regression coefficients, a second-order empirical equation was evaluated between the adsorption capacity (q i ) and the coded variables tested (x i ). Optimum values of the variables were also evaluated for maximum boron adsorption by vermiculite-HDTMA (HDTMA-Verm) and vermiculite-GA (GA-Verm).

Longitudinal dispersion coefficients for numerical modeling of groundwater solute transport in heterogeneous formations.

PubMed

Lee, Jonghyun; Rolle, Massimo; Kitanidis, Peter K

2017-09-15

Most recent research on hydrodynamic dispersion in porous media has focused on whole-domain dispersion while other research is largely on laboratory-scale dispersion. This work focuses on the contribution of a single block in a numerical model to dispersion. Variability of fluid velocity and concentration within a block is not resolved and the combined spreading effect is approximated using resolved quantities and macroscopic parameters. This applies whether the formation is modeled as homogeneous or discretized into homogeneous blocks but the emphasis here being on the latter. The process of dispersion is typically described through the Fickian model, i.e., the dispersive flux is proportional to the gradient of the resolved concentration, commonly with the Scheidegger parameterization, which is a particular way to compute the dispersion coefficients utilizing dispersivity coefficients. Although such parameterization is by far the most commonly used in solute transport applications, its validity has been questioned. Here, our goal is to investigate the effects of heterogeneity and mass transfer limitations on block-scale longitudinal dispersion and to evaluate under which conditions the Scheidegger parameterization is valid. We compute the relaxation time or memory of the system; changes in time with periods larger than the relaxation time are gradually leading to a condition of local equilibrium under which dispersion is Fickian. The method we use requires the solution of a steady-state advection-dispersion equation, and thus is computationally efficient, and applicable to any heterogeneous hydraulic conductivity K field without requiring statistical or structural assumptions. The method was validated by comparing with other approaches such as the moment analysis and the first order perturbation method. We investigate the impact of heterogeneity, both in degree and structure, on the longitudinal dispersion coefficient and then discuss the role of local dispersion and mass transfer limitations, i.e., the exchange of mass between the permeable matrix and the low permeability inclusions. We illustrate the physical meaning of the method and we show how the block longitudinal dispersivity approaches, under certain conditions, the Scheidegger limit at large Péclet numbers. Lastly, we discuss the potential and limitations of the method to accurately describe dispersion in solute transport applications in heterogeneous aquifers. Copyright © 2017. Published by Elsevier B.V.

Stable, concentrated solutions of high molecular weight polyaniline and articles therefrom

DOEpatents

Mattes, Benjamin R.; Wang, Hsing-Lin

2000-01-01

Stable, concentrated solutions of high molecular weight polyaniline. In order to process high quality fibers and other articles possessing good mechanical properties, it is known that solution concentrations of the chosen polymer should be in the range from 15-30% (w/w). Moreover, it is desirable to use the highest molecular weight consistent with the solubility properties of the polymer. However, such solutions are inherently unstable, forming gels before processing can be achieved. The present invention describes the addition gel inhibitors (GIs) to the polymer solution, thereby permitting high concentrations (>15% (w/w)) of high molecular weight ((M.sub.w)>120,000, and (M.sub.n)>30,000) emeraldine base (EB) polyaniline to be dissolved. Secondary amines have been used for this purpose in concentrations which are small compared to those which might otherwise be used in a cosolvent role therefor. The resulting solutions are useful for generating excellent fibers, films, coatings and other objects, since the solutions are stable for significant time periods, and the GIs are present in too small concentrations to cause polymer deterioration. It is demonstrated that the GIs found to be useful do not act as cosolvents, and that gelation times of the solutions are directly proportional to the concentration of GI. In particular, there is a preferred concentration of GI, which if exceeded causes structural and electrical conductivity degradation of resulting articles. Heating of the solutions significantly improves solubility.

Long-term Stability of Vancomycin Hydrochloride in Glucose 5% Polyolefin Bags: The Brand Name Versus a Generic Product.

PubMed

Huvelle, Sophie; Godet, Marie; Hecq, Jean-Daniel; Gillet, Patricia; Jamart, Jacques; Galanti, Laurence M

2016-01-01

The objectives of this study were to determine if the preparation of vancomycin hydrochloride in advance of infusion could improve the quality of the drug, time management of drug delivery, cost savings of drug delivery, and to investigate the long-term stability of vancomycin hydrochloride (brand name Vancocin®) infusion in glucose 5% polyolefin bags versus the generic (Vancomycine®) at 5°C ± 3°C. Five bags of each infusion 1 g/100 mL vancomycin hydrochloride in 5% glucose (Vancocin ® and Vancomycine®) were stored up to 57 days at 5°C ± 3°C. A visual inspection and pH measurement were performed periodically during the storage, and the concentrations were measured by high-performance liquid chromatography-diode array detection. No color change or precipitation in the solution was observed throughout the study period. As recommended by the U.S. Food and Drug Administration, the lower confidence limit at 95% of the concentration for the solutions remained superior to 90% of the initial concentration up to 43 days for the brand vancomycin (Vancocin®) infusion (96% ± 2%) and up to 57 days for the generic (Vancomycine®) (95% ± 4%). The solutions prepared either from brand or generic vancomycin hydrochloride were chemically stable more than one month (43 days for the brand and 57 days for the generic solution) and could be prepared in advance in a centralized intravenous additive service facility. Copyright© by International Journal of Pharmaceutical Compounding, Inc.

Landfill cover soil, soil solution, and vegetation responses to municipal landfill leachate applications.

PubMed

Macdonald, Neil W; Rediske, Richard R; Scull, Brian T; Wierzbicki, David

2008-01-01

Municipal solid waste landfill leachate must be removed and treated to maintain landfill cover integrity and to prevent contamination of surface and ground waters. From 2003 to 2007, we studied an onsite disposal system in Ottawa County, Michigan, where leachate was spray irrigated on the vegetated landfill cover. We established six 20-m-diameter circular experimental plots on the landfill; three were spray irrigated as part of the operational system, and three remained as untreated control plots. We quantified the effects of leachate application on soil properties, soil solution chemistry, vegetative growth, and estimated solute leaching. The leachate had high mean levels of electrical conductivity (0.6-0.7 S m(-1)), Cl (760-900 mg L(-1)), and NH(4)-N (290-390 mg L(-1)) but was low in metals and volatile organic compounds. High rates of leachate application in 2003 (32 cm) increased soil electrical conductivity and NO(3)-N leaching, so a sequential rotation of spray areas was implemented to limit total leachate application to <9.6 cm yr(-1) per spray area. Concentrations of NO(3)-N and leaching losses remained higher on irrigated plots in subsequent years but were substantially reduced by spray area rotation. Leachate irrigation increased plant biomass but did not significantly affect soil metal concentrations, and plant metal concentrations remained within normal ranges. Rotating spray areas and timing irrigation to conform to seasonal capacities for evapotranspiration reduced the localized impacts of leachate application observed in 2003. Careful monitoring of undiluted leachate applications is required to avoid adverse impacts to vegetation or soils and elevated solute leaching losses.

Distribution and bioavailability of Cr in central Euboea, Greece

NASA Astrophysics Data System (ADS)

Megremi, Ifigeneia

2010-06-01

Plants and soils from central Euboea, were analyzed for Cr(totai), Cr(VI), Ni, Mn, Fe and Zn. The range of metal concentrations in soils is typical to those developed on Fe-Ni laterites and ultramafic rocks. Their bioavailability was expressed in terms of concentrations extractable with EDTA and 1 M HNO3, with EDTA having a limited effect on metal recovery. Cr(VI) concentrations in soils evaluated by alkaline digestion solution were lower than phytotoxic levels. Chromium and Ni — and occasionally Zn — in the majority of plants were near or above toxicity levels. Cr(VI) concentrations in plants were extremely low compared to total chromium concentrations. Cr(total) in ground waters ranged from <1 μg.L-1 to 130 μg.L-1, with almost all chromium present as Cr(VI). With the exception of Cr(total) and in some cases Zn, all elements were below regulatory limits for drinking water. On the basis of Ca, Mg, Cr(total) and Si ground waters were classified into three groups: Group(I) with Cr concentrations less than 1 μg.L-1 from a karstic aquifer; Group(II) with average concentrations of 24 μg.L-1 of Cr and relatively high Si associated with ophiolites; and Group(III) with Cr concentrations of up to 130 μg.L-1, likely due to anthropogenic activity. Group(III) is comparable to ground waters from Assopos basin, characterized by high Cr(VI) concentrations, probably due to industrial actrivities.

Comprehensive evaluation on effective leaching of critical metals from spent lithium-ion batteries.

PubMed

Gao, Wenfang; Liu, Chenming; Cao, Hongbin; Zheng, Xiaohong; Lin, Xiao; Wang, Haijuan; Zhang, Yi; Sun, Zhi

2018-05-01

Recovery of metals from spent lithium-ion batteries (LIBs) has attracted worldwide attention because of issues from both environmental impacts and resource supply. Leaching, for instance using an acidic solution, is a critical step for effective recovery of metals from spent LIBs. To achieve both high leaching efficiency and selectivity of the targeted metals, improved understanding on the interactive features of the materials and leaching solutions is highly required. However, such understanding is still limited at least caused by the variation on physiochemical properties of different leaching solutions. In this research, a comprehensive investigation and evaluation on the leaching process using acidic solutions to recycle spent LIBs is carried out. Through analyzing two important parameters, i.e. leaching speed and recovery rate of the corresponding metals, the effects of hydrogen ion concentration, acid species and concentration on these two parameters were evaluated. It was found that a leachant with organic acids may leach Co and Li from the cathode scrap and leave Al foil as metallic form with high leaching selectivity, while that with inorganic acids typically leach all metals into the solution. Inconsistency between the leaching selectivity and efficiency during spent LIBs recycling is frequently noticed. In order to achieve an optimal status with both high leaching selectivity and efficiency (especially at high solid-to-liquid ratios), it is important to manipulate the average leaching speed and recovery rate of metals to optimize the leaching conditions. Subsequently, it is found that the leaching speed is significantly dependent on the hydrogen ion concentration and the capability of releasing hydrogen ions of the acidic leachant during leaching. With this research, it is expected to improve understanding on controlling the physiochemical properties of a leaching solution and to potentially design processes for spent LIBs recycling with high industrial viability. Copyright © 2018 Elsevier Ltd. All rights reserved.

Evanescent Wave Absorption Based Fiber Sensor for Measuring Glucose Solution Concentration

NASA Astrophysics Data System (ADS)

Marzuki, Ahmad; Candra Pratiwi, Arni; Suryanti, Venty

2018-03-01

An optical fiber sensor based on evanescent wave absorption designed for measuring glucose solution consentration was proposed. The sensor was made to detect absorbance of various wavelength in the glucose solution. The sensing element was fabricated by side polishing of multimode polymer optical fiber to form a D-shape. The sensing element was immersed in different concentration of glucoce solution. As light propagated through the optical fiber, the evanescent wave interacted with the glucose solution. Light was absorbed by the glucose solution. The larger concentration the glucose solution has, the more the evanescent wave was absorbed in particular wavelenght. Here in this paper, light absorbtion as function of glucose concentration was measured as function of wavelength (the color of LED). We have shown that the proposed sensor can demonstrated an increase of light absorption as function of glucose concentration.

Diffusiophoresis in one-dimensional solute gradients

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

Ault, Jesse T.; Warren, Patrick B.; Shin, Sangwoo

Here, the diffusiophoretic motion of suspended colloidal particles under one-dimensional solute gradients is solved using numerical and analytical techniques. Similarity solutions are developed for the injection and withdrawal dynamics of particles into semi-infinite pores. Furthermore, a method of characteristics formulation of the diffusion-free particle transport model is presented and integrated to realize particle trajectories. Analytical solutions are presented for the limit of small particle diffusiophoretic mobility Γ p relative to the solute diffusivity D s for particle motions in both semi-infinite and finite domains. Results confirm the build up of local maxima and minima in the propagating particle front dynamics.more » The method of characteristics is shown to successfully predict particle motions and the position of the particle front, although it fails to accurately predict suspended particle concentrations in the vicinity of sharp gradients, such as at the particle front peak seen in some injection cases, where particle diffusion inevitably plays an important role. Results inform the design of applications in which the use of applied solute gradients can greatly enhance particle injection into and withdrawal from pores.« less

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).

An Ion-Selective Electrode for the Determination of Phencyclidine (PCP).

DTIC Science & Technology

1980-08-06

as an indicator_ ectrode in potentiometric titration of PCPA at concentrations DD 1473 EDITION or I Nov soIS OSSOOL TC SEPURqITY CLAWSFICATION Of...and ISE detection limits determined as described previous (25). The PCP electrode was used as the indicator electrode in potentiometric titrations of...was standardized by potentiometric titration with a dodecyltrimethyl- ammonium bromide (DoTAB) solution using a DoTA+ ISE (25) as the indicator

Elastic-plastic analysis of annular plate problems using NASTRAN

NASA Technical Reports Server (NTRS)

Chen, P. C. T.

1983-01-01

The plate elements of the NASTRAN code are used to analyze two annular plate problems loaded beyond the elastic limit. The first problem is an elastic-plastic annular plate loaded externally by two concentrated forces. The second problem is stressed radially by uniform internal pressure for which an exact analytical solution is available. A comparison of the two approaches together with an assessment of the NASTRAN code is given.

Eliminating Size-Associated Diffusion Constraints for Rapid On-Surface Bioassays with Nanoparticle Probes.

PubMed

Li, Junwei; Zrazhevskiy, Pavel; Gao, Xiaohu

2016-02-24

Nanoparticle probes enable implementation of advanced on-surface assay formats, but impose often underappreciated size-associated constraints, in particular on assay kinetics and sensitivity. The present study highlights substantially slower diffusion-limited assay kinetics due to the rapid development of a nanoprobe depletion layer next to the surface, which static incubation and mixing of bulk solution employed in conventional assay setups often fail to disrupt. In contrast, cyclic solution draining and replenishing yields reaction-limited assay kinetics irrespective of the probe size. Using common surface bioassays, enzyme-linked immunosorbent assays and immunofluorescence, this study shows that this conceptually distinct approach effectively "erases" size-dependent diffusion constraints, providing a straightforward route to rapid on-surface bioassays employing bulky probes and procedures involving multiple labeling cycles, such as multicycle single-cell molecular profiling. For proof-of-concept, the study demonstrates that the assay time can be shortened from hours to minutes with the same probe concentration and, at a typical incubation time, comparable target labeling can be achieved with up to eight times lower nanoprobe concentration. The findings are expected to enable realization of novel assay formats and stimulate development of rapid on-surface bioassays with nanoparticle probes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of Nanoparticles and Colloids in Aquatic Systems 1. Small Angle Neutron Scattering Investigations of Suwannee River Fulvic Acid Aggregates in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Diallo, Mamadou S.; Glinka, Charles J.; Goddard, William A.; Johnson, James H.

2005-10-01

Fulvic acids (FA) and humic acids (HA) constitute 30-50% of dissolved organic matter in natural aquatic systems. In aqueous solutions, a commonly accepted view is that FA and HA exist as soluble macroligands at low concentration and as supramolecular aggregates at higher concentration. The size, shape and structure of these aggregates are still the subject of ongoing debate in the environmental chemistry literature. In this article, we use small angle neutron scattering (SANS) to assess the effects of solute concentration, solution pH and background electrolyte (NaCl) concentration on the structures of Suwannee River FA (SRFA) aggregates in D2O. The qualitative features of the SANS curves and data analysis are not consistent with the view point that SRFA forms micelle-like aggregates as its concentration in aqueous solution increases. We find that SRFA forms fractal aggregates in D20 with size greater than 242 nm. The SRFA aggregates undergo a significant degree of restructuring in compactness as solution pH, solute concentration and NaCl concentration increase.

Convective flow effects on protein crystal growth

NASA Technical Reports Server (NTRS)

Rosenberger, Franz; Monaco, Lisa A.

1994-01-01

A high-resolution microscopic interferometric setup for the monitoring of protein morphologies has been developed. Growth or dissolution of a crystal can be resolved with a long-term depth resolution of 200 A and a lateral resolution of 2 microns. This capability of simultaneously monitoring the interfacial displacement with high local depth resolution has yielded several novel results. We have found with lysozyme that (1) the normal growth rate is oscillatory, and (2) depending on the impurity content of the solution, the growth step density is either greater or lower at the periphery of a facet than in its center. The repartitioning of Na plus and Cl minus ions between lysozyme solutions and crystals was studied for a wide range of crystallization conditions. A nucleation-growth-repartitioning model was developed, to interpret the large body of data in unified way. The results strongly suggest that (1) the ion to lysozyne ratio in the crystal depends mostly on kinetic rather than crystallographic parameters, and (2) lysozyme crystals possess a salt-rich core with a diameter electron microscopy results appear to confirm this finding, which could have far-reaching consequences for x-ray diffraction studies. A computational model for diffusive-convective transport in protein crystallization has been applied to a realistic growth cell geometry, taking into account the findings of the above repartitioning studies and our kinetics data for the growth of lysozyme. The results show that even in the small cell employed, protein concentration nonuniformities and gravity-driven solutal convection can be significant. The calculated convection velocities are of the same order to magnitude as those found in earlier experiments. As expected, convective transport, i.e., at Og, lysozyme crystal growth remains kinetically limited. The salt distribution in the crystal is predicted to be non-uniform at both 1g and 0g, as a consequence of protein depletion in the solution. Static and dynamic light scattering studies in undersaturated and supersaturated solutions have been performed. Diffusivities in undersaturated solutions, were found to vary with lysozyme concentrations. Depending on the salt concentration, the diffusivities either increase or decrease. Interestingly, the corresponding static scattering intensities behave oppositely, Our current analysis indicates that these changes are inconsistent with aggregation in undersaturated solutions. However, the data are compatible with concentration-dependent changes of the interactions between protein and salt.

Determination of Aluminum in Dialysis Concentrates by Atomic Absorption Spectrometry after Coprecipitation with Lanthanum Phosphate.

PubMed

Selvi, Emine Kılıçkaya; Şahin, Uğur; Şahan, Serkan

2017-01-01

This method was developed for the determination of trace amounts of aluminum(III) in dialysis concentrates using atomic absorption spectrometry after coprecipitation with lanthanum phosphate. The analytical parameters that influenced the quantitative coprecipitation of analyte including amount of lanthanum, amount of phosfate, pH and duration time were optimized. The % recoveries of the analyte ion were in the range of 95-105 % with limit of detection (3s) of 0.5 µg l -1 . Preconcentration factor was found as 1000 and Relative Standard Deviation (RSD) % value obtained from model solutions was 2.5% for 0.02 mg L -1 . The accuracy of the method was evaluated with standard reference material (CWW-TMD Waste Water). The method was also applied to most concentrated acidic and basic dialysis concentrates with satisfactory results.

Selection of forward osmosis draw solutes for subsequent integration with anaerobic treatment to facilitate resource recovery from wastewater.

PubMed

Ansari, Ashley J; Hai, Faisal I; Guo, Wenshan; Ngo, Hao H; Price, William E; Nghiem, Long D

2015-09-01

Forward osmosis (FO) can be used to extract clean water and pre-concentrate municipal wastewater to make it amenable to anaerobic treatment. A protocol was developed to assess the suitability of FO draw solutes for pre-concentrating wastewater for potential integration with anaerobic treatment to facilitate resource recovery from wastewater. Draw solutes were evaluated in terms of their ability to induce osmotic pressure, water flux, and reverse solute flux. The compatibility of each draw solute with subsequent anaerobic treatment was assessed by biomethane potential analysis. The effect of each draw solute (at concentrations corresponding to the reverse solute flux at ten-fold pre-concentration of wastewater) on methane production was also evaluated. The results show that ionic organic draw solutes (e.g., sodium acetate) were most suitable for FO application and subsequent anaerobic treatment. On the other hand, the reverse solute flux of inorganic draw solutions could inhibit methane production from FO pre-concentrated wastewater. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

[Computer modeling the hydrostatic pressure characteristics of the membrane potential for polymeric membrane, separated non-homogeneous electrolyte solutions].

PubMed

Slezak, Izabella H; Jasik-Slezak, Jolanta; Rogal, Mirosława; Slezak, Andrzej

2006-01-01

On the basis of model equation depending the membrane potential deltapsis, on mechanical pressure difference (deltaP), concentration polarization coefficient (zetas), concentration Rayleigh number (RC) and ratio concentration of solutions separated by membrane (Ch/Cl), the characteristics deltapsis = f(deltaP)zetas,RC,Ch/Cl for steady values of zetas, RC and Ch/Cl in single-membrane system were calculated. In this system neutral and isotropic polymeric membrane oriented in horizontal plane, the non-homogeneous binary electrolytic solutions of various concentrations were separated. Nonhomogeneity of solutions is results from creations of the concentration boundary layers on both sides of the membrane. Calculations were made for the case where on a one side of the membrane aqueous solution of NaCl at steady concentration 10(-3) mol x l(-1) (Cl) was placed and on the other aqueous solutions of NaCl at concentrations from 10(-3) mol x l(-1) to 2 x 10(-2) mol x l(-1) (Ch). Their densities were greater than NaCl solution's at 10(-3) mol x l(-1). It was shown that membrane potential depends on hydrodynamic state of a complex concentration boundary layer-membrane-concentration boundary layer, what is controlled by deltaP, Ch/Cl, RC and zetas.

Quality by design in formulation and process development for a freeze-dried, small molecule parenteral product: a case study.

PubMed

Mockus, Linas N; Paul, Timothy W; Pease, Nathan A; Harper, Nancy J; Basu, Prabir K; Oslos, Elizabeth A; Sacha, Gregory A; Kuu, Wei Y; Hardwick, Lisa M; Karty, Jacquelyn J; Pikal, Michael J; Hee, Eun; Khan, Mansoor A; Nail, Steven L

2011-01-01

A case study has been developed to illustrate one way of incorporating a Quality by Design approach into formulation and process development for a small molecule, freeze-dried parenteral product. Sodium ethacrynate was chosen as the model compound. Principal degradation products of sodium ethacrynate result from hydrolysis of the unsaturated ketone in aqueous solution, and dimer formation from a Diels-Alder condensation in the freeze-dried solid state. When the drug crystallizes in a frozen solution, the eutectic melting temperature is above -5°C. Crystallization in the frozen system is affected by pH in the range of pH 6-8 and buffer concentration in the range of 5-50 mM, where higher pH and lower buffer concentration favor crystallization. Physical state of the drug is critical to solid state stability, given the relative instability of amorphous drug. Stability was shown to vary considerably over the ranges of pH and buffer concentration examined, and vial-to-vial variability in degree of crystallinity is a potential concern. The formulation design space was constructed in terms of pH and drug concentration, and assuming a constant 5 mM concentration of buffer. The process design space is constructed to take into account limitations on the process imposed by the product and by equipment capability.

Effects of artificial enclosure of young lettuce leaves on tipburn incidence and leaf calcium concentration

NASA Technical Reports Server (NTRS)

Barta, D. J.; Tibbitts, T. W.

1986-01-01

The young developing leaves of 20-day-old lettuce plants (Lactuca sativa L. 'Buttercrunch') were enclosed by aluminized polyethylene sheaths to decrease transpiration and reduce Ca transport. The plants were grown in recirculating solution culture system using a modified half-strength Hoagland's solution under cool-white fluorescent lamps with a photosynthetic photon flux of 350 micromoles s-1 m-2 in a 16:8-hr (light:dark) period. Air temperature and humidity were 20 degrees C and 65%, respectively. After 4 days of enclosure, 53% of the inner leavers (leaves one to 3 cm in length) were tipburned. After the same period, less than 1% of the inner leaves on control plants were tipburned. The concentration of Ca in enclosed inner leaves was 0.63 mg g-1 dry weight, compared to 1.48 mg g-1 dry weight in inner leaves that were not enclosed. The Ca concentration in transpiring outer leaves of all plants was 9.9 mg g-1 dry weight. The Mg concentration in enclosed inner leaves was 2.25 mg g-1 dry weight, compared to 2.34 mg g-1 dry weight in inner leaves that were not enclosed. This research documents that enclosures of leaves at the growing point, as would occur with normal head development, is sufficient to create a limiting concentration of Ca in the enclosed tissue and encourage tipburn development.

Rapid and high-precision measurement of sulfur isotope and sulfur concentration in sediment pore water by multi-collector inductively coupled plasma mass spectrometry.

PubMed

Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

2015-01-01

We have developed a technique for the rapid, precise and accurate determination of sulfur isotopes (δ(34)S) by MC-ICP-MS applicable to a range of sulfur-bearing solutions of different sulfur content. The 10 ppm Alfa-S solution (ammonium sulfate solution, working standard of the lab of the authors) was used to bracket other Alfa-S solutions of different concentrations and the measured δ(34)SV-CDT values of Alfa-S solutions deviate from the reference value to varying degrees (concentration effect). The stability of concentration effect has been verified and a correction curve has been constructed based on Alfa-S solutions to correct measured δ(34)SV-CDT values. The curve has been applied to AS solutions (dissolved ammonium sulfate from the lab of the authors) and pore water samples successfully, validating the reliability of our analytical method. This method also enables us to measure the sulfur concentration simultaneously when analyzing the sulfur isotope composition. There is a strong linear correlation (R(2)>0.999) between the sulfur concentrations and the intensity ratios of samples and the standard. We have constructed a regression curve based on Alfa-S solutions and this curve has been successfully used to determine sulfur concentrations of AS solutions and pore water samples. The analytical technique presented here enable rapid, precise and accurate S isotope measurement for a wide range of sulfur-bearing solutions - in particular for pore water samples with complex matrix and varying sulfur concentrations. Also, simultaneous measurement of sulfur concentrations is available. Copyright © 2014 Elsevier B.V. All rights reserved.

Polymer optical fiber grating as water activity sensor

NASA Astrophysics Data System (ADS)

Zhang, Wei; Webb, David J.

2014-05-01

Controlling the water content within a product has long been required in the chemical processing, agriculture, food storage, paper manufacturing, semiconductor, pharmaceutical and fuel industries. The limitations of water content measurement as an indicator of safety and quality are attributed to differences in the strength with which water associates with other components in the product. Water activity indicates how tightly water is "bound," structurally or chemically, in products. Water absorption introduces changes in the volume and refractive index of poly(methyl methacrylate) PMMA. Therefore for a grating made in PMMA based optical fiber, its wavelength is an indicator of water absorption and PMMA thus can be used as a water activity sensor. In this work we have investigated the performance of a PMMA based optical fiber grating as a water activity sensor in sugar solution, saline solution and Jet A-1 aviation fuel. Samples of sugar solution with sugar concentration from 0 to 8%, saline solution with concentration from 0 to 22%, and dried (10ppm), ambient (39ppm) and wet (68ppm) aviation fuels were used in experiments. The corresponding water activities are measured as 1.0 to 0.99 for sugar solution, 1.0 to 0.86 for saline solution, and 0.15, 0.57 and 1.0 for the aviation fuel samples. The water content in the measured samples ranges from 100% (pure water) to 10 ppm (dried aviation fuel). The PMMA based optical fiber grating exhibits good sensitivity and consistent response, and Bragg wavelength shifts as large as 3.4 nm when the sensor is transferred from dry fuel to wet fuel.

Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-09-12

Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 inmore » 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.« less

High sensitivity pyrogen testing in water and dialysis solutions.

PubMed

Daneshian, Mardas; Wendel, Albrecht; Hartung, Thomas; von Aulock, Sonja

2008-07-20

The dialysis patient is confronted with hundreds of litres of dialysis solution per week, which pass the natural protective barriers of the body and are brought into contact with the tissue directly in the case of peritoneal dialysis or indirectly in the case of renal dialysis (hemodialysis). The components can be tested for living specimens or dead pyrogenic (fever-inducing) contaminations. The former is usually detected by cultivation and the latter by the endotoxin-specific Limulus Amoebocyte Lysate Assay (LAL). However, the LAL assay does not reflect the response of the human immune system to the wide variety of possible pyrogenic contaminations in dialysis fluids. Furthermore, the test is limited in its sensitivity to detect extremely low concentrations of pyrogens, which in their sum result in chronic pathologies in dialysis patients. The In vitro Pyrogen Test (IPT) employs human whole blood to detect the spectrum of pyrogens to which humans respond by measuring the release of the endogenous fever mediator interleukin-1beta. Spike recovery checks exclude interference. The test has been validated in an international study for pyrogen detection in injectable solutions. In this study we adapted the IPT to the testing of dialysis solutions. Preincubation of 50 ml spiked samples with albumin-coated microspheres enhanced the sensitivity of the assay to detect contaminations down to 0.1 pg/ml LPS or 0.001 EU/ml in water or saline and allowed pyrogen detection in dialysis concentrates or final working solutions. This method offers high sensitivity detection of human-relevant pyrogens in dialysis solutions and components.

The kinetics of competitive antagonists on guinea-pig ileum.

PubMed Central

Roberts, F; Stephenson, R P

1976-01-01

1 The kinetics of action of some competitive muscarinic and histamine antagonists were examined on guinea-pig isolated ileum and their behaviour compared with the predictions of the interaction-limited model described by Paton (1961). 2 The kinetics of antagonism were not consistent with the predictions of this model: (1) The apparent dissociation rate constant calculated from the decrease in occupancy on washout was not independent of the concentration of antagonist. (2) The dissociation rate constant of a 'slow' antagonist calculated from the change in occupancy when a 'fast' antagonist was superimposed varied with the concentration of fast antagonist. (3) If the concentration of slow antagonist was increased when the fast antagonist was superimposed so that the equilibrium occupancy of the 'slow' was the same as before, a transitional phase was observed. 3 The kinetics of antagonism were observed in longitudinal muscle strips and intact pieces of ileum, bathed in Tyrode or Krebs solution, and with isometric and isotonic recording. No evidence was found that the discrepancies between the interaction-limited model and the observed kinetics could be accounted for by the experimental method used. 4 It is therefore concluded that either access is rate-limiting in these circumstances or, if interaction is rate-limiting, some alternative interaction-limited model is required to describe the kinetics of antagonism. In either case it would seem unwise at this time to calculate antagonist-receptor rate constants from the observed kinetics of antagonism. PMID:974378

[Computer modeling the dependences of the membrane potential for polymeric membrane separated non-homogeneous electrolyte solutions on concentration Rayleigh number].

PubMed

Slezak, Izabella H; Jasik-Slezak, Jolanta; Bilewicz-Wyrozumska, Teresa; Slezak, Andrzej

2006-01-01

On the basis of model equation describing the membrane potential delta psi(s) on concentration Rayleigh number (R(C)), mechanical pressure difference (deltaP), concentration polarization coefficient (zeta s) and ratio concentration of solutions separated by membrane (Ch/Cl), the characteristics delta psi(s) = f(Rc)(delta P, zeta s, Ch/Cl) for steady values of zeta s, R(C) and Ch/Cl in single-membrane system were calculated. In this system neutral and isotropic polymeric membrane oriented in horizontal plane, the non-homogeneous binary electrolytic solutions of various concentrations were separated. Nonhomogeneity of solutions is results from creations of the concentration boundary layers on both sides of the membrane. Calculations were made for the case where on a one side of the membrane aqueous solution of NaCl at steady concentration 10(-3) mol x l(-1) (Cl) was placed and on the other aqueous solutions of NaCl at concentrations from 10(-3) mol x l(-1) to 2 x 10(-2) mol x l(-1) (Ch). Their densities were greater than NaCl solution's at 10(-3) mol x l(-1). It was shown that membrane potential depends on hydrodynamic state of a complex concentration boundary layer-membrane-concentration boundary layer, what is controlled by deltaP, Ch/Cl, Rc and Zeta(s).

Stability of nitroglycerin in intravenous admixtures.

PubMed

Klamerus, K J; Ueda, C T; Newton, D W

1984-02-01

The stability of nitroglycerin in intravenous admixtures was studied. Admixtures containing nitroglycerin 400 micrograms/ml and each of seven injectable drugs in concentrations used clinically were prepared in triplicate in 5% dextrose and 0.9% sodium chloride injections. Admixtures were stored in glass bottles at room temperature for 24 hours in the upright position and then for 24 hours in the inverted position to ensure contact of the solution with the rubber stopper of the container. At 0, 24, and 48 hours, samples of each admixture were assayed by high-performance liquid chromatography for nitroglycerin concentration. The pH of one randomly chosen bottle of each admixture was measured at 0, 24, and 48 hours. A significant loss of nitroglycerin potency at 48 hours was observed only in admixtures containing phenytoin; in these solutions, a 9% decrease in initial nitroglycerin concentration was noted. Phenytoin crystallization was present in all phenytoin admixtures by 24 hours. Compared with initial values, no significant differences in the pH values of any admixture samples assayed at 24 and 48 hours were noted; however, admixtures containing phenytoin had the most alkaline pH values. Under the conditions studied, nitroglycerin concentrations remained above 90% of their initial values for 48 hours in all tested admixtures; however, phenytoin crystallization limits the stability of phenytoin admixtures.

Electrochemical probing of high-level radioactive waste tanks containing washed sludge and precipitates

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

Bickford, D.F.; Congdon, J.W.; Oblath, S.B.

1986-12-01

At the US Department of Energy's Savannah River Plant, corrosion of carbon steel storage tanks containing alkaline, high-level radioactive waste is controlled by specification of limits on waste composition and temperature. Processes for the preparation of waste for final disposal will result in waste with low corrosion inhibitor concentrations and, in some cases, high aromatic organic concentrations, neither of which are characteristic of previous operations. Laboratory tests, conducted to determine minimum corrosion inhibitor levels indicated pitting of carbon steel near the waterline for proposed storage conditions. In situ electrochemical measurements of full-scale radioactive process demonstrations have been conducted to assessmore » the validity of laboratory tests. Probes included pH, Eh (potential relative to a standard hydrogen electrode), tank potential, and alloy coupons. In situ results are compared to those of the laboratory tests, with particular regard given to simulated solution composition. Transition metal hydroxide sludge contains strong passivating species for carbon steel. Washed precipitate contains organic species that lower solution pH and tend to reduce passivating films, requiring higher inhibitor concentrations than the 0.01 molar nitrite required for reactor fuel reprocessing wastes. Periodic agitation, to keep the organic phase suspended, or cathodic protection are possible alternatives to higher nitrite inhibitor concentrations.« less

Porous structures of polymer films prepared by spin coating with mixed solvents under humid condition.

PubMed

Park, Min Soo; Joo, Wonchul; Kim, Jin Kon

2006-05-09

We investigate the effects of interfacial energy between water and solvent as well as polymer concentration on the formation of porous structures of polymer films prepared by spin coating of cellulose acetate butyrate (CAB) in mixed solvent of tetrahydrofuran (THF) and chloroform under humid condition. The interfacial energy between water and the solvent was gradually changed by the addition of chloroform to the solvent. At a high polymer concentration (0.15 g/cm3 in THF), porous structures were limited only at the top surfaces of CAB films, regardless of interfacial energies, due to the high viscosity of the solution. At a medium concentration (approximately 0.08 g/cm3 in THF), CAB film had relatively uniform pores at the top surface and very small pores inside the film because of the mixing of the water droplets with THF solution. When chloroform was added to THF, pores at the inner CAB film had a comparable size with those at the top surface because of the reduced degree of the mixing between the water droplets and the mixed solvent. A further decrease in polymer concentration (0.05 g/cm3 in THF) caused the final films to have a two-layer porous structure, and the size of pores at each layer was almost the same.

Attractive interactions between reverse aggregates and phase separation in concentrated malonamide extractant solutions

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

Erlinger, C.; Belloni, L.; Zemb, T.

1999-03-30

Using small angle X-ray scattering, conductivity, and phase behavior determination, the authors show that concentrated solutions of malonamide extractants, dimethyldibutyltetradecylmalonamide (DMDBTDMA), are organized in reverse oligomeric aggregates which have many features in common with reverse micelles. The aggregation numbers of these reverse globular aggregates as well as their interaction potential are determined from absolute scattering curves. An attractive interaction is responsible for the demixing of the oil phase when in equilibrium with excess oil. Prediction of conductivity as well as the formation conditions for the third phase is possible using standard liquid theory applied to the extractant aggregates. The interactions,more » modeled with the sticky sphere model proposed by Baster, are shown to be due to steric interactions resulting from the hydrophobic tails of the extractant molecule and van der Waals forces between the highly polarizable water core of the reverse micelles. The attractive interaction in the oil phase, equilibrated with water, is determined as a function of temperature, extractant molecule concentration, and proton and neodynium(III) cation concentration. It is shown that van der Waals interactions, with an effective Hamaker constant of 3kT, quantitatively explain the behavior of DMDBTDMA in n-dodecane in terms of scattering as well as phase stability limits.« less

Transdermal gelation of methacrylated macromers with near-infrared light and gold nanorods

NASA Astrophysics Data System (ADS)

Gramlich, William M.; Holloway, Julianne L.; Rai, Reena; Burdick, Jason A.

2014-01-01

Injectable hydrogels provide locally controlled tissue bulking and a means to deliver drugs and cells to the body. The formation of hydrogels in vivo may involve the delivery of two solutions that spontaneously crosslink when mixed, with pH or temperature changes, or with light (e.g., visible or ultraviolet). With these approaches, control over the kinetics of gelation, introduction of the initiation trigger (e.g., limited penetration of ultraviolet light through tissues), or alteration of the material physical properties (e.g., mechanics) may be difficult to achieve. To overcome these limitations, we used the interaction of near-infrared (NIR) light with gold nanorods (AuNRs) to generate heat through the photothermal effect. NIR light penetrates tissues to a greater extent than other wavelengths and provides a means to indirectly initiate radical polymerization. Specifically, this heating coupled with a thermal initiator (VA-044) produced radicals that polymerized methacrylated hyaluronic acid (MeHA) and generated hydrogels. A range of VA-044 concentrations changed the gelation time, yielding a system stable at 37 ° C for 22 min that gels quickly (˜3 min) when heated to 55 ° C. With a constant irradiation time (10 min) and laser power (0.3 W), different VA-044 and AuNR concentrations tuned the compressive modulus of the hydrogel. By changing the NIR irradiation time we attained a wide range of moduli at a set solution composition. In vivo mouse studies confirmed that NIR laser irradiation through tissue could gel an injected precursor solution transdermally.

Coupled metal partitioning dynamics and toxicodynamics at biointerfaces: a theory beyond the biotic ligand model framework.

PubMed

Duval, Jérôme F L

2016-04-14

A mechanistic understanding of the processes governing metal toxicity to microorganisms (bacteria, algae) calls for an adequate formulation of metal partitioning at biointerfaces during cell exposure. This includes the account of metal transport dynamics from bulk solution to biomembrane and the kinetics of metal internalisation, both potentially controlling the intracellular and surface metal fractions that originate cell growth inhibition. A theoretical rationale is developed here for such coupled toxicodynamics and interfacial metal partitioning dynamics under non-complexing medium conditions with integration of the defining cell electrostatic properties. The formalism explicitly considers intertwined metal adsorption at the biointerface, intracellular metal excretion, cell growth and metal depletion from bulk solution. The theory is derived under relevant steady-state metal transport conditions on the basis of coupled Nernst-Planck equation and continuous logistic equation modified to include metal-induced cell growth inhibition and cell size changes. Computational examples are discussed to identify limitations of the classical Biotic Ligand Model (BLM) in evaluating metal toxicity over time. In particular, BLM is shown to severely underestimate metal toxicity depending on cell exposure time, metal internalisation kinetics, cell surface electrostatics and initial cell density. Analytical expressions are provided for the interfacial metal concentration profiles in the limit where cell-growth is completely inhibited. A rigorous relationship between time-dependent cell density and metal concentrations at the biosurface and in bulk solution is further provided, which unifies previous equations formulated by Best and Duval under constant cell density and cell size conditions. The theory is sufficiently flexible to adapt to toxicity scenarios with involved cell survival-death processes.

Concentration Dependence of Solution Shear Viscosity and Solute Mass Diffusivity in Crystal Growth from Solutions

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.

1995-01-01

The physical properties of a supersaturated binary solution such as its density rho, shear viscosity eta, and solute mass diffusivity D are dependent on the solute concentration c: rho = rho(c), eta = eta(c), and D = D(c). The diffusion boundary layer equations related to crystal growth from solution are derived for the case of natural convection with a solution density, a shear viscosity, and a solute diffusivity that are all depen- dent on solute concentration. The solution of these equations has demonstrated the following. (1) At the vicinity of the saturation concentration c(sub s) the solution shear viscosity eta depends on rho as eta(sub s) = eta(rho(sub s))varies as square root of rho(c(sub s)). This theoretically derived result has been verified in experiments with several aqueous solutions of inorganic and organic salts. (2) The maximum solute mass transfer towards the growing crystal surface can be achieved for values of c where the ratio of d ln(D(c)/dc) to d ln(eta(c)/dc) is a maximum.

Structure-activity relationship for hydrophobic salts as viscosity-lowering excipients for concentrated solutions of monoclonal antibodies.

PubMed

Guo, Zheng; Chen, Alvin; Nassar, Roger A; Helk, Bernhard; Mueller, Claudia; Tang, Yu; Gupta, Kapil; Klibanov, Alexander M

2012-11-01

To discover, elucidate the structure-activity relationship (SAR), and explore the mechanism of action of excipients able to drastically lower the viscosities of concentrated aqueous solutions of humanized monoclonal antibodies (MAbs). Salts prepared from hydrophobic cations and anions were dissolved into humanized MAbs solutions. Viscosities of the resulting solutions were measured as a function of the nature and concentration of the salts and MAbs. Even at moderate concentrations, some of the salts prepared herein were found to reduce over 10-fold the viscosities of concentrated aqueous solutions of several MAbs at room temperature. To be potent viscosity-lowering excipients, the ionic constituents of the salts must be hydrophobic, bulky, and aliphatic. A mechanistic hypothesis explaining the observed salt effects on MAb solutions' viscosities was proposed and verified.

Changes in apple liquid phase concentration throughout equilibrium in osmotic dehydration.

PubMed

Barat, J M; Barrera, C; Frías, J M; Fito, P

2007-03-01

Previous results on apple tissue equilibration during osmotic dehydration showed that, at very long processing times, the solute concentrations of the fruit liquid phase and the osmotic solution were the same. In the present study, changes in apple liquid phase composition throughout equilibrium in osmotic dehydration were analyzed and modeled. Results showed that, by the time osmosed samples reached the maximum weight and volume loss, solute concentration of the fruit liquid phase was higher than that of the osmotic solution. The reported overconcentration could be explained in terms of the apple structure shrinkage that occurred during the osmotic dehydration with highly concentrated osmotic solutions due to the elastic response of the food structure to the loss of water and intake of solutes. The fruit liquid phase overconcentration rate was observed to depend on the concentration of the osmotic solution, the processing temperature, the sample size, and shape of the cellular tissue.

Metal carbonyl vapor generation coupled with dielectric barrier discharge to avoid plasma quench for optical emission spectrometry.

PubMed

Cai, Yi; Li, Shao-Hua; Dou, Shuai; Yu, Yong-Liang; Wang, Jian-Hua

2015-01-20

The scope of dielectric barrier discharge (DBD) microplasma as a radiation source for optical emission spectrometry (OES) is extended by nickel carbonyl vapor generation. We proved that metal carbonyl completely avoids the extinguishing of plasma, and it is much more suitable for matching the DBD excitation and OES detection with respect to significant DBD quenching by concomitant hydrogen when hydride generation is used. A concentric quartz UV reactor allows sample solution to flow through the central channel wherein to efficiently receive the uniformly distributed UV irradiation in the confined cylindrical space between the concentric tubes, which facilitates effective carbonyl generation in a nickel solution. The carbonyl is transferred into the DBD excitation chamber by an argon stream for nickel excitation, and the characteristic emission of nickel at 232.0 nm is detected by a charge-coupled device (CCD) spectrometer. A 1.0 mL sample solution results in a linear range of 5-100 μg L(-1) along with a detection limit of 1.3 μg L(-1) and a precision of 2.4% RSD at 50 μg L(-1). The present DBD-OES system is validated by nickel in certified reference materials.

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.

General solutions for the oxidation kinetics of polymers

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

Gillen, K.T.; Clough, R.L.; Wise, J.

1996-08-01

The simplest general kinetic schemes applicable to the oxidation of polymers are presented, discussed and analyzed in terms of the underlying kinetic assumptions. For the classic basic autoxidation scheme (BAS), which involves three bimolecular termination steps and is applicable mainly to unstabilized polymers, typical assumptions used singly or in groups include (1) long kinetic chain length, (2) a specific ratio of the termination rate constants and (3) insensitivity to the oxygen concentration (e.g., domination by a single termination step). Steady-state solutions for the rate of oxidation are given in terms of one, two, three, or four parameters, corresponding respectively tomore » three, two, one, or zero kinetic assumptions. The recently derived four-parameter solution predicts conditions yielding unusual dependencies of the oxidation rate on oxygen concentration and on initiation rate, as well as conditions leading to some unusual diffusion-limited oxidation profile shapes. For stabilized polymers, unimolecular termination schemes are typically more appropriate than bimolecular. Kinetics incorporating unimolecular termination reactions are shown to result in very simple oxidation expressions which have been experimentally verified for both radiation-initiated oxidation of an EPDM and thermoxidative degradation of nitrile and chloroprene elastomers.« less

On the Debye-Hückel effect of electric screening

NASA Astrophysics Data System (ADS)

Campos, L. M. B. C.; Lau, F. J. P.

2014-07-01

The paper considers non-linear self-consistent electric potential equation (Sec. I), due to a cloud made of a single species of electric charges, satisfying a Boltzmann distribution law (Sec. II). Exact solutions are obtained in a simple logarithmic form, in three cases: (Sec. III) spherical radial symmetry; (Sec. IV) plane parallel symmetry; (Sec. V) a special case of azimuthal-cylindrical symmetry. All these solutions, and their transformations (Sec. VI), involve the Debye-Hückel radius; the latter was originally defined from a solution of the linearized self-consistent potential equation. Using an exact solution of the self-consistent potential equation, the distance at which the potential vanishes differs from the Debye-Hückel radius by a factor of √2 . The preceding (Secs. II-VI) simple logarithmic exact solutions of the self-consistent potential equations involve no arbitrary constants, and thus are special or singular integrals not the general integral. The general solution of the self-consistent potential equation is obtained in the plane parallel case (Sec. VII), and it involves two arbitrary constants that can be reduced to one via a translation (Sec. VIII). The plots of dimensionless potential (Figure 1), electric field (Figure 2), charge density (Figure 3), and total charge between ζ and infinity (Figure 4), versus distance normalized to Debye-Hückel radius ζ ≡ z/a, show that (Sec. IX) there is a continuum of solutions, ranging from a charge distribution concentrated inside the Debye-Hückel radius to one spread-out beyond it. The latter case leads to the limiting case of logarithmic potential, and stronger electric field; the former case, of very concentrated charge distribution, leads to a fratricide effect and weaker electric field.

On the Debye–Hückel effect of electric screening

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

Campos, L. M. B. C.; Lau, F. J. P.

2014-07-15

The paper considers non-linear self-consistent electric potential equation (Sec. I), due to a cloud made of a single species of electric charges, satisfying a Boltzmann distribution law (Sec. II). Exact solutions are obtained in a simple logarithmic form, in three cases: (Sec. III) spherical radial symmetry; (Sec. IV) plane parallel symmetry; (Sec. V) a special case of azimuthal-cylindrical symmetry. All these solutions, and their transformations (Sec. VI), involve the Debye-Hückel radius; the latter was originally defined from a solution of the linearized self-consistent potential equation. Using an exact solution of the self-consistent potential equation, the distance at which the potentialmore » vanishes differs from the Debye-Hückel radius by a factor of √(2). The preceding (Secs. II–VI) simple logarithmic exact solutions of the self-consistent potential equations involve no arbitrary constants, and thus are special or singular integrals not the general integral. The general solution of the self-consistent potential equation is obtained in the plane parallel case (Sec. VII), and it involves two arbitrary constants that can be reduced to one via a translation (Sec. VIII). The plots of dimensionless potential (Figure 1), electric field (Figure 2), charge density (Figure 3), and total charge between ζ and infinity (Figure 4), versus distance normalized to Debye-Hückel radius ζ ≡ z/a, show that (Sec. IX) there is a continuum of solutions, ranging from a charge distribution concentrated inside the Debye-Hückel radius to one spread-out beyond it. The latter case leads to the limiting case of logarithmic potential, and stronger electric field; the former case, of very concentrated charge distribution, leads to a fratricide effect and weaker electric field.« less

Simulation of oil bioremediation in a tidally influenced beach: Spatiotemporal evolution of nutrient and dissolved oxygen

NASA Astrophysics Data System (ADS)

Geng, Xiaolong; Pan, Zhong; Boufadel, Michel C.; Ozgokmen, Tamay; Lee, Kenneth; Zhao, Lin

2016-04-01

Numerical experiments of oil bioremediation of tidally influenced beach were simulated using the model BIOMARUN. Nutrient and dissolved oxygen were assumed present in a solution applied on the exposed beach face, and the concentration of these amendments was tracked throughout the beach for up to 6 months. It was found that, in comparison to natural attenuation, bioremediation increased the removal efficiency by 76% and 65% for alkanes and aromatics, respectively. Increasing the nutrient concentration in the applied solution did not always enhance biodegradation as oxygen became limiting even when the beach was originally oxygen-rich. Therefore, replenishment of oxygen to oil-contaminated zone was also essential. Stimulation of oil biodegradation was more evident in the upper and midintertidal zone of the beach, and less in the lower intertidal zone. This was due to reduced nutrient and oxygen replenishment, as very little of the amendment solution reached that zone. It was found that under continual application, most of the oil biodegraded within 2 months, while it persisted for 6 months under natural conditions. While the difference in duration suggests minimal long-term effects, there are situations where the beach would need to be cleaned for major ecological functions, such as temporary nesting or feeding for migratory birds. Biochemical retention time map (BRTM) showed that the duration of solution application was dependent upon the stimulated oil biodegradation rate. By contrast, the application rate of the amendment solution was dependent upon the subsurface extent of the oil-contaminated zone. Delivery of nutrient and oxygen into coastal beach involved complex interaction among amendment solution, groundwater, and seawater. Therefore, approaches that ignore the hydrodynamics due to tide are unlikely to provide the optimal solutions for shoreline bioremediation.

Oxidant effect of La(NO3)3·6H2O solution on the crystalline characteristics of nanocrystalline ZrO2 films grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Oh, Nam Khen; Kim, Jin-Tae; Kang, Goru; An, Jong-Ki; Nam, Minwoo; Kim, So Yeon; Park, In-Sung; Yun, Ju-Young

2017-02-01

Nanocrystalline ZrO2 films were synthesized by atomic layer deposition method using CpZr[N(CH3)2]3 (Cp = C5H5) as the metal precursor and La(NO3)3·6H2O solution as the oxygen source. La element in the deposited ZrO2 films could not be detected as its content was below the resolution limit of the X-ray photoelectron spectroscopy. The alternative introduction of La(NO3)3·6H2O solution to conventionally used H2O as the oxidant effectively altered the crystalline structure, grain size, and surface roughness of the grown ZrO2 films. Specifically, the crystalline structure of the ZrO2 film changed from a mixture of tetragonal and monoclinic phases to monoclinic phase. The average grain size also increased, and the resulting film surface became rougher. The average grain sizes of the ZrO2 films prepared from La(NO3)3·6H2O solution at concentrations of 10, 20, 30, and 40% were 280, 256, 208, and 200 nm, respectively, whereas that prepared using H2O oxidant was 142 nm. However, the concentration of La(NO3)3·6H2O solution minimally influenced the crystalline characteristics of the nanocrystalline ZrO2 films i.e., the crystalline structure, grain size, and surface roughness except for crystallite size.

Determination of total tin in silicate rocks by graphite furnace atomic absorption spectrometry

USGS Publications Warehouse

Elsheimer, H.N.; Fries, T.L.

1990-01-01

A method is described for the determination of total tin in silicate rocks utilizing a graphite furnace atomic absorption spectrometer with a stabilized-temperature platform furnace and Zeeman-effect background correction. The sample is decomposed by lithium metaborate fusion (3 + 1) in graphite crucibles with the melt being dissolved in 7.5% hydrochloric acid. Tin extractions (4 + 1 or 8 + 1) are executed on portions of the acid solutions using a 4% solution of tricotylphosphine oxide in methyl isobutyl ketone (MIBK). Ascorbic acid is added as a reducing agent prior to extraction. A solution of diammonium hydrogenphosphate and magnesium nitrate is used as a matrix modifier in the graphite furnace determination. The limit of detection is > 10 pg, equivalent to > 1 ??g l-1 of tin in the MIBK solution or 0.2-0.3 ??g g-61 in the rock. The concentration range is linear between 2.5 and 500 ??g l-1 tin in solution. The precision, measured as relative standard deviation, is < 20% at the 2.5 ??g l-1 level and < 7% at the 10-30 ??g l-1 level of tin. Excellent agreement with recommended literature values was found when the method was applied to the international silicate rock standards BCR-1, PCC-1, GSP-1, AGV-1, STM-1, JGb-1 and Mica-Fe. Application was made to the determination of tin in geological core samples with total tin concentrations of the order of 1 ??g g-1 or less.

Test of aerobic TCE degradation by willows (Salix viminalis) and willows inoculated with TCE-cometabolizing strains of Burkholderia cepacia.

PubMed

Clausen, Lauge Peter Westergaard; Broholm, Mette Martina; Gosewinkel, Ulrich; Trapp, Stefan

2017-08-01

Trichloroethylene (TCE) is a widespread soil and groundwater pollutant and clean-up is often problematic and expensive. Phytoremediation may be a cost-effective solution at some sites. This study investigates TCE degradation by willows (S. viminalis) and willows inoculated with three strains of B. cepacia (301C, PR1-31 and VM1330-pTOM), using chloride formation as an indicator of dehalogenation. Willows were grown in non-sterile, hydroponic conditions for 3 weeks in chloride-free nutrient solution spiked with TCE. TCE was added weekly due to rapid loss by volatilization. Chloride and TCE in solution were measured every 2-3 days and chloride and metabolite concentrations in plants were measured at test termination. Based on transpiration, no tree toxicity of TCE exposure was observed. However, trees grown in chloride-free solution showed severely inhibited transpiration. No or very little chloride was formed during the test, and levels of chloride in TCE-exposed trees were not elevated. Chloride concentrations in chloride containing TCE-free nutrient solution doubled within 23 days, indicating active exclusion of chloride by root cell membranes. Only traces of TCE-metabolites were detected in plant tissue. We conclude that TCE is not, or to a limited extent (less than 3%), aerobically degraded by the willow trees. The three strains of B. cepacia did not enhance TCE mineralization. Future successful application of rhizo- and phytodegradation of TCE requires measures to be taken to improve the degradation rates.

Fate of acetone in an outdoor model stream in southern Mississippi, U.S.A.

USGS Publications Warehouse

Rathbun, R.E.; Stephens, D.W.; Shultz, D.J.; Tai, D.Y.

1988-01-01

The fate of acetone in water was investigated in an outdoor model stream located in southern Mississippi, U.S.A. Acetone was injected continuously for 32 days resulting in small milligram-perliter concentrations in the stream. Rhodamine-WT dye was injected at the beginning and at the end of the study to determine the time-of-travel and dispersion characteristics of the stream. A 12-h injection of t-butyl alcohol (TBA) was used to determine the volatilization characteristics of the stream. Volatilization controlled the acetone concentration in the stream. Significant bacterial degradation of acetone did not occur, contrary to expectations based on previous laboratory studies. Attempts to induce degradation of the acetone by injecting glucose and a nutrient solution containing bacteria acclimated to acetone were unsuccessful. Possible explanations for the lack of bacterial degradation included a nitrate limitation and a limited residence time in the stream system. ?? 1988.

Analytic Models of Oxygen and Nutrient Diffusion, Metabolism Dynamics, and Architecture Optimization in Three-Dimensional Tissue Constructs with Applications and Insights in Cerebral Organoids

PubMed Central

2016-01-01

Diffusion models are important in tissue engineering as they enable an understanding of gas, nutrient, and signaling molecule delivery to cells in cell cultures and tissue constructs. As three-dimensional (3D) tissue constructs become larger, more intricate, and more clinically applicable, it will be essential to understand internal dynamics and signaling molecule concentrations throughout the tissue and whether cells are receiving appropriate nutrient delivery. Diffusion characteristics present a significant limitation in many engineered tissues, particularly for avascular tissues and for cells whose viability, differentiation, or function are affected by concentrations of oxygen and nutrients. This article seeks to provide novel analytic solutions for certain cases of steady-state and nonsteady-state diffusion and metabolism in basic 3D construct designs (planar, cylindrical, and spherical forms), solutions that would otherwise require mathematical approximations achieved through numerical methods. This model is applied to cerebral organoids, where it is shown that limitations in diffusion and organoid size can be partially overcome by localizing metabolically active cells to an outer layer in a sphere, a regionalization process that is known to occur through neuroglial precursor migration both in organoids and in early brain development. The given prototypical solutions include a review of metabolic information for many cell types and can be broadly applied to many forms of tissue constructs. This work enables researchers to model oxygen and nutrient delivery to cells, predict cell viability, study dynamics of mass transport in 3D tissue constructs, design constructs with improved diffusion capabilities, and accurately control molecular concentrations in tissue constructs that may be used in studying models of development and disease or for conditioning cells to enhance survival after insults like ischemia or implantation into the body, thereby providing a framework for better understanding and exploring the characteristics and behaviors of engineered tissue constructs. PMID:26650970

Stable, concentrated solutions of high molecular weight polyaniline and articles therefrom

DOEpatents

Mattes, Benjamin R.; Wang, Hsing-Lin

1999-11-09

Stable, concentrated solutions of high molecular weight polyaniline. In order to process high quality fibers and other articles possessing good mechanical properties, it is known that solution concentrations of the chosen polymer should be in the range from 15-30% (w/w). Moreover, it is desirable to use the highest molecular weight consistent with the solubility properties of the polymer. However, such solutions are inherently unstable, forming gels before processing can be achieved. The present invention describes the addition gel inhibitors (GIs) to the polymer solution, thereby permitting high concentrations (between 15% and 30% (w/w)) of high molecular weight ((M.sub.w)>120,000, and (M.sub.n)>30,000) emeraldine base (EB) polyaniline to be dissolved. Secondary amines have been used for this purpose in concentrations which are small compared to those which might otherwise be used in a cosolvent role therefor. The resulting solutions are useful for generating excellent fibers, films, coatings and other objects, since the solutions are stable for significant time periods, and the GIs are present in too small concentrations to cause polymer deterioration. It is demonstrated that the GIs found to be useful do not act as cosolvents, and that gelation times of the solutions are directly proportional to the concentration of GI. In particular, there is a preferred concentration of GI, which if exceeded causes structural and electrical conductivity degradation of resulting articles. Heating of the solutions significantly improves solubility.

Active Brownian agents with concentration-dependent chemotactic sensitivity.

PubMed

Meyer, Marcel; Schimansky-Geier, Lutz; Romanczuk, Pawel

2014-02-01

We study a biologically motivated model of overdamped, autochemotactic Brownian agents with concentration-dependent chemotactic sensitivity. The agents in our model move stochastically and produce a chemical ligand at their current position. The ligand concentration obeys a reaction-diffusion equation and acts as a chemoattractant for the agents, which bias their motion towards higher concentrations of the dynamically altered chemical field. We explore the impact of concentration-dependent response to chemoattractant gradients on large-scale pattern formation, by deriving a coarse-grained macroscopic description of the individual-based model, and compare the conditions for emergence of inhomogeneous solutions for different variants of the chemotactic sensitivity. We focus primarily on the so-called receptor-law sensitivity, which models a nonlinear decrease of chemotactic sensitivity with increasing ligand concentration. Our results reveal qualitative differences between the receptor law, the constant chemotactic response, and the so-called log law, with respect to stability of the homogeneous solution, as well as the emergence of different patterns (labyrinthine structures, clusters, and bubbles) via spinodal decomposition or nucleation. We discuss two limiting cases, where the model can be reduced to the dynamics of single species: (I) the agent density governed by a density-dependent effective diffusion coefficient and (II) the ligand field with an effective bistable, time-dependent reaction rate. In the end, we turn to single clusters of agents, studying domain growth and determining mean characteristics of the stationary inhomogeneous state. Analytical results are confirmed and extended by large-scale GPU simulations of the individual based model.

Development of a thresholding algorithm for calcium classification at multiple CT energies

NASA Astrophysics Data System (ADS)

Ng, LY.; Alssabbagh, M.; Tajuddin, A. A.; Shuaib, I. L.; Zainon, R.

2017-05-01

The objective of this study was to develop a thresholding method for calcium classification with different concentration using single-energy computed tomography. Five different concentrations of calcium chloride were filled in PMMA tubes and placed inside a water-filled PMMA phantom (diameter 10 cm). The phantom was scanned at 70, 80, 100, 120 and 140 kV using a SECT. CARE DOSE 4D was used and the slice thickness was set to 1 mm for all energies. ImageJ software inspired by the National Institute of Health (NIH) was used to measure the CT numbers for each calcium concentration from the CT images. The results were compared with a developed algorithm for verification. The percentage differences between the measured CT numbers obtained from the developed algorithm and the ImageJ show similar results. The multi-thresholding algorithm was found to be able to distinguish different concentrations of calcium chloride. However, it was unable to detect low concentrations of calcium chloride and iron (III) nitrate with CT numbers between 25 HU and 65 HU. The developed thresholding method used in this study may help to differentiate between calcium plaques and other types of plaques in blood vessels as it is proven to have a good ability to detect the high concentration of the calcium chloride. However, the algorithm needs to be improved to solve the limitations of detecting calcium chloride solution which has a similar CT number with iron (III) nitrate solution.

Anisotropic In Situ-Coated AuNPs on Screen-Printed Carbon Surface for Enhanced Prostate-Specific Antigen Impedimetric Aptasensor

NASA Astrophysics Data System (ADS)

Do, Tram T. N.; Van Phi, Toan; Nguy, Tin Phan; Wagner, Patrick; Eersels, Kasper; Vestergaard, Mun'delanji C.; Truong, Lien T. N.

2017-06-01

An impedimetric aptasensor has been used to study the effect of charge transfer on the binding of prostate-specific antigen (PSA) to its aptamer. Full understanding of this mechanism will be beneficial to further improve its sensitivity for PSA detection in human semen at physiologically relevant concentrations. Bare gold electrodes (SPAuEs) and gold nanoparticles (AuNPs)-coated screen-printed carbon ink electrodes (AuNPs/SPCEs) were coated with aptamer solution at various concentrations and the sensor response to increasing PSA concentration in buffer solution examined. AuNPs were deposited onto carbon electrodes in 10 cycles. AuNPs/SPCEs were then coated with a self-assembled monolayer (SAM) of 16-mercaptohexadecanoic acid prior to aptamer immobilization at dose of 5 μg mL-1. The results indicate that anisotropic AuNPs/SPCEs outperform bare gold electrodes in terms of decreased amount of aptamer bunches as well as the number of intermediate PSA-aptamer complexes formed on the electrode surface. The key finding is that the fabricated aptasensor is sensitive enough [limit of detection (LoD) 1.95 ng mL-1] for early diagnosis of prostate cancer and displays linear response in the physiologically relevant concentration range (0 ng mL-1 to 10 ng mL-1), as shown by the calibration curve of the relative change in electron transfer resistance (Δ R CT) versus PSA concentration when aptamer/SAM/AuNPs/SPCEs were exposed to buffer containing PSA at different concentrations.

Coupling between fluid dynamics and energy addition in arcjet and microwave thrusters

NASA Technical Reports Server (NTRS)

Micci, M. M.

1986-01-01

A new approach to numerically solving the problem of the constricted electric arcjet is presented. An Euler Implicit finite difference scheme is used to solve the full compressible Navier Stokes equations in two dimensions. The boundary and initial conditions represent the constrictor section of the arcjet, and hydrogen is used as a propellant. The arc is modeled as a Gaussian distribution across the centerline of the constrictor. Temperature, pressure and velocity profiles for steady state converged solutions show both axial and radial changes in distributions resulting from their interaction with the arc energy source for specific input conditions. The temperature rise is largest at the centerline where there is a the greatest concentration arc energy. The solution does not converge for all initial inputs and the limitations in the range of obtainable solutions are discussed.

Ultra low-level measurements of actinides by sector field ICP-MS.

PubMed

Pointurier, F; Baglan, N; Hémet, P

2004-01-01

In the present work, a double-focusing sector field inductively coupled plasma-mass spectrometer was optimised for ultra trace and isotopic analyses of actinide long-lived isotopes in low concentration solutions of the fgml(-1) to the ngml(-1) range. Sensitivities of about 3GHz/(microgml(-1)), with as low a background as 0.1cps, were obtained for U using a conventional concentric pneumatic nebuliser. Detection limits are below the fg range for 239Pu and 240Pu. With natural U, a precision lower than 0.5% RSD is currently obtained for 235U/238U isotopic ratio at the 200pgml(-1) level.

A new method to measure effective soil solution concentration predicts copper availability to plants.

PubMed

Zhang, H; Zhao, F J; Sun, B; Davison, W; McGrath, S P

2001-06-15

Risk assessments of metal contaminated soils need to address metal bioavailability. To predict the bioavailability of metals to plants, it is necessary to understand both solution and solid phase supply processes in soils. In striving to find surrogate chemical measurements, scientists have focused either on soil solution chemistry, including free ion activities, or operationally defined fractions of metals. Here we introduce the new concept of effective concentration, CE, which includes both the soil solution concentration and an additional term, expressed as a concentration, that represents metal supplied from the solid phase. CE was measured using the technique of diffusive gradients in thin films (DGT) which, like a plant, locally lowers soil solution concentrations, inducing metal supply from the solid phase, as shown by a dynamic model of the DGT-soil system. Measurements of Cu as CE, soil solution concentration, by EDTA extraction and as free Cu2+ activity in soil solution were made on 29 different soils covering a large range of copper concentrations. Theywere compared to Cu concentrations in the plant material of Lepidium heterophyllum grown on the same soils. Plant concentrations were linearly related and highly correlated with CE but were more scattered and nonlinear with respect to free Cu2+ activity, EDTA extraction, or soil solution concentrations. These results demonstrate that the dominant supply processes in these soils are diffusion and labile metal release, which the DGT-soil system mimics. The quantity CE is shown to have promise as a quantitative measure of the bioavailable metal in soils.

Laser-induced breakdown spectroscopic detection of trace level heavy metal in solutions on a laser-pretreated metallic target.

PubMed

Niu, Sheng; Zheng, Lijuan; Khan, Abdul Qayyum; Feng, Guang; Zeng, Heping

2018-03-01

A fast and sensitive analysis for trace level heavy metals in aqueous solution was realized by using an improved laser induced breakdown spectroscopy (LIBS) methodology. Solutions containing heavy metal elements, Ni, Cr, and Cd, were concentrated in a laser-pretreated area (25 × 20mm 2 ) of a polished aluminum target surface, wherein pretreated grooves enabled homogeneous distribution of the metallic solutions in the well-defined area, and laser ablation of the aluminum target produced unique plasma excitation of various metallic ions. For 1-mL solutions deposited, we obtained an analytical precision of about 7% relative standard deviation (RSD), and limits of detection (LODs) of 22, 19, and 184μg/L for Ni, Cr, and Cd, respectively. Moreover, the laser-pretreated metallic microstructure allowed more solution deposited with the help of a hot plate, which supported improvement of LODs to sub-μg/L level for Cr and Ni and μg/L level for Cd with about 20-mL solution engaged in the enrichment processes. The applicability of the proposed methodology was validated on certified reference materials and real river water. Copyright © 2017 Elsevier B.V. All rights reserved.

Cadmium and Zn availability as affected by pH manipulation and its assessment by soil extraction, DGT and indicator plants.

PubMed

Muhammad, Iqbal; Puschenreiter, Markus; Wenzel, Walter W

2012-02-01

Manipulation of soil pH by soil additives and / or rhizosphere processes may enhance the efficiency of metal phytoextraction. Here we report on the effect of nitric acid additions to four polluted soils on Cd and Zn concentrations in soil solution (C(soln)) and 0.005M Ca(NO(3))(2) extracts, and related changes in the diffusive fluxes and resupply of the metals as assessed by diffusive gradients in thin films (DGT). The responses of these chemical indicators of bioavailability were compared to metal uptake in two indicator plant species, common dandelion (Taraxacum officinale F.H. Wigg) and narrow leaf plantain (Plantago lanceolata L.) grown for 75days in a pot experiment. Lowering soil pH increased C(soln), the 0.005M Ca(NO(3))(2)-soluble fractions and the DGT-measured Cd and Zn concentrations (C(DGT)) in the experimental soils. This was associated with enhanced uptake of Cd and Zn on soils acidified to pH 4.5 whereas plants did not survive at pH 3.5. Toxicity along with decreased kinetics of metal resupply (calculated by the 2D DIFS model) in the strong acidification treatment suggests that moderate acidification is more appropriate to enhance the phytoextraction process. Each of the chemical indicators of bioavailability predicted well (R(2)>0.70) the Cd and Zn concentrations in plantain shoots but due to metal toxicity not for dandelion. Concentration factors, i.e. the ratio between metal concentrations in shoots and in soil solution (CF) indicate that Cd and Zn uptake in plantain was not limited by diffusion which may explain that DGT did not perform better than C(soln). However, DGT is expected to predict plant uptake better in diffusion-limited conditions such as in the rhizosphere of metal-accumulating phytoextraction crops. Copyright © 2011 Elsevier B.V. All rights reserved.

Evaluating Transport Properties and Ionic Dissociation of LiPF 6 in Concentrated Electrolyte

DOE PAGES

Feng, Zhange; Higa, Kenneth; Han, Kee Sung; ...

2017-08-17

The presence of lithium hexafluorophosphate (LiPF 6) ion pairs in carbonate-based electrolyte solutions is widely accepted in the field of battery electrolyte research and is expected to affect solution transport properties. No existing techniques are capable of directly quantifying salt dissociation in these solutions. Previous publications by others have provided estimates of dissociation degrees using dilute solution theory and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR) measurements of self-diffusivity. However, the behavior of a concentrated electrolyte solution can deviate significantly from dilute solution theory predictions. This paper, for the first time, instead uses Onsager–Stefan–Maxwell concentrated solution theory and themore » generalized Darken relation with PFG-NMR measurements to quantify the degrees of dissociation in electrolyte solutions (LiPF 6 in ethylene carbonate/diethyl carbonate, 1:1 by weight). At LiPF 6 concentrations ranging from 0.1 M to 1.5 M, the salt dissociation degree is found to range from 61% to 37%. Finally, transport properties are then calculated through concentrated solution theory with corrections for these significant levels of ion pairing.« less

Evaluating Transport Properties and Ionic Dissociation of LiPF 6 in Concentrated Electrolyte

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

Feng, Zhange; Higa, Kenneth; Han, Kee Sung

2017-01-01

The presence of lithium hexafluorophosphate (LiPF6) ion pairs in carbonate-based electrolyte solutions is widely accepted in the field of battery electrolyte research and is expected to affect solution transport properties. No existing techniques are capable of directly quantifying salt dissociation in these solutions. Previous publications by others have provided estimates of dissociation degrees using dilute solution theory and pulsed field gradient nuclear magnetic resonance spectroscopy (PFG-NMR) measurements of self-diffusivity. However, the behavior of a concentrated electrolyte solution can deviate significantly from dilute solution theory predictions. This work, for the first time, instead uses Onsager–Stefan–Maxwell concentrated solution theory and the generalized.more » Darken relation with PFG-NMR measurements to quantify the degrees of dissociation in electrolyte solutions (LiPF6 in ethylene carbonate/diethyl carbonate, 1:1 by weight). At LiPF6 concentrations ranging from 0.1 M to 1.5 M, the salt dissociation degree is found to range from 61% to 37%. Transport properties are then calculated through concentrated solution theory with corrections for these significant levels of ion pairing.« less

Concentration and purification of plutonium or thorium

DOEpatents

Hayden, John A.; Plock, Carl E.

1976-01-01

In this invention a first solution obtained from such as a plutonium/thorium purification process or the like, containing plutonium (Pu) and/or thorium (Th) in such as a low nitric acid (HNO.sub.3) concentration may have the Pu and/or Th separated and concentrated by passing an electrical current from a first solution having disposed therein an anode to a second solution having disposed therein a cathode and separated from the first solution by a cation permeable membrane, the Pu or Th cation permeating the cation membrane and forming an anionic complex within the second solution, and electrical current passage affecting the complex formed to permeate an anion membrane separating the second solution from an adjoining third solution containing disposed therein an anode, thereby effecting separation and concentration of the Pu and/or Th in the third solution.

NUTRITION AND METABOLISM OF MARINE BACTERIA1

PubMed Central

Takacs, Frank P.; Matula, Tibor I.; MacLeod, Robert A.

1964-01-01

Takacs, Frank P. (McGill University, Montreal, Quebec, Canada), Tibor I. Matula, and Robert A. MacLeod. Nutrition and metabolism of marine bacteria. XIII. Intracellular concentrations of sodium and potassium ions in a marine pseudomonad. J. Bacteriol. 87:510–518. 1964.—Washed cells of a marine pseudomonad were suspended in buffered salt solutions containing, in addition to MgSO4, NaCl and KCl at various concentrations. The cells were centrifuged from the medium and analyzed for Na+ and K+. Inulin and C14-carboxypolyglucose were employed to estimate the volume of extracellular fluid associated with the packed cells. Intracellular Na+ and K+ concentrations were determined by correcting for the amount of Na+ and K+ in the extracellular fluid. At all levels of Na+ in the suspending medium (0 to 1 m), the intracellular and extracellular Na+ concentrations within the limits of experimental error were the same. The intracellular K+ concentrations were approximately double the extracellular concentrations at the two levels of K+ tested (0.01 and 0.15 m) and were not influenced by the amount of Na+ present. Intracellular and extracellular Cl− concentrations were the same at the one level of Cl− examined. The intracellular fluid volume varied with the NaCl or KCl concentration of the suspending medium, being greatest in the absence of added salts, decreasing to a minimum at 0.3 m salt, and then increasing slightly at higher salt concentrations. Most of the intracellular Na+ could be removed by washing with solutions of MgSO4 or sucrose, but a small amount [10 to 15 μmoles/g (dry weight)] remained bound to the cells. PMID:14129666

Solution identification and quantitative analysis of fiber-capacitive drop analyzer based on multivariate statistical methods

NASA Astrophysics Data System (ADS)

Chen, Zhe; Qiu, Zurong; Huo, Xinming; Fan, Yuming; Li, Xinghua

2017-03-01

A fiber-capacitive drop analyzer is an instrument which monitors a growing droplet to produce a capacitive opto-tensiotrace (COT). Each COT is an integration of fiber light intensity signals and capacitance signals and can reflect the unique physicochemical property of a liquid. In this study, we propose a solution analytical and concentration quantitative method based on multivariate statistical methods. Eight characteristic values are extracted from each COT. A series of COT characteristic values of training solutions at different concentrations compose a data library of this kind of solution. A two-stage linear discriminant analysis is applied to analyze different solution libraries and establish discriminant functions. Test solutions can be discriminated by these functions. After determining the variety of test solutions, Spearman correlation test and principal components analysis are used to filter and reduce dimensions of eight characteristic values, producing a new representative parameter. A cubic spline interpolation function is built between the parameters and concentrations, based on which we can calculate the concentration of the test solution. Methanol, ethanol, n-propanol, and saline solutions are taken as experimental subjects in this paper. For each solution, nine or ten different concentrations are chosen to be the standard library, and the other two concentrations compose the test group. By using the methods mentioned above, all eight test solutions are correctly identified and the average relative error of quantitative analysis is 1.11%. The method proposed is feasible which enlarges the applicable scope of recognizing liquids based on the COT and improves the concentration quantitative precision, as well.

Biochar from malt spent rootlets for the removal of mercury from aqueous solutions

NASA Astrophysics Data System (ADS)

Boutsika, Lamprini; Manariotis, Ioannis; Karapanagioti, Hrissi K.

2013-04-01

Biochar is receiving increased attention as a promising material in environmental applications. It is obtained from the incomplete combustion of carbon-rich biomass under oxygen-limited conditions. One of the many proposed applications of biochars is the removal of metals (e.g., lead, mercury, etc.) from aqueous solutions. Mercury is one of the heavy metals of particular concern due to its toxicity even at relatively low concentration and thus, its removal from aqueous systems is desirable. Malt spent rootlets is a by-product formed during beer production, it is inexpensive and it is produced in high quantities. The objective of the present study was to evaluate the potential use of biochar, produced from malt spent rootlets, to remove mercury from aqueous solutions. Batch experiments were conducted at room temperature (25oC) to obtain the optimum sorption conditions under different pH values, biomass dose, contact time, and solution ionic strength. Sorption kinetics and equilibrium capacity constants were determined at the optimum pH value. Furthermore, the effect of different leaching solutions on mercury desorption from the biochar was examined. All studies with mercury and biochar were conducted at pH 5 that was determined to be the optimum pH for sorption. The proportion of mercury removal increased with the increased dose of the biochar, i.e. from 71% removal for biochar dose of 0.3 g/L, it reached almost 100% removal for biochar dose ˜1 g/L. Based on the isotherm data, the maximum biochar sorption capacity (qmax) for mercury was 99 mg/g. Based on the sorption kinetic data, (qmax) was achieved after 2 h; it should be mentioned that 30% of the (qmax) was observed within the first 5 min. Five leaching solutions were tested for mercury desorption (H2O, HCl, EDTA, NaCl and HNO3). HCl resulted in the highest extraction percentage of the sorbed mercury. The desorbing mercury percentages at 24 h for HCl concentrations 0.1, 0.2, 0.4, 0.8, and 2 M were 62, 59, 62, 69, and 95%, respectively. Finally, the influence of solution salinity in mercury sorption onto biochar was tested by adjusting the solution ionic strength with two different salts, NaCl and NaNO3. The salts were added at concentrations 1, 0.5, 0.1, 0.01, 0.001, and 0.0001 mol/L. Mercury removal was not affected by the presence of NaNO3 and high metal removal percentages were obtained even at high NaNO3 concentrations (about 53% at concentration 1 mol/L NaNO3). However, a significant decrease of mercury adsorption was observed with the increase of NaCl concentration, i.e. from 55% removal at concentration 0.0001 mol/LNaCl, it reached 20% removal at a concentration of 1 mol/L NaCl. These differences can be related to the different counter ion present in the salts. NO3- does not interfere in mercury sorption but Cl- forms mercury species with negative charge, which do not favor the sorption process. Generally, biochar from malt spent rootlets seemed as a promising novel sorbent that could be used for aqueous system remediation under most environmental conditions.

Phase-field-crystal study of solute trapping

NASA Astrophysics Data System (ADS)

Humadi, Harith; Hoyt, Jeffrey J.; Provatas, Nikolas

2013-02-01

In this study we have incorporated two time scales into the phase-field-crystal model of a binary alloy to explore different solute trapping properties as a function of crystal-melt interface velocity. With only diffusive dynamics, we demonstrate that the segregation coefficient, K as a function of velocity for a binary alloy is consistent with the model of Kaplan and Aziz where K approaches unity in the limit of infinite velocity. However, with the introduction of wavelike dynamics in both the density and concentration fields, the trapping follows the kinetics proposed by Sobolev [Phys. Lett. A10.1016/0375-9601(95)00084-G 199, 383 (1995)], where complete trapping occurs at a finite velocity.

Measurement of Eu and Yb in aqueous solutions by underwater laser induced breakdown spectroscopy

DOE PAGES

Bhatt, Chet R.; Jain, Jinesh C.; Goueguel, Christian L.; ...

2017-09-13

In this paper, we report the use of laser induced breakdown spectroscopy (LIBS) to detect dissolved Eu and Yb in bulk aqueous solutions. Ten strong emission lines of Eu and one strong emission line of Yb were identified in the underwater LIBS spectra obtained by using Czerny–Turner spectrometer within the wavelength range of 375–515 nm. Temporal evolution of plasma and the effect of laser pulse energy on the spectral emission were studied. Finally, calibration curves using the concentration range from 500 to 10,000 ppm were developed and limits of detection for Eu and Yb were estimated to be 209 andmore » 156 ppm, respectively.« less

Measurement of Eu and Yb in aqueous solutions by underwater laser induced breakdown spectroscopy

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

Bhatt, Chet R.; Jain, Jinesh C.; Goueguel, Christian L.

In this paper, we report the use of laser induced breakdown spectroscopy (LIBS) to detect dissolved Eu and Yb in bulk aqueous solutions. Ten strong emission lines of Eu and one strong emission line of Yb were identified in the underwater LIBS spectra obtained by using Czerny–Turner spectrometer within the wavelength range of 375–515 nm. Temporal evolution of plasma and the effect of laser pulse energy on the spectral emission were studied. Finally, calibration curves using the concentration range from 500 to 10,000 ppm were developed and limits of detection for Eu and Yb were estimated to be 209 andmore » 156 ppm, respectively.« less

Flow injection chemiluminescence determination of naphazoline hydrochloride in pharmaceuticals.

PubMed

Iranifam, Mortaza; Sorouraddin, Mohammad H

2014-02-01

A simple and sensitive flow injection chemiluminescence (FI-CL) method was developed for the determination of naphazoline hydrochloride (NPZ). The method is based on the enhancing effect of NPZ on the weak CL signal from the reaction of KIO4 with H2 O2 . Experimental parameters that affected the CL signal, including the pH of the KIO4 solution, concentrations of KIO4 , H2 O2 and disodium-EDTA and flow rate were optimized. Under the optimum conditions, the increment of CL intensity was linearly proportional to the concentration of NPZ in the range 5.0 × 10(-6) to 70 × 10(-6) mol/L. The detection limit was 1.0 × 10(-6) mol/L and the relative standard deviation for 50 × 10(-6) mol/L NPZ solution was 2.8% (n = 11). In addition, a high throughput of 120 samples/h was achieved. The utility of this method was demonstrated by determining NPZ in pharmaceuticals. Copyright © 2013 John Wiley & Sons, Ltd.

Multidimensional equilibria and their stability in copolymer-solvent mixtures

NASA Astrophysics Data System (ADS)

Glasner, Karl; Orizaga, Saulo

2018-06-01

This paper discusses localized equilibria which arise in copolymer-solvent mixtures. A free boundary problem associated with the sharp-interface limit of a density functional model is used to identify both lamellar and concentric domain patterns composed of a finite number of layers. Stability of these morphologies is studied through explicit linearization of the free boundary evolution. For the multilayered lamellar configuration, transverse instability is observed for sufficiently small dimensionless interfacial energies. Additionally, a crossover between small and large wavelength instabilities is observed depending on whether solvent-polymer or monomer-monomer interfacial energy is dominant. Concentric domain patterns resembling multilayered micelles and vesicles exhibit bifurcations wherein they only exist for sufficiently small dimensionless interfacial energies. The bifurcation of large radii vesicle solutions is studied analytically, and a crossover from a supercritical case with only one solution branch to a subcritical case with two is observed. Linearized stability of these configurations shows that azimuthal perturbation may lead to instabilities as interfacial energy is decreased.

Effect of pH adjustment, homogenization and diafiltration on physicochemical, reconstitution, functional and rheological properties of medium protein milk protein concentrates (MPC70).

PubMed

Meena, Ganga Sahay; Singh, Ashish Kumar; Gupta, Vijay Kumar; Borad, Sanket; Arora, Sumit; Tomar, Sudhir Kumar

2018-04-01

Poor solubility is the major limiting factor in commercial applications of milk protein concentrates (MPC) powders. Retentate treatments such as pH adjustment using disodium phosphate (Na 2 HPO 4 ), also responsible for calcium chelation with homogenization and; its diafiltration with 150 mM NaCl solution were hypothesized to improve the functional properties of treated MPC70 powders. These treatments significantly improved the solubility, heat stability, water binding, dispersibility, bulk density, flowability, buffer index, foaming and emulsifying capacity of treated powders over control. Rheological behaviour of reconstituted MPC solutions was best explained by Herschel Bulkley model. Compared to rough, large globular structures with dents in control; majorly intact, separate, smaller particles of smooth surface, without any aggregation were observed in SEM micrograph of treated powders. Applied treatments are easy, cost-effective and capable to improve functional properties of treated powders that could replace control MPC70 powder in various food applications where protein functionality is of prime importance.