A Theory of the von Weimarn Rules Governing the Average Size of Crystals Precipitated from a Supersaturated Solution

NASA Technical Reports Server (NTRS)

Barlow, Douglas A.; Baird, James K.; Su, Ching-Hua

2003-01-01

More than 75 years ago, von Weimarn summarized his observations of the dependence of the average crystal size on the initial relative concentration supersaturation prevailing in a solution from which crystals were growing. Since then, his empirically derived rules have become part of the lore of crystal growth. The first of these rules asserts that the average crystal size measured at the end of a crystallization increases as the initial value of the relative supersaturation decreases. The second rule states that for a given crystallization time, the average crystal size passes through a maximum as a function of the initial relative supersaturation. Using a theory of nucleation and growth due to Buyevich and Mansurov, we calculate the average crystal size as a function of the initial relative supersaturation. We confirm the von Weimarn rules for the case where the nucleation rate is proportional to the third power or higher of the relative supersaturation.

Use of a screening method to determine excipients which optimize the extent and stability of supersaturated drug solutions and application of this system to solid formulation design.

PubMed

Vandecruys, Roger; Peeters, Jef; Verreck, Geert; Brewster, Marcus E

2007-09-05

Assessing the effect of excipients on the ability to attain and maintain supersaturation of drug-based solution may provide useful information for the design of solid formulations. Judicious selection of materials that affect either the extent or stability of supersaturating drug delivery systems may be enabling for poorly soluble drug candidates or other difficult-to-formulate compounds. The technique suggested herein is aimed at providing a screening protocol to allow preliminary assessment of these factors based on small to moderate amounts of drug substance. A series of excipients were selected that may, by various mechanisms, affect supersaturation including pharmaceutical polymers such as HMPC and PVP, surfactants such as Polysorbate 20, Cremophor RH40 and TPGS and hydrophilic cyclodextrins such as HPbetaCD. Using a co-solvent based method and 25 drug candidates, the data suggested, on the whole, that the surfactants and the selected cyclodextrin seemed to best augment the extent of supersaturation but had variable benefits as stabilizers, while the pharmaceutical polymers had useful effect on supersaturation stability but were less helpful in increasing the extent of supersaturation. Using these data, a group of simple solid dosage forms were prepared and tested in the dog for one of the drug candidates. Excipients that gave the best extent and stability for the formed supersaturated solution in the screening assay also gave the highest oral bioavailability in the dog.

Crystallization of highly supersaturated solutions - An experimental study

NASA Technical Reports Server (NTRS)

Queen, Brian; Hallett, John

1990-01-01

The crystallization of ammonium sulfate solutions under very high supersaturation is investigated. The results imply that high saturation ratios can exist at least to 30 +/- 5 and possibly higher in smaller drops. Under certain atmospheric conditions highly supersaturated drops can persist at even lower temperatures and humidities.

Numerical simulation of flow and mass transfer for large KDP crystal growth via solution-jet method

NASA Astrophysics Data System (ADS)

Yin, Huawei; Li, Mingwei; Hu, Zhitao; Zhou, Chuan; Li, Zhiwei

2018-06-01

A novel technique of growing large crystals of potassium dihydrogen phosphate (KDP) named solution-jet method is proposed. The aim is to increase supersaturation on the pyramidal face, especially for crystal surface regions close to the rotation axis. The fluid flow and surface supersaturation distribution of crystals grown under different conditions were computed using the finite-volume method. Results indicate that the time-averaged supersaturation of the pyramidal face in the proposed method significantly increases and the supersaturation difference from the crystal center to edge clearly decreases compared with the rotating-crystal method. With increased jet velocity, supersaturation on the pyramidal face steadily increases. Rotation rate considerably affects the magnitude and distribution of the prismatic surface supersaturation. With increased crystal size, the mean value of surface supersaturation averaged over the pyramid gradually decreases; conversely, standard deviation increases, which is detrimental to crystal growth. Moreover, the significant roles played by natural and forced convection in the process of mass transport are discussed. Results show that further increased jet velocity to 0.6 m/s renders negligible the effects of natural convection around the pyramid. The simulation for step propagation indicates that solution-jet method can promote a steady step migration and enhance surface morphology stability, which can improve the crystal quality.

Polymeric Precipitation Inhibitors Promote Fenofibrate Supersaturation and Enhance Drug Absorption from a Type IV Lipid-Based Formulation.

PubMed

Suys, Estelle J A; Chalmers, David K; Pouton, Colin W; Porter, Christopher J H

2018-06-04

The ability of lipid-based formulations (LBFs) to increase the solubilization, and prolong the supersaturation, of poorly water-soluble drugs (PWSDs) in the gastrointestinal (GI) fluids has generated significant interest in the past decade. One mechanism to enhance the utility of LBFs is to prolong supersaturation via the addition of polymers that inhibit drug precipitation (polymeric precipitation inhibitors or PPIs) to the formulation. In this work, we have evaluated the performance of a range of PPIs and have identified PPIs that are sufficiently soluble in LBF to allow the construction of single phase formulations. An in vitro model was first employed to assess drug (fenofibrate) solubilization and supersaturation on LBF dispersion and digestion. An in vitro-in situ model was subsequently employed to simultaneously evaluate the impact of PPI enhanced drug supersaturation on drug absorption in rats. The stabilizing effect of the polymers was polymer specific and most pronounced at higher drug loads. Polymers that were soluble in LBF allowed simple processing as single phase formulations, while formulations containing more hydrophilic polymers required polymer suspension in the formulation. The lipid-soluble polymers Eudragit (EU) RL100 and poly(propylene glycol) bis(2-aminopropyl ether) (PPGAE) and the water-soluble polymer hydroxypropylmethyl cellulose (HPMC) E4M were identified as the most effective PPIs in delaying fenofibrate precipitation in vitro. An in vitro model of lipid digestion was subsequently coupled directly to an in situ single pass intestinal perfusion assay to evaluate the influence of PPIs on fenofibrate absorption from LBFs in vivo. This coupled model allowed for real-time evaluation of the impact of supersaturation stabilization on absorptive drug flux and provided better discrimination between the different PPIs and formulations. In the presence of the in situ absorption sink, increased fenofibrate supersaturation resulted in increased drug exposure, and a good correlation was found between the degree of in vitro supersaturation and in vivo drug exposure. An improved in vitro-in vivo correlation was apparent when comparing the same formulation under different supersaturation conditions. These observations directly exemplify the potential utility of PPIs in promoting drug absorption from LBF, via stabilization of supersaturation, and further confirm that relatively brief periods of supersaturation may be sufficient to promote drug absorption, at least for highly permeable drugs such as fenofibrate.

Supersaturation of zafirlukast in fasted and fed state intestinal media with and without precipitation inhibitors.

PubMed

Madsen, Cecilie Maria; Boyd, Ben; Rades, Thomas; Müllertz, Anette

2016-08-25

Poor water solubility is a bottle neck in the development of many new drug candidates, and understanding and circumventing this is essential for a more effective drug development. Zafirlukast (ZA) is a leukotriene antagonist marketed for the treatment of asthma (Accolate®). ZA is poorly water soluble, and is formulated in an amorphous form (aZA) to improve its solubility and oral bioavailability. It has been shown that upon dissolution of aZa, the concentration of ZA in solution is supersaturated with respect to its stable crystalline form (ZA monohydrate), and thus, in theory, the bioavailability increases upon amorphization of ZA. The polymers hydroxypropylmethylcellulose (HPMC) and polyvinylpyrrolidone (PVP), often used as stabilizers of the supersaturated state, are in the excipient list of Accolate®. It is not recommended to take Accolate® with food, as this reduces the bioavailability by 40%. The aim of this study was to investigate the effect of simulated fasted and fed state intestinal media as well as the effect of HPMC and PVP on the supersaturation and precipitation of ZA in vitro. Supersaturation of aZA was studied in vitro in a small scale setup using the μDiss Profiler™. Several media were used for this study: One medium simulating the fasted state intestinal fluids and three media simulating different fed state intestinal fluids. Solid state changes of the drug were investigated by small angle x-ray scattering. The duration wherein aZA was maintained at a supersaturated state was prolonged in the presence of HPMC and lasted more than 20h in the presence of PVP in a fasted state intestinal medium. The presence of PVP increased the concentration of drug dissolved in the supersaturated state. The duration of supersaturation was shorter in fed than in a fasted state simulated intestinal media, but the concentration during supersaturation was higher. It was thus not possible to predict any positive or negative food effects from the dissolution/precipitation curves from different media. Lipolysis products in the fed state simulated media seemed to cause both a negative effect on the duration of supersaturation, and an increased drug concentration during supersaturation. In contrast, when testing the effect of a fed state simulated medium compared to the fasted state medium, in the presence of PVP, a clear negative effect was seen on the dissolution/precipitation curved of the fed state medium. The drug concentration during supersaturation was marginally different in the two media, but a precipitation of ZA was seen in the fed state medium, which was not observed in the fasted state medium. Solid state transformation from aZA to ZA monohydrate (mhZA) upon precipitation of the supersaturated solutions was confirmed by small angle x-ray scattering. All of these results can explain the described in vivo behavior of ZA. For ZA simple dissolution experiments in vitro can be used to examine supersaturation, effectiveness of PI and potential food effects on these. Copyright © 2016 Elsevier B.V. All rights reserved.

Calibration Uncertainties in the Droplet Measurement Technologies Cloud Condensation Nuclei Counter

NASA Astrophysics Data System (ADS)

Hibert, Kurt James

Cloud condensation nuclei (CCN) serve as the nucleation sites for the condensation of water vapor in Earth's atmosphere and are important for their effect on climate and weather. The influence of CCN on cloud radiative properties (aerosol indirect effect) is the most uncertain of quantified radiative forcing changes that have occurred since pre-industrial times. CCN influence the weather because intrinsic and extrinsic aerosol properties affect cloud formation and precipitation development. To quantify these effects, it is necessary to accurately measure CCN, which requires accurate calibrations using a consistent methodology. Furthermore, the calibration uncertainties are required to compare measurements from different field projects. CCN uncertainties also aid the integration of CCN measurements with atmospheric models. The commercially available Droplet Measurement Technologies (DMT) CCN Counter is used by many research groups, so it is important to quantify its calibration uncertainty. Uncertainties in the calibration of the DMT CCN counter exist in the flow rate and supersaturation values. The concentration depends on the accuracy of the flow rate calibration, which does not have a large (4.3 %) uncertainty. The supersaturation depends on chamber pressure, temperature, and flow rate. The supersaturation calibration is a complex process since the chamber's supersaturation must be inferred from a temperature difference measurement. Additionally, calibration errors can result from the Kohler theory assumptions, fitting methods utilized, the influence of multiply-charged particles, and calibration points used. In order to determine the calibration uncertainties and the pressure dependence of the supersaturation calibration, three calibrations are done at each pressure level: 700, 840, and 980 hPa. Typically 700 hPa is the pressure used for aircraft measurements in the boundary layer, 840 hPa is the calibration pressure at DMT in Boulder, CO, and 980 hPa is the average surface pressure at Grand Forks, ND. The supersaturation calibration uncertainty is 2.3, 3.1, and 4.4 % for calibrations done at 700, 840, and 980 hPa respectively. The supersaturation calibration change with pressure is on average 0.047 % supersaturation per 100 hPa. The supersaturation calibrations done at UND are 42-45 % lower than supersaturation calibrations done at DMT approximately 1 year previously. Performance checks confirmed that all major leaks developed during shipping were fixed before conducting the supersaturation calibrations. Multiply-charged particles passing through the Electrostatic Classifier may have influenced DMT's activation curves, which is likely part of the supersaturation calibration difference. Furthermore, the fitting method used to calculate the activation size and the limited calibration points are likely significant sources of error in DMT's supersaturation calibration. While the DMT CCN counter's calibration uncertainties are relatively small, and the pressure dependence is easily accounted for, the calibration methodology used by different groups can be very important. The insights gained from the careful calibration of the DMT CCN counter indicate that calibration of scientific instruments using complex methodology is not trivial.

Effect of Extent of Supersaturation on the Evolution of Kinetic Solubility Profiles.

PubMed

Han, Yi Rang; Lee, Ping I

2017-01-03

Solubility limited compounds require enabling formulations such as amorphous solid dispersions (ASDs) to increase the apparent solubility by dissolving to a concentration higher than the equilibrium solubility of the drug. This may lead to subsequent precipitation and thus the loss of the solubility advantage. Although higher supersaturation is known to result in faster precipitation, the overall effect of this faster precipitation on the bioavailability is not well understood. The objective of this study is to gain a better understanding of the impact of extent of supersaturation (i.e., dose) on the resulting kinetic solubility profiles of supersaturating dosage forms. Experimental concentration-time curves of two model compounds with different recrystallization tendencies, indomethacin (IND) and naproxen (NAP), were explored under varying sink indices (SIs) by infusing varying volumes of dissolved drug (e.g., in ethanol) into the dissolution medium. The experimental results were simulated with a mechanistic model considering classical nucleation theory and interface controlled growth on the nucleus surface. In the absence of dissolved polymer to inhibit precipitation, experimental and predicted results show that there exists a critical supersaturation below which no precipitation is observed, and due to this supersaturation maintenance, there exists an optimal dose which maximizes the area under the curve (AUC) of the kinetic solubility concentration-time profile. In the presence of dissolved polymer from ASD dissolution, similar trends were observed except the critical supersaturation was increased due to crystallization inhibition by the dissolved polymer. The importance of measuring the experimental "kinetic solubility" is emphasized. However, we show that the true solubility advantage of amorphous solids depends not on the "kinetic solubility" of amorphous dosage forms, typically arising from the balance between the rate of supersaturation generation and the precipitation kinetics, but rather on the critical supersaturation below which precipitation is not observed for a sufficiently long period.

Deposition Ice Nuclei Concentration at Different Temperatures and Supersaturations

NASA Astrophysics Data System (ADS)

López, M. L.; Avila, E.

2013-05-01

Ice formation is one of the main processes involved in the initiation of precipitation. Some aerosols serve to nucleate ice in clouds. They are called ice nuclei (IN) and they are generally solid particles, insoluble in water. At temperatures warmer than about -36°C the only means for initiation of the ice phase in the atmosphere involves IN, and temperature and supersaturation required to activate IN are considered as key information for the understanding of primary ice formation in clouds. The objective of this work is to quantify the IN concentration at ground level in Córdoba City, Argentina, under the deposition mode, that is to say that ice deposits on the IN directly from the vapor phase. It happens when the environment is supersaturated with respect to ice and subsaturated with respect to liquid water. Ice nuclei concentrations were measured in a cloud chamber placed in a cold room with temperature control down to -35°C. The operating temperature was varied between -15°C and -30°C. Ice supersaturation was ranged between 2 and 20 %. In order to quantify the number of ice particles produced in each experiment, a dish containing a supercooled solution of cane sugar, water and glycerol was placed on the floor of the cloud chamber. The activated IN grew at the expense of vapor until ice crystals were formed and these then fell down onto the sugar solution. Once there, these crystals could grow enough to be counted easily with a naked eye after a period of about three minutes, when they reach around 2 mm in diameter. In order to compare the present results with previously reported results, the data were grouped in three different ranges of supersaturation: the data with supersaturations between 2 and 8 %, the data with supersaturations between 8 and 14% and the data with supersaturations between 14 and 20 %. In the same way, in order to analize the behavior of IN concentration with supersaturation, the data were grouped for three different temperatures, the data with temperatures between -15°C and -20°C, the data with temperatures between -20°C and -25°C and the data with temperatures between -25°C and -30°C. The results confirm that for each temperature range, the concentration of IN increases at higher supersaturation, and show the tendency of the IN concentration to increase with increasing ice supersaturation. Based on previous parameterizations, a combination of IN concentration in relation with temperature and ice supersaturation is proposed in this work. As far as we know, this is among the first work to measure and parameterize the concentration of deposition ice nuclei in the Southern Hemisphere.

Advantageous Solubility-Permeability Interplay When Using Amorphous Solid Dispersion (ASD) Formulation for the BCS Class IV P-gp Substrate Rifaximin: Simultaneous Increase of Both the Solubility and the Permeability.

PubMed

Beig, Avital; Fine-Shamir, Noa; Lindley, David; Miller, Jonathan M; Dahan, Arik

2017-05-01

Rifaximin is a BCS class IV (low-solubility, low-permeability) drug and also a P-gp substrate. The aims of this work were to assess the efficiency of different rifaximin amorphous solid dispersion (ASDs) formulations in achieving and maintaining supersaturation and to investigate the consequent solubility-permeability interplay. Spray-dried rifaximin ASDs were prepared with different hydrophilic polymers and their ability to achieve and maintain supersaturation was assessed. Then, rifaximin's apparent intestinal permeability was investigated as a function of increasing supersaturation both in vitro using the parallel artificial membrane permeability assay (PAMPA) and in vivo using the single-pass rat intestinal perfusion (SPIP) model. The efficiency of the different ASDs to achieve and maintain supersaturation of rifaximin was found to be highly polymer dependent, and the copovidone/HPC-SL formulation was found to be superior to the other two, allowing supersaturation of 200× that of the crystalline solubility for 20 h. In vitro, rifaximin flux was increased and the apparent permeability was constant as a function of increasing supersaturation level. In vivo, on the other hand, absorption rate coefficient (k a ) was first constant as a function of increasing supersaturation, but at 250×, the crystalline solubility k a was doubled, similar to the k a in the presence of the strong P-gp inhibitor GF120918. In conclusion, a new and favorable nature of solubility-permeability interplay was revealed in this work: delivering high supersaturation level of the BCS class IV drug rifaximin via ASD, thereby saturating the drugs' P-gp-mediated efflux transport, led to the favorable unique win-win situation, where both the solubility and the permeability increased simultaneously.

Precipitation of calcium carbonate in aqueous solutions in presence of ethylene glycol and dodecane.

NASA Astrophysics Data System (ADS)

Natsi, Panagiota D.; Rokidi, Stamatia; Koutsoukos, Petros G.

2015-04-01

The formation of calcium carbonate (CaCO3) in aqueous supersaturated solutions has been intensively studied over the past decades, because of its significance for a number of processes of industrial and environmental interest. In the oil and gas production industry the deposition of calcium carbonate affects adversely the productivity of the wells. Calcium carbonate scale deposits formation causes serious problems in water desalination, CO2 sequestration in subsoil wells, in geothermal systems and in heat exchangers because of the low thermal coefficient of the salt. Amelioration of the operational conditions is possible only when the mechanisms underlying nucleation and crystal growth of calcium carbonate in the aqueous fluids is clarified. Given the fact that in oil production processes water miscible and immiscible hydrocarbons are present the changes of the dielectric constant of the fluid phase has serious impact in the kinetics of calcium carbonate precipitation, which remains largely unknown. The problem becomes even more complicated if polymorphism exhibited by calcium carbonate is also taken into consideration. In the present work, the stability of aqueous solutions supersaturated with respect to all calcium carbonate polymorphs and the subsequent kinetics of calcium carbonate precipitation were measured. The measurements included aqueous solutions and solutions in the presence of water miscible (ethylene glycol, MEG) and water immiscible organics (n-dodecane). All measurements were done at conditions of sustained supersaturation using the glass/ Ag/AgCl combination electrode as a probe of the precipitation and pH as the master variable for the addition of titrant solutions with appropriate concentration needed to maintenance the solution supersaturation. Initially, the metastable zone width was determined from measurements of the effect of the solution supersaturation on the induction time preceding the onset of precipitation at free-drift conditions. The rates of crystal growth were measured as a function of the solution supersaturation using the highly accurate and reproducible methodology of constant supersaturation. The dependence of the rates of crystal growth on supersaturation suggested surface diffusion controlled mechanism. At constant supersaturation it was possible to extend the time period for the growth of the initially forming polymorph, in a way that sufficient amount is precipitated for characterization with X-ray diffraction (XRD). Moreover, scanning electron microscopy (SEM) was used for the characterization of the morphology of the precipitated solid. In all cases and depending on the solution supersaturation vaterite formed first from solutions of high supersaturation while at low supersaturations calcite formed exclusively. The presence of dodecane reduced the stability of the supersaturated solutions with the crystals forming at the oil-water interface. The presence of ethylene glycol (concentrations between 10-80%) also affected the stability and the kinetics of calcium carbonate precipitation. The morphology of the formed crystals showed habit modifications: Spherical formations consisting of aggregated nanocrystals and calcite crystals with profound pits on the faces were the characteristic feature in the presence of dodecane. ACKNOWLEDGMENT This research was partially funded by the European Union (European Social Fund-ESF) and Greek National Funds through the Operational program Education and Lifelong Learning under the action Aristeia II( Code No 4420).

In-line bulk supersaturation measurement by electrical conductometry in KDP crystal growth from aqueous solution

NASA Astrophysics Data System (ADS)

Bordui, P. F.; Loiacono, G. M.

1984-07-01

A method is presented for in-line bulk supersaturation measurement in crystal growth from aqueous solution. The method is based on a computer-controlled concentration measurement exploiting an experimentally predetermined cross-correlation between the concentration, electrical conductivity, and temperature of the growth solution. The method was applied to Holden crystallization of potassium dihydrogen phosphate (KDP). An extensive conductivity-temperature-concentration data base was generated for this system over a temperature range of 31 to 41°C. The method yielded continous, automated bulk supersaturation output accurate to within ±0.05 g KDP100 g water (±0.15% relative supersaturation).

Mineral saturation states in natural waters and their sensitivity to thermodynamic and analytical errors

USGS Publications Warehouse

Nordstrom, D. Kirk; Ball, James W.

1989-01-01

Saturation indices computed with WATEQ4F chemical analyses from a groundwater in crystalline bedrock and a surface water receiving acid mine drainage are frequently at or above saturation with respect to calcite, fluorite, barite, gibbsite and ferrihydrite. Deep granitic groundwaters from Stripa, Sweden, are supersaturated with respect to calcite and fluorite. Acid mine waters from the Leviathan Mine drainage basin in California are supersaturated with respect to barite by about a factor of three. These mine waters also are 10 times supersaturated with respect to the most soluble form of ferric hydroxide but are near saturation with respect to microcrystalline gibbsite. A sensitivity analysis has been performed by varying the analytic and thermodynamic parameters for which the saturation indices are most sensitive. For calcite, fluorite and barite, the supersaturation effect appears to be real because it is only slightly decreased by sources of uncertainty. Apparent supersaturation for gibbsite is most likely caused by the degree of crystallinity on solubility behavior. Apparent supersaturation for ferric hydroxide is likely caused by small colloidal particles (< 0.1 µm) in the water sample that cannot be removed by standard field filtration, although several other possible explanations cannot be easily excluded.

Toward the establishment of standardized in vitro tests for lipid-based formulations, part 3: understanding supersaturation versus precipitation potential during the in vitro digestion of type I, II, IIIA, IIIB and IV lipid-based formulations.

PubMed

Williams, Hywel D; Sassene, Philip; Kleberg, Karen; Calderone, Marilyn; Igonin, Annabel; Jule, Eduardo; Vertommen, Jan; Blundell, Ross; Benameur, Hassan; Müllertz, Anette; Pouton, Colin W; Porter, Christopher J H

2013-12-01

Recent studies have shown that digestion of lipid-based formulations (LBFs) can stimulate both supersaturation and precipitation. The current study has evaluated the drug, formulation and dose-dependence of the supersaturation - precipitation balance for a range of LBFs. Type I, II, IIIA/B LBFs containing medium-chain (MC) or long-chain (LC) lipids, and lipid-free Type IV LBF incorporating different doses of fenofibrate or tolfenamic acid were digested in vitro in a simulated intestinal medium. The degree of supersaturation was assessed through comparison of drug concentrations in aqueous digestion phases (APDIGEST) during LBF digestion and the equilibrium drug solubility in the same phases. Increasing fenofibrate or tolfenamic acid drug loads (i.e., dose) had negligible effects on LC LBF performance during digestion, but promoted drug crystallization (confirmed by XRPD) from MC and Type IV LBF. Drug crystallization was only evident in instances when the calculated maximum supersaturation ratio (SR(M)) was >3. This threshold SR(M) value was remarkably consistent across all LBF and was also consistent with previous studies with danazol. The maximum supersaturation ratio (SR(M)) provides an indication of the supersaturation 'pressure' exerted by formulation digestion and is strongly predictive of the likelihood of drug precipitation in vitro. This may also prove effective in discriminating the in vivo performance of LBFs.

Implications of Observed High Supersaturation for TTL Cloud Formation and Dehydration

NASA Technical Reports Server (NTRS)

Jensen, Eric

2004-01-01

In situ measurements of water vapor concentration made during the CRYSTAL-FACE and Pre-AVE missions indicate higher than expected supersaturations in both clear and cloudy air near the cold tropical tropopause: (1) steady-state ice supersaturations of 20-30% were measured within cirrus at T < 200 K; (2) supersaturations exceeding 100% (near water saturation) were observed under cloud-free conditions near 187 K. The in-cloud measurements challenge the conventional belief that any water vapor in excess of ice saturation should be depleted by crystal growth given sufficient time. The high clear-sky supersaturations imply that thresholds for ice nucleation due to homogeneous freezing of aerosols (or any other mechanism) are much higher than those inferred from laboratory measurements. We will use simulations of Tropical Tropopause Layer (TTL) transport and cloud formation throughout the tropics to show that these effects have important implications for TTL cloud frequency and freeze-drying of air crossing the tropical tropopause cold trap.

Effect of ethanol on crystallization of the polymorphs of L-histidine

NASA Astrophysics Data System (ADS)

Wantha, Lek; Punmalee, Neeranuch; Sawaddiphol, Vanida; Flood, Adrian E.

2018-05-01

It is known that the antisolvents used for crystallization can affect the crystallization outcome and may promote the crystallization of a specific polymorph. In this study L-histidine (L-his) is used as a model substance, and ethanol was selected to be an antisolvent. The formation of the polymorphs of L-his in antisolvent crystallization as a function of supersaturation, ethanol volume fraction, and temperature was studied. The induction time for the antisolvent crystallization was also measured. The results showed that the induction time decreases with higher supersaturation and ethanol volume fraction, indicating that the nucleation rate of L-his from antisolvent crystallization (where water was used as the solvent and ethanol as the antisolvent) increases with higher supersaturation, as expected, and ethanol fraction. At all temperatures studied, the pure metastable polymorph B of L-his was obtained initially at higher ethanol volume fraction and supersaturation, while a mixture of the polymorphs A and B was obtained at lower ethanol volume fraction and supersaturation.

Can Supersaturation Affect Protein Crystal Quality?

NASA Technical Reports Server (NTRS)

Gorti, Sridhar

2013-01-01

In quiescent environments (microgravity, capillary tubes, gels) formation of a depletion zone is to be expected, due either to limited sedimentation, density driven convection or a combination of both. The formation of a depletion zone can: Modify solution supersaturation near crystal; Give rise to impurity partitioning. It is conjectured that both supersaturation and impurity partitioning affect protein crystal quality and size. Further detailed investigations on various proteins are needed to assess above hypothesis.

Molecular mechanism of polymer-assisting supersaturation of poorly water-soluble loratadine based on experimental observations and molecular dynamic simulations.

PubMed

Zhang, Shenwu; Sun, Mengchi; Zhao, Yongshan; Song, Xuyang; He, Zhonggui; Wang, Jian; Sun, Jin

2017-10-01

Polymers have been usually used to retard nucleation and crystal growth in order to maintain supersaturation, yet their roles in inhibition of nucleation and crystal growth are poorly understood. In our work, the polymer-based supersaturation performances and molecular mechanisms of poorly aqueous soluble loratadine were investigated. Two common hydrophilic polymers (hydroxylpropylmethyl cellulose acetate succinate (HPMC-AS) and poly(vinylpyrrolidone-co-vinyl-acetate) (PVP-VA)) were used. It was found that HPMC-AS was a better polymer to prevent drug molecules from aggregation and to maintain the supersaturated state in solution than PVP-VA. The in vitro dissolution experiments showed that HPMC-AS solid dispersions had more rapid release at pH 4.5 and 6.8 media than PVP-VA solid dispersions under the un-sink condition. Moreover, molecular dynamic simulation results showed that HPMC-AS was more firmly absorbed onto a surface of the drug nanoparticles than PVP-VA due to bigger hydrophobic areas of HPMC-AS. Thereby, crystallization process of loratadine was inhibited in the presence of water to provide prolonged stability of the supersaturated state. In conclusion, polymers played a key role in maintaining supersaturation state of loratadine solid dispersions by strong drug-polymer interactions and the hydrophobic characteristic of polymers.

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

PubMed

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

2015-08-01

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

Atmospheric moisture supersaturatons in the near-surface atmosphere of Dome C, Antarctic Plateau

NASA Astrophysics Data System (ADS)

Genthon, Christophe; Piard, Luc; Vignon, Etienne; Madeleine, Jean-Baptiste; Casado, Mathieu; Gallée, Hubert

2017-04-01

Moisture supersaturations occur at the top of the troposphere where cirrus clouds form, but is comparatively unusual near the surface where the air is generally warmer and laden with liquid and/or ice condensation nuclei. One exception is the surface of the high antarctic plateau. This study presents one year of atmospheric moisture measurement at the surface of Dome C on the East Antarctic plateau. The measurements are obtained using commercial hygrometry sensors adapted to allow air sampling without affecting the moisture content even in case of supersaturation. Supersaturation is found to be very frequent. Common unadapted hygrometry sensors generally fail to report supersaturation, and most reports of atmospheric moisture on the antarctic plateau are thus likely biased low. The measurements are compared with results from 2 models with cold microphysics parametrizations: the European Center for Medium-range Weather Forecasts through its operational analyses, and the Model Atmosphérique Régional. As in the observations, supersaturation is frequent in the models but the statistical distribution differs both between models and observations and between the 2 models, leaving much room for model improvement. The representation of supersaturations is not critical for the estimations of surface sublimation since they are more frequent as temperature is lower i.e. as moisture quantities and water fluxes are small. However, ignoring near-surface supersaturation may be a more serious issue for the modeling of fog and when considering water isotopes, a tracer of phase change and temperature, largely used to reconstruct past climates and environments from ice cores. Because observations are easier in the surface atmosphere, longer and more continuous in situ observation series of atmospheric supersaturation can be obtained than higher in the atmosphere to test parameterizations of cold microphysics, such as those used in the formation of high altitude cirrus clouds in meteorological models.

Mass-transfer and supersaturation in crystal growth in gels. Application to CaSO 4·2H 2O

NASA Astrophysics Data System (ADS)

Prieto, M.; Viedma, C.; López-Acevedo, V.; Martín-Vivaldi, J. L.; López-Andrés, S.

1988-10-01

Supersaturation evaluation is an essential requirement to describe, confront and explain crystal growth experiences. However, in the particular case of crystal growth in gels, experiences are often described by attending to the initial concentration of reagent. This fact is connected with deficiencies in the theoretical quantification of mass-transfer, and therefore in both time and location prediction for the first precipitate. In this paper laboratory experiences have been specifically designed to test supersaturation evolution through an actual (finite) diffusion system. The problem is carried out by keeping into account several complexity factors: free ions as well as complexes and silica gel Na + and Cl - "unloading" are considered to evaluate the supersaturation.

Membrane penetration enhancement of ibuprofen using supersaturation.

PubMed

Iervolino, M; Raghavan, S L; Hadgraft, J

2000-04-05

Permeation enhancement of ibuprofen from supersaturated solutions formed using the cosolvent technique was investigated using silicone as a model membrane. Hydroxpropyl methyl cellulose and hydroxpropyl-beta-cyclodextrin were used to stabilise the supersaturated states. Physical stability studies showed best results for low drug concentrations in a 40:60 propylene glycol/water cosolvent system. Variations in flux across model silicone membranes from saturated solutions were observed as the PG content was increased. The flux of IBU increased with the degree of saturation for solutions prepared in a 40:60 PG/water cosolvent mixture. HPMC and CD were found to be effective in enhancing the stability of supersaturated solutions of IBU. The mechanisms of action are different for the two additives and are discussed.

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.

Maintenance of supersaturation I: indomethacin crystal growth kinetic modeling using an online second-derivative ultraviolet spectroscopic method.

PubMed

Patel, Dhaval D; Joguparthi, Vijay; Wang, Zeren; Anderson, Bradley D

2011-07-01

Formulations that produce supersaturated solutions after their oral administration have received increased attention as a means to improve bioavailability of poorly water-soluble drugs. Although it is widely recognized that excipients can prolong supersaturation, the mechanisms by which these beneficial effects are realized are generally unknown. Difficulties in separately measuring the kinetics of nucleation and crystal growth have limited progress in understanding the mechanisms by which excipients contribute to the supersaturation maintenance. This paper describes the crystal growth kinetic modeling of indomethacin, a poorly water-soluble drug, from supersaturated aqueous suspensions using a newly developed, online second-derivative ultraviolet spectroscopic method. The apparent indomethacin equilibrium solubility after crystal growth at a high degree of supersaturation (S=6) was approximately 55% higher than the indomethacin equilibrium solubility determined prior to growth, which was attributed to the deposition of a higher energy indomethacin form on the seed crystals. The indomethacin crystal growth kinetics (S=6) was of first order. By comparing the mass transfer coefficients from indomethacin dissolution and crystal growth, it was shown that the indomethacin crystal growth kinetics at S=6 was bulk diffusion controlled. The change in indomethacin seed crystal size distribution before and after crystal growth was determined and modeled using a mass-balance relationship. Copyright © 2011 Wiley-Liss, Inc. and the American Pharmacists Association

Glass-liquid phase separation in highly supersaturated aqueous solutions of telaprevir.

PubMed

Mosquera-Giraldo, Laura I; Taylor, Lynne S

2015-02-02

Amorphous solid dispersions are of great current interest because they can improve the delivery of poorly water-soluble compounds. It has been recently noted that the highly supersaturated solutions generated by dissolution of some ASDs can undergo a phase transition to a colloidal, disordered, drug-rich phase when the concentration exceeds the "amorphous solubility" of the drug. The purpose of this study was to investigate the phase behavior of supersaturated solutions of telaprevir, which is formulated as an amorphous solid dispersion in the commercial product. Different analytical techniques including proton nuclear magnetic resonance spectroscopy (NMR), ultraviolet spectroscopy (UV), fluorescence spectroscopy and flux measurements were used to evaluate the properties of aqueous supersaturated solutions of telaprevir. It was found that highly supersaturated solutions of telaprevir underwent glass-liquid phase separation (GLPS) when the concentration exceeded 90 μg/mL, forming a water-saturated colloidal, amorphous drug-rich phase with a glass transition temperature of 52 °C. From flux measurements, it was observed that the "free" drug concentration reached a maximum at the concentration where GLPS occurred, and did not increase further as the concentration was increased. This phase behavior, which results in a precipitate and a metastable equilibrium between a supersaturated solution and a drug-rich phase, is obviously important in the context of evaluating amorphous solid dispersion formulations and their crystallization routes.

Gypsum crystallization from cadmium-poisoned solutions

NASA Astrophysics Data System (ADS)

Rinaudo, C.; Franchini-Angela, M.; Boistelle, R.

1988-06-01

Gypsum crystals, CaSO4⋯2H2O, are grown from solutions containing large amounts of cadmium chloride as an impurity. The initial supersaturations necessary for the gypsum nucleation increase with increasing cadmium concentration. Accordingly, at constant initial supersaturation, the induction periods also increase with increasing cadmium concentration. Cadmium and chlorine are incorporated into the crystals probably as CdCl+ or CdCl2, which are the most abundant complexes in the solutions. Consequently, the gypsum crystals grow curved, distorted and exhibit fractures along the [100] direction. The amount of incorporated cadmium increases with increasing supersaturation. Cadmium is mainly detected near the {120} faces in the area where the fractures release the internal stresses. Supersaturation and concentration of free ions and complexes are calculated for all solutions. Adsorption on {120} is discussed.

Crystallization of a salt of a weak organic acid and base: solubility relations, supersaturation control and polymorphic behavior.

PubMed

Jones, H P; Davey, R J; Cox, B G

2005-03-24

Control of crystallization processes for organic salts is of importance to the pharmaceutical industry as many active pharmaceutical materials are marketed as salts. In this study, a method for estimating the solubility product of a salt of a weak acid and weak base from measured pH-solubility data is described for the first time. This allows calculation of the supersaturation of solutions at known pH. Ethylenediammonium 3,5-dinitrobenzoate is a polymorphic organic salt. A detailed study of the effects of pH, supersaturation, and temperature of crystallization on the physical properties of this salt shows that the desired polymorph may be produced by appropriate selection of the pH and supersaturation of crystallization. Crystal morphology is also controlled by these crystallization conditions.

Effect of surfactants, gastric emptying, and dosage form on supersaturation of dipyridamole in an in vitro model simulating the stomach and duodenum.

PubMed

Mitra, A; Fadda, H M

2014-08-04

The purpose of this study was to investigate the influence of gastric emptying patterns, surfactants, and dosage form on the supersaturation of a poorly soluble weakly basic drug, dipyridamole, using an in vitro model mimicking the dynamic environment of the upper gastrointestinal tract, and, furthermore, to evaluate the usefulness of this model in establishing correlations to in vivo bioavailability for drugs with solubility/dissolution limited absorption. A simulated stomach duodenum model comprising four compartments was used to assess supersaturation and precipitation kinetics as a function of time. It integrates physiologically relevant fluid volumes, fluid transfer rates, and pH changes of the upper GI tract. Monoexponential gastric emptying patterns simulating the fasted state were compared to linear gastric emptying patterns simulating the fed state. The effect of different surfactants commonly used in oral preparations, specifically, sodium lauryl sulfate (SLS), poloxamer-188, and polysorbate-80, on dipyridamole supersaturation was investigated while maintaining surface tension of the simulated gastric fluids at physiological levels and without obtaining artificial micellar solubilization of the drug. The supersaturation behavior of different dose strengths of dipyridamole was explored. Significant levels of dipyridamole supersaturation were observed in the duodenal compartment under all the different in vivo relevant conditions explored. Dipyridamole supersaturation ratios of up to 11-fold have been observed, and supersaturation has been maintained for up to 120 min. Lower duodenal concentrations of dipyridamole were observed under linear gastric emptying patterns compared to mononexponential gastric emptying. The mean duodenal area under concentration-time curves (AUC60min) for the dipyridamole concentration profile in the duodenal compartment is significantly different for all the surfactants explored (P < 0.05). Our investigations with the different surfactants and comparison of dosage form (solution versus suspension) on the precipitation of dipyridamole revealed that crystal growth, rather than nucleation, is the rate-limiting step for the precipitation of dipyridamole. A linear dose-response relationship was found for the mean in vitro duodenal area under concentration-time curves (AUC∞) in the dose range of 25 mg to 100 mg (R(2) = 0.886). This is in agreement with the pharmacokinetic data of dipyridamole reported in the literature. The simulated stomach duodenum model can provide a reliable and discriminative screening tool for exploring the effect of different physiological variables or formulations on the supersaturation/precipitation kinetics of weakly basic drugs with solubility limited absorption. The amount of drug in solution in the duodenal compartment of the SSD correlates to bioavailability for the weakly basic drug, dipyridamole, which has solubility limited absorption and undergoes supersaturation/precipitation.

The impact of supersaturation level for oral absorption of BCS class IIb drugs, dipyridamole and ketoconazole, using in vivo predictive dissolution system: Gastrointestinal Simulator (GIS).

PubMed

Tsume, Yasuhiro; Matsui, Kazuki; Searls, Amanda L; Takeuchi, Susumu; Amidon, Gregory E; Sun, Duxin; Amidon, Gordon L

2017-05-01

The development of formulations and the assessment of oral drug absorption for Biopharmaceutical Classification System (BCS) class IIb drugs is often a difficult issue due to the potential for supersaturation and precipitation in the gastrointestinal (GI) tract. The physiological environment in the GI tract largely influences in vivo drug dissolution rates of those drugs. Thus, those physiological factors should be incorporated into the in vitro system to better assess in vivo performance of BCS class IIb drugs. In order to predict oral bioperformance, an in vitro dissolution system with multiple compartments incorporating physiologically relevant factors would be expected to more accurately predict in vivo phenomena than a one-compartment dissolution system like USP Apparatus 2 because, for example, the pH change occurring in the human GI tract can be better replicated in a multi-compartmental platform. The Gastrointestinal Simulator (GIS) consists of three compartments, the gastric, duodenal and jejunal chambers, and is a practical in vitro dissolution apparatus to predict in vivo dissolution for oral dosage forms. This system can demonstrate supersaturation and precipitation and, therefore, has the potential to predict in vivo bioperformance of oral dosage forms where this phenomenon may occur. In this report, in vitro studies were performed with dipyridamole and ketoconazole to evaluate the precipitation rates and the relationship between the supersaturation levels and oral absorption of BCS class II weak base drugs. To evaluate the impact of observed supersaturation levels on oral absorption, a study utilizing the GIS in combination with mouse intestinal infusion was conducted. Supersaturation levels observed in the GIS enhanced dipyridamole and ketoconazole absorption in mouse, and a good correlation between their supersaturation levels and their concentration in plasma was observed. The GIS, therefore, appears to represent in vivo dissolution phenomena and demonstrate supersaturation and precipitation of dipyridamole and ketoconazole. We therefore conclude that the GIS has been shown to be a good biopredictive tool to predict in vivo bioperformance of BCS class IIb drugs that can be used to optimize oral formulations. Copyright © 2017. Published by Elsevier B.V.

Variation in Supersaturation and Phase Behavior of Ezetimibe Amorphous Solid Dispersions upon Dissolution in Different Biorelevant Media.

PubMed

Elkhabaz, Ahmed; Sarkar, Sreya; Dinh, Janny K; Simpson, Garth J; Taylor, Lynne S

2018-01-02

The delivery of poorly water-soluble drugs using amorphous solid dispersions (ASDs) has been widely acknowledged as a promising strategy for enhancing oral bioavailability. Upon dissolution, ASDs have accelerated dissolution rates and yield supersaturated solutions leading to higher apparent solubilities. Understanding the complex phase behavior of ASDs during dissolution is crucial for developing an effective formulation. Since the absorption of a lipophilic, high permeability drug is determined primarily by the intraluminal dissolution process and the final concentration achieved, there is a need for evaluation in biorelevant dissolution media that simulate both fasting and fed gastrointestinal states. In this study, using ezetimibe as a model drug, three different ASDs were prepared using poly(acrylic acid) (PAA), polyvinylpyrrolidone (PVP), and hydroxypropyl methylcellulose acetyl succinate (HPMC-AS). Dissolution of ASDs was carried out in sodium phosphate buffer, fed-state simulated intestinal fluid (FeSSIF), and Ensure Plus to evaluate the impact of different dissolution media on release profile, supersaturation, and phase behavior. The supersaturation level and crystallization kinetics varied among the dispersions and were found to be highly dependent on the medium employed. The presence of solubilizing additives in biorelevant media greatly affected the generation and stabilization of supersaturated solutions. Second harmonic generation microscopy was found to enable the detection of crystals in all media including the highly turbid Ensure Plus system. In conclusion, it is important to evaluate the impact of complex biorelevant media on the dissolution performance of ASDs to better design supersaturating formulations for oral delivery.

Review of isothermal haze chamber performance

NASA Technical Reports Server (NTRS)

Fitzgerald, J. W.; Rogers, C. F.; Hudson, J. G.

1981-01-01

The theory of this method of characterizing cloud condensation nuclei (CCN) over the critical supersaturation range of about 0.01% to 0.2% was reviewed, and guidelines for the design and operation of IHC's are given. IHC data are presented and critically analyzed. Two of the four IHC's agree to about 40% over the entire range of critical. a third chamber shows similar agreement with the first two over the lower part of the critical supersaturation range but only a factor of two agreement at higher supersaturation. Some reasons for the discrepancies are given.

Crystallization of pure anhydrous polymorphs of carbamazepine by solution enhanced dispersion with supercritical fluids (SEDS).

PubMed

Edwards, A D; Shekunov, B Y; Kordikowski, A; Forbes, R T; York, P

2001-08-01

Pure anhydrous polymorphs of carbamazepine were prepared by solution-enhanced dispersion with supercritical fluids (SEDS). Crystallization of the polymorphs was studied. Mechanisms are proposed that consider the thermodynamics of carbamazepine, supersaturation in the SEDS process, and the binary phase equilibria of organic solvents and the carbon dioxide antisolvent. alpha-Carbamazepine was crystallized at high supersaturations and low temperatures, beta-carbamazepine crystallized from a methanol-carbon dioxide phase split, and gamma-carbamazepine crystallized via nucleation at high temperatures and low supersaturation. Copyright 2001 Wiley-Liss, Inc.

Molecular dynamics simulations of the surface tension of oxygen-supersaturated water

NASA Astrophysics Data System (ADS)

Jain, S.; Qiao, L.

2017-04-01

In this work, non-reactive molecular dynamic simulations were conducted to determine the surface tension of water as a function of the concentration of the dissolved gaseous molecules (O2), which would in turn help to predict the pressure inside the nanobubbles under supersaturation conditions. Knowing the bubble pressure is a prerequisite for understanding the mechanisms behind the spontaneous combustion of the H2/O2 gases inside the nanobubbles. First, the surface tension of pure water was determined using the planar interface method and the Irving and Kirkwood formula. Next, the surface tension of water containing four different supersaturation concentrations (S) of O2 gas molecules was computed considering the curved interface of a nanobubble. The surface tension of water was found to decrease with an increase in the supersaturation ratio or the concentration of the dissolved O2 gas molecules.

Effect of supersaturation on L-glutamic acid polymorphs under droplet-based microchannels

NASA Astrophysics Data System (ADS)

Jiang, Nan; Wang, Zhanzhong; Dang, Leping; Wei, Hongyuan

2016-07-01

Supersaturation is an important controlling factor for crystallization process and polymorphism. Droplet-based microchannels and conventional crystallization were used to investigate polymorphs of L-gluatamic acid in this work. The results illustrate that it is easy to realize the accurate and rapid control of the crystallization temperature in the droplets, which is especially beneficial to heat and mass transfer during crystallization. It is also noted that higher degree of supersaturation favors the nucleation of α crystal form, while lower degree of supersaturation favors the nucleation of β crystal form under droplet-based microchannels for L-gluatamic acid. In addition, there is a different nucleation behavior to be found under droplet-based microchannels both for the β form and α form of L-glutamic acid. This new finding can provide important insight into the development and design of investigation meanings for drug polymorph.

Utilisation of adsorption and desorption for simultaneously improving protein crystallisation success rate and crystal quality

NASA Astrophysics Data System (ADS)

Guo, Yun-Zhu; Sun, Li-Hua; Oberthuer, Dominik; Zhang, Chen-Yan; Shi, Jian-Yu; di, Jiang-Lei; Zhang, Bao-Liang; Cao, Hui-Ling; Liu, Yong-Ming; Li, Jian; Wang, Qian; Huang, Huan-Huan; Liu, Jun; Schulz, Jan-Mirco; Zhang, Qiu-Yu; Zhao, Jian-Lin; Betzel, Christian; He, Jian-Hua; Yin, Da-Chuan

2014-12-01

High-quality protein crystals of suitable size are an important prerequisite for applying X-ray crystallography to determine the 3-dimensional structure of proteins. However, it is often difficult to obtain protein crystals of appropriate size and quality because nucleation and growth processes can be unsuccessful. Here, we show that by adsorbing proteins onto porous polystyrene-divinylbenzene microspheres (SDB) floating on the surface of the crystallisation solution, a localised high supersaturation region at the surface of the microspheres and a low supersaturation region below the microspheres can coexist in a single solution. The crystals will easily nucleate in the region of high supersaturation, but when they grow to a certain size, they will sediment to the region of low supersaturation and continue to grow. In this way, the probability of crystallisation and crystal quality can be simultaneously increased in a single solution without changing other crystallisation parameters.

Penetration enhancement of ibuprofen from supersaturated solutions through human skin.

PubMed

Iervolino, M; Cappello, B; Raghavan, S L; Hadgraft, J

2001-01-05

Systematic investigations on the diffusion of ibuprofen (IBU) from supersaturated solutions through human epidermis are reported. Significant flux enhancement was obtained from supersaturated solutions compared to the saturated solution. Hydroxypropyl methylcellulose (HPMC), when used as an additive was found to be effective in maintaining the high activity state at high degrees of saturation (DS). The increase in the flux was proportional to the DS. In the presence of 2-hydroxypropyl-beta-cyclodextrin (CD) at DS 2 and 3 a lower flux was observed compared to HPMC. At DS 5 a higher flux enhancement was found suggesting that CD might act as a penetration enhancer at certain CD/drug ratios. Studies on the mechanism of stabilisation of HPMC and CD on IBU crystallisation from supersaturated systems showed that HPMC acts as a growth inhibitor and habit modifier whereas CD does not influence the crystallisation process.

Metastable Solution Thermodynamic Properties and Crystal Growth Kinetics

NASA Technical Reports Server (NTRS)

Kim, Soojin; Myerson, Allan S.

1996-01-01

The crystal growth rates of NH4H2PO4, KH2PO4, (NH4)2SO4, KAl(SO4)2 central dot 12H2O, NaCl, and glycine and the nucleation rates of KBr, KCl, NaBr central dot 2H2O, (NH4)2Cl, and (NH4)2SO4 were expressed in terms of the fundamental driving force of crystallization calculated from the activity of supersaturated solutions. The kinetic parameters were compared with those from the commonly used kinetic expression based on the concentration difference. From the viewpoint of thermodynamics, rate expressions based on the chemical potential difference provide accurate kinetic representation over a broad range of supersaturation. The rates estimated using the expression based on the concentration difference coincide with the true rates of crystallization only in the concentration range of low supersaturation and deviate from the true kinetics as the supersaturation increases.

The growth of oscillating bubbles in an ultrasound field

NASA Astrophysics Data System (ADS)

Yamauchi, Risa; Yamashita, Tatsuya; Ando, Keita

2017-11-01

From our recent experiments to test particle removal by underwater ultrasound, dissolved gas supersaturation is found to play an important role in physical cleaning; cavitation bubble nucleation can be triggered easily by weak ultrasound under the supersaturation and mild motion of the bubbles contributes to efficient cleaning without erosion. The state of gas bubble nuclei in water is critical to the determination of a cavitation inception threshold. Under ultrasound forcing, the size of bubble nuclei is varied by the transfer of dissolved gas (i.e., rectified diffusion); the growth rate will be promoted by the supersaturation and is thus expected to contribute to cavitation activity enhancement. In the present work, we experimentally study rectified diffusion for bubbles attached at glass surfaces in an ultrasound field. We will present the evolution of bubble nuclei sizes with varying parameters such as dissolved oxygen supersaturation, and ultrasound intensity and frequency. the Research Grant of Keio Leading-edge Laboratory of Science & Technology.

Stable supersaturated aqueous solutions of silatecan 7-t-butyldimethylsilyl-10-hydroxycamptothecin via chemical conversion in the presence of a chemically modified beta-cyclodextrin.

PubMed

Xiang, Tian-Xiang; Anderson, Bradley D

2002-08-01

A method for obtaining clear supersaturated aqueous solutions for parenteral administration of the poorly soluble experimental anti-cancer drug silatecan 7-t-butyldimethylsilyl-10-hydroxycamptothecin (DB-67) has been developed. Equilibrium solubilities of DB-67 were determined in various solvents and pH values, and in the presence of chemically modified water-soluble beta-cyclodextrins. The stoichiometry and binding constants for complexes of the lactone form of DB-67 and its ring-opened carboxylate with sulfobutyl ether and 2-hydroxypropyl substituted beta-cyclodextrins (SBE-CD and HP-CD) were obtained by solubility and circular dichroism spectroscopy, respectively. Kinetics for the reversible ring-opening of DB-67 in aqueous solution and for lactone precipitation were determined by HPLC with UV detection. Solubilities of DB-67 lactone in various injectable solvent systems were found to be at least one order of magnitude below the target concentration (2 mg/ml). DB-67 forms inclusion complexes with SBE-CD and HP-CD but the solubilization attainable is substantially less than the target concentration. Slow addition of DB-67/ DMSO into 22.2% (w/v) SBE-CD failed to yield stable supersaturated solutions due to precipitation. Stable supersatured solutions were obtained, however, by mixing a concentrated alkaline aqueous solution of DB-67 carboxylate with an acidified 22.2% (w/v) SBE-CD solution. Ring-closure yielded supersaturated solutions that could be lyophilized and reconstituted to clear, stable, supersaturated solutions. The method developed provides an alternative to colloidal dispersions (e.g., liposomal suspensions, emulsions, etc.) for parenteral administration of lipophilic camptothecin analogs.

Effect of Potassium Citrate on Calcium Phosphate Stones in a Model of Hypercalciuria

PubMed Central

Asplin, John R.; Frick, Kevin K.; Granja, Ignacio; Culbertson, Christopher D.; Ng, Adeline; Grynpas, Marc D.; Bushinsky, David A.

2015-01-01

Potassium citrate is prescribed to decrease stone recurrence in patients with calcium nephrolithiasis. Citrate binds intestinal and urine calcium and increases urine pH. Citrate, metabolized to bicarbonate, should decrease calcium excretion by reducing bone resorption and increasing renal calcium reabsorption. However, citrate binding to intestinal calcium may increase absorption and renal excretion of both phosphate and oxalate. Thus, the effect of potassium citrate on urine calcium oxalate and calcium phosphate supersaturation and stone formation is complex and difficult to predict. To study the effects of potassium citrate on urine supersaturation and stone formation, we utilized 95th-generation inbred genetic hypercalciuric stone-forming rats. Rats were fed a fixed amount of a normal calcium (1.2%) diet supplemented with potassium citrate or potassium chloride (each 4 mmol/d) for 18 weeks. Urine was collected at 6, 12, and 18 weeks. At 18 weeks, stone formation was visualized by radiography. Urine citrate, phosphate, oxalate, and pH levels were higher and urine calcium level was lower in rats fed potassium citrate. Furthermore, calcium oxalate and calcium phosphate supersaturation were higher with potassium citrate; however, uric acid supersaturation was lower. Both groups had similar numbers of exclusively calcium phosphate stones. Thus, potassium citrate effectively raises urine citrate levels and lowers urine calcium levels; however, the increases in urine pH, oxalate, and phosphate levels lead to increased calcium oxalate and calcium phosphate supersaturation. Potassium citrate induces complex changes in urine chemistries and resultant supersaturation, which may not be beneficial in preventing calcium phosphate stone formation. PMID:25855777

Investigation of novel supersaturating drug delivery systems of chlorthalidone: The use of polymer-surfactant complex as an effective carrier in solid dispersions.

PubMed

França, Maria Terezinha; Nicolay Pereira, Rafael; Klüppel Riekes, Manoela; Munari Oliveira Pinto, Juliana; Stulzer, Hellen Karine

2018-01-01

Supersaturating drug delivery systems (SDDS), as solid dispersions (SDs), stand out among strategies to enhance bioavailability of poorly soluble drugs. After oral administration, their dissolution in gastrointestinal fluids often leads to supersaturation, which drives to a rapid and sustained absorption. Polymers and surfactants play important roles in SDs through inhibiting precipitation caused by transitions from amorphous into crystalline form, in supersaturated solutions, and also through improving SDs physical stability. Novel chlorthalidone SDs, a BCS IV drug, were developed using polymeric and non-polymeric carriers, specially a polymer-surfactant complex. SDs drug releases were evaluated using sink and non-sink conditions in water and biorelevant medium. Their physical stability was also monitored under different storage conditions. Polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (SOL), sodium lauryl sulfate (SLS) and a combination of both showed promising results in apparent solubility studies, and therefore they were selected to compose the spray dried SDs. Dissolution studies demonstrated the SOL-SLS complex potential for providing chlorthalidone fast release (>80% in 15min), producing and maintaining in vitro supersaturation. This formulation comprising high drug loading (75%) reached a high supersaturation degree under non-sink condition (up to 6-fold the equilibrium solubility) once maintained for 6h in biorelevant medium. In addition, this SD presented better physical stability when compared to the chlorthalidone neat amorphous. The SOL-SLS complex impacts positively on chlorthalidone release and physical stability, highlighting its potential as carrier in SDDS of a poorly soluble drug. Copyright © 2017. Published by Elsevier B.V.

Enhancements and limits in drug membrane transport using supersaturated solutions of poorly water soluble drugs.

PubMed

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

2014-09-01

Amorphous solid dispersions (ASDs) give rise to supersaturated solutions (solution concentration greater than equilibrium crystalline solubility). We have recently found that supersaturating dosage forms can exhibit the phenomenon of liquid-liquid phase separation (LLPS). Thus, the high supersaturation generated by dissolving ASDs can lead to a two-phase system wherein one phase is an initially nanodimensioned and drug-rich phase and the other is a drug-lean continuous aqueous phase. Herein, the membrane transport of supersaturated solutions, at concentrations above and below the LLPS concentration has been evaluated using a side-by-side diffusion cell. Measurements of solution concentration with time in the receiver cell yield the flux, which reflects the solute thermodynamic activity in the donor cell. As the nominal concentration of solute in the donor cell increases, a linear increase in flux was observed up to the concentration where LLPS occurred. Thereafter, the flux remained essentially constant. Both nifedipine and felodipine solutions exhibit such behavior as long as crystallization is absent. This suggests that there is an upper limit in passive membrane transport that is dictated by the LLPS concentration. These results have several important implications for drug delivery, especially for poorly soluble compounds requiring enabling formulation technologies. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Stabilization of a supersaturated solution of mefenamic acid from a solid dispersion with EUDRAGIT(®) EPO.

PubMed

Kojima, Taro; Higashi, Kenjirou; Suzuki, Toyofumi; Tomono, Kazuo; Moribe, Kunikazu; Yamamoto, Keiji

2012-10-01

The stabilization mechanism of a supersaturated solution of mefenamic acid (MFA) from a solid dispersion with EUDRAGIT(®) EPO (EPO) was investigated. The solid dispersions were prepared by cryogenic grinding method. Powder X-ray diffractometry, in vitro dissolution test, in vivo oral absorption study, infrared spectroscopy, and solid- and solution-state NMR spectroscopies were used to characterize the solid dispersions. Dissolution tests in acetate buffer (pH 5.5) revealed that solid dispersion showed > 200-fold higher concentration of MFA. Supersaturated solution was stable over 1 month and exhibited improved oral bioavailability of MFA in rats, with a 7.8-fold higher area under the plasma concentration-versus-time curve. Solid-state (1)H spin-lattice relaxation time (T(1)) measurement showed that MFA was almost monomolecularly dispersed in the EPO polymer matrix. Intermolecular interaction between MFA and EPO was indicated by solid-state infrared and (13)C-T(1) measurements. Solution-state (1)H-NMR measurement demonstrated that MFA existed in monomolecular state in supersaturated solution. (1)H-T(1) and difference nuclear Overhauser effect measurements indicated that cross relaxation occurred between MFA and EPO due to the small distance between them. The formation and high stability of the supersaturated solution were attributable to the specifically formed intermolecular interactions between MFA and EPO.

Dehydration process in NaCl solutions under various external electric fields

NASA Astrophysics Data System (ADS)

Kadota, Kazunori; Shimosaka, Atsuko; Shirakawa, Yoshiyuki; Hidaka, Jusuke

2007-06-01

Ionic motions at solid-liquid interface in supersaturated NaCl solutions have been investigated by molecular dynamics (MD) simulation for understanding crystal growth processes. The density profile in the vicinity of the interfaces between NaCl(100) and the supersaturated NaCl solution was calculated. Diffusion coefficients of water molecules in the solution were estimated as a function of distance from the crystal interface. It turned out that the structure and dynamics of the solution in the interfaces was different from those of bulk solution owing to electric fields depending on the surface charge. Therefore, the electric field was applied to the supersaturated solutions and dehydration phenomenon occurring in the process of the crystal growth was discussed. As the electric field increased, it was observed that the Na+ keeping strongly hydration structure broke out by the electric force. In supersaturated concentration, the solution structure is significantly different from that of dilution and has a complicated structure with hydration ions and clusters of NaCl. If the electric fields were applied to the solutions, the breakout of hydration structure was not affected with increasing the supersaturated ratio. This reason is that the cluster structures are destroyed by the electric force. The situation depends on the electric field or crystal surface structure.

Nucleation control and separation of paracetamol polymorphs through swift cooling crystallization process

NASA Astrophysics Data System (ADS)

Sudha, C.; Srinivasan, K.

2014-09-01

Polymorphic nucleation behavior of pharmaceutical solid paracetamol has been investigated by performing swift cooling crystallization process. Saturated aqueous solution prepared at 318 K was swiftly cooled to 274 K in steps of every 1 K in the temperature range from 274 K to 313 K with uniform stirring of 100 rpm. The resultant supersaturation generated in the mother solution favours the nucleation of three different polymorphs of paracetamol. Lower supersaturation region σ=0.10-0.83 favours stable mono form I; the intermediate supersaturation region σ=0.92-1.28 favours metastable ortho form II and the higher supersaturation region σ=1.33-1.58 favours unstable form III polymorphic nucleation. Depending upon the level of supersaturation generated during swift cooling process and the corresponding solubility limit and metastable zone width (MSZW) of each polymorph, the nucleation of a particular polymorph occurs in the system. The type of polymorphs was identified by in-situ optical microscopy and the internal structure was confirmed by Powder X-ray diffraction (PXRD) study. By this novel approach, the preferred nucleation regions of all the three polymorphs of paracetamol are optimized in terms of different cooling ranges employed during the swift cooling process. Also solution mediated polymorphic transformations from unstable to mono and ortho to mono polymorphs have been studied by in-situ.

Aspects of calcium oxalate crystallization: theory, in vitro studies, and in vivo implementation.

PubMed

Rodgers, A

1999-11-01

There are three main approaches to urolithiasis research: theory, basic science, and clinical implementation. Although each approach has yielded meaningful results, there does not appear to be complete synergy between them. This article examines these approaches as they pertain to urinary calcium oxalate crystallization processes. Theoretical calculations were performed to examine the role of oxalate concentration on calcium oxalate supersaturation. The effects of magnesium, citrate, and combinations thereof on calcium oxalate crystallization kinetics were examined in a mixed suspension, mixed product removal crystallizer. Finally, male volunteers were given supplements of calcium alone and binary combinations of calcium, magnesium, and citrate to investigate their effects on the urinary supersaturation of calcium oxalate. Calculations showed that oxalate is 23 times more potent than calcium in its effect on the supersaturation of calcium oxalate. In the in vitro experiments, magnesium and citrate reduced the growth and nucleation kinetics as well as the supersaturation. In combination, these two components were more effective than the individual components in reducing the growth rate and the supersaturation. All of the supplements favorably altered the kinetic and thermodynamic risk factors. Calcium was the most effective in reducing the urinary excretion of oxalate. Articulation of these three approaches is essential for the meaningful investigation and understanding of urolithiasis.

Improved Cloud Condensation Nucleus Spectrometer

NASA Technical Reports Server (NTRS)

Leu, Ming-Taun

2010-01-01

An improved thermal-gradient cloud condensation nucleus spectrometer (CCNS) has been designed to provide several enhancements over prior thermal- gradient counters, including fast response and high-sensitivity detection covering a wide range of supersaturations. CCNSs are used in laboratory research on the relationships among aerosols, supersaturation of air, and the formation of clouds. The operational characteristics of prior counters are such that it takes long times to determine aerosol critical supersaturations. Hence, there is a need for a CCNS capable of rapid scanning through a wide range of supersaturations. The present improved CCNS satisfies this need. The improved thermal-gradient CCNS (see Figure 1) incorporates the following notable features: a) The main chamber is bounded on the top and bottom by parallel thick copper plates, which are joined by a thermally conductive vertical wall on one side and a thermally nonconductive wall on the opposite side. b) To establish a temperature gradient needed to establish a supersaturation gradient, water at two different regulated temperatures is pumped through tubes along the edges of the copper plates at the thermally-nonconductive-wall side. Figure 2 presents an example of temperature and supersaturation gradients for one combination of regulated temperatures at the thermally-nonconductive-wall edges of the copper plates. c) To enable measurement of the temperature gradient, ten thermocouples are cemented to the external surfaces of the copper plates (five on the top plate and five on the bottom plate), spaced at equal intervals along the width axis of the main chamber near the outlet end. d) Pieces of filter paper or cotton felt are cemented onto the interior surfaces of the copper plates and, prior to each experimental run, are saturated with water to establish a supersaturation field inside the main chamber. e) A flow of monodisperse aerosol and a dilution flow of humid air are introduced into the main chamber at the inlet end. The inlet assembly is designed to offer improved (relative to prior such assemblies) laminar-flow performance within the main chamber. Dry aerosols are subjected to activation and growth in the supersaturation field. f) After aerosol activation, at the outlet end of the main chamber, a polished stainless-steel probe is used to sample droplets into a laser particle counter. The probe features an improved design for efficient sampling. The counter has six channels with size bins in the range of 0.5- to 5.0-micron diameter. g) To enable efficient sampling, the probe is scanned along the width axis of the main chamber (thereby effecting scanning along the temperature gradient and thereby, further, effecting scanning along the supersaturation gradient) by means of a computer-controlled translation stage.

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.

Decoupling of bilayer leaflets under gas supersaturation: nitrogen nanobubbles in a membrane and their implication in decompression sickness

NASA Astrophysics Data System (ADS)

Li, Jing; Zhang, Xianren; Cao, Dapeng

2018-05-01

Decompression sickness (also known as diver’s sickness) is a disease that arises from the formation of a bubble inside the body caused by rapid decompression from high atmospheric pressures. However, the nature of pre-existing micronuclei that are proposed for interpreting the formation and growth of the bubble, as well as their very existence, is still highly controversial. In this work, atomistic molecular dynamics simulations are employed to investigate the nucleation of gas bubbles under the condition of nitrogen supersaturation, in the presence of a lipid bilayer and lipid micelle representing other macromolecules with a smaller hydrophobic region. Our simulation results demonstrate that by crossing a small energy barrier, excess nitrogen molecules can enter the lipid bilayer nearly spontaneously, for which the hydrophobic core serves as a potential well for gas enrichment. At a rather low nitrogen supersaturation, gas molecules in the membrane are dispersed in the hydrophobic region of the bilayer, with a slight increase in membrane thickness. But as the level of gas supersaturation reaches a threshold, the accumulation of N2 molecules in the bilayer center causes the two leaflets to be decoupled and the formation of nanobubbles. Therefore, we propose a nucleation mechanism for bubble formation in a supersaturated solution of inert gas: a cell membrane acts as a potential well for gas enrichment, being an ideal location for forming nanobubbles that induce membrane damage at a high level of gas supersaturation. As opposed to previous models, the new mechanism involves forming gas nuclei in a very low-tension hydrophobic environment, and thus a rather low energy barrier is required and pre-existing bubble micronuclei are not needed.

Development of a Video-Microscopic Tool To Evaluate the Precipitation Kinetics of Poorly Water Soluble Drugs: A Case Study with Tadalafil and HPMC.

PubMed

Christfort, Juliane Fjelrad; Plum, Jakob; Madsen, Cecilie Maria; Nielsen, Line Hagner; Sandau, Martin; Andersen, Klaus; Müllertz, Anette; Rades, Thomas

2017-12-04

Many drug candidates today have a low aqueous solubility and, hence, may show a low oral bioavailability, presenting a major formulation and drug delivery challenge. One way to increase the bioavailability of these drugs is to use a supersaturating drug delivery strategy. The aim of this study was to develop a video-microscopic method, to evaluate the effect of a precipitation inhibitor on supersaturated solutions of the poorly soluble drug tadalafil, using a novel video-microscopic small scale setup. Based on preliminary studies, a degree of supersaturation of 29 was chosen for the supersaturation studies with tadalafil in FaSSIF. Different amounts of hydroxypropyl methyl cellulose (HPMC) were predissolved in FaSSIF to give four different concentrations, and the supersaturated system was then created using a solvent shift method. Precipitation of tadalafil from the supersaturated solutions was monitored by video-microscopy as a function of time. Single-particle analysis was possible using commercially available software; however, to investigate the entire population of precipitating particles (i.e., their number and area covered in the field of view), an image analysis algorithm was developed (multiparticle analysis). The induction time for precipitation of tadalafil in FaSSIF was significantly prolonged by adding 0.01% (w/v) HPMC to FaSSIF, and the maximum inhibition was reached at 0.1% (w/v) HPMC, after which additional HPMC did not further increase the induction time. The single-particle and multiparticle analyses yielded the same ranking of the HPMC concentrations, regarding the inhibitory effect on precipitation. The developed small scale method to assess the effect of precipitation inhibitors can speed up the process of choosing the right precipitation inhibitor and the concentration to be used.

Measurements of upper troposheric humidity at low temperatures during CRYSTAL-FACE

NASA Technical Reports Server (NTRS)

Herman, Robert L.; Heymsfield, Andrew J.; Ridley, Brian A.; Bui, Paul T.

2003-01-01

Aircraft condensation trails (contrails) and thin cirrus were studied by instruments on the NASA WB-57F high-altitude aircraft during contrails and optically thing cirrus are contrasted by different levels of supersaturation with respect to ice. During the July 13, 2002, flight of the WB-57F aircraft intercepted visible contrails produced by both the WB-57F and ER-2 aircraft. These contrails were located immediately below the local tropopause, where ambient temperatures were very low (-76 degree C). The contrails were clearly indicated by an abrupt increase in NO and a simultaneous, abrupt decrease in ice supersaturation. With in the contrail, the relative humidity was close to 130% with respect to ice, higher than expected from theory. Outside the contrails was a persistent layer of subvisible currus extending from approximately 13 to 15 km altitude. This layer was characterized y significant supersaturations because the ambient concentrations of ice particles were insufficient to significantly deplete the ice supersaturation. We will discuss in situ measurements and models simulations of humidity.

Energy Levels of Defects Created in Silicon Supersaturated with Transition Metals

NASA Astrophysics Data System (ADS)

García, H.; Castán, H.; Dueñas, S.; García-Hemme, E.; García-Hernansaz, R.; Montero, D.; González-Díaz, G.

2018-03-01

Intermediate-band semiconductors have attracted much attention for use in silicon-based solar cells and infrared detectors. In this work, n-Si substrates have been implanted with very high doses (1013 cm-2 and 1014 cm-2) of vanadium, which gives rise to a supersaturated layer inside the semiconductor. However, the Mott limit was not exceeded. The energy levels created in the supersaturated silicon were studied in detail by means of thermal admittance spectroscopy. We found a single deep center at energy near E C - 200 meV. This value agrees with one of the levels found for vanadium in silicon. The capture cross-section values of the deep levels were also calculated, and we found a relationship between the capture cross-section and the energy position of the deep levels which follows the Meyer-Neldel rule. This process usually appears in processes involving multiple excitations. The Meyer-Neldel energy values agree with those previously obtained for silicon supersaturated with titanium and for silicon contaminated with iron.

On the influence of atmospheric super-saturation layer on China's heavy haze-fog events

NASA Astrophysics Data System (ADS)

Wang, Jizhi; Yang, Yuanqin; Zhang, Xiaoye; Liu, Hua; Che, Huizheng; Shen, Xiaojing; Wang, Yaqiang

2017-12-01

With the background of global change, the air quality in Earth's atmosphere has significantly decreased. The North China Plain (NCP), Yangtze River Delta (YRD), Pearl River Delta (PRD) and Si-Chuan Basin (SCB) are the major areas suffering the decreasing air quality and frequent pollution events in recent years. Studying the effect of meteorological conditions on the concentration of pollution aerosols in these pollution sensitive regions is a hot focus now. This paper analyses the characteristics of atmospheric super-saturation and the corresponding H_PMLs (height of supersaturated pollution mixing layer), investigating their contribution to the frequently-seen heavy haze-fog weather. The results suggest that: (1) in the above-mentioned pollution sensitive regions in China, super-saturated layers repeatedly appear in the low altitude and the peak value of supersaturation S can reach 6-10%, which makes pollution particles into the wet adiabatic uplift process in the stable-static atmosphere. After low-level atmosphere reaches the super-saturation state below the H_PMLs, meteorological condition contributes to humidification and condensation of pollution particles. (2) Caculation of condensation function Fc, one of PLAM sensetive parameter, indicates that super-saturation state helps promote condensation, beneficial to the formation of Condensational Kink (CK) in the pollution sensitive areas. This favors the formation of new aerosol particles and intensities the cumulative growth of aerosol concentration. (3) By calculating the convective inhibition energy on average │CIN│ > 1.0 × 104 J kg-1, we found the value is about 100 times higher than the stable critical value. The uplifting diffusion of the particles is inhibited by the ambient airflow. So, this is the important reason for the aggravation and persistence of aerosol pollutants in local areas. (4) H_PMLs is negatively correlated to the pollution meteorological condition index PLAM which can describe the change of PM2.5 concentration. The lower the H_PMLs is, the higher the PLAM becomes, and the more conductive the air condition is to aggravation of pollutant aerosol concentration.

Favorite Demonstrations: Exothermic Crystallization from a Supersaturated Solution.

ERIC Educational Resources Information Center

Kauffman, George B.; And Others

1986-01-01

The use of sodium acetate solution to show supersaturation is a favorite among lecture demonstrations. However, careful adjustment of the solute-to-water ratio must be made to attain the most spectacular effect--complete solidification of the solution. Procedures to accomplish this are provided and discussed. (JN)

Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors.

PubMed

Abdelsayed, Victor; El-Shall, M Samy

2014-08-07

This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicates that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.

Direct observation of metal nanoparticles as heterogeneous nuclei for the condensation of supersaturated organic vapors: Nucleation of size-selected aluminum nanoparticles in acetonitrile and n-hexane vapors

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

Abdelsayed, Victor; Samy El-Shall, M., E-mail: mselshal@vcu.edu

This work reports the direct observation and separation of size-selected aluminum nanoparticles acting as heterogeneous nuclei for the condensation of supersaturated vapors of both polar and nonpolar molecules. In the experiment, we study the condensation of supersaturated acetonitrile and n-hexane vapors on charged and neutral Al nanoparticles by activation of the metal nanoparticles to act as heterogeneous nuclei for the condensation of the organic vapor. Aluminum seed nanoparticles with diameters of 1 and 2 nm are capable of acting as heterogeneous nuclei for the condensation of supersaturated acetonitrile and hexane vapors. The comparison between the Kelvin and Fletcher diameters indicatesmore » that for the heterogeneous nucleation of both acetonitrile and hexane vapors, particles are activated at significantly smaller sizes than predicted by the Kelvin equation. The activation of the Al nanoparticles occurs at nearly 40% and 65% of the onset of homogeneous nucleation of acetonitrile and hexane supersaturated vapors, respectively. The lower activation of the charged Al nanoparticles in acetonitrile vapor is due to the charge-dipole interaction which results in rapid condensation of the highly polar acetonitrile molecules on the charged Al nanoparticles. The charge-dipole interaction decreases with increasing the size of the Al nanoparticles and therefore at low supersaturations, most of the heterogeneous nucleation events are occurring on neutral nanoparticles. No sign effect has been observed for the condensation of the organic vapors on the positively and negatively charged Al nanoparticles. The present approach of generating metal nanoparticles by pulsed laser vaporization within a supersaturated organic vapor allows for efficient separation between nucleation and growth of the metal nanoparticles and, consequently controls the average particle size, particle density, and particle size distribution within the liquid droplets of the condensing vapor. Strong correlation is found between the seed nanoparticle's size and the degree of the supersaturation of the condensing vapor. This result and the agreement among the calculated Kelvin diameters and the size of the nucleating Al nanoparticles determined by transmission electron microscopy provide strong proof for the development of a new approach for the separation and characterization of heterogeneous nuclei formed in organic vapors. These processes can take place in the atmosphere by a combination of several organic species including polar compounds which could be very efficient in activating charged nanoparticles and cluster ions of atmospheric relevance.« less

Theory of the intermediate stage of crystal growth with applications to insulin crystallization

NASA Astrophysics Data System (ADS)

Barlow, D. A.

2017-07-01

A theory for the intermediate stage of crystal growth, where two defining equations one for population continuity and another for mass-balance, is used to study the kinetics of the supersaturation decay, the homogeneous nucleation rate, the linear growth rate and the final distribution of crystal sizes for the crystallization of bovine and porcine insulin from solution. The cited experimental reports suggest that the crystal linear growth rate is directly proportional to the square of the insulin concentration in solution for bovine insulin and to the cube of concentration for porcine. In a previous work, it was shown that the above mentioned system could be solved for the case where the growth rate is directly proportional to the normalized supersaturation. Here a more general solution is presented valid for cases where the growth rate is directly proportional to the normalized supersaturation raised to the power of any positive integer. The resulting expressions for the time dependent normalized supersaturation and crystal size distribution are compared with experimental reports for insulin crystallization. An approximation for the maximum crystal size at the end of the intermediate stage is derived. The results suggest that the largest crystal size in the distribution at the end of the intermediate stage is maximized when nucleation is restricted to be only homogeneous. Further, the largest size in the final distribution depends only weakly upon the initial supersaturation.

Spinal motor neuron protein supersaturation patterns are associated with inclusion body formation in ALS

PubMed Central

Ciryam, Prajwal; Lambert-Smith, Isabella A.; Bean, Daniel M.; Freer, Rosie; Cid, Fernando; Tartaglia, Gian Gaetano; Saunders, Darren N.; Wilson, Mark R.; Morimoto, Richard I.; Dobson, Christopher M.; Vendruscolo, Michele; Favrin, Giorgio; Yerbury, Justin J.

2017-01-01

Amyotrophic lateral sclerosis (ALS) is a heterogeneous degenerative motor neuron disease linked to numerous genetic mutations in apparently unrelated proteins. These proteins, including SOD1, TDP-43, and FUS, are highly aggregation-prone and form a variety of intracellular inclusion bodies that are characteristic of different neuropathological subtypes of the disease. Contained within these inclusions are a variety of proteins that do not share obvious characteristics other than coaggregation. However, recent evidence from other neurodegenerative disorders suggests that disease-affected biochemical pathways can be characterized by the presence of proteins that are supersaturated, with cellular concentrations significantly greater than their solubilities. Here, we show that the proteins that form inclusions of mutant SOD1, TDP-43, and FUS are not merely a subset of the native interaction partners of these three proteins, which are themselves supersaturated. To explain the presence of coaggregating proteins in inclusions in the brain and spinal cord, we observe that they have an average supersaturation even greater than the average supersaturation of the native interaction partners in motor neurons, but not when scores are generated from an average of other human tissues. These results suggest that inclusion bodies in various forms of ALS result from a set of proteins that are metastable in motor neurons, and thus prone to aggregation upon a disease-related progressive collapse of protein homeostasis in this specific setting. PMID:28396410

Measurable characteristics of lysozyme crystal growth

NASA Technical Reports Server (NTRS)

Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

2005-01-01

The behavior of protein crystal growth is estimated from measurements performed at both the microscopic and molecular levels. In the absence of solutal flow, it was determined that a model that balances the macromolecular flux toward the crystal surface with the flux of the crystal surface well characterizes crystal growth observed using microscopic methods. Namely, it was determined that the model provides accurate estimates for the crystal-growth velocities upon evaluation of crystal-growth measurements obtained in time. Growth velocities thus determined as a function of solution supersaturation were further interpreted using established deterministic models. From analyses of crystal-growth velocities, it was found that the mode of crystal growth varies with respect to increasing solution supersaturation, possibly owing to kinetic roughening. To verify further the hypothesis of kinetic roughening, crystal growth at the molecular level was examined using atomic force microscopy (AFM). From the AFM measurements, it was found that the magnitude of surface-height fluctuations, h(x), increases with increasing solution supersaturation. In contrast, the estimated characteristic length, xi, decreases rapidly upon increasing solution supersaturation. It was conjectured that the magnitude of both h(x) and xi could possibly determine the mode of crystal growth. Although the data precede any exact theory, the non-critical divergence of h(x) and xi with respect to increasing solution supersaturation was nevertheless preliminarily established. Moreover, approximate models to account for behavior of both h(x) and xi are also presented.

Effect of stabilizer on the maximum degree and extent of supersaturation and oral absorption of tacrolimus made by ultra-rapid freezing.

PubMed

Overhoff, Kirk A; McConville, Jason T; Yang, Wei; Johnston, Keith P; Peters, Jay I; Williams, Robert O

2008-01-01

Solid dispersions containing various stabilizers and tacrolimus (TAC) prepared by an Ultra-rapid Freezing (URF) process were investigated to determine the effect on their ability to form supersaturated solutions in aqueous media and on enhancing transport across biological membranes. The stabilizers included poly(vinyl alcohol; PVA), poloxamer 407 (P407), and sodium dodecyl sulfate (SDS). In vivo absorption enhancement in rats was also investigated. Dissolution studies were conducted at supersaturated conditions in both acidic media for 24 h and at delayed release (enteric) conditions to simulate intestinal transit. The rank order of C/Ceq(max) in the dissolution studies at acidic conditions was URF-P407 > URF-SDS > Prograf (PRO) > URF-PVA:P407. For C/Ceq(max) under enteric conditions, the order was URF-SDS > PRO > URF-PVA:P407 > URF-P407, and for the extent of supersaturation (AUC) in acidic and pH shift conditions it was URF-SDS>PRO>URF-PVA:P407>URF-P407. The pharmacokinetic data suggests URF-P407 had the greatest absorption having higher C (max) with a 1.5-fold increase in AUC compared to PRO. All URF compositions had a shorter T (max) compared to PRO. The nanostructured powders containing various stabilizing polymers formed by the URF process offer enhanced supersaturation characteristics leading to increased oral absorption of TAC.

Supersaturation of aqueous species and hydrothermal crystal growth of ZnO

NASA Astrophysics Data System (ADS)

Gelabert, M. C.

2015-05-01

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

Theory, Electro-Optical Design, Testing, and Calibration of a Prototype Atmospheric Supersaturation, Humidity, and Temperature Sensor.

DTIC Science & Technology

1982-07-15

Bergeron- Findeisen process, the dominant mid and high latitude precipitation forming mechanism. 1.1.2 Ice Supersaturation Measurements Lala (1969), in an...experimentally verified in strong cumulus updrafts, they would constitute a new mechanism of precipitation formation to augment the Bergeron- Findeisen and

Thermodynamic Studies of Levitated Microdroplets of Highly Supersaturated Electrolyte Solutions

NASA Technical Reports Server (NTRS)

Myerson, Allan S.; Izmailov, Alexander F.; Na, Han-Soo

1996-01-01

Highly supersaturated electrolyte solutions are studied by employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. A correspondence of 96-99% between the theory and experiment for the all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin) and its calculation for various electrolyte solutions at 298 K.

The Chemical Composition of Honey

ERIC Educational Resources Information Center

Ball, David W.

2007-01-01

Honey is a supersaturated sugar solution, created by bees, and used by human beings as a sweetener. However, honey is more than just a supersaturated sugar solution; it also contains acids, minerals, vitamins, and amino acids in varying quantities. In this article, we will briefly explore the chemical composition of honey. (Contains 2 figures and…

Unsteady-state transfer of impurities during crystal growth of sucrose in sugarcane solutions

NASA Astrophysics Data System (ADS)

Martins, P. M.; Ferreira, A.; Polanco, S.; Rocha, F.; Damas, A. M.; Rein, P.

2009-07-01

In this work, we present growth rate data of sucrose crystals in the presence of impurities that can be used by both sugar technologists and crystal growth scientists. Growth rate curves measured in a pilot-scale evaporative crystallizer suggest a period of slow growth that follows the seeding of crystals into supersaturated technical solutions. The observed trend was enhanced by adding typical sugarcane impurities such as starch, fructose or dextran to the industrial syrups. Maximum growth rates of sucrose resulted at intermediate rather than high supersaturation levels in the presence of the additives. The effects of the additives on the sucrose solubility and sucrose mass transfer in solution were taken into account to explain the observed crystal growth kinetics. A novel mechanism was identified of unsteady-state adsorption of impurities at the crystal surface and their gradual replacement by the crystallizing solute towards the equilibrium occupation of the active sites for growth. Specifically designed crystallization experiments at controlled supersaturation confirmed this mechanism by showing increasing crystal growth rates with time until reaching a steady-state value for a given supersaturation level and impurity content.

Global Simulations of Ice nucleation and Ice Supersaturation with an Improved Cloud Scheme in the Community Atmosphere Model

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

Gettelman, A.; Liu, Xiaohong; Ghan, Steven J.

2010-09-28

A process-based treatment of ice supersaturation and ice-nucleation is implemented in the National Center for Atmospheric Research (NCAR) Community Atmosphere Model (CAM). The new scheme is designed to allow (1) supersaturation with respect to ice, (2) ice nucleation by aerosol particles and (3) ice cloud cover consistent with ice microphysics. The scheme is implemented with a 4-class 2 moment microphysics code and is used to evaluate ice cloud nucleation mechanisms and supersaturation in CAM. The new model is able to reproduce field observations of ice mass and mixed phase cloud occurrence better than previous versions of the model. Simulations indicatemore » heterogeneous freezing and contact nucleation on dust are both potentially important over remote areas of the Arctic. Cloud forcing and hence climate is sensitive to different formulations of the ice microphysics. Arctic radiative fluxes are sensitive to the parameterization of ice clouds. These results indicate that ice clouds are potentially an important part of understanding cloud forcing and potential cloud feedbacks, particularly in the Arctic.« less

Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet

PubMed Central

Lee, Sooheyong; Wi, Haeng Sub; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Jeong, Se-Young; Kim, Yong-Il; Lee, Geun Woo

2016-01-01

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH2PO4 (KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation. PMID:27791068

An improved model of homogeneous nucleation for high supersaturation conditions: aluminum vapor.

PubMed

Savel'ev, A M; Starik, A M

2016-12-21

A novel model of stationary nucleation, treating the thermodynamic functions of small clusters, has been built. The model is validated against the experimental data on the nucleation rate of water vapor obtained in a broad range of supersaturation values (S = 10-120), and, at high supersaturation values, it reproduces the experimental data much better than the traditional classical nucleation model. A comprehensive analysis of the nucleation of aluminum vapor with the usage of developed stationary and non-stationary nucleation models has been performed. It has been shown that, at some value of supersaturation, there exists a double potential nucleation barrier. It has been revealed that the existence of this barrier notably delayed the establishment of a stationary distribution of subcritical clusters. It has also been demonstrated that the non-stationary model of the present work and the model of liquid-droplet approximation predict different values of nucleation delay time, τ s . In doing so, the liquid-droplet model can underestimate notably (by more than an order of magnitude) the value of τ s .

Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet.

PubMed

Lee, Sooheyong; Wi, Haeng Sub; Jo, Wonhyuk; Cho, Yong Chan; Lee, Hyun Hwi; Jeong, Se-Young; Kim, Yong-Il; Lee, Geun Woo

2016-11-29

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH 2 PO 4 (KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation.

Physical cleaning by bubbly streaming flow in an ultrasound field

NASA Astrophysics Data System (ADS)

Yamashita, Tatsuya; Ando, Keita

2017-11-01

Low-intensity ultrasonic cleaning with gas-supersaturated water is a promising method of physical cleaning without erosion; we are able to trigger cavitation bubble nucleation by weak ultrasound under gas supersaturation and thus clean material surfaces by mild bubble dynamics. Here, we perform particle image velocimetry (PIV) measurement of liquid flow and cavitation bubble translation in an ultrasonic cleaning bath driven at 28 kHz and then relate it to cleaning tests using glass slides at which silica particles are attached. The ultrasound pressure amplitude at the cleaning spot is set at 1.4 atm. We select the supersaturation level of dissolved oxygen (DO) as a parameter and control it by oxygen microbubble aeration. It follows from the PIV measurement that the liquid flow is enhanced by the cavitation bubble translation driven by acoustic radiation force; this trend becomes clearer when the bubbles appear more densely as the DO supersaturation increases. In the cleaning tests, the cleaned areas appear as straight streaks. This suggests that physical cleaning is achieved mainly by cavitation bubbles that translate in ultrasound fields.

Combined use of crystalline sodium salt and polymeric precipitation inhibitors to improve pharmacokinetic profile of ibuprofen through supersaturation.

PubMed

Terebetski, Jenna L; Cummings, John J; Fauty, Scott E; Michniak-Kohn, Bozena

2014-10-01

To maximize the pharmacological effect of a pain reliever such as ibuprofen, early onset of action is critical. Unfortunately, the acidic nature of ibuprofen minimizes the amount of drug that can be solubilized under gastric conditions and would be available for immediate absorption upon entry into the intestine. Although the sodium salt of ibuprofen has higher solubility, rapid conversion from the salt to the poorly soluble free acid phase occurs under gastric conditions. Therefore, the combination of the highly soluble sodium salt form of ibuprofen with polymers was evaluated as an approach to prolong supersaturation of ibuprofen during the disproportionation of the salt. Binary combinations of ibuprofen sodium with polymers resulted in the identification of several formulations that demonstrated high degrees and extended durations of supersaturation during in vitro dissolution experiments. These formulations included HPMC, polyvinyl pyrrolidone-vinyl acetate copolymer (PVP-VA64), methylcellulose (MC), and hydroxypropyl cellulose (HPC). The in vitro supersaturation observed with these ibuprofen-polymer formulations translated to an increase in Cmax and an earlier Tmax for the PVP-VA64, MC, and HPC formulations relative to ibuprofen only controls when administered orally to rats under fasted conditions. Based on these observations, combining ibuprofen sodium with polymers such as PVP-VA64, MC, or HPC is a viable formulation approach to prolong supersaturation in the stomach and enable an optimized pharmacokinetic profile in vivo where rapid onset of action is desired.

Investigating the Influence of Polymers on Supersaturated Flufenamic Acid Cocrystal Solutions.

PubMed

Guo, Minshan; Wang, Ke; Hamill, Noel; Lorimer, Keith; Li, Mingzhong

2016-09-06

The development of enabling formulations is a key stage when demonstrating the effectiveness of pharmaceutical cocrystals to maximize the oral bioavailability for poorly water soluble drugs. Inhibition of drug crystallization from a supersaturated cocrystal solution through a fundamental understanding of the nucleation and crystal growth is important. In this study, the influence of the three polymers of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and a copolymer of N-vinly-2-pyrrodidone (60%) and vinyl acetate (40%) (PVP-VA) on the flufenamic acid (FFA) crystallization from three different supersaturated solutions of the pure FFA and two cocrystals of FFA-NIC CO and FFA-TP CO has been investigated by measuring nucleation induction times and desupersaturation rates in the presence and absence of seed crystals. It was found that the competition of intermolecular hydrogen bonding among drug/coformer, drug/polymer, and coformer/polymer was a key factor responsible for maintaining supersaturation through nucleation inhibition and crystal growth modification in a cocrystal solution. The supersaturated cocrystal solutions with predissolved PEG demonstrated more effective stabilization in comparison to the pure FFA in the presence of the same polymer. In contrast, neither of the two cocrystal solutions, in the presence of PVP or PVP-VA, exhibited a better performance than the pure FFA with the same predissolved polymer. The study suggests that the selection of a polymeric excipient in a cocrystal formulation should not be solely dependent on the interplay of the parent drug and polymer without considering the coformer effects.

Biological and physical controls on O2/Ar, Ar and pCO2 variability at the Western Antarctic Peninsula and in the Drake Passage

NASA Astrophysics Data System (ADS)

Eveleth, R.; Cassar, N.; Doney, S. C.; Munro, D. R.; Sweeney, C.

2017-05-01

Using simultaneous sub-kilometer resolution underway measurements of surface O2/Ar, total O2 and pCO2 from annual austral summer surveys in 2012, 2013 and 2014, we explore the impacts of biological and physical processes on the O2 and pCO2 system spatial and interannual variability at the Western Antarctic Peninsula (WAP). In the WAP, mean O2/Ar supersaturation was (7.6±9.1)% and mean pCO2 supersaturation was (-28±22)%. We see substantial spatial variability in O2 and pCO2 including sub-mesoscale/mesoscale variability with decorrelation length scales of 4.5 km, consistent with the regional Rossby radius. This variability is embedded within onshore-offshore gradients. O2 in the LTER grid region is driven primarily by biological processes as seen by the median ratio of the magnitude of biological oxygen (O2/Ar) to physical oxygen (Ar) supersaturation anomalies (%) relative to atmospheric equilibrium (2.6), however physical processes have a more pronounced influence in the southern onshore region of the grid where we see active sea-ice melting. Total O2 measurements should be interpreted with caution in regions of significant sea-ice formation and melt and glacial meltwater input. pCO2 undersaturation predominantly reflects biological processes in the LTER grid. In contrast we compare these results to the Drake Passage where gas supersaturations vary by smaller magnitudes and decorrelate at length scales of 12 km, in line with latitudinal changes in the regional Rossby radius. Here biological processes induce smaller O2/Ar supersaturations (mean (0.14±1.3)%) and pCO2 undersaturations (mean (-2.8±3.9)%) than in the WAP, and pressure changes, bubble and gas exchange fluxes drive stable Ar supersaturations.

Supersaturation of Calcipotriene and Betamethasone Dipropionate in a Novel Aerosol Foam Formulation for Topical Treatment of Psoriasis Provides Enhanced Bioavailability of the Active Ingredients.

PubMed

Lind, Marianne; Nielsen, Kim Troensegaard; Schefe, Line Hollesen; Nørremark, Kasper; Eriksson, André Huss; Norsgaard, Hanne; Pedersen, Brian Thoning; Petersson, Karsten

2016-09-01

Previous studies have demonstrated the superior efficacy of a novel aerosol foam formulation of fixed combination calcipotriene 0.005% (Cal) and betamethasone dipropionate 0.064% (BD), compared with the ointment formulation. The aim of this study is to ascertain whether enhanced bioavailability of the active ingredients due to supersaturation and/or occlusive properties can explain the observed greater clinical efficacy. Solubility and evaporation experiments were conducted to examine the abilities of Cal/BD aerosol foam ingredients to create a supersaturated environment. Optical microscopy, Raman imaging and X-ray powder diffraction were used to examine the physical state of Cal and BD in the formulations after application, and determine whether a supersaturated state remained stable for clinically relevant time periods. In vitro skin penetration and ex vivo biomarker assays were conducted to compare the skin penetration and bioavailability of Cal and BD from the aerosol foam and ointment formulations, respectively. Occlusive properties were examined via transepidermal water loss. Solubility studies showed that Cal and BD solubility increased with increasing dimethyl ether (DME) content. Both active ingredients are completely dissolved in the final aerosol foam formulation. DME rapidly evaporates after spraying, and the amount was reduced to 0.5% of the initial amount after 2 min. This led to the formation of a supersaturated environment, where Cal and BD crystals were absent for at least 26 h after application. Cal/BD aerosol foam had significantly greater in vitro skin penetration and had increased bioavailability compared with Cal/BD ointment. Both formulations effectively occluded the skin. A stable supersaturated solution of Cal/BD in the aerosol foam leads to increased bioavailability and explains the improved clinical effect when compared to the Cal/BD ointment. The studies included in the paper are all conducted by LEO Pharma A/S or CROs on behalf of LEO Pharma A/S.

Relative Humidity in the Tropopause Saturation Layer

NASA Astrophysics Data System (ADS)

Selkirk, H. B.; Schoeberl, M. R.; Pfister, L.; Thornberry, T. D.; Bui, T. V.

2017-12-01

The tropical tropopause separates two very different atmospheric regimes: the stable lower stratosphere where the air is both extremely dry and nearly always so, and a transition layer in the uppermost tropical troposphere, where humidity on average increases rapidly downward but can undergo substantial temporal fluctuations. The processes that control the humidity in this layer below the tropopause include convective detrainment (which can result in either a net hydration or dehydration), slow ascent, wave motions and advection. Together these determine the humidity of the air that eventually passes through the tropopause and into the stratosphere, and we refer to this layer as the tropopause saturation layer or TSL. We know from in situ water vapor observations such as Ticosonde's 12-year balloonsonde record at Costa Rica that layers of supersaturation are frequently observed in the TSL. While their frequency is greatest during the local rainy season from June through October, supersaturation is also observed in the boreal winter dry season when deep convection is well south of Costa Rica. In other words, local convection is not a necessary condition for the presence of supersaturation. Furthermore, there are indications from airborne measurements during the recent POSIDON campaign at Guam that if anything deep convection tends to `reset' the TSL locally to a state of just-saturation. Conversely, it may be that layers of supersaturation are the result of slow ascent. To explore these ideas we take Ticosonde water vapor observations from the TSL, stratify them on the basis of relative humidity and report on the differences in the the history of upstream convective influence between supersaturated parcels and those that are not.

Relationship between supersaturation ratio and supply rate of solute in the growth process of monodisperse colloidal particles and application to AgBr systems.

PubMed

Shiba, Fumiyuki; Okawa, Yusuke

2005-11-24

Supersaturation ratio, S, has been theoretically related to the supply rate of solute, Q, from growth rate and mass-balance equations in the quasi-steady state in the growth process of isotropic monodisperse particles. The derived equation, (S - 1) = (1/D + 1/kr)(Q/betaC(0)nr) + 2V(m)gamma/rRT, suggests a linear dependence of S on Q under constant n and r, where D is the diffusion coefficient, k is the rate constant for surface-reaction, C(0) is the solubility, n and r are the number and radius of growing particles, respectively, V(m) is the molar volume of particles, R is the gas constant, T is the absolute temperature, and beta is the shape factor defined by beta identical with (1/r(2)) dupsilon/dr, where upsilon is the volume of an individual particle. The equation was applied to the analysis of growth kinetics and determinations of critical supersaturation ratio in monodisperse AgBr particles in the controlled double-jet system with the assistance of a potentiometric supersaturation measurement. In both cubic and octahedral particles, growth rates were completely limited by diffusion and surface-reaction at pBr ( identical with -log[Br(-)]) 3.0 and 1.0, respectively, while the growths were intermediate of them at pBr 2.0 and 4.0. The growth parameters, DC(0) and kC(0), were experimentally determined. Also, critical supersaturation ratio was estimated as 1.28 as an average in the present study.

Effectiveness of supersaturation promoting excipients on albendazole concentrations in upper gastrointestinal lumen of fasted healthy adults.

PubMed

Kourentas, Alexandros; Vertzoni, Maria; Symillides, Mira; Goumas, Konstantinos; Gibbon, Robert; Butler, James; Reppas, Christos

2016-08-25

To evaluate the impact of dosage form relevant levels of a polymeric precipitation inhibitor and of lipid excipients on supersaturation of upper gastrointestinal contents with albendazole, a lipophilic weak base. Albendazole concentrations in stomach and in duodenum were evaluated after administration of 1) a suspension in water (Susp-Control), 2) a suspension in water in which hydroxyprolylmethylcellulose E5 (HPMC E5) had been pre-dissolved (Susp-HPMC), and 3) and 4) two contrasting designs of lipid based suspensions dispersed in water (Susp-IIIA and Susp-IV), on a cross-over basis to fasted healthy adults. Limited, but statistically significant supersaturation of duodenal contents was observed after Susp-HPMC, Susp-IIIA, and Susp-IV; supersaturation was more consistent after Susp-HPMC administration. Based on total albendazole amount per volume, gastric secretions did not significantly alter volumes of bulk gastric contents during the first 40min post administration of a glass of non-caloric water-based fluid. Αlbendazole gastric concentrations were higher than in the administered suspensions, but similar for all four formulations. Gastric emptying of albendazole after administration of Susp-Control or Susp-HPMC was slower than after administration of Susp-IIIA or Susp-IV. Small amounts of HPMC E5 were as effective as lipid excipients in achieving supersaturation of duodenal contents with albendazole, a fast precipitating weak base, in fasted adults. However, compared with the effect of HPMC E5 the effect of lipid excipients was delayed and variable. Copyright © 2016 Elsevier B.V. All rights reserved.

Diet, but not oral probiotics, effectively reduces urinary oxalate excretion and calcium oxalate supersaturation.

PubMed

Lieske, John C; Tremaine, William J; De Simone, Claudio; O'Connor, Helen M; Li, Xujian; Bergstralh, Eric J; Goldfarb, David S

2010-12-01

We examined the effect of a controlled diet and two probiotic preparations on urinary oxalate excretion, a risk factor for calcium oxalate kidney stone formation, in patients with mild hyperoxaluria. Patients were randomized to a placebo, a probiotic, or a synbiotic preparation. This tested whether these probiotic preparations can increase oxalate metabolism in the intestine and/or decrease oxalate absorption from the gut. Patients were maintained on a controlled diet to remove the confounding variable of differing oxalate intake from food. Urinary oxalate excretion and calcium oxalate supersaturation on the controlled diet were significantly lower compared with baseline on a free-choice diet. Neither study preparation reduced urinary oxalate excretion nor calcium oxalate supersaturation. Fecal lactobacilli colony counts increased on both preparations, whereas enterococcal and yeast colony counts were increased on the synbiotic. Total urine volume and the excretion of oxalate and calcium were all strong independent determinants of urinary calcium oxalate supersaturation. Hence, dietary oxalate restriction reduced urinary oxalate excretion, but the tested probiotics did not influence urinary oxalate levels in patients on a restricted oxalate diet. However, this study suggests that dietary oxalate restriction is useful for kidney stone prevention.

Vanadium supersaturated silicon system: a theoretical and experimental approach

NASA Astrophysics Data System (ADS)

Garcia-Hemme, Eric; García, Gregorio; Palacios, Pablo; Montero, Daniel; García-Hernansanz, Rodrigo; Gonzalez-Diaz, Germán; Wahnon, Perla

2017-12-01

The effect of high dose vanadium ion implantation and pulsed laser annealing on the crystal structure and sub-bandgap optical absorption features of V-supersaturated silicon samples has been studied through the combination of experimental and theoretical approaches. Interest in V-supersaturated Si focusses on its potential as a material having a new band within the Si bandgap. Rutherford backscattering spectrometry measurements and formation energies computed through quantum calculations provide evidence that V atoms are mainly located at interstitial positions. The response of sub-bandgap spectral photoconductance is extended far into the infrared region of the spectrum. Theoretical simulations (based on density functional theory and many-body perturbation in GW approximation) bring to light that, in addition to V atoms at interstitial positions, Si defects should also be taken into account in explaining the experimental profile of the spectral photoconductance. The combination of experimental and theoretical methods provides evidence that the improved spectral photoconductance up to 6.2 µm (0.2 eV) is due to new sub-bandgap transitions, for which the new band due to V atoms within the Si bandgap plays an essential role. This enables the use of V-supersaturated silicon in the third generation of photovoltaic devices.

Do "inhibitors of crystallisation" play any role in the prevention of kidney stones? A critique.

PubMed

Robertson, William G

2017-02-01

A critical examination of data in the literature and in as yet unpublished laboratory records on the possible role of so-called inhibitors of crystallisation in preventing the formation of calcium-containing kidney stones leads to the following conclusions. So-called inhibitors of spontaneous "self-nucleation" are unlikely to play any role in the initiation of the crystallisation of CaOx or CaP in urine because excessive urinary supersaturation of urine with respect to these salts dominates the onset of "self-nucleation" within the normal time frame of the transit of tubular fluid through the nephron (3-4 min). Inhibitors of the crystal growth of CaOx crystals may or may not play a significant role in the prevention of CaOx stone-formation since once again excessive supersaturation of urine can overwhelm any potential effect of the inhibitors on the growth process. However, they may play a role as inhibitors of crystal growth at lower levels of metastable supersaturation when the balance between supersaturation and inhibitors is more equal. Inhibitors of CaOx crystal aggregation may play a significant role in the prevention of stones, since they do not appear to be strongly affected by excessive supersaturation, either in vitro or in vivo. Inhibitors of CaOx crystal binding to renal tubular epithelium may exist but further studies are necessary to elucidate their importance in reducing the risk of initiating stones in the renal tubules. Inhibitors of CaOx crystal binding to Randall's Plaques and Randall's Plugs may exist but further studies are necessary to elucidate their importance in reducing the risk of initiating stones on renal papillae. There may be an alternative explanation other than a deficiency in the excretion of inhibitors for the observations that there is a difference between CaOx crystal size and degree of aggregation in the fresh, warm urines of normal subjects compared those in urine from patients with recurrent CaOx stones. This difference may depend more on the site of "self-nucleation" of CaOx crystals in the renal tubule rather than on a deficiency in the excretion of so-called inhibitors of crystallisation by patients with CaOx stones. The claim that administration of potassium citrate, potassium magnesium citrate or magnesium hydroxide reduces the rate of stone recurrence may be due to the effect of these forms of medication on the supersaturation of urine with respect to CaOx and CaP rather than to any increase in "inhibitory activity" attributed to these forms of treatment. In summary, there is a competition between supersaturation and so-called inhibitors of crystallisation which ultimately determines the pattern of crystalluria in stone-formers and normals. If the supersaturation of urine with respect to CaOx reaches or exceeds the 3-4 min formation product of that salt, then it dominates the crystallisation process both in terms of "self-nucleation" and crystal growth but appears to have little or no effect on the degree of aggregation of the crystals produced. At supersaturation levels of urine with respect to CaOx well below the 3-4 min formation product of that salt, the influence of inhibitors increases and some may affect not only the degree of aggregation but also the crystal growth of any pre-formed crystals of CaOx at these lower levels of metastability.

Gas-liquid nucleation at large metastability: unusual features and a new formalism

NASA Astrophysics Data System (ADS)

Santra, Mantu; Singh, Rakesh S.; Bagchi, Biman

2011-03-01

Nucleation at large metastability is still largely an unsolved problem, even though it is a problem of tremendous current interest, with wide-ranging practical value, from atmospheric research to materials science. It is now well accepted that the classical nucleation theory (CNT) fails to provide a qualitative picture and gives incorrect quantitative values for such quantities as activation-free energy barrier and supersaturation dependence of nucleation rate, especially at large metastability. In this paper, we present an alternative formalism to treat nucleation at large supersaturation by introducing an extended set of order parameters in terms of the kth largest liquid-like clusters, where k = 1 is the largest cluster in the system, k = 2 is the second largest cluster and so on. At low supersaturation, the size of the largest liquid-like cluster acts as a suitable order parameter. At large supersaturation, the free energy barrier for the largest liquid-like cluster disappears. We identify this supersaturation as the one at the onset of kinetic spinodal. The kinetic spinodal is system-size-dependent. Beyond kinetic spinodal many clusters grow simultaneously and competitively and hence the nucleation and growth become collective. In order to describe collective growth, we need to consider the full set of order parameters. We derive an analytic expression for the free energy of formation of the kth largest cluster. The expression predicts that, at large metastability (beyond kinetic spinodal), the barrier of growth for several largest liquid-like clusters disappears, and all these clusters grow simultaneously. The approach to the critical size occurs by barrierless diffusion in the cluster size space. The expression for the rate of barrier crossing predicts weaker supersaturation dependence than what is predicted by CNT at large metastability. Such a crossover behavior has indeed been observed in recent experiments (but eluded an explanation till now). In order to understand the large numerical discrepancy between simulation predictions and experimental results, we carried out a study of the dependence on the range of intermolecular interactions of both the surface tension of an equilibrium planar gas-liquid interface and the free energy barrier of nucleation. Both are found to depend significantly on the range of interaction for the Lennard-Jones potential, both in two and three dimensions. The value of surface tension and also the free energy difference between the gas and the liquid phase increase significantly and converge only when the range of interaction is extended beyond 6-7 molecular diameters. We find, with the full range of interaction potential, that the surface tension shows only a weak dependence on supersaturation, so the reason for the breakdown of CNT (with simulated values of surface tension and free energy gap) cannot be attributed to the supersaturation dependence of surface tension. This remains an unsettled issue at present because of the use of the value of surface tension obtained at coexistence.

Measurements of Protein Crystal Face Growth Rates

NASA Technical Reports Server (NTRS)

Gorti, S.

2014-01-01

Protein crystal growth rates will be determined for several hyperthermophile proteins.; The growth rates will be assessed using available theoretical models, including kinetic roughening.; If/when kinetic roughening supersaturations are established, determinations of protein crystal quality over a range of supersaturations will also be assessed.; The results of our ground based effort may well address the existence of a correlation between fundamental growth mechanisms and protein crystal quality.

Enhanced active liposomal loading of a poorly soluble ionizable drug using supersaturated drug solutions.

PubMed

Modi, Sweta; Xiang, Tian-Xiang; Anderson, Bradley D

2012-09-10

Nanoparticulate drug carriers such as liposomal drug delivery systems are of considerable interest in cancer therapy because of their ability to passively accumulate in solid tumors. For liposomes to have practical utility for antitumor therapy in patients, however, optimization of drug loading, retention, and release kinetics are necessary. Active loading is the preferred method for optimizing loading of ionizable drugs in liposomes as measured by drug-to-lipid ratios, but the extremely low aqueous solubilities of many anticancer drug candidates may limit the external driving force, thus slowing liposomal uptake during active loading. This report demonstrates the advantages of maintaining drug supersaturation during active loading. A novel method was developed for creating and maintaining supersaturation of a poorly soluble camptothecin analogue, AR-67 (7-t-butyldimethylsilyl-10-hydroxycamptothecin), using a low concentration of a cyclodextrin (sulfobutylether-β-cyclodextrin) to inhibit crystallization over a 48 h period. Active loading into liposomes containing high concentrations of entrapped sodium or calcium acetate was monitored using drug solutions at varying degrees of supersaturation. Liposomal uptake rates increased linearly with the degree of supersaturation of drug in the external loading solution. A mathematical model was developed to predict the rate and extent of drug loading versus time, taking into account the chemical equilibria inside and outside of the vesicles and the transport kinetics of various permeable species across the lipid bilayer and the dialysis membrane. Intraliposomal sink conditions were maintained by the high internal pH caused by the efflux of acetic acid and exchange with AR-67, which undergoes lactone ring-opening, ionization, and membrane binding in the interior of the vesicles. The highest drug to lipid ratio achieved was 0.17 from a supersaturated solution at a total drug concentration of 0.6 mg/ml. The rate and extent of loading was similar when a different intraliposomal metal cation (sodium) was used instead of calcium. The proposed method may have general application in overcoming the formulation challenges associated with the liposomal delivery of poorly soluble, ionizable anticancer agents. Copyright © 2012 Elsevier B.V. All rights reserved.

Quantitative analysis of the effect of supersaturation on in vivo drug absorption.

PubMed

Takano, Ryusuke; Takata, Noriyuki; Saito, Ryoichi; Furumoto, Kentaro; Higo, Shoichi; Hayashi, Yoshiki; Machida, Minoru; Aso, Yoshinori; Yamashita, Shinji

2010-10-04

The purpose of this study is to clarify the effects of intestinal drug supersaturation on solubility-limited nonlinear absorption. Oral absorption of a novel farnesyltransferase inhibitor (FTI-2600) from its crystalline free base and its HCl salt was determined in dogs. To clarify the contribution of supersaturation on improving drug absorption, in vivo intraluminal concentration of FTI-2600 after oral administration was estimated from the pharmacokinetics data using a physiologically based model. Dissolution and precipitation characteristics of FTI-2600 in a biorelevant media were investigated in vitro using a miniscale dissolution test and powder X-ray diffraction analysis. In the in vitro study, the HCl salt immediately dissolved but precipitated rapidly. The metastable amorphous free base precipitant, which did not convert into the stable crystalline free base in the simulated intestinal fluids for several hours, generated a 5-fold increase in dissolved concentration compared to the equilibrium solubility of the crystalline free base. By computer simulation, the intraluminal drug concentration after administration of the free base was estimated to reach the saturated solubility, indicating solubility-limited absorption. On the other hand, administration of the HCl salt resulted in an increased intraluminal concentration and the plasma concentration was 400% greater than that after administration of the free base. This in vivo/in vitro correlation of the increased drug concentrations in the small intestine provide clear evidence that not only the increase in the dissolution rate, but also the supersaturation phenomenon, improved the solubility-limited absorption of FTI-2600. These results indicate that formulation technologies that can induce supersaturation may be of great assistance to the successful development of poorly water-soluble drugs.

Cloud condensation nuclei closure study on summer arctic aerosol

NASA Astrophysics Data System (ADS)

Martin, M.; Chang, R. Y.-W.; Sierau, B.; Sjogren, S.; Swietlicki, E.; Abbatt, J. P. D.; Leck, C.; Lohmann, U.

2011-03-01

We present an aerosol - cloud condensation nuclei CCN) closure study on summer high Arctic aerosol based on measurements that were carried out in summer 2008 during the Arctic Summer Cloud Ocean Study (ASCOS) on board the Swedish ice breaker Oden. The data presented here were collected during a three-week time period in the pack ice (>85° N) when the icebreaker Oden was moored to an ice floe and drifted passively during the most biological active period into autumn freeze up conditions. CCN number concentrations were obtained using two CCN counters measuring at different supersaturations. The directly measured CCN number concentration is then compared with a CCN number concentration calculated using both bulk aerosol mass composition data from an aerosol mass spectrometer and aerosol number size distributions obtained from a differential mobility particle sizer, assuming κ-Köhler theory and an internally mixed aerosol. For the two highest measured supersaturations, 0.73 and 0.41%, closure could not be achieved with the investigated settings concerning hygroscopicity and density. The calculated CCN number concentration was always higher than the measured one. One possible explanation is that the smaller particles that activate at these supersaturations have a relative larger insoluble organic mass fraction and thus are less good CCN than the larger particles. At 0.20, 0.15 and 0.10% supersaturation, the measured CCN number can be represented with different parameters for the hygroscopicity and density of the particles. For the best agreement of the calculated CCNnumber concentration with the measured one the organic fraction of the aerosol needs to be nearly insoluble (қorg=0.02). However, this is not unambigious and қorg=0.2 is found as an upper limit at 0.1% supersaturation.

Direct comparison of the hygroscopic properties of ammonium sulfate and sodium chloride aerosol at relative humidities approaching saturation.

PubMed

Walker, Jim S; Wills, Jon B; Reid, Jonathan P; Wang, Liangyu; Topping, David O; Butler, Jason R; Zhang, Yun-Hong

2010-12-09

Holographic optical tweezers are used to make comparative measurements of the hygroscopic properties of single component aqueous aerosol containing sodium chloride and ammonium sulfate over a range of relative humidity from 84% to 96%. The change in RH over the course of the experiment is monitored precisely using a sodium chloride probe droplet with accuracy better than ±0.09%. The measurements are used to assess the accuracy of thermodynamic treatments of the relationship between water activity and solute mass fraction with particular attention focused on the dilute solute limit approaching saturation vapor pressure. The consistency of the frequently used Clegg-Brimblecombe-Wexler (CBW) treatment for predicting the hygroscopic properties of sodium chloride and ammonium sulfate aerosol is confirmed. Measurements of the equilibrium size of ammonium sulfate aerosol are found to agree with predictions to within an uncertainty of ±0.2%. Given the accuracy of treating equilibrium composition, the inconsistencies highlighted in recent calibration measurements of critical supersaturations of sodium chloride and ammonium sulfate aerosol cannot be attributed to uncertainties associated with the thermodynamic predictions and must have an alternative origin. It is concluded that the CBW treatment can allow the critical supersaturation to be estimated for sodium chloride and ammonium sulfate aerosol with an accuracy of better than ±0.002% in RH. This corresponds to an uncertainty of ≤1% in the critical supersaturation for typical supersaturations of 0.2% and above. This supports the view that these systems can be used to accurately calibrate instruments that measure cloud condensation nuclei concentrations at selected supersaturations. These measurements represent the first study in which the equilibrium properties of two particles of chemically distinct composition have been compared simultaneously and directly alongside each other in the same environment.

Solute Nucleation and Growth in Supercritical Fluid Mixtures

NASA Technical Reports Server (NTRS)

Smedley, Gregory T.; Wilemski, Gerald; Rawlins, W. Terry; Joshi, Prakash; Oakes, David B.; Durgin, William W.

1996-01-01

This research effort is directed toward two primary scientific objectives: (1) to determine the gravitational effect on the measurement of nucleation and growth rates near a critical point and (2) to investigate the nucleation process in supercritical fluids to aid in the evaluation and development of existing theoretical models and practical applications. A nucleation pulse method will be employed for this investigation using a rapid expansion to a supersaturated state that is maintained for approximately 1 ms followed by a rapid recompression to a less supersaturated state that effectively terminates nucleation while permitting growth to continue. Nucleation, which occurs during the initial supersaturated state, is decoupled from growth by producing rapid pressure changes. Thermodynamic analysis, condensation modeling, apparatus design, and optical diagnostic design necessary for the initiation of a theoretical and experimental investigation of naphthalene nucleation from supercritical CO2 have been completed.

Hopper Growth of Salt Crystals.

PubMed

Desarnaud, Julie; Derluyn, Hannelore; Carmeliet, Jan; Bonn, Daniel; Shahidzadeh, Noushine

2018-06-07

The growth of hopper crystals is observed for many substances, but the mechanism of their formation remains ill understood. Here we investigate their growth by performing evaporation experiments on small volumes of salt solutions. We show that sodium chloride crystals that grow very fast from a highly supersaturated solution form a peculiar form of hopper crystal consisting of a series of connected miniature versions of the original cubic crystal. The transition between cubic and such hopper growth happens at a well-defined supersaturation where the growth rate of the cubic crystal reaches a maximum (∼6.5 ± 1.8 μm/s). Above this threshold, the growth rate varies as the third power of supersaturation, showing that a new mechanism, controlled by the maximum speed of surface integration of new molecules, induces the hopper growth of cubic crystals in cascade.

Growth habit and surface morphology of L-arginine phosphate monohydrate single crystals

NASA Astrophysics Data System (ADS)

Sangwal, K.; Veintemillas-Verdaguer, S.; Torrent-Burgués, J.

1995-10-01

The results of a study of the growth habit and the surface topography of L-arginine phosphate monohydrate (LAP) single crystals as a function of supersaturation are described and discussed. Apart from a change in the growth habit with supersaturation, it was observed that most of the as-grown faces of LAP exhibit isolated growth hillocks and macrohillocks and parallel bunched layers and that the formation of bunched layers is pronounced on faces showing macrohillocks. Observations of bunching of growth layers emitted by macrohillocks on the {100} faces revealed that, for the onset of bunching close to a macrospiral, there is a characteristic threshold distance whose value depends on the interstep distance and supersaturation, but is independent of step height. The theoretical habit of LAP deduced from PBC analysis showed that all faces exhibiting growth hillocks and macrohillocks are F faces. Analysis of the results on bunch formation revealed that growth of LAP takes place by the direct integration of growth entities at the growth steps, that the bunching is facilitated by an increasing value of the activation energy for their integration, and that the observed dependencies of threshold distance on interstep distance, supersaturation and step height are qualitatively in agreement with van der Eerden and Müller-Krumbhaar's theory of bunch formation.

Observations of supersaturation in the presence of cirrus at the tropical and sub-tropical tropopause

NASA Astrophysics Data System (ADS)

Smith, J. B.; Weinstock, E. M.; Pittman, J. V.; Sayres, D.; Moyer, E. J.; Anderson, J. G.; Herman, R. L.; Bui, T. P.; Thompson, T. L.

2003-04-01

We present in situ observations of water vapor and total water in the tropical and sub-tropical upper troposphere obtained aboard the WB-57 aircraft on flights out of Costa Rica during the Clouds and Water Vapor in the Climate System mission in August of 2001, and out of Key West, Florida during the CRYSTAL-FACE mission in July of 2002. The recently developed Harvard total water instrument merges the established Lyman-alpha photo-fragment fluorescence detection technique with a specially designed sampling inlet and heater, to make accurate and precise measurements of water in both the vapor and condensed phase. The combination of the Harvard total water and water vapor instruments allows for simultaneous measurement of water vapor, total water, and the net ice water content of cirrus. Data from the two instruments agree in dry air and demonstrate sufficient sensitivity to detect thin cirrus. Further analysis indicates frequent ice-supersaturation both in clear air and in cirrus. These data present a substantial contribution to in situ observations of ice-supersaturation, particularly in the presence of cirrus near the cold tropical tropopause. We will discuss the implications of high ice-supersaturation in the context of cloud microphysics, and the processes controlling water vapor in the upper troposphere and lower stratosphere.

Effect of CaCO3(S) nucleation modes on algae removal from alkaline water.

PubMed

Choi, Jin Yong; Kinney, Kerry A; Katz, Lynn E

2016-02-29

The role of calcite heterogeneous nucleation was studied in a particle coagulation treatment process for removing microalgae from water. Batch experiments were conducted with Scenedesmus sp. and Chlorella sp. in the presence and absence of carbonate and in the presence and absence of Mg to delineate the role of CaCO 3(S) nucleation on microalgae removal. The results indicate that effective algae coagulation (e.g., up to 81 % algae removal efficiency) can be achieved via heterogeneous nucleation with CaCO 3(S) ; however, supersaturation ratios between 120 and 200 are required to achieve at least 50% algae removal, depending on ion concentrations. Algae removal was attributed to adsorption of Ca 2+ onto the cell surface which provides nucleation sites for CaCO 3(S) precipitation. Bridging of calcite particles between the algal cells led to rapid aggregation and formation of larger flocs. However, at higher supersaturation conditions, algae removal was diminished due to the dominance of homogeneous nucleation of CaCO 3(S) . Removal of algae in the presence of Ca 2+ and Mg 2+ required higher supersaturation values; however, the shift from heteronucleation to homonucleation with increasing supersaturation was still evident. The results suggest that water chemistry, pH, ionic strength, alkalinity and Ca 2+ concentration can be optimized for algae removal via coagulation-sedimentation.

Using Environment-Sensitive Fluorescent Probes to Characterize Liquid-Liquid Phase Separation in Supersaturated Solutions of Poorly Water Soluble Compounds.

PubMed

Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

2015-11-01

Highly supersaturated aqueous solutions of poorly soluble compounds can undergo liquid-liquid phase separation (LLPS) when the concentration exceeds the "amorphous solubility". This phenomenon has been widely observed during high throughput screening of new molecular entities as well as during the dissolution of amorphous solid dispersions. In this study, we have evaluated the use of environment-sensitive fluorescence probes to investigate the formation and properties of the non-crystalline drug-rich aggregates formed in aqueous solutions as a result of LLPS. Six different environment-sensitive fluorophores were employed to study LLPS in highly supersaturated solutions of several model compounds, all dihydropyridine derivatives. Each fluoroprobe exhibited a large hypsochromic shift with decreasing environment polarity. Upon drug aggregate formation, the probes partitioned into the drug-rich phase and exhibited changes in emission wavelength and intensity consistent with sensing a lower polarity environment. The LLPS onset concentrations determined using the fluorescence measurements were in good agreement with light scattering measurements as well as theoretically estimated amorphous solubility values. Environment-sensitive fluorescence probes are useful to help understand the phase behavior of highly supersaturated aqueous solutions, which in turn is important in the context of developing enabling formulations for poorly soluble compounds.

Biofilm exopolymers control microbialite formation at thermal springs discharging into the alkaline Pyramid Lake, Nevada, USA

NASA Astrophysics Data System (ADS)

Arp, Gernot; Thiel, Volker; Reimer, Andreas; Michaelis, Walter; Reitner, Joachim

1999-07-01

Calcium carbonate precipitation and microbialite formation at highly supersaturated mixing zones of thermal spring waters and alkaline lake water have been investigated at Pyramid Lake, Nevada. Without precipitation, pure mixing should lead to a nearly 100-fold supersaturation at 40°C. Physicochemical precipitation is modified or even inhibited by the properties of biofilms, dependent on the extent of biofilm development and the current precipitation rate. Mucus substances (extracellular polymeric substances, EPS, e.g., of cyanobacteria) serve as effective Ca 2+-buffers, thus preventing seed crystal nucleation even in a highly supersaturated macroenvironment. Carbonate is then preferentially precipitated in mucus-free areas such as empty diatom tests or voids. After the buffer capacity of the EPS is surpassed, precipitation is observed at the margins of mucus areas. Hydrocarbon biomarkers extracted from (1) a calcifying Phormidium-biofilm, (2) the stromatolitic carbonate below, and (3) a fossil `tufa' of the Pleistocene pinnacles, indicate that the cyanobacterial primary producers have been subject to significant temporal changes in their species distribution. Accordingly, the species composition of cyanobacterial biofilms does not appear to be relevant for the formation of microbial carbonates in Pyramid Lake. The results demonstrate the crucial influence of mucus substances on carbonate precipitation in highly supersaturated natural environments.

Susceptibility of contrail ice crystal numbers to aircraft soot particle emissions

NASA Astrophysics Data System (ADS)

Kärcher, B.; Voigt, C.

2017-08-01

We develop an idealized, physically based model describing combined effects of ice nucleation and sublimation on ice crystal number during persistent contrail formation. Our study represents the first effort to predict ice numbers at the point where contrails transition into contrail cirrus—several minutes past formation—by connecting them to aircraft soot particle emissions and atmospheric supersaturation with respect to ice. Results averaged over an observed exponential distribution of ice supersaturation (mean value 15%) indicate that large reductions in soot particle numbers are needed to lower contrail ice crystal numbers significantly for soot emission indices around 1015 (kg fuel)-1, because reductions in nucleated ice number are partially compensated by sublimation losses. Variations in soot particle (-50%) and water vapor (+10%) emission indices at threefold lower soot emissions resulting from biofuel blending cause ice crystal numbers to change by -35% and <5%, respectively. The efficiency of reduction depends on ice supersaturation and the size distribution of nucleated ice crystals in jet exhaust plumes and on atmospheric ice supersaturation, making the latter another key factor in contrail mitigation. We expect our study to have important repercussions for planning airborne measurements targeting contrail formation, designing parameterization schemes for use in large-scale models, reducing uncertainties in predicting contrail cirrus, and mitigating the climate impact of aviation.

Nucleation and Crystal Growth of Organic-Inorganic Lead Halide Perovskites under Different Relative Humidity.

PubMed

Gao, Hao; Bao, Chunxiong; Li, Faming; Yu, Tao; Yang, Jie; Zhu, Weidong; Zhou, Xiaoxin; Fu, Gao; Zou, Zhigang

2015-05-06

Organic-inorganic lead halide perovskite compounds are very promising materials for high-efficiency perovskite solar cells. But how to fabricate high-quality perovksite films under controlled humidity conditions is still an important issue due to their sensitivity to moisture. In this study, we investigated the influence of ambient humidity on crystallization and surface morphology of one-step spin-coated perovskite films, as well as the performance of solar cells based on these perovskite films. On the basis of experimental analyses and thin film growth theory, we conclude that the influence of ambient humidity on nucleation at spin-coating stage is quite different from that on crystal growth at annealing stage. At the spin-coating stage, high nucleation density induced by high supersaturation prefers to appear under anhydrous circumstances, resulting in layer growth and high coverage of perovskite films. But at the annealing stage, the modest supersaturation benefits formation of perovskite films with good crystallinity. The films spin-coated under low relative humidity (RH) followed by annealing under high RH show an increase of crystallinity and improved performance of devices. Therefore, a mechanism of fast nucleation followed by modest crystal growth (high supersaturation at spin-coating stage and modest supersaturation at annealing stage) is suggested in the formation of high-quality perovskite films.

Modeling the Growth Rates of Tetragonal Lysozyme Crystal Faces

NASA Technical Reports Server (NTRS)

Li, Meirong; Nadarajah, Arunan; Pusey, Marc L.

1998-01-01

The measured macroscopic growth rates of the (110) and (101) faces of tetragonal lysozyme show an unexpectedly complex dependence on the supersaturation. The growth rates decay asymptotically to zero when the supersaturation is lowered to zero and increase rapidly when the supersaturation is increased. When supersaturations are increased still further the growth rates attain a maximum before starting to decrease. However, growth of these crystals is known to proceed by the classical dislocation and 2D nucleation growth mechanisms. This anomaly can be explained if growth is assumed to occur not by monomer units but by lysozyme aggregates. Analysis of the molecular packing of these crystals revealed that they were constructed of strongly bonded 4(sub 3) helices, while weaker bonds were responsible for binding the helices to each other. It follows that during crystal growth the stronger bonds are formed before the weaker ones. Thus, the growth of these crystals could be viewed as a two step process: aggregate growth units corresponding to the 4(sub 3) helix are first formed in the bulk solution by stronger intermolecular bonds and then attached to the crystal face by weaker bonds on dislocation hillocks or 2D islands. This will lead to a distribution of aggregates in the solution with monomers and lower order aggregates being predominant at low supersaturations and higher order aggregates being predominant at high supersaturations. If the crystal grows mostly by higher order aggregates, such as tetramers and octamers, it would explain the anomalous dependence of the growth rates on the supersaturation. Besides the analysis of molecular packing, a comprehensive analysis of the measured (110) and (101) growth rates was also undertaken in this study. The distribution of aggregates in lysozyme nutrient solutions at various solution conditions were determined from reversible aggregation reactions at equilibrium. The supersaturation was defined for each aggregate species with respect to its concentration at saturation in order to apply growth rate models to this process. The measured growth rates were then compared with the predicted ones from several dislocation and 2D nucleation growth models, employing tetramer and octamer growth units in polydisperse solutions and monomer units in monodisperse solutions. For the (110) face, the calculations consistently showed that the measured growth rates followed the expected model relations with octamer growth units. For the (101) face, it is not possible to obtain a clear agreement between the predicted and measured growth rates for a single growth unit as done for the (110) face. However, the calculations do indicate that the average size of the growth unit is between a tetramer and an octamer. This suggests that tetramers, octamers and other intermediate size growth units all participate in the growth process for this face. These calculations show that it is possible to model the macroscopic protein crystal growth rates if the molecular level processes can be account for, particularly protein aggregation processes in the bulk solution. Our recent investigations of tetragonal lysozyme crystals employing high resolution atomic force microscopy scans have further confirmed the growth of these crystals by aggregate growth units corresponding to 4(sub 3) helices.

Nucleation theory without Maxwell demons

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

Katz, J.L.; Wiedersich, H.

1977-09-01

The equations for steady-state nucleation are derived from the rates of growth and decay of clusters with emphasis on a clear distinction between thermodynamic quantities and inherently kinetic quantities. It is shown that the emission rates of molecules from embryos can be related to the equilibrium size distribution of clusters in a saturated vapor. It is therefore not necessary to invoke the existence of an embryo size distribution constrained be in equilibrium with a supersaturated vapor. The driving force for nucleation is shown to be a kinetic quantity called the condensation rate ratio, i.e., the ratio of the rates ofmore » acquisition of molecules by clusters in the supersaturated vapor to that in a saturated vapor at the same temperature, and not a thermodynamic quantity known as the supersaturation, i.e., the ratio of the actual pressure to the equilibrium vapor pressure.« less

Towards bulk syntheses of nanomaterials: a homeostatically supersaturated synthesis of polymer-like Bi 2S 3 nanowires with nearly 100% yield and no injection

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

Yuan, Bin; Iowa State Univ. of Science and Technology, Ames, IA; Brandt, Jordan Aaron

This article reports the implementation of a one-pot strategy for the synthesis of polymer-like Bi 2S 3 nanowires from supersaturated precursors. These conditions result in (i) a homeostatically regulated supersaturation of the growing phase during most of the reaction, (ii) a nearly 100% conversion of the limiting reagent, and (iii) an improved colloidal stability and polydispersity of the product (when compared to the hot-injection product) that allows the identification of three new exciton transitions in the absorption spectrum (one of them, importantly, being a weakly absorbing ground state at 1.64 eV). Three different commercial sources of ligands do not yieldmore » significantly different conversion rates. Scalability is further improved by lack of stirring after the initial stage of reaction and a lower reaction temperature (90 °C).« less

Towards bulk syntheses of nanomaterials: a homeostatically supersaturated synthesis of polymer-like Bi 2S 3 nanowires with nearly 100% yield and no injection

DOE PAGES

Yuan, Bin; Iowa State Univ. of Science and Technology, Ames, IA; Brandt, Jordan Aaron; ...

2016-11-25

This article reports the implementation of a one-pot strategy for the synthesis of polymer-like Bi 2S 3 nanowires from supersaturated precursors. These conditions result in (i) a homeostatically regulated supersaturation of the growing phase during most of the reaction, (ii) a nearly 100% conversion of the limiting reagent, and (iii) an improved colloidal stability and polydispersity of the product (when compared to the hot-injection product) that allows the identification of three new exciton transitions in the absorption spectrum (one of them, importantly, being a weakly absorbing ground state at 1.64 eV). Three different commercial sources of ligands do not yieldmore » significantly different conversion rates. Scalability is further improved by lack of stirring after the initial stage of reaction and a lower reaction temperature (90 °C).« less

Struvite formation and the fouling propensity of different materials.

PubMed

Doyle, J D; Oldring, K; Churchley, J; Parsons, S A

2002-09-01

Struvite (MgNH4PO4 x 6H2O) fouling was investigated to identify the impact supersaturation and material had on scaling rates. Tests were undertaken at three supersaturation ratios and with three different materials: stainless steel, teflon and acrylic. Impellers consisting of a clasp unit and two corrosion coupons that could be attached were used to mix centrate liquor and precipitation was initiated by the change in pH caused by degassing. Increasing the supersaturation ratio from 1.7 to 5.3 led to a doubling in the scaling rate of stainless-steel coupons. Experiments with acrylic and teflon coupons showed the influence of surface roughness upon scaling propensity. Coarsely roughened coupons following 40 h of mixing had a mass of 413 mg of struvite attached compared to smooth coupons that had a mass of 240 mg attached. Material did have an influence upon struvite fouling but this influence diminished with increasing surface roughness.

Effect of Elastic Strain Fluctuation on Atomic Layer Growth of Epitaxial Silicide in Si Nanowires by Point Contact Reactions.

PubMed

Chou, Yi-Chia; Tang, Wei; Chiou, Chien-Jyun; Chen, Kai; Minor, Andrew M; Tu, K N

2015-06-10

Effects of strain impact a range of applications involving mobility change in field-effect-transistors. We report the effect of strain fluctuation on epitaxial growth of NiSi2 in a Si nanowire via point contact and atomic layer reactions, and we discuss the thermodynamic, kinetic, and mechanical implications. The generation and relaxation of strain shown by in situ TEM is periodic and in synchronization with the atomic layer reaction. The Si lattice at the epitaxial interface is under tensile strain, which enables a high solubility of supersaturated interstitial Ni atoms for homogeneous nucleation of an epitaxial atomic layer of the disilicide phase. The tensile strain is reduced locally during the incubation period of nucleation by the dissolution of supersaturated Ni atoms in the Si lattice but the strained-Si state returns once the atomic layer epitaxial growth of NiSi2 occurs by consuming the supersaturated Ni.

An Assessment of the Radiative Effects of Ice Supersaturation Based on in Situ Observations

NASA Technical Reports Server (NTRS)

Tan, Xiaoxiao; Huang, i; Diao, Minghui; Bansemer, Aaron; Zondlo, Mark A.; DiGangi, Joshua P.; Volkamer, Rainer; Hu, Yongyun

2016-01-01

We use aircraft observations combined with the reanalysis data to investigate the radiative effects of ice supersaturation (ISS). Our results show that although the excess water vapor over ice saturation itself has relatively small radiative effects, mistaking it as ice crystals in climate models would lead to considerable impacts: on average, +2.49 W/m(exp 2) change in the top of the atmosphere (TOA) radiation, -2.7 W/m(exp 2) change in surface radiation, and 1.47 K/d change in heating rates. The radiative effects of ISS generally increase with the magnitudes of supersaturation. However, there is a strong dependence on the preexisting ice water path, which can even change the sign of the TOA radiative effect. It is therefore important to consider coexistence between ISS and ice clouds and to validate their relationship in the parameterizations of ISS in climate models.

Behaviour of calcium carbonate in sea water

USGS Publications Warehouse

Cloud, P.E.

1962-01-01

Anomalies in the behaviour of calcium carbonate in natural solutions diminish when considered in context. Best values found by traditional oceanographie methods for the apparent solubility product constant K'CaCO3 in sea water at atmospheric pressure are consistent mineralogically-at 36 parts per thousand salinity and T-25??C, K'aragonlte is estimated as 1.12 ?? 10-6 and K'calcite as 0.61 ?? 10-6. At 30??C the corresponding values are 0.98 ?? 10-6 for aragonite and 0.53 ?? 10-6 for calcite. Because the K' computations do not compensate for ionic activity, however, they cannot give thermodynamically satisfactory results. It is of interest, therefore, that approximate methods and information now available permit the estimation from the same basic data of an activity product constant KCaCO3 close to that found in solutions to which Debye-Hu??ckel theory applies. Such methods indicate approximate Karagonite 7.8 ?? 10-9 for surface sea water at 29??C; Kcalcite would be proportionately lower. Field data and experimental results indicate that the mineralogy of precipitated CaCO3 depends primarily on degree of supersaturation, thus also on kinetic or biologic factors that facilitate or inhibit a high degree of supersaturation. The shallow, generally hypersaline bank waters west of Andros Island yield aragonitic sediments with O18 O16 ratios that imply precipitation mainly during the warmer months, when the combination of a high rate of evaporation, increasing salinity (and ionic strength), maximal temperatures and photosynthetic removal of CO2 result in high apparent supersaturation. The usual precipitate from solutions of low ionic strength is calcite, except where the aragonite level of supersaturation is reached as a result of diffusion phenomena (e.g. dripstones), gradual and marked evaporation, or biologic intervention. Published data also suggest the possibility of distinct chemical milieus for crystallographic variations in skeletal calcium carbonate. It appears that in nature aragonite precipitates from solutions that are supersaturated with respect to both calcite and aragonite and calcite between saturation levels for the two species. Such a relation is consistent with Ostwald's rule of successive reactions. Aragonitc of marine origin persists in contact with supersaturated interstitial solutions at ordinary temperature and pressure. Conversion to calcite follows transfer to solutions undersaturated with respect to aragonite or upon exposure to the moist atmosphere. ?? 1962.

Silica-Induced Protein (Sip) in Thermophilic Bacterium Thermus thermophilus Responds to Low Iron Availability

PubMed Central

Fujino, Yasuhiro; Nagayoshi, Yuko; Iwase, Makoto; Yokoyama, Takushi; Ohshima, Toshihisa

2016-01-01

ABSTRACT Thermus thermophilus HB8 expresses silica-induced protein (Sip) when cultured in medium containing supersaturated silicic acids. Using genomic information, Sip was identified as a Fe3+-binding ABC transporter. Detection of a 1-kb hybridized band in Northern analysis revealed that sip transcription is monocistronic and that sip has its own terminator and promoter. The sequence of the sip promoter showed homology with that of the σA-dependent promoter, which is known as a housekeeping promoter in HB8. Considering that sip is transcribed when supersaturated silicic acids are added, the existence of a repressor is presumed. DNA microarray analysis suggested that supersaturated silicic acids and iron deficiency affect Thermus cells similarly, and enhanced sip transcription was detected under both conditions. This suggested that sip transcription was initiated by iron deficiency and that the ferric uptake regulator (Fur) controlled the transcription. Three Fur gene homologues (TTHA0255, TTHA0344, and TTHA1292) have been annotated in the HB8 genome, and electrophoretic mobility shift assays revealed that the TTHA0344 product interacts with the sip promoter region. In medium containing supersaturated silicic acids, free Fe3+ levels were decreased due to Fe3+ immobilization on colloidal silica. This suggests that, because Fe3+ ions are captured by colloidal silica in geothermal water, Thermus cells are continuously exposed to the risk of iron deficiency. Considering that Sip is involved in iron acquisition, Sip production may be a strategy to survive under conditions of low iron availability in geothermal water. IMPORTANCE The thermophilic bacterium Thermus thermophilus HB8 produces silica-induced protein (Sip) in the presence of supersaturated silicic acids. Sip has homology with iron-binding ABC transporter; however, the mechanism by which Sip expression is induced by silicic acids remains unexplained. We demonstrate that Sip captures iron and its transcription is regulated by the repressor ferric uptake regulator (Fur). This implies that Sip is expressed with iron deficiency. In addition, it is suggested that negatively charged colloidal silica in supersaturated solution absorbs Fe3+ ions and decreases iron availability. Considering that geothermal water contains ample silicic acids, it is suggested that thermophilic bacteria are always facing iron starvation. Sip production may be a strategy for surviving under conditions of low iron availability in geothermal water. PMID:26994077

Correlation between mobility collapse and carbon impurities in Si-doped GaN grown by low pressure metalorganic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Kaess, Felix; Mita, Seiji; Xie, Jingqiao; Reddy, Pramod; Klump, Andrew; Hernandez-Balderrama, Luis H.; Washiyama, Shun; Franke, Alexander; Kirste, Ronny; Hoffmann, Axel; Collazo, Ramón; Sitar, Zlatko

2016-09-01

In the low doping range below 1 × 1017 cm-3, carbon was identified as the main defect attributing to the sudden reduction of the electron mobility, the electron mobility collapse, in n-type GaN grown by low pressure metalorganic chemical vapor deposition. Secondary ion mass spectroscopy has been performed in conjunction with C concentration and the thermodynamic Ga supersaturation model. By controlling the ammonia flow rate, the input partial pressure of Ga precursor, and the diluent gas within the Ga supersaturation model, the C concentration in Si-doped GaN was controllable from 6 × 1019 cm-3 to values as low as 2 × 1015 cm-3. It was found that the electron mobility collapsed as a function of free carrier concentration, once the Si concentration closely approached the C concentration. Lowering the C concentration to the order of 1015 cm-3 by optimizing Ga supersaturation achieved controllable free carrier concentrations down to 5 × 1015 cm-3 with a peak electron mobility of 820 cm2/V s without observing the mobility collapse. The highest electron mobility of 1170 cm2/V s was obtained even in metalorganic vapor deposition-grown GaN on sapphire substrates by optimizing growth parameters in terms of Ga supersaturation to reduce the C concentration.

Thermodynamics of Highly Supersaturated Aqueous Solutions of Poorly Water-Soluble Drugs-Impact of a Second Drug on the Solution Phase Behavior and Implications for Combination Products.

PubMed

Trasi, Niraj S; Taylor, Lynne S

2015-08-01

There is increasing interest in formulating combination products that contain two or more drugs. Furthermore, it is also common for different drug products to be taken simultaneously. This raises the possibility of interactions between different drugs that may impact formulation performance. For poorly water-soluble compounds, the supersaturation behavior may be a critical factor in determining the extent of oral absorption. The goal of the current study was to evaluate the maximum achievable supersaturation for several poorly water-soluble compounds alone, and in combination. Model compounds included ritonavir, lopinavir, paclitaxel, felodipine, and diclofenac. The "amorphous solubility" for the pure drugs was determined using different techniques and the change in this solubility was then measured in the presence of differing amounts of a second drug. The results showed that "amorphous solubility" of each component in aqueous solution is substantially decreased by the second component, as long as the two drugs are miscible in the amorphous state. A simple thermodynamic model could be used to predict the changes in solubility as a function of composition. This information is of great value when developing co-amorphous or other supersaturating formulations and should contribute to a broader understanding of drug-drug physicochemical interactions in in vitro assays as well as in the gastrointestinal tract. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

The Effect of Solution Conditions on the Nucleation Kinetics of Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Judge, Russell A.; Baird, James K.; Pusey, Marc L.

1998-01-01

An understanding of protein crystal nucleation rates and the effect of solution conditions upon them, is fundamental to the preparation of protein crystals of the desired size and shape for X-ray diffraction analysis. The ability to predict the effect of supersaturation, temperature, pH and precipitant concentration on the number and size of crystals formed is of great benefit in the pursuit of protein structure analysis. In this study we experimentally examine the effect of supersaturation, temperature, pH and sodium chloride concentration on the nucleation rate of tetragonal chicken egg white lysozyme crystals. In order to do this batch crystallization plates were prepared at given solution concentrations and incubated at three different temperatures over the period of one week. The number of crystals per well with their size and dimensions were recorded and correlated against solution conditions. Duplicate experiments indicate the reproducibility of the technique. Although it is well known that crystal numbers increase with increasing supersaturation, large changes in crystal number were also correlated against solution conditions of temperature, pH and salt concentration over the same supersaturation ranges. Analysis of these results enhance our understanding of the effect of solution conditions such as the dramatic effect that small changes in charge and ionic strength can have on the number of tetragonal lysozyme crystals that form and grow in solution.

Silicates Do Nucleate in Oxygen-rich Circumstellar Outflows: New Vapor Pressure Data for SiO

NASA Astrophysics Data System (ADS)

Nuth, Joseph A., III; Ferguson, Frank T.

2006-10-01

We have measured the vapor pressure of solid SiO as a function of temperature over the range from 1325 up to 1785 K in vacuo using a modified Thermo-Cahn thermogravimetric system. Although an extrapolation of the current vapor pressure data to 2200 K is close to that predicted from the work of Schick under reducing conditions, the vapor pressures measured at successively lower temperatures diverge significantly from such predictions and are several orders of magnitude lower than predicted at 1200 K. This new vapor pressure data has been inserted into a simple model for the gas expanding from a late-stage star. Using the new vapor pressure curve makes a significant difference in the temperature and stellar radius at which SiO gas becomes supersaturated, although SiO still becomes supersaturated at temperatures that are too low to be consistent with observations. We have therefore also explored the effects of vibrational disequilibrium (as explored by Nuth & Donn) of SiO in the expanding shell on the conditions under which nucleation occurs. These calculations are much more interesting in that supersaturation now occurs at much higher kinetic temperatures. We note, however, that both vibrational disequilibrium and the new vapor pressure curve are required to induce SiO supersaturation in stellar outflows at temperatures above 1000 K.

Evaluating the predictability of the in vitro transfer model and in vivo rat studies as a surrogate to investigate the supersaturation and precipitation behaviour of different Albendazole formulations for humans.

PubMed

Ruff, Aaron; Holm, René; Kostewicz, Edmund S

2017-07-15

The present study investigated the ability of the in vitro transfer model and an in vivo pharmacokinetic study in rats to investigate the supersaturation and precipitation behaviour of albendazole (ABZ) relative to data from a human intestinal aspiration study reported in the literature. Two lipid based formulation systems, a hydroxypropyl-β-cyclodextrin (HPβCD) solution and the addition of a crystallization inhibitor (HPMC-E5) on the behaviour of ABZ was investigated. These formulations were investigated to represent differences in their ability to facilitate supersaturation within the small intestine. Overall, both the in vitro transfer model and the in vivo rat study were able to rank order the formulations (as aqueous suspension±HPMC

In Silico Modeling Approach for the Evaluation of Gastrointestinal Dissolution, Supersaturation, and Precipitation of Posaconazole.

PubMed

Hens, Bart; Pathak, Shriram M; Mitra, Amitava; Patel, Nikunjkumar; Liu, Bo; Patel, Sanjaykumar; Jamei, Masoud; Brouwers, Joachim; Augustijns, Patrick; Turner, David B

2017-12-04

The aim of this study was to evaluate gastrointestinal (GI) dissolution, supersaturation, and precipitation of posaconazole, formulated as an acidified (pH 1.6) and neutral (pH 7.1) suspension. A physiologically based pharmacokinetic (PBPK) modeling and simulation tool was applied to simulate GI and systemic concentration-time profiles of posaconazole, which were directly compared with intraluminal and systemic data measured in humans. The Advanced Dissolution Absorption and Metabolism (ADAM) model of the Simcyp Simulator correctly simulated incomplete gastric dissolution and saturated duodenal concentrations of posaconazole in the duodenal fluids following administration of the neutral suspension. In contrast, gastric dissolution was approximately 2-fold higher after administration of the acidified suspension, which resulted in supersaturated concentrations of posaconazole upon transfer to the upper small intestine. The precipitation kinetics of posaconazole were described by two precipitation rate constants, extracted by semimechanistic modeling of a two-stage medium change in vitro dissolution test. The 2-fold difference in exposure in the duodenal compartment for the two formulations corresponded with a 2-fold difference in systemic exposure. This study demonstrated for the first time predictive in silico simulations of GI dissolution, supersaturation, and precipitation for a weakly basic compound in part informed by modeling of in vitro dissolution experiments and validated via clinical measurements in both GI fluids and plasma. Sensitivity analysis with the PBPK model indicated that the critical supersaturation ratio (CSR) and second precipitation rate constant (sPRC) are important parameters of the model. Due to the limitations of the two-stage medium change experiment the CSR was extracted directly from the clinical data. However, in vitro experiments with the BioGIT transfer system performed after completion of the in silico modeling provided an almost identical CSR to the clinical study value; this had no significant impact on the PBPK model predictions.

pH-Dependent Liquid-Liquid Phase Separation of Highly Supersaturated Solutions of Weakly Basic Drugs.

PubMed

Indulkar, Anura S; Box, Karl J; Taylor, Robert; Ruiz, Rebeca; Taylor, Lynne S

2015-07-06

Supersaturated solutions of poorly aqueous soluble drugs can be formed both in vivo and in vitro. For example, increases in pH during gastrointestinal transit can decrease the aqueous solubility of weakly basic drugs resulting in supersaturation, in particular when exiting the acidic stomach environment. Recently, it has been observed that highly supersaturated solutions of drugs with low aqueous solubility can undergo liquid-liquid phase separation (LLPS) prior to crystallization, forming a turbid solution such that the concentration of the drug in the continuous solution phase corresponds to the amorphous solubility while the colloidal phase is composed of a disordered drug-rich phase. Although it is well established that the equilibrium solubility of crystalline weakly basic drugs follows the Henderson-Hasselbalch relationship, the impact of pH on the LLPS phenomenon or the amorphous solubility has not been explored. In this work, the LLPS concentration of three weakly basic compounds-clotrimazole, nicardipine, and atazanavir-was determined as a function of pH using three different methods and was compared to the predicted amorphous solubility, which was calculated from the pH-dependent crystalline solubility and by estimating the free energy difference between the amorphous and crystalline forms. It was observed that, similar to crystalline solubility, the experimental amorphous solubility at any pH follows the Henderson-Hasselbalch relation and can be predicted if the amorphous solubility of the free base is known. Excellent agreement between the LLPS concentration and the predicted amorphous solubility was observed. Dissolution studies of amorphous drugs showed that the solution concentration can reach the corresponding LLPS concentration at that pH. Solid-state analysis of the precipitated material confirmed the amorphous nature. This work provides insight into the pH-dependent precipitation behavior of poorly water-soluble compounds and provides a fundamental basis with which to understand the performance of supersaturating dosage forms.

Construction, Analysis, and Data-Driven Augmentation of Supersaturated Designs

DTIC Science & Technology

2013-09-01

guidelines and considerations. 27 Table 7. Supersaturated Design Example with 8 Runs and 14 Factors Design Factors Run x1 x2 x3 x4 x5 x6 x7 x8 x9 x10 x11...much larger than the guidelines proposed by Marley 55 and Woods (2010). They recommend the factor-to-run ratio should be less than 2. Because our ratio...established approach in experimental design: Box (1992) provided general guidelines to consider, and traditional augmentation strategies like fold-over

Experimental Study of the Low Supersaturation Nucleation in Crystal Growth by Contactless Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Grasza, K.; Palosz, W.; Trivedi, S. B.

1998-01-01

The process of the development of the nuclei and of subsequent seeding in 'contactless' physical vapor transport is investigated experimentally. Consecutive stages of the Low Supersaturation Nucleation in 'contactless' geometry for growth of CdTe crystals from the vapor are shown. The effects of the temperature field, geometry of the system, and experimental procedures on the process are presented and discussed. The experimental results are found to be consistent with our earlier numerical modeling results.

Nucleation of insulin crystals in a wide continuous supersaturation gradient.

PubMed

Penkova, Anita; Dimitrov, Ivaylo; Nanev, Christo

2004-11-01

Modifying the classical double pulse technique, by using a supersaturation gradient along an insulin solution contained in a glass capillary tube, we found conditions appropriate for the direct measurement of nucleation parameters. The nucleation time lag has been measured. Data for the number of crystal nuclei versus the nucleation time were obtained for this hormone. Insulin was chosen as a model protein because of the availability of solubility data in the literature. A comparison with the results for hen-egg-white lysozyme, HEWL was performed.

Electrocrystallization and Properties of Supersaturated Solid Solutions of Copper

NASA Astrophysics Data System (ADS)

Povetkin, V. V.; Ivanova, T. E.; Ismagilova, A. V.

2018-03-01

The role of the alloying element in the formation of the structure and properties of electrolytic copper alloys has been determined. The X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) have shown that electrochemical alloying of copper with low-melting metals leads to the formation of supersaturated solid solutions (SSS) on the cathode, crushing of the crystal structure, smoothing of the surface relief, hardening of the deposits obtained, increasing their solderability and corrosive resistance to acidic media.

Solid-solution thermodynamics in Al-Li alloys

NASA Astrophysics Data System (ADS)

Alekseev, A. A.; Lukina, E. A.

2016-05-01

The relative equilibrium concentrations of lithium atoms distributed over different electron-structural states has been estimated. The possibility of the existence of various nonequilibrium electron-structural states of Li atoms in the solid solution in Al has been substantiated thermodynamically. Upon the decomposition of the supersaturated solid solution, the supersaturation on three electron-structural states of Li atoms that arises upon the quenching of the alloy can lead to the formation of lithium-containing phases in which the lithium atoms enter in one electron-structural state.

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.

Ice crystal growth in a dynamic thermal diffusion chamber

NASA Technical Reports Server (NTRS)

Keller, V. W.

1980-01-01

Ice crystals were grown in a supersaturated environment produced by a dynamic thermal diffusion chamber, which employed two horizontal plates separated by a distance of 2.5 cm. Air was circulated between and along the 1.2 m length of the plates past ice crystals which nucleated and grew from a fiber suspended vertically between the two plates. A zoom stereo microscope with a magnification which ranged from 3X to 80X and both 35 mm still photographs and 16 mm time lapse cine films taken through the microscope were used to study the variation of the shape and linear growth rate of ice crystals as a function of the ambient temperature, the ambient supersaturation, and the forced ventilation velocity. The ambient growth conditions were varied over the range of temperature 0 to -40 C, over the range of supersaturation 4% to 50% with respect to ice, and over the range of forced ventilation velocities 0 cm/s to 20 cm/s.

Overcoming time scale and finite size limitations to compute nucleation rates from small scale well tempered metadynamics simulations.

PubMed

Salvalaglio, Matteo; Tiwary, Pratyush; Maggioni, Giovanni Maria; Mazzotti, Marco; Parrinello, Michele

2016-12-07

Condensation of a liquid droplet from a supersaturated vapour phase is initiated by a prototypical nucleation event. As such it is challenging to compute its rate from atomistic molecular dynamics simulations. In fact at realistic supersaturation conditions condensation occurs on time scales that far exceed what can be reached with conventional molecular dynamics methods. Another known problem in this context is the distortion of the free energy profile associated to nucleation due to the small, finite size of typical simulation boxes. In this work the problem of time scale is addressed with a recently developed enhanced sampling method while contextually correcting for finite size effects. We demonstrate our approach by studying the condensation of argon, and showing that characteristic nucleation times of the order of magnitude of hours can be reliably calculated. Nucleation rates spanning a range of 10 orders of magnitude are computed at moderate supersaturation levels, thus bridging the gap between what standard molecular dynamics simulations can do and real physical systems.

Overcoming time scale and finite size limitations to compute nucleation rates from small scale well tempered metadynamics simulations

NASA Astrophysics Data System (ADS)

Salvalaglio, Matteo; Tiwary, Pratyush; Maggioni, Giovanni Maria; Mazzotti, Marco; Parrinello, Michele

2016-12-01

Condensation of a liquid droplet from a supersaturated vapour phase is initiated by a prototypical nucleation event. As such it is challenging to compute its rate from atomistic molecular dynamics simulations. In fact at realistic supersaturation conditions condensation occurs on time scales that far exceed what can be reached with conventional molecular dynamics methods. Another known problem in this context is the distortion of the free energy profile associated to nucleation due to the small, finite size of typical simulation boxes. In this work the problem of time scale is addressed with a recently developed enhanced sampling method while contextually correcting for finite size effects. We demonstrate our approach by studying the condensation of argon, and showing that characteristic nucleation times of the order of magnitude of hours can be reliably calculated. Nucleation rates spanning a range of 10 orders of magnitude are computed at moderate supersaturation levels, thus bridging the gap between what standard molecular dynamics simulations can do and real physical systems.

Hydrothermal growth of ZnO nanowire arrays: fine tuning by precursor supersaturation

DOE PAGES

Yan, Danhua; Cen, Jiajie; Zhang, Wenrui; ...

2016-12-20

In this paper, we develop a technique that fine tunes the hydrothermal growth of ZnO nanowires to address the difficulties in controlling their growth in a conventional one-pot hydrothermal method. In our technique, precursors are separately and slowly supplied with the assistance of a syringe pump, through the entire course of the growth. Compared to the one-pot method, the significantly lowered supersaturation of precursors helps eliminating competitive homogeneous nucleation and improves the reproducibility. The supersaturation degree can be readily tuned by the precursor quantity and injection rate, thus forming ZnO nanowire arrays of various geometries and packing densities in amore » highly controllable fashion. The precise control of ZnO nanowire growth enables systematic studies on the correlation between the material's properties and its morphology. Finally, in this work, ZnO nanowire arrays of various morphologies are studied as photoelectrochemical (PEC) water splitting photoanodes, in which we establish clear correlations between the water splitting performance and the nanowires' size, shape, and packing density.« less

Aerosol indirect effect from turbulence-induced broadening of cloud-droplet size distributions.

PubMed

Chandrakar, Kamal Kant; Cantrell, Will; Chang, Kelken; Ciochetto, David; Niedermeier, Dennis; Ovchinnikov, Mikhail; Shaw, Raymond A; Yang, Fan

2016-12-13

The influence of aerosol concentration on the cloud-droplet size distribution is investigated in a laboratory chamber that enables turbulent cloud formation through moist convection. The experiments allow steady-state microphysics to be achieved, with aerosol input balanced by cloud-droplet growth and fallout. As aerosol concentration is increased, the cloud-droplet mean diameter decreases, as expected, but the width of the size distribution also decreases sharply. The aerosol input allows for cloud generation in the limiting regimes of fast microphysics ([Formula: see text]) for high aerosol concentration, and slow microphysics ([Formula: see text]) for low aerosol concentration; here, [Formula: see text] is the phase-relaxation time and [Formula: see text] is the turbulence-correlation time. The increase in the width of the droplet size distribution for the low aerosol limit is consistent with larger variability of supersaturation due to the slow microphysical response. A stochastic differential equation for supersaturation predicts that the standard deviation of the squared droplet radius should increase linearly with a system time scale defined as [Formula: see text], and the measurements are in excellent agreement with this finding. The result underscores the importance of droplet size dispersion for aerosol indirect effects: increasing aerosol concentration changes the albedo and suppresses precipitation formation not only through reduction of the mean droplet diameter but also by narrowing of the droplet size distribution due to reduced supersaturation fluctuations. Supersaturation fluctuations in the low aerosol/slow microphysics limit are likely of leading importance for precipitation formation.

Modeling Tetragonal Lysozyme Crystal Growth Rates

NASA Technical Reports Server (NTRS)

Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

2003-01-01

Tetragonal lysozyme 110 face crystal growth rates, measured over 5 orders of magnitude in range, can be described using a model where growth occurs by 2D nucleation on the crystal surface for solution supersaturations of c/c(sub eq) less than or equal to 7 +/- 2. Based upon the model, the step energy per unit length, beta was estimated to be approx. 5.3 +/- 0.4 x 10(exp -7) erg/mol-cm, which for a step height of 56 A corresponds to barrier of approx. 7 +/- 1 k(sub B)T at 300 K. For supersaturations of c/c(sub eq) > 8, the model emphasizing crystal growth by 2D nucleation not only could not predict, but also consistently overestimated, the highest observable crystal growth rates. Kinetic roughening is hypothesized to occur at a cross-over supersaturation of c/c(sub eq) > 8, where crystal growth is postulated to occur by a different process such as adsorption. Under this assumption, all growth rate data indicated that a kinetic roughening transition and subsequent crystal growth by adsorption for all solution conditions, varying in buffer pH, temperature and precipitant concentration, occurs for c/c(sub eq)(T, pH, NaCl) in the range between 5 and 10, with an energy barrier for adsorption estimated to be approx. 20 k(sub B)T at 300 K. Based upon these and other estimates, we determined the size of the critical surface nucleate, at the crossover supersaturation and higher concentrations, to range from 4 to 10 molecules.

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

PubMed

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

2018-03-01

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

Improved arterial blood oxygenation following intravenous infusion of cold supersaturated dissolved oxygen solution.

PubMed

Grady, Daniel J; Gentile, Michael A; Riggs, John H; Cheifetz, Ira M

2014-01-01

One of the primary goals of critical care medicine is to support adequate gas exchange without iatrogenic sequelae. An emerging method of delivering supplemental oxygen is intravenously rather than via the traditional inhalation route. The objective of this study was to evaluate the gas-exchange effects of infusing cold intravenous (IV) fluids containing very high partial pressures of dissolved oxygen (>760 mm Hg) in a porcine model. Juvenile swines were anesthetized and mechanically ventilated. Each animal received an infusion of cold (13 °C) Ringer's lactate solution (30 mL/kg/hour), which had been supersaturated with dissolved oxygen gas (39.7 mg/L dissolved oxygen, 992 mm Hg, 30.5 mL/L). Arterial blood gases and physiologic measurements were repeated at 15-minute intervals during a 60-minute IV infusion of the supersaturated dissolved oxygen solution. Each animal served as its own control. Five swines (12.9 ± 0.9 kg) were studied. Following the 60-minute infusion, there were significant increases in PaO2 and SaO2 (P < 0.05) and a significant decrease in PaCO2 (P < 0.05), with a corresponding normalization in arterial blood pH. Additionally, there was a significant decrease in core body temperature (P < 0.05) when compared to the baseline preinfusion state. A cold, supersaturated dissolved oxygen solution may be intravenously administered to improve arterial blood oxygenation and ventilation parameters and induce a mild therapeutic hypothermia in a porcine model.

Kinetic Roughening and Energetics of Tetragonal Lysozyme Crystal Growth: A Preliminary Atomic Force Microscopy Investigation

NASA Technical Reports Server (NTRS)

Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

2004-01-01

We examined particulars of crystal growth from measurements obtained at both microscopic and molecular levels. The crystal growth measurements performed at the microscopic level are well characterized by a model that balances the flux of macromolecules towards the crystal surface with the flux of the crystal surface. Numerical evaluation of model with measurements of crystal growth, in time, provided accurate estimates for the average growth velocities. Growth velocities thus obtained were also interpreted using well-established phenomenological theories. Moreover, we find that microscopic measurements of growth velocity measurements obtained as a function of temperature best characterizes changes in crystal growth modes, when present. We also examined the possibility of detecting a change in crystal growth modes at the molecular level using atomic force microscopy, AFM. From preliminary AFM measurements performed at various supersaturations, we find that magnitude of surface height fluctuations, h(x), increases with supersaturation. Further examination of surface height fluctuations using methods established for fluctuation spectroscopy also enabled the discovery of the existence of a characteristic length, c, which may possibly determine the mode of crystal growth. Although the results are preliminary, we establish the non- critical divergence of 5 and the root-mean-square (rms) magnitude of height-height fluctuations as the kinetic roughening transition temperatures are approached. Moreover, we also examine approximate models for interpreting the non-critical behavior of both 6 and rms magnitude of height-height fluctuations, as the solution supersaturation is increased towards the kinetic roughening supersaturation.

Amorphization strategy affects the stability and supersaturation profile of amorphous drug nanoparticles.

PubMed

Cheow, Wean Sin; Kiew, Tie Yi; Yang, Yue; Hadinoto, Kunn

2014-05-05

Amorphous drug nanoparticles have recently emerged as a promising bioavailability enhancement strategy of poorly soluble drugs attributed to the high supersaturation solubility generated by the amorphous state and fast dissolution afforded by the nanoparticles. Herein we examine the effects of two amorphization strategies in the nanoscale, i.e., (1) molecular mobility restrictions and (2) high energy surface occupation, both by polymer excipient stabilizers, on the (i) morphology, (ii) colloidal stability, (iii) drug loading, (iv) amorphous state stability after three-month storage, and (v) in vitro supersaturation profiles, using itraconazole (ITZ) as the model drug. Drug-polyelectrolyte complexation is employed in the first strategy to prepare amorphous ITZ nanoparticles using dextran sulfate as the polyelectrolyte (ITZ nanoplex), while the second strategy employs pH-shift precipitation using hydroxypropylmethylcellulose as the surface stabilizer (nano-ITZ), with both strategies resulting in >90% ITZ utilization. Both amorphous ITZ nanoparticles share similar morphology (∼300 nm spheres) with the ITZ nanoplex exhibiting better colloidal stability, albeit at lower ITZ loading (65% versus 94%), due to the larger stabilizer amount used. The ITZ nanoplex also exhibits superior amorphous state stability, attributed to the ITZ molecular mobility restriction by electrostatic complexation with dextran sulfate. The higher stability, however, is obtained at the expense of slower supersaturation generation, which is maintained over a prolonged period, compared to the nano-ITZ. The present results signify the importance of selecting the optimal amorphization strategy, in addition to formulating the excipient stabilizers, to produce amorphous drug nanoparticles having the desired characteristics.

Improved Arterial Blood Oxygenation Following Intravenous Infusion of Cold Supersaturated Dissolved Oxygen Solution

PubMed Central

Grady, Daniel J; Gentile, Michael A; Riggs, John H; Cheifetz, Ira M

2014-01-01

BACKGROUND One of the primary goals of critical care medicine is to support adequate gas exchange without iatrogenic sequelae. An emerging method of delivering supplemental oxygen is intravenously rather than via the traditional inhalation route. The objective of this study was to evaluate the gas-exchange effects of infusing cold intravenous (IV) fluids containing very high partial pressures of dissolved oxygen (>760 mm Hg) in a porcine model. METHODS Juvenile swines were anesthetized and mechanically ventilated. Each animal received an infusion of cold (13 °C) Ringer’s lactate solution (30 mL/kg/hour), which had been supersaturated with dissolved oxygen gas (39.7 mg/L dissolved oxygen, 992 mm Hg, 30.5 mL/L). Arterial blood gases and physiologic measurements were repeated at 15-minute intervals during a 60-minute IV infusion of the supersaturated dissolved oxygen solution. Each animal served as its own control. RESULTS Five swines (12.9 ± 0.9 kg) were studied. Following the 60-minute infusion, there were significant increases in PaO2 and SaO2 (P < 0.05) and a significant decrease in PaCO2 (P < 0.05), with a corresponding normalization in arterial blood pH. Additionally, there was a significant decrease in core body temperature (P < 0.05) when compared to the baseline preinfusion state. CONCLUSIONS A cold, supersaturated dissolved oxygen solution may be intravenously administered to improve arterial blood oxygenation and ventilation parameters and induce a mild therapeutic hypothermia in a porcine model. PMID:25249764

X-ray transparent Microfluidics for Protein Crystallization and Biomineralization

NASA Astrophysics Data System (ADS)

Opathalage, Achini

Protein crystallization demands the fundamental understanding of nucleation and applying techniques to find the optimal conditions to achieve the kinetic pathway for a large and defect free crystal. Classical nucleation theory predicts that the nucleation occurs at high supersaturation conditions. In this dissertation we sought out to develop techniques to attain optimal supersaturation profile to a large defect free crystal and subject it to in-situ X-ray diffraction using microfluidics. We have developed an emulsion-based serial crystallographic technology in nanolitre-sized droplets of protein solution encapsulated in to nucleate one crystal per drop. Diffraction data are measured, one crystal at a time, from a series of room temperature crystals stored on an X-ray semi-transparent microfluidic chip, and a 93% complete data set is obtained by merging single diffraction frames taken from different un-oriented crystals. As proof of concept, the structure of Glucose Isomerase was solved to 2.1 A. We have developed a suite of X-ray semi-transparent micrfluidic devices which enables; controlled evaporation as a method of increasing supersaturation and manipulating the phase space of proteins and small molecules. We exploited the inherently high water permeability of the thin X-ray semi-transparent devices as a mean of increasing the supersaturation by controlling the evaporation. We fabricated the X-ray semi-transparent version of the PhaseChip with a thin PDMS membrane by which the storage and the reservoir layers are separated, and studies the phase transition of amorphous CaCO3.

Ultrasound assisted nucleation and growth characteristics of glycine polymorphs--a combined experimental and analytical approach.

PubMed

Renuka Devi, K; Raja, A; Srinivasan, K

2015-05-01

For the first time, the effect of ultrasound in the diagnostic frequency range of 1-10 MHz on the nucleation and growth characteristics of glycine has been explored. The investigation employing the ultrasonic interferometer was carried out at a constant insonation time over a wide range of relative supersaturation from σ=-0.09 to 0.76 in the solution. Ultrasound promotes only α nucleation and completely inhibits both the β and γ nucleation in the system. The propagation of ultrasound assisted mass transport facilitates nucleation even at very low supersaturation levels in the solution. The presence of ultrasound exhibits a profound effect on nucleation and growth characteristics in terms of decrease in induction period, increase in nucleation rate and decrease in crystal size than its absence in the solution. With an increase in the frequency of ultrasound, a further decrease in induction period, increase in nucleation rate and decrease in the size of the crystal is noticed even at the same relative supersaturation levels. The increase in the nucleation rate explains the combined dominating effects of both the ultrasound frequency and the supersaturation in the solution. Analytically, the nucleation parameters of the nucleated polymorph have been deduced at different ultrasonic frequencies based on the classical nucleation theory and correlations with the experimental results have been obtained. Structural affirmation of the nucleated polymorph has been ascertained by powder X-ray diffraction. Copyright © 2014 Elsevier B.V. All rights reserved.

Inhibition of calcium carbonate crystal growth by organic additives using the constant composition method in conditions of recirculating cooling circuits

NASA Astrophysics Data System (ADS)

Chhim, Norinda; Kharbachi, Chams; Neveux, Thibaut; Bouteleux, Céline; Teychené, Sébastien; Biscans, Béatrice

2017-08-01

The cooling circuits used in power plants are subject to mineral crystallization which can cause scaling on the surfaces of equipment and construction materials reducing their heat exchange efficiency. Precipitated calcium carbonate is the predominant mineral scale commonly observed in cooling systems. Supersaturation is the key parameter controlling the nucleation and growth of calcite in these systems. The present work focuses on the precipitation of calcite using the constant composition method at constant supersaturation, through controlled addition of reactants to a semi-batch crystallizer, in order to maintain constant solution pH. The determination of the thermodynamic driving force (supersaturation) was based on the relevant chemical equilibria, total alkalinity and calculation of the activity coefficients. Calcite crystallization rates were derived from the experiments performed at supersaturation levels similar to those found in industrial station cooling circuits. Several types of seeds particles were added into the aqueous solution to mimic natural river water conditions in terms of suspended particulate matters content, typically: calcite, silica or illite particles. The effect of citric and copolycarboxylic additive inhibitors added to the aqueous solution was studied. The calcium carbonate growth rate was reduced by 38.6% in the presence of the citric additive and a reduction of 92.7% was observed when the copolycarboxylic additive was used under identical experimental conditions. These results are explained by the location of the adsorbed inhibitor at the crystal surface and by the degree of chemical bonding to the surface.

Study of the influence of the supersaturation coefficient on scaling rate using the pre-calcified surface of a quartz crystal microbalance.

PubMed

Cheap-Charpentier, Hélène; Horner, Olivier; Lédion, Jean; Perrot, Hubert

2018-05-29

Scale deposition is a common issue in industrial plants, which creates technical problems, i.e. reduction of heat transfer, decrease of flow rate due to an obstruction of pipes. Therefore, the development of some appropriate methods based on well suitable in situ sensors to evaluate and predict the scaling propensity of water is a major concern in current research. This would be a good strategy for the optimization of anti-scaling treatments. In this study, scaling tests were carried out using a sensitive sensor, which has been developed using a quartz crystal microbalance with a pre-calcified electrode surface (SQCM). This technique allowed studying the influence of the supersaturation on the scaling rate. The set-up was tested with different water samples which were brought to a given supersaturation coefficient by degassing the dissolved CO 2 . The prediction of the scaling propensity of water was then possible through the relationship between the scaling rate on a pre-calcified surface and the supersaturation coefficient. In addition, the kinetics of CaCO 3 deposit on the pre-calcified SQCM surface was found to be slower for natural water than for synthetic water (same calcium concentration). Furthermore, the activation energy for scale deposit, in synthetic water, was found to be 22 kJ.mol -1 , which may be related to the diffusion of ions and/or CaCO 3 nuclei in solution. Copyright © 2018 Elsevier Ltd. All rights reserved.

Formation of a Tropopause Cirrus Layer Observed over Florida during CRYSTAL-FACE

NASA Technical Reports Server (NTRS)

Jensen, Eric; Pfister, Leonhard; Bui, Thaopaul; Weinheimer, Andrew; Weinstock, Elliot; Smith, Jessica; Pittman, Jasna; Baumgardner, Darrel; Lawson, Paul; McGill, Matthew J.

2005-01-01

On July 13, 2002 a widespread, subvisible tropopause cirrus layer occurred over the Florida region. This cloud was observed in great detail with the NASA Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) instrumentation, including in situ measurements with the WB-57 aircraft. In this paper, we use the 13 July cloud as a case study to evaluate the physical processes controlling the formation and evolution of tropopause cirrus layers. Microphysics measurements indicate that ice crystal diameters in the cloud layer ranged from about 7 to 50 microns, and the peak number mode was about 10-25 microns. In situ water vapor and temperature measurements in the cloud indicated supersaturation with respect to ice throughout, with ice saturation ratios as large as 1.8. Even when the ice surface area density was as high as about 500 sq microns/cu cm, ice supersaturations of 20-30% were observed. Trajectory analysis shows that the air sampled near the tropopause on this day generally came from the north and cooled considerably during the previous few days. Examination of infrared satellite imagery along air parcel back trajectories from the WB-57 flight track indicates that the tropopause cloud layer formation was, in general, not simply left over ice from recently generated anvil cirrus. Simulations of cloud formation using time-height curtains of temperature along the trajectory paths show that the cloud could have formed in situ near the tropopause as the air was advected into the south Florida region and cooled to unusually low temperatures. If we assume a high threshold for ice nucleation via homogeneous freezing of aqueous sulfate aerosols, the model reproduces the observed cloud structure, ice crystal size distributions, and ice supersaturation statistics. Inclusion of observed gravity wave temperature perturbations in the simulations is essential to reproduce the observed cloud properties. Without waves, crystal number densities are too low, crystal sizes are too large, and the crystals fall out too fast, leaving very little cloud persisting at the end of the simulations. In the cloud simulations, coincidence of high supersaturations and high surface areas can be produced by either recent nucleation or sedimentation of crystals into supersaturated layers. The agreement between model results and observed supersaturations is improved somewhat if we assume that the steady state relative humidity within cirrus at T<200 K is enhanced by about 30%. The WB-57 measurements and the model results suggest that the cloud layer irreversibly dehydrated air near the tropopause.

Cloud condensation nuclei closure study on summer arctic aerosol

NASA Astrophysics Data System (ADS)

Martin, M.; Chang, R. Y.-W.; Sierau, B.; Sjogren, S.; Swietlicki, E.; Abbatt, J. P. D.; Leck, C.; Lohmann, U.

2011-11-01

We present an aerosol - cloud condensation nuclei (CCN) closure study on summer high Arctic aerosol based on measurements that were carried out in 2008 during the Arctic Summer Cloud Ocean Study (ASCOS) on board the Swedish ice breaker Oden. The data presented here were collected during a three-week time period in the pack ice (>85° N) when the icebreaker Oden was moored to an ice floe and drifted passively during the most biological active period into autumn freeze up conditions. CCN number concentrations were obtained using two CCN counters measuring at different supersaturations. The directly measured CCN number concentration was then compared with a CCN number concentration calculated using both bulk aerosol mass composition data from an aerosol mass spectrometer (AMS) and aerosol number size distributions obtained from a differential mobility particle sizer, assuming κ-Köhler theory, surface tension of water and an internally mixed aerosol. The last assumption was supported by measurements made with a hygroscopic tandem differential mobility analyzer (HTDMA) for particles >70 nm. For the two highest measured supersaturations, 0.73 and 0.41%, closure could not be achieved with the investigated settings concerning hygroscopicity and density. The calculated CCN number concentration was always higher than the measured one for those two supersaturations. This might be caused by a relative larger insoluble organic mass fraction of the smaller particles that activate at these supersaturations, which are thus less good CCN than the larger particles. On average, 36% of the mass measured with the AMS was organic mass. At 0.20, 0.15 and 0.10% supersaturation, closure could be achieved with different combinations of hygroscopic parameters and densities within the uncertainty range of the fit. The best agreement of the calculated CCN number concentration with the observed one was achieved when the organic fraction of the aerosol was treated as nearly water insoluble (κorg=0.02), leading to a mean total κ, κtot, of 0.33 ± 0.13. However, several settings led to closure and κorg=0.2 is found to be an upper limit at 0.1% supersaturation. κorg≤0.2 leads to a κtot range of 0.33 ± 013 to 0.50 ± 0.11. Thus, the organic material ranges from being sparingly soluble to effectively insoluble. These results suggest that an increase in organic mass fraction in particles of a certain size would lead to a suppression of the Arctic CCN activity.

Total Dissolved Gas Effects on Fishes of the Lower Columbia River

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

McGrath, Kathy E.; Dawley, Earl; Geist, David R.

2006-03-31

Gas supersaturation problems generated by spill from dams on the Columbia River were first identified in the 1960s. Since that time, considerable research has been conducted on effects of gas supersaturation on aquatic life, primarily juvenile salmonids. Also since that time, modifications to dam structures and operations have reduced supersaturated gas levels produced by the dams. The limit for total dissolved gas saturation (TDGS) as mandated by current Environmental Protection Agency water quality standards is 110%. State management agencies issue limited waivers to water quality, allowing production of levels of up to 120% TDGS to facilitate the downstream migration ofmore » juvenile salmonids. Recently, gas supersaturation as a water quality issue has resurfaced as concerns have grown regarding chronic effects of spill-related total dissolved gas on salmonids, including incubating embryos and larvae, resident fish species, and other aquatic organisms. Because of current concerns, and because the last comprehensive review of research on supersaturation effects on fishes was conducted in 1997, we reviewed recent supersaturation literature to identify new or ongoing issues that may not be adequately addressed by the current 110% TDGS limit and the 120% TDGS water quality waiver. We found that recent work supports older research indicating that short-term exposure to levels up to 120% TDGS does not produce acute effects on migratory juvenile or adult salmonids when compensating depths are available. Monitoring programs at Snake and Columbia river dams from 1995 to the early 2000s documented a low incidence of significant gas bubble disease or mortality in Columbia River salmonids, resident fishes, or other taxa. We did, however, identify five areas of concern in which total dissolved gas levels lower than water quality limits may produce sublethal effects on fishes of the Columbia River. These areas of concern are 1) sensitive and vulnerable species or life stages, 2) long-term chronic or multiple exposure, 3) vulnerable habitats and reaches, 4) effects on incubating fish in hyporheic habitats, and 5) community and ecosystem effects. Although some of these areas of concern may have been identified previously in earlier works, we suggest that consideration of the issues is warranted to avoid detrimental impacts on aquatic resources of the Columbia River system. We discuss these issues and provide recommendations to regulatory and management agencies based on our review of recent literature. In general, we recommend that additional attention be directed toward resolving the uncertainties within these five areas.« less

Probing the mechanisms of drug release from amorphous solid dispersions in medium-soluble and medium-insoluble carriers.

PubMed

Sun, Dajun D; Lee, Ping I

2015-08-10

The objective of the current study is to mechanistically differentiate the dissolution and supersaturation behaviors of amorphous drugs from amorphous solid dispersions (ASDs) based on medium-soluble versus medium-insoluble carriers under nonsink dissolution conditions through a direct head-to-head comparison. ASDs of indomethacin (IND) were prepared in several polymers which exhibit different solubility behaviors in acidic (pH1.2) and basic (pH7.4) dissolution media. The selected polymers range from water-soluble (e.g., PVP and Soluplus) and water-insoluble (e.g., ethylcellulose and Eudragit RL PO) to those only soluble in an acidic or basic dissolution medium (e.g., Eudragit E100, Eudragit L100, and HPMCAS). At 20wt.% drug loading, DSC and powder XRD analysis confirmed that the majority of incorporated IND was present in an amorphous state. Our nonsink dissolution results confirm that whether the carrier matrix is medium soluble determines the release mechanism of amorphous drugs from ASD systems which has a direct impact on the rate of supersaturation generation, thus in turn affecting the evolution of supersaturation in amorphous systems. For example, under nonsink dissolution conditions, the release of amorphous IND from medium-soluble carriers is governed by a dissolution-controlled mechanism leading to an initial surge of supersaturation followed by a sharp decline in drug concentration due to rapid nucleation and crystallization. In contrast, the dissolution of IND ASD from medium-insoluble carriers is more gradual as drug release is regulated by a diffusion-controlled mechanism by which drug supersaturation is built up gradually and sustained over an extended period of time without any apparent decline. Since several tested carrier polymers can be switched from soluble to insoluble by simply changing the pH of the dissolution medium, the results obtained here provide unequivocal evidence of the proposed transition of kinetic solubility profiles from the same ASD system induced by changes in the drug release mechanism in dissolution medium of a different pH. Copyright © 2015 Elsevier B.V. All rights reserved.

Understanding the generation and maintenance of supersaturation during the dissolution of amorphous solid dispersions using modulated DSC and 1H NMR.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2018-01-30

In this study, the dissolution behaviour of dipyridamole (DPM) and cinnarizine (CNZ) spray-dried amorphous solid dispersions (ASDs) using polyvinyl pyrrolidone (PVP) and polyacrylic acid (PAA) as a carrier matrix were evaluated and compared. The drug concentrations achieved from the dissolution of PVP and PAA solid dispersions were significantly greater than the equilibrium solubility of crystalline DPM and CNZ in phosphate buffer pH 6.8 (PBS 6.8). The maximum drug concentration achieved by dissolution of PVP and PAA solid dispersions did not exceed the theoretically calculated apparent solubility of amorphous DPM and CNZ. However, the degree of supersaturation of DPM and CNZ increased considerably as the polymer weight fraction within the solid dispersion increased. In addition, the supersaturation profile of DPM and CNZ were studied in the presence and absence of the polymers. PAA was found to maintain a higher level of supersaturation compared to PVP. The enhanced drug solution concentration following dissolution of ASDs can be attributed to the reduced crystal growth rates of DPM and CNZ at an equivalent supersaturation. We have also shown that, for drugs having high crystallization tendency and weak drug-polymer interaction, the feasible way to increase dissolution might be increase the polymer weight fraction in the ASD. Solution 1 H NMR spectra were used to understand dissolution mechanism and to identify drug-polymer interaction. The change in electron densities of proton attached to different groups in DPM and CNZ suggested drug-polymer interaction in solution. The relative intensities of peak shift and nature of interaction between drug and polymer in different systems are different. These different effects suggest that DPM and CNZ interacts in a different way with PVP and PAA in solution which goes some way towards explaining the different polymeric effect, particularly in terms of inhibition of drug recrystallization and dissolution of DPM and CNZ ASDs. These results established that the different drug/polymer interactions in the solid state and in solution give rise to the variation in dissolution profile observed for different systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Syn-eruptive CO2 Degassing of Submarine Lavas Flows: Constraints on Eruption Dynamics

NASA Astrophysics Data System (ADS)

Soule, S. A.; Boulahanis, B.; Fundis, A.; Clague, D. A.; Chadwick, B.

2013-12-01

At fast- and intermediate-spreading rate mid-ocean ridges, quenched lava samples are commonly supersaturated in CO2 with concentrations similar to the pressure/depth of shallow crustal melt lenses. This supersaturation is attributed to rapid ascent and decompression rates that exceed the kinetic rates of bubble nucleation and growth. During emplacement, CO2 supersaturated lavas experience nearly isothermal and isobaric conditions over a period of hours. A recent study has demonstrated systematic decreases in CO2 with increasing transport distance (i.e. time) along a single flow pathway within the 2005-06 eruption at the East Pacific Rise (~2500 m.b.s.l.). Based on analysis of vesicle population characteristics and complementary noble gas measurements, it is proposed that diffusion of CO2 into bubbles can be used as a basis to model the gas loss from the melt and thus place constraints on the dynamics of the eruption. We suggest that submarine lava flows represent a natural experiment in degassing that isolates conditions of low to moderate supersaturation and highlights timescales of diffusion and vesiculation processes that are relevant to shallow crustal and conduit processes in subaerial basaltic volcanic systems. Here we report a new suite of volatile concentration analyses and vesicle size distributions from the 2011 eruption of Axial Volcano along the Juan de Fuca Ridge (~1500 m.b.s.l.). The lava flows from this eruption are mapped by differencing of repeat high-resolution bathymetric surveys, so that the geologic context of the samples is known. In addition, in-situ instrument records record the onset of the eruption and place constraints on timing that can be used to verify estimates of eruption dynamics derived from degassing. This sample suite provides a comprehensive view of the variability in volatile concentrations within a submarine eruption and new constraints for evaluating models of degassing and vesiculation. Initial results show systematic variability in CO2 supersaturation along eruptive fissures as well as with increasing distance along flows pathways providing constraints on threshold decompression rates required to nucleate and grow bubbles in a basaltic melt, timescales of degassing in natural systems, and the properties of consequent vesicle populations.

Aerosol indirect effect from turbulence-induced broadening of cloud-droplet size distributions

PubMed Central

Chandrakar, Kamal Kant; Cantrell, Will; Chang, Kelken; Ciochetto, David; Niedermeier, Dennis; Ovchinnikov, Mikhail; Shaw, Raymond A.; Yang, Fan

2016-01-01

The influence of aerosol concentration on the cloud-droplet size distribution is investigated in a laboratory chamber that enables turbulent cloud formation through moist convection. The experiments allow steady-state microphysics to be achieved, with aerosol input balanced by cloud-droplet growth and fallout. As aerosol concentration is increased, the cloud-droplet mean diameter decreases, as expected, but the width of the size distribution also decreases sharply. The aerosol input allows for cloud generation in the limiting regimes of fast microphysics (τc<τt) for high aerosol concentration, and slow microphysics (τc>τt) for low aerosol concentration; here, τc is the phase-relaxation time and τt is the turbulence-correlation time. The increase in the width of the droplet size distribution for the low aerosol limit is consistent with larger variability of supersaturation due to the slow microphysical response. A stochastic differential equation for supersaturation predicts that the standard deviation of the squared droplet radius should increase linearly with a system time scale defined as τs−1=τc−1+τt−1, and the measurements are in excellent agreement with this finding. The result underscores the importance of droplet size dispersion for aerosol indirect effects: increasing aerosol concentration changes the albedo and suppresses precipitation formation not only through reduction of the mean droplet diameter but also by narrowing of the droplet size distribution due to reduced supersaturation fluctuations. Supersaturation fluctuations in the low aerosol/slow microphysics limit are likely of leading importance for precipitation formation. PMID:27911802

Aerosol indirect effect from turbulence-induced broadening of cloud-droplet size distributions

DOE PAGES

Chandrakar, Kamal Kant; Cantrell, Will; Chang, Kelken; ...

2016-11-28

Here, the influence of aerosol concentration on cloud droplet size distribution is investigated in a laboratory chamber that enables turbulent cloud formation through moist convection. The experiments allow steady-state microphysics to be achieved, with aerosol input balanced by cloud droplet growth and fallout. As aerosol concentration is increased the cloud droplet mean diameter decreases as expected, but the width of the size distribution also decreases sharply. The aerosol input allows for cloud generation in the limiting regimes of fast microphysics (τ c < τ t) for high aerosol concentration, and slow microphysics (τ c > τ t) for low aerosolmore » concentration; here, τ c is the phase relaxation time and τ t is the turbulence correlation time. The increase in the width of the droplet size distribution for the low aerosol limit is consistent with larger variability of supersaturation due to the slow microphysical response. A stochastic differential equation for supersaturation predicts that the standard deviation of the squared droplet radius should increase linearly with a system time scale defined as τ s -1 =τ c -1 + τ t -1, and the measurements are in excellent agreement with this finding. This finding underscores the importance of droplet size dispersion for the aerosol indirect effect: increasing aerosol concentration not only suppresses precipitation formation through reduction of the mean droplet diameter, but perhaps more importantly, through narrowing of the droplet size distribution due to reduced supersaturation fluctuations. Supersaturation fluctuations in the low aerosol / slow microphysics limit are likely of leading importance for precipitation formation.« less

A simple method to relate microwave radiances to upper tropospheric humidity

NASA Astrophysics Data System (ADS)

Buehler, S. A.; John, V. O.

2005-01-01

A brightness temperature (BT) transformation method can be applied to microwave data to retrieve Jacobian weighted upper tropospheric relative humidity (UTH) in a broad layer centered roughly between 6 and 8 km altitude. The UTH bias is below 4% RH, and the relative UTH bias below 20%. The UTH standard deviation is between 2 and 6.5% RH in absolute numbers, or between 10 and 27% in relative numbers. The standard deviation is dominated by the regression noise, resulting from vertical structure not accounted for by the simple transformation relation. The UTH standard deviation due to radiometric noise alone has a relative standard deviation of approximately 7% for a radiometric noise level of 1 K. The retrieval performance was shown to be of almost constant quality for all viewing angles and latitudes, except for problems at high latitudes due to surface effects. A validation of AMSU UTH against radiosonde UTH shows reasonable agreement if known systematic differences between AMSU and radiosonde are taken into account. When the method is applied to supersaturation studies, regression noise and radiometric noise could lead to an apparent supersaturation even if there were no supersaturation. For a radiometer noise level of 1 K the drop-off slope of the apparent supersaturation is 0.17% RH-1, for a noise level of 2 K the slope is 0.12% RH-1. The main conclusion from this study is that the BT transformation method is very well suited for microwave data. Its particular strength is in climatological applications where the simplicity and the a priori independence are key advantages.

Microstructures of Randall's plaques and their interfaces with calcium oxalate monohydrate kidney stones reflect underlying mineral precipitation mechanisms.

PubMed

Sethmann, Ingo; Wendt-Nordahl, Gunnar; Knoll, Thomas; Enzmann, Frieder; Simon, Ludwig; Kleebe, Hans-Joachim

2017-06-01

Randall's plaques (RP) are preferred sites for the formation of calcium oxalate monohydrate (COM) kidney stones. However, although processes of interstitial calcium phosphate (CaP) plaque formation are not well understood, the potential of plaque microstructures as indicators of CaP precipitation conditions received only limited attention. We investigated RP-associated COM stones for structural details of the calcified tissues and microstructural features of plaque-stone interfaces as indicators of the initial processes of stone formation. Significantly increased CaP supersaturation can be expected for interstitial fluid, if reabsorbed ions from the tubular system continuously diffuse into the collagenous connective tissue. Densely packed, fine-grained CaP particles were found in dense textures of basement membranes while larger, laminated particles were scattered in coarse-meshed interstitial tissue, which we propose to be due to differential spatial confinements and restrictions of ion diffusion. Particle morphologies suggest an initial precipitation as metastable amorphous calcium phosphate (ACP). Morphologies and arrangements of first COM crystals at the RP-stone interface ranged from stacked euhedral platelets to skeletal morphologies and even porous, dendritic structures, indicating, in this order, increasing levels of COM supersaturation. Furthermore, these first COM crystals were often coated with CaP. On this basis, we propose that ions from CaP-supersaturated interstitial fluid may diffuse through porous RP into the urine, where a resulting local increase in COM supersaturation could trigger crystal nucleation and, hence, initiate stone formation. Ion-depleted fluid in persistent pores of initial COM layers may get replenished from interstitial fluid, leading to CaP precipitation in porous COM.

Contrail formation in the tropopause region caused by emissions from an Ariane 5 rocket

NASA Astrophysics Data System (ADS)

Voigt, Ch.; Schumann, U.; Graf, K.

2016-07-01

Rockets directly inject water vapor and aerosol into the atmosphere, which promotes the formation of ice clouds in ice supersaturated layers of the atmosphere. Enhanced mesospheric cloud occurrence has frequently been detected near 80-kilometer altitude a few days after rocket launches. Here, unique evidence for cirrus formation in the tropopause region caused by ice nucleation in the exhaust plume from an Ariane 5-ECA rocket is presented. Meteorological reanalysis data from the European Centre for Medium-Range Weather Forecasts show significant ice supersaturation at the 100-hectopascal level in the American tropical tropopause region on November 26, 2011. Near 17-kilometer altitudes, the temperatures are below the Schmidt-Appleman threshold temperature for rocket condensation trail formation on that day. Immediately after the launch from the Ariane 5-ECA at 18:39 UT (universal time) from Kourou, French Guiana, the formation of a rocket contrail is detected in the high resolution visible channel from the SEVIRI (Spinning Enhanced Visible and InfraRed Imager) on the METEOSAT9 satellite. The rocket contrail is transported to the south and its dispersion is followed in SEVIRI data for almost 2 h. The ice crystals predominantly nucleated on aluminum oxide particles emitted by the Ariane 5-ECA solid booster and further grow by uptake of water vapor emitted from the cryogenic main stage and entrained from the ice supersaturated ambient atmosphere. After rocket launches, the formation of rocket contrails can be a frequent phenomenon under ice supersaturated conditions. However, at present launch rates, the global climate impact from rocket contrail cirrus in the tropopause region is small.

Amplification of seismic waves beneath active volcanoes

NASA Astrophysics Data System (ADS)

Navon, O.; Lensky, N. G.; Collier, L.; Neuberg, J.; Lyakhovsky, V.

2003-04-01

Long-period (LP) seismic events are typical for many volcanoes and are attributed to energy leaking from waves traveling along the conduit - country-rock interface. While the wave propagation is well understood, their actual trigger mechanism and their energy source are not. Here we test the hypothesis that energy may be supplied by volatile-release from a supersaturated melt. If bubbles are initially in equilibrium with the melt in the conduit, and the melt is suddenly decompressed, the transfer of volatiles from the supersaturated melt into the bubbles transforms stored potential energy into expansion work. For example, small dome collapse, opening of a crack or a displacement along the brittle part of the conduit may decompress the magma by a few bars and create the needed supersaturation. This energy is released over the timescale of accelerated expansion, which is longer than a typical LP event. Following decompression, when the transfer of volatiles into bubbles is fast enough, expansion accelerates and the bulk viscosity of the bubbly magma is negative (Lensky et al., 2002). New calculations show that under such conditions a sinusoidal P-wave is amplified. We note that seismic waves created by tectonic earthquakes that are not associated with net decompression, do not lead to net release of volatiles or to net expansion. In this case, the bulk viscosity is positive and waves traveling through the magma should attenuate. The proposed model explains how weak seismic signals may be amplified as they travel through a conduit that contains supersaturated bubbly magma. It provides the general framework for amplifying volcanic seismicity such as long-period events.

Aerosol indirect effect from turbulence-induced broadening of cloud-droplet size distributions

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

Chandrakar, Kamal Kant; Cantrell, Will; Chang, Kelken

Here, the influence of aerosol concentration on cloud droplet size distribution is investigated in a laboratory chamber that enables turbulent cloud formation through moist convection. The experiments allow steady-state microphysics to be achieved, with aerosol input balanced by cloud droplet growth and fallout. As aerosol concentration is increased the cloud droplet mean diameter decreases as expected, but the width of the size distribution also decreases sharply. The aerosol input allows for cloud generation in the limiting regimes of fast microphysics (τ c < τ t) for high aerosol concentration, and slow microphysics (τ c > τ t) for low aerosolmore » concentration; here, τ c is the phase relaxation time and τ t is the turbulence correlation time. The increase in the width of the droplet size distribution for the low aerosol limit is consistent with larger variability of supersaturation due to the slow microphysical response. A stochastic differential equation for supersaturation predicts that the standard deviation of the squared droplet radius should increase linearly with a system time scale defined as τ s -1 =τ c -1 + τ t -1, and the measurements are in excellent agreement with this finding. This finding underscores the importance of droplet size dispersion for the aerosol indirect effect: increasing aerosol concentration not only suppresses precipitation formation through reduction of the mean droplet diameter, but perhaps more importantly, through narrowing of the droplet size distribution due to reduced supersaturation fluctuations. Supersaturation fluctuations in the low aerosol / slow microphysics limit are likely of leading importance for precipitation formation.« less

Improved oral absorption of dutasteride via Soluplus®-based supersaturable self-emulsifying drug delivery system (S-SEDDS).

PubMed

Lee, Dong Hoon; Yeom, Dong Woo; Song, Ye Seul; Cho, Ha Ra; Choi, Yong Seok; Kang, Myung Joo; Choi, Young Wook

2015-01-15

A novel supersaturable self-emulsifying drug delivery system (S-SEDDS) was formulated to improve the oral absorption of dutasteride (DTS), a 5α-reductase inhibitor that is poorly water-soluble. A supersaturable system was prepared by employing Soluplus(®) (polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer) as a precipitation inhibitor with a conventional SEDDS vehicle consisted of Capryol™ 90, Cremophor(®) EL and Transcutol(®) HP (DTS:SEDDS vehicle:Soluplus(®)=1.0:67.6:10.0 w/v/w). In an in vitro dissolution test in a non-sink condition, the drug dissolution rate from SEDDS was rapidly increased to 72% for an initial period of 5min, but underwent rapid drug precipitation within 2h, decreasing the amount of drug dissolved to one-seventh of its original amount. On the other hand, S-SEDDS resulted in a slower crystallization of DTS by virtue of a precipitation inhibitor, maintaining a 3 times greater dissolution rate after 2h compared to SEDDS. In an in vivo pharmacokinetic study in rats, the S-SEDDS formulation exhibited 3.9-fold greater area-under-curve value than that of the drug suspension and 1.3-fold greater than that of SEDDS. The maximum plasma concentration of S-SEDDS was 5.6- and 2.0-fold higher compared to drug suspension and SEDDS, respectively. The results of this study suggest that the novel supersaturable system may be a promising tool for improving the physicochemical property and oral absorption of the 5α-reductase inhibitor. Copyright © 2014 Elsevier B.V. All rights reserved.

Precipitate Evolution and Strengthening in Supersaturated Rapidly Solidified Al-Sc-Zr Alloys

NASA Astrophysics Data System (ADS)

Deane, Kyle; Kampe, S. L.; Swenson, Douglas; Sanders, P. G.

2017-04-01

Because of the low diffusivities of scandium and zirconium in aluminum, trialuminide precipitates containing these elements have been reported to possess excellent thermal stability at temperatures of 573 K (300 °C) and higher. However, the relatively low equilibrium solubilities of these elements in aluminum limit the achievable phase fraction and, in turn, strengthening contributions from these precipitates. One method of circumventing this limitation involves the use of rapid solidification techniques to suppress the initial formation of precipitates in alloys containing higher solute compositions. This work specifically discusses the fabrication of supersaturated Al-Sc, Al-Zr, and Al-Sc-Zr alloys via melt spinning, in which supersaturations of at least 0.55 at. pct Zr and 0.8 at. pct Sc are shown to be attainable through XRD analysis. The resulting ribbons were subjected to a multistep aging heat treatment in order to encourage a core-shell precipitate morphology, the precipitate evolution behavior was monitored with XRD and TEM, and the aging behavior was observed. While aging in these alloys is shown to follow similar trends to conventionally processed materials reported in literature, with phase fraction increasing until higher aging temperatures causing a competing dissolution effect, the onset of precipitation begins at lower temperatures than previously observed and the peak hardnesses occurred at higher temperature steps due to an increased aging time associated with increased solute concentration. Peaking in strength at a higher temperature doesn't necessarily mean an increase in thermal stability, but rather emphasizes the need for intelligently designed heat treatments to take full advantage of the potential strengthening of supersaturated Al-Sc-Zr alloys.

Aerosol indirect effect from turbulence-induced broadening of cloud-droplet size distributions

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

Chandrakar, Kamal Kant; Cantrell, Will; Chang, Kelken

2016-11-28

The influence of aerosol concentration on cloud droplet size distribution is investigated in a laboratory chamber that enables turbulent cloud formation through moist convection. The experiments allow steady-state microphysics to be achieved, with aerosol input balanced by cloud droplet growth and fallout. As aerosol concentration is increased the cloud droplet mean diameter decreases as expected, but the width of the size distribution also decreases sharply. The aerosol input allows for cloud generation in the limiting regimes of fast microphysics (τ c < τ t) for high aerosol concentration, and slow microphysics (τ c > τ t) for low aerosol concentration;more » here, τ c is the phase relaxation time and τ t is the turbulence correlation time. The increase in the width of the droplet size distribution for the low aerosol limit is consistent with larger variability of supersaturation due to the slow microphysical response. A stochastic differential equation for supersaturation predicts that the standard deviation of the squared droplet radius should increase linearly with a system time scale defined as τ s -1 =τ c -1 + τ t -1, and the measurements are in excellent agreement with this finding. This finding underscores the importance of droplet size dispersion for the aerosol indirect effect: increasing aerosol concentration not only suppresses precipitation formation through reduction of the mean droplet diameter, but perhaps more importantly, through narrowing of the droplet size distribution due to reduced supersaturation fluctuations. Supersaturation fluctuations in the low aerosol / slow microphysics limit are likely of leading importance for precipitation formation.« less

Inhibitory effect of hydroxypropyl methylcellulose acetate succinate on drug recrystallization from a supersaturated solution assessed using nuclear magnetic resonance measurements.

PubMed

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

2013-10-07

We examined the inhibitory effect of hydroxypropyl methylcellulose acetate succinate (HPMC-AS) on drug recrystallization from a supersaturated solution using carbamazepine (CBZ) and phenytoin (PHT) as model drugs. HPMC-AS HF grade (HF) inhibited the recrystallization of CBZ more strongly than that by HPMC-AS LF grade (LF). 1D-1H NMR measurements showed that the molecular mobility of CBZ was clearly suppressed in the HF solution compared to that in the LF solution. Interaction between CBZ and HF in a supersaturated solution was directly detected using nuclear Overhauser effect spectroscopy (NOESY). The cross-peak intensity obtained using NOESY of HF protons with CBZ aromatic protons was greater than that with the amide proton, which indicated that CBZ had hydrophobic interactions with HF in a supersaturated solution. In contrast, no interaction was observed between CBZ and LF in the LF solution. Saturation transfer difference NMR measurement was used to determine the interaction sites between CBZ and HF. Strong interaction with CBZ was observed with the acetyl substituent of HPMC-AS although the interaction with the succinoyl substituent was quite small. The acetyl groups played an important role in the hydrophobic interaction between HF and CBZ. In addition, HF appeared to be more hydrophobic than LF because of the smaller ratio of the succinoyl substituent. This might be responsible for the strong hydrophobic interaction between HF and CBZ. The intermolecular interactions between CBZ and HPMC-AS shown by using NMR spectroscopy clearly explained the strength of inhibition of HPMC-AS on drug recrystallization.

Oxygen supersaturated fluid using fine micro/nanobubbles

PubMed Central

Matsuki, Noriaki; Ishikawa, Takuji; Ichiba, Shingo; Shiba, Naoki; Ujike, Yoshihito; Yamaguchi, Takami

2014-01-01

Microbubbles show peculiar properties, such as shrinking collapse, long lifetime, high gas solubility, negative electric charge, and free radical production. Fluids supersaturated with various gases can be easily generated using microbubbles. Oxygen microbubble fluid can be very useful for oxygen delivery to hypoxic tissues. However, there have been no reports of comparative investigations into adding fluids containing oxygen fine micro/nanobubbles (OFM-NBs) to common infusion solutions in daily medical care. In this study, it was demonstrated that OFMNBs can generate oxygen-supersaturated fluids, and they may be sufficiently small to infuse safely into blood vessels. It was found that normal saline solution is preferable for generating an oxygen-rich infusion fluid, which is best administered as a 30-minute intravenous infusion. It was also concluded that dextran solution is suitable for drug delivery substances packing oxygen gas over a 1-hour intravenous infusion. In addition, normal saline solution containing OFMNBs was effective for improving blood oxygenation. Thus, the use of OFMNB-containing fluids is a potentially effective novel method for improving blood oxygenation in cases involving hypoxia, ischemic diseases, infection control, and anticancer chemoradiation therapies. PMID:25285003

Oxygen supersaturated fluid using fine micro/nanobubbles.

PubMed

Matsuki, Noriaki; Ishikawa, Takuji; Ichiba, Shingo; Shiba, Naoki; Ujike, Yoshihito; Yamaguchi, Takami

2014-01-01

Microbubbles show peculiar properties, such as shrinking collapse, long lifetime, high gas solubility, negative electric charge, and free radical production. Fluids supersaturated with various gases can be easily generated using microbubbles. Oxygen microbubble fluid can be very useful for oxygen delivery to hypoxic tissues. However, there have been no reports of comparative investigations into adding fluids containing oxygen fine micro/nanobubbles (OFM-NBs) to common infusion solutions in daily medical care. In this study, it was demonstrated that OFMNBs can generate oxygen-supersaturated fluids, and they may be sufficiently small to infuse safely into blood vessels. It was found that normal saline solution is preferable for generating an oxygen-rich infusion fluid, which is best administered as a 30-minute intravenous infusion. It was also concluded that dextran solution is suitable for drug delivery substances packing oxygen gas over a 1-hour intravenous infusion. In addition, normal saline solution containing OFMNBs was effective for improving blood oxygenation. Thus, the use of OFMNB-containing fluids is a potentially effective novel method for improving blood oxygenation in cases involving hypoxia, ischemic diseases, infection control, and anticancer chemoradiation therapies.

Lidar Measurements of Relative Humidity and Ice Supersaturation in the Upper Troposphere

NASA Technical Reports Server (NTRS)

Ferrare, Richard A.; Browell, Edward V.; Ismail, Syed; Brackett, Vincent G.; Clayton, Marian B.; Fenn, Marta; Heilman, Lorraine; Kooi, Susan A.; Turner, David D.; Mahoney, Michael J.

2000-01-01

We compute upper tropospheric relative humidity profiles using water vapor profiles measured by an airborne DIAL and a ground-based Raman lidar. LASE water vapor and MTP temperature profiles acquired from the NASA DC-8 aircraft during the recent Pacific Exploratory Mission Tropics B (PEM Tropics B) field mission in the tropical Pacific and the SAGE-III Ozone Loss and Validation Experiment (SOLVE) in the Arctic as well as water vapor profiles derived from the ground-based DOE ARM Southern Great Plains (SGP) CART Raman lidar are used. Comparisons of the lidar water vapor measurements with available in situ measurements show reasonable agreement for water vapor mixing ratios above 0.05 g/kg. Relative humidity frequency distributions computed using LASE data indicate that ice supersaturation occurred about 5-11% of the time when temperatures were below -35 C. While a higher frequency of ice supersaturation was observed during SOLVE, higher peak values of relative humidity were observed during PEM Tropics B. The relative humidity fields associated with cirrus clouds are also examined.

Microgravity nucleation and particle coagulation experiments support

NASA Technical Reports Server (NTRS)

Lilleleht, L. U.; Lass, T. J.

1987-01-01

A hollow sphere model is developed to predict the range of supersaturation ratio values for refractory metal vapors in a proposed experimental nucleation apparatus. Since the experiments are to be carried out in a microgravity environment, the model neglects the effects of convection and assumes that the only transfer of vapors through an inert gas atmosphere is by conduction and molecular diffusion. A consistent set of physical properties data is assembled for the various candidate metals and inert ambient gases expected to be used in the nucleation experiments. Transient partial pressure profiles are computed for the diffusing refractory species for two possible temperature distributions. The supersaturation ratio values from both candidate temperature profiles are compared with previously obtained experimetnal data on a silver-hydrogen system. The model is used to simulate the diffusion of magnesium vapor through argon and other inert gas atmospheres over ranges of initial and boundary conditions. These results identify different combinations of design and operating parameters which are liekly to produce supersaturation ratio values high enough to induce homogeneous nucleation in the apparatus being designed for the microgravity nucleation experiments.

Antisolvent membrane crystallization of pharmaceutical compounds.

PubMed

Di Profio, Gianluca; Stabile, Carmen; Caridi, Antonella; Curcio, Efrem; Drioli, Enrico

2009-12-01

This article describes a modification of the conventional membrane crystallization technique in which a membrane is used to dose the solvent/antisolvent composition to generate supersaturation and induce crystallization in a drug solution. Two operative configurations are proposed: (a) solvent/antisolvent demixing crystallization, where the solvent is removed in at higher flow rate than the antisolvent so that phase inversion promotes supersaturation and (b) antisolvent addition, in which the antisolvent is dosed into the crystallizing drug solution. In both cases, solvent/antisolvent migration occurs in vapor phase and it is controlled by the porous membrane structure, acting on the operative process parameters. This mechanism is different than that observed when forcing the liquid phases through the pores and the more finely controllable supersaturated environment would generate crystals with the desired characteristics. Two organic molecules of relevant industrial implication, like paracetamol and glycine, were used to test the new systems. Experiments demonstrated that, by using antisolvent membrane crystallization in both configurations, accurate control of solution composition at the crystallization point has been achieved with effects on crystals morphology. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

PubMed

Lienhard, Daniel M; Bones, David L; Zuend, Andreas; Krieger, Ulrich K; Reid, Jonathan P; Peter, Thomas

2012-10-11

Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

Statistical steady states in turbulent droplet condensation

NASA Astrophysics Data System (ADS)

Bec, Jeremie; Krstulovic, Giorgio; Siewert, Christoph

2017-11-01

We investigate the general problem of turbulent condensation. Using direct numerical simulations we show that the fluctuations of the supersaturation field offer different conditions for the growth of droplets which evolve in time due to turbulent transport and mixing. This leads to propose a Lagrangian stochastic model consisting of a set of integro-differential equations for the joint evolution of the squared radius and the supersaturation along droplet trajectories. The model has two parameters fixed by the total amount of water and the thermodynamic properties, as well as the Lagrangian integral timescale of the turbulent supersaturation. The model reproduces very well the droplet size distributions obtained from direct numerical simulations and their time evolution. A noticeable result is that, after a stage where the squared radius simply diffuses, the system converges exponentially fast to a statistical steady state independent of the initial conditions. The main mechanism involved in this convergence is a loss of memory induced by a significant number of droplets undergoing a complete evaporation before growing again. The statistical steady state is characterised by an exponential tail in the droplet mass distribution.

Cocrystals to facilitate delivery of poorly soluble compounds beyond-rule-of-5.

PubMed

Kuminek, Gislaine; Cao, Fengjuan; Bahia de Oliveira da Rocha, Alanny; Gonçalves Cardoso, Simone; Rodríguez-Hornedo, Naír

2016-06-01

Besides enhancing aqueous solubilities, cocrystals have the ability to fine-tune solubility advantage over drug, supersaturation index, and bioavailability. This review presents important facts about cocrystals that set them apart from other solid-state forms of drugs, and a quantitative set of rules for the selection of additives and solution/formulation conditions that predict cocrystal solubility, supersaturation index, and transition points. Cocrystal eutectic constants are shown to be the most important cocrystal property that can be measured once a cocrystal is discovered, and simple relationships are presented that allow for prediction of cocrystal behavior as a function of pH and drug solubilizing agents. Cocrystal eutectic constant is a stability or supersatuation index that: (a) reflects how close or far from equilibrium a cocrystal is, (b) establishes transition points, and (c) provides a quantitative scale of cocrystal true solubility changes over drug. The benefit of this strategy is that a single measurement, that requires little material and time, provides a principled basis to tailor cocrystal supersaturation index by the rational selection of cocrystal formulation, dissolution, and processing conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

The solubility of hen egg-white lysozyme

NASA Technical Reports Server (NTRS)

Howard, Sandra B.; Twigg, Pamela J.; Baird, James K.; Meehan, Edward J.

1988-01-01

The equilibrium solubility of chicken egg-white lysozyme in the presence of crystalline solid state was determined as a function of NaCl concentration, pH, and temperature. The solubility curves obtained represent a region of the lysozyme phase diagram. This diagram makes it possible to determine the supersaturation of a given set of conditions or to achieve identical supersaturations by different combinations of parameters. The temperature dependence of the solubility permits the evaluation of Delta-H of crystallization. The data indicate a negative heat of crystallization for the tetragonal crystal form but a positive heat of crystallization for the high-temperature orthorhombic form.

Control of solvent evaporation in hen egg white lysozyme crystallization

NASA Technical Reports Server (NTRS)

Wilson, L. J.; Suddath, F. L.

1992-01-01

An investigation of the role of solvent evaporation in tetragonal lysozyme crystallization was preformed with a device that employs N2(g) to control the evaporation of solvent from a micro-volume crystallization hanging drop. The number of crystals was found to vary with the rate at which the final supersaturation level was achieved. It was found that the more rapid the approach to supersaturation the larger the number of crystals. Accordingly, the crystals reached a smaller terminal size. Elongation of the (110) face parallel to the four-fold axis was observed with the slower evaporation rates.

Quantifying Main Trends in Lysozyme Nucleation: The Effects of Precipitant Concentration, Supersaturation and Impurities

NASA Technical Reports Server (NTRS)

Burke, Michael W.; Leardi, Riccardo; Judge, Russell A.; Pusey, Marc L.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Full factorial experimental design incorporating multi-linear regression analysis of the experimental data allows quick identification of main trends and effects using a limited number of experiments. In this study these techniques were employed to identify the effect of precipitant concentration, supersaturation, and the presence of an impurity, the physiological lysozyme dimer, on the nucleation rate and crystal dimensions of the tetragonal forin of chicken egg white lysozyme. Decreasing precipitant concentration, increasing supers aturation, and increasing impurity, were found to increase crystal numbers. The crystal axial ratio decreased with increasing precipitant concentration, independent of impurity.

Pore-scale interfacial dynamics during gas-supersaturated water injection in porous media - on nucleation, growth and advection of disconnected fluid phases (Invited)

NASA Astrophysics Data System (ADS)

Or, D.; Ioannidis, M.

2010-12-01

Degassing and in situ development of a mobile gas bubbles occur when injecting supersaturated aqueous phase into water-saturated porous media. Supersaturated water injection (SWI) has potentially significant applications in remediation of soils contaminated by non-aqueous phase liquids and in enhanced oil recovery. Pore network simulations indicate the formation of a region near the injection boundary where gas phase nuclei are activated and grow by mass transfer from the flowing supersaturated aqueous phase. Ramified clusters of gas-filled pores develop which, owing to the low prevailing Bond number, grow laterally to a significant extent prior to the onset of mobilization, and are thus likely to coalesce. Gas cluster mobilization invariably results in fragmentation and stranding, such that a macroscopic region containing few tenuously connected large gas clusters is established. Beyond this region, gas phase nucleation and mass transfer from the aqueous phase are limited by diminishing supply of dissolved gas. New insights into SWI dynamics are obtained using rapid micro-visualization in transparent glass micromodels. Using high-speed imaging, we observe the nucleation, initial growth and subsequent fate (mobilization, fragmentation, collision, coalescence and stranding) of CO2 bubbles and clusters of gas-filled pores and analyze cluster population statistics. We find significant support for the development of invasion-percolation-like patterns, but also report on hitherto unaccounted for gas bubble behavior. Additionally, we report for the first time on the acoustic emission signature of SWI in porous media and relate it to the dynamics of bubble nucleation and growth. Finally, we identify the pore-scale mechanisms associated with the mobilization and subsequent recovery of a residual non-aqueous phase liquid due to gas bubble dynamics during SWI.

Nucleation and growth of crystals under cirrus and polar stratospheric cloud conditions

NASA Technical Reports Server (NTRS)

Hallett, John; Queen, Brian; Teets, Edward; Fahey, James

1995-01-01

Laboratory studies examine phase changes of hygroscopic substances which occur as aerosol in stratosphere and troposphere (sodium chloride, ammonium sulfate, ammonium bisulfate, nitric acid, sulfuric acid), under controlled conditions, in samples volume 1 to 10(exp -4) ml. Crystallization of salts from supersaturated solutions is examined by slowly evaporating a solution drop on a substrate, under controlled relative humidity, until self nucleation occurs; controlled nucleation of ice in a mm capillary U-tube gives a measured ice crystallization velocity at known supercooling. Two states of crystallization occur for regions where hydrates exist. It is inferred that all of the materials readily exist as supersaturated/supercooled solutions; the degree of metastability appears to be slightly enhanced by inclusion of aircraft produced soot. The crystallization velocity is taken as a measure of viscosity. Results suggest an approach to a glass transition at high molality, supersaturation and/or supercooling within the range of atmospheric interest. It is hypothesized that surface reactions occur more readily on solidified particles - either crystalline or glass, whereas volume reactions are more important on droplets with sufficiently low viscosity and volume diffusivity. Implications are examined for optical properties of such particles in the atmosphere. In a separate experiment, crystal growth was examined in a modified thermal vapor diffusion chamber over the range of cirrus temperature (-30 to -70 C) and under controlled supersaturation and air pressure. The crystals grew at a velocity of 1-2 microns/s, thickness 60-70 micron, in the form of thin column crystals. Design criteria are given for a system to investigate particle growth down to -100 C, (PSC temperatures) where nitric acid particles can be grown under similar control and in the form of hydrate crystals.

Ice Cloud Formation and Dehydration in the Tropical Tropopause Layer

NASA Technical Reports Server (NTRS)

Jensen, Eric; Pfister, Leonhard; Gore, Warren J. (Technical Monitor)

2002-01-01

Stratospheric water vapor is important not only for its greenhouse forcing, but also because it plays a significant role in stratospheric chemistry. several recent studies have focused on the potential for dehydration due to ice cloud formation in air rising slowly through the tropical tropopause layer. Holton and Gettelman showed that temperature variations associated with horizontal transport of air in the tropopause layer can drive ice cloud formation and dehydration, and Gettelman et al. recently examined the cloud formation and dehydration along kinematic trajectories using simple assumptions about the cloud properties. In this study, we use a Lagrangian, one-dimensional cloud model to further investigate cloud formation and dehydration as air is transported horizontally and vertically through the tropical tropopause layer. Time-height curtains of temperature are extracted from meteorological analyses. The model tracks the growth and sedimentation of individual cloud particles. The regional distribution of clouds simulated in the model is comparable to the subvisible cirrus distribution indicated by SAGE II. The simulated cloud properties depend strongly on the assumed ice supersaturation threshold for ice nucleation. with effective nuclei present (low supersaturation threshold), ice number densities are high (0.1--10 cm(circumflex)-3), and ice crystals do not grow large enough to fall very far, resulting in limited dehydration. With higher supersaturation thresholds, ice number densities are much lower (less than 0.01 cm(circumflex)-3), and ice crystals grow large enough to fall substantially; however, supersaturated air often crosses the tropopause without cloud formation. The clouds typically do not dehydrate the air along trajectories down to the temperature minimum saturation mixing ratio. Rather the water vapor mixing ratio crossing the tropopause along trajectories is typically 10-50% larger than the saturation mixing ratio.

Rationalising polymer selection for supersaturated film forming systems produced by an aerosol spray for the transdermal delivery of methylphenidate.

PubMed

Edwards, A; Qi, S; Liu, F; Brown, M B; McAuley, W J

2017-05-01

Film forming systems offer a number of advantages for topical and transdermal drug delivery, in particular enabling production of a supersaturated state which can greatly improve drug absorption and bioavailability. However the suitability of individual film forming polymers to stabilise the supersaturated state and optimise delivery of drugs is not well understood. This study reports the use of differential scanning calorimetry (DSC) to measure the solubility of methylphenidate both as the free base and as the hydrochloride salt in two polymethacrylate copolymers, Eudragit RS (EuRS) and Eudragit E (EuE) and relates this to the ability of films formed using these polymers to deliver methylphenidate across a model membrane. EuRS provided greater methylphenidate delivery when the drug was formulated as the free base in comparison EuE because the lower solubility of the drug in EuRS provided a higher degree of drug saturation in the polymeric film. In contrast EuE provided greater delivery of methylphenidate hydrochloride as EuRS could not prevent its crystallisation from a supersaturated state. Methylphenidate flux across the membrane could be directly related to degree of saturation of the drug in the film formulation as estimated by the drug solubility in the individual polymers demonstrating the importance of drug solubility in the polymer included in film forming systems for topical/transdermal drug delivery. In addition DSC has been demonstrated to be a useful tool for determining the solubility of drugs in polymers used in film forming systems and the approaches outlined here are likely to be useful for predicting the suitability of polymers for particular drugs in film forming transdermal drug delivery systems. Copyright © 2017. Published by Elsevier B.V.

Measurements of cloud condensation nuclei spectra within maritime cumulus cloud droplets: Implications for mixing processes

NASA Technical Reports Server (NTRS)

Twohy, Cynthia H.; Hudson, James G.

1995-01-01

In a cloud formed during adiabatic expansion, the droplet size distribution will be systematically related to the critical supersaturation of the cloud condensation nuclei (CNN), but this relationship can be complicated in entraining clouds. Useful information about cloud processes, such as mixing, can be obtained from direct measurements of the CNN involved in droplet nucleation. This was accomplished by interfacing two instruments for a series of flights in maritime cumulus clouds. One instrument, the counterflow virtual impactor, collected cloud droplets, and the nonvolatile residual nuclei of the droplets was then passed to a CCN spectrometer, which measured the critical supersaturation (S(sub c)) spectrum of the droplet nuclei. The measured S(sub c) spectra of the droplet nuclei were compared with the S(sub c) spectra of ambient aerosol particles in order to identify which CCN were actually incorporated into droplets and to determine when mixing processes were active at different cloud levels. The droplet nuclei nearly always exhibited lower median S(sub c)'s than the ambient aerosol, as expected since droplets nucleate perferentially on particles with lower critical supersaturations. Critical supersaturation spectra from nuclei of droplets near cloud base were similar to those predicted for cloud regions formed adiabatically, but spectra of droplet nuclei from middle cloud levels showed some evidence that mixing had occurred. Near cloud top, the greatest variation in the spectra of the droplet nuclei was observed, and nuclei with high S(sub c)'s were sometimes present even within relatively large droplets. This suggests that the extent of mixing increases with height in cumulus clouds and that inhomogeneous mixing may be important near cloud top. These promising initial results suggest improvements to the experimental technique that will permit more quantitative results in future experiments.

The free energy of the metastable supersaturated vapor via restricted ensemble simulations. III. An extension to the Corti and Debenedetti subcell constraint algorithm

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

Nie, Chu; Geng, Jun; Marlow, William H.

2016-04-14

In order to improve the sampling of restricted microstates in our previous work [C. Nie, J. Geng, and W. H. Marlow, J. Chem. Phys. 127, 154505 (2007); 128, 234310 (2008)] and quantitatively predict thermal properties of supersaturated vapors, an extension is made to the Corti and Debenedetti subcell constraint algorithm [D. S. Corti and P. Debenedetti, Chem. Eng. Sci. 49, 2717 (1994)], which restricts the maximum allowed local density at any point in a simulation box. The maximum allowed local density at a point in a simulation box is defined by the maximum number of particles N{sub m} allowed tomore » appear inside a sphere of radius R, with this point as the center of the sphere. Both N{sub m} and R serve as extra thermodynamic variables for maintaining a certain degree of spatial homogeneity in a supersaturated system. In a restricted canonical ensemble, at a given temperature and an overall density, series of local minima on the Helmholtz free energy surface F(N{sub m}, R) are found subject to different (N{sub m}, R) pairs. The true equilibrium metastable state is identified through the analysis of the formation free energies of Stillinger clusters of various sizes obtained from these restricted states. The simulation results of a supersaturated Lennard-Jones vapor at reduced temperature 0.7 including the vapor pressure isotherm, formation free energies of critical nuclei, and chemical potential differences are presented and analyzed. In addition, with slight modifications, the current algorithm can be applied to computing thermal properties of superheated liquids.« less

Focused beam reflectance measurement as a tool for in situ monitoring of the lactose crystallization process.

PubMed

Pandalaneni, K; Amamcharla, J K

2016-07-01

Lactose accounts for about 75 and 85% of the solids in whey and deproteinized whey, respectively. Production of lactose is usually carried out by a process called crystallization. Several factors including rate of cooling, presence of impurities, and mixing speed influence the crystal size characteristics. To optimize the lactose crystallization process parameters to maximize the lactose yield, it is important to monitor the crystallization process. However, efficient in situ tools to implement at concentrations relevant to the dairy industry are lacking. The objective of the present work was to use a focused beam reflectance measurement (FBRM) system for in situ monitoring of lactose crystallization at supersaturated concentrations (wt/wt) 50, 55, and 60% at 20 and 30°C. The FBRM data were compared with Brix readings collected using a refractometer during isothermal crystallization. Chord length distributions obtained from FBRM in the ranges of <50 µm (fine crystals) and 50 to 300 µm (coarse crystals) were recorded and evaluated in relation to the extent of crystallization and rate constants deduced from the refractometer measurements. Extent of crystallization and rate constants increased with increasing supersaturation concentration and temperature. The measured fine crystal counts from FBRM increased at higher supersaturated concentration and temperature during isothermal crystallization. On the other hand, coarse counts were observed to increase with decreasing supersaturated concentration and temperature. Square weighted chord length distribution obtained from FBRM showed that as concentration increased, a decrease in chord lengths occurred at 20°C and similar observations were made from microscopic images. The robustness of FBRM in understanding isothermal lactose crystallization at various concentrations and temperatures was successfully assessed in the study. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Phosphate recovery through struvite precipitation by CO2 removal: effect of magnesium, phosphate and ammonium concentrations.

PubMed

Korchef, Atef; Saidou, Hassidou; Ben Amor, Mohamed

2011-02-15

In the present study, the precipitation of struvite (MgNH(4)PO(4)·6H(2)O) using the CO(2) degasification technique is investigated. The precipitation of struvite was done from supersaturated solutions in which precipitation was induced by the increase of the solution supersaturation concomitant with the removal of dissolved carbon dioxide. The effect of magnesium, phosphate and ammonium concentrations on the kinetics and the efficiency of struvite precipitation was measured monitoring the respective concentrations in solution. In all cases struvite precipitated exclusively and the solid was characterized by powder XRD and FTIR. The morphology of the precipitated crystals was examined by scanning electronic microscopy and it was found that it exhibited the typical prismatic pattern of the struvite crystals with sizes in the range between 100 and 300 μm. The increase of magnesium concentration in the supersaturated solutions, resulted for all phosphate concentration tested, in significantly higher phosphate removal efficiency. Moreover, it is interesting to note that in this case the adhesion of the suspended struvite crystals to the reactor walls was reduced suggesting changes in the particle characteristics. The increase of phosphate concentration in the supersaturated solutions, for the magnesium concentrations tested resulted to the reduction of struvite suppression which reached complete suppression of the precipitate formation. Excess of ammonium in solution was found favour struvite precipitation. Contrary to the results found with increasing the magnesium concentration in solution, higher ammonium concentrations resulted to higher adhesion of the precipitated crystallites to the reactor walls. The results of the present work showed that it is possible to recover phosphorus in the form of struvite from wastewater reducing water pollution and at the same time saving valuable resources. Copyright © 2010 Elsevier B.V. All rights reserved.

Insulin Particle Formation in Supersaturated Aqueous Solutions of Poly(Ethylene Glycol)

PubMed Central

Bromberg, Lev; Rashba-Step, Julia; Scott, Terrence

2005-01-01

Protein microspheres are of particular utility in the field of drug delivery. A novel, completely aqueous, process of microsphere fabrication has been devised based on controlled phase separation of protein from water-soluble polymers such as polyethylene glycols. The fabrication process results in the formation of spherical microparticles with narrow particle size distributions. Cooling of preheated human insulin-poly(ethylene glycol)-water solutions results in the facile formation of insulin particles. To map out the supersaturation conditions conducive to particle nucleation and growth, we determined the temperature- and concentration-dependent boundaries of an equilibrium liquid-solid phase separation. The kinetics of formation of microspheres were followed by dynamic and continuous-angle static light scattering techniques. The presence of PEG at a pH that was close to the protein's isoelectric point resulted in rapid nucleation and growth. The time elapsed from the moment of creation of a supersaturated solution and the detection of a solid phase in the system (the induction period, tind) ranged from tens to several hundreds of seconds. The dependence of tind on supersaturation could be described within the framework of classical nucleation theory, with the time needed for the formation of a critical nucleus (size <10 nm) being much longer than the time of the onset of particle growth. The growth was limited by cluster diffusion kinetics. The interfacial energies of the insulin particles were determined to be 3.2–3.4 and 2.2 mJ/m2 at equilibrium temperatures of 25 and 37°C, respectively. The insulin particles formed as a result of the process were monodisperse and uniformly spherical, in clear distinction to previously reported processes of microcrystalline insulin particle formation. PMID:16254391

Hot water, fresh beer, and salt

NASA Astrophysics Data System (ADS)

Crawford, Frank S.

1990-11-01

In the ``hot chocolate effect'' the best musical scales (those with the finest tone quality, largest range, and best tempo) are obtained by adding salt to a glass of hot water supersaturated with air. Good scales can also be obtained by adding salt to a glass of freshly opened beer (supersaturated with CO2) provided you first (a) get rid of much of the excess CO2 so as to produce smaller, hence slower, rising bubbles, and (b) get rid of the head of foam, which damps the standing wave and ruins the tone quality. Finally the old question, ``Do ionizing particles produce bubbles in fresh beer?'' is answered experimentally.

Nano Precipitation and Hardening of Die-Quenched 6061 Aluminum Alloy.

PubMed

Utsunomiya, Hiroshi; Tada, Koki; Matsumoto, Ryo; Watanabe, Katsumi; Matsuda, Kenji

2018-03-01

Die quenching is applied to an age-hardenable aluminium alloys to obtain super-saturated solid solution. The application is advantageous because it can reduce number of manufacturing processes, and may increase strength by strain aging. If die quenching is realized in forging as well as sheet forming, it may widen industrial applicability further. In this study, Al-Mg-Si alloy AA6061 8 mm-thick billets were reduced 50% in height without cracks by die-quench forging. Supersaturated solid solution was successfully obtained. The die-quenched specimen shows higher hardness with nano precipitates at shorter aging time than the conventional water-quenched specimen.

Theoretical modeling of the urinary supersaturation of calcium salts in healthy individuals and kidney stone patients: Precursors, speciation and therapeutic protocols for decreasing its value

NASA Astrophysics Data System (ADS)

Rodgers, Allen L.; Allie-Hamdulay, Shameez; Jackson, Graham E.; Durbach, Ian

2013-11-01

BackgroundSupersaturation (SS) of urinary salts has been extensively invoked for assessing the risk of renal stone formation, but precursors have often been ignored. Our objectives were to establish by computer modeling, which urinary components are essential for calculating reliable SS values, to investigate whether unique equilibrium processes occur in the urine of stone formers (SF) which might account for their higher SS levels relative to healthy controls (N), to determine the relative efficacies of three different, widely-used protocols for lowering urinary SS of calcium salts and to examine the influence of precursors.

Influence of solution conditions on deposition of calcium phosphate on titanium by NaOH-treatment

NASA Astrophysics Data System (ADS)

Feng, Q. L.; Cui, F. Z.; Wang, H.; Kim, T. N.; Kim, J. O.

2000-03-01

The present paper demonstrated a biomimetic method to coat calcium phosphate (Ca-P) on the surface of titanium induced by NaOH-treatment from a simple supersaturated hydroxyapatite solution (SHS). The influence of pH value and calcium ions concentration on the precipitation process was investigated. It is necessary for the solution to be supersaturated than the critical concentration of octacalcium phosphate (OCP) to get Ca-P coatings on titanium surface. In the precipitating process, it seems that amorphous calcium phosphate (ACP) precipitated first, then OCP, and finally hydroxyapatite (HA). The system was in continuous evolution and the phase transitions occurred in sequence.

Size Fluctuations of Near Critical Nuclei and Gibbs Free Energy for Nucleation of BDA on Cu(001)

NASA Astrophysics Data System (ADS)

Schwarz, Daniel; van Gastel, Raoul; Zandvliet, Harold J. W.; Poelsema, Bene

2012-07-01

We present a low-energy electron microscopy study of nucleation and growth of BDA on Cu(001) at low supersaturation. At sufficiently high coverage, a dilute BDA phase coexists with c(8×8) crystallites. The real-time microscopic information allows a direct visualization of near-critical nuclei, determination of the supersaturation and the line tension of the crystallites, and, thus, derivation of the Gibbs free energy for nucleation. The resulting critical nucleus size nicely agrees with the measured value. Nuclei up to 4-6 times larger still decay with finite probability, urging reconsideration of the classic perception of a critical nucleus.

Size fluctuations of near critical nuclei and Gibbs free energy for nucleation of BDA on Cu(001).

PubMed

Schwarz, Daniel; van Gastel, Raoul; Zandvliet, Harold J W; Poelsema, Bene

2012-07-06

We present a low-energy electron microscopy study of nucleation and growth of BDA on Cu(001) at low supersaturation. At sufficiently high coverage, a dilute BDA phase coexists with c(8×8) crystallites. The real-time microscopic information allows a direct visualization of near-critical nuclei, determination of the supersaturation and the line tension of the crystallites, and, thus, derivation of the Gibbs free energy for nucleation. The resulting critical nucleus size nicely agrees with the measured value. Nuclei up to 4-6 times larger still decay with finite probability, urging reconsideration of the classic perception of a critical nucleus.

Development of a digital video-microscopy technique to study lactose crystallisation kinetics in situ.

PubMed

Arellano, María Paz; Aguilera, José Miguel; Bouchon, Pedro

2004-11-15

Polarised light microscopy was employed non-invasively to monitor lactose crystallisation from non-seeded supersaturated solutions in real time. Images were continuously recorded, processed and characterised by image analysis, and the results were compared with those obtained by refractometry. Three crystallisation temperatures (10, 20 and 30 degrees C) and three different levels of initial relative supersaturation (C/C(s)=1.95; 2.34; 3.15) were investigated. Induction times using the imaging technique proved to be substantially lower than those determined using refractive index. Lactose crystals were isolated digitally to determine geometrical parameters of interest, such as perimeter, diameter, area, roundness and Feret mean, and to derive crystal growth rates. Mean growth rates obtained for single crystals were fitted to a combined mass transfer model (R(2)=0.9766). The model allowed the effects of temperature and supersaturation on crystallisation rate to be clearly identified. It also suggested that, in this set of experiments, surface integration seemed to be the rate controlling step. It is believed that a similar experimental set-up could be implemented in a real food system to characterise a particular process where crystallisation control is of interest and where traditional techniques are difficult to implement.

Modeling of glycine solubility in aqueous HCl-MgCl2 system and its application in phase transition of glycine by changing media and supersaturation

NASA Astrophysics Data System (ADS)

Ansari, Ziaul Haque; Zeng, Yan; Zhang, Yan; Demopoulos, George P.; Li, Zhibao

2017-06-01

The solubility of glycine in HCl and HCl-MgCl2 solutions was measured from 283.15 to 343.15 K and found to increase with temperature and increase linearly with the concentration of HCl. The MSE model integrated in the OLI platform was modified by regressing the experimental and literature solubility data through the adjustment of the middle-range interaction parameters. After parameterization, the model can accurately calculate the solubility with the average absolute deviation lower than 3.5% and thus be able to predict supersaturation of glycine. Crystallization of different polymorphs of glycine in water, HCl, NaOH, MgCl2, and HCl-MgCl2 aqueous solutions was performed. The effects of medium, temperature, supersaturation, and time on the crystallization were investigated. It was found that only in the HCl solution the formation of single α-glycine phase was achieved under all the investigated temperature and holding time. α-glycine or its mixture with γ-glycine or C4H18N2O4·HCl was produced in systems other than HCl solution depending on the conditions.

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.

Nucleation kinetics of MgCl2-ethanol adduct for the supported Ziegler-Natta catalysts with a thermodynamic approach

NASA Astrophysics Data System (ADS)

Ansari, Ziaul Haque; Zeng, Yan; Demopoulos, George P.; Li, Zhibao

2018-07-01

MgCl2-ethanol adducts play a key role in the synthesis of supported Ziegler-Natta catalysts. The morphology of the MgCl2-ethanol adducts, which is controlled by their crystallization process, can determine the structure and thus the property of the polyolefin products. Here we study the nucleation kinetics of MgCl2-ethanol adducts by measuring the metastable zone width (MSZW) and induction time at different temperatures. Supersaturation ratios used in induction time measurements were predicted by the Mixed Solvent Electrolyte (MSE) model embedded in OLI System. Nývlt‧s approach was applied to determine MSZW. By the induction time measurement, the effect of temperature, and supersaturation were studied. It was found that induction time decreases as either temperature or supersaturation increases. The measured MSZW and induction time are used to estimate the nucleation kinetics of the system, and thereby distinguishing between the homogeneous and heterogeneous mechanisms. The interfacial tension and other related nucleation parameters were calculated from the induction time data. XRD and TGA indicate that the MgCl2-ethanol adduct has the stoichiometry of MgCl2·6C2H5OH.

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.

Supersaturated calcium carbonate solutions are classical

PubMed Central

Henzler, Katja; Fetisov, Evgenii O.; Galib, Mirza; Baer, Marcel D.; Legg, Benjamin A.; Borca, Camelia; Xto, Jacinta M.; Pin, Sonia; Fulton, John L.; Schenter, Gregory K.; Govind, Niranjan; Siepmann, J. Ilja; Mundy, Christopher J.; Huthwelker, Thomas; De Yoreo, James J.

2018-01-01

Mechanisms of CaCO3 nucleation from solutions that depend on multistage pathways and the existence of species far more complex than simple ions or ion pairs have recently been proposed. Herein, we provide a tightly coupled theoretical and experimental study on the pathways that precede the initial stages of CaCO3 nucleation. Starting from molecular simulations, we succeed in correctly predicting bulk thermodynamic quantities and experimental data, including equilibrium constants, titration curves, and detailed x-ray absorption spectra taken from the supersaturated CaCO3 solutions. The picture that emerges is in complete agreement with classical views of cluster populations in which ions and ion pairs dominate, with the concomitant free energy landscapes following classical nucleation theory. PMID:29387793

Supersaturated calcium carbonate solutions are classical.

PubMed

Henzler, Katja; Fetisov, Evgenii O; Galib, Mirza; Baer, Marcel D; Legg, Benjamin A; Borca, Camelia; Xto, Jacinta M; Pin, Sonia; Fulton, John L; Schenter, Gregory K; Govind, Niranjan; Siepmann, J Ilja; Mundy, Christopher J; Huthwelker, Thomas; De Yoreo, James J

2018-01-01

Mechanisms of CaCO 3 nucleation from solutions that depend on multistage pathways and the existence of species far more complex than simple ions or ion pairs have recently been proposed. Herein, we provide a tightly coupled theoretical and experimental study on the pathways that precede the initial stages of CaCO 3 nucleation. Starting from molecular simulations, we succeed in correctly predicting bulk thermodynamic quantities and experimental data, including equilibrium constants, titration curves, and detailed x-ray absorption spectra taken from the supersaturated CaCO 3 solutions. The picture that emerges is in complete agreement with classical views of cluster populations in which ions and ion pairs dominate, with the concomitant free energy landscapes following classical nucleation theory.

Morphology evolution of hierarchical ZnO nanostructures modulated by supersaturation and growth temperature

NASA Astrophysics Data System (ADS)

Yan, Youguo; Zhou, Lixia; Yu, Lianqing; Zhang, Ye

2008-07-01

Three kinds of ZnO hierarchical structures, nanocombs with tube- and needle-shaped teeth and hierarchical nanorod arrays, were successfully synthesized through the chemical vapor deposition method. Combining the experimental parameters, the microcosmic growing conditions (growth temperature and supersaturation) along the flux was discussed at length, and, based on the conclusions, three reasonable growth processes were proposed. The results and discussions were beneficial to further realize the relation between the growing behavior of the nanomaterial and microcosmic conditions, and the hierarchical nanostructures obtained were also expected to have potential applications as functional blocks in future nanodevices. Furthermore, the study of photoluminescence further indicated that the physical properties were strongly dependent on the crystal structure.

Surface Nanobubbles Are Stabilized by Hydrophobic Attraction.

PubMed

Tan, Beng Hau; An, Hongjie; Ohl, Claus-Dieter

2018-04-20

The remarkably long lifetime of surface nanobubbles has perplexed researchers for two decades. The current understanding is that both contact line pinning and supersaturation of the ambient liquid are strictly required for the stability of nanobubbles, yet experiments show nanobubbles surviving in open systems and undersaturated environments. We find that this discrepancy can be addressed if the effects of an attractive hydrophobic potential at the solid substrate on the spatial distribution of the gas concentration is taken into account. We also show that, in our model, only substrate pinning is strictly required for stabilization; while hydrophobicity and supersaturation both aid stability, neither is mandatory-the absence of one can be compensated by an excess of the other.

Method for production of hydrocarbons from hydrates

DOEpatents

McGuire, Patrick L.

1984-01-01

A method of recovering natural gas entrapped in frozen subsurface gas hydrate formations in arctic regions. A hot supersaturated solution of CaCl.sub.2 or CaBr.sub.2, or a mixture thereof, is pumped under pressure down a wellbore and into a subsurface hydrate formation so as to hydrostatically fracture the formation. The CaCl.sub.2 /CaBr.sub.2 solution dissolves the solid hydrates and thereby releases the gas entrapped therein. Additionally, the solution contains a polymeric viscosifier, which operates to maintain in suspension finely divided crystalline CaCl.sub.2 /CaBr.sub.2 that precipitates from the supersaturated solution as it is cooled during injection into the formation.

Hot water, fresh beer, and salt

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

Crawford, F.S.

1990-11-01

In the hot chocolate effect'' the best musical scales (those with the finest tone quality, largest range, and best tempo) are obtained by adding salt to a glass of hot water supersaturated with air. Good scales can also be obtained by adding salt to a glass of freshly opened beer (supersaturated with CO{sub 2}) provided you first (a) get rid of much of the excess CO{sub 2} so as to produce smaller, hence slower, rising bubbles, and (b) get rid of the head of foam, which damps the standing wave and ruins the tone quality. Finally the old question, Domore » ionizing particles produce bubbles in fresh beer '' is answered experimentally.« less

Acoustic levitation: recent developments and emerging opportunities in biomaterials research.

PubMed

Weber, Richard J K; Benmore, Chris J; Tumber, Sonia K; Tailor, Amit N; Rey, Charles A; Taylor, Lynne S; Byrn, Stephen R

2012-04-01

Containerless sample environments (levitation) are useful for study of nucleation, supercooling, and vitrification and for synthesis of new materials, often with non-equilibrium structures. Elimination of extrinsic nucleation by container walls extends access to supercooled and supersaturated liquids under high-purity conditions. Acoustic levitation is well suited to the study of liquids including aqueous solutions, organics, soft materials, polymers, and pharmaceuticals at around room temperature. This article briefly reviews recent developments and applications of acoustic levitation in materials R&D. Examples of experiments yielding amorphous pharmaceutical materials are presented. The implementation and results of experiments on supercooled and supersaturated liquids using an acoustic levitator at a high-energy X-ray beamline are described.

Supersaturation of dissolved H(2) and CO (2) during fermentative hydrogen production with N(2) sparging.

PubMed

Kraemer, Jeremy T; Bagley, David M

2006-09-01

Dissolved H(2) and CO(2) were measured by an improved manual headspace-gas chromatographic method during fermentative H(2) production with N(2) sparging. Sparging increased the yield from 1.3 to 1.8 mol H(2)/mol glucose converted, although H(2) and CO(2) were still supersaturated regardless of sparging. The common assumption that sparging increases the H(2) yield because of lower dissolved H(2) concentrations may be incorrect, because H(2) was not lowered into the range necessary to affect the relevant enzymes. More likely, N(2) sparging decreased the rate of H(2) consumption via lower substrate concentrations.

Surface Nanobubbles Are Stabilized by Hydrophobic Attraction

NASA Astrophysics Data System (ADS)

Tan, Beng Hau; An, Hongjie; Ohl, Claus-Dieter

2018-04-01

The remarkably long lifetime of surface nanobubbles has perplexed researchers for two decades. The current understanding is that both contact line pinning and supersaturation of the ambient liquid are strictly required for the stability of nanobubbles, yet experiments show nanobubbles surviving in open systems and undersaturated environments. We find that this discrepancy can be addressed if the effects of an attractive hydrophobic potential at the solid substrate on the spatial distribution of the gas concentration is taken into account. We also show that, in our model, only substrate pinning is strictly required for stabilization; while hydrophobicity and supersaturation both aid stability, neither is mandatory—the absence of one can be compensated by an excess of the other.

Stratospheric CCN sampling program

NASA Technical Reports Server (NTRS)

Rogers, C. F.

1981-01-01

When Mt. St. Helens produced several major eruptions in the late spring of 1980, there was a strong interest in the characterization of the cloud condensation nuclei (CCN) activity of the material that was injected into the troposphere and stratosphere. The scientific value of CCN measurements is two fold: CCN counts may be directly applied to calculations of the interaction of the aerosol (enlargement) at atmospherically-realistic relative humidities or supersaturations; and if the chemical constituency of the aerosol can be assumed, the number-versus-critical supersaturation spectrum may be converted into a dry aerosol size spectrum covering a size region not readily measured by other methods. The sampling method is described along with the instrumentation used in the experiments.

Photoinduced nucleation: a novel tool for detecting molecules in air at ultra-low concentrations

DOEpatents

Katz, Joseph L.; Lihavainen, Heikki; Rudek, Markus M.; Salter, Brian C.

2002-01-01

A method and apparatus for determining the presence of molecules in a gas at concentrations of less than about 100 ppb. Light having wavelengths in the range from about 200 nm to about 350 nm is used to illuminate a flowing sample of the gas causing the molecules if present to form clusters. A mixture of the illuminated gas and a vapor is cooled until the vapor is supersaturated so that there is a small rate of homogeneous nucleation. The supersaturated vapor condenses on the clusters thus causing the clusters to grow to a size sufficient to be counted by light scattering and then the clusters are counted.

Atomic force microscopic study of step bunching and macrostep formation during the growth of L-arginine phosphate monohydrate single crystals

NASA Astrophysics Data System (ADS)

Sangwal, K.; Torrent-Burgues, J.; Sanz, F.; Gorostiza, P.

1997-02-01

The experimental results of the formation of step bunches and macrosteps on the {100} face of L-arginine phosphate monohydrate crystals grown from aqueous solutions at different supersaturations studied by using atomic force microscopy are described and discussed. It was observed that (1) the step height does not remain constant with increasing time but fluctuates within a particular range of heights, which depends on the region of step bunches, (2) the maximum height and the slope of bunched steps increases with growth time as well as supersaturation used for growth, and that (3) the slope of steps of relatively small heights is usually low with a value of about 8° and does not depend on the region of formation of step bunches, but the slope of steps of large heights is up to 21°. Analysis of the experimental results showed that (1) at a particular value of supersaturation the ratio of the average step height to the average step spacing is a constant, suggesting that growth of the {100} face of L-arginine phosphate monohydrate crystals occurs by direct integration of growth entities to growth steps, and that (2) the formation of step bunches and macrosteps follows the dynamic theory of faceting, advanced by Vlachos et al.

The risk of renal stone formation during and after long duration space flight

NASA Technical Reports Server (NTRS)

Whitson, P. A.; Pietrzyk, R. A.; Morukov, B. V.; Sams, C. F.

2001-01-01

BACKGROUND: The formation of a renal stone during space flight may have serious negative effects on the health of the crewmember and the success of the mission. Urinary biochemical factors and the influence of dietary factors associated with renal stone development were assessed during long duration Mir Space Station missions. METHODS: Twenty-four-hour urine samples were collected prior to, during and following long duration space flight. The relative urinary supersaturation of calcium oxalate, calcium phosphate (brushite), sodium urate, struvite and uric acid were determined. RESULTS: Changes in the urinary biochemistry of crewmembers during long duration spaceflight demonstrated increases in the supersaturation of the stone-forming salts. In-flight hypercalciuria was evident in a number of individual crewmembers and 24-hour dietary fluid intake and urine volume were significantly lower. During flight, there was a significant increase in brushite supersaturation. CONCLUSIONS: These data suggest acute effects of space flight and postflight changes in the urinary biochemistry favoring increased crystallization in the urine. The effects of dietary intake, especially fluid intake, may have a significant impact on the potential for renal stone formation. Efforts are now underway to assess the efficacy of a countermeasure to mitigate the increased risk. Copyright 2001 S. Karger AG, Basel.

Investigation on nanoscale processes on the BaF{sub 2}(111) surface in various solutions by frequency modulation atomic force microscopy

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

Kobayashi, Naritaka, E-mail: naritaka@mail.saitama-u.ac.jp; Kawamura, Ryuzo; Yoshikawa, Hiroshi Y.

2016-06-07

In this study, we have directly observed nanoscale processes that occur on BaF{sub 2}(111) surfaces in various solutions using liquid-environment frequency modulation atomic force microscopy (FM-AFM) with a true atomic resolution. In addition, to investigate atomic-scale mechanisms of crystal growth process of BaF{sub 2}, we determined a suitable solution for atomic-resolution FM-AFM imaging of the BaF{sub 2}(111) surface. For undersaturated solutions, the surface is roughened by barium hydroxo complexes in the case of high pH, whereas by dissolution and proton or water molecule adsorption throughout the surface in the case of low pH. On the other hand, for supersaturated solutions,more » the surface shows two-dimensional nucleation and growth (σ = 0.1) and three-dimensional crystal growth with tetrahedral structures (σ = 1), where σ is the degree of supersaturation. The atomic-resolution imaging of the BaF{sub 2}(111) surface has been demonstrated in potassium fluoride (KF) and the supersaturated (σ = 0.1 and 1) solutions, wherein atomically flat terraces are shown at least for about 30 min.« less

"Supersaturated" self-assembled charge-selective interfacial layers for organic solar cells.

PubMed

Song, Charles Kiseok; Luck, Kyle A; Zhou, Nanjia; Zeng, Li; Heitzer, Henry M; Manley, Eric F; Goldman, Samuel; Chen, Lin X; Ratner, Mark A; Bedzyk, Michael J; Chang, Robert P H; Hersam, Mark C; Marks, Tobin J

2014-12-24

To achieve densely packed charge-selective organosilane-based interfacial layers (IFLs) on the tin-doped indium oxide (ITO) anodes of organic photovoltaic (OPV) cells, a series of Ar2N-(CH2)n-SiCl3 precursors with Ar = 3,4-difluorophenyl, n = 3, 6, 10, and 18, was synthesized, characterized, and chemisorbed on OPV anodes to serve as IFLs. To minimize lateral nonbonded -NAr2···Ar2N- repulsions which likely limit IFL packing densities in the resulting self-assembled monolayers (SAMs), precursor mixtures having both small and large n values are simultaneously deposited. These "heterogeneous" SAMs are characterized by a battery of techniques: contact angle measurements, X-ray reflectivity, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy (UPS), cyclic voltammetry, and DFT computation. It is found that the headgroup densities of these "supersaturated" heterogeneous SAMs (SHSAMs) are enhanced by as much as 17% versus their homogeneous counterparts. Supersaturation significantly modifies the IFL properties including the work function (as much as 16%) and areal dipole moment (as much as 49%). Bulk-heterojunction OPV devices are fabricated with these SHSAMs: ITO/IFL/poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][2-[[(2-ethylhexyl)oxy]carbonyl]-3-fluorothieno[3,4-b]thiophenediyl

Interpretation of the microwave effect on induction time during CaSO4 primary nucleation by a cluster coagulation model

NASA Astrophysics Data System (ADS)

Guo, Zhichao; Li, Liye; Han, Wenxiang; Li, Jiawei; Wang, Baodong; Xiao, Yongfeng

2017-10-01

The effects of microwave on the induction time of CaSO4 are studied experimentally and theoretically. In the experiments, calcium sulfate is precipitated by mixing aqueous CaCl2 solution and Na2SO4 solution. The induction time is measured by recording the change of turbidity in solution. Various energy inputs are used to investigate the effect of energy input on nucleation. The results show that the induction time decreases with increasing supersaturation and increasing energy input. Employing the classical nucleation theory, the interfacial tension is estimated. In addition, the microwave effects on nucleation order (n) and nucleation coefficient (kN) are also investigated, and the corresponding values of homogeneous nucleation are compared with the values of heterogeneous nucleation in the microwave field. A cluster coagulation model, which brings together the classic nucleation models and the theories describing the behavior of colloidal suspension, was applied to estimate the induction time under various energy inputs. It is found that when nucleation is prominently homogeneous, the microwave energy input does not change the number of monomers in dominating clusters. And when nucleation is prominently heterogeneous, although the dominating cluster size increases with supersaturation increasing, at the same supersaturation level, the dominating cluster size remains constant in the microwave field.

Crosslinked hydrogels-a promising class of insoluble solid molecular dispersion carriers for enhancing the delivery of poorly soluble drugs.

PubMed

Sun, Dajun D; Lee, Ping I

2014-02-01

Water-insoluble materials containing amorphous solid dispersions (ASD) are an emerging category of drug carriers which can effectively improve dissolution kinetics and kinetic solubility of poorly soluble drugs. ASDs based on water-insoluble crosslinked hydrogels have unique features in contrast to those based on conventional water-soluble and water-insoluble carriers. For example, solid molecular dispersions of poorly soluble drugs in poly(2-hydroxyethyl methacrylate) (PHEMA) can maintain a high level of supersaturation over a prolonged period of time via a feedback-controlled diffusion mechanism thus avoiding the initial surge of supersaturation followed by a sharp decline in drug concentration typically encountered with ASDs based on water-soluble polymers. The creation of both immediate- and controlled-release ASD dosage forms is also achievable with the PHEMA based hydrogels. So far, ASD systems based on glassy PHEMA have been shown to be very effective in retarding precipitation of amorphous drugs in the solid state to achieve a robust physical stability. This review summarizes recent research efforts in investigating the potential of developing crosslinked PHEMA hydrogels as a promising alternative to conventional water-soluble ASD carriers, and a related finding that the rate of supersaturation generation does affect the kinetic solubility profiles implications to hydrogel based ASDs.

Crosslinked hydrogels—a promising class of insoluble solid molecular dispersion carriers for enhancing the delivery of poorly soluble drugs

PubMed Central

Sun, Dajun D.; Lee, Ping I.

2014-01-01

Water-insoluble materials containing amorphous solid dispersions (ASD) are an emerging category of drug carriers which can effectively improve dissolution kinetics and kinetic solubility of poorly soluble drugs. ASDs based on water-insoluble crosslinked hydrogels have unique features in contrast to those based on conventional water-soluble and water-insoluble carriers. For example, solid molecular dispersions of poorly soluble drugs in poly(2-hydroxyethyl methacrylate) (PHEMA) can maintain a high level of supersaturation over a prolonged period of time via a feedback-controlled diffusion mechanism thus avoiding the initial surge of supersaturation followed by a sharp decline in drug concentration typically encountered with ASDs based on water-soluble polymers. The creation of both immediate- and controlled-release ASD dosage forms is also achievable with the PHEMA based hydrogels. So far, ASD systems based on glassy PHEMA have been shown to be very effective in retarding precipitation of amorphous drugs in the solid state to achieve a robust physical stability. This review summarizes recent research efforts in investigating the potential of developing crosslinked PHEMA hydrogels as a promising alternative to conventional water-soluble ASD carriers, and a related finding that the rate of supersaturation generation does affect the kinetic solubility profiles implications to hydrogel based ASDs. PMID:26579361

Theory of Ostwald ripening in a two-component system

NASA Technical Reports Server (NTRS)

Baird, J. K.; Lee, L. K.; Frazier, D. O.; Naumann, R. J.

1986-01-01

When a two-component system is cooled below the minimum temperature for its stability, it separates into two or more immiscible phases. The initial nucleation produces grains (if solid) or droplets (if liquid) of one of the phases dispersed in the other. The dynamics by which these nuclei proceed toward equilibrium is called Ostwald ripening. The dynamics of growth of the droplets depends upon the following factors: (1) The solubility of the droplet depends upon its radius and the interfacial energy between it and the surrounding (continuous) phase. There is a critical radius determined by the supersaturation in the continuous phase. Droplets with radii smaller than critical dissolve, while droplets with radii larger grow. (2) The droplets concentrate one component and reject the other. The rate at which this occurs is assumed to be determined by the interdiffusion of the two components in the continuous phase. (3) The Ostwald ripening is constrained by conservation of mass; e.g., the amount of materials in the droplet phase plus the remaining supersaturation in the continuous phase must equal the supersaturation available at the start. (4) There is a distribution of droplet sizes associated with a mean droplet radius, which grows continuously with time. This distribution function satisfies a continuity equation, which is solved asymptotically by a similarity transformation method.

Investigation of the operating conditions to morphology evolution of β-L-glutamic acid during seeded cooling crystallization

NASA Astrophysics Data System (ADS)

Zhang, Fangkun; Liu, Tao; Huo, Yan; Guan, Runduo; Wang, Xue Z.

2017-07-01

In this paper the effects of operating conditions including cooling rate, initial supersaturation, and seeding temperature were investigated on the morphology evolution of β-L-glutamic acid (β-LGA) during seeded cooling crystallization. Based on the results of in-situ image acquisition of the crystal morphology evolution during the crystallization process, it was found that the crystal products tend to be plate-like or short rod-like under a slow cooling rate, low initial supersaturation, and low seeding temperature. In the opposite, the operating conditions of a faster cooling rate, higher initial supersaturation, and higher seeding temperature tend to produce long rod-like or needle-like crystals, and meanwhile, the length and width of crystal products will be increased together with a wider crystal size distribution (CSD). The aspect ratio of crystals, defined by the crystal length over width measured from in-situ or sample images, was taken as a shape index to analyze the crystal morphologies. Based on comparative analysis of the experimental results, guidelines on these operating conditions were given for obtaining the desired crystal shapes, along with the strategies for obtaining a narrower CSD for better product quality. Experimental verifications were performed to illustrate the proposed guidelines on the operating conditions for seeded cooling crystallization of LGA solution.

Urine risk factors in children with calcium kidney stones and their siblings

PubMed Central

Bergsland, Kristin J.; Coe, Fredric L.; White, Mark D.; Erhard, Michael J.; DeFoor, William R.; Mahan, John D.; Schwaderer, Andrew L.; Asplin, John R.

2012-01-01

Calcium nephrolithiasis in children is increasing in prevalence and tends to be recurrent. Although children have a lower incidence of nephrolithiasis than adults, its etiology in children is less well understood; hence treatments targeted for adults may not be optimal in children. To better understand metabolic abnormalities in stone forming children, we compared chemical measurements and the crystallization properties of 24-hour urine collections from 129 stone formers matched to 105 non-stone forming siblings and 183 normal, healthy children with no family history of stones; all aged 6 to 17 years. The principal risk factor for calcium stone formation was hypercalciuria. Stone formers have strikingly higher calcium excretion along with high supersaturation for calcium oxalate and calcium phosphate, and a reduced distance between the upper limit of metastability and supersaturation for calcium phosphate, indicating increased risk of calcium phosphate crystallization. Other differences in urine chemistry that exist between adult stone formers and normal individuals such as hyperoxaluria, hypocitraturia, abnormal urine pH and low urine volume were not found in these children. Hence, hypercalciuria and a reduction in the gap between calcium phosphate upper limit of metastability and supersaturation are crucial determinants of stone risk. This highlights the importance of managing hypercalciuria in children with calcium stones. PMID:22358148

Production method of carbamazepine/saccharin cocrystal particles by using two solution mixing based on the ternary phase diagram

NASA Astrophysics Data System (ADS)

Kudo, Shoji; Takiyama, Hiroshi

2014-04-01

In the pharmaceutical field, improvement of drug solubility is required, and an interest in cocrystals is growing. Crystallization methods for industrial production of cocrystals have not been developed enough whereas many cocrystals have been prepared in order to find a new crystal form by screening in the laboratory. The objective of this study was the development of the crystallization method which is useful for the industrial production of cocrystal particles based on the phase diagram. A cocrystal of carbamazepine and saccharin was selected as a model substance. The ternary phase diagram of carbamazepine and saccharin in methanol at 303 K was measured. A cocrystallization method of mixing two kinds of different eutectic solutions was designed based on the ternary phase diagram. In order to adjust the cocrystallization conditions, the determination method of the driving force for cocrystal deposition such as supersaturation based on mass balance was proposed. The cocrystal particles were obtained under all the conditions of the five mixing ratios. From these experimental results, the relationship between the supersaturation and the induction time for nucleation was confirmed as well as conventional crystallization. In conclusion, the crystallization method for industrial production of cocrystal particles including the determination of the supersaturation was suggested.

Ultrasound assisted cocrystallization from solution (USSC) containing a non-congruently soluble cocrystal component pair: Caffeine/maleic acid.

PubMed

Aher, Suyog; Dhumal, Ravindra; Mahadik, Kakasaheb; Paradkar, Anant; York, Peter

2010-12-23

Ultrasound assisted solution cocrystallization (USSC) has been studied using a non-congruently soluble pair of caffeine and maleic acid in methanol. USSC was compared with solvent cooling and slurry sonication using different molar ratios of caffeine:maleic acid (1:0.5, 1:1, 1:2, 1:3 and 1:3.5) in solution/slurry. Products were characterized by PXRD and Raman spectroscopy techniques. In USSC trials, the content of cocrystal in the product was observed to increase with increase in amount of maleic acid in solution. Only USSC offered pure caffeine/maleic acid 2:1 cocrystal product when caffeine:maleic acid; 1:3.5 molar ratio was taken in solution. Caffeine/maleic acid 1:1 cocrystal and maleic acid were not obtained in neither of the techniques. Products of solvent cooling and slurry sonication experiments were mixtures of caffeine and caffeine/maleic acid 2:1 cocrystal in varying amounts. In USSC, ultrasound application must have attained simultaneous supersaturation of cocrystal components in solution due to altered supersaturation conditions resulting in cocrystal formation. For this simultaneous attainment of supersaturation, molar ratio of cocrystal components in solution was identified as an important parameter while designing experiments for a non-congruently soluble pair having large solubility difference. Copyright © 2010 Elsevier B.V. All rights reserved.

Self-Organization of Microscale Condensate for Delayed Flooding of Nanostructured Superhydrophobic Surfaces.

PubMed

Ölçeroğlu, Emre; McCarthy, Matthew

2016-03-02

Superhydrophobic surfaces enhance condensation by inhibiting the formation of an insulating liquid layer. While this produces efficient heat transfer at low supersaturations, superhydrophobicity has been shown to break down at increased supersaturations. As heat transfer increases, the random distribution and high density of nucleation sites produces pinned droplets, which lead to uncontrollable flooding. In this work, engineered variations in wettability are used to promote the self-organization of microscale droplets, which is shown to effectively delay flooding. Virus-templated superhydrophobic surfaces are patterned with an array of superhydrophilic islands designed to minimize surface adhesion while promoting spatial order. By use of optical and electron microscopy, the surfaces are optimized and characterized during condensation. Mixed wettability imparts spatial order not only through preferential nucleation but more importantly through the self-organization of coalescing droplets at high supersaturations. The self-organization of microscale droplets (diameters of <25 μm) is shown to effectively delay flooding and govern the global wetting behavior of larger droplets (diameters of >1 mm) on the surface. As heat transfer increases, the surfaces transition from jumping-mode to shedding-mode removal with no flooding. This demonstrates the ability to engineer surfaces to resist flooding and can act as the basis for developing robust superhydrophobic surfaces for condensation applications.

Urine risk factors in children with calcium kidney stones and their siblings.

PubMed

Bergsland, Kristin J; Coe, Fredric L; White, Mark D; Erhard, Michael J; DeFoor, William R; Mahan, John D; Schwaderer, Andrew L; Asplin, John R

2012-06-01

Calcium nephrolithiasis in children is increasing in prevalence and tends to be recurrent. Although children have a lower incidence of nephrolithiasis than adults, its etiology in children is less well understood; hence, treatments targeted for adults may not be optimal in children. To better understand metabolic abnormalities in stone-forming children, we compared chemical measurements and the crystallization properties of 24-h urine collections from 129 stone formers matched to 105 non-stone-forming siblings and 183 normal, healthy children with no family history of stones, all aged 6 to 17 years. The principal risk factor for calcium stone formation was hypercalciuria. Stone formers have strikingly higher calcium excretion along with high supersaturation for calcium oxalate and calcium phosphate, and a reduced distance between the upper limit of metastability and supersaturation for calcium phosphate, indicating increased risk of calcium phosphate crystallization. Other differences in urine chemistry that exist between adult stone formers and normal individuals such as hyperoxaluria, hypocitraturia, abnormal urine pH, and low urine volume were not found in these children. Hence, hypercalciuria and a reduction in the gap between calcium phosphate upper limit of metastability and supersaturation are crucial determinants of stone risk. This highlights the importance of managing hypercalciuria in children with calcium stones.

A supersaturating delivery system of silibinin exhibiting high payload achieved by amorphous nano-complexation with chitosan.

PubMed

Nguyen, Minh-Hiep; Yu, Hong; Dong, Bingxue; Hadinoto, Kunn

2016-06-30

The therapeutic potentials of silibinin - a phytochemical isolated from milk thistle plants - have not been fully realized due to its poor oral bioavailability caused by the low aqueous solubility. Existing solubility enhancement strategies of silibinin by nanonization were limited by their low payload. Herein we developed a supersaturating delivery system of silibinin exhibiting a high payload (≈76%) in the form of amorphous silibinin-chitosan nanoparticle complex (or silibinin nanoplex in short) prepared by self-assembly drug-polysaccharide complexation. The effects of (1) pH and (2) charge ratio of chitosan to silibinin on the nanoplex's physical characteristics (i.e. size, zeta potential, and payload) and preparation efficiency (i.e. silibinin utilization, overall yield) were investigated. The formation of nanoplex (≈240nm) was feasible only in a narrow pH range (5.1-5.8) and favored charge ratio below unity. At the optimal condition (pH 5.8 and charge ratio of 0.30), the nanoplex preparation exhibited 87% silibinin utilization rate and 63% yield signifying its high efficiency. The amorphous state and colloidal stabilities of the nanoplex during storage, and prolonged supersaturation generation (3h) at more than 10× of the saturation solubility were successfully demonstrated. Copyright © 2016 Elsevier B.V. All rights reserved.

Droplet activation, separation, and compositional analysis: laboratory studies and atmospheric measurements

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Kohn, M.; Pekour, M. S.; Nelson, D. A.; Shilling, J. E.; Cziczo, D. J.

2011-10-01

Droplets produced in a cloud condensation nuclei chamber (CCNC) as a function of supersaturation have been separated from unactivated aerosol particles using counterflow virtual impaction. Residual material after droplets were evaporated was chemically analyzed with an Aerodyne Aerosol Mass Spectrometer (AMS) and the Particle Analysis by Laser Mass Spectrometry (PALMS) instrument. Experiments were initially conducted to verify activation conditions for monodisperse ammonium sulfate particles and to determine the resulting droplet size distribution as a function of supersaturation. Based on the observed droplet size, the counterflow virtual impactor cut-size was set to differentiate droplets from unactivated interstitial particles. Validation experiments were then performed to verify that only droplets with sufficient size passed through the counterflow virtual impactor for subsequent analysis. A two-component external mixture of monodisperse particles was also exposed to a supersaturation which would activate one of the types (hygroscopic salts) but not the other (polystyrene latex spheres or adipic acid). The mass spectrum observed after separation indicated only the former, validating separation of droplets from unactivated particles. Results from ambient measurements using this technique and AMS analysis were inconclusive, showing little chemical differentiation between ambient aerosol and activated droplet residuals, largely due to low signal levels. When employing as single particle mass spectrometer for compositional analysis, however, we observed enhancement of sulfate in droplet residuals.

CCN characteristics over a tropical coastal station during south-west monsoon: observations and closure studies

NASA Astrophysics Data System (ADS)

Jayachandran, V.; Nair, Vijayakumar S.; Babu, S. Suresh

2017-09-01

Number concentration measurements of cloud condensation nuclei (CCN) at five supersaturation values between 0.2 and 1.0% were made from a coastal site (Thiruvananthapuram) of peninsular India using a single column CCN counter during the summer monsoon period (June-September) of 2013 and 2014. The CCN concentration over this site showed diurnal variations of high values during nighttime and low values during daytime in association with the change in mesoscale circulation patterns. The inter-annual variations of CCN (CCN0.4% = 2,232 ± 672 cm-3 during August 2013 and CCN0.4% = 941 ± 325 cm-3 during August 2014) are mostly associated with the varying intensity of monsoon rainfall. The variation of CCN number concentration with supersaturation is found to be steeper during nighttime (indicating a less CCN active aerosol system) than during daytime (CCN active system). The CCN activation ratio estimated using simultaneous measurements of CCN and aerosol number (CN) concentration clearly depict the role of land-sea breeze circulations with higher values during daytime than the nighttime. The CCN number concentration predicted for different supersaturations, from measured aerosol number size distribution using Kohler theory, indicate the importance of the change in aerosol composition associated with different airmasses in a coastal environment.

The influence of non-ionisable excipients on precipitation parameters measured using the CheqSol method.

PubMed

Etherson, Kelly; Halbert, Gavin; Elliott, Moira

2016-09-01

The aim of this study was to determine the influence of non-ionisable excipients hydroxypropyl-β-cyclodextrin (HPβCD) and poloxamers 407 and 188 on the supersaturation and precipitation kinetics of ibuprofen, gliclazide, propranolol and atenolol induced through solution pH shifts using the CheqSol method. The drug's kinetic and intrinsic aqueous solubilities were measured in the presence of increasing excipient concentrations using the CheqSol method. Experimental data rate of change of pH with time was also examined to determine excipient-induced parachute effects and influence on precipitation rates. The measured kinetic and intrinsic solubilities provide a determination of the influence of each excipient on supersaturation index, and the area under the CheqSol curve can measure the parachute capability of excipients. The excipients influence on precipitation kinetics can be measured with novel parameters; for example, the precipitation pH or percentage ionised drug at the precipitation point, which provide further information on the excipient-induced changes in precipitation performance. This method can therefore be employed to measure the influence of non-ionisable excipients on the kinetic solubility behaviour of supersaturated solutions of ionisable drugs and to provide data, which discriminates between excipient systems during precipitation. © 2016 Royal Pharmaceutical Society.

TED of boron in the presence of EOR defects: the use of the theory of Ostwald ripening to calculate Si-interstitial supersaturation in the vicinity of extrinsic defects

NASA Astrophysics Data System (ADS)

Bonafos, C.; Alquier, D.; Martinez, A.; Mathiot, D.; Claverie, A.

1996-05-01

When end-of-range defects are located close to or within doping profiles they render diffusion "anomalous" by both enhancing the dopant diffusivity and trapping it, both phenomena decreasing with time. Upon annealing, these defects grow in size and their density is reduced through the emission and capture of Si-interstitial atoms by a coarsening process called Ostwald ripening. In this paper, we report on how, by coupling the Ostwald ripening theory with TEM observations of the time evolution of the dislocation loops upon annealing, quantitative information allowing the enhanced diffusivity to be understood can be extracted. Indeed, during the coarsening process, a supersaturation, {C}/{C e}, of Si self-interstitial atoms is maintained between the loops and decreases with time. The enhanced diffusivity is assumed to be linked to the evolution of this interstitial supersaturation during annealing through the interstitial component of boron diffusion. We show that C drastically decreases during the first second of the anneal to asymptotically reach a value just above the equilibrium concentration Ce. This rapid decay is precisely at the origin of the transient enhanced diffusivity of dopants in the vicinity of the loops.

Effect of precipitation inhibitors on indomethacin supersaturation maintenance: mechanisms and modeling.

PubMed

Patel, Dhaval D; Anderson, Bradley D

2014-05-05

This study quantitatively explores the mechanisms underpinning the effects of model pharmaceutical polymeric precipitation inhibitors (PPIs) on the crystal growth and, in turn, maintenance of supersaturation of indomethacin, a model poorly water-soluble drug. A recently developed second-derivative UV spectroscopy method and a first-order empirical crystal growth model were used to determine indomethacin crystal growth rates in the presence of model PPIs. All three model PPIs including HP-β-CD, PVP, and HPMC inhibited indomethacin crystal growth at both high and low degrees of supersaturation (S). The bulk viscosity changes in the presence of model PPIs could not explain their crystal growth inhibitory effects. At 0.05% w/w, PVP (133-fold) and HPMC (28-fold) were better crystal growth inhibitors than HP-β-CD at high S. The inhibitory effect of HP-β-CD on the bulk diffusion-controlled indomethacin crystal growth at high S was successfully modeled using reactive diffusion layer theory, which assumes reversible complexation in the diffusion layer. Although HP-β-CD only modestly inhibited indomethacin crystal growth at either high S (∼15%) or low S (∼2-fold), the crystal growth inhibitory effects of PVP and HPMC were more dramatic, particularly at high S (0.05% w/w). The superior crystal growth inhibitory effects of PVP and HPMC as compared with HP-β-CD at high S were attributed to a change in the indomethacin crystal growth rate-limiting step from bulk diffusion to surface integration. Indomethacin crystal growth inhibitory effects of all three model PPIs at low S were attributed to retardation of the rate of surface integration of indomethacin, a phenomenon that may reflect the adsorption of PPIs onto the growing crystal surface. The quantitative approaches outlined in this study should be useful in future studies to develop tools to predict supersaturation maintenance effects of PPIs.

Protein crystal growth in low gravity

NASA Technical Reports Server (NTRS)

Feigelson, Robert S.

1993-01-01

This Final Technical Report for NASA Grant NAG8-774 covers the period from April 27, 1989 through December 31, 1992. It covers five main topics: fluid flow studies, the influence of growth conditions on the morphology of isocitrate lyase crystals, control of nucleation, the growth of lysozyme by the temperature gradient method and graphoepitaxy of protein crystals. The section on fluid flow discusses the limits of detectability in the Schlieren imaging of fluid flows around protein crystals. The isocitrate lyase study compares crystals grown terrestrially under a variety of conditions with those grown in space. The controlling factor governing the morphology of the crystals is the supersaturation. The lack of flow in the interface between the drop and the atmosphere in microgravity causes protein precipitation in the boundary layer and a lowering of the supersaturation in the drop. This lowered supersaturation leads to improved crystal morphology. Preliminary experiments with lysozyme indicated that localized temperature gradients could be used to nucleate crystals in a controlled manner. An apparatus (thermonucleator) was designed to study the controlled nucleation of protein crystals. This apparatus has been used to nucleate crystals of materials with both normal (ice-water, Rochelle salt and lysozyme) and retrograde (horse serum albumin and alpha chymotrypsinogen A) solubility. These studies have lead to the design of an new apparatus that small and more compatible with use in microgravity. Lysozyme crystals were grown by transporting nutrient from a source (lysozyme powder) to the crystal in a temperature gradient. The influence of path length and cross section on the growth rate was demonstrated. This technique can be combined with the thermonucleator to control both nucleation and growth. Graphoepitaxy utilizes a patterned substrate to orient growing crystals. In this study, silicon substrates with 10 micron grooves were used to grow crystals of catalase, lysozyme and canavalin. In all cases, the crystals grew oriented to the substrate. The supersaturation needed for nucleation and growth was lower on the patterned substrates. In some cases, isolated, large crystals were grown.

Differentiating Calcium Oxalate and Hydroxyapatite Stones In Vivo Using Dual-Energy CT and Urine Supersaturation and pH Values

PubMed Central

Liu, Yu; Qu, Mingliang; Carter, Rickey E.; Leng, Shuai; Ramirez-Giraldo, Juan Carlos; Jaramillo, Giselle; Krambeck, Amy E.; Lieske, John C.; Vrtiska, Terri J.; McCollough, Cynthia H.

2014-01-01

Rationale and Objectives Knowledge of urinary stone composition can guide therapeutic intervention for patients with calcium oxalate (CaOx) or hydroxyapatite (HA) stones. In this study, we determined the accuracy of noninvasive differentiation of these two stone types using dual-energy CT (DECT) and urine supersaturation (SS) and pH values. Materials and Methods Patients who underwent clinically indicated DECT scanning for stone disease and subsequent surgical intervention were enrolled. Stone composition was determined using infrared spectroscopy. DECT images were processed using custom-developed software that evaluated the ratio of CT numbers between low- and high-energy images. Clinical information, including patient age, gender, and urine pH and supersaturation profile, was obtained from electronic medical records. Simple and multiple logistic regressions were used to determine if the ratio of CT numbers could discriminate CaOx from HA stones alone or in conjunction with urine supersaturation and pH. Results Urinary stones (CaOx n = 43, HA n = 18) from 61 patients were included in this study. In a univariate model, DECT data, urine SS-HA, and urine pH had an area under the receiver operating characteristic curve of 0.78 (95% confidence interval [CI] 0.66–0.91, P = .016), 0.76 (95%CI 0.61–0.91, P = .003), and 0.60 (95% CI 0.44–0.75, P = .20), respectively, for predicting stone composition. The combination of CT data and the urinary SS-HA had an area under the receiver operating characteristic curve of 0.79 (95%CI 0.66–0.92, P = .007) for correctly differentiating these two stone types. Conclusions DECT differentiated between CaOx and HA stones similarly to SS-HA, whereas pH was a poor discriminator. The combination of DECT and urine SS or pH data did not improve this performance. PMID:24200478

In situ molecular elucidation of drug supersaturation achieved by nano-sizing and amorphization of poorly water-soluble drug.

PubMed

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

2015-09-18

Quantitative evaluation of drug supersaturation and nanoparticle formation was conducted using in situ evaluation techniques, including nuclear magnetic resonance (NMR) spectroscopy. We prepared a ternary complex of carbamazepine (CBZ) with hydroxypropyl methylcellulose (HPMC) and sodium dodecyl sulfate (SDS) to improve the drug concentration. Different preparation methods, including grinding and spray drying, were performed to prepare the ternary component products, ground mixture (GM) and spray-dried sample (SD), respectively. Although CBZ was completely amorphized in the ternary SD, CBZ was partially amorphized with the remaining CBZ crystals in the ternary GM. Aqueous dispersion of the ternary GM formed nanoparticles of around 150 nm, originating from the CBZ crystals in the ternary GM. In contrast, the ternary SD formed transparent solutions without a precipitate. The molecular-level evaluation using NMR measurements revealed that approximately half a dose of CBZ in the ternary GM dispersion was present as nanoparticles; however, CBZ in the ternary SD was completely dissolved in the aqueous solution. The characteristic difference between the solid states, followed by different preparation methods, induced different solution characteristics in the ternary GM and SD. The permeation study, using a dialysis membrane, showed that the CBZ concentration dissolved in the bulk water phase rapidly reduced in the ternary SD dispersion compared to the ternary GM dispersion; this demonstrated the advantage of ternary GM dispersion in the maintenance of CBZ supersaturation. Long-term maintenance of a supersaturated state of CBZ observed in the ternary GM dispersion rather than in the ternary SD dispersion was achieved by the inhibition of CBZ crystallization owing to the existence of CBZ nanoparticles in the ternary GM dispersion. Nanoparticle formation, combined with drug amorphization, could be a promising approach to improve drug concentrations. The detailed elucidation of solution characteristics using in situ evaluation techniques will lead to the formation of useful solid dispersion and nanoparticle formulations, resulting in improved drug absorption. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigating ice nucleation in cirrus clouds with an aerosol-enabled Multiscale Modeling Framework

DOE PAGES

Zhang, Chengzhu; Wang, Minghuai; Morrison, H.; ...

2014-11-06

In this study, an aerosol-dependent ice nucleation scheme [Liu and Penner, 2005] has been implemented in an aerosol-enabled multi-scale modeling framework (PNNL MMF) to study ice formation in upper troposphere cirrus clouds through both homogeneous and heterogeneous nucleation. The MMF model represents cloud scale processes by embedding a cloud-resolving model (CRM) within each vertical column of a GCM grid. By explicitly linking ice nucleation to aerosol number concentration, CRM-scale temperature, relative humidity and vertical velocity, the new MMF model simulates the persistent high ice supersaturation and low ice number concentration (10 to 100/L) at cirrus temperatures. The low ice numbermore » is attributed to the dominance of heterogeneous nucleation in ice formation. The new model simulates the observed shift of the ice supersaturation PDF towards higher values at low temperatures following homogeneous nucleation threshold. The MMF models predict a higher frequency of midlatitude supersaturation in the Southern hemisphere and winter hemisphere, which is consistent with previous satellite and in-situ observations. It is shown that compared to a conventional GCM, the MMF is a more powerful model to emulate parameters that evolve over short time scales such as supersaturation. Sensitivity tests suggest that the simulated global distribution of ice clouds is sensitive to the ice nucleation schemes and the distribution of sulfate and dust aerosols. Simulations are also performed to test empirical parameters related to auto-conversion of ice crystals to snow. Results show that with a value of 250 μm for the critical diameter, Dcs, that distinguishes ice crystals from snow, the model can produce good agreement to the satellite retrieved products in terms of cloud ice water path and ice water content, while the total ice water is not sensitive to the specification of Dcs value.« less

Raman spectroscopic studies on single supersaturated droplets of sodium and magnesium acetate.

PubMed

Wang, Liang-Yu; Zhang, Yun-Hong; Zhao, Li-Jun

2005-02-03

Raman spectroscopy was used to study structural changes, in particular, the formation of contact-ion pairs in supersaturated aqueous NaCH(3)COO and Mg(CH(3)COO)(2) droplets at ambient temperatures. The single droplets levitated in an electrodynamic balance (EDB), lost water, and became supersaturated when the relative humidity (RH) decreased. For NaCH(3)COO droplet the water-to-solute molar ratio (WSR) was 3.87 without solidification when water molecules were not enough to fill in the first hydration layer of Na(+), in favor of the formation of contact-ion pairs. However, the symmetric stretching vibration band (nu(3) mode) of free -COO(-) constantly appeared at 1416 cm(-1), and no spectroscopic information related to monodentate, bidentate, or bridge bidentate contact-ion pairs was observed due to the weak interactions between the Na(+) and acetate ion. On the other hand, the band of methyl deformation blue shifted from 1352 to 1370 cm(-1) (at RH = 34.2%, WSR = 2.43), corresponding to the solidification process of a novel metastable phase in the highly supersaturated solutions. With further decreasing RH, a small amount of supersaturated solution still existed and was proposed to be hermetically covered by the metastable phase of the particle. In contrast, the interaction between Mg(2+) and acetate ion is much stronger. When WSR decreased from 21.67 to 2.58 for the Mg(CH(3)COO)(2) droplet, the band of C-C-symmetric stretching (nu(4) mode) had a blue shift from 936 to 947 cm(-1). The intensity of the two new shoulders (approximately 1456 and approximately 1443 cm(-1)) of the nu(3) band of free -COO(-) at 1420 cm(-1) increased with the decrease of WSR. These changes were attributed to the formation of contact-ion pairs with bidentate structures. In particular, the small frequency difference between the shoulder at approximately 1443 cm(-1) and the nu(3) band of the free -COO(-) group (approximately 1420 cm(-1)) was proposed to be related to the formation of a chain structure based on the contact-ion pairs of bridge bidentate. The continuous formation of various contact-ion pairs started at higher WSR value (WSR = 15.5) greatly reduced the hygroscopic properties of Mg(CH(3)COO)(2) droplet, so that the WSR of Mg(CH(3)COO)(2) droplets was even lower than that of NaCH(3)COO in the RH range of 40-60%.

Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

NASA Astrophysics Data System (ADS)

Rossi, Carlos; Lozano, Rafael P.

2016-11-01

Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO32- concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at ≈1.1 mol/mol. Within the analyzed ranges of pH (8.2-8.6), CO32- concentration (1-6 mg/L), supersaturation (SIaragonite: 0.08-1.08; SIcalcite: 0.23-1.24), drip rate (0.2-81 drops/min) and dissolved Zn (6-90 μg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above ∼1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at ∼11 °C from dripwaters with initial Mg/Ca approaching ∼1.1 incorporate ∼5 mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is favored from a solubility viewpoint. We also show that unaccounted CaCO3 precipitation in intermediate sampling containers and splash effects may in cases result in underestimating dripwater Ca concentration and alkalinity, potentially leading to incorrect conclusions regarding the role of fluid Mg/Ca ratio and supersaturation on CaCO3 mineralogy. A simple way to elude the first effect is by taking water samples directly from stalactites and by titrating alkalinity in the same containers used to collect dripwaters.

Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

DOEpatents

Anderson, Iver E.; Lograsso, Barbara K.; Ellis, Timothy W.

1994-01-01

A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material.

Oxygen budget of a perennially ice-covered Antarctic lake

NASA Technical Reports Server (NTRS)

Wharton, R. A., Jr.; Mckay, C. P.; Simmons, G. M., Jr.; Parker, B. C.

1986-01-01

A bulk O2 budget for Lake Hoare, Antarctica, is presented. Five years of seasonal data show the lake to be persistently supersaturated with O2. Oxygen is carried into the lake in glacial meltstreams and is left behind when this water is removed as ice by ablation and sublimation. A diffusive loss of O2 from the lake through the summer moat is suggested. Measured values of the total O2 in the water column indicate that the time scale of O2 turnover is much longer than a year. Based on these results, it is suggested that the amount of O2 in the water does not change significantly throughout the year and that the lake is also supersaturated with N2.

Ice Particle Growth Under Conditions of the Upper Troposphere

NASA Technical Reports Server (NTRS)

Peterson, Harold S.; Bailey, Matthew; Hallett, John

2010-01-01

Atmospheric conditions for growth of ice crystals (temperature and ice supersaturation) are often not well constrained and it is necessary to simulate such conditions in the laboratory to investigate such growth under well controlled conditions over many hours. The growth of ice crystals from the vapour in both prism and basal planes was observed at temperatures of -60 C and -70 C under ice supersaturation up to 100% (200% relative humidity) at pressures derived from the standard atmosphere in a static diffusion chamber. Crystals grew outward from a vertical glass filament, thickening in the basal plane by addition of macroscopic layers greater than 2 microns, leading to growth in the prism plane by passing of successive layers conveniently viewed by time lapse video.

Ice Particle Growth Rates Under Upper Troposphere Conditions

NASA Technical Reports Server (NTRS)

Peterson, Harold; Bailey, Matthew; Hallett, John

2010-01-01

Atmospheric conditions for growth of ice crystals (temperature and ice supersaturation) are often not well constrained and it is necessary to simulate such conditions in the laboratory to investigate such growth under well controlled conditions over many hours. The growth of ice crystals from the vapour in both prism and basal planes was observed at temperatures of -60 C and -70 C under ice supersaturation up to 100% (200% relative humidity) at pressures derived from the standard atmosphere in a static diffusion chamber. Crystals grew outward from a vertical glass filament, thickening in the basal plane by addition of macroscopic layers greater than 2 m, leading to growth in the prism plane by passing of successive layers conveniently viewed by time lapse video.

Ice Crystal Growth Rates Under Upper Troposphere Conditions

NASA Technical Reports Server (NTRS)

Peterson, Harold S.; Bailey, Matthew; Hallett, John

2010-01-01

Atmospheric conditions for growth of ice crystals (temperature and ice supersaturation) are often not well constrained and it is necessary to simulate such conditions in the laboratory to investigate such growth under well controlled conditions over many hours. The growth of ice crystals from the vapour in both prism and basal planes was observed at temperatures of -60 C and -70 C under ice supersaturation up to 100% (200% relative humidity) at pressures derived from the standard atmosphere in a static diffusion chamber. Crystals grew outward from a vertical glass filament, thickening in the basal plane by addition of macroscopic layers greater than 2 m, leading to growth in the prism plane by passing of successive layers conveniently viewed by time lapse video.

Ground based experiments on the growth and characterization of L-Arginine Phosphate (LAP) crystals

NASA Technical Reports Server (NTRS)

Rao, S. M.; Cao, C.; Batra, A. K.; Lal, R. B.; Mookherji, T. K.

1991-01-01

L-Arginine Phosphate (LAP) is a new nonlinear optical material with higher efficiency for harmonic generation compared to KDP. Crystals of LAP were grown in the laboratory from supersaturated solutions by temperature lowering technique. Investigations revealed the presence of large dislocation densities inside the crystals which are observed to produce refractive index changes causing damage at high laser powers. This is a result of the convection during crystal growth from supersaturated solutions. It is proposed to grow these crystals in a diffusion controlled growth condition under microgravity environment and compare the crystals grown in space with those grown on ground. Physical properties of the solutions needed for modelling of crystal growth are also presented.

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

Fan, Jiwen; Rosenfeld, Daniel; Zhang, Yuwei

Aerosol-cloud interactions remain the largest uncertainty in climate projections. Ultrafine aerosol particles smaller than 50 nanometers (UAP <50) can be abundant in the troposphere, but are conventionally considered too small to affect cloud formation. However, observational evidence and numerical simulations of deep convective clouds (DCCs) over the Amazon show that DCCs forming in a low aerosol environment can develop very large vapor supersaturation because fast droplet coalescence reduces integrated droplet surface area and subsequent condensation. UAP <50 from pollution plumes that are ingested into such clouds can be activated to form additional cloud droplets on which excess supersaturation condenses andmore » forms additional cloud water and latent heating, thus intensifying convective strength. This mechanism suggests a strong anthropogenic invigoration of DCCs in previously pristine regions of the world.« less

Influence of the supersaturation on the nucleation-growth process of scale electrodeposition by in situ observation through a transparent quartz crystal microbalance.

PubMed

Devos, O; Gabrielli, C; Tribollet, B

2004-01-01

An original technique allowed three in situ measurements to be obtained simultaneously, i.e. electrochemical and mass measurements and a microscope image of the interface between electrode and solution. The nucleation-growth process of CaCO3 deposition was investigated by varying different parameters which influenced the supersaturation coefficient, the Ca2+ concentration, pH and convection of the carbonically pure water near the substrate. The results showed that the variation of the scaling rate was due, for the two first cases, to an influence of the nucleation process whereas for the last case, the kinetics of scale deposition were modified by a shift of the growth rate.

The occurence of uric acids and the growth morphology of the anhydrous monoclinic modification : C 5H 4N 4O 3

NASA Astrophysics Data System (ADS)

Rinaudo, C.; Boistelle, R.

1980-07-01

Anhydrous and hydrated uric acid crystals which frequently occur in human urolithiasis have been grown from pure aqueous solutions at 25 and 37°C. The appearance domain of either modification is given as a function of initial uric acid concentration at pH values ranging from 3.0 to 5.5. The present paper mostly deals with the anhydrous phase and it is shown that its experimental and theoretical growth morphologies are in agreement, the crystals exhibiting the {100}, {210}, {121}, {001} and {201} forms. Crystal habit depends on supersaturation; {100} has always the largest extension at low supersaturation {121} develops to the detriment of {210}, {001} and {201}.

Effects of temperature and pressure on the nucleation and growth of silver clusters from supersaturated vapor: A molecular dynamics analysis

NASA Astrophysics Data System (ADS)

Wang, Qin; Xie, Hui; Chen, Yongshi; Liu, Chao

2017-04-01

The nucleation and growth of silver nanoparticles in the supersaturated system are investigated by molecular dynamics simulation at different temperatures and pressures. The variety of the atoms in the biggest cluster and the size of average clusters in the system versus the time are estimated to reveal the relationship between the nucleation as well as cluster growth. The nucleation rates in different situations are calculated with the threshold method. The effect of temperature and pressure on the nucleation rate is identified as obeying a linear function. Finally, the development of basal elements, such as monomers, dimers and trimmers, is revealed how the temperature and pressure affect the nucleation and growth of the silver cluster.

Can Solution Supersaturation Affect Protein Crystal Quality?

NASA Technical Reports Server (NTRS)

Gorti, Sridhar

2013-01-01

The formation of large protein crystals of "high quality" is considered a characteristic manifestation of microgravity. The physical processes that predict the formation of large, high quality protein crystals in the microgravity environment of space are considered rooted in the existence of a "depletion zone" in the vicinity of crystal. Namely, it is considered reasonable that crystal quality suffers in earth-grown crystals as a result of the incorporation of large aggregates, micro-crystals and/or large molecular weight "impurities", processes which are aided by density driven convective flow or mixing at the crystal-liquid interface. Sedimentation and density driven convection produce unfavorable solution conditions in the vicinity of the crystal surface, which promotes rapid crystal growth to the detriment of crystal size and quality. In this effort, we shall further present the hypothesis that the solution supersaturatoin at the crystal surface determines the growth mechanism, or mode, by which protein crystals grow. It is further hypothesized that protein crystal quality is affected by the mechanism or mode of crystal growth. Hence the formation of a depletion zone in microgravity environment is beneficial due to inhibition of impurity incorporatoin as well as preventing a kinetic roughening transition. It should be noted that for many proteins the magnitude of neither protein crystal growth rates nor solution supersaturation are predictors of a kinetic roughening transition. That is, the kinetic roughening transition supersaturation must be dtermined for each individual protein.

Development and Implementation of an Optimization Model for Hydropower and Total Dissolved Gas in the Mid-Columbia River System

DOE PAGES

Witt, Adam; Magee, Timothy; Stewart, Kevin; ...

2017-08-10

Managing energy, water, and environmental priorities and constraints within a cascade hydropower system is a challenging multiobjective optimization effort that requires advanced modeling and forecasting tools. Within the mid-Columbia River system, there is currently a lack of specific solutions for predicting how coordinated operational decisions can mitigate the impacts of total dissolved gas (TDG) supersaturation while satisfying multiple additional policy and hydropower generation objectives. In this study, a reduced-order TDG uptake equation is developed that predicts tailrace TDG at seven hydropower facilities on the mid-Columbia River. The equation is incorporated into a general multiobjective river, reservoir, and hydropower optimization toolmore » as a prioritized operating goal within a broader set of system-level objectives and constraints. A test case is presented to assess the response of TDG and hydropower generation when TDG supersaturation is optimized to remain under state water-quality standards. Satisfaction of TDG as an operating goal is highly dependent on whether constraints that limit TDG uptake are implemented at a higher priority than generation requests. According to the model, an opportunity exists to reduce TDG supersaturation and meet hydropower generation requirements by shifting spillway flows to different time periods. In conclusion, a coordinated effort between all project owners is required to implement systemwide optimized solutions that satisfy the operating policies of all stakeholders.« less

The artificial membrane insert system as predictive tool for formulation performance evaluation.

PubMed

Berben, Philippe; Brouwers, Joachim; Augustijns, Patrick

2018-02-15

In view of the increasing interest of pharmaceutical companies for cell- and tissue-free models to implement permeation into formulation testing, this study explored the capability of an artificial membrane insert system (AMI-system) as predictive tool to evaluate the performance of absorption-enabling formulations. Firstly, to explore the usefulness of the AMI-system in supersaturation assessment, permeation was monitored after induction of different degrees of loviride supersaturation. Secondly, to explore the usefulness of the AMI-system in formulation evaluation, a two-stage dissolution test was performed prior to permeation assessment. Different case examples were selected based on the availability of in vivo (intraluminal and systemic) data: (i) a suspension of posaconazole (Noxafil ® ), (ii) a cyclodextrin-based formulation of itraconazole (Sporanox ® ), and (iii) a micronized (Lipanthyl ® ) and nanosized (Lipanthylnano ® ) formulation of fenofibrate. The obtained results demonstrate that the AMI-system is able to capture the impact of loviride supersaturation on permeation. Furthermore, the AMI-system correctly predicted the effects of (i) formulation pH on posaconazole absorption, (ii) dilution on cyclodextrin-based itraconazole absorption, and (iii) food intake on fenofibrate absorption. Based on the applied in vivo/in vitro approach, the AMI-system combined with simple dissolution testing appears to be a time- and cost-effective tool for the early-stage evaluation of absorption-enabling formulations. Copyright © 2017 Elsevier B.V. All rights reserved.

The effects of dissolved gas supersaturation on white sturgeon larvae

USGS Publications Warehouse

Counihan, T.D.; Miller, Allen I.; Mesa, M.G.; Parsley, M.J.

2000-01-01

Spill at dams has caused supersaturation of atmospheric gas in waters of the Columbia and Snake rivers and raised concerns about the effects of dissolved gas supersaturation (DGS) on white sturgeons Acipenser transmontanus. The timing and location of white sturgeon spawning and the dispersal of white sturgeon larvae from incubation areas makes the larval stage potentially vulnerable to the effects of DGS. To assess the effects of DGS on white sturgeon larvae, we exposed larvae to mean total dissolved gas (TDG) levels of 118% and 131% saturation in laboratory bioassay tests. Gas bubble trauma (GBT) was manifested as a gas bubble in the buccal cavity, nares, or both and it first occurred at developmental stages characterized by the formation of the mouth and gills. Exposure times of 15 min were sufficient to elicit these signs in larvae in various stages of development. No mortality was observed in larvae exposed to 118% TDG for 10 d, but 50% mortality occurred after a 13-d exposure to 131% TDG. The signs of GBT we observed resulted in positive buoyancy and alterations in behavior that may affect the dispersal and predation vulnerability of white sturgeon larvae. The exact depth distribution of dispersing white sturgeon larvae in the Columbia River currently is unknown. Thus, our results may represent a worst-case scenario if white sturgeon larvae are dispersed at depths with insufficient hydrostatic pressure to compensate for high TDG levels.

Photoacoustic assay for probing amyloid formation: feasibility study

NASA Astrophysics Data System (ADS)

Petrova, Elena; Yoon, Soon Joon; Pelivanov, Ivan; O'Donnell, Matthew

2018-02-01

The formation of amyloid - aggregate of misfolded proteins - is associated with more than 50 human pathologies, including Alzheimer's disease, Parkinson's disease, and Type 2 diabetes mellitus. Investigating protein aggregation is a critical step in drug discovery and development of therapeutics targeted to these pathologies. However, screens to identify protein aggregates are challenging due to the stochastic character of aggregate nucleation. Here we employ photoacoustics (PA) to screen thermodynamic conditions and solution components leading to formation of protein aggregates. Particularly, we study the temperature dependence of the Gruneisen parameter in optically-contrasted, undersaturated and supersaturated solutions of glycoside hydrolase (lysozyme). As nucleation of protein aggregates proceeds in two steps, where the first is liquid-liquid separation (rearrangement of solute's density), the PA response from complex solutions and its temperature-dependence monitor nucleation and differentiate undersaturated and supersaturated protein solutions. We demonstrate that in the temperature range from 22 to 0° C the PA response of contrasted undersaturated protein solution behaves similar to water and exhibits zero thermal expansion at 4°C or below, while the response of contrasted supersaturated protein solution is nearly temperature independent, similar to the behavior of oils. These results can be used to develop a PA assay for high-throughput screening of multi-parametric conditions (pH, ionic strength, chaperone, etc.) for protein aggregation that can become a key tool in drug discovery, targeting aggregate formation for a variety of amyloids.

Compositions of supersaturated solutions for enhanced growth of {alpha}-NiSO{sub 4} . 6H{sub 2}O, Me{sub 2}Ni(SO{sub 4}){sub 2} . 6H{sub 2}O, MeH{sub 2}PO{sub 4} [Me = Li, Na, K, Rb, Cs, NH{sub 4}], and K(H{sub x}D{sub 1-x}){sub 2}PO{sub 4} single crystals

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

Soboleva, L. V., E-mail: afkonst@ns.crys.ras.ru

2008-05-15

The possibility of determining the optimal compositions and temperatures of supersaturated solutions for enhanced growth of single crystals of congruently and incongruently dissolving solid phases from the solubility diagrams of ternary systems is shown, and this approach is justified. The NiSO{sub 4}-H{sub 2}SO{sub 4}-H{sub 2}O, Me{sub 2}SO{sub 4}-NiSO{sub 4}-H{sub 2}O, and Me{sub 2}O-P{sub 2}O{sub 5}-H{sub 2}O(D{sub 2}O) systems have been used to determine the optimal compositions and temperatures of supersaturated solutions for growth of {alpha}-NiSO{sub 4} . 6H{sub 2}O, Me{sub 2}Ni(SO{sub 4}){sub 2} . 6H{sub 2}O, MeH{sub 2}PO{sub 4} [Me = Li, Na, K, Rb, Cs, NH{sub 4}], and Kmore » (H{sub x} D{sub 1-x}){sub 2}PO{sub 4} (D is deuterium) single crystals.« less

Understanding the Differences Between Cocrystal and Salt Aqueous Solubilities.

PubMed

Cavanagh, Katie L; Maheshwari, Chinmay; Rodríguez-Hornedo, Naír

2018-01-01

This work challenges the popular notion that pharmaceutical salts are more soluble than cocrystals. There are cocrystals that are more soluble than salt forms of a drug and vice-versa. It all depends on the interplay between the chemistry of both the solid and solution phases. Aqueous solubility, pH max , and supersaturation index (SA = S CC /S D or S salt /S D ) of cocrystals and salts of a basic drug, lamotrigine (LTG), were determined, and mathematical models that predict the influence of cocrystal/salt K sp and K a were derived. K sp and SA followed the order LTG-nicotinamide cocrystal (18) > LTG-HCl salt (12) > LTG-saccharin salt (5) > LTG-methylparaben cocrystal (1) > LTG-phenobarbital cocrystal (0.2). The values in parenthesis represent SA under nonionizing conditions. Cocrystal/salt solubility and thermodynamic stability are determined by pH and will drastically change with a single unit change in pH. pH max values ranged from 5.0 (saccharin salt) to 6.4 (methylparaben cocrystal) to 9.0 (phenobarbital cocrystal). Cocrystal/salt pH max dependence on pK sp and pK a shows that cocrystals and salts exhibit different behavior. Solubility and pH max are as important as supersaturation index in assessing the stability and risks associated with conversions of supersaturating forms. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Amelogenin-assisted ex vivo remineralization of human enamel: effects of supersaturation degree and fluoride concentration

PubMed Central

Fan, Yuwei; Nelson, James R.; Alvarez, Jason R.; Hagan, Joseph; Berrier, Allison; Xu, Xiaoming

2011-01-01

The formation of organized nanocrystals that resemble enamel is crucial for successful enamel remineralization. Calcium, phosphate and fluoride ions and amelogenin are important ingredients for the formation of organized hydroxyapatite (HAP) crystals in vitro. However, the effects of these remineralization agents on the enamel crystal morphology have not been thoroughly studied. The objective of this study was to investigate the effects of fluoride ions, supersaturation degree and amelogenin on the crystal morphology and organization of ex vivo remineralized human enamel. Extracted third molars were sliced thin and acid-etched to provide the enamel surface for immersion in different remineralization solutions. The crystal morphology and mineral phase of the remineralized enamel surface were analyzed by FE-SEM, ATR-FTIR and XRD. The concentration of fluoride and supersaturation degree of hydroxyapatite had significant effects on the crystal morphology and crystal organization, which varied from plate-like loose crystals to rod-like densely packed nanocrystal arrays. Densely packed arrays of fluoridated hydroxyapatite nanorods were observed under the following conditions: σ(HAP) = 10.2±2.0 with fluoride 1.5±0.5 mg/L and amelogenin 40±10 µg/mL, pH 6.8±0.4. A phase diagram summarized the conditions that form dense or loose hydroxyapatite nanocrystal structures. This study provides the basis for the development of novel dental materials for caries management. PMID:21256987

Development and Implementation of an Optimization Model for Hydropower and Total Dissolved Gas in the Mid-Columbia River System

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

Witt, Adam; Magee, Timothy; Stewart, Kevin

Managing energy, water, and environmental priorities and constraints within a cascade hydropower system is a challenging multiobjective optimization effort that requires advanced modeling and forecasting tools. Within the mid-Columbia River system, there is currently a lack of specific solutions for predicting how coordinated operational decisions can mitigate the impacts of total dissolved gas (TDG) supersaturation while satisfying multiple additional policy and hydropower generation objectives. In this study, a reduced-order TDG uptake equation is developed that predicts tailrace TDG at seven hydropower facilities on the mid-Columbia River. The equation is incorporated into a general multiobjective river, reservoir, and hydropower optimization toolmore » as a prioritized operating goal within a broader set of system-level objectives and constraints. A test case is presented to assess the response of TDG and hydropower generation when TDG supersaturation is optimized to remain under state water-quality standards. Satisfaction of TDG as an operating goal is highly dependent on whether constraints that limit TDG uptake are implemented at a higher priority than generation requests. According to the model, an opportunity exists to reduce TDG supersaturation and meet hydropower generation requirements by shifting spillway flows to different time periods. In conclusion, a coordinated effort between all project owners is required to implement systemwide optimized solutions that satisfy the operating policies of all stakeholders.« less

UV-vis Imaging of Piroxicam Supersaturation, Precipitation, and Dissolution in a Flow-Through Setup.

PubMed

Sun, Yu; Chapman, Alex; Larsen, Susan W; Jensen, Henrik; Petersen, Nickolaj J; Goodall, David M; Østergaard, Jesper

2018-06-05

Evaluation of drug precipitation is important in order to address challenges regarding low and variable bioavailability of poorly water-soluble drugs, to assess potential risk of patient safety with infusion therapy, and to explore injectable in situ suspension-forming drug delivery systems. Generally, drug precipitation is assessed in vitro through solution concentration analysis methods. Dual-wavelength UV-vis imaging is a novel imaging technique that may provide an opportunity for simultaneously monitoring changes in both solution and solid phases during precipitation. In the present study, a multimodal approach integrating UV-vis imaging, light microscopy, and Raman spectroscopy was developed for characterization of piroxicam supersaturation, precipitation, and dissolution in a flow-through setup. A solution of piroxicam dissolved in 1-methyl-2-pyrrolidinone was injected into a flowing aqueous environment (pH 7.4), causing piroxicam to precipitate. Imaging at 405 and 280 nm monitored piroxicam concentration distributions during precipitation and revealed different supersaturation levels dependent on the initial concentration of the piroxicam solution. The combination with imaging at 525 nm, light microscopy, and Raman spectroscopy measurements demonstrated concentration-dependent precipitation and the formation, growth, and dissolution of individual particles. Results emphasize the importance of the specific hydrodynamic conditions on the piroxicam precipitation. The approach used may facilitate comprehensive understanding of drug precipitation and dissolution processes and may be developed further into a basic tool for formulation screening and development.

Enhanced oral bioavailability of valsartan using a polymer-based supersaturable self-microemulsifying drug delivery system.

PubMed

Yeom, Dong Woo; Chae, Bo Ram; Son, Ho Yong; Kim, Jin Han; Chae, Jun Soo; Song, Seh Hyon; Oh, Dongho; Choi, Young Wook

2017-01-01

A novel, supersaturable self-microemulsifying drug delivery system (S-SMEDDS) was successfully formulated to enhance the dissolution and oral absorption of valsartan (VST), a poorly water-soluble drug, while reducing the total quantity for administration. Poloxamer 407 is a selectable, supersaturating agent for VST-containing SMEDDS composed of 10% Capmul ® MCM, 45% Tween ® 20, and 45% Transcutol ® P. The amounts of SMEDDS and Poloxamer 407 were chosen as formulation variables for a 3-level factorial design. Further optimization was established by weighting different levels of importance on response variables for dissolution and total quantity, resulting in an optimal S-SMEDDS in large quantity (S-SMEDDS_LQ; 352 mg in total) and S-SMEDDS in reduced quantity (S-SMEDDS_RQ; 144.6 mg in total). Good agreement was observed between predicted and experimental values for response variables. Consequently, compared with VST powder or suspension and SMEDDS, both S-SMEDDS_LQ and S-SMEDDS_RQ showed excellent in vitro dissolution and in vivo oral bioavailability in rats. The magnitude of dissolution and absorption-enhancing capacities using quantity-based comparisons was in the order S-SMEDDS_RQ > S-SMEDDS_LQ > SMEDDS > VST powder or suspension. Thus, we concluded that, in terms of developing an effective SMEDDS preparation with minimal total quantity, S-SMEDDS_RQ is a promising candidate.

A comparative study of vitamin E TPGS/HPMC supersaturated system and other solubilizer/polymer combinations to enhance the permeability of a poorly soluble drug through the skin.

PubMed

Ghosh, Indrajit; Michniak-Kohn, Bozena

2012-11-01

In transdermal drug delivery systems (TDDS), it is a challenge to achieve stable and prolonged high permeation rates across skin, because the concentration of the drug dissolved in the matrix has to be high in order to maintain zero order release kinetics of the drug. In case of poorly soluble drugs, due to thermodynamic challenges, there is a high tendency for the drug to nucleate immediately after formulating or even during storage. The present study focuses on the efficiency of vitamin E TPGS/HPMC supersaturated solution and other solubilizer/polymer systems to improve the solubility of the drug and inhibit crystal growth in the transdermal formulation. Effect of several solubilizers, for example, Pluronic F-127, vitamin E TPGS and co-solvent, for example, propylene glycol (PG) were studied on the supersaturated systems of ibuprofen as model drug. Various stabilizers such as hydroxylpropyl methylcellulose (HPMC 3 cps) and polyvinylpyrrolidone (PVP K-30) were examined to evaluate their crystal inhibitory effects. Different analytical tools were used in this study to detect the growth of crystals in the systems. Vitamin E TPGS and HPMC 3 cps formulation produced the highest permeation rate of the drug as compared to other systems. In addition, the onset of crystallization time was shown to be longer with this formulation as compared to other solubilizer/polymer combinations.

Impurity effect of iron(III) on the growth of potassium sulfate crystal in aqueous solution

NASA Astrophysics Data System (ADS)

Kubota, Noriaki; Katagiri, Ken-ichi; Yokota, Masaaki; Sato, Akira; Yashiro, Hitoshi; Itai, Kazuyoshi

1999-01-01

Growth rates of the {1 1 0} faces of a potassium sulfate crystal were measured in a flow cell in the presence of traces of impurity Fe(III) (up to 2 ppm) over the range of pH=2.5-6.0. The growth rate was significantly suppressed by the impurity. The effect became stronger as the impurity concentration was increased and at pH<5. It became weaker with increasing supersaturation. It also became weaker as the pH was increased and at pH>5 it finally disappeared completely. The concentration and supersaturation effects on the impurity action were reasonably explained with a model proposed by Kubota and Mullin [J. Crystal Growth, 152 (1995) 203]. The surface coverage of the active sites by Fe(III) is estimated to increase linearly on increasing its concentration in solution in the range examined by growth experiments. The impurity effectiveness factor is confirmed to increase inversely proportional to the supersaturation as predicted by the model. Apart from the discussion based on the model, the pH effect on the impurity action is qualitatively explained by assuming that the first hydrolysis product of aqua Fe(III) complex compound, [Fe(H 2O) 5(OH)] 2+, is both growth suppression and adsorption active, but the second hydrolysis product, [Fe(H 2O) 4(OH) 2] +, is only adsorption active.

Nitrous oxide measurements in the eastern tropical Pacific Ocean

NASA Technical Reports Server (NTRS)

Pierotti, D.; Rasmussen, R. A.

1980-01-01

The paper considers nitrous oxide measurements in the eastern tropical Pacific Ocean. The concentration of N2O in the marine air showed a direct relationship to the N2O in the surface sea water, with the highest N2O mixing ratios over highly supersaturated regions; water samples were also collected down to depths of 300 m at seven hydrocast stations. The stations showed two distribution patterns for N2O concentration vs depth for the region between the surface and 300 m; two stations in the oxygen deficient region off the coast of Peru showed considerable N2O super-saturation at all depths, and results indicate that the role of N2O in the nitrogen cycle of the ocean may be more complex than previously suggested.

Crystallization of calcium sulfate dihydrate in the presence of some metal ions

NASA Astrophysics Data System (ADS)

Hamdona, Samia K.; Al Hadad, Umaima A.

2007-02-01

Crystallization of calcium sulfate dihydrate (CaSO 4·2H 2O gypsum) in sodium chloride solutions in the presence of some metal ions, and over a range of relative super-saturation has been studied. The addition of metal ions, even at relatively low concentration (10 -6 mol l -1), markedly retard the rate of crystallization of gypsum. Retardation effect was enhanced with increase in the additives contents. Moreover, the effect was enhanced as the relative super-saturation decreases. Influence of mixed additives on the rate of crystallization (Cd 2++Arg, Cd 2++H 3PO 4 and Cd 2++PAA) has also been studied. Direct adsorption experiments of these metal ions on the surface of gypsum crystals have been made for comparison.

Formation of an ascorbate-apatite composite layer on titanium.

PubMed

Ito, Atsuo; Sogo, Yu; Ebihara, Yuko; Onoguchi, Masahiro; Oyane, Ayako; Ichinose, Noboru

2007-09-01

An ascorbate-apatite composite layer was successfully formed on NaOH- and heat-treated titanium by coprecipitating L-ascorbic acid phosphate and low-crystalline apatite in a supersaturated calcium phosphate solution at 37 degrees C for 48 h. The supersaturated calcium phosphate solutions used have chemical compositions attainable by mixing infusion fluids officially approved for clinical use. The amount of immobilized L-ascorbic acid phosphate ranged from 1.0 to 2.3 microg mm(-2), which is most likely to be sufficient for the in vitro osteogenic differentiation of mesenchymal stem cells on titanium. Since ascorbate is important for the collagen synthesis and subsequent osteogenesis of mesenchymal stem cells, titanium coated with the ascorbate-apatite composite layer would be useful as a scaffold in bone tissue engineering and as a bone substitute.

Homogeneous nucleation in supersaturated vapors of methane, ethane, and carbon dioxide predicted by brute force molecular dynamics.

PubMed

Horsch, Martin; Vrabec, Jadran; Bernreuther, Martin; Grottel, Sebastian; Reina, Guido; Wix, Andrea; Schaber, Karlheinz; Hasse, Hans

2008-04-28

Molecular dynamics (MD) simulation is applied to the condensation process of supersaturated vapors of methane, ethane, and carbon dioxide. Simulations of systems with up to a 10(6) particles were conducted with a massively parallel MD program. This leads to reliable statistics and makes nucleation rates down to the order of 10(30) m(-3) s(-1) accessible to the direct simulation approach. Simulation results are compared to the classical nucleation theory (CNT) as well as the modification of Laaksonen, Ford, and Kulmala (LFK) which introduces a size dependence of the specific surface energy. CNT describes the nucleation of ethane and carbon dioxide excellently over the entire studied temperature range, whereas LFK provides a better approach to methane at low temperatures.

Crystal growth in a microgravity environment

NASA Technical Reports Server (NTRS)

Kroes, Roger L. (Inventor); Reiss, Donald A. (Inventor); Lehoczky, Sandor L. (Inventor)

1992-01-01

Gravitational phenomena, including convection, sedimentation, and interactions of materials with their containers all affect the crystal growth process. If they are not taken into consideration they can have adverse effects on the quantity and quality of crystals produced. As a practical matter, convection, and sedimentation can be completely eliminated only under conditions of low gravity attained during orbital flight. There is, then, an advantage to effecting crystallization in space. In the absence of convection in a microgravity environment cooling proceeds by thermal diffusion from the walls to the center of the solution chamber. This renders control of nucleation difficult. Accordingly, there is a need for a new improved nucleation process in space. Crystals are nucleated by creating a small localized region of high relative supersaturation in a host solution at a lower degree of supersaturation.

Evidence of water vapor in excess of saturation in the atmosphere of Mars.

PubMed

Maltagliati, L; Montmessin, F; Fedorova, A; Korablev, O; Forget, F; Bertaux, J-L

2011-09-30

The vertical distribution of water vapor is key to the study of Mars' hydrological cycle. To date, it has been explored mainly through global climate models because of a lack of direct measurements. However, these models assume the absence of supersaturation in the atmosphere of Mars. Here, we report observations made using the SPICAM (Spectroscopy for the Investigation of the Characteristics of the Atmosphere of Mars) instrument onboard Mars Express that provide evidence of the frequent presence of water vapor in excess of saturation, by an amount far surpassing that encountered in Earth's atmosphere. This result contradicts the widespread assumption that atmospheric water on Mars cannot exist in a supersaturated state, directly affecting our long-term representation of water transport, accumulation, escape, and chemistry on a global scale.

Substantial convection and precipitation enhancements by ultrafine aerosol particles

DOE PAGES

Fan, Jiwen; Rosenfeld, Daniel; Zhang, Yuwei; ...

2018-01-26

Aerosol-cloud interactions remain the largest uncertainty in climate projections. Ultrafine aerosol particles smaller than 50 nanometers (UAP <50) can be abundant in the troposphere, but are conventionally considered too small to affect cloud formation. However, observational evidence and numerical simulations of deep convective clouds (DCCs) over the Amazon show that DCCs forming in a low aerosol environment can develop very large vapor supersaturation because fast droplet coalescence reduces integrated droplet surface area and subsequent condensation. UAP <50 from pollution plumes that are ingested into such clouds can be activated to form additional cloud droplets on which excess supersaturation condenses andmore » forms additional cloud water and latent heating, thus intensifying convective strength. This mechanism suggests a strong anthropogenic invigoration of DCCs in previously pristine regions of the world.« less

Solid-Phase and Oscillating Solution Crystallization Behavior of (+)- and (-)-N-Methylephedrine.

PubMed

Tulashie, Samuel Kofi; Polenske, Daniel; Seidel-Morgenstern, Andreas; Lorenz, Heike

2016-11-01

This work involves the study of the solid-phase and solution crystallization behavior of the N-methylephedrine enantiomers. A systematic investigation of the melt phase diagram of the enantiomeric N-methylephedrine system was performed considering polymorphism. Two monotropically related modifications of the enantiomer were found. Solubilities and the ternary solubility phase diagrams of N-methylephedrine enantiomers in 2 solvents [isopropanol:water, 1:3 (Vol) and (2R, 3R)-diethyl tartrate] were determined in the temperature ranges between 15°C and 25°C, and 25°C and 40°C, respectively. Preferential nucleation and crystallization experiments at higher supersaturation leading to an unusual oscillatory crystallization behavior as well as a successful preferential crystallization experiment at lower supersaturation are presented and discussed. Copyright © 2016. Published by Elsevier Inc.

Novel cationic supersaturable nanomicellar systems of raloxifene hydrochloride with enhanced biopharmaceutical attributes.

PubMed

Jain, Atul; Kaur, Rajpreet; Beg, Sarwar; Kushwah, Varun; Jain, Sanyog; Singh, Bhupinder

2018-06-01

The work describes systematic development of nanomicellar cationic supersaturable self-nanoemulsifying drug delivery systems (CS-SNEDDS) for augmenting oral biopharmaceutical performance of raloxifene hydrochloride. Plain SNEDDS formulation containing Capryol 90, Cremophor RH 40, and Transcutol HP was optimized using D-optimal mixture design. SNEDDS were characterized for emulsification time, globule size, in vitro drug release, and ex vivo permeation. The CS-SNEDDS formulation was prepared from the optimized SNEDDS by adding oleylamine as the cationic charge inducer and HPMC as the polymeric precipitation inhibitor. Evaluation of CS-SNEDDS was carried out through in vitro cell line studies on Caco-2 and MCF-7 cells, in situ perfusion, and in vivo pharmacokinetic studies, which indicated significant improvement in biopharmaceutical attributes of the drug from CS-SNEDDS over plain drug.

Dynamics of gas bubble growth in a supersaturated solution with Sievert's solubility law.

PubMed

Gor, G Yu; Kuchma, A E

2009-07-21

This paper presents a theoretical description of diffusion growth of a gas bubble after its nucleation in supersaturated liquid solution. We study systems where gas molecules completely dissociate in the solvent into two parts, thus making Sievert's solubility law valid. We show that the difference between Henry's and Sievert's laws for chemical equilibrium conditions causes the difference in bubble growth dynamics. Assuming that diffusion flux is steady we obtain a differential equation on bubble radius. Bubble dynamics equation is solved analytically for the case of homogeneous nucleation of a bubble, which takes place at a significant pressure drop. We also obtain conditions of diffusion flux steadiness. The fulfillment of these conditions is studied for the case of nucleation of water vapor bubbles in magmatic melts.

Gas atomization synthesis of refractory or intermetallic compounds and supersaturated solid solutions

DOEpatents

Anderson, I.E.; Lograsso, B.K.; Ellis, T.W.

1994-11-29

A metallic melt is atomized using a high pressure atomizing gas wherein the temperature of the melt and the composition of the atomizing gas are selected such that the gas and melt react in the atomization spray zone to form a refractory or intermetallic compound in the as-atomized powder particles. A metallic melt is also atomized using a high pressure atomizing gas mixture gas wherein the temperature of the melt and the ratio of a reactive gas to a carrier gas are selected to form powder particles comprising a supersaturated solid solution of the atomic species of the reactive gas in the particles. The powder particles are then heat treated to precipitate dispersoids in-situ therein to form a dispersion strengthened material. 9 figures.

Toward the development of erosion-free ultrasonic cavitation cleaning with gas-supersaturated water

NASA Astrophysics Data System (ADS)

Yamashita, Tatsuya; Ando, Keita

2015-11-01

In ultrasonic cleaning, contaminant particles attached at target surfaces are removed by liquid flow or acoustic waves that are induced by acoustic cavitation bubbles. However, the inertial collapse of such bubbles often involve strong shock emission or water hammer by re-entrant jets, thereby giving rise to material erosion. Here, we aim at developing an erosion-free ultrasonic cleaning technique with the aid of gas-supersaturated water. The key idea is that (gaseous) cavitation is triggered easily even with low-intensity sonication in water where gases are dissolved beyond Henry's saturation limit, allowing us to buffer violent bubble collapse. In this presentation, we report on observations of the removal of micron/submicron-sized particles attached at glass surfaces by the action of gaseous cavitation bubbles under low-intensity sonication.

Diffusion, Viscosity and Crystal Growth in Microgravity

NASA Technical Reports Server (NTRS)

Myerson, Allan S.

1996-01-01

The diffusivity of TriGlycine Sulfate (TGS), Potassium Dihydrogen Phosphate (KDP), Ammonium Dihydrogen Phosphate (ADF) and other compounds of interest to microgravity crystal growth, in supersaturated solutions as a function of solution concentration, 'age' and 'history was studied experimentally. The factors that affect the growth of crystals from water solutions in microgravity have been examined. Three non-linear optical materials have been studied, potassium dihydrogen phosphate (KDP), ammonium dihydrogen phosphate (ADP) and triglycine sulfate (TGC). The diffusion coefficient and viscosity of supersaturated water solutions were measured. Also theoretical model of diffusivity and viscosity in a metastable state, model of crystal growth from solution including non-linear time dependent diffusivity and viscosity effect and computer simulation of the crystal growth process which allows simulation of the microgravity crystal growth were developed.

Growth and adhesion properties of monosodium urate monohydrate (MSU) crystals

NASA Astrophysics Data System (ADS)

Perrin, Clare M.

The presence of monosodium urate monohydrate (MSU) crystals in the synovial fluid has long been associated with the joint disease gout. To elucidate the molecular level growth mechanism and adhesive properties of MSU crystals, atomic force microscopy (AFM), scanning electron microscopy, and dynamic light scattering (DLS) techniques were employed in the characterization of the (010) and (1-10) faces of MSU, as well as physiologically relevant solutions supersaturated with urate. Topographical AFM imaging of both MSU (010) and (1-10) revealed the presence of crystalline layers of urate arranged into v-shaped features of varying height. Growth rates were measured for both monolayers (elementary steps) and multiple layers (macrosteps) on both crystal faces under a wide range of urate supersaturation in physiologically relevant solutions. Step velocities for monolayers and multiple layers displayed a second order polynomial dependence on urate supersaturation on MSU (010) and (1-10), with step velocities on (1-10) generally half of those measured on MSU (010) in corresponding growth conditions. Perpendicular step velocities on MSU (010) were obtained and also showed a second order polynomial dependence of step velocity with respect to urate supersaturation, which implies a 2D-island nucleation growth mechanism for MSU (010). Extensive topographical imaging of MSU (010) showed island adsorption from urate growth solutions under all urate solution concentrations investigated, lending further support for the determined growth mechanism. Island sizes derived from DLS experiments on growth solutions were in agreement with those measured on MSU (010) topographical images. Chemical force microscopy (CFM) was utilized to characterize the adhesive properties of MSU (010) and (1-10). AFM probes functionalized with amino acid derivatives and bio-macromolecules found in the synovial fluid were brought into contact with both crystal faces and adhesion forces were tabulated into histograms for comparison. AFM probes functionalized with -COO-, -CH3, and -OH functionalities displayed similar adhesion force with both crystal surfaces of MSU, while adhesion force on (1-10) was three times greater than (010) for -NH2+ probes. For AFM probes functionalized with bovine serum albumin, adhesion force was three times greater on MSU (1-10) than (010), most likely due to the more ionic nature of (1-10).

Comparisons of Anvil Cirrus Spatial Characteristics between Airborne Observations in DC3 Campaign and WRF Simulations

NASA Astrophysics Data System (ADS)

D'Alessandro, J.; Diao, M.; Chen, M.

2015-12-01

John D'Alessandro1, Minghui Diao1, Ming Chen2, George Bryan2, Hugh Morrison21. Department of Meteorology and Climate Science, San Jose State University2. Mesoscale & Microscale Meteorology Division, National Center for Atmospheric Research, Boulder, CO, 80301 Ice crystal formation requires the prerequisite condition of ice supersaturation, i.e., relative humidity with respect to ice (RHi) greater than 100%. The formation and evolution of ice supersaturated regions (ISSRs) has large impact on the subsequent formation of ice clouds. To examine the characteristics of simulated ice supersaturated regions at various model spatial resolutions, case studies between airborne in-situ measurements in the NSF Deep Convective, Clouds and Chemistry (DC3) campaign (May - June 2012) and WRF simulations are conducted in this work. Recent studies using ~200 m in-situ observations showed that ice supersaturated regions are mostly around 1 km in horizontal scale (Diao et al. 2014). Yet it is still unclear if such observed characteristics can be represented by WRF simulations at various spatial resolutions. In this work, we compare the WRF simulated anvil cirrus spatial characteristics with those observed in the DC3 campaign over the southern great plains in US. The WRF model is run at 1 km and 3 km horizontal grid spacing with a recent update of Thompson microphysics scheme. Our comparisons focus on the spatial characteristics of ISSRs and cirrus clouds, including the distributions of their horizontal scales, the maximum relative humidity with respect to ice (RHi) and the relationship between RHi and temperature. Our previous work on the NCAR CM1 cloud-resolving model shows that the higher resolution runs (i.e., 250m and 1km) generally have better agreement with observations than the coarser resolution (4km) runs. We will examine if similar trend exists for WRF simulations in deep convection cases. In addition, we will compare the simulation results between WRF and CM1, particularly for spatial correlations between ISSRs and cirrus and their evolution (based on the method of Diao et al. 2013). Overall, our work will help to assess the representation of ISSRs and cirrus in WRF simulation based on comparisons with in-situ observations.

O the Size Dependence of the Chemical Properties of Cloud Droplets: Exploratory Studies by Aircraft

NASA Astrophysics Data System (ADS)

Twohy, Cynthia H.

1992-09-01

Clouds play an important role in the climate of the earth and in the transport and transformation of chemical species, but many questions about clouds remain unanswered. In particular, the chemical properties of droplets may vary with droplet size, with potentially important consequences. The counterflow virtual impactor (CVI) separates droplets from interstitial particles and gases in a cloud and also can collect droplets in discrete size ranges. As such, the CVI is a useful tool for investigating the chemical components present in droplets of different sizes and their potential interactions with cloud processes. The purpose of this work is twofold. First, the sampling characteristics of the airborne CVI are investigated, using data from a variety of experiments. A thorough understanding of CVI properties is necessary in order to utilize the acquired data judiciously and effectively. Although the impaction characteristics of the CVI seem to be predictable by theory, the airborne instrument is subject to influences that may result in a reduced transmission efficiency for droplets, particularly if the inlet is not properly aligned. Ways to alleviate this problem are being investigated, but currently the imperfect sampling efficiency must be taken into account during data interpretation. Relationships between the physical and chemical properties of residual particles from droplets collected by the CVI and droplet size are then explored in both stratiform and cumulus clouds. The effects of various cloud processes and measurement limitations upon these relationships are discussed. In one study, chemical analysis of different -sized droplets sampled in stratiform clouds showed a dependence of chemical composition on droplet size, with larger droplets containing higher proportions of sodium than non-sea-salt sulfate and ammonium. Larger droplets were also associated with larger residual particles, as expected from simple cloud nucleation theory. In a study of marine cumulus clouds, the CVI was combined with a cloud condensation nucleus spectrometer to study the supersaturation spectra of residual particles from droplets. The median critical supersaturation of the droplet residual particles was consistently less than or equal to the median critical supersaturation of ambient particles except at cloud top, where residual particles exhibited a variety of critical supersaturations.

Study of thermal properties of the metastable supersaturated vapor with the integral equation method

NASA Astrophysics Data System (ADS)

Nie, Chu; Geng, Jun; Marlow, W. H.

2008-02-01

Pressure, excess chemical potential, and excess free energy data for different densities of the supersaturated argon vapor at reduced temperatures from 0.7 to 1.2 are obtained by solving the integral equation with perturbation correction to the radial distribution function [F. Lado, Phys. Rev. 135, A1013 (1964)]. For those state points where there is no solution, the integral equation is solved with the interaction between argon atoms modeled by Lennard-Jones potential plus a repulsive potential with one controlling parameter, αexp(-r /σ) and in the end, all the thermal properties are mapped back to the α =0 case. Our pressure data and the spinodal obtained from the current method are compared with a molecular dynamics simulation study [A. Linhart et al., J. Chem. Phys. 122, 144506 (2005)] of the same system.

Hidden Nanobubbles in Undersaturated Liquids.

PubMed

Guo, Zhenjiang; Liu, Yawei; Xiao, Qianxiang; Zhang, Xianren

2016-11-01

Here, we propose theoretically the existence of a new type of nanobubble in undersaturated liquids. These nanobubbles have a concave vapor-liquid interface featured with a negative curvature rather than a positive curvature for nanobubbles in supersaturated liquids, so that they often hide inside of the substrate textures and it might not be easy to characterize them through atomic force microscopy (AFM) measurements. However, these hidden nanobubbles are still stabilized by the contact line pinning effect and stay at the thermodynamically metastable state. We further demonstrate that similar to the nanobubbles in supersaturated liquids the contact angle of the hidden nanobubbles is more sensitive to the nanobubble size rather than the substrate chemistry, and their curvature radius is dependent on the chemical potential but independent of the base radius. Finally, we show several potential situations for the appearance of the hidden nanobubbles.

Crystal nucleation of colloidal hard dumbbells

NASA Astrophysics Data System (ADS)

Ni, Ran; Dijkstra, Marjolein

2011-01-01

Using computer simulations, we investigate the homogeneous crystal nucleation in suspensions of colloidal hard dumbbells. The free energy barriers are determined by Monte Carlo simulations using the umbrella sampling technique. We calculate the nucleation rates for the plastic crystal and the aperiodic crystal phase using the kinetic prefactor as determined from event driven molecular dynamics simulations. We find good agreement with the nucleation rates determined from spontaneous nucleation events observed in event driven molecular dynamics simulations within error bars of one order of magnitude. We study the effect of aspect ratio of the dumbbells on the nucleation of plastic and aperiodic crystal phases, and we also determine the structure of the critical nuclei. Moreover, we find that the nucleation of the aligned close-packed crystal structure is strongly suppressed by a high free energy barrier at low supersaturations and slow dynamics at high supersaturations.

Investigation of the L-Glutamic acid polymorphism: Comparison between stirred and stagnant conditions

NASA Astrophysics Data System (ADS)

Tahri, Yousra; Gagnière, Emilie; Chabanon, Elodie; Bounahmidi, Tijani; Mangin, Denis

2016-02-01

This work highlights the effect of the stirring, the temperature and the supersaturation on the cooling crystallization of L-Glutamic acid (LGlu) polymorphs. First, solubility measurements of the metastable polymorph α and the stable polymorph β were performed. Then, crystallization experiments were carried out in stirred vessel and in stagnant cell. All these experiments were monitored by in situ devices. The effect of the temperature on the LGlu polymorphs was found to be more relevant than the supersaturation in the stirred crystallizer. In the stagnant cell, only the stable form β crystallized regardless of the operating conditions. Moreover, an unexpected and new habit of the β form was discovered and confirmed. These results suggest that the temperature and the stirring can strongly affect the nucleation and the growth kinetics of polymorphic forms.

Cloud Condensation Nuclei Particle Counter (CCN) Instrument Handbook

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

Uin, Janek

2016-04-01

The Cloud Condensation Nuclei Counter—CCN (Figure 1) is a U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility instrument for measuring the concentration of aerosol particles that can act as cloud condensation nuclei [1, 2]. The CCN draws the sample aerosol through a column with thermodynamically unstable supersaturated water vapor that can condense onto aerosol particles. Particles that are activated, i.e., grown larger in this process, are counted (and sized) by an Optical Particle Counter (OPC). Thus, activated ambient aerosol particle number concentration as a function of supersaturation is measured. Models CCN-100 and CCN-200 differ only inmore » the number of humidifier columns and related subsystems: CCN-100 has one column and CCN-200 has two columns along with dual flow systems and electronics.« less

Damping and Amplification of Seismic Waves in Gas-Charged Magma

NASA Astrophysics Data System (ADS)

Neuberg, J. W.; Lensky, N. G.

2001-12-01

Low-frequency seismic signals are generated at the interface betweeen a solid medium and a magmatic melt. The existence of gas bubbles in the magma introduces a damping mechanism which depends mainly on the gas volume fraction and on the viscosity of the melt. However, in case of a sudden unloading (e.g. by lava dome failure) a decompressional wave propagates through the magma which becomes now supersaturated. Diffusion of gas into the bubbles leads to an exponential bubble growth which is in general frequency dependent. Such a system can be represented by a negative bulk viscosity which results in a net amplification rather than damping of the decompressional wave. Furthermore, the effects of a harmonically varying pressure on the supersaturated melt is explored, as it is caused by seismic tremor and prolongued conduit resonance.

Understanding the sensitivity of nucleation free energies: The role of supersaturation and temperature

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

Keasler, Samuel J., E-mail: samuel.keasler@vcsu.edu; Department of Science, Valley City State University, 101 College Street SW, Valley City, North Dakota 58072; Siepmann, J. Ilja

2015-10-28

Simulations are used to investigate the vapor-to-liquid nucleation of water for several different force fields at various sets of physical conditions. The nucleation free energy barrier is found to be extremely sensitive to the force field at the same absolute conditions. However, when the results are compared at the same supersaturation and reduced temperature or the same metastability parameter and reduced temperature, then the differences in the nucleation free energies of the different models are dramatically reduced. This finding suggests that comparisons of experimental data and computational predictions are most meaningful at the same relative conditions and emphasizes the importancemore » of knowing the phase diagram of a given computational model, but such information is usually not available for models where the interaction energy is determined directly from electronic structure calculations.« less

High-pressure injection of dissolved oxygen for hydrocarbon remediation in a fractured dolostone aquifer.

PubMed

Greer, K D; Molson, J W; Barker, J F; Thomson, N R; Donaldson, C R

2010-10-21

A field experiment was completed at a fractured dolomite aquifer in southwestern Ontario, Canada, to assess the delivery of supersaturated dissolved oxygen (supersaturated with respect to ambient conditions) for enhanced bioremediation of petroleum hydrocarbons in groundwater. The injection lasted for 1.5h using iTi's gPro® oxygen injection technology at pressures of up to 450 kPa and at concentrations of up to 34 mg O₂/L. A three-dimensional numerical model for advective-dispersive transport of dissolved oxygen within a discretely-fractured porous medium was calibrated to the observed field conditions under a conservative (no-consumption) scenario. The simulation demonstrated that oxygen rapidly filled the local intersecting fractures as well as the porous matrix surrounding the injection well. Following injection, the local fractures were rapidly flushed by the natural groundwater flow system but slow back-diffusion ensured a relatively longer residence time in the matrix. A sensitivity analysis showed significant changes in behaviour with varying fracture apertures and hydraulic gradients. Applying the calibrated model to a 7-day continuous injection scenario showed oxygen residence times (at the 3mg/L limit), within a radius of 2-4m from the injection well, of up to 100 days. This study has demonstrated that supersaturated dissolved oxygen can be effectively delivered to this type of a fractured and porous bedrock system at concentrations and residence times potentially sufficient for enhanced aerobic biodegradation. Copyright © 2010 Elsevier B.V. All rights reserved.

Effect of Ramadan fasting on urinary risk factors for calculus formation.

PubMed

Miladipour, Amir Hossein; Shakhssalim, Nasser; Parvin, Mahmoud; Azadvari, Mohaddeseh

2012-01-01

Even though dehydration could aggravate formation of urinary calculi, the effects of fluid and food restriction on calculus formation is not thoroughly defined. The purpose of this study is to evaluate the effects of fluid and food restriction in Ramadan fasting on urinary factors in kidney and urinary calculus formation. Fifty-seven men aged 30 to 55 years old, including 37 recurrent calcium calculus formers and 20 with no history of kidney calculi were evaluated for blood tests, ultrasonography investigations, urinalysis, urine culture, and also 24-hour urine collection test. Metabolites including calcium, oxalate, citrate, uric acid, magnesium, phosphate, potassium, sodium, and creatinine were measured before and during Ramadan fasting. The values of calculus-precipitating solutes as well as inhibitory factors were documented thoroughly. Total excretion of calcium, phosphate, and magnesium in 24-hour urine and also urine volume during fasting were significantly lower than those in the nonfasting period. Urine concentration of calcium during fasting was significantly lower than nonfasting (P < .001). Urine concentrations of uric acid, citrate, phosphate, sodium, and potassium during fasting were significantly higher than nonfasting. Uric acid supersaturation was accentuated, and calcium phosphate supersaturation was decreased significantly during fasting. There was no significant increase in calcium oxalate supersaturation during the fasting period. Fasting during Ramadan has different effects on total excretion and concentrations of urinary precipitate and inhibitory factors contributing to calculus formation. We did not find enough evidence in favor of increased risks of calculus formation during Ramadan fasting.

A unifying model for adsorption and nucleation of vapors on solid surfaces.

PubMed

Laaksonen, Ari

2015-04-23

Vapor interaction with solid surfaces is traditionally described with adsorption isotherms in the undersaturated regime and with heterogeneous nucleation theory in the supersaturated regime. A class of adsorption isotherms is based on the idea of vapor molecule clustering around so-called active sites. However, as the isotherms do not account for the surface curvature effects of the clusters, they predict an infinitely thick adsorption layer at saturation and do not recognize the existence of the supersaturated regime. The classical heterogeneous nucleation theory also builds on the idea of cluster formation, but describes the interactions between the surface and the cluster with a single parameter, the contact angle, which provides limited information compared with adsorption isotherms. Here, a new model of vapor adsorption on nonporous solid surfaces is derived. The basic assumption is that adsorption proceeds via formation of molecular clusters, modeled as liquid caps. The equilibrium of the individual clusters with the vapor phase is described with the Frenkel-Halsey-Hill (FHH) adsorption theory modified with the Kelvin equation that corrects for the curvature effect on vapor pressure. The new model extends the FHH adsorption isotherm to be applicable both at submonolayer surface coverages and at supersaturated conditions. It shows good agreement with experimental adsorption data from 12 different adsorbent-adsorbate systems. The model predictions are also compared against heterogeneous nucleation data, and they show much better agreement than predictions of the classical heterogeneous nucleation theory.

Growth and melting of droplets in cold vapors.

PubMed

L'Hermite, Jean-Marc

2009-11-01

A model has been developed to investigate the growth of droplets in a supersaturated cold vapor taking into account their possible solid-liquid phase transition. It is shown that the solid-liquid phase transition is nontrivially coupled, through the energy released in attachment, to the nucleation process. The model is based on the one developed by J. Feder, K. C. Russell, J. Lothe, and G. M. Pound [Adv. Phys. 15, 111 (1966)], where the nucleation process is described as a thermal diffusion motion in a two-dimensional field of force given by the derivatives of a free-energy surface. The additional dimension accounts for droplets internal energy. The solid-liquid phase transition is introduced through a bimodal internal energy distribution in a Gaussian approximation derived from small clusters physics. The coupling between nucleation and melting results in specific nonequilibrium thermodynamical properties, exemplified in the case of water droplets. Analyzing the free-energy landscapes gives an insight into the nucleation dynamics. This landscape can be complex but generally exhibits two paths: the first one can generally be ascribed to the solid state, while the other to the liquid state. Especially at high supersaturation, the growth in the liquid state is often favored, which is not unexpected since in a supersaturated vapor the droplets can stand higher internal energy than at equilibrium. From a given critical temperature that is noticeably lower than the bulk melting temperature, nucleation may end in very large liquid droplets. These features can be qualitatively generalized to systems other than water.

Preparation and characterization of fusion processed solid dispersions containing a viscous thermally labile polymeric carrier.

PubMed

Hughey, Justin R; Keen, Justin M; Miller, Dave A; Brough, Chris; McGinity, James W

2012-11-15

The primary aim of the present study was to investigate the ability of hydroxypropyl and methoxyl substituted cellulose ethers to stabilize supersaturated concentrations of itraconazole (ITZ), a poorly water-soluble weak base, after an acid-to-neutral pH transition. A secondary aim of the study was to evaluate the effect of fusion processes on polymer stability and molecular weight. Polymer screening studies showed that stabilization of ITZ supersaturation was related to the molecular weight of the polymer and levels of hydroxypropyl and methoxyl substitution. METHOCEL E50LV (E50LV), which is characterized as having a high melt viscosity, was selected for solid dispersion formulation studies. Hot-melt extrusion processing of E50LV based compositions resulted in high torque loads, low material throughput and polymer degradation. KinetiSol Dispersing, a novel fusion based processing technique, was evaluated as a method to prepare the solid dispersions with reduced levels of polymer degradation. An experimental design revealed that polymer molecular weight was sensitive to shearing forces and high temperatures. However, optimal processing conditions resulted in significantly reduced E50LV degradation relative to HME processing. The technique was effectively utilized to prepare homogenous solid solutions of E50LV and ITZ, characterized as having a single glass transition temperature over a wide range of drug loadings. All prepared compositions provided for a high degree of ITZ supersaturation stabilization. Copyright © 2012 Elsevier B.V. All rights reserved.

Cloud Microphysics Budget in the Tropical Deep Convective Regime

NASA Technical Reports Server (NTRS)

Li, Xiao-Fan; Sui, C.-H.; Lau, K.-M.; Einaudi, Franco (Technical Monitor)

2001-01-01

Cloud microphysics budgets in the tropical deep convective regime are analyzed based on a 2-D cloud resolving simulation. The model is forced by the large-scale vertical velocity and zonal wind and large-scale horizontal advections derived from TOGA COARE for a 20-day period. The role of cloud microphysics is first examined by analyzing mass-weighted mean heat budget and column-integrated moisture budget. Hourly budgets show that local changes of mass-weighted mean temperature and column-integrated moisture are mainly determined by the residuals between vertical thermal advection and latent heat of condensation and between vertical moisture advection and condensation respectively. Thus, atmospheric thermodynamics depends on how cloud microphysical processes are parameterized. Cloud microphysics budgets are then analyzed for raining conditions. For cloud-vapor exchange between cloud system and its embedded environment, rainfall and evaporation of raindrop are compensated by the condensation and deposition of supersaturated vapor. Inside the cloud system, the condensation of supersaturated vapor balances conversion from cloud water to raindrop, snow, and graupel through collection and accretion processes. The deposition of supersaturated vapor balances conversion from cloud ice to snow through conversion and riming processes. The conversion and riming of cloud ice and the accretion of cloud water balance conversion from snow to graupel through accretion process. Finally, the collection of cloud water and the melting of graupel increase raindrop to compensate the loss of raindrop due to rainfall and the evaporation of raindrop.

Phase transformation in SiOx/SiO₂ multilayers for optoelectronics and microelectronics applications.

PubMed

Roussel, M; Talbot, E; Pratibha Nalini, R; Gourbilleau, F; Pareige, P

2013-09-01

Due to the quantum confinement, silicon nanoclusters (Si-ncs) embedded in a dielectric matrix are of prime interest for new optoelectronics and microelectronics applications. In this context, SiO(x)/SiO₂ multilayers have been prepared by magnetron sputtering and subsequently annealed to induce phase separation and Si clusters growth. The aim of this paper is to study phase separation processes and formation of nanoclusters in SiO(x)/SiO₂ multilayers by atom probe tomography. Influences of the silicon supersaturation, annealing temperature and SiO(x) and SiO₂ layer thicknesses on the final microstructure have been investigated. It is shown that supersaturation directly determines phase separation regime between nucleation/classical growth and spinodal decomposition. Annealing temperature controls size of the particles and interface with the surrounding matrix. Layer thicknesses directly control Si-nc shapes from spherical to spinodal-like structures. Copyright © 2012 Elsevier B.V. All rights reserved.

Si nanowire growth on sapphire: Classical incubation, reverse reaction, and steady state supersaturation

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

Shakthivel, Dhayalan; Rathkanthiwar, Shashwat; Raghavan, Srinivasan, E-mail: sraghavan@cense.iisc.ernet.in

2015-04-28

Si nanowire growth on sapphire substrates by the vapor-liquid-solid (VLS) method using Au catalyst particles has been studied. Sapphire was chosen as the substrate to ensure that the vapor phase is the only source of Si. Three hitherto unreported observations are described. First, an incubation period of 120–480 s, which is shown to be the incubation period as defined in classical nucleation theory, is reported. This incubation period permits the determination of a desolvation energy of Si from Au-Si alloys of 15 kT. Two, transmission electron microscopy studies of incubation, point to Si loss by reverse reaction as an important partmore » of the mechanism of Si nanowire growth by VLS. Three, calculations using these physico-chemical parameters determined from incubation and measured steady state growth rates of Si nanowires show that wire growth happens from a supersaturated catalyst droplet.« less

Thermodynamics of Surface Nanobubbles.

PubMed

Zargarzadeh, Leila; Elliott, Janet A W

2016-11-01

In this paper, we examine the thermodynamic stability of surface nanobubbles. The appropriate free energy is defined for the system of nanobubbles on a solid surface submerged in a supersaturated liquid solution at constant pressure and temperature, under conditions where an individual nanobubble is not in diffusive contact with a gas phase outside of the system or with other nanobubbles on the time scale of the experiment. The conditions under which plots of free energy versus the radius of curvature of the nanobubbles show a global minimum, which denotes the stable equilibrium state, are explored. Our investigation shows that supersaturation and an anomalously high contact angle (measured through the liquid) are required to have stable surface nanobubbles. In addition, the anomalously high contact angle of surface nanobubbles is discussed from the standpoint of a framework recently proposed by Koch, Amirfazli, and Elliott that relates advancing and receding contact angles to thermodynamic equilibrium contact angles, combined with the existence of a gas enrichment layer.

DKDP crystal growth controlled by cooling rate

NASA Astrophysics Data System (ADS)

Xie, Xiaoyi; Qi, Hongji; Shao, Jianda

2017-08-01

The performance of deuterated potassium dihydrogen phosphate (DKDP) crystal directly affects beam quality, energy and conversion efficiency in the Inertial Confinement Fusion（ICF）facility, which is related with the initial saturation temperature of solution and the real-time supersaturation during the crystal growth. However, traditional method to measure the saturation temperature is neither efficient nor accurate enough. Besides, the supersaturation is often controlled by experience, which yields the higher error and leads to the instability during the crystal growth. In this paper, DKDP solution with 78% deuteration concentration is crystallized in different temperatures. We study the relation between solubility and temperature of DKDP and fit a theoretical curve with a parabola model. With the model, the measurement of saturation temperature is simplified and the control precision of the cooling rate is improved during the crystal growth, which is beneficial for optimizing the crystal growth process.

Gasometer: An inexpensive device for continuous monitoring of dissolved gases and supersaturation

USGS Publications Warehouse

Bouck, G.R.

1982-01-01

The “gasometer” is a device that measures differential dissolved-gas pressures (δP) in water relative to barometric pressure (as does the “Weiss saturometer”), but operates continuously without human attention. The gasometer can be plumbed into a water-supply system and requires 8 liters/minute of water or more at 60 kilopascals. The gasometer's surfaces are nontoxic, and flow-through water can be used for fish culture. The gasometer may be connected to a small submersible pump and operated as a portable unit. The gasometer can activate an alarm system and thus protect fish from hyperbaric (supersaturation) or hypobaric gas pressures (usually due to low dissolved oxygen). Instructions are included for calculating and reporting data including the pressure and saturation of individual gases. Construction and performance standards are given for the gasometer. Occasional cleaning is required to remove biofouling from the gas-permeable tubing.PDF

Compositional Pathways and Capillary Effects during Early-stage Isothermal Precipitation in a Nondilute Ni-Al-Cr Alloy

NASA Technical Reports Server (NTRS)

Sudbrack, Chantal K.; Noebe, Ronald D.; Seidman, David N.

2006-01-01

For a Ni-5.2 Al-14.2 Cr at.% alloy with moderate solute supersaturations, the compositional pathways, as measured with atom-probe tomography, during early to later stage y'(LI2)-precipitation (R = 0.45-10 nm), aged at 873 K, are discussed in light of a multi-component coarsening model. Employing nondilute thermodynamics, detailed model analyses during quasistationary coarsening of the experimental data establish that the y/y' interfacial free-energy is 22- 23+/-7 mJ/sq m. Additionally, solute diffusivities are significantly slower than model estimates. Strong quantitative evidence indicates that an observed y'-supersaturation of Al results from the Gibbs-Thomson effect, providing the first experimental verification of this phenomenon. The Gibbs-Thomson relationship, for a ternary system, as well as differences in measured phase equilibria with CALPHAD assessments, are considered in great detail.

Scanning electron microscope observations of sublimates from Merapi Volcano, Indonesia

USGS Publications Warehouse

Symonds, R.

1993-01-01

Sublimates were sampled from high-temperature (up to 800??C) fumaroles at Merapi volcano in January 1984. Sampling is accomplished by inserting silica tubes into high-temperature vents. Volcanic glass flows through the tubes and sublimates precipitate on the inner walls in response to the temperature gradient. With decreasing temperature (800-500??C) in the tubes, there are five sublimate zones. Texturally, the sublimate phases grade from large, well-formed crystals at their highest-temperature occurrence to more numerous, smaller crystals that are less perfect at lower temperatures. These changes imply that the crystal nucleation and growth rates increase and decrease, respectively, as temperature decreases. Overall, the textural data suggest that the gas is saturated or slightly super-saturated with the phases at their hottest occurrence, but that the gas becomes increasingly super-saturated with the phases at lower temperatures. -from Author

Bubble nucleation in stout beers

NASA Astrophysics Data System (ADS)

Lee, W. T.; McKechnie, J. S.; Devereux, M. G.

2011-05-01

Bubble nucleation in weakly supersaturated solutions of carbon dioxide—such as champagne, sparkling wines, and carbonated beers—is well understood. Bubbles grow and detach from nucleation sites: gas pockets trapped within hollow cellulose fibers. This mechanism appears not to be active in stout beers that are supersaturated solutions of nitrogen and carbon dioxide. In their canned forms these beers require additional technology (widgets) to release the bubbles which will form the head of the beer. We extend the mathematical model of bubble nucleation in carbonated liquids to the case of two gases and show that this nucleation mechanism is active in stout beers, though substantially slower than in carbonated beers and confirm this by observation. A rough calculation suggests that despite the slowness of the process, applying a coating of hollow porous fibers to the inside of a can or bottle could be a potential replacement for widgets.

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

Fan, Jiwen; Rosenfeld, Daniel; Zhang, Yuwei

Aerosol-cloud interaction remains the largest uncertainty in climate projections. Ultrafine aerosol particles (UAP; size <50nm) are considered too small to serve as cloud condensation nuclei conventionally. However, this study provides observational evidence to accompany insights from numerical simulations to support that deep convective clouds (DCCs) over Amazon have strong capability of nucleating UAP from an urban source and forming greater numbers of droplets, because fast drop coalescence in these DCCs reduces drop surface area available for condensation, leading to high vapor supersaturation. The additional droplets subsequently decrease supersaturation and release more condensational latent heating, a dominant contributor to convection intensification,more » whereas enhanced latent heat from ice-related processes plays a secondary role. Therefore, the addition of anthropogenic UAP may play a much greater role in modulating clouds than previously believed over the Amazon region and possibly in other relatively pristine regions such as maritime and forest locations.« less

Dependence of Morphology of SiOx Nanowires on the Supersaturation of Au-Si Alloy Liquid Droplets Formed on the Au-Coated Si Substrate

NASA Astrophysics Data System (ADS)

Zhang, Han; Li, Ji-Xue; Jin, Ai-Zi; Zhang, Ze

2001-11-01

A thermodynamic theory about the dependence of morphology of SiOx nanowires on the super-saturation of alloy liquid droplets has been proposed on the basis of the vapour-liquid-solid growth mechanism and has been supported experimentally. By changing the Si concentration in the Au-Si liquid droplets formed on the Au-coated Si substrate, firework-, tulip- and bud-shaped SiOx nanowires were synthesized by a thermal evaporation method and distributed concentrically around some void defects in the Si substrate. Voids were formed underneath the surface of the Si substrate during the thermal evaporation at 850°C and resulted in the Si-concentration deficient thus different saturation of Au-Si droplets. Electron microscopy analysis showed that the nanowires had an amorphous structure and were terminated by Au-Si particles.

Observation of enhanced infrared absorption in silicon supersaturated with gold by pulsed laser melting of nanometer-thick gold films

NASA Astrophysics Data System (ADS)

Chow, Philippe K.; Yang, Wenjie; Hudspeth, Quentin; Lim, Shao Qi; Williams, Jim S.; Warrender, Jeffrey M.

2018-04-01

We demonstrate that pulsed laser melting (PLM) of thin 1, 5, and 10 nm-thick vapor-deposited gold layers on silicon enhances its room-temperature sub-band gap infrared absorption, as in the case of ion-implanted and PLM-treated silicon. The former approach offers reduced fabrication complexity and avoids implantation-induced lattice damage compared to ion implantation and pulsed laser melting, while exhibiting comparable optical absorptance. We additionally observed strong broadband absorptance enhancement in PLM samples made using 5- and 10-nm-thick gold layers. Raman spectroscopy and Rutherford backscattering analysis indicate that such an enhancement could be explained by absorption by a metastable, disordered and gold-rich surface layer. The sheet resistance and the diode electrical characteristics further elucidate the role of gold-supersaturation in silicon, revealing the promise for future silicon-based infrared device applications.

Crystallization of hard spheres revisited. I. Extracting kinetics and free energy landscape from forward flux sampling.

PubMed

Richard, David; Speck, Thomas

2018-03-28

We investigate the kinetics and the free energy landscape of the crystallization of hard spheres from a supersaturated metastable liquid though direct simulations and forward flux sampling. In this first paper, we describe and test two different ways to reconstruct the free energy barriers from the sampled steady state probability distribution of cluster sizes without sampling the equilibrium distribution. The first method is based on mean first passage times, and the second method is based on splitting probabilities. We verify both methods for a single particle moving in a double-well potential. For the nucleation of hard spheres, these methods allow us to probe a wide range of supersaturations and to reconstruct the kinetics and the free energy landscape from the same simulation. Results are consistent with the scaling predicted by classical nucleation theory although a quantitative fit requires a rather large effective interfacial tension.

Crystallization of hard spheres revisited. I. Extracting kinetics and free energy landscape from forward flux sampling

NASA Astrophysics Data System (ADS)

Richard, David; Speck, Thomas

2018-03-01

We investigate the kinetics and the free energy landscape of the crystallization of hard spheres from a supersaturated metastable liquid though direct simulations and forward flux sampling. In this first paper, we describe and test two different ways to reconstruct the free energy barriers from the sampled steady state probability distribution of cluster sizes without sampling the equilibrium distribution. The first method is based on mean first passage times, and the second method is based on splitting probabilities. We verify both methods for a single particle moving in a double-well potential. For the nucleation of hard spheres, these methods allow us to probe a wide range of supersaturations and to reconstruct the kinetics and the free energy landscape from the same simulation. Results are consistent with the scaling predicted by classical nucleation theory although a quantitative fit requires a rather large effective interfacial tension.

[Theoretical evaluation of the risk of decompression illness during simulated extravehicular activity].

PubMed

Nikolaev, V P

2008-01-01

Theoretical analysis of the risk of decompression illness (DI) during extravehicular activity following the Russian and NASA decompression protocols (D-R and D-US, respectively) was performed. In contrast to the tradition approach to decompression stress evaluation by the factor of tissue supersaturation with nitrogen, our probabilistic theory of decompression safety provides a completely reasoned evaluation and comparison of the levels of hazard of these decompression protocols. According to this theory, the function of cumulative DI risk is equal to the sum of functions of cumulative risk of lesion of all body tissues by gas bubbles and their supersaturation by solute gases. Based on modeling of dynamics of these functions, growth of the DI cumulative risk in the course of D-R and D-US follows essentially similar trajectories within the time-frame of up to 330 minutes. However, further extension of D-US but not D-R raises the risk of DI drastically.

Mechanism for enhanced absorption of a solid dispersion formulation of LY2300559 using the artificial stomach duodenum model.

PubMed

Polster, Christopher S; Wu, Sy-Juen; Gueorguieva, Ivelina; Sperry, David C

2015-04-06

An artificial stomach duodenum (ASD) model has been used to demonstrate the performance difference between two formulations of LY2300559, a low-solubility acidic developmental drug. The two formulations investigated were a conventional high-shear wet granulation (HSWG) formulation and a solid dispersion formulation. A pharmacokinetic study in humans demonstrated the enhanced performance of the solid dispersion formulation relative to the HSWG formulation. The Cmax and AUC of the solid dispersion was 2.6 and 1.9 times greater, respectively, compared to the HSWG formulation. In the ASD, the solid dispersion formulation performance was characterized by three main phases: (1) rapid release in the stomach, creating a supersaturated concentration of drug, (2) precipitation in the stomach, and (3) rapid redissolution of the precipitate in the duodenum to concentration levels that are supersaturated relative to crystalline drug. A series of complementary experiments were employed to describe this performance behavior mechanistically. Imaging experiments with a pH indicating dye showed that local pH gradients from meglumine in the solid dispersion formulation were responsible for creating a high initial supersaturation concentration in the stomach. Upon dissipation of meglumine, the drug precipitated in the stomach as an amorphous solid. Because the precipitated drug is in an amorphous form, it can then rapidly redissolve as it transits to the more neutral environment of the duodenum. This unexpected sequence of physical state changes gives a mechanistic explanation for the enhanced in vivo performance of the solid dispersion formulation relative to the HSWG formulation.

Influence of Aluminum on the Formation Behavior of Zn-Al-Fe Intermetallic Particles in a Zinc Bath

NASA Astrophysics Data System (ADS)

Park, Joo Hyun; Park, Geun-Ho; Paik, Doo-Jin; Huh, Yoon; Hong, Moon-Hi

2012-01-01

The shape, size, and composition of dross particles as a function of aluminum content at a fixed temperature were investigated for aluminum added to the premelted Zn-Fe melt simulating the hot-dip galvanizing bath by a sampling methodology. In the early stage, less than 30 minutes after Al addition, local supersaturation and depletion of the aluminum concentration occurred simultaneously in the bath, resulting in the nucleation and growth of both Fe2Al5Zn x and FeZn13. However, the aluminum was homogenized continuously as the reaction proceeded, and fine and stable FeZn10Al x formed after 30 minutes. An Al-depleted zone (ADZ) mechanism was newly proposed for the "η→η+ζ→δ" phase transformations. The ζ phase bottom dross partly survived for a relatively long period, i.e., 2 hours in this work, whereas the η phase disappeared after 30 minutes. In the early stage of dross formation, both Al-free large particles as well as high-Al tiny particles were formed. The dross particle size decreased slightly with increased reaction time before reaching a plateau. The opposite tendency was observed when the Al content was 0.130 mass pct; with a relatively high Al content, the nucleation of tiny η phase dross was significantly enhanced because of the high degree of supersaturation. This unstable η phase dissolved continuously and underwent simple transformation to the stable δ phase. The relationship between nucleation potential and supersaturation ratio of species is discussed based on the thermodynamics of classical nucleation theory.

Site specific solubility improvement using solid dispersions of HPMC-AS/HPC SSL--mixtures.

PubMed

Zecevic, Damir Elmar; Meier, Robin; Daniels, Rolf; Wagner, Karl-Gerhard

2014-07-01

Many upcoming drug candidates are pH-dependent poorly soluble weak bases in the pH range of the gastrointestinal tract. This often leads to a high in vivo variability and bioavailability issues. Aiming to overcome these limitations, the design of solid dispersions for site specific dissolution improvement or maintenance of a potent supersaturation over the entire gastro-intestinal pH-range, is proposed to assure a reliable drug therapy. Solid dispersions containing different ratios of Dipyridamole (DPD) or Griseofulvin (GRI) and the enteric polymer hydroxypropylmethylcellulose-acetate succinate (HPMC-AS) and the water soluble low-viscosity hydroxypropylcellulose (HPC-SSL) were prepared by hot melt extrusion (HME). The solid dispersions were evaluated for their solid state, dissolution characteristics applying a three pH-step dissolution method following an acidic to neutral pH transition and stability. The use of HPMC-AS in binary mixtures with DPD and GRI facilitated increased solubility and supersaturation at pH-controlled release of the preserved amorphous state of the dispersed drug, which even inverted the pH-dependent solubility profile of the weakly basic model drug (Dipyridamole). I.e. a potent site specific delivery system was created. With ternary solid dispersions of API, HPMC-AS and HPC-SSL, tailored release profiles with superior supersaturation over the applied pH-range could be obtained. At the same time, binary and ternary mixtures showed favorable stability properties at a temperature difference between glass transition temperature and the applied storage temperature of down to 16°C. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation and modeling of Al3(Sc, Zr) precipitation strengthening in the presence of enhanced supersaturation and within Al-Cu binary alloys

NASA Astrophysics Data System (ADS)

Deane, Kyle

Diffuse Al-Sc and Al-Zr alloys have been demonstrated in literature to be relatively coarsening resistant at higher temperatures when compared with commonly used precipitation strengthening alloys (e.g. 2000 series, 6000 series). However, because of a limited strengthening due to the low solubility of scandium and zirconium in aluminum, and owing to the scarcity and therefore sizeable price tag attached to scandium, little research has been done in the way of optimizing these alloys for commercial applications. With this in mind, this dissertation describes research which aims to tackle several important areas of Al-Sc-Zr research that have been yet unresolved. In Chapter 4, rapid solidification was utilized to enhance the achievable supersaturation of the alloy in an effort to increase the achievable precipitate strengthening. In Chapter 5, Additive Friction Stir processing (AFS), a novel method of mechanically combining materials without melting, was employed in an attempt to pass the benefits of supersaturation from melt spun ribbon into a more structurally useful bulk material. In Chapter 6, a Matlab program written to predict precipitate nucleation, growth, and coarsening with a modified Kampmann and Wagner Numerical (KWN) model, was used to predict heat treatment regimens for more efficient strengthening. Those predictions were then tested experimentally to test the validity of the results. And lastly, in Chapter 7, the effect of zirconium on Al-Cu secondary precipitates was studied in an attempt to increase their thermal stability, as much higher phase fractions of Al-Cu precipitates are achievable than Al-Zr precipitates.

Effects of chitosan molecular weight on the physical and dissolution characteristics of amorphous curcumin-chitosan nanoparticle complex.

PubMed

Yu, Hong; Nguyen, Minh-Hiep; Hadinoto, Kunn

2018-01-01

To investigate the effects of varying molecular weight (MW) of chitosan (CHI) used in the complexation with curcumin (CUR) on the physical and dissolution characteristics of the amorphous CUR-CHI nanoparticle complex produced. Amorphous CUR-CHI nanoparticle complex (or CUR nanoplex in short) recently emerged as a promising bioavailability enhancement strategy of CUR attributed to its fast dissolution, supersaturation generation capability, and simple preparation. Existing CUR nanoplex prepared using low MW CHI, however, exhibited poor colloidal stability during storage. Herein we hypothesized that the colloidal stability could be improved by using CHI of higher MW. The effects of this approach on the nanoplex's other characteristics were simultaneously investigated. The CUR nanoplex was prepared by electrostatically driven self-assembled complexation between CUR and oppositely charged CHI of three different MWs (i.e. low, medium, and high). Besides colloidal stability, the effects of MW variation were investigated for the nanoplex's (1) other physical characteristics (i.e. size, zeta potential, CUR payload, amorphous state stability), (2) preparation efficiency (i.e. CUR utilization rate, yield), and (3) dissolutions under sink condition and supersaturation generation. CUR nanoplex prepared using CHI of high MW exhibited improved colloidal stability, larger size, superior morphology, and prolonged supersaturation generation. On the other hand, the effects of MW variation on the payload, amorphous state stability, preparation efficiency, and dissolution under sink condition were found to be insignificant. Varying MW of CHI used was an effective means to improve certain aspects of the CUR nanoplex characteristics with minimal adverse effects on the others.

Transport and transformation of soil-derived CO2, CH4 and DOC sustain CO2 supersaturation in small boreal streams.

PubMed

Rasilo, Terhi; Hutchins, Ryan H S; Ruiz-González, Clara; Del Giorgio, Paul A

2017-02-01

Streams are typically supersaturated in carbon dioxide (CO 2 ) and methane (CH 4 ), and are recognized as important components of regional carbon (C) emissions in northern landscapes. Whereas there is consensus that in most of the systems the CO 2 emitted by streams represents C fixed in the terrestrial ecosystem, the pathways delivering this C to streams are still not well understood. We assessed the contribution of direct soil CO 2 injection versus the oxidation of soil-derived dissolved organic C (DOC) and CH 4 in supporting CO 2 supersaturation in boreal streams in Québec. We measured the concentrations of CO 2 , CH 4 and DOC in 43 streams and adjacent soil waters during summer base-flow period. A mass balance approach revealed that all three pathways are significant, and that the mineralization of soil-derived DOC and CH 4 accounted for most of the estimated stream CO 2 emissions (average 75% and 10%, respectively), and that these estimated contributions did not change significantly between the studied low order (≤3) streams. Whereas some of these transformations take place in the channel proper, our results suggest that they mainly occur in the hyporheic zones of the streams. Our results further show that stream CH 4 emissions can be fully explained by soil CH 4 inputs. This study confirms that these boreal streams, and in particular their hyporheic zones, are extremely active processors of soil derived DOC and CH 4 , not just vents for soil produced CO 2 . Copyright © 2016 Elsevier B.V. All rights reserved.

Combining laboratory results, numerical modeling, and in situ measurements to investigate the relative contributions of homogeneous and heterogeneous nucleation to ice formation in the tropical tropopause layer

NASA Astrophysics Data System (ADS)

Jensen, E. J.; Karcher, B.; Ueyama, R.; Pfister, L.; Bui, T. V.; Diskin, G. S.; DiGangi, J. P.; Woods, S.; Lawson, P.; Froyd, K. D.; Murphy, D. M.

2017-12-01

Laboratory experiments over the past decade have advanced our understanding of the physical state and ice nucleation efficacy of aerosols with atmospherically-relevant compositions at low temperatures. We use these laboratory results along with measurements of upper-tropospheric aerosol composition to develop a parameterization if the ice nuclei number, and activity dependence on ice supersaturation and temperature in the cold tropical tropopause layer (TTL, 13-18 km). We show that leading candidates for aerosol types serving as effective ice nuclei are glassy organic-containing aerosols, crystalline ammonium sulfate, and mineral dust. We apply the low-temperature heterogeneous ice nucleation parameterization in a detailed model of TTL transport and cirrus formation. The model treats heterogeneous ice nucleation and homogeneous freezing of aqueous aerosols, deposition growth and sublimation of ice crystals, and sedimentation of ice crystals. The model is driven by meteorological fields with high-frequency waves superimposed, and simulated cirrus microphysical properties are statistically compared with recent measurements of TTL cirrus microphysical properties and ice supersaturation from recent high-altitude aircraft campaigns. We show that effective ice nuclei concentrations on the order of 50-100/L can dominate over homogeneous freezing production of TTL cirrus ice crystals. Glassy organic-containing aerosols or crystalline ammonium sulfate could conceivably provide more abundant sources of ice nuclei, but the simulations indicate that high concentrations of effective IN would prevent observed occurrence of large supersaturations and high ice concentrations. We will also show the impact of heterogeneous ice nuclei on TTL cirrus microphysical properties and occurrence frequencies.

Molecular implications of drug-polymer solubility in understanding the destabilization of solid dispersions by milling.

PubMed

Yang, Ziyi; Nollenberger, Kathrin; Albers, Jessica; Qi, Sheng

2014-07-07

The solubility of drugs in polymer matrixes has been recognized as one of the key factors governing the physical stability of solid dispersions. This study has explored the implications of drug solubility on the destabilization that occurs on milling, which is often used as an additional process for hot melt extruded (HME) solid dispersions. The theoretical drug solubility in the polymer was first predicted using various theoretical and experimental approaches. The destabilization effects of high-energy mechanical milling on the solid dispersions with drug loadings below and above the predicted solubility were then investigated using a range of thermal, microscopic, and spectroscopic techniques. Four model drug-polymer combinations were studied. The HME formulations with drug loading below the predicted solid solubility (undersaturated and true molecular dispersion) showed good stability against milling. In contrast, milling destabilized supersaturated HME dispersions via increasing molecular mobility and creating phase-separated, amorphous, drug-rich domains. However, these additional amorphous drug-rich domains created by milling show good stability under ambient conditions, though crystallization can be accelerated by additional heating. These results highlighted that the processing method used to prepare the solid dispersions may play a role in facilitating the stabilization of amorphous drug in supersaturated solid dispersions. The degree of supersaturation of the drug in the polymer showed significant impact on the destabilization behavior of milling on solid dispersions. An improved understanding of the destabilization behavior of solid dispersions upon milling can provide new insights into the processing related apparent solubility of drugs in polymers.

An Effective Continuum Model for the Gas Evolution in Internal Steam Drives

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

Tsimpanogiannis, Ioannis N.; Yortsos, Yanis C.

This report examines the gas phase growth from a supersaturated, slightly compressible, liquid in a porous medium, driven by heat transfer and controlled by the application of a constant-rate decline of the system pressure.

Fluorapatite crystal growth from modified seawater solutions

NASA Astrophysics Data System (ADS)

Van Cappellen, Philippe; Berner, Robert A.

Seeded precipitation experiments were conducted in a pH/fluoride-stat system to study the crystal growth of fluorapatite ( FAP ) in carbonate-free NaCl-CaCl 2-NaF-Na 2HPO 4 solutions, at seawater calcium concentration, chlorinity, and pH. With increasing supersaturation, the dependence of the growth rate on the relative supersaturation changes from parabolic to exponential. This is interpreted as reflecting a transition in the crystal growth mechanism from growth at dislocation-induced surface steps to surface nucleation-controlled growth. The analysis of the kinetic data leads to a mineral-aqueous solution interfacial tension for FAP of 289 mJ/m 2. The Arrhenius activation energy of the growth reaction in the temperature range 12 to 35°C is 47 kJ/mol. The inhibition of FAP growth by Mg 2+ ions was investigated over a range of total dissolved Mg of 0 to 60 mM. At dissolved magnesium concentrations typical of marine pore waters (40-60 mM), the rate of FAP growth is 15 to 20 times slower than in the absence of Mg 2+, for the same degree of supersaturation, at 25 °C and pH = 8. The inhibitory effect can be explained by the blocking of growth sites at the surface of FAP crystals by adsorbed Mg 2+ ions. A simple Langmuir adsorption model for the retardation effect of Mg 2+ is supported by the results. The effect of pH on FAP growth was tested for pH values from 7 to 8.5. In this range, growth of FAP is catalyzed by hydrogen ions. The apparent growth rate constant is proportional to ( aH+) m where m, the rate order with respect to H +, is a non-integral number which depends on pH. At identical degrees of supersaturation, the growth rate of FAP at pH = 7 is nearly twice that at pH = 8. When corrected for bottom water temperatures, pore water pH, and the retardation of Mg 2+, the experimental growth rates predict that during burial in modern phosphatic sediments, apatite particles grow to sizes on the order of 0.1-10 μrn. The relatively slow growth kinetics of FAP are consistent with the observed small particle sizes of marine sedimentary apatite.

The Solubility of Nickel Sulfate-6-Water: A General Chemistry Experiment.

ERIC Educational Resources Information Center

Pacer, Richard A.

1984-01-01

Background information, procedures used, and typical results are provided for a solubility experiment. Among the 12 objectives of the experiment are: acquiring understanding of the terms "saturated,""unsaturated," and "supersaturated;" learning meaning of the expression "to approach equilibrium;" gaining…

MIXING OF SUPERSATURATED ASSEMBLAGES AND THE PRECIPITOUS LOSS OF SPECIES

EPA Science Inventory

Louisiana shelf hypoxia is thought to be caused by the combination of vertical stratification that isolates sub-pycnocline waters from atmospheric oxygen and the “rain” of organic rich particles from primary production (edible and inedible phytoplankton) and allochthonous sources...

Geochemistry of highly basic calcium hydroxide groundwater in Jordan

USGS Publications Warehouse

Barnes, I.; Presser, T.S.; Saines, M.; Dickson, P.; Van Groos, A. F. K.

1982-01-01

Highly-alkaline (pH > 12.5) meteoric waters of a Ca2+OH--type issue from naturally calcined bituminous marl. The cold (16.5 ??? T(??C) ??? 19.1) waters are super-saturated with minerals thought to be of high-temperature origin. ?? 1982.

The relationship between dissolved hydrogen and nitrogen fixation in ocean waters

NASA Astrophysics Data System (ADS)

Moore, Robert M.; Punshon, Stephen; Mahaffey, Claire; Karl, David

2009-09-01

Fixed nitrogen is a key nutrient involved in regulating global marine productivity and hence the global oceanic carbon cycle. Oceanic nitrogen (N 2) fixation is estimated to supply 8×10 12 moles N y -1 to the ocean, approximately equal to current riverine and the atmospheric inputs of fixed N, and between 50 and 100% of current estimates of oceanic denitrification. However, the spatial and temporal variability of N 2 fixation remains uncertain, mostly because of the normal low resolution sampling for diazotroph distribution and fixation rates. It is well established that N 2 fixation, mediated by the enzyme nitrogenase, is a source of hydrogen (H 2), but the extent to which it leads to supersaturation of H 2 in oceanic waters is unresolved. Here, we present simultaneous measurements of upper ocean dissolved H 2 concentration (nmol L -1), and rates of N 2 fixation (μmol N m -3 d -1), determined using 15N 2 tracer techniques (at 7 or 15 m), on a transect from Fiji to Hawaii. We find a significant correlation ( r=0.98) between dissolved H 2 and rates of N 2 fixation, with the greatest supersaturation of H 2 and highest rates of N 2 fixation being observed in the subtropical gyres at the southern (˜18°S) and northern (18°N) reaches of the transect. The lowest H 2 saturation and N 2 fixation were observed in the equatorial region between 8°S and 14°N. We propose that an empirical relationship between H 2 supersaturations and N 2 fixation measurements could be used to guide sampling for 15N fixation measurements or to aid the spatial interpolation of such measurements.

High-throughput Analysis of Ultrasonication-forced Amyloid Fibrillation Reveals the Mechanism Underlying the Large Fluctuation in the Lag Time*

PubMed Central

Umemoto, Ayaka; Yagi, Hisashi; So, Masatomo; Goto, Yuji

2014-01-01

Amyloid fibrils form in supersaturated solutions of precursor proteins by a nucleation and growth mechanism characterized by a lag time. Although the lag time provides a clue to understanding the complexity of nucleation events, its long period and low reproducibility have been obstacles for exact analysis. Ultrasonication is known to effectively break supersaturation and force fibrillation. By constructing a Handai amyloid burst inducer, which combines a water bath-type ultrasonicator and a microplate reader, we examined the ultrasonication-forced fibrillation of several proteins, with a focus on the fluctuation in the lag time. Amyloid fibrillation of hen egg white lysozyme was examined at pH 2.0 in the presence of 1.0–5.0 M guanidine hydrochloride (GdnHCl), in which the dominant species varied from the native to denatured conformations. Although fibrillation occurred at various concentrations of GdnHCl, the lag time varied largely, with a minimum being observed at ∼3.0 m, the concentration at which GdnHCl-dependent denaturation ended. The coefficient of variation of the lag time did not depend significantly on the GdnHCl concentration and was 2-fold larger than that of the ultrasonication-dependent oxidation of iodide, a simple model reaction. These results suggest that the large fluctuation observed in the lag time for amyloid fibrillation originated from a process associated with a common amyloidogenic intermediate, which may have been a relatively compact denatured conformation. We also suggest that the Handai amyloid burst inducer system will be useful for studying the mechanism of crystallization of proteins because proteins form crystals by the same mechanism as amyloid fibrils under supersaturation. PMID:25118286

Two-moment bulk stratiform cloud microphysics in the GFDL AM3 GCM: description, evaluation, and sensitivity tests

NASA Astrophysics Data System (ADS)

Salzmann, M.; Ming, Y.; Golaz, J.-C.; Ginoux, P. A.; Morrison, H.; Gettelman, A.; Krämer, M.; Donner, L. J.

2010-08-01

A new stratiform cloud scheme including a two-moment bulk microphysics module, a cloud cover parameterization allowing ice supersaturation, and an ice nucleation parameterization has been implemented into the recently developed GFDL AM3 general circulation model (GCM) as part of an effort to treat aerosol-cloud-radiation interactions more realistically. Unlike the original scheme, the new scheme facilitates the study of cloud-ice-aerosol interactions via influences of dust and sulfate on ice nucleation. While liquid and cloud ice water path associated with stratiform clouds are similar for the new and the original scheme, column integrated droplet numbers and global frequency distributions (PDFs) of droplet effective radii differ significantly. This difference is in part due to a difference in the implementation of the Wegener-Bergeron-Findeisen (WBF) mechanism, which leads to a larger contribution from super-cooled droplets in the original scheme. Clouds are more likely to be either completely glaciated or liquid due to the WBF mechanism in the new scheme. Super-saturations over ice simulated with the new scheme are in qualitative agreement with observations, and PDFs of ice numbers and effective radii appear reasonable in the light of observations. Especially, the temperature dependence of ice numbers qualitatively agrees with in-situ observations. The global average long-wave cloud forcing decreases in comparison to the original scheme as expected when super-saturation over ice is allowed. Anthropogenic aerosols lead to a larger decrease in short-wave absorption (SWABS) in the new model setup, but outgoing long-wave radiation (OLR) decreases as well, so that the net effect of including anthropogenic aerosols on the net radiation at the top of the atmosphere (netradTOA = SWABS-OLR) is of similar magnitude for the new and the original scheme.

Two-moment bulk stratiform cloud microphysics in the GFDL AM3 GCM: description, evaluation, and sensitivity tests

NASA Astrophysics Data System (ADS)

Salzmann, M.; Ming, Y.; Golaz, J.-C.; Ginoux, P. A.; Morrison, H.; Gettelman, A.; Krämer, M.; Donner, L. J.

2010-03-01

A new stratiform cloud scheme including a two-moment bulk microphysics module, a cloud cover parameterization allowing ice supersaturation, and an ice nucleation parameterization has been implemented into the recently developed GFDL AM3 general circulation model (GCM) as part of an effort to treat aerosol-cloud-radiation interactions more realistically. Unlike the original scheme, the new scheme facilitates the study of cloud-ice-aerosol interactions via influences of dust and sulfate on ice nucleation. While liquid and cloud ice water path associated with stratiform clouds are similar for the new and the original scheme, column integrated droplet numbers and global frequency distributions (PDFs) of droplet effective radii differ significantly. This difference is in part due to a difference in the implementation of the Wegener-Bergeron-Findeisen (WBF) mechanism, which leads to a larger contribution from super-cooled droplets in the original scheme. Clouds are more likely to be either completely glaciated or liquid due to the WBF mechanism in the new scheme. Super-saturations over ice simulated with the new scheme are in qualitative agreement with observations, and PDFs of ice numbers and effective radii appear reasonable in the light of observations. Especially, the temperature dependence of ice numbers qualitatively agrees with in-situ observations. The global average long-wave cloud forcing decreases in comparison to the original scheme as expected when super-saturation over ice is allowed. Anthropogenic aerosols lead to a larger decrease in short-wave absorption (SWABS) in the new model setup, but outgoing long-wave radiation (OLR) decreases as well, so that the net effect of including anthropogenic aerosols on the net radiation at the top of the atmosphere (netradTOA = SWABS-OLR) is of similar magnitude for the new and the original scheme.

Evaluation of CO2 Efflux From Soils: A New Method Using Streamwater CO2 Measurements, Field Data and a Watershed Model

NASA Astrophysics Data System (ADS)

Sullivan, A. B.; Mulholland, P. J.; Jones, J. B.

2001-05-01

Headwater streams are almost always supersaturated with CO2 compared to concentrations expected in equilibrium with atmospheric CO2. Direct measurements of CO2 in two streams in eastern Tennessee with different bedrock lithologies (Walker Branch, Upper Gum Hollow Branch) over a year revealed levels of supersaturation of two to five times atmospheric CO2. Highest levels were generally found during the summer months. Springs discharging into the stream had dissolved CO2 concentration up to an order of magnitude higher than that in streamwater. These levels of supersaturation are a reflection of the high concentrations of CO2 in soil produced by root respiration and organic matter decomposition. The hydrologic connection between soil CO2 and streamwater CO2 forms the basis of our method to determine soil CO2 concentrations and efflux from the soil to the atmosphere. The method starts with streamwater measurements of CO2. Then corrections are made for evasion from the stream surface using injections of a conservative solute tracer and volatile gas, and for instream metabolism using a dissolved oxygen change technique. The approach then works backward along the hydrologic flowpath and evaluates the contribution of bedrock weathering, which consumes CO2, by examining the changes in major ion chemistry between precipitation and the stream. This produces estimates of CO2 concentration in soil water and soil atmosphere, which when coupled with soil porosity, allows estimation of CO2 efflux from soil. The hydrologic integration of CO2 signals from whole watersheds into streamwater allows calculation of soil CO2 efflux at large scales. These estimates are at scales larger than current chamber or tower methods, and can provide broad estimates of soil CO2 efflux with easily collected stream chemistry data.

Measuring the CCN and IN ability of bacterial isolates: implications for the southeastern United States and Puerto Rico

NASA Astrophysics Data System (ADS)

Purdue, S.; Waters, S.; Konstantinidis, K.; Nenes, A.; DeLeon-Rodriguez, N.

2015-12-01

Ice nucleation is an important process in the climate system as it influences global precipitation processes, and can affect the vertical distribution of clouds with effects that both cool and warm the atmosphere. Of the pathways to ice nucleation, immersion mode, which occurs when ice nuclei (IN) particles are surrounded by an aqueous phase that subsequently freezes, dominates primary ice production in mixed-phase clouds. A simple but effective method to study immersion freezing is to utilize a droplet freezing assay (DFA) that consists of an aluminum plate, precisely cooled by a continuous flow of an ethylene glycol-water mixture. Using such a system we study the immersion IN characteristics of bacterial isolates (for temperatures ranging from -15oC to 0oC) isolated from rainwater and air collected in Atlanta, GA and Puerto Rico, over storms throughout the year. Despite their relatively large size and the presence of hydrophilic groups on the outer membranes of many bacteria, it is unclear if bacteria possess an inherent ability to nucleate an aqueous phase (a requirement for immersion freezing) for the wide range of supersaturations found in clouds. For this, we measure the cloud condensation nucleation (CCN) activity of each isolate (over the 0.05% to 0.6% supersaturation range) using a Continuous Flow Streamwise Thermal Gradient CCN Counter. Initial results have shown certain isolates to be very efficient CCN, allowing them to form droplets even for the very low supersaturations found in radiation fogs. In combination, these experiments provide insight into the potential dual-ability of some bacteria, isolated from the southeastern United States and Puerto Rico, to act as both efficient CCN and IN.

Continuous high-frequency dissolved O2/Ar measurements by equilibrator inlet mass spectrometry.

PubMed

Cassar, Nicolas; Barnett, Bruce A; Bender, Michael L; Kaiser, Jan; Hamme, Roberta C; Tilbrook, Bronte

2009-03-01

The oxygen (O(2)) concentration in the surface ocean is influenced by biological and physical processes. With concurrent measurements of argon (Ar), which has similar solubility properties as oxygen, we can remove the physical contribution to O(2) supersaturation and determine the biological oxygen supersaturation. Biological O(2) supersaturation in the surface ocean reflects the net metabolic balance between photosynthesis and respiration, i.e., the net community productivity (NCP). We present a new method for continuous shipboard measurements of O(2)/Ar by equilibrator inlet mass spectrometry (EIMS). From these measurements and an appropriate gas exchange parametrization, NCP can be estimated at high spatial and temporal resolution. In the EIMS configuration, seawater from the ship's continuous intake flows through a cartridge enclosing a gas-permeable microporous membrane contactor. Gases in the headspace of the cartridge equilibrate with dissolved gases in the flowing seawater. A fused-silica capillary continuously samples headspace gases, and the O(2)/Ar ratio is measured by mass spectrometry. The ion current measurements on the mass spectrometer reflect the partial pressures of dissolved gases in the water flowing through the equilibrator. Calibration of the O(2)/Ar ion current ratio (32/40) is performed automatically every 2 h by sampling ambient air through a second capillary. A conceptual model demonstrates that the ratio of gases reaching the mass spectrometer is dependent on several parameters, such as the differences in molecular diffusivities and solubilities of the gases. Laboratory experiments and field observations performed by EIMS are discussed. We also present preliminary evidence that other gas measurements, such as N(2)/Ar and pCO(2) measurements, may potentially be performed with EIMS. Finally, we compare the characteristics of the EIMS with the previously described membrane inlet mass spectrometry (MIMS) approach.

Study of the hygroscopic properties of selected pharmaceutical aerosols using single particle levitation.

PubMed

Peng, C; Chow, A H; Chan, C K

2000-09-01

To use a single particle levitation technique to investigate the equilibrium water sorption characteristics in both the evaporation and growth of four respiratory drugs at 37 degrees C: atropine sulfate (AS), isoproterenol hydrochloride (IPHC) and isoproterenol hemisulfate (IPHS) and disodium cromoglycate (DSCG). The equilibrium water content was measured as a function of relative humidity (RH) by a single particle levitation technique using an electrodynamic balance (EDB). The change of water content was determined by the voltage required to balance the weight of the levitated particle electrostatically. The water activities of bulk samples were also measured. Growth ratios were determined and compared with values in the literature. Crystallization or deliquescence was not observed for AS, IPHC and IPHS. The hysteresis in the water cycle was not observed for any of the drugs. At RH approximately 0%, AS particles still contain about 5% water but IPHC and IPHS particles do not contain any residual water. The aerodynamic growth ratio from RH 0% to 99.5% is 2.60, 2.86, 2.42 and 1.26 for AS, IPHC, IPHS and DSCG, respectively. Supersaturated droplets of IPHC and IPHS are expected to exist in the ambient conditions. DSCG is in a solid state in the RH range of 10-90%. It is expected that some aerosolized drugs of low solubility may experience supersaturation before they enter the human body and this could exert a significant influence both on particle loss before inhalation and on the deposition of the drugs in the lungs. The EDB is a convenient and reliable tool for studying the hygroscopic properties of pharmaceutical aerosols, especially for supersaturated solutions.

Carbonate chemistry of surface waters in a temperate karst region: the southern Yorkshire Dales, UK

NASA Astrophysics Data System (ADS)

Pentecost, Allan

1992-11-01

A detailed study of surface water chemistry is described from an important limestone region in northern England. Major ions and pH were determined for 485 sites (springs, seeps, streams, rivers and lakes) during summertime. The saturation state of the waters with respect to calcite was determined as the calcite saturation ratio (Ω). An unexpectedly large number of samples were found to be supersaturated (65.5% of the 268 km of watercourses surveyed). As a consequence, several streams entering major cave systems were incapable of further limestone solution, at least during periods of low flow. Many waters were supersaturated from their source and some deposited travertine. A significant negative correlation was found between spring discharge and both (Ω) and pH. Supersaturation was caused primarily by atmospheric degassing, with some contribution from aquatic plant photosynthesis. The median total dissolved inorganic carbon and Ca concentrations were 2.49 and 1.35 millimoles 1 -1 respectively. Calcium originated exclusively from limestone, and carbon dioxide mainly from the soil and dissolved limestone. South facing catchments provided springwaters with significantly higher levels of TDIC and Ca when compared with north facing catchments. The study suggests that acid rain made a measurable contribution to limestone dissolution. Carboniferous limestone denudation rates were estimated as 54 to 63 m 3 km -2 a -1 (54 to 63 mm 1000 years -1). About 50% of the Mg came from limestone and the remainder, together with most K, Na, SO 4 and Cl from precipitation. Concentrations of dissolved nutrients were low, medians for NO 3, NH 4, total PO 4 and SiO 3 were 24 μmol, 1.4 μmol, 0.64 μmol and 15.5 μmol 1 -1 respectively. The concentration of a further 23 trace elements was determined.

Formulation of a danazol cocrystal with controlled supersaturation plays an essential role in improving bioavailability.

PubMed

Childs, Scott L; Kandi, Praveen; Lingireddy, Sreenivas Reddy

2013-08-05

Cocrystals have become an established and adopted approach for creating crystalline solids with improved physical properties, but incorporating cocrystals into enabling pre-clinical formulations suitable for animal dosing has received limited attention. The dominant approach to in vivo evaluation of cocrystals has focused on deliberately excluding additional formulation in favor of "neat" aqueous suspensions of cocrystals or loading neat cocrystal material into capsules. However, this study demonstrates that, in order to take advantage of the improved solubility of a 1:1 danazol:vanillin cocrystal, a suitable formulation was required. The neat aqueous suspension of the danazol:vanillin cocrystal had a modest in vivo improvement of 1.7 times higher area under the curve compared to the poorly soluble crystal form of danazol dosed under identical conditions, but the formulated aqueous suspension containing 1% vitamin E-TPGS (TPGS) and 2% Klucel LF Pharm hydroxypropylcellulose improved the bioavailability of the cocrystal by over 10 times compared to the poorly soluble danazol polymorph. In vitro powder dissolution data obtained under non-sink biorelevant conditions correlate with in vivo data in rats following 20 mg/kg doses of danazol. In the case of the danazol:vanillin cocrystal, using a combination of cocrystal, solubilizer, and precipitation inhibitor in a designed supersaturating drug delivery system resulted in a dramatic improvement in the bioavailability. When suspensions of neat cocrystal material fail to return the anticipated bioavailability increase, a supersaturating formulation may be able to create the conditions required for the increased cocrystal solubility to be translated into improved in vivo absorption at levels competitive with existing formulation approaches used to overcome solubility limited bioavailability.

Is it Possible to have the Similar Unit Cell in Crystals of Different form from the same Macromolecule? (A Case Study of Ribosome Crystals)

NASA Technical Reports Server (NTRS)

Karpova, E. A.; Rose, M. Franklin (Technical Monitor)

2000-01-01

Three different types of ribosome crystals were grown by the vapor diffusion technique in hanging drops as described in (1,2). The ribosome is a large asymmetric RNA-protein complex (2.3 million Da), which is protein syntheses machinery of the cell. In this poster we would like to discuss the features of ribosome crystallization. Ribosomes were purified from the thermophilic bacteria Thermus thermophilus by centrifugation (3). Three types of crystals (needle, flat tetragonal and tetragonal-like pyramid) can be grown from the same solution; furthermore, in the same drop using 10-15% 2-methyl-2,4- pentanediol as a precipitant. The crystals appeared in 5-48 hours. The crystals were stable and can co-exist in solution over long period of time. The kinetics of appearance of different crystal forms was different: first the needle crystals were grown, then the tetragonal, and finally the tetragonal pyramids. Later studies of the process of ribosome crystal growth depending on supersaturation showed that low supersaturation results in the appearance of tetragonal plates or tetragonal-like pyramids. An electron microscopy study, together with computer modeling, has shown that crystals of different forms have a high probability of having the same unit cell parameters. According to these experiments the following conclusion can be dranvn: the level of supersaturation of the macromolecule in a crystallizing solution is one of the major factors for forming three-dimensional crystals convenient for X-rays diffraction analysis. From the same macromolecule solution, crystals of different forms can be grown at approximately the same conditions by varying the concentration of macromolecule in the solution. Ion-macromolecule and water-macromolecule interactions, apparently, play the main role in the formation of the unit cell of the crystals.

Structure of selenium incorporated in pyrite and mackinawite as determined by XAFS analyses

NASA Astrophysics Data System (ADS)

Diener, A.; Neumann, T.; Kramar, U.; Schild, D.

2012-05-01

Selenium has a toxic potential leading to diseases by ingestion and a radiotoxic potential as 79Se radionuclide if discharged from a high-level nuclear waste repository in deep geological formations into the biosphere. Selenium is often associated with sulfides, such as pyrite, the most important near-surface iron sulfide and constituent of host rocks and bentonite backfills considered for radioactive waste disposal. This study was aimed at investigating the incorporation of Se2- and Se4+ into pyrite and mackinawite to determine the relevance of iron sulfides to Se retention and the type of structural bonding. The syntheses of pyrite and mackinawite occurred via direct precipitation in batches and also produced coatings on natural pyrite in mixed-flow reactor experiments (MFR) under anoxic conditions at Se concentrations in the solutions of up to 10- 3 mol/L. Mineralogical analyses by SEM and XRD reveal the formation of pyrite and mackinawite phases. The average Se2- uptake in pyrite in batch experiments amounts to 98.6%. In MFR syntheses, it reaches 99.5%, both suggesting a high potential for retention. XAFS results indicate a substitution of sulfur by selenide during instantaneous precipitation in highly supersaturated solutions only. In selenide-doted mackinawite S2- was substituted by Se2-, resulting in a mackinawite-type compound. S- is substituted by Se- in selenide-doted pyrite, yielding a FeSSe compound as a slightly distorted pyrite structure. Under slighter supersaturated conditions, XAFS results indicate an incorporation of Se2- and Se4+ predominantly as Se0. This study shows that a substitution of S by Se in iron sulfides is probable only for highly supersaturated solutions under acidic and anoxic conditions. Under closer equilibrium conditions, Se0 is expected to be the most stable species.

Enhanced stability of steep channel beds to mass failure and debris flow initiation

NASA Astrophysics Data System (ADS)

Prancevic, J.; Lamb, M. P.; Ayoub, F.; Venditti, J. G.

2015-12-01

Debris flows dominate bedrock erosion and sediment transport in very steep mountain channels, and are often initiated from failure of channel-bed alluvium during storms. While several theoretical models exist to predict mass failures, few have been tested because observations of in-channel bed failures are extremely limited. To fill this gap in our understanding, we performed laboratory flume experiments to identify the conditions necessary to initiate bed failures in non-cohesive sediment of different sizes (D = 0.7 mm to 15 mm) on steep channel-bed slopes (S = 0.45 to 0.93) and in the presence of water flow. In beds composed of sand, failures occurred under sub-saturated conditions on steep bed slopes (S > 0.5) and under super-saturated conditions at lower slopes. In beds of gravel, however, failures occurred only under super-saturated conditions at all tested slopes, even those approaching the dry angle of repose. Consistent with theoretical models, mass failures under super-saturated conditions initiated along a failure plane approximately one grain-diameter below the bed surface, whereas the failure plane was located near the base of the bed under sub-saturated conditions. However, all experimental beds were more stable than predicted by 1-D infinite-slope stability models. In partially saturated sand, enhanced stability appears to result from suction stress. Enhanced stability in gravel may result from turbulent energy losses in pores or increased granular friction for failures that are shallow with respect to grain size. These grain-size dependent effects are not currently included in stability models for non-cohesive sediment, and they may help to explain better the timing and location of debris flow occurrence.

Amplification of seismic waves beneath active volcanoes

NASA Astrophysics Data System (ADS)

Navon, O.; Lensky, N. G.; Collier, L.; Neuberg, J.; Lyakhovsky, V.

2003-04-01

Long-period (LP) seismic events are typical of many volcanoes and are attributed to energy leaking from waves traveling through the volcanic conduit or along the conduit - country-rock interface. The LP events are triggered locally, at the volcanic edifice, but the source of energy for the formation of tens of events per day is not clear. Energy may be supplied by volatile-release from a supersaturated melt. If bubbles are present in equilibrium with the melt in the conduit, and the melt is suddenly decompressed, transfer of volatiles from the supersaturated melt into the bubbles transforms stored potential energy into expansion work. For example, small dome collapses may decompress the conduit by a few bars and lead to solubility decrease, exsolution of volatiles and, consequently, to work done by the expansion of the bubbles under pressure. This energy is released over a timescale that is similar to that of LP events and may amplify the original weak seismic signals associated with the collapse. Using the formulation of Lensky et al. (2002), following the decompression, when the transfer of volatiles into bubbles is fast enough, expansion accelerates and the bulk viscosity of the bubbly magma is negative. New calculations show that under such conditions a sinusoidal P-wave is amplified. We note that seismic waves created by tectonic earthquakes that are not associated with net decompression, do not lead to net release of volatiles or to net expansion. In this case, the bulk viscosity is positive and waves traveling through the magma should attenuate. The proposed model explains how weak seismic signals may be amplified as they travel through a conduit that contains supersaturated bubbly magma. It provides the general framework for amplifying volcanic seismicity such as the signals associated with long-period events.

Physiological (antioxidant) responses of estuarine fishes to variability in dissolved oxygen.

PubMed

Ross, S W; Dalton, D A; Kramer, S; Christensen, B L

2001-11-01

Cycles of dissolved oxygen (DO) in estuaries can range from anoxia to various levels of supersaturation (200-300%) over short time periods. Aerobic metabolism causes formation of damaging reactive oxygen species (ROS), a process exacerbated by high or low DO. Fish can generate physiological defenses (e.g. antioxidant enzymes) against ROS, however, there are little data tying this to environmental conditions. We investigated physiological defenses generated by estuarine fishes in response to high DO and various DO cycles. We hypothesized that chemical defenses and/or oxidative damage are related to patterns of DO supersaturation. Specific activities of antioxidants in fish tissues should be positively correlated with increasing levels of DO, if high DO levels are physiologically stressful. We caged common benthic fishes (longjaw mudsucker, Gillichthys mirabilis, and staghorn sculpin, Leptocottus armatus, in CA and spot, Leiostomus xanthurus and pinfish, Lagodon rhomboides, in NC) during summer 1998 in two estuarine sites in southern North Carolina and two in central California. At each site a water quality meter measured bottom DO, salinity, temperature, depth, pH and turbidity at 30 min intervals throughout the study. These sites exhibited a wide variety of dissolved oxygen patterns. After 2 weeks in the cages, fish gills and livers were analyzed for antioxidant enzymes (glutathione peroxidase, catalase and superoxide dismutase) and the metabolite glutathione. All fish exhibited antioxidant enzyme activity. There was a significant site-dependent effect on all enzyme activities at the NC sites, with the most activity at the site with the highest DO cycling and the most DO supersaturation. There was a trend towards higher enzyme activities under high DO levels at the CA sites.

The role of mass transport in protein crystallization.

PubMed

García-Ruiz, Juan Manuel; Otálora, Fermín; García-Caballero, Alfonso

2016-02-01

Mass transport takes place within the mesoscopic to macroscopic scale range and plays a key role in crystal growth that may affect the result of the crystallization experiment. The influence of mass transport is different depending on the crystallization technique employed, essentially because each technique reaches supersaturation in its own unique way. In the case of batch experiments, there are some complex phenomena that take place at the interface between solutions upon mixing. These transport instabilities may drastically affect the reproducibility of crystallization experiments, and different outcomes may be obtained depending on whether or not the drop is homogenized. In diffusion experiments with aqueous solutions, evaporation leads to fascinating transport phenomena. When a drop starts to evaporate, there is an increase in concentration near the interface between the drop and the air until a nucleation event eventually takes place. Upon growth, the weight of the floating crystal overcomes the surface tension and the crystal falls to the bottom of the drop. The very growth of the crystal then triggers convective flow and inhomogeneities in supersaturation values in the drop owing to buoyancy of the lighter concentration-depleted solution surrounding the crystal. Finally, the counter-diffusion technique works if, and only if, diffusive mass transport is assured. The technique relies on the propagation of a supersaturation wave that moves across the elongated protein chamber and is the result of the coupling of reaction (crystallization) and diffusion. The goal of this review is to convince protein crystal growers that in spite of the small volume of the typical protein crystallization setup, transport plays a key role in the crystal quality, size and phase in both screening and optimization experiments.

Supersaturated Electrolyte Solutions: Theory and Experiment

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.; Na, Han-Soo

1995-01-01

Highly supersaturated electrolyte solutions can be prepared and studied employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. In the approach suggested the metastable state for electrolyte solutions is described in terms of the conserved order parameter omega(r,t) associated with fluctuations of the mean solute concentration n(sub 0). Parameters of the corresponding Ginzburg-Landau free energy functional which defines the dynamics of metastable state relaxation are determined and expressed through the experimentally measured quantities. A correspondence of 96-99 % between theory and experiment for all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin), and its calculation for various electrolyte solutions at 298 K. The assumption that subcritical solute clusters consist of the electrically neutral Bjerrum pairs has allowed both analytical and numerical investigation of the number-size N(sub c) of nucleation monomers (aggregates of the Bjerrum pairs) which are elementary units of the solute critical clusters. This has also allowed estimations for the surface tension Alpha, and equilibrium bulk energy Beta per solute molecule in the nucleation monomers. The dependence of these properties on the temperature T and on the solute concentration n(sub 0) through the entire metastable zone (from saturation concentration n(sub sat) to spinodal n(sub spin) is examined. It has been demonstrated that there are the following asymptotics: N(sub c), = I at spinodal concentration and N(sub c) = infinity at saturation.

Microstructural investigation of D2 tool steel during rapid solidification

NASA Astrophysics Data System (ADS)

Delshad Khatibi, Pooya

Solidification is considered as a key processing step in developing the microstructure of most metallic materials. It is, therefore, important that the solidification process can be designed and controlled in such a way so as to obtain the desirable properties in the final product. Rapid solidification refers to the system's high undercooling and high cooling rate, which can yield a microstructure with unique chemical composition and mechanical properties. An area of interest in rapid solidification application is high-chromium, high-carbon tool steels which experience considerable segregation of alloying elements during their solidification in a casting process. In this dissertation, the effect of rapid solidification (undercooling and cooling rate) of D2 tool steel on the microstructure and carbide precipitation during annealing was explored. A methodology is described to estimate the eutectic and primary phase undercooling of solidifying droplets. The estimate of primary phase undercooling was confirmed using an online measurement device that measured the radiation energy of the droplets. The results showed that with increasing primary phase and eutectic undercooling and higher cooling rate, the amount of supersaturation of alloying element in metastable retained austenite phase also increases. In the case of powders, the optimum hardness after heat treatment is achieved at different temperatures for constant periods of time. Higher supersaturation of austenite results in obtaining secondary hardness at higher annealing temperature. D2 steel ingots generated using spray deposition have high eutectic undercooling and, as a result, high supersaturation of alloying elements. This can yield near net shape D2 tool steel components with good mechanical properties (specifically hardness). The data developed in this work would assist in better understanding and development of near net shape D2 steel spray deposit products with good mechanical properties.

Inorganic carbon loading as a primary driver of dissolved carbon dioxide concentrations in the lakes and reservoirs of the contiguous United States

USGS Publications Warehouse

McDonald, Cory P.; Stets, Edward; Striegl, Robert G.; Butman, David

2013-01-01

Accurate quantification of CO2 flux across the air-water interface and identification of the mechanisms driving CO2 concentrations in lakes and reservoirs is critical to integrating aquatic systems into large-scale carbon budgets, and to predicting the response of these systems to changes in climate or terrestrial carbon cycling. Large-scale estimates of the role of lakes and reservoirs in the carbon cycle, however, typically must rely on aggregation of spatially and temporally inconsistent data from disparate sources. We performed a spatially comprehensive analysis of CO2 concentration and air-water fluxes in lakes and reservoirs of the contiguous United States using large, consistent data sets, and modeled the relative contribution of inorganic and organic carbon loading to vertical CO2 fluxes. Approximately 70% of lakes and reservoirs are supersaturated with respect to the atmosphere during the summer (June–September). Although there is considerable interregional and intraregional variability, lakes and reservoirs represent a net source of CO2 to the atmosphere of approximately 40 Gg C d–1 during the summer. While in-lake CO2 concentrations correlate with indicators of in-lake net ecosystem productivity, virtually no relationship exists between dissolved organic carbon and pCO2,aq. Modeling suggests that hydrologic dissolved inorganic carbon supports pCO2,aq in most supersaturated systems (to the extent that 12% of supersaturated systems simultaneously exhibit positive net ecosystem productivity), and also supports primary production in most CO2-undersaturated systems. Dissolved inorganic carbon loading appears to be an important determinant of CO2concentrations and fluxes across the air-water interface in the majority of lakes and reservoirs in the contiguous United States.

Fluorapatite crystal growth from modified seawater solutions

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

Van Cappellen, P.; Berner, R.A.

Seeded precipitation experiments were conducted in a pH/fluoride-stat system to study the crystal growth of fluorapatite (FAP) in carbonate-free NaCl-CaCl{sub 2}-NaF-Na{sub 2}HPO{sub 4} solutions, at seawater calcium concentration, chlorinity, and pH. With increasing supersaturation, the dependence of the growth rate on the relative supersaturation changes from parabolic to exponential. This is interpreted as reflecting a transition in the crystal growth mechanism from growth at dislocation-induced surface steps to surface nucleation-controlled growth. The analysis of the kinetic data leads to a mineral-aqueous solution interfacial tension for FAP of 289 mJ/M{sup 2}. The Arrhenius activation energy of the growth reaction in themore » temperature range 12 to 35C is 47 kJ/mol. The effect of pH on FAP growth was tested for pH values from 7 to 8.5. In this range, growth of FAP is catalyzed by hydrogen ions. The apparent growth rate constant is proportional to (a{sub H{sup +}}){sup m} where m, the rate order with respect to H{sup +}, is a non-integral number which depends on pH. At identical degrees of supersaturation, the growth rate of FAP at pH = 7 is nearly twice that at pH = 8. When corrected for bottom water temperatures, pore water pH, and the retardation of Mg{sup 2+}, the experimental growth rates predict that during burial in modern phosphatic sediments, apatite particles grow to sizes on the order of 0.1-10{mu}m. The relatively slow growth kinetics of FAP are consistent with the observed small particle sizes of marine sedimentary apatite.« less

Effects of tablet formulation and subsequent film coating on the supersaturated dissolution behavior of amorphous solid dispersions.

PubMed

Sakai, Toshiro; Hirai, Daiki; Kimura, Shin-Ichiro; Iwao, Yasunori; Itai, Shigeru

2018-04-05

The effects of tablet preparation and subsequent film coating with amorphous solid dispersion (ASD) particles that were composed of a drug with poor water solubility and hydrophilic polymers were investigated. ASD particles were prepared with a drug and vinylpyrrolidone-vinyl acetate copolymer (PVPVA) or polyvinylpyrrolidone (PVP) at a weight ratio of 1:1 or 1:2 using a melt extrusion technique. Tablets were prepared by conventional direct compression followed by pan coating. A mathematical model based on the Noyes-Whitney equation assuming that stable crystals precipitated at the changeable surface area of the solid-liquid interface used to estimate drug dissolution kinetics in a non-sink dissolution condition. All the ASD particles showed a maximum dissolution concentration approximately ten times higher than that of the crystalline drug. The ASD particles with PVPVA showed higher precipitation rate with lower polymer ratio, while PVP did not precipitate within 960 min regardless of the polymer ratio, suggesting the ASD particles of 1:1 drug:PVPVA (ASD-1) were the most unstable among the ASD particles considered. The dissolution of a core tablet with ASD-1 showed less supersaturation and a much higher precipitation rate than those of ASD-1 particles. However, a film-coated tablet or core tablet with a trace amount of hydroxypropylmethylcellulose (HPMC) showed a similar dissolution profile to that of the ASD-1 particles, indicating HPMC had a remarkable precipitation inhibition effect. Overall, these results suggest that tablet preparation with ASD may adversely affect the maintenance of supersaturation; however, this effect can be mitigated by adding an appropriate precipitation inhibitor to the formulation. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of grapefruit juice on urinary lithogenicity.

PubMed

Goldfarb, D S; Asplin, J R

2001-07-01

An increased risk of nephrolithiasis has been associated with the ingestion of grapefruit juice in epidemiological studies. To our knowledge the basis of this effect of grapefruit juice has not been studied previously. We studied the effect of grapefruit juice consumption on urinary chemistry and measures of lithogenicity. Ten healthy men and women between ages of 25 and 40 years participated. Each subject drank 240 ml. of tap water at least 3 times daily for 7 days during the control period. This period was followed by a second 7 days experimental period during which they drank 240 ml. of grapefruit juice 3 times daily. In each 7-day period urine was collected for 24 hours during the last 3 days. Urine chemical analysis was performed, supersaturations of calcium oxalate, calcium phosphate and uric acid were calculated and urinary lithogenicity was measured. Urine volume and creatinine excretion were the same during the control and experimental periods. Grapefruit juice ingestion was associated with an increase in mean oxalate excretion plus or minus standard deviation of 41.1 +/- 9.2 to 51.9 +/- 12.0 mg. per 24 hours (p = 0.001) and in mean citrate excretion of 504.8 +/- 226.5 to 591.4 +/- 220.0 mg. per 24 hours (p = 0.01). There was no net change in the supersaturation or upper limit of metastability of calcium oxalate, calcium phosphate or uric acid. Crystal aggregation and growth inhibition by urinary macromolecules was not affected by grapefruit juice ingestion. Offsetting changes in urine chemistry caused by the ingestion of grapefruit juice led to no net change in calculated supersaturation. No changes in lithogenicity were demonstrated. The results do not demonstrate an effect of grapefruit juice for increasing lithogenicity. The basis of the observations of epidemiological studies remain unexplained.

Anachronistic facies from a drowned Lower Triassic carbonate platform: Lower member of the Alwa Formation (Ba'id Exotic), Oman Mountains

NASA Astrophysics Data System (ADS)

Woods, Adam D.; Baud, Aymon

2008-09-01

The lower member of the Alwa Formation (Lower Olenekian), found within the Ba'id Exotic in the Oman Mountains (Sultanate of Oman), consists of ammonoid-bearing, pelagic limestones that were deposited on an isolated, drowned carbonate platform on the Neotethyan Gondwana margin. The strata contain a variety of unusual carbonate textures and features, including thrombolites, Frutexites-bearing microbialites that contain synsedimentary cements, matrix-free breccias surrounded by isopachous calcite cement, and fissures and cavities filled with large botryoidal cements. Thrombolites are found throughout the study interval, and occur as 0.5-1.0 m thick lenses or beds that contain laterally laterally-linked stromatactis cavities. The Frutexites-bearing microbialites occur less frequently, and also form lenses or beds, up to 30 cm thick; the microbialites may be laminated, and often developed on hardgrounds. In addition, the Frutexites-bearing microbialites also contain synsedimentary calcite cement crusts and botryoids (typically < 1 cm thick) that harbour layers or pockets of what appear to be bacterial sheaths and coccoids, and are indicative of biologically mediated precipitation of the cement bodies. Slumping following lithification led to fracturing of the limestone and the precipitation of large, botryoidal aragonite cements in fissures that cut across the primary fabric. Environmental conditions, specifically palaeoxygenation and the degree of calcium carbonate supersaturation, likely controlled whether the thrombolites (high level of calcium carbonate supersaturation associated with vertical mixing of water masses and dysoxic conditions) or Frutexites-bearing microbialites (low level of calcium carbonate supersaturation associated with anoxic conditions and deposition below a stable chemocline) formed. The results of this study point to continued environmental stress in the region during the Early Triassic that likely contributed to the uneven recovery from the Permian-Triassic mass extinction.

Influence of high-pressure torsion on formation/destruction of nano-sized spinodal structures

NASA Astrophysics Data System (ADS)

Alhamidi, Ali; Edalati, Kaveh; Horita, Zenji

2018-04-01

The microstructures and hardness of Al - 30 mol.% Zn are investigated after processing by high-pressure torsion (HPT) for different numbers of revolutions, N = 1, 3, 10 or 25, as well as after post-HPT annealing at different temperatures, T = 373 K, 473 K, 573 K and 673 K. It was found that a work softening occurs by decreasing the grain size to the submicrometer level and increasing the fraction of high-angle boundaries. As a result of HPT processing, a complete decomposition of supersaturated solid solution of Zn in Al occurs and the spinodal structure is destroyed. This suggests that softening of the Al-Zn alloys after HPT is due to the decomposition of the supersaturated solid solution and destruction of spinodal decomposition. After post-HPT annealing, ultrafine-grained Al-Zn alloys show an unusual mechanical properties and its hardness increased to 187 HV. Microstructural analysis showed that the high hardness after post-HPT annealing is due to the formation of spinodal structures.

Lateral line pore diameters correlate with the development of gas bubble trauma signs in several Columbia River fishes

USGS Publications Warehouse

Morris, R.G.; Beeman, J.W.; VanderKooi, S.P.; Maule, A.G.

2003-01-01

Gas bubble trauma (GBT) caused by gas supersaturation of river water continues to be a problem in the Columbia River Basin. A common indicator of GBT is the percent of the lateral line occluded with gas bubbles; however, this effect has never been examined in relation to lateral line morphology. The effects of 115, 125 and 130% total dissolved gas levels were evaluated on five fish species common to the upper Columbia River. Trunk lateral line pore diameters differed significantly (P<0.0001) among species (longnose sucker>largescale sucker>northern pikeminnow≥chinook salmon≥redside shiner). At all supersaturation levels evaluated, percent of lateral line occlusion exhibited an inverse correlation to pore size but was not generally related to total dissolved gas level or time of exposure. This study suggests that the differences in lateral line pore diameters between species should be considered when using lateral line occlusion as an indicator of gas bubble trauma.

Influence of Polymers on the Crystal Growth Rate of Felodipine: Correlating Adsorbed Polymer Surface Coverage to Solution Crystal Growth Inhibition.

PubMed

Schram, Caitlin J; Taylor, Lynne S; Beaudoin, Stephen P

2015-10-20

The bioavailability of orally administered drugs that exhibit poor aqueous solubility can be enhanced with the use of supersaturating dosage forms. Stabilization of these forms by preventing or inhibiting crystallization in solution is an important area of study. Polymers can be used to stabilize supersaturated systems; however, the properties that impact their effectiveness as crystal growth rate inhibitors are not yet fully understood. In this study, the impact of various polymers on the crystal growth rate of felodipine and the conformation of these polymers adsorbed to crystalline felodipine was investigated in order to gain a mechanistic understanding of crystal growth inhibition. It was determined that polymer hydrophobicity impacted polymer adsorption as well as adsorbed polymer conformation. Polymer conformation impacts its surface coverage, which was shown to directly correlate to the polymer's effectiveness as a growth rate inhibitor. By modeling this correlation, it is possible to predict polymer effectiveness given the surface coverage of the polymer.

Properties of jet engine combustion particles during the PartEmis experiment. Hygroscopic growth at supersaturated conditions

NASA Astrophysics Data System (ADS)

Hitzenberger, R.; Giebl, H.; Petzold, A.; Gysel, M.; Nyeki, S.; Weingartner, E.; Baltensperger, U.; Wilson, C. W.

2003-07-01

During the EU Project PartEmis, the microphysical properties of aircraft combustion aerosol were investigated. This study is focused on the ability of exhaust aerosols to act as cloud condensation nuclei (CCN). The combustor was operated at two different conditions representing old and modern aircraft engine technology. CCN concentrations were measured with the University of Vienna CCN counter [ Giebl et al., 2002] at supersaturations around 0.7%. The activation ratio (fraction of CCN in total aerosol) depended on the fuel sulphur content (FSC) and also on the operation conditions. CCN/CN ratios increased from 0.93 through 1.43 to 5.15 . 10-3 (old cruise conditions) and 0.67 through 3.04 to 7.94 . 10-3 (modern cruise conditions) when FSC increased from 50 through 410 to1270 μg/g. The activation behaviour was modelled using classical theories and with a semi-empirical model [ Gysel et al., 2003] based on measured hygroscopicity of the aerosol under subsaturated conditions, which gave the best agreement.

Face-by-face growth of sucrose crystals from aqueous solutions in the presence of raffinose—II: Growth morphology and segregation

NASA Astrophysics Data System (ADS)

Sgualdino, G.; Aquilano, D.; Pastero, L.; Vaccari, G.

2007-10-01

Raffinose segregation into sucrose crystals is experimentally determined along with the modifications of the quantitative sucrose growth morphology, which are in turn related to the different growth conditions. ( Craff, σ) morphodromes nicely represent the conflict between the supersaturation and the raffinose concentration in the solution on the growth morphology, while the overall segregation rate is nearly proportional to the linear overall crystal growth rate. Chernov and Burton-Prim-Slichter models, checked to fit our keff and ln(keff-1-1) coefficients as a function of the supersaturation and of the mean linear overall growth rate, do not allow to know whether the segregation occurs either by a process dominated by surface integration, or by additive transfer dominated by volume diffusion within the boundary layer. The distribution of segregated raffinose strictly depends on the { h k l} growth sectors and doped crystals contain deformed lattice zones, as it comes out from X-ray powder diagrams.

Enhancement of physical stability and bioaccessibility of tangeretin by soy protein isolate addition.

PubMed

Wan, Jiawei; Li, Dong; Song, Rong; Shah, Bakht Ramin; Li, Bin; Li, Yan

2017-04-15

Soy protein isolate (SPI) was selected to fabricate supersaturated self-emulsifying nanoemulsions, aiming to enhance physical stability and bioaccessibility of hydrophobic tangeretin. Dissolution studies demonstrated that tangeretin had the highest solubility in Tween 80, followed by oil phase solutions, and polymer solutions. Supersaturated tangeretin in oil phases easily formed crystals. That metastable zone was found to vary with its initial concentrations. After encapsulation by nanoemulsions, the addition of glycerol compressed the retention amount of tangeretin from 76% to 53%, but benefited the transparency. Whereas, the combination of glycerol and SPI could not only maintain high-loading tangeretin (>85%), but also provide high transparency for nanoemulsions. When tangeretin concentration was 4.83mM, combination of 50% glycerol and 1% SPI could maintain around 88% tangeretin in the nanoemulsion within one month. Its bioaccessibility of different systems were at 60-65%. These findings can provide useful information for protein to be a potential precipitation inhibitor. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetic Roughening Transition and Energetics of Tetragonal Lysozyme Crystal Growth

NASA Technical Reports Server (NTRS)

Gorti, Sridhar; Forsythe, Elizabeth L.; Pusey, Marc L.

2004-01-01

Interpretation of lysozyme crystal growth rates using well-established physical theories enabled the discovery of a phenomenon possibly indicative of kinetic roughening. For example, lysozyme crystals grown above a critical supersaturation sigma, (where supersaturation sigma = ln c/c(sub eq), c = the protein concentration and c(sub eq) = the solubility concentration) exhibit microscopically rough surfaces due to the continuous addition of growth units anywhere on the surface of a crystal. The rate of crystal growth, V(sub c), for the continuous growth process is determined by the continuous flux of macromolecules onto a unit area of the crystal surface, a, from a distance, xi, per unit time due to diffusion, and a probability of attachment onto the crystal surface, expressed. Based upon models applied, the energetics of lysozyme crystal growth was determined. The magnitudes of the energy barriers of crystal growth for both the (110) and (101) faces of tetragonal lysozyme crystals are compared. Finally, evidence supportive of the kinetic roughening hypothesis is presented.

Gas depletion through single gas bubble diffusive growth and its effect on subsequent bubbles

NASA Astrophysics Data System (ADS)

Moreno Soto, Alvaro; Prosperetti, Andrea; Lohse, Detlef; van der Meer, Devaraj; Physics of Fluid Group Collaboration; MCEC Netherlands CenterMultiscale Catalytic Energy Conversion Collaboration

2016-11-01

In weakly supersaturated mixtures, bubbles are known to grow quasi-statically as diffusion-driven mass transfer governs the process. In the final stage of the evolution, before detachment, there is an enhancement of mass transfer, which changes from diffusion to natural convection. Once the bubble detaches, it leaves behind a gas-depleted area. The diffusive mass transfer towards that region cannot compensate for the amount of gas which is taken away by the bubble. Consequently, the consecutive bubble will grow in an environment which contains less gas than for the previous one. This reduces the local supersaturation of the mixture around the nucleation site, leading to a reduced bubble growth rate. We present quantitative experimental data on this effect and the theoretical model for depletion during the bubble growth rate. This work was supported by the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation programme funded by the Ministry of Education, Culture and Science of the government of the Netherlands.

Experimental research of heterogeneous nuclei in superheated steam

NASA Astrophysics Data System (ADS)

Bartoš, Ondřej; Kolovratník, Michal; Šmíd, Bohuslav; Hrubý, Jan

2016-03-01

A mobile steam expansion chamber has been developed to investigate experimentally homogeneous and heterogeneous nucleation processes in steam, both in the laboratory and at power plants using the steam withdrawn from the steam turbine. The purpose of the device is to provide new insight into the physics of nonequilibrium wet steam formation, which is one of the factors limiting the efficiency and reliability of steam turbines. The expanded steam or a mixture of steam with a non-condensable gas rapidly expands in the expansion chamber. Due to adiabatic cooling, the temperature drops below the dew point of the steam at a given pressure. When reaching a sufficiently high supersaturation, droplets are nucleated. By tuning the supersaturation in the so-called nucleation pulse, particles of various size ranges can be activated. This fact is used in the present study to measure the aerosol particles present in the air. Homogeneous nucleation was negligible in this case. The experiment demonstrates the functionality of the device, data acquisition system and data evaluation methods.

Carbon dioxide supersaturation in the surface waters of lakes

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

Cole, J.J.; Caraco, N.F.; Kling, G.W.

1994-09-09

Data on the partial pressure of carbon dioxide (CO{sub 2}) in the surface waters from a large number of lakes (1835) with a worldwide distribution show that only a small proportion of the 4665 samples analyzed (less than 10 percent) were within {+-}20 percent of equilibrium with the atmosphere and that most samples (87 percent) were supersaturated. The mean partial pressure of CO{sub 2} averaged 1036 microatmospheres, about three times the value in the overlying atmosphere, indicating that lakes are sources rather than sinks of atmospheric CO{sub 2}. On a global scale, the potential efflux of CO{sub 2} from lakesmore » (about 0.14 x 10{sup 15} grams of carbon per year) is about half as large as riverine transport of organic plus inorganic carbon to the ocean. Lakes are a small but potentially important conduit for carbon for terrestrial sources to the atmospheric sink. 18 refs., 2 figs., 1 tab.« less

Solute mixing regulates heterogeneity of mineral precipitation in porous media: Effect of Solute Mixing on Precipitation

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

Cil, Mehmet B.; Xie, Minwei; Packman, Aaron I.

Synchrotron X-ray microtomography was used to track the spatiotemporal evolution of mineral precipitation and the consequent alteration of the pore structure. Column experiments were conducted by injecting CaCl2 and NaHCO3 solutions into granular porous media either as a premixed supersaturated solution (external mixing) or as separate solutions that mixed within the specimen (internal mixing). The two mixing modes produced distinct mineral growth patterns. While internal mixing promoted transverse heterogeneity with precipitation at the mixing zone, external mixing favored relatively homogeneous precipitation along the flow direction. The impact of precipitation on pore water flow and permeability was assessed via 3-D flowmore » simulations, which indicated anisotropic permeability evolution for both mixing modes. Under both mixing modes, precipitation decreased the median pore size and increased the skewness of the pore size distribution. Such similar pore-scale evolution patterns suggest that the clogging of individual pores depends primarily on local supersaturation state and pore geometry.« less

Should bulk cloudwater or fogwater samples obey Henry's law?

NASA Astrophysics Data System (ADS)

Pandis, Spyros N.; Seinfeld, John H.

1991-06-01

Mixing of droplets with different pH that are individually in Henry's law equilibrium with the surrounding atmosphere always results in a bulk mixture that is supersaturated with weak acids like S(IV) and HCOOH, and bases like NH3 with respect to the original atmosphere. High supersaturations result only when the pH of the bulk droplet mixture exceeds the pKa of the species, in which pH range large pH differences among droplets of different sizes lead to large deviations from Henry's law for the bulk mixture. The deviation is shown to depend on the ratio of the arithmetic mean to the harmonic mean of the hydrogen ion concentrations of the droplets with the liquid water content used as weighting factor in the calculation of the means. The theory developed can explain observed discrepancies from Henry's law in atmospheric samples and also other observed phenomena like the reported increase of pH values of bulk aqueous samples during storage.

Heat of supersaturation-limited amyloid burst directly monitored by isothermal titration calorimetry.

PubMed

Ikenoue, Tatsuya; Lee, Young-Ho; Kardos, József; Yagi, Hisashi; Ikegami, Takahisa; Naiki, Hironobu; Goto, Yuji

2014-05-06

Amyloid fibrils form in supersaturated solutions via a nucleation and growth mechanism. Although the structural features of amyloid fibrils have become increasingly clearer, knowledge on the thermodynamics of fibrillation is limited. Furthermore, protein aggregation is not a target of calorimetry, one of the most powerful approaches used to study proteins. Here, with β2-microglobulin, a protein responsible for dialysis-related amyloidosis, we show direct heat measurements of the formation of amyloid fibrils using isothermal titration calorimetry (ITC). The spontaneous fibrillation after a lag phase was accompanied by exothermic heat. The thermodynamic parameters of fibrillation obtained under various protein concentrations and temperatures were consistent with the main-chain dominated structural model of fibrils, in which overall packing was less than that of the native structures. We also characterized the thermodynamics of amorphous aggregation, enabling the comparison of protein folding, amyloid fibrillation, and amorphous aggregation. These results indicate that ITC will become a promising approach for clarifying comprehensively the thermodynamics of protein folding and misfolding.

Grain size tuning of nanostructured Cu{sub 2}O films through vapour phase supersaturation control and their characterization for practical applications

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

Anu, A.; Abdul Khadar, M., E-mail: mabdulkhadar@rediffmail.com

2015-09-15

A strategy for creating nanostructured films is the alignment of nanoparticles into ordered superstructures as living organisms synthesize biomaterials with superior physical properties using nanoparticle building blocks. We synthesized nanostructured films of Cu{sub 2}O of variable grain size by establishing the condition of supersaturation for creation of nanoparticles of copper which deposited as nanograined films and which was then oxidized. This technique has the advantage of being compatible with conventional vacuum processes for electronic device fabrication. The Cu{sub 2}O film samples consisted of a secondary structure of spherical particles of almost uniform size, each particle being an agglomerate of primarymore » nanocrystals. Fractal analysis of the AFM images of the samples is carried out for studying the aggregation mechanism. Grain size tuning of the nanostructured Cu{sub 2}O films has been studied using XRD, and micro-Raman and photoluminescence spectroscopy.« less

Transient enhanced diffusion in preamorphized silicon: the role of the surface

NASA Astrophysics Data System (ADS)

Cowern, N. E. B.; Alquier, D.; Omri, M.; Claverie, A.; Nejim, A.

1999-01-01

Experiments on the depth dependence of transient enhanced diffusion (TED) of boron during rapid thermal annealing of Ge-preamorphized layers reveal a linear decrease in the diffusion enhancement between the end-of-range (EOR) defect band and the surface. This behavior, which indicates a quasi-steady-state distribution of excess interstitials, emitted from the EOR band and absorbed at the surface, is observed for annealing times as short as 1 s at 900°C. Using an etching procedure we vary the distance xEOR from the EOR band to the surface in the range 80-175 nm, and observe how this influences the interstitial supersaturation, s( x). The supersaturations at the EOR band and the surface remain unchanged, while the gradient d s/d x, and thus the flux to the surface, varies inversely with xEOR. This confirms the validity of earlier modelling of EOR defect evolution in terms of Ostwald ripening, and provides conclusive evidence that the surface is the dominant sink for interstitials during TED.

Ab initio-aided CALPHAD thermodynamic modeling of the Sn-Pb binary system under current stressing

PubMed Central

Lin, Shih-kang; Yeh, Chao-kuei; Xie, Wei; Liu, Yu-chen; Yoshimura, Masahiro

2013-01-01

Soldering is an ancient process, having been developed 5000 years ago. It remains a crucial process with many modern applications. In electronic devices, electric currents pass through solder joints. A new physical phenomenon – the supersaturation of solders under high electric currents – has recently been observed. It involves (1) un-expected supersaturation of the solder matrix phase, and (2) the formation of unusual “ring-shaped” grains. However, the origin of these phenomena is not yet understood. Here we provide a plausible explanation of these phenomena based on the changes in the phase stability of Pb-Sn solders. Ab initio-aided CALPHAD modeling is utilized to translate the electric current-induced effect into the excess Gibbs free energies of the phases. Hence, the phase equilibrium can be shifted by current stressing. The Pb-Sn phase diagrams with and without current stressing clearly demonstrate the change in the phase stabilities of Pb-Sn solders under current stressing. PMID:24060995

Supersaturation, droplet spectra, and turbulent mixing in clouds

NASA Technical Reports Server (NTRS)

Gerber, H.

1990-01-01

Much effort has recently gone into explaining the observed broad precoalescence size distribution of droplets in cloud and fogs, because this differs from the results of condensational growth calculations which lead to much narrower distributions. A good example of droplet size-distribution broadening was observed on flight 17 (25 July) of the NRL tethered balloon during the 1987 FIRE San Nicolas Island IFO. These observations caused the interactions between cloud microphysics and turbulent mixing to be re-examined. The findings of Broadwell and Breidenthal (1982) who conducted laboratory and theoretical studies of mixing in shear flow, and those of Baker et al. (1984) who applied the earlier work to mixing in clouds, were used. Rather than looking at the 25 July case at SNI, earlier fog observations made at SUNY (6 Oct. 1982) which also indicated that shear-induced mixing was taking place, and which had a better collection of microphysical measurements including more precise supersaturation measurements and detailed vertical profiles of meteorological parameters were chosen instead.

Overhead Projector Demonstrations: Some Ideas from the Past.

ERIC Educational Resources Information Center

Kolb, Doris

1987-01-01

Describes nine chemistry demonstrations that can be done using an overhead projector. Includes demonstrations on common ion effect, crystal formation from supersaturated solutions, making iron positive with nitric acid, optical activity, carbon dioxide in human breath, amphoteric hydroxides, the surface tension of mercury, and natural acid-base…

The effects of ambient temperature, humidity and season of year on urine composition in patients with nephrolithiasis.

PubMed

Eisner, Brian H; Sheth, Sonali; Herrick, Benjamin; Pais, Vernon M; Sawyer, Mark; Miller, Nicole; Hurd, Kimberly J; Humphreys, Mitchell R

2012-12-01

Study Type--Prognosis (cohort series) Level of Evidence 2b. What's known on the subject? and What does the study add? Epidemiologic studies have shown that warmer climates are associated with increased incidence of nephrolithiasis. Many hypothesize that this is due to dehydration and lower urine volumes. The current study of stone formers reports that greater temperatures are associated with significant increases in urine calcium which may shed light on the mechanism underlying the increased stone incidence associated with increased ambient temperature. • To understand the effects of temperature, humidity and season of year on 24-h urine composition in patients with nephrolithiasis. • A retrospective review was performed of patients evaluated at four metabolic stone clinics. • Multivariate linear regression models examined the relationship between mean temperature, average humidity, season of year and 24-h urine composition. • Multivariate models adjusted for known risk factors for stone disease. • Mean temperature and average humidity data were obtained from http://www.weatherunderground.com based on patient-provided addresses. • A total of 599 patients were included in the study, comprising 239 women and 360 men with a mean age of 53.6 years (sd 15.0). • Mean temperature was 16.9 °C (sd 4.8, range -21.1 to 38.3 °C) and average humidity was 58.1% (sd 23.5, range 11-100%). • On multivariate linear regression, increasing temperature was associated with increasing urine calcium (β = 11.3, 95% CI 2.2-20.0), super-saturation of calcium oxalate (β = 0.6, 95% CI 0.2-0.9), super-saturation of calcium phosphate (β = 0.14, 95% CI 0.03-0.2), and decreasing urine sodium (β = -5.2, 95% CI -10.3 to -0.1). • As seasons become warmer (i.e. from winter to autumn to spring to summer), changes were increased urine volume (β = 0.09, 95% CI 0.01-0.2) and decreased super-saturation of calcium phosphate (β = -0.2, 95% CI -0.3 to -0.03). • There were no associations between quintile of humidity and any 24-h urine constituents. • Increasing temperature may increase stone risk by increasing urine excretion of calcium, and the super-saturation of calcium oxalate and calcium phosphate. • These findings were independent of humidity and of season of year. • This appears to be related to a physiological impact of temperature itself, rather than to geographic location. © 2012 BJU INTERNATIONAL.

An assessment of calcite crystal growth mechanisms based on crystal size distributions

USGS Publications Warehouse

Kile, D.E.; Eberl, D.D.; Hoch, A.R.; Reddy, M.M.

2000-01-01

Calcite crystal growth experiments were undertaken to test a recently proposed model that relates crystal growth mechanisms to the shapes of crystal size distributions (CSDs). According to this approach, CSDs for minerals have three basic shapes: (1) asymptotic, which is related to a crystal growth mechanism having constant-rate nucleation accompanied by surface-controlled growth; (2) lognormal, which results from decaying-rate nucleation accompanied by surface-controlled growth; and (3) a theoretical, universal, steady-state curve attributed to Ostwald ripening. In addition, there is a fourth crystal growth mechanism that does not have a specific CSD shape, but which preserves the relative shapes of previously formed CSDs. This mechanism is attributed to supply-controlled growth. All three shapes were produced experimentally in the calcite growth experiments by modifying nucleation conditions and solution concentrations. The asymptotic CSD formed when additional reactants were added stepwise to the surface of solutions that were supersaturated with respect to calcite (initial Ω = 20, where Ω = 1 represents saturation), thereby leading to the continuous nucleation and growth of calcite crystals. Lognormal CSDs resulted when reactants were added continuously below the solution surface, via a submerged tube, to similarly supersaturated solutions (initial Ω = 22 to 41), thereby leading to a single nucleation event followed by surface-controlled growth. The Ostwald CSD resulted when concentrated reactants were rapidly mixed, leading initially to high levels of supersaturation (Ω >100), and to the formation and subsequent dissolution of very small nuclei, thereby yielding CSDs having small crystal size variances. The three CSD shapes likely were produced early in the crystallization process, in the nanometer crystal size range, and preserved during subsequent growth. Preservation of the relative shapes of the CSDs indicates that a supply-controlled growth mechanism was established and maintained during the constant-composition experiments. CSDs having shapes intermediate between lognormal and Ostwald also were generated by varying the initial levels of supersaturation (initial Ω = 28.2 to 69.2) in rapidly mixed solutions. Lognormal CSDs were observed for natural calcite crystals that are found in septarian concretions occurring in southeastern Colorado. Based on the model described above, these CSDs indicate initial growth by surface control, followed by supply-controlled growth. Thus, CSDs may be used to deduce crystal growth mechanisms from which geologic conditions early in the growth history of a mineral can be inferred. Conversely, CSD shape can be predicted during industrial crystallization by applying the appropriate conditions for a particular growth mechanism.

Structural alterations in lecithin-cholesterol vesicles following interactions with monomeric and micellar bile salts: physical-chemical basis for subselection of biliary lecithin species and aggregative states of biliary lipids during bile formation.

PubMed

Cohen, D E; Angelico, M; Carey, M C

1990-01-01

Using complementary physical-chemical methods including turbidimetry, quasielastic light scattering, gel filtration, and phase analysis, we examined the interactions between dilute concentrations of the common bile salt, taurochenodeoxycholate (TCDC), and uni- and multilamellar vesicles (MLVs) composed of defined molecular species of lecithin (L) and varying contents of cholesterol (Ch). Dissolution rates of MLVs with micellar TCDC, as assessed by turbidimetry, were more rapid with vesicles composed of sn-1 palmitoyl species, typical of biliary L, compared with those composed of the more hydrophobic sn-1 stearoyl species. Incorporation of Ch retarded MLV dissolution rates in proportion to the Ch content, and only at high Ch contents were dissolution rates appreciably influenced by the sn-2 fatty acid composition of L. When MLVs contained Ch in amounts characteristic of intracellular membranes (Ch/L approximately 0.1), the dissolution rates of the individual L species by TCDC accurately predicted the steady state L composition of human bile. TCDC interacted with small unilamellar L/Ch vesicles (SUVs) at concentrations well below, as well as appreciably above, its critical micellar concentration. In accordance with the TCDC-egg yolk L-H2O phase diagram, perimicellar concentrations of TCDC interacted with SUVs to form aggregates that were approximately twice the size of the SUVs. These were consistent with the formation of a dispersed hexagonal (rod-like) phase, which co-existed with aqueous bile salt (BS) monomers and either micellar or unilamellar SUV phases. Micellar TCDC completely solubilized SUVs as mixed micelles, putatively via this transient hexagonal phase. With modest Ch-supersaturation, dissolution was followed by the reemergence of a new vesicle population that coexisted metastably with mixed micelles. With high Ch supersaturation, TCDC extracted L and Ch molecules from SUVs in different proportions to form Ch-supersaturated mixed micelles and Ch-enriched SUVs, in accordance with the metastable phase diagram. These experiments are consistent with the hypothesis that sn-1 palmitoyl L species are subselected for bile, in part, by physical-chemical interactions of intracellular BS concentrations with Ch-poor membranes and that the subsequent evolution of Ch-rich vesicles and Ch-saturated mixed micelles occurs via a transitional hexagonal (rod) phase. These liquid-crystalline states are likely to be transient in Ch-unsaturated biles, but may persist in Ch-supersaturated human biles because of their high Ch contents which retard or inhibit these phase transitions.

Laboratory Experiments to Study Spherical, Iron Oxide Concretion Growth Without Solid Nuclei: Implications for Understanding Meridiani "Blueberries"

NASA Astrophysics Data System (ADS)

Ormö, J.; Souza-Egipsy, V.; Chan, M. A.; Park, A. J.; Stich, M.; Komatsu, G.

2006-03-01

Spherical hematite concretions can form without a nucleus. Self-organized zones of super-saturated solution cause spherical precipitates of amorphous iron-hydroxide. Diffusion of Fe ions towards the outer perimeter of the amorphous sphere forms a rind, which then grows inwards.

Buffer gas cooling and mixture analysis

DOEpatents

Patterson, David S.; Doyle, John M.

2018-03-06

An apparatus for spectroscopy of a gas mixture is described. Such an apparatus includes a gas mixing system configured to mix a hot analyte gas that includes at least one analyte species in a gas phase into a cold buffer gas, thereby forming a supersaturated mixture to be provided for spectroscopic analysis.

Fizz-Ball Fizzics

ERIC Educational Resources Information Center

Moinester, Murray; Gerland, Lars; Liger-Belair, Gerard; Ocherashvili, Aharon

2012-01-01

We describe the fluid dynamics principles governing the up-down oscillatory cycling of a bubble-covered, low-density, low-mass ball of material (referred to henceforth as a "fizz-ball") immersed inside a glass of bubbling (super-saturated) carbonated liquid. The bubbles serve to desaturate the liquid of excess CO[subscript 2]. The fizz-ball acts…

Impact of mixing state and hygroscopicity on CCN activity of biomass burning aerosol in Amazonia

NASA Astrophysics Data System (ADS)

Sánchez Gácita, Madeleine; Longo, Karla M.; Freire, Julliana L. M.; Freitas, Saulo R.; Martin, Scot T.

2017-02-01

Smoke aerosols prevail throughout Amazonia because of widespread biomass burning during the dry season, and external mixing, low variability in the particle size distribution and low particle hygroscopicity are typical. There can be profound effects on cloud properties. This study uses an adiabatic cloud model to simulate the activation of smoke particles as cloud condensation nuclei (CCN) for three hypothetical case studies, chosen as to resemble biomass burning aerosol observations in Amazonia. The relative importance of variability in hygroscopicity, mixing state, and activation kinetics for the activated fraction and maximum supersaturation is assessed. For a population with κp = 0.04, an overestimation of the cloud droplet number concentration Nd for the three selected case studies between 22.4 ± 1.4 and 54.3 ± 3.7 % was obtained when assuming a hygroscopicity parameter κp = 0.20. Assuming internal mixing of the aerosol population led to overestimations of up to 20 % of Nd when a group of particles with medium hygroscopicity was present in the externally mixed population cases. However, the overestimations were below 10 % for external mixtures between very low and low-hygroscopicity particles, as seems to be the case for Amazon smoke particles. Kinetic limitations were significant for medium- and high-hygroscopicity particles, and much lower for very low and low-hygroscopicity particles. When particles were assumed to be at equilibrium and to respond instantly to changes in the air parcel supersaturation, the overestimation of the droplet concentration was up to ˜ 100 % in internally mixed populations, and up to ˜ 250 % in externally mixed ones, being larger for the higher values of hygroscopicity. In addition, a perceptible delay between the times when maximum supersaturation and maximum aerosol activated fraction are reached was noticed and, for aerosol populations with effective hygroscopicity κpeff higher than a certain threshold value, the delay in particle activation was such that no particles were activated at the time of maximum supersaturation. Considering internally mixed populations, for an updraft velocity W = 0.5 m s-1 this threshold of no activation varied between κpeff = 0.35 and κpeff = 0.5 for the different case studies. However, for low hygroscopicity, kinetic limitations played a weaker role for CCN activation of particles, even when taking into account the large aerosol mass and number concentrations. For the very low range of hygroscopicities, the overestimation of the droplet concentration due to the equilibrium assumption was lowest and the delay between the times when maximum supersaturation and maximum activated fraction were reached was greatly reduced or no longer observed (depending on the case study). These findings on uncertainties and sensitivities provide guidance on appropriate simplifications that can be used for modeling of smoke aerosols within general circulation models. The use of medium values of hygroscopicity representative of smoke aerosols for other biomass burning regions on Earth can lead to significant errors compared to the use of low hygroscopicity for Amazonia (between 0.05 and 0.13, according to available observations). Also in this region, consideration of the biomass burning population as internally mixed will lead to small errors in the droplet concentration, while significantly increasing the computational burden. Regardless of the large smoke aerosol loads in the region during the dry season, kinetic limitations are expected to be low.

An evaluation of a micro programmable logic controller for oxygen monitoring and control in tanks of a recirculating aquaculture system

USDA-ARS?s Scientific Manuscript database

Control of dissolved gases, especially oxygen is an essential component of recirculating aquaculture systems. The use of pure oxygen in a recirculating aquaculture system creates supersaturated concentrations of dissolved oxygen and can reduce fish production costs by supporting greater fish and fee...

Controlled in situ etch-back

NASA Technical Reports Server (NTRS)

Mattauch, R. J.; Seabaugh, A. C. (Inventor)

1981-01-01

A controlled in situ etch-back technique is disclosed in which an etch melt and a growth melt are first saturated by a source-seed crystal and thereafter etch-back of a substrate takes place by the slightly undersaturated etch melt, followed by LPE growth of a layer by the growth melt, which is slightly supersaturated.

Supersaturating Silicon with Titanium by Continuous-Wave Laser Irradiation of Sputtered Titanium Film on Silicon

NASA Astrophysics Data System (ADS)

Bao-Dian, Fan; Yu, Qiu; Rong, Chen; Miao, Pan; Li-Han, Cai; Jiang-Hui, Zheng; Chao, Chen

2016-02-01

Not Available Supported by the National Natural Science Foundation of China under Grant No 61076056, and the Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure of Shanghai Institute of Ceramics of Chinese Academy of Sciences under Grant No SKL201404SIC.

Bubble growth as a means to measure dissolved nitrogen concentration in aerated water

NASA Astrophysics Data System (ADS)

Ando, Keita; Yamashita, Tatsuya

2017-11-01

Controlling the amount of dissolved gases in water is important, for example, to food processing; it is essential to quantitatively evaluate dissolved gas concentration. The concentration of dissolved oxygen (DO) can be measured by commercial DO meters, but that of dissolved nitrogen (DN) cannot be obtained easily. Here, we propose a means to measure DN concentration based on Epstein-Plesset-type analysis of bubble growth under dissolved gas supersaturation. DO supersaturation in water is produced by oxygen microbubble aeration. The diffusion-driven growth of bubbles nucleated at glass surfaces in contact with the aerated water is first observed. The observed growth is then compared to the extended Epstein-Plesset theory that considers Fick's mass transfer of both DO and DN across bubble interfaces; in this comparison, the unknown DN concentration is treated as a fitting parameter. Comparisons between the experiment and the theory suggest, as expected, that DN can be effectively purged by oxygen microbubble aeration. This study was supported in part by the Mizuho Foundation for the Promotion of Science and by a MEXT Grant-in-Aid for the Program for Leading Graduate Schools.

Modelling heterogeneous ice nucleation on mineral dust and soot with parameterizations based on laboratory experiments

NASA Astrophysics Data System (ADS)

Hoose, C.; Hande, L. B.; Mohler, O.; Niemand, M.; Paukert, M.; Reichardt, I.; Ullrich, R.

2016-12-01

Between 0 and -37°C, ice formation in clouds is triggered by aerosol particles acting as heterogeneous ice nuclei. At lower temperatures, heterogeneous ice nucleation on aerosols can occur at lower supersaturations than homogeneous freezing of solutes. In laboratory experiments, the ability of different aerosol species (e.g. desert dusts, soot, biological particles) has been studied in detail and quantified via various theoretical or empirical parameterization approaches. For experiments in the AIDA cloud chamber, we have quantified the ice nucleation efficiency via a temperature- and supersaturation dependent ice nucleation active site density. Here we present a new empirical parameterization scheme for immersion and deposition ice nucleation on desert dust and soot based on these experimental data. The application of this parameterization to the simulation of cirrus clouds, deep convective clouds and orographic clouds will be shown, including the extension of the scheme to the treatment of freezing of rain drops. The results are compared to other heterogeneous ice nucleation schemes. Furthermore, an aerosol-dependent parameterization of contact ice nucleation is presented.

Ambulation During Periods of Supersaturation Increase Decompression Stress in Spacewalk Simulations

NASA Technical Reports Server (NTRS)

Pollock, N. W.; Natoli, M. J.; Martina, S. D.; Conkin, J.; Wessel, J. H., III; Gernhardt, M. L.

2016-01-01

Musculoskeletal activity accelerates inert gas elimination during oxygen breathing prior to decompression (prebreathe), but may also promote bubble formation (nucleation) and increase the risk of decompression sickness (DCS). The timing, pattern and intensity of musculoskeletal activity and the level of tissue supersaturation are likely critical to the net effect. Understanding the relationships is important to evaluate exercise prebreathe protocols and quantify decompression risk in gravity and microgravity environments. The NASA Prebreathe Reduction Program (PRP) combined oxygen prebreathe and exercise preceding a low pressure (4.3 psia; altitude equivalent of 30,300 ft [9,235 m]) simulation exposure of non-ambulatory subjects (a microgravity analog) to produce two protocols now used by astronauts preparing for extravehicular activity. One protocol included both upright cycling and non-cycling exercise (CEVIS: 'cycle ergometer vibration isolation system') and one protocol relied on non-cycling exercise only (ISLE: 'in-suit light exercise'). CEVIS trial data serve as control data for the current study to investigate the influence of ambulation exercise in 1G environments on bubble formation and the subsequent risk of DCS.

Spatial Control of Condensation using Chemical Micropatterns

NASA Astrophysics Data System (ADS)

Murphy, Kevin; Hansen, Ryan; Nath, Saurabh; Retterer, Scott; Collier, Patrick; Boreyko, Jonathan; Nature-Inspired Fluids; Interfaces Team; CenterNanophase Materials Sciences Team

2015-11-01

Surfaces exhibiting wettability patterns can spatially control the nucleation of condensation to enable enhanced fog harvesting and phase-change heat transfer. To date, studies of patterned condensation have utilized a combination of chemical and topographical features, making it difficult to isolate the effects of intrinsic wettability versus surface roughness on spatially controlling the condensate. Here, we fabricate chemical micropatterns consisting of hydrophilic silicon oxide and a smooth hydrophobic silane monolayer to isolate the effects of changes in intrinsic wettability on the spatial control of condensation. Complete spatial control, defined as every nucleation and growth event occurring exclusively on the hydrophilic features, was observed even for supercooled droplets at high water vapor supersaturation. However, this complete spatial control was found to break down beyond a critical spacing that depended upon the extent of supersaturation. The average diameter of condensate was found to be smaller for the chemically micropatterned surfaces compared to a uniformly hydrophobic surface. Control of inter-droplet spacing between supercooled condensate through chemical patterning can be employed to minimize the growth of inter-droplet frost on cold surfaces.

Nanobubbles in confined solution: Generation, contact angle, and stability.

PubMed

Wei, Jiachen; Zhang, Xianren; Song, Fan; Shao, Yingfeng

2018-02-14

The formation of gas bubbles presents a frequent challenge to microfluidic operations, for which fluids are geometrically confined to a microscale space. Here, to understand the mechanism of nucleating gas bubbles in microfluidic devices, we investigate the formation and stability of nanobubbles in confined solutions. Our molecular dynamics simulations show that while pinning of the contact line is a prerequisite for the stability of surface nanobubbles in open systems that can exchange gas with surrounding environment, in confined solutions, stable nanobubbles can exist even without pinning. In supersaturated condition, stable bubbles can be found in confined solutions with acute or obtuse contact angle, depending on the substrate hydrophobicity. We also demonstrate that when open to the bulk solution, the stable nanobubbles in closed systems would become unstable unless both supersaturation and pinning of the contact line are satisfied. Our results not only shed light on the design of novel heterogeneous surfaces for generating nanobubbles in confined space with controllable shape and stability but also address the crucial effect of gas exchange with the surroundings in determining the stability of nanobubbles.

Nanobubbles in confined solution: Generation, contact angle, and stability

NASA Astrophysics Data System (ADS)

Wei, Jiachen; Zhang, Xianren; Song, Fan; Shao, Yingfeng

2018-02-01

The formation of gas bubbles presents a frequent challenge to microfluidic operations, for which fluids are geometrically confined to a microscale space. Here, to understand the mechanism of nucleating gas bubbles in microfluidic devices, we investigate the formation and stability of nanobubbles in confined solutions. Our molecular dynamics simulations show that while pinning of the contact line is a prerequisite for the stability of surface nanobubbles in open systems that can exchange gas with surrounding environment, in confined solutions, stable nanobubbles can exist even without pinning. In supersaturated condition, stable bubbles can be found in confined solutions with acute or obtuse contact angle, depending on the substrate hydrophobicity. We also demonstrate that when open to the bulk solution, the stable nanobubbles in closed systems would become unstable unless both supersaturation and pinning of the contact line are satisfied. Our results not only shed light on the design of novel heterogeneous surfaces for generating nanobubbles in confined space with controllable shape and stability but also address the crucial effect of gas exchange with the surroundings in determining the stability of nanobubbles.

Simultaneous determination of interfacial energy and growth activation energy from induction time measurements

NASA Astrophysics Data System (ADS)

Shiau, Lie-Ding; Wang, Hsu-Pei

2016-05-01

A model is developed in this work to calculate the interfacial energy and growth activation energy of a crystallized substance from induction time data without the knowledge of the actual growth rate. Induction time data for αL-glutamic acid measured with a turbidity probe for various supersaturations at temperatures from 293 to 313 K are employed to verify the developed model. In the model a simple empirical growth rate with growth order 2 is assumed because experiments are conducted at low supersaturation. The results indicate for αL-glutamic acid that the growth activation energy is 39 kJ/mol, which suggests that the growth rate of small nuclei in the agitated induction time experiments is integration controlled. The interfacial energy obtained from the current model is in the range of 5.2-7.4 mJ/m2, which is slightly greater than that obtained from the traditional method (ti-1∝J) for which the value is in the range 4.1-5.7 mJ/m2.

Mathematical model to estimate risk of calcium-containing renal stones

NASA Technical Reports Server (NTRS)

Pietrzyk, R. A.; Feiveson, A. H.; Whitson, P. A.

1999-01-01

BACKGROUND/AIMS: Astronauts exposed to microgravity during the course of spaceflight undergo physiologic changes that alter the urinary environment so as to increase the risk of renal stone formation. This study was undertaken to identify a simple method with which to evaluate the potential risk of renal stone development during spaceflight. METHOD: We used a large database of urinary risk factors obtained from 323 astronauts before and after spaceflight to generate a mathematical model with which to predict the urinary supersaturation of calcium stone forming salts. RESULT: This model, which involves the fewest possible analytical variables (urinary calcium, citrate, oxalate, phosphorus, and total volume), reliably and accurately predicted the urinary supersaturation of the calcium stone forming salts when compared to results obtained from a group of 6 astronauts who collected urine during flight. CONCLUSIONS: The use of this model will simplify both routine medical monitoring during spaceflight as well as the evaluation of countermeasures designed to minimize renal stone development. This model also can be used for Earth-based applications in which access to analytical resources is limited.

Moderated, Water-Based, Condensational Particle Growth in a Laminar Flow

PubMed Central

Hering, Susanne V.; Spielman, Steven R.; Lewis, Gregory S.

2014-01-01

Presented is a new approach for laminar-flow water condensation that produces saturations above 1.5 while maintaining temperatures of less than 30°C in the majority of the flow and providing an exiting dew point below 15°C. With the original laminar flow water condensation method, the particle activation and growth occurs in a region with warm, wetted walls throughout, which has the side-effect of heating the flow. The “moderated” approach presented here replaces this warm region with a two sections – a short, warm, wet-walled “initiator”, followed by a cool-walled “moderator”. The initiator provides the water vapor that creates the supersaturation, while the moderator provides the time for particle growth. The combined length of the initiator and moderator sections is the same as that of the original, warm-walled growth section. Model results show that this new approach reduces the added heat and water vapor while achieving the same peak supersaturation and similar droplet growth. Experimental measurements confirm the trends predicted by the modeling. PMID:24839342

Doppler indices of gas phase formation in hypobaric environments: Time-intensity analysis

NASA Technical Reports Server (NTRS)

Powell, Michael R.

1991-01-01

A semi-quantitative method to analyze decompression data is described. It possesses the advantage that it allows a graded response to decompression rather than the dichotomous response generally employed. A generalized critical volume (C-V), or stoichiometric time-dependent equilibrium model is examined that relates the constant of the equation P sub i equals m P sub f plus b to variable tissue supersaturation and gas washout terms. The effects of the tissue ratio on gas phase formation indicate that a decreased ratio yields fewer individuals with Doppler detectable gas bubbles, but those individuals still present with Spencer Grade 3 or 4. This might indicate a local collapse of tissue saturation. The individuals with Grade 3 or 4 could be at risk for type 2 decompression sickness by transpulmonic arterialization. The primary regulator of the problems of decompression sickness is the reduction of local supersaturation, presumably governed by the presence and number of gas micronuclei. It is postulated that a reduction in these nuclei will favor a low incidence of decompression sickness in microgravity secondary to hypokinesia and adynamia.

The role of impurities on the process of growing potassium hydrogen phthalate crystals from solution; A quantitative approach

NASA Astrophysics Data System (ADS)

Hottenhuis, M. H. J.; Lucasius, C. B.

1988-09-01

Quantitative information about the influence of impurities on the crystal growth process of potassium hydrogen phthalate from its aqueous solution was obtained at two levels: microscopic and macroscopic. At the microscopic level, detailed in situ observations of spiral steps at the (010) face were performed. The velocity of these steps was measured, as well in a "clean" as in a contaminated solution, where the influence of a number of different impurities was investigated. This resulted in a measure of effectiveness of step retardation for each of these impurities. From the same microscopic observations it was observed how these effectiveness factors were influenced by the supersaturation σ, the saturation temperature Ts of the solution and the concentration cimp of the impurity that w as used. At the macroscopic level, ICP (inductively coupled plasma) measurements were carried out in order to determine the distribution coefficient of the same impurities. In these measurements again the influence of the impurity concentration and the supersaturation on the distribution coefficient kD was determined.

Preparation of La 0.75Sr 0.25Cr 0.5Mn 0.5O 3- δ fine powders by carbonate coprecipitation for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ha, Sang Bu; Cho, Pyeong-Seok; Cho, Yoon Ho; Lee, Dokyol; Lee, Jong-Heun

A range of La 0.75Sr 0.25Cr 0.5Mn 0.5O 3- δ (LSCM) powders is prepared by the carbonate coprecipitation method for use as anodes in solid oxide fuel cells. The supersaturation ratio (R = [(NH 4) 2CO 3]/([La 3+] + [Sr 2+] + [Cr 3+] + [Mn 2+])) during the coprecipitation determines the relative compositions of La, Sr, Cr, and Mn. The composition of the precursor approaches the stoichiometric one at the supersaturation range of 4 ≤ R ≤ 12.5, whereas Sr and Mn components are deficient at R < 4 and excessive at R = 25. The fine and phase-pure LSCM powders are prepared by heat treatment at very low temperature (1000 °C) at R = 7.5 and 12.5. By contrast, the solid-state reaction requires a higher heat-treatment temperature (1400 °C). The catalytic activity of the LSCM electrodes is enhanced by using carbonate-derived powders to manipulate the electrode microstructures.

Mapping the pharmaceutical design space by amorphous ionic liquid strategies.

PubMed

Wiest, Johannes; Saedtler, Marco; Balk, Anja; Merget, Benjamin; Widmer, Toni; Bruhn, Heike; Raccuglia, Marc; Walid, Elbast; Picard, Franck; Stopper, Helga; Dekant, Wolfgang; Lühmann, Tessa; Sotriffer, Christoph; Galli, Bruno; Holzgrabe, Ulrike; Meinel, Lorenz

2017-12-28

Poor water solubility of drugs fuels complex formulations and jeopardizes patient access to medication. Simplifying these complexities we systematically synthesized a library of 36 sterically demanding counterions and mapped the pharmaceutical design space for amorphous ionic liquid strategies for Selurampanel, a poorly water soluble drug used against migraine. Patients would benefit from a rapid uptake after oral administration to alleviate migraine symptoms. Therefore, we probed the ionic liquids for the flux, supersaturation period and hygroscopicity leading to algorithms linking molecular counterion descriptors to predicted pharmaceutical outcome. By that, 30- or 800-fold improvements of the supersaturation period and fluxes were achieved as were immediate to sustained release profiles through structural counterions' optimization compared to the crystalline free acid of Selurampanel. Guided by ionic liquid structure, in vivo profiles ranged from rapid bioavailability and high maximal plasma concentrations to sustained patterns. In conclusion, the study outlined and predicted the accessible pharmaceutical design space of amorphous ionic liquid based and excipient-free formulations pointing to the enormous pharmaceutical potential of ionic liquid designs. Copyright © 2017 Elsevier B.V. All rights reserved.

Different Effect of Co on the Formation of Topologically Close-Packed Phases in Ni-Cr-Mo and Ni-Cr-Re Alloys

NASA Astrophysics Data System (ADS)

Shi, Qianying; An, Ning; Huo, Jiajie; Ding, Xianfei; Zheng, Yunrong; Feng, Qiang

2017-11-01

In current study, two sets of Ni-based alloys (Ni-Cr-Mo and Ni-Cr-Re series) containing 0 to 15 at. pct of Co addition were investigated to understand the formation behavior of TCP phases. Significant difference on the formation behavior of TCP phases and corresponding Co effect was found in two series alloys. TCP precipitates ( P and µ phase) were observed in both grain interiors and boundaries in Ni-Cr-Mo series alloys. Higher levels of Co addition increased the supersaturation of Mo in the γ matrix, which explained that Co addition promoted µ phase formation. In contrast, the TCP precipitates ( σ phase) formed by the manner of discontinuous precipitation transformation in the grain boundaries in Ni-Cr-Re series alloys. More Co additions suppressed the formation of σ phase, which was mainly attributed to the decreased supersaturation of Re in thermodynamically metastable γ matrix. The information obtained from simplified alloy systems in this study is helpful for the design of multicomponent Ni-based superalloys.

Protein Crystallization.

PubMed

McPherson, Alexander

2017-01-01

Protein crystallization was discovered by chance nearly 200 years ago and was developed in the late nineteenth century as a powerful purification tool, and a demonstration of chemical purity. The crystallization of proteins, nucleic acids, and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule, but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by manipulation of various parameters that include temperature, ionic strength, and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors, or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch, and liquid-liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years due to the advent of practical, easy-to-use screening kits, and the application of laboratory robotics.

Improved Success of Sparse Matrix Protein Crystallization Screening with Heterogeneous Nucleating Agents

PubMed Central

Thakur, Anil S.; Robin, Gautier; Guncar, Gregor; Saunders, Neil F. W.; Newman, Janet; Martin, Jennifer L.; Kobe, Bostjan

2007-01-01

Background Crystallization is a major bottleneck in the process of macromolecular structure determination by X-ray crystallography. Successful crystallization requires the formation of nuclei and their subsequent growth to crystals of suitable size. Crystal growth generally occurs spontaneously in a supersaturated solution as a result of homogenous nucleation. However, in a typical sparse matrix screening experiment, precipitant and protein concentration are not sampled extensively, and supersaturation conditions suitable for nucleation are often missed. Methodology/Principal Findings We tested the effect of nine potential heterogenous nucleating agents on crystallization of ten test proteins in a sparse matrix screen. Several nucleating agents induced crystal formation under conditions where no crystallization occurred in the absence of the nucleating agent. Four nucleating agents: dried seaweed; horse hair; cellulose and hydroxyapatite, had a considerable overall positive effect on crystallization success. This effect was further enhanced when these nucleating agents were used in combination with each other. Conclusions/Significance Our results suggest that the addition of heterogeneous nucleating agents increases the chances of crystal formation when using sparse matrix screens. PMID:17971854

Gas hydrate formation rates from dissolved-phase methane in porous laboratory specimens

USGS Publications Warehouse

Waite, William F.; Spangenberg, E.K.

2013-01-01

Marine sands highly saturated with gas hydrates are potential energy resources, likely forming from methane dissolved in pore water. Laboratory fabrication of gas hydrate-bearing sands formed from dissolved-phase methane usually requires 1–2 months to attain the high hydrate saturations characteristic of naturally occurring energy resource targets. A series of gas hydrate formation tests, in which methane-supersaturated water circulates through 100, 240, and 200,000 cm3 vessels containing glass beads or unconsolidated sand, show that the rate-limiting step is dissolving gaseous-phase methane into the circulating water to form methane-supersaturated fluid. This implies that laboratory and natural hydrate formation rates are primarily limited by methane availability. Developing effective techniques for dissolving gaseous methane into water will increase formation rates above our observed (1 ± 0.5) × 10−7 mol of methane consumed for hydrate formation per minute per cubic centimeter of pore space, which corresponds to a hydrate saturation increase of 2 ± 1% per day, regardless of specimen size.

Bubbles in live-stranded dolphins.

PubMed

Dennison, S; Moore, M J; Fahlman, A; Moore, K; Sharp, S; Harry, C T; Hoppe, J; Niemeyer, M; Lentell, B; Wells, R S

2012-04-07

Bubbles in supersaturated tissues and blood occur in beaked whales stranded near sonar exercises, and post-mortem in dolphins bycaught at depth and then hauled to the surface. To evaluate live dolphins for bubbles, liver, kidneys, eyes and blubber-muscle interface of live-stranded and capture-release dolphins were scanned with B-mode ultrasound. Gas was identified in kidneys of 21 of 22 live-stranded dolphins and in the hepatic portal vasculature of 2 of 22. Nine then died or were euthanized and bubble presence corroborated by computer tomography and necropsy, 13 were released of which all but two did not re-strand. Bubbles were not detected in 20 live wild dolphins examined during health assessments in shallow water. Off-gassing of supersaturated blood and tissues was the most probable origin for the gas bubbles. In contrast to marine mammals repeatedly diving in the wild, stranded animals are unable to recompress by diving, and thus may retain bubbles. Since the majority of beached dolphins released did not re-strand it also suggests that minor bubble formation is tolerated and will not lead to clinically significant decompression sickness.

Heterogeneous Nucleation of Dicalcium Phosphate Dihydrate on Modified Silica Surfaces

PubMed Central

Miller, Carrie; Komunjer, Ljepša; Hlady, Vladimir

2012-01-01

Heterogeneous nucleation of dicalcium phosphate dihydrate, CaHPO4•2H2O (DCPD) was studied on untreated planar fused silica and on three modified silica surfaces: octadecylsilyl (OTS) modified silica, human serum albumin treated OTS silica, and UV-oxidized 3-mercaptopropyltriethoxysilyl (MTS) modified silica. The supersaturation ratio of calcium and phosphate solution with respect to DCPD was kept below ~10. The nucleated crystals were observed 24 hours and one week after initial contact between supersaturated solutions and substrate surfaces using bright field and reflectance interference contrast microscopy. No DCPD crystals nucleated on albumin-treated OTS-silica. Majority of the DCDP crystals formed on the other modified silica surfaces appeared to be morphologically similar irrespective of the nature of nucleating substrate. Reflectance interference contrast microscopy provided a proof that the majority of the crystals on these substrates do not develop an extended contact with the substrate surface. The images showed that the most extended contact planes were between the DCPD crystals and MTS modified silica surface. The crystals nucleated on OTS-treated and untreated silica surfaces showed only few or none well-developed contact planes. PMID:25264399

On the relevance of volume increase for the length changes of mortar bars in sulfate solutions

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

Kunther, Wolfgang, E-mail: wkunther@googlemail.com; Lothenbach, Barbara; Scrivener, Karen L.

2013-04-01

The ingress of sulfate ions into cementitious materials leads to the formation of ettringite, gypsum and other phases. The increase in solid volume through the formation of these phases is often assumed to be the only reason for expansion. In this paper we systematically compare the volume increase predicted by thermodynamic modeling to macroscopic expansion for mortars made with CEM I in different sulfate solutions and for mortars made with a range of blended cements in sodium sulfate solution. It is shown that the length changes cannot be explained by simple volume increase alone. A more plausible explanation of expansionmore » lies in the theory of crystallization pressure, in which crystals forming from a supersaturated solution may exert pressure on their surroundings. It is observed that expansion occurs in systems where thermodynamic modeling predicts the co-existence of ettringite with gypsum. In such a case, if monosulfate and gypsum are both present locally, the solution can be highly supersaturated with respect to ettringite, whose formation in confined conditions (such as within C–S–H) can then exert expansive forces.« less

Energy levels distribution in supersaturated silicon with titanium for photovoltaic applications

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

Pérez, E., E-mail: eduper@ele.uva.es; Castán, H.; García, H.

2015-01-12

In the attempt to form an intermediate band in the bandgap of silicon substrates to give it the capability to absorb infrared radiation, we studied the deep levels in supersaturated silicon with titanium. The technique used to characterize the energy levels was the thermal admittance spectroscopy. Our experimental results showed that in samples with titanium concentration just under Mott limit there was a relationship among the activation energy value and the capture cross section value. This relationship obeys to the well known Meyer-Neldel rule, which typically appears in processes involving multiple excitations, like carrier capture/emission in deep levels, and itmore » is generally observed in disordered systems. The obtained characteristic Meyer-Neldel parameters were Tmn = 176 K and kTmn = 15 meV. The energy value could be associated to the typical energy of the phonons in the substrate. The almost perfect adjust of all experimental data to the same straight line provides further evidence of the validity of the Meyer Neldel rule, and may contribute to obtain a deeper insight on the ultimate meaning of this phenomenon.« less

Diameter Dependence of Planar Defects in InP Nanowires

PubMed Central

Wang, Fengyun; Wang, Chao; Wang, Yiqian; Zhang, Minghuan; Han, Zhenlian; Yip, SenPo; Shen, Lifan; Han, Ning; Pun, Edwin Y. B.; Ho, Johnny C.

2016-01-01

In this work, extensive characterization and complementary theoretical analysis have been carried out on Au-catalyzed InP nanowires in order to understand the planar defect formation as a function of nanowire diameter. From the detailed transmission electron microscopic measurements, the density of stacking faults and twin defects are found to monotonically decrease as the nanowire diameter is decreased to 10 nm, and the chemical analysis clearly indicates the drastic impact of In catalytic supersaturation in Au nanoparticles on the minimized planar defect formation in miniaturized nanowires. Specifically, during the chemical vapor deposition of InP nanowires, a significant amount of planar defects is created when the catalyst seed sizes are increased with the lower degree of In supersaturation as dictated by the Gibbs-Thomson effect, and an insufficient In diffusion (or Au-rich enhancement) would lead to a reduced and non-uniform In precipitation at the NW growing interface. The results presented here provide an insight into the fabrication of “bottom-up” InP NWs with minimized defect concentration which are suitable for various device applications. PMID:27616584

Diameter Dependence of Planar Defects in InP Nanowires.

PubMed

Wang, Fengyun; Wang, Chao; Wang, Yiqian; Zhang, Minghuan; Han, Zhenlian; Yip, SenPo; Shen, Lifan; Han, Ning; Pun, Edwin Y B; Ho, Johnny C

2016-09-12

In this work, extensive characterization and complementary theoretical analysis have been carried out on Au-catalyzed InP nanowires in order to understand the planar defect formation as a function of nanowire diameter. From the detailed transmission electron microscopic measurements, the density of stacking faults and twin defects are found to monotonically decrease as the nanowire diameter is decreased to 10 nm, and the chemical analysis clearly indicates the drastic impact of In catalytic supersaturation in Au nanoparticles on the minimized planar defect formation in miniaturized nanowires. Specifically, during the chemical vapor deposition of InP nanowires, a significant amount of planar defects is created when the catalyst seed sizes are increased with the lower degree of In supersaturation as dictated by the Gibbs-Thomson effect, and an insufficient In diffusion (or Au-rich enhancement) would lead to a reduced and non-uniform In precipitation at the NW growing interface. The results presented here provide an insight into the fabrication of "bottom-up" InP NWs with minimized defect concentration which are suitable for various device applications.

Thermal Optimization of Growth and Quality in Protein Crystals

NASA Technical Reports Server (NTRS)

Wiencek, John M.

1996-01-01

Experimental evidence suggests that larger and higher quality crystals can be attained in the microgravity of space; however, the effect of growth rate on protein crystal quality is not well documented. This research is the first step towards providing strategies to grow crystals under constant rates of growth. Controlling growth rates at a constant value allows for direct one-to-one comparison of results obtained in microgravity and on earth. The overall goal of the project was to control supersaturation at a constant value during protein crystal growth by varying temperature in a predetermined manner. Applying appropriate theory requires knowledge of specific physicochemical properties of the protein solution including the effect of supersaturation on growth rates and the effect of temperature on protein solubility. Such measurements typically require gram quantities of protein and many months of data acquisition. A second goal of the project applied microcalorimetry for the rapid determination of these physicochemical properties using a minimum amount of protein. These two goals were successfully implemented on hen egg-white lysozyme. Results of these studies are described in the attached reprints.

Exploiting the Phenomenon of Liquid-Liquid Phase Separation for Enhanced and Sustained Membrane Transport of a Poorly Water-Soluble Drug.

PubMed

Indulkar, Anura S; Gao, Yi; Raina, Shweta A; Zhang, Geoff G Z; Taylor, Lynne S

2016-06-06

Recent studies on aqueous supersaturated lipophilic drug solutions prepared by methods including antisolvent addition, pH swing, or dissolution of amorphous solid dispersions (ASDs) have demonstrated that when crystallization is slow, these systems undergo liquid-liquid phase separation (LLPS) when the concentration of the drug in the medium exceeds its amorphous solubility. Following LLPS, a metastable equilibrium is formed where the concentration of drug in the continuous phase corresponds to the amorphous solubility while the dispersed phase is composed of a nanosized drug-rich phase. It has been reasoned that the drug-rich phase may act as a reservoir, enabling the rate of passive transport of the drug across a membrane to be maintained at the maximum value for an extended period of time. Herein, using clotrimazole as a model drug, and a flow-through diffusion cell, the reservoir effect is demonstrated. Supersaturated clotrimazole solutions at concentrations below the amorphous solubility show a linear relationship between the maximum flux and the initial concentration. Once the concentration exceeds the amorphous solubility, the maximum flux achieved reaches a plateau. However, the duration for which the high flux persists was found to be highly dependent on the number of drug-rich nanodroplets present in the donor compartment. Macroscopic amorphous particles of clotrimazole did not lead to the same reservoir effect observed with the nanodroplets formed through the process of LLPS. A first-principles mathematical model was developed which was able to fit the experimental receiver concentration-time profiles for concentration regimes both below and above amorphous solubility, providing support for the contention that the nanodroplet phase does not directly diffuse across the membrane but, instead, rapidly replenishes the drug in the aqueous phase that has been removed by transport across the membrane. This study provides important insight into the properties of supersaturated solutions and how these might in turn impact oral absorption through effects on passive membrane transport rates.

Organic Aerosols as Cloud Condensation Nuclei

NASA Astrophysics Data System (ADS)

Hudson, J. G.

2002-05-01

The large organic component of the atmospheric aerosol contributes to both natural and anthropogenic cloud condensation nuclei (CCN). Moreover, some organic substances may reduce droplet surface tension (Facchini et al. 1999), while others may be partially soluble (Laaksonen et al. 1998), and others may inhibit water condensation. The interaction of organics with water need to be understood in order to better understand the indirect aerosol effect. Therefore, laboratory CCN spectral measurements of organic aerosols are presented. These are measurements of the critical supersaturation (Sc), the supersaturation needed to produce an activated cloud droplet, as a function of the size of the organic particles. Substances include sodium lauryl (dodecyl) sulfate, oxalic, adipic, pinonic, hexadecanedioic, glutaric, stearic, succinic, phthalic, and benzoic acids. These size-Sc relationships are compared with theoretical and measured size-Sc relationships of common inorganic compounds (e.g., NaCl, KI, ammonium and calcium sulfate). Unlike most inorganics some organics display variations in solubility per unit mass as a function of particle size. Those showing relatively greater solubility at smaller sizes may be attributable to surface tension reduction, which is greater for less water dilution, as is the case for smaller particles, which are less diluted at the critical sizes. This was the case for sodium dodecyl sulfate, which does reduce surface tension. Relatively greater solubility for larger particles may be caused by greater dissolution at the higher dilutions that occur with larger particles; this is partial solubility. Measurements are also presented of internal mixtures of various organic and inorganic substances. These measurements were done with two CCN spectrometers (Hudson 1989) operating simultaneously. These two instruments usually displayed similar results in spite of the fact that they have different flow rates and supersaturation profiles. The degree of agreement between these cloud chambers then tests and defines the limits of possible alterations of conventional Kohler theory (e.g., Kulmala et al. 1993).

Probabilistic description of ice-supersaturated layers in low resolution profiles of relative humidity

NASA Astrophysics Data System (ADS)

Dickson, N. C.; Gierens, K. M.; Rogers, H. L.; Jones, R. L.

2010-07-01

The global observation, assimilation and prediction in numerical models of ice super-saturated (ISS) regions (ISSR) are crucial if the climate impact of aircraft condensation trails (contrails) is to be fully understood, and if, for example, contrail formation is to be avoided through aircraft operational measures. Given their small scales compared to typical atmospheric model grid sizes, statistical representations of the spatial scales of ISSR are required, in both horizontal and vertical dimensions, if global occurrence of ISSR is to be adequately represented in climate models. This paper uses radiosonde launches made by the UK Meteorological Office, from the British Isles, Gibraltar, St. Helena and the Falkland Islands between January 2002 and December 2006, to investigate the probabilistic occurrence of ISSR. Each radiosonde profile is divided into 50- and 100-hPa pressure layers, to emulate the coarse vertical resolution of some atmospheric models. Then the high resolution observations contained within each thick pressure layer are used to calculate an average relative humidity and an ISS fraction for each individual thick pressure layer. These relative humidity pressure layer descriptions are then linked through a probability function to produce an s-shaped curve which empirically describes the ISS fraction in any average relative humidity pressure layer. Using this empirical understanding of the s-shaped relationship a mathematical model was developed to represent the ISS fraction within any arbitrary thick pressure layer. Two models were developed to represent both 50- and 100-hPa pressure layers with each reconstructing their respective s-shapes within 8-10% of the empirical curves. These new models can be used, to represent the small scale structures of ISS events, in modelled data where only low vertical resolution is available. This will be useful in understanding, and improving the global distribution, both observed and forecasted, of ice super-saturation.

Role of Molecular Interactions for Synergistic Precipitation Inhibition of Poorly Soluble Drug in Supersaturated Drug-Polymer-Polymer Ternary Solution.

PubMed

Prasad, Dev; Chauhan, Harsh; Atef, Eman

2016-03-07

We are reporting a synergistic effect of combined Eudragit E100 and PVP K90 in precipitation inhibition of indomethacin (IND) in solutions at low polymer concentration, a phenomenon that has significant implications on the usefulness of developing novel ternary solid dispersion of poorly soluble drugs. The IND supersaturation was created by cosolvent technique, and the precipitation studies were performed in the absence and the presence of individual and combined PVP K90 and Eudragit E100. The studies were also done with PEG 8000 as a noninteracting control polymer. A continuous UV recording of the IND absorption was used to observe changes in the drug concentration over time. The polymorphic form and morphology of precipitated IND were characterized by Raman spectroscopy and scanning electron microscopy. The change in the chemical shift in solution (1)H NMR was used as novel approach to probe IND-polymer interactions. Molecular modeling was used for calculating binding energy between IND-polymer as another indication of IND-polymer interaction. Spontaneous IND precipitation was observed in the absence of polymers. Eudragit E100 showed significant inhibitory effect on nuclei formation due to stronger interaction as reflected in higher binding energy and greater change in chemical shift by NMR. PVP K90 led to significant crystal growth inhibition due to adsorption on growing IND crystals as confirmed by modified crystal habit of precipitate in the presence of PVP K90. Combination of polymers resulted in a synergistic precipitation inhibition and extended supersaturation. The NMR confirmed interaction between IND-Eudragit E100 and IND-PVP K90 in solution. The combination of polymers showed similar peak shift albeit using lower polymer concentration indicating stronger interactions. The results established the significant synergistic precipitation inhibition effect upon combining Eudragit E100 and PVP K90 due to drug-polymer interaction.

The impact of dissolved fluorine on bubble nucleation in hydrous rhyolite melts

NASA Astrophysics Data System (ADS)

Gardner, James E.; Hajimirza, Sahand; Webster, James D.; Gonnermann, Helge M.

2018-04-01

Surface tension of hydrous rhyolitic melt is high enough that large degrees of supersaturation are needed to homogeneously nucleate H2O bubbles during eruptive magma ascent. This study examines whether dissolved fluorine lowers surface tension of hydrous rhyolite, and thus lowers the supersaturation required for bubble nucleation. Fluorine was targeted because it, like H2O, changes melt properties and is highly soluble, unlike all other common magmatic volatiles. Rhyolite melts were saturated at Ps = 245 MPa with H2O fluid that contained F, generating rhyolite with 6.7 ± 0.4 wt.% H2O and 1.1-1.3 wt.% F. When these melts were decompressed rapidly to Pf = 149-202 MPa and quenched after 60 s, bubbles nucleated at supersaturations of ΔP = Ps - Pf ≥52 MPa, and reached bubble number densities of NB = 1012-13 m-3 at ΔP = 78-101 MPa. In comparison, rhyolite saturated with 6.34 ± 0.09 wt.% H2O, but only 0.25 wt.% F, did not nucleate bubbles until ΔP ≥ 100-116 MPa, and even then, at significantly lower NB (<1010 m-3). Numerical modeling of bubble nucleation and growth was used to estimate the values of surface tension required to generate the observed values of NB. Slight differences in melt compositions (i.e., alkalinity and H2O content), H2O diffusivity, or melt viscosity cannot explain the observed differences in NB. Instead, surface tension of F-rich rhyolite must be lower by approximately 4% than that of F-poor rhyolite. This difference in surface tension is significant and, for example, exceeds that found between hydrous basaltic andesite and hydrous rhyolite. These results suggest that is likely that surface tension for F-rich magmas, such as topaz rhyolite, is significantly lower than for F-poor magmas.

Airborne measurement of submicron aerosol number concentration and CCN activity in and around the Korean Peninsula and their comparison to ground measurement in Seoul

NASA Astrophysics Data System (ADS)

Park, M.; Kim, N.; Yum, S. S.

2016-12-01

Aerosols exert impact not only on human health and visibility but also on climate change directly by scattering or absorbing solar radiation and indirectly by acting as cloud condensation nuclei (CCN) and thus altering cloud radiative and microphysical properties. Aerosol indirect effects on climate has been known to have large uncertainty because of insufficient measurement data on aerosol and CCN activity distribution. Submicron aerosol number concentration (NCN, TSI CPC) and CCN number concentration (NCCN, DMT CCNC) were measured on board the NASA DC-8 research aircraft and at a ground site at Olympic Park in Seoul from May 2nd to June 10th, 2016. CCNC on the airborne platform was operated with the fixed internal supersaturation of 0.6% and CCNC at the ground site was operated with the five different supersaturations (0.2%, 0.4%, 0.6%, 0.8%, and 1.0%). The NASA DC-8 conducted 20 research flights (about 150 hours) in and around the Korean Peninsula and the ground measurement at Olympic Park was continuously made during the measurement period. Both airborne and ground measurements showed spatially and temporally varied aerosol number concentration and CCN activity. Aerosol number concentration in the boundary layer measured on airborne platform was highly affected by pollution sources on the ground. The average diurnal distribution of ground aerosol number concentration showed distinct peaks are located at about 0800, 1500, and 2000. The middle peak indicates that new particle formation events frequently occurred during the measurement period. CCN activation ratio at 0.6% supersaturation (NCCN/NCN) of the airborne measurement ranged from 0.1 to 0.9, indicating that aerosol properties in and around the Korean Peninsula varied so much (e. g. size, hygroscopicity). Comprehensive analysis results will be shown at the conference.

Cost-effective alternative to nano-encapsulation: Amorphous curcumin-chitosan nanoparticle complex exhibiting high payload and supersaturation generation.

PubMed

Nguyen, Minh Hiep; Yu, Hong; Kiew, Tie Yi; Hadinoto, Kunn

2015-10-01

While the wide-ranging therapeutic activities of curcumin have been well established, its successful delivery to realize its true therapeutic potentials faces a major challenge due to its low oral bioavailability. Even though nano-encapsulation has been widely demonstrated to be effective in enhancing the bioavailability of curcumin, it is not without drawbacks (i.e. low payload and costly preparation). Herein we present a cost-effective bioavailability enhancement strategy of curcumin in the form of amorphous curcumin-chitosan nanoparticle complex (or curcumin nanoplex in short) exhibiting a high payload (>80%). The curcumin nanoplex was prepared by a simple yet highly efficient drug-polysaccharide complexation method that required only mixing of the curcumin and chitosan solutions under ambient condition. The effects of (1) pH and (2) charge ratio of chitosan to curcumin on the (i) physical characteristics of the nanoplex (i.e. size, colloidal stability and payload), (ii) complexation efficiency, and (iii) production yield were investigated from which the optimal preparation condition was determined. The nanoplex formation was found to favor low acidic pH and charge ratio below unity. At the optimal condition (i.e. pH 4.4. and charge ratio=0.8), stable curcumin nanoplex (≈260nm) was prepared at >90% complexation efficiency and ≈50% production yield. The amorphous state stability, colloidal stability, and in vitro non-cytotoxicity of the nanoplex were successfully established. The curcumin nanoplex produced prolonged supersaturation (3h) in the presence of hydroxypropyl methylcellulose (HPMC) at five times of the saturation solubility of curcumin. In addition, curcumin released from the nanoplex exhibited improved chemical stability owed to the presence of chitosan. Both results (i.e. high supersaturation and improved chemical stability) bode well for the ability of the curcumin nanoplex to enhance the bioavailability of curcumin clinically. Copyright © 2015 Elsevier B.V. All rights reserved.

Elucidating the impacts of initial supersaturation and seed crystal loading on struvite precipitation kinetics, fines production, and crystal growth.

PubMed

Agrawal, Shantanu; Guest, Jeremy S; Cusick, Roland D

2018-04-01

To reduce intra-plant nutrient cycling, and recover phosphorus (P) fertilizers from nutrient-rich sidestreams, wastewater utilities increasingly elect to employ struvite precipitation processes without a clear understanding of the inherent tradeoffs associated with specific design and operating decisions. Specifically, the impact of reactor conditions on struvite crystallization rate, and distribution between formation of fines particles and secondary growth onto large diameter seed crystals represent critical knowledge gaps limiting the predictive capabilities of existing process models. In this work, the relative impacts of initial supersaturation (S i ), and seed loading, on P removal kinetics, and struvite solids distribution were investigated. In experiments conducted at different levels of initial supersaturation (1.7-2.4) and seed loading (0-25 g L -1 ), struvite fines represented the majority of phosphate solids formed in 10 of 12 conditions. While total P removal was dependent on S i , and primarily attributed to formation of fines, the concentration of struvite seed granules had a significant impact on the rate of P removal. Struvite seed granules increased the rate of precipitation by reducing induction time of primary nucleation of struvite fines. Secondary crystal growth represented the majority of struvite solids formed at high seed loading and low S i , but presented the tradeoff of low total removal and low rate of removal. To convey the significance of these findings on process modeling, we show how a prominent kinetic model with a first-order dependency on solid struvite concentration over-predicts P removal rate when total mass is dominated by large diameter seeds (0.9 mm). This works reveals the critical role of struvite fines in P removal, and highlights the need to account for their production and kinetic importance in struvite process design and operation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Unprecedented Al supersaturation in single-phase rock salt structure VAlN films by Al+ subplantation

NASA Astrophysics Data System (ADS)

Greczynski, G.; Mráz, S.; Hans, M.; Primetzhofer, D.; Lu, J.; Hultman, L.; Schneider, J. M.

2017-05-01

Modern applications of refractory ceramic thin films, predominantly as wear-protective coatings on cutting tools and on components utilized in automotive engines, require a combination of excellent mechanical properties, thermal stability, and oxidation resistance. Conventional design approaches for transition metal nitride coatings with improved thermal and chemical stability are based on alloying with Al. It is well known that the solubility of Al in NaCl-structure transition metal nitrides is limited. Hence, the great challenge is to increase the Al concentration substantially while avoiding precipitation of the thermodynamically favored wurtzite-AlN phase, which is detrimental to mechanical properties. Here, we use VAlN as a model system to illustrate a new concept for the synthesis of metastable single-phase NaCl-structure thin films with the Al content far beyond solubility limits obtained with conventional plasma processes. This supersaturation is achieved by separating the film-forming species in time and energy domains through synchronization of the 70-μs-long pulsed substrate bias with intense periodic fluxes of energetic Al+ metal ions during reactive hybrid high power impulse magnetron sputtering of the Al target and direct current magnetron sputtering of the V target in the Ar/N2 gas mixture. Hereby, Al is subplanted into the cubic VN grains formed by the continuous flux of low-energy V neutrals. We show that Al subplantation enables an unprecedented 42% increase in metastable Al solubility limit in V1-xAlxN, from x = 0.52 obtained with the conventional method to 0.75. The elastic modulus is 325 ± 5 GPa, in excellent agreement with density functional theory calculations, and approximately 50% higher than for corresponding films grown by dc magnetron sputtering. The extension of the presented strategy to other Al-ion-assisted vapor deposition methods or materials systems is straightforward, which opens up the way for producing supersaturated single-phase functional ceramic alloy thin films combining excellent mechanical properties with high oxidation resistance.

HOW DO STONES FORM? IS UNIFICATION OF THEORIES ON STONE FORMATION POSSIBLE?

PubMed Central

Bird, Victoria Y.; Khan, Saeed R.

2017-01-01

Summary There are two basic pathways for formation of calcium based kidney stones. Most idiopathic calcium oxalate (CaOx) stones are formed in association with sub-epithelial plaques of calcium phosphate (CaP), known as Randall’s plaques, on renal papillary surfaces. Crystal formation and retention within the terminal collecting ducts, the ducts of Bellini, leading to the formation of Randall’s plugs, is the other pathway. Both pathways require supersaturation leading to crystallization, regulated by various crystallization modulators produced in response to changing urinary conditions. High supersaturation, as a result of a variety of genetic and environmental factors, leads to crystallization in the terminal collecting ducts, eventually plugging their openings into the renal pelvis. Stasis behind the plugs may lead to the formation of attached or unattached stones in the tubular lumen. Deposition of crystals on the plug surface facing the pelvic or tubular urine may result in stone formation on the Randall’s plugs. Kidneys of idiopathic stone formers may be subjected to oxidative stress as a result of increased urinary excretion of calcium/oxalate/phosphate and/or decrease in the production of functional crystallization inhibitors or in relation to co-morbidities such as hypertension, atherosclerosis, or acute kidney injury. We have proposed that production of reactive oxygen species (ROS) causes dedifferentiation of epithelial/endothelial cells into osteoblast type cells and deposition of CaP in the basement membrane of renal tubules or vessels. Growth, aggregation and melding of CaP crystals leads to the formation of plaque which grows by further calcification of interstitial collagen and membranous vesicles. Plaque becomes exposed to pelvic urine once the covering papillary epithelium is breached. Surface layers of CaP are replaced by CaOx through direct transformation or demineralization of CaP and mineralization of CaOx. Alternatively, or in addition, CaOx crystals nucleate directly on the plaque surface. Stone growth may also depend upon supersaturation in the pelvic urine, triggering further nucleation, growth and aggregation. PMID:28221139

Acute exposure to gas-supersaturated water does not affect reproductive success of female adult chinook salmon late in maturation

USGS Publications Warehouse

Gale, William L.; Maule, A.G.; Postera, A.; Peters, M.H.

2004-01-01

At times, total dissolved gas concentrations in the Columbia and Snake rivers have been elevated due to involuntary spill from high spring runoff and voluntary spill used as a method to pass juvenile salmonids over dams. The goal of this project was to determine if acute exposure to total dissolved gas supersaturation (TDGS) affects the reproductive performance of female chinook salmon late in their maturation. During this study, adult female spring chinook salmon were exposed to mean TDGS levels of 114.1 % to 125.5%. We ended exposures at first mortality, or at the appearance of impending death. Based on this criterion, exposures lasted from 10 to 68 h and were inversely related to TDGS. There was no effect of TDGS on pre-spawning mortality or fecundity when comparing treatment fish to experimental controls or the general hatchery population four to six weeks after exposures. Egg quality, based on egg weight and egg diameter, did not differ between treatment and control fish. Fertilization rate and survival to eyed-stage was high (>94%) for all groups. With the exception of Renibacterium salmoninarum (the causative agent of bacterial kidney disease; BKD), no viral or bacterial fish pathogens were isolated from experimental fish. The prevalence (about 45%) and severity of R. salmoninarum did not differ among the groups or the general hatchery population. We conclude that these acute exposures to moderate levels of gas-supersaturated water-perhaps similar to that experienced by immigrating adult salmon as they approach and pass a hydropower dam on the Columbia River-did not affect reproductive success of female chinook salmon late in their maturation. These results are most applicable to summer and fall chinook salmon, which migrate in the summer/fall and spawn shortly after reaching their natal streams. Published in 2004 by John Wiley and Sons, Ltd.

Diblock Terpolymers Are Tunable and pH Responsive Vehicles To Increase Hydrophobic Drug Solubility for Oral Administration.

PubMed

Tale, Swapnil; Purchel, Anatolii A; Dalsin, Molly C; Reineke, Theresa M

2017-11-06

Synthetic polymers offer tunable platforms to create new oral drug delivery vehicles (excipients) to increase solubility, supersaturation maintenance, and bioavailability of poorly aqueous soluble pharmaceutical candidates. Five well-defined diblock terpolymers were synthesized via reversible addition-fragmentation chain transfer polymerization (RAFT) and consist of a first block of either poly(ethylene-alt-propylene) (PEP), poly(N-isopropylacrylamide) (PNIPAm), or poly(N,N-diethylaminoethyl methacrylate) (PDEAEMA) and a second hydrophilic block consisting of a gradient copolymer of N,N-dimethylacrylamide (DMA) and 2-methacrylamidotrehalose (MAT). This family of diblock terpolymers offers hydrophobic, hydrophilic, or H-bonding functionalities to serve as noncovalent sites of drug binding. Drug-polymer spray dried dispersions (SDDs) were created with a model drug, probucol, and characterized by differential scanning calorimetry (DSC). These studies revealed that probucol crystallinity decreased with increasing H-bonding sites available in the polymer. The PNIPAm-b-P(DMA-grad-MAT) systems revealed the best performance at pH 6.5, where immediate probucol release and effective maintenance of 100% supersaturation was found, which is important for facilitating drug solubility in more neutral conditions (intestinal environment). However, the PDEAEMA-b-P(DMA-grad-MAT) system revealed poor probucol dissolution at pH 6.5 and 5.1. Alternatively, at an acidic pH of 3.1, a rapid and high dissolution profile and effective supersaturation maintenance of up to 90% of the drug was found, which could be useful for triggering drug release in acidic environments (stomach). The PEP-b-P(DMA-grad-MAT) system showed poor performance (only ∼20% of drug solubility at pH 6.5), which was attributed to the low solubility of the polymers in the dissolution media. This work demonstrates the utility of diblock terpolymers as a potential new excipient platform to optimize design parameters for triggered release and solubilizing hydrophobic drug candidates for oral delivery.

Observed aerosol effects on marine cloud nucleation and supersaturation

NASA Astrophysics Data System (ADS)

Russell, Lynn M.; Sorooshian, Armin; Seinfeld, John H.; Albrecht, Bruce A.; Nenes, Athanasios; Leaitch, W. Richard; Macdonald, Anne Marie; Ahlm, Lars; Chen, Yi-Chun; Coggon, Matthew; Corrigan, Ashley; Craven, Jill S.; Flagan, Richard C.; Frossard, Amanda A.; Hawkins, Lelia N.; Jonsson, Haflidi; Jung, Eunsil; Lin, Jack J.; Metcalf, Andrew R.; Modini, Robin; Mülmenstädt, Johannes; Roberts, Greg C.; Shingler, Taylor; Song, Siwon; Wang, Zhen; Wonaschütz, Anna

2013-05-01

Aerosol particles in the marine boundary layer include primary organic and salt particles from sea spray and combustion-derived particles from ships and coastal cities. These particle types serve as nuclei for marine cloud droplet activation, although the particles that activate depend on the particle size and composition as well as the supersaturation that results from cloud updraft velocities. The Eastern Pacific Emitted Aerosol Cloud Experiment (EPEACE) 2011 was a targeted aircraft campaign to assess how different particle types nucleate cloud droplets. As part of E-PEACE 2011, we studied the role of marine particles as cloud droplet nuclei and used emitted particle sources to separate particle-induced feedbacks from dynamical variability. The emitted particle sources included shipboard smoke-generated particles with 0.05-1 μm diameters (which produced tracks measured by satellite and had drop composition characteristic of organic smoke) and combustion particles from container ships with 0.05-0.2 μm diameters (which were measured in a variety of conditions with droplets containing both organic and sulfate components) [1]. Three central aspects of the collaborative E-PEACE results are: (1) the size and chemical composition of the emitted smoke particles compared to ship-track-forming cargo ship emissions as well as background marine particles, with particular attention to the role of organic particles, (2) the characteristics of cloud track formation for smoke and cargo ships, as well as the role of multi-layered low clouds, and (3) the implications of these findings for quantifying aerosol indirect effects. For comparison with the E-PEACE results, the preliminary results of the Stratocumulus Observations of Los-Angeles Emissions Derived Aerosol-Droplets (SOLEDAD) 2012 provided evidence of the cloud-nucleating roles of both marine organic particles and coastal urban pollution, with simultaneous measurements of the effective supersaturations of the clouds in the California coastal region.

Riverine CO2 supersaturation and outgassing in a subtropical monsoonal mountainous area (Three Gorges Reservoir Region) of China

NASA Astrophysics Data System (ADS)

Li, Siyue; Ni, Maofei; Mao, Rong; Bush, Richard T.

2018-03-01

Rivers are an important source of CO2 to the atmosphere, however, mountainous rivers and streams with high emission rates are not well studied particularly in China. We report the first detailed investigation on monsoonal mountainous rivers in the Three Gorges Reservoir (TGR) region, with a focus on the riverine CO2 partial pressure (pCO2), CO2 degassing and their potential controls. The pCO2 levels ranged from 50 to 6019 μatm with averages of 1573 (SD. ±1060) in dry Autumn and 1276 (SD. ±1166) μatm in wet Summer seasons. 94% of samples were supersaturated with CO2 with respect to the atmospheric equilibrium (410 μatm). Monsoonal precipitation controlled pCO2 seasonality, with both the maximal and minimal levels occurring in the wet season, and showing the overall effects of dilution. Riverine pCO2 could be predicted better in the dry season using pH, DO% and DTP, whereas pH and DOC were better predictors in the wet season. We conclude that in-situ respiration of allochthonous organic carbon, rather than photosynthesis, resulted in negative relationships between pCO2 and DO and pH, and thus CO2 supersaturation. Photosynthetic primary production was effectively limited by rapid flow velocity and short residence time. The estimated water-to-air CO2 emission rate in the TGR rivers was 350 ± 319 in the Autumn and lower, yet more variable at 326 ± 439 mmol/m2/d in Summer. Our calculated CO2 areal fluxes were in the upper-level magnitude of published data, demonstrating the importance of mountainous rivers and streams as a global greenhouse gas source, and urgency for more detailed studies on CO2 degassing, to address a global data gap for these environments.

Water uptake of clay and desert dust aerosol particles at sub- and supersaturated water vapor conditions.

PubMed

Herich, Hanna; Tritscher, Torsten; Wiacek, Aldona; Gysel, Martin; Weingartner, Ernest; Lohmann, Ulrike; Baltensperger, Urs; Cziczo, Daniel J

2009-09-28

Airborne mineral dust particles serve as cloud condensation nuclei (CCN), thereby influencing the formation and properties of warm clouds. It is therefore of atmospheric interest how dust aerosols with different mineralogy behave when exposed to high relative humidity (RH) or supersaturation (SS) with respect to liquid water. In this study the subsaturated hygroscopic growth and the supersaturated cloud condensation nucleus activity of pure clays and real desert dust aerosols were determined using a hygroscopicity tandem differential mobility analyzer (HTDMA) and a cloud condensation nuclei counter (CCNC), respectively. Five different illite, montmorillonite and kaolinite clay samples as well as three desert dust samples (Saharan dust (SD), Chinese dust (CD) and Arizona test dust (ATD)) were investigated. Aerosols were generated both with a wet and a dry disperser. The water uptake was parameterized via the hygroscopicity parameter kappa. The hygroscopicity of dry generated dust aerosols was found to be negligible when compared to processed atmospheric aerosols, with CCNC derived kappa values between 0.00 and 0.02 (the latter corresponds to a particle consisting of 96.7% by volume insoluble material and approximately 3.3% ammonium sulfate). Pure clay aerosols were generally found to be less hygroscopic than natural desert dust particles. The illite and montmorillonite samples had kappa approximately 0.003. The kaolinite samples were less hygroscopic and had kappa=0.001. SD (kappa=0.023) was found to be the most hygroscopic dry-generated desert dust followed by CD (kappa=0.007) and ATD (kappa=0.003). Wet-generated dust showed an increased water uptake when compared to dry-generated samples. This is considered to be an artifact introduced by redistribution of soluble material between the particles. Thus, the generation method is critically important when presenting such data. These results indicate any atmospheric processing of a fresh mineral dust particle which leads to the addition of more than approximately 3% soluble material will significantly enhance its hygroscopicity and CCN activity.

Mathematical model to analyze the dissolution behavior of metastable crystals or amorphous drug accompanied with a solid-liquid interface reaction.

PubMed

Hirai, Daiki; Iwao, Yasunori; Kimura, Shin-Ichiro; Noguchi, Shuji; Itai, Shigeru

2017-04-30

Metastable crystals and the amorphous state of poorly water-soluble drugs in solid dispersions (SDs), are subject to a solid-liquid interface reaction upon exposure to a solvent. The dissolution behavior during the solid-liquid interface reaction often shows that the concentration of drugs is supersaturated, with a high initial drug concentration compared with the solubility of stable crystals but finally approaching the latter solubility with time. However, a method for measuring the precipitation rate of stable crystals and/or the potential solubility of metastable crystals or amorphous drugs has not been established. In this study, a novel mathematical model that can represent the dissolution behavior of the solid-liquid interface reaction for metastable crystals or amorphous drug was developed and its validity was evaluated. The theory for this model was based on the Noyes-Whitney equation and assumes that the precipitation of stable crystals at the solid-liquid interface occurs through a first-order reaction. Moreover, two models were developed, one assuming that the surface area of the drug remains constant because of the presence of excess drug in the bulk and the other that the surface area changes in time-dependency because of agglomeration of the drug. SDs of Ibuprofen (IB)/polyvinylpyrrolidone (PVP) were prepared and their dissolution behaviors under non-sink conditions were fitted by the models to evaluate improvements in solubility. The model assuming time-dependent surface area showed good agreement with experimental values. Furthermore, by applying the model to the dissolution profile, parameters such as the precipitation rate and the potential solubility of the amorphous drug were successfully calculated. In addition, it was shown that the improvement in solubility with supersaturation was able to be evaluated quantitatively using this model. Therefore, this mathematical model would be a useful tool to quantitatively determine the supersaturation concentration of a metastable drug from solid dispersions. Copyright © 2017 Elsevier B.V. All rights reserved.

Balloon-borne match measurements of mid-latitude cirrus clouds

NASA Astrophysics Data System (ADS)

Cirisan, A.; Luo, B. P.; Engel, I.; Wienhold, F. G.; Krieger, U. K.; Weers, U.; Romanens, G.; Levrat, G.; Jeannet, P.; Ruffieux, D.; Philipona, R.; Calpini, B.; Spichtinger, P.; Peter, T.

2013-10-01

Observations of persistent high supersaturations with respect to ice inside cirrus clouds are challenging our understanding of cloud microphysics and of climate feedback processes in the upper troposphere. Single measurements of a cloudy air mass provide only a snapshot from which the persistence of ice supersaturation cannot be judged. We introduce here the "cirrus match technique" to obtain information of the evolution of clouds and their saturation ratio. The aim of these coordinated balloon soundings is to analyze the same air mass twice. To this end the standard radiosonde equipment is complemented by a frost point hygrometer "SnowWhite" and a particle backscatter detector "COBALD" (Compact Optical Backscatter Aerosol Detector). Extensive trajectory calculations based on regional weather model COSMO forecasts are performed for flight planning and COSMO analyses are used as basis for comprehensive microphysical box modeling (with grid scale 2 km and 7 km, respectively). Here we present the results of matching a cirrus cloud to within 2-15 km, realized on 8 June 2010 over Payerne, Switzerland, and a location 120 km downstream close to Zurich. A thick cirrus was detected over both measurement sites. We show that in order to quantitatively reproduce the measured particle backscatter ratios, the small-scale temperature fluctuations not resolved by COSMO must be superimposed on the trajectories. The stochastic nature of the fluctuations is captured by ensemble calculations. Possibilities for further improvements in the agreement with the measured backscatter data are investigated by assuming a very slow mass accommodation of water on ice, the presence of heterogeneous ice nuclei, or a wide span of (spheroidal) particle shapes. However, the resulting improvements from microphysical refinements are moderate and comparable in magnitude with changes caused by assuming different regimes of temperature fluctuations for clear sky or cloudy sky conditions, highlighting the importance of a proper treatment of subscale fluctuations. The model yields good agreement with the measured backscatter over both sites and reproduces the measured saturation ratios with respect to ice over Payerne. Conversely, the 30% in-cloud supersaturation measured in a massive, 4-km thick cloud layer over Zurich cannot be reproduced, irrespective of the choice of meteorological or microphysical model parameters. The measured supersaturation can only be explained by either resorting to an unknown physical process, which prevents the ice particles from consuming the excess humidity, or - much more likely - by a measurement error, such as a contamination of the sensor housing of the SnowWhite hygrometer by a precipitation drop from a mixed phase cloud just below the cirrus layer or from some very slight rain in the boundary layer. This uncertainty calls for in-flight checks or calibrations of hygrometers under the extreme humidity conditions in the upper troposphere.

Plasma Processing of Materials

DTIC Science & Technology

1985-02-22

inert gas or in a reduced pressure environment) one can obtain rapidly solidified metastable (i.e., amorphous, microcrystalline, and supersaturated...integrated circuits dnd thus is an area of’vital : importance to our electronics industry. Applications utilizing noble gas plasmas, such as ion-plating...phenomena and probably will not benefit -ubstantially from acditional basic research. Applications utilizing molecular gas plasmas, where reactive species

SURVIVAL OF STEELHEAD TROUT (SALMO GAIRDNERI) EGGS, EMBRYOS, AND FRY IN AIR-SUPERSATURATED WATER

EPA Science Inventory

Egg, embryo, fry, and swim-up stages of steelhead trout (Salmo gairdneri) were exposed to water at total gas saturation levels ranging from 130 to 115%. Eggs, embryos, and newly hatched fry were not affected at 126.7%, but at about day 16 posthatch when the fish began swimming up...

New Demonstrations and New Insights on the Mechanism of the Candy-Cola Soda Geyser

ERIC Educational Resources Information Center

Kuntzleman, Thomas S.; Davenport, Laura S.; Cothran, Victoria I.; Kuntzleman, Jacob T.; Campbell, Dean J.

2017-01-01

When carbonated beverages (which are supersaturated solutions of aqueous carbon dioxide) are confined within a narrow-necked container, events which rapidly release the gas from solution produce a fountain out of the beverage. One well-known variant of this experiment is the addition of Mentos candies to a bottle of Diet Coke. Previous reports…

Effect of Interaction of the Temperature Field and Supersaturation on the Morphology of the Solid-Vapor Interface in Crystal Growth by Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Grasza, K.; Palosz, W.; Curreri, Peter A. (Technical Monitor)

2002-01-01

An in-situ study of the morphology of the solid-vapor interface during iodine crystal growth was done. The conditions for terrace growth, flat faces formation and retraction, competition between sources of steps, formation of protrusions, surface roughening, and defect overgrowth are demonstrated and discussed.

Supersaturated Self-Assembled Charge-Selective Interfacial Layers for Organic Solar Cells

DTIC Science & Technology

2014-11-24

N. E.; Ratcliff, E. L.; Jenkins, J. L.; Armstrong, N. R.; Giordano, A. J.; Hotchkiss, P. J.; Marder, S. R.; Campbell, C. T.; Ginger , D. S. J. Phys...H. X.; Schlenker, C. W.; Giordano, A. J.; Garcia, A.; Smith, O. L.; Olson, D. C.; Marder, S. R.; Ginger , D. S. J. Phys. Chem. Lett. 2013, 4, 4038

Impurity effects in crystal growth from solutions: Steady states, transients and step bunch motion

NASA Astrophysics Data System (ADS)

Ranganathan, Madhav; Weeks, John D.

2014-05-01

We analyze a recently formulated model in which adsorbed impurities impede the motion of steps in crystals grown from solutions, while moving steps can remove or deactivate adjacent impurities. In this model, the chemical potential change of an atom on incorporation/desorption to/from a step is calculated for different step configurations and used in the dynamical simulation of step motion. The crucial difference between solution growth and vapor growth is related to the dependence of the driving force for growth of the main component on the size of the terrace in front of the step. This model has features resembling experiments in solution growth, which yields a dead zone with essentially no growth at low supersaturation and the motion of large coherent step bunches at larger supersaturation. The transient behavior shows a regime wherein steps bunch together and move coherently as the bunch size increases. The behavior at large line tension is reminiscent of the kink-poisoning mechanism of impurities observed in calcite growth. Our model unifies different impurity models and gives a picture of nonequilibrium dynamics that includes both steady states and time dependent behavior and shows similarities with models of disordered systems and the pinning/depinning transition.

Growth Mechanism of Pumpkin-Shaped Vaterite Hierarchical Structures

NASA Astrophysics Data System (ADS)

Ma, Guobin; Xu, Yifei; Wang, Mu

2015-03-01

CaCO3-based biominerals possess sophisticated hierarchical structures and promising mechanical properties. Recent researches imply that vaterite may play an important role in formation of CaCO3-based biominerals. However, as a less common polymorph of CaCO3, the growth mechanism of vaterite remains not very clear. Here we report the growth of a pumpkin-shaped vaterite hierarchical structure with a six-fold symmetrical axis and lamellar microstructure. We demonstrate that the growth is controlled by supersaturation and the intrinsic crystallographic anisotropy of vaterite. For the scenario of high supersaturation, the nucleation rate is higher than the lateral extension rate, favoring the ``double-leaf'' spherulitic growth. Meanwhile, nucleation occurs preferentially in < 11 2 0 > as determined by the crystalline structure of vaterite, modulating the grown products with a hexagonal symmetry. The results are beneficial for an in-depth understanding of the biomineralization of CaCO3. The growth mechanism may also be applicable to interpret the formation of similar hierarchical structures of other materials. The authors gratefully acknowledge the financial support from National Science Foundation of China (Grant Nos. 51172104 and 50972057) and National Key Basic Research Program of China (Grant No. 2010CB630705).

Height Dependency of Aerosol-Cloud Interaction Regimes: Height Dependency of ACI Regime

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

Chen, Jingyi; Liu, Yangang; Zhang, Minghua

This study investigates the height dependency of aerosol-cloud interaction regimes in terms of the joint dependence of the key cloud microphysical properties (e.g. cloud droplet number concentration, cloud droplet relative dispersion, etc.) on aerosol number concentration (N a) and vertical velocity (w). The three distinct regimes with different microphysical features are the aerosol-limited regime, the updraft-limited regime, and the transitional regime. The results reveal two new phenomena in updraft-limited regime: 1) The “condensational broadening” of cloud droplet size distribution in contrast to the well-known “condensational narrowing” in the aerosol-limited regime; 2) Above the level of maximum supersaturation, some cloud dropletsmore » are deactivated into interstitial aerosols in the updraft-limited regime whereas all droplets remain activated in the aerosol-limited regime. Further analysis shows that the particle equilibrium supersaturation plays important role in understanding these unique features. Also examined is the height of warm rain initiation and its dependence on N a and w. The rain initiation height is found to depend primarily on either N a or w or both in different N a-w regimes, thus suggesting a strong regime dependence of the second aerosol indirect effect.« less

Height Dependency of Aerosol-Cloud Interaction Regimes: Height Dependency of ACI Regime

DOE PAGES

Chen, Jingyi; Liu, Yangang; Zhang, Minghua; ...

2018-01-10

This study investigates the height dependency of aerosol-cloud interaction regimes in terms of the joint dependence of the key cloud microphysical properties (e.g. cloud droplet number concentration, cloud droplet relative dispersion, etc.) on aerosol number concentration (N a) and vertical velocity (w). The three distinct regimes with different microphysical features are the aerosol-limited regime, the updraft-limited regime, and the transitional regime. The results reveal two new phenomena in updraft-limited regime: 1) The “condensational broadening” of cloud droplet size distribution in contrast to the well-known “condensational narrowing” in the aerosol-limited regime; 2) Above the level of maximum supersaturation, some cloud dropletsmore » are deactivated into interstitial aerosols in the updraft-limited regime whereas all droplets remain activated in the aerosol-limited regime. Further analysis shows that the particle equilibrium supersaturation plays important role in understanding these unique features. Also examined is the height of warm rain initiation and its dependence on N a and w. The rain initiation height is found to depend primarily on either N a or w or both in different N a-w regimes, thus suggesting a strong regime dependence of the second aerosol indirect effect.« less

Facet-controlled phase separation in supersaturated Au-Ni nanoparticles upon shape equilibration

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

Herz, A., E-mail: andreas.herz@tu-ilmenau.de, E-mail: dong.wang@tu-ilmenau.de; Rossberg, D.; Hentschel, M.

2015-08-17

Solid-state dewetting is used to fabricate supersaturated, submicron-sized Au-Ni solid solution particles out of thin Au/Ni bilayers by means of a rapid thermal annealing technique. Phase separation in such particles is studied with respect to their equilibrium crystal (or Wulff) shape by subsequent annealing at elevated temperature. It is found that (100) faceting planes of the equilibrated particles are enriched with Ni and (111) faces with Au. Both phases are considered by quantum-mechanical calculations in combination with an error-reduction scheme that was developed to compensate for a missing exchange-correlation potential that would reliably describe both Au and Ni. The observedmore » phase configuration is then related to the minimization of strongly anisotropic elastic energies of Au- and Ni-rich phases and results in a rather unique nanoparticle composite state that is characterized by nearly uniform value of elastic response to epitaxial strains all over the faceted surface. The same conclusion is yielded also by evaluating bi-axial elastic moduli when employing interpolated experimental elastic constants. This work demonstrates a useful route for studying features of physical metallurgy at the mesoscale.« less

Supersaturation-Limited and Unlimited Phase Spaces Compete to Produce Maximal Amyloid Fibrillation near the Critical Micelle Concentration of Sodium Dodecyl Sulfate.

PubMed

So, Masatomo; Ishii, Akira; Hata, Yasuko; Yagi, Hisashi; Naiki, Hironobu; Goto, Yuji

2015-09-15

Although various natural and synthetic compounds have been shown to accelerate or inhibit the formation of amyloid fibrils, the mechanisms by which they achieve these adverse effects in a concentration-dependent manner currently remain unclear. Sodium dodecyl sulfate (SDS), one of the compounds that has adverse effects on fibrillation, is the most intensively studied. Here we examined the effects of a series of detergents including SDS on the amyloid fibrillation of β2-microglobulin at pH 7.0, a protein responsible for dialysis-related amyloidosis. In all the detergents examined (i.e., SDS, sodium decyl sulfate, sodium octyl sulfate, and sodium deoxycholate), amyloid fibrillation was accelerated and inhibited at concentrations near the critical micelle concentration (CMC) and higher than CMC, respectively. The most stable conformation changed from monomers with a β-structure to amyloid fibrils with a β-structure and then to α-helical complexes with micelles with an increase in detergent concentrations. These results suggest that competition between supersaturation-limited fibrillation and unlimited mixed micelle formation between proteins and micelles underlies the detergent concentration-dependent complexity of amyloid fibrillation.

Impact of mineral precipitation on flow and mixing in porous media determined by microcomputed tomography and MRI

DOE PAGES

Bray, Joshua M.; Lauchnor, Ellen G.; Redden, George D.; ...

2016-12-21

Here, precipitation reactions in porous media influence transport properties of the environment and can control advective and dispersive transport. In subsurface environments, mixing of saline groundwater or injected solutions for remediation with fresh groundwater can induce supersaturation of constituents and drive precipitation reactions. Magnetic resonance imaging (MRI) and micro-computed tomography (µ-CT) were employed as complimentary techniques to evaluate advection, dispersion and formation of precipitate in a 3D porous media flow cell. Two parallel fluids were flowed concentrically through the porous media under two flow rate conditions with Na 2CO 3 and CaCl 2 in the inner and outer fluids, respectively.more » Upon mixing, calcium carbonate became supersaturated and formed a precipitate at the interface of the two fluids. Spatial maps of changing local velocity fields and dispersion in the flow cell were generated from MRI, while high resolution imaging of the precipitate formed in the porous media was achieved via µ-CT imaging. Formation of a precipitate layer minimized dispersive and advective transport between the two fluids and the shape of the precipitation was influenced by the flow rate condition.« less

Optical properties and CCN activity of aerosols in a high-altitude Himalayan environment: Results from RAWEX-GVAX: CCN activity of aerosols over Himalayas

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

Gogoi, Mukunda M.; Babu, S. Suresh; Jayachandran, V.

2015-03-27

The seasonality and mutual dependence of aerosol optical properties and cloud condensation nuclei (CCN) activity under varying meteorological conditions at the high-altitude Nainital site (~2 km) in the Indo-Gangetic Plains were examined using nearly year-round measurements (June 2011 to March 2012) at the Atmospheric Radiation Measurement (ARM) mobile facility as part of the RAWEX-GVAX experiment of the Indian Space Research Organization and the U.S. Department of Energy. The results from collocated measurements provided enhanced aerosol scattering and absorption coefficients, CCN concentrations and total condensation nuclei (CN) concentrations during the dry autumn and winter months. The CCN concentration (at a supersaturationmore » of 0.46) was higher during periods of high aerosol absorption (single-scattering albedo (SSA) < 0.80) than during periods of high aerosol scattering (SSA > 0.85), indicating that the aerosol composition seasonally changes and influences the CCN activity. The monthly mean CCN activation ratio (at a supersaturation of 0.46) was highest (> 0.7) in late autumn (November); this finding is attributed to the contribution of biomass-burning aerosols to CCN formation at high supersaturation conditions.« less

Idiopathic hypercalciuria and formation of calcium renal stones

PubMed Central

Coe, Fredric L.; Worcester, Elaine M.; Evan, Andrew P.

2018-01-01

The most common presentation of nephrolithiasis is idiopathic calcium stones in patients without systemic disease. Most stones are primarily composed of calcium oxalate and form on a base of interstitial apatite deposits, known as Randall’s plaque. By contrast some stones are composed largely of calcium phosphate, as either hydroxyapatite or brushite (calcium monohydrogen phosphate), and are usually accompanied by deposits of calcium phosphate in the Bellini ducts. These deposits result in local tissue damage and might serve as a site of mineral overgrowth. Stone formation is driven by supersaturation of urine with calcium oxalate and brushite. The level of supersaturation is related to fluid intake as well as to the levels of urinary citrate and calcium. Risk of stone formation is increased when urine citrate excretion is <400 mg per day, and treatment with potassium citrate has been used to prevent stones. Urine calcium levels >200 mg per day also increase stone risk and often result in negative calcium balance. Reduced renal calcium reabsorption has a role in idiopathic hypercalciuria. Low sodium diets and thiazide-type diuretics lower urine calcium levels and potentially reduce the risk of stone recurrence and bone diseas PMID:27452364

Ion Transport and Precipitation Kinetics as Key Aspects of Stress Generation on Pore Walls Induced by Salt Crystallization

NASA Astrophysics Data System (ADS)

Naillon, A.; Joseph, P.; Prat, M.

2018-01-01

The stress generation on pore walls due to the growth of a sodium chloride crystal in a confined aqueous solution is studied from evaporation experiments in microfluidic channels in conjunction with numerical computations of crystal growth. The study indicates that the stress buildup on the pore walls is a highly transient process taking place over a very short period of time (in less than 1 s in our experiments). The analysis makes clear that what matters for the stress generation is not the maximum supersaturation at the onset of the crystal growth but the supersaturation at the interface between the solution and the crystal when the latter is about to be confined between the pore walls. The stress generation is summarized in a simple stress diagram involving the pore aspect ratio and the Damkhöler number characterizing the competition between the precipitation reaction kinetics and the ion transport towards the growing crystal. This opens up the route for a better understanding of the damage of porous materials induced by salt crystallization, an important issue in Earth sciences, reservoir engineering, and civil engineering.

Evaluation of surface tension and Tolman length as a function of droplet radius from experimental nucleation rate and supersaturation ratio: metal vapor homogeneous nucleation.

PubMed

Onischuk, A A; Purtov, P A; Baklanov, A M; Karasev, V V; Vosel, S V

2006-01-07

Zinc and silver vapor homogeneous nucleations are studied experimentally at the temperature from 600 to 725 and 870 K, respectively, in a laminar flow diffusion chamber with Ar as a carrier gas at atmospheric pressure. The size, shape, and concentration of aerosol particles outcoming the diffusion chamber are analyzed by a transmission electron microscope and an automatic diffusion battery. The wall deposit is studied by a scanning electron microscope (SEM). Using SEM data the nucleation rate for both Zn and Ag is estimated as 10(10) cm(-3) s(-1). The dependence of critical supersaturation on temperature for Zn and Ag measured in this paper as well as Li, Na, Cs, Ag, Mg, and Hg measured elsewhere is analyzed. To this aim the classical nucleation theory is extended by the dependence of surface tension on the nucleus radius. The preexponent in the formula for the vapor nucleation rate is derived using the formula for the work of formation of noncritical embryo [obtained by Nishioka and Kusaka [J. Chem. Phys. 96, 5370 (1992)] and later by Debenedetti and Reiss [J. Chem. Phys. 108, 5498 (1998)

Source limitation of carbon gas emissions in high-elevation mountain streams and lakes

USGS Publications Warehouse

Crawford, John T.; Dornblaser, Mark M.; Stanley, Emily H.; Clow, David W.; Striegl, Robert G.

2015-01-01

Inland waters are an important component of the global carbon cycle through transport, storage, and direct emissions of CO2 and CH4 to the atmosphere. Despite predictions of high physical gas exchange rates due to turbulent flows and ubiquitous supersaturation of CO2—and perhaps also CH4—patterns of gas emissions are essentially undocumented for high mountain ecosystems. Much like other headwater networks around the globe, we found that high-elevation streams in Rocky Mountain National Park, USA, were supersaturated with CO2 during the growing season and were net sources to the atmosphere. CO2concentrations in lakes, on the other hand, tended to be less than atmospheric equilibrium during the open water season. CO2 and CH4 emissions from the aquatic conduit were relatively small compared to many parts of the globe. Irrespective of the physical template for high gas exchange (high k), we found evidence of CO2 source limitation to mountain streams during the growing season, which limits overall CO2emissions. Our results suggest a reduced importance of aquatic ecosystems for carbon cycling in high-elevation landscapes having limited soil development and high CO2 consumption via mineral weathering.

Direct Coexistence Methods to Determine the Solubility of Salts in Water from Numerical Simulations. Test Case NaCl.

PubMed

Manzanilla-Granados, Héctor M; Saint-Martín, Humberto; Fuentes-Azcatl, Raúl; Alejandre, José

2015-07-02

The solubility of NaCl, an equilibrium between a saturated solution of ions and a solid with a crystalline structure, was obtained from molecular dynamics simulations using the SPC/E and TIP4P-Ew water models. Four initial setups on supersaturated systems were tested on sodium chloride (NaCl) solutions to determine the equilibrium conditions and computational performance: (1) an ionic solution confined between two crystal plates of periodic NaCl, (2) a solution with all the ions initially distributed randomly, (3) a nanocrystal immersed in pure water, and (4) a nanocrystal immersed in an ionic solution. In some cases, the equilibration of the system can take several microseconds. The results from this work showed that the solubility of NaCl was the same, within simulation error, for the four setups, and in agreement with previously reported values from simulations with the setup (1). The system of a nanocrystal immersed in supersaturated solution was found to equilibrate faster than others. In agreement with laser-Doppler droplet measurements, at equilibrium with the solution the crystals in all the setups had a slight positive charge.

Clinical, demographic, and laboratory characteristics of children with nephrolithiasis.

PubMed

Sas, David J; Becton, Lauren J; Tutman, Jeffrey; Lindsay, Laura A; Wahlquist, Amy H

2016-06-01

While the incidence of pediatric kidney stones appears to be increasing, little is known about the demographic, clinical, laboratory, imaging, and management variables in this patient population. We sought to describe various characteristics of our stone-forming pediatric population. To that end, we retrospectively reviewed the charts of pediatric patients with nephrolithiasis confirmed by imaging. Data were collected on multiple variables from each patient and analyzed for trends. For body mass index (BMI) controls, data from the general pediatrics population similar to our nephrolithiasis population were used. Data on 155 pediatric nephrolithiasis patients were analyzed. Of the 54 calculi available for analysis, 98 % were calcium based. Low urine volume, elevated supersaturation of calcium phosphate, elevated supersaturation of calcium oxalate, and hypercalciuria were the most commonly identified abnormalities on analysis of 24-h urine collections. Our stone-forming population did not have a higher BMI than our general pediatrics population, making it unlikely that obesity is a risk factor for nephrolithiasis in children. More girls presented with their first stone during adolescence, suggesting a role for reproductive hormones contributing to stone risk, while boys tended to present more commonly at a younger age, though this did not reach statistical significance. These intriguing findings warrant further investigation.

Impact of mineral precipitation on flow and mixing in porous media determined by microcomputed tomography and MRI

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

Bray, Joshua M.; Lauchnor, Ellen G.; Redden, George D.

Here, precipitation reactions in porous media influence transport properties of the environment and can control advective and dispersive transport. In subsurface environments, mixing of saline groundwater or injected solutions for remediation with fresh groundwater can induce supersaturation of constituents and drive precipitation reactions. Magnetic resonance imaging (MRI) and micro-computed tomography (µ-CT) were employed as complimentary techniques to evaluate advection, dispersion and formation of precipitate in a 3D porous media flow cell. Two parallel fluids were flowed concentrically through the porous media under two flow rate conditions with Na 2CO 3 and CaCl 2 in the inner and outer fluids, respectively.more » Upon mixing, calcium carbonate became supersaturated and formed a precipitate at the interface of the two fluids. Spatial maps of changing local velocity fields and dispersion in the flow cell were generated from MRI, while high resolution imaging of the precipitate formed in the porous media was achieved via µ-CT imaging. Formation of a precipitate layer minimized dispersive and advective transport between the two fluids and the shape of the precipitation was influenced by the flow rate condition.« less

Development, current applications and future roles of biorelevant two-stage in vitro testing in drug development.

PubMed

Fiolka, Tom; Dressman, Jennifer

2018-03-01

Various types of two stage in vitro testing have been used in a number of experimental settings. In addition to its application in quality control and for regulatory purposes, two-stage in vitro testing has also been shown to be a valuable technique to evaluate the supersaturation and precipitation behavior of poorly soluble drugs during drug development. The so-called 'transfer model', which is an example of two-stage testing, has provided valuable information about the in vivo performance of poorly soluble, weakly basic drugs by simulating the gastrointestinal drug transit from the stomach into the small intestine with a peristaltic pump. The evolution of the transfer model has resulted in various modifications of the experimental model set-up. Concomitantly, various research groups have developed simplified approaches to two-stage testing to investigate the supersaturation and precipitation behavior of weakly basic drugs without the necessity of using a transfer pump. Given the diversity among the various two-stage test methods available today, a more harmonized approach needs to be taken to optimize the use of two stage testing at different stages of drug development. © 2018 Royal Pharmaceutical Society.

Dissolved atmospheric gas in xylem sap measured with membrane inlet mass spectrometry.

PubMed

Schenk, H Jochen; Espino, Susana; Visser, Ate; Esser, Bradley K

2016-04-01

A new method is described for measuring dissolved gas concentrations in small volumes of xylem sap using membrane inlet mass spectrometry. The technique can be used to determine concentrations of atmospheric gases, such as argon, as reported here, or for any dissolved gases and their isotopes for a variety of applications, such as rapid detection of trace gases from groundwater only hours after they were taken up by trees and rooting depth estimation. Atmospheric gas content in xylem sap directly affects the conditions and mechanisms that allow for gas removal from xylem embolisms, because gas can dissolve into saturated or supersaturated sap only under gas pressure that is above atmospheric pressure. The method was tested for red trumpet vine, Distictis buccinatoria (Bignoniaceae), by measuring atmospheric gas concentrations in sap collected at times of minimum and maximum daily temperature and during temperature increase and decline. Mean argon concentration in xylem sap did not differ significantly from saturation levels for the temperature and pressure conditions at any time of collection, but more than 40% of all samples were supersaturated, especially during the warm parts of day. There was no significant diurnal pattern, due to high variability between samples. © 2015 John Wiley & Sons Ltd.

Trends in the precipitation and crystallization behavior of supersaturated aqueous solutions of poorly water-soluble drugs assessed using synchrotron radiation.

PubMed

Raina, Shweta A; Van Eerdenbrugh, Bernard; Alonzo, David E; Mo, Huaping; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

2015-06-01

Amorphous materials are high-energy solids that can potentially enhance the bioavailability of poorly soluble compounds. A major impediment to their widespread use as a formulation platform is the tendency of amorphous materials to crystallize. The aim of this study was to evaluate the relative crystallization tendency of six structural analogues belonging to the dihydropyridine class, in an aqueous environment in the absence and presence of polymers, using wide-angle X-ray scattering synchrotron radiation and polarized light microscopy. The crystallization behavior of precipitates generated from supersaturated solutions of the active pharmaceutical ingredients was found to be highly variable ranging from immediate to several hours in the absence of polymers. Polymers with intermediate hydrophilicity/hydrophobicity were found to substantially delay crystallization, whereas strongly hydrophilic or hydrophobic polymers were largely ineffective. Nuclear magnetic resonance spectroscopy experiments supported the supposition that polymers need to have affinity for both the drug-rich precipitate and the aqueous phase in order to be effective crystallization inhibitors. This study highlights the variability in the crystallization tendency of different compounds and provides insight into the mechanism of inhibition by polymeric additives. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Introduction to protein crystallization

PubMed Central

McPherson, Alexander; Gavira, Jose A.

2014-01-01

Protein crystallization was discovered by chance about 150 years ago and was developed in the late 19th century as a powerful purification tool and as a demonstration of chemical purity. The crystallization of proteins, nucleic acids and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by the manipulation of various parameters that include temperature, ionic strength and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch and liquid–liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years owing to the advent of practical, easy-to-use screening kits and the application of laboratory robotics. A brief review will be given here of the most popular methods, some guiding principles and an overview of current technologies. PMID:24419610

Introduction to protein crystallization.

PubMed

McPherson, Alexander; Gavira, Jose A

2014-01-01

Protein crystallization was discovered by chance about 150 years ago and was developed in the late 19th century as a powerful purification tool and as a demonstration of chemical purity. The crystallization of proteins, nucleic acids and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by the manipulation of various parameters that include temperature, ionic strength and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch and liquid-liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years owing to the advent of practical, easy-to-use screening kits and the application of laboratory robotics. A brief review will be given here of the most popular methods, some guiding principles and an overview of current technologies.

Supersaturation and crystallization: non-equilibrium dynamics of amorphous solid dispersions for oral drug delivery.

PubMed

Kawakami, Kohsaku

2017-06-01

Amorphous solid dispersions (ASDs) are one of the key formulation technologies that aid the development of poorly soluble candidates. However, their dynamic behaviors, including dissolution and crystallization processes, are still full of mystery. Further understanding of these processes should enhance their wider use. Areas covered: The first part of this review describes the current understanding of the dissolution of ASDs, where phase separation behavior is frequently involved and attempts to develop appropriate dissolution tests to achieve an in vitro-in vivo correlation are examined. The second part of this review discusses crystallization of the drug molecule with the eventual aim of establishing an accelerated testing protocol for predicting its physical stability. Expert opinion: The phase separation behavior from the supersaturated state during the dissolution test must be understood, and its relevance to the oral absorption behavior needs to be clarified. Research efforts should focus on the differences between the phase behavior in in vitro and in vivo situations. Initiation time of the crystallization was shown to be predicted only from storage and glass transition temperatures. This finding should encourage the establishment of testing protocol of the physical stability of ASDs.

The Effect of Temperature and Solution pH on the Nucleation of Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Judge, Russell A.; Jacobs, Randolph S.; Frazier, Tyralynn; Snell, Edward H.; Pusey, Marc L.

1999-01-01

Part of the challenge of macromolecular crystal growth for structure determination is obtaining crystals with a volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature, and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over 1 week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions. Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable, however, was pH; crystal numbers changed by two orders of magnitude over the pH range 4.0-5.2. Crystal size also varied with solution conditions, with the largest crystals obtained at pH 5.2. Having optimized the crystallization conditions, we prepared a batch of crystals under the same initial conditions, and 50 of these crystals were analyzed by x-ray diffraction techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.

The system water-sodium oxide-silicon dioxide at 200, 250, and 300°

USGS Publications Warehouse

Rowe, Jack J.; Fournier, Robert O.; Morey, G.W.

1967-01-01

Studies were made of the H2O-Na2O-SiO2 system at its vapor pressure at 200, 250, and 300??. Three different sodium trisilicate hydrates were encountered in the investigation. At 300??, Na2Si3O7??5H2O is found: at 250??, Na2Si3O7??6H2O; and at 200??, Na2Si3O7??11H2O. The liquid immiscibility previously reported to exist in the system was found to be a quenching phenomenon caused by the decomposition of the hydrates to unstable, supersaturated, viscous liquids. Under conditions where equilibrium is maintained, as temperature is lowered, the hydrates decompose to quartz, sodium disilicate, and liquid. The retrograde solubility of sodium disilicate and its tendency to form supersaturated solutions during heating from 25 to 250?? account for higher solubilities reported by others than were found in this study. The solubility of sodium disilicate in water is 26% at 200??, 9% at 250??, and 5% at 300??. Sodium metasilicate solubility is 38% at 200?? and 34% at 250??; this compound is incongruently soluble at 300??.

Characterization and parameterization of aerosol cloud condensation nuclei activation under different pollution conditions

PubMed Central

Che, H. C.; Zhang, X. Y.; Wang, Y. Q.; Zhang, L.; Shen, X. J.; Zhang, Y. M.; Ma, Q. L.; Sun, J. Y.; Zhang, Y. W.; Wang, T. T.

2016-01-01

To better understand the cloud condensation nuclei (CCN) activation capacity of aerosol particles in different pollution conditions, a long-term field experiment was carried out at a regional GAW (Global Atmosphere Watch) station in the Yangtze River Delta area of China. The homogeneity of aerosol particles was the highest in clean weather, with the highest active fraction of all the weather types. For pollution with the same visibility, the residual aerosol particles in higher relative humidity weather conditions were more externally mixed and heterogeneous, with a lower hygroscopic capacity. The hygroscopic capacity (κ) of organic aerosols can be classified into 0.1 and 0.2 in different weather types. The particles at ~150 nm were easily activated in haze weather conditions. For CCN predictions, the bulk chemical composition method was closer to observations at low supersaturations (≤0.1%), whereas when the supersaturation was ≥0.2%, the size-resolved chemical composition method was more accurate. As for the mixing state of the aerosol particles, in haze, heavy haze, and severe haze weather conditions CCN predictions based on the internal mixing assumption were robust, whereas for other weather conditions, predictions based on the external mixing assumption were more accurate. PMID:27075947

Cluster Nucleation and Growth from a Highly Supersaturated Adatom Phase: Silver on Magnetite

PubMed Central

2014-01-01

The atomic-scale mechanisms underlying the growth of Ag on the (√2×√2)R45°-Fe3O4(001) surface were studied using scanning tunneling microscopy and density functional theory based calculations. For coverages up to 0.5 ML, Ag adatoms populate the surface exclusively; agglomeration into nanoparticles occurs only with the lifting of the reconstruction at 720 K. Above 0.5 ML, Ag clusters nucleate spontaneously and grow at the expense of the surrounding material with mild annealing. This unusual behavior results from a kinetic barrier associated with the (√2×√2)R45° reconstruction, which prevents adatoms from transitioning to the thermodynamically favorable 3D phase. The barrier is identified as the large separation between stable adsorption sites, which prevents homogeneous cluster nucleation and the instability of the Ag dimer against decay to two adatoms. Since the system is dominated by kinetics as long as the (√2×√2)R45° reconstruction exists, the growth is not well described by the traditional growth modes. It can be understood, however, as the result of supersaturation within an adsorption template system. PMID:24945923

CCN activity of thermodenuded aerosol particles downwind of the Sacramento area urban plume

NASA Astrophysics Data System (ADS)

Hiranuma, N.; Cziczo, D. J.; Nelson, D.; Zhang, Q.; Setyan, A.; Song, C.; Shrivastava, M.; Shilling, J. E.

2010-12-01

This study focuses on the characterization of cloud condensation nuclei (CCN) properties of aerosol particles measured during the Carbonaceous Aerosols and Radiative Effects Study (CARES) near Sacramento, CA in June 2010. Supersaturation-dependant CCN activity (0.07 - 0.5% supersaturation) was measured with DMT CCN counters at two locations; one near the city center (T0) and the other in Cool, CA, a small town located ~40 kilometers downwind of the urban plume in the Sierra Nevada foothills (T1). The T1 CCN counter was operated behind a thermodenuder to study volatility-dependant CCN activity of the urban aerosol plume as it was transported into the biogenically influenced foothills. Preliminary analysis indicated that activated fraction was inversely proportional to the thermodenuder temperature, suggesting that the more-volatile fraction of the aerosol might have played an important role in the CCN activity of the aerosol. The relationship between the chemical composition and CCN activity of the aerosol will be discussed. The physical and chemical transformations of particles aged in the foothills as well as the diurnal profiles of CCN both at T0 and T1 will also be discussed for the transport event of 15 June 2010.

Evaluating host-associated sources of marine methane supersaturation

NASA Astrophysics Data System (ADS)

Blanton, J. M.; Pieper, L. M.; Allen, E. E.

2013-12-01

Methane can be found in surface ocean waters at levels from 5% to 75% greater than expected from exchange with the atmosphere. Because oceanic emissions account for up to 4% of the planet's annual methane inventory, understanding marine sources and sinks is relevant to global greenhouse gas budgets. These methane levels are presumed to result from the activity of microorganisms in the water column, yet this presents a paradox: how can biotic methanogensis, primarily understood as an anaerobic process, take place in oxic waters? One working theory is that methanogens find safe harbor in the gastrointestinal tracts of marine animals. We investigate the possibility that microbial communities within fish, and the fecal material they produce, contribute to in-situ methane production in the open ocean. Using genetic markers, we test the GI tracts of benthic and pelagic marine teleosts for the presence of methanogenic organisms and for components of the methanogenesis pathway. Our results indicate that methanogens may be present in fish, but in low numbers. This work sets the scene for measurement of methane production rates from these gut-associated communities in order to elucidate their contribution to oceanic methane supersaturation.

Renal stone risk in a simulated microgravity environment: impact of treadmill exercise with lower body negative pressure.

PubMed

Monga, Manoj; Macias, Brandon; Groppo, Eli; Kostelec, Monica; Hargens, Alan

2006-07-01

Prolonged exposure to microgravity during spaceflight causes metabolic changes that increase the risk of renal stone formation. Studies during the Gemini, Apollo, Skylab and Shuttle missions demonstrated alterations in renal function, fluid homeostasis and bone resorption that result in increased urinary supersaturation of calcium oxalate, brushite, sodium urate and uric acid. Developing countermeasures to increased urinary supersaturation is an important priority as the duration of space missions increases. A total of 11 sets of identical twins remained on 6-degree head down, tilt bed rest for 30 days to simulate prolonged microgravity. One twin per pair was randomly selected to exercise while supine in a lower body negative pressure chamber 6 days weekly for 40 minutes, followed by 5 minutes of resting lower body negative pressure at 50 mm Hg. The other twin served as a nonexercise control. Pressure in the exercise lower body negative pressure chamber (52 to 63 mm Hg) was adjusted to produce footward forces equivalent to those for upright running on Earth at 1.0 to 1.2 x body weight. Pre-bed rest urinary stone risk profiles were done elsewhere after 5 days of a standardized diet, consisting of 170 mEq sodium, 1,000 mg calcium, 0.8 gm/kg animal protein and 2,500 kcal, and then throughout the bed rest and recovery phases of the protocol. A significant increase in urinary calcium after just 1 week of bed rest was noted in the nonexercise control group (p = 0.001). However, no such increase was noted in the exercise group. Brushite supersaturation increased significantly from bed rest in each group, although the increase was significantly higher in the nonexercise control group than in the exercise group (p = 0.006). Calcium oxalate supersaturation increased during bed rest in the exercise group (p = 0.004). It trended toward a higher level in the nonexercise control group, although this did not achieve significance (p = 0.055) Mean urine volume +/- SD was significantly higher in the nonexercise control group than in the exercise group at bed rest week 2 and at week 3 (2.01 +/- 0.21 vs 1.63 0.18 l and 2.03 +/- 0.22 vs 1.81 +/- 0.20, respectively). Urinary pH was significantly higher in the nonexercise control group than in the exercise group at week 1 and week 3 (6.62 +/- 0.7 vs 6.49 +/- 0.5 and 6.58 +/- 0.6 vs 6.49 +/- 0.8, respectively, p = 0.01). Bed rest significantly alters the urinary environment to favor calculous formation. Lower body negative pressure chamber treadmill exercise offers some protection against increases in stone risk during simulated microgravity, particularly with regard to the risks of hypercalciuria and brushite stone formation. The use of lower body negative pressure to augment aerobic exercise in space may decrease the risk of stone formation in astronauts. Adjunct measures, including aggressive hydration and alkalinization therapy, should be considered.

Balloon-borne match measurements of midlatitude cirrus clouds

NASA Astrophysics Data System (ADS)

Cirisan, A.; Luo, B. P.; Engel, I.; Wienhold, F. G.; Sprenger, M.; Krieger, U. K.; Weers, U.; Romanens, G.; Levrat, G.; Jeannet, P.; Ruffieux, D.; Philipona, R.; Calpini, B.; Spichtinger, P.; Peter, T.

2014-07-01

Observations of high supersaturations with respect to ice inside cirrus clouds with high ice water content (> 0.01 g kg-1) and high crystal number densities (> 1 cm-3) are challenging our understanding of cloud microphysics and of climate feedback processes in the upper troposphere. However, single measurements of a cloudy air mass provide only a snapshot from which the persistence of ice supersaturation cannot be judged. We introduce here the "cirrus match technique" to obtain information about the evolution of clouds and their saturation ratio. The aim of these coordinated balloon soundings is to analyze the same air mass twice. To this end the standard radiosonde equipment is complemented by a frost point hygrometer, "SnowWhite", and a particle backscatter detector, "COBALD" (Compact Optical Backscatter AerosoL Detector). Extensive trajectory calculations based on regional weather model COSMO (Consortium for Small-Scale Modeling) forecasts are performed for flight planning, and COSMO analyses are used as a basis for comprehensive microphysical box modeling (with grid scale of 2 and 7 km, respectively). Here we present the results of matching a cirrus cloud to within 2-15 km, realized on 8 June 2010 over Payerne, Switzerland, and a location 120 km downstream close to Zurich. A thick cirrus cloud was detected over both measurement sites. We show that in order to quantitatively reproduce the measured particle backscatter ratios, the small-scale temperature fluctuations not resolved by COSMO must be superimposed on the trajectories. The stochastic nature of the fluctuations is captured by ensemble calculations. Possibilities for further improvements in the agreement with the measured backscatter data are investigated by assuming a very slow mass accommodation of water on ice, the presence of heterogeneous ice nuclei, or a wide span of (spheroidal) particle shapes. However, the resulting improvements from these microphysical refinements are moderate and comparable in magnitude with changes caused by assuming different regimes of temperature fluctuations for clear-sky or cloudy-sky conditions, highlighting the importance of proper treatment of subscale fluctuations. The model yields good agreement with the measured backscatter over both sites and reproduces the measured saturation ratios with respect to ice over Payerne. Conversely, the 30% in-cloud supersaturation measured in a massive 4 km thick cloud layer over Zurich cannot be reproduced, irrespective of the choice of meteorological or microphysical model parameters. The measured supersaturation can only be explained by either resorting to an unknown physical process, which prevents the ice particles from consuming the excess humidity, or - much more likely - by a measurement error, such as a contamination of the sensor housing of the SnowWhite hygrometer by a precipitation drop from a mixed-phase cloud just below the cirrus layer or from some very slight rain in the boundary layer. This uncertainty calls for in-flight checks or calibrations of hygrometers under the special humidity conditions in the upper troposphere.

In-situ measurements of ice nucleating particles with FINCH (Fast Ice Nucleus Chamber)

NASA Astrophysics Data System (ADS)

Kohl, Rebecca; Frank, Fabian; Curtius, Joachim; Rose, Diana

2017-04-01

Ice nucleating particles (INPs), which are a small fraction of the total aerosol population, are capable of triggering ice formation under atmospheric conditions. Since INPs play an important role for the radiative properties of clouds as well as for the formation of precipitation it is important to get quantitative information on the ice activity of various atmospheric aerosol species. With the Fast Ice Nucleus Chamber (FINCH; Bundke et al., 2008) the number concentration of INP is determined at different freezing temperatures and supersaturations. In contrast to other commonly used INP counters, i.e., continuous flow diffusion chambers (CFDCs, DeMott et al., 2011), in FINCH the supersaturation is reached by mixing the sample flow of ambient aerosol with a warm moist as well as a cold dry airflow. By changing the flow rates and temperatures of the individual airflows the freezing temperature (down to -50°C) and supersaturation (up to above water saturation) can be varied relatively quickly. Particles that are ice active at the prescribed freezing temperature and supersaturation grow to crystals and are counted by a home-built optical particle counter (OPC) mounted below the chamber (Bundke et al., 2010). FINCH was operated during the four-week INUIT-BACCHUS-ACTRIS field campaign in Cyprus in April 2016. The measuring site was the location of the Cyprus Atmospheric Observatory (CAO) at Agia Marina Xyliatou, which is typically influenced by dust from the Sahara and the Middle East, an aerosol that is known to have relatively good ice nucleating ability. First results from this campaign will be presented. Acknowledgements: The authors thank the entire INUIT-BACCHUS-ACTRIS campaign team for their cooperation and support. The INUIT-2 project is financed by the German Research Foundation DFG (FOR 1525). The INUIT-Cyprus campaign is a cooperation with the EU-funded project BACCHUS and is also funded by ACTRIS-TNA. References: Bundke, U., Nillius, B., Jaenicke, R., Wetter, T., Klein, H., and Bingemer, H.: The fast Ice Nucleus chamber FINCH, Atmos. Res., 90, 180-186, 10.1016/j.atmosres.2008.02.008, 2008. Bundke, U., Reimann, B., Nillius, B., Jaenicke, R., and Bingemer, H.: Development of a Bioaerosol single particle detector (BIO IN) for the Fast Ice Nucleus CHamber FINCH, Atmos. Meas. Tech., 3, 263-271, doi:10.5194/amt-3-263-2010, 2010. DeMott, P. J., Moehler, O., Stetzer, O., Vali, G., Levin, Z., Petters, M. D., Murakami, M., Leisner, T., Bundke, U., Klein, H., Kanji, Z. A., Cotton, R., Jones, H., Benz, S., Brinkmann, M., Rzesanke, D., Saathoff, H., Nicolet, M., Saito, A., Nillius, B., Bingemer, H., Abbatt, J., Ardon, K., Ganor, E., Georgakopoulos, D. G., and Saunders, C.: Resurgence in ice nuclei measurement research, Bulletin of the American Meteorological Society, 92, 1623-1635, 10.1175/bams-d-10-3119.1, 2011.

Cloud condensation nuclei and ice nucleation activity of hydrophobic and hydrophilic soot particles.

PubMed

Koehler, Kirsten A; DeMott, Paul J; Kreidenweis, Sonia M; Popovicheva, Olga B; Petters, Markus D; Carrico, Christian M; Kireeva, Elena D; Khokhlova, Tatiana D; Shonija, Natalia K

2009-09-28

Cloud condensation nuclei (CCN) activity and ice nucleation behavior (for temperatures

Chemical properties of ground water and their corrosion and encrustation effects on wells

USGS Publications Warehouse

Barnes, Ivan; Clarke, Frank Eldridge

1969-01-01

Well waters in Egypt, Nigeria, and West Pakistan were studied for their chemical properties and corrosive or encrusting behavior. From the chemical composition of the waters, reaction states with reference to equilibrium were tested for 29 possible coexisting oxides, carbonates, sulfides, and elements. Of the 29 solids considered, only calcite, CaCO3, and ferric hydroxide, Fe(OH)3, showed any correlation with the corrosiveness of the waters to mild steel (iron metal). All 39 of the waters tested were out of equilibrium with iron metal, but those waters in equilibrium or supersaturated with both calcite and ferric hydroxide were the least corrosive. Supersaturation with other solid phases apparently was unrelated to corrosion. A number of solids may form surface deposits in wells and lead to decreased yields by fouling well intakes (screens and gravel packs) or increasing friction losses in casings. Calcite, CaCO3; ferric hydroxide, Fe(OH)3; magnetite, Fe3O4; siderite, FeCO3; hausmannite, Mn304 (tetragonal); manganese spinel, Mn3O4 (isometric); three iron sulfides mackinawite, FeS (tetragonal); greigite, Fe3S4 (isometric); and smythite, Fe3S4 (rhombohedral)-copper hydroxide, Co(OH)2; and manganese hydroxide, Mn(OH)2, were all at least tentatively identified in the deposits sampled. Of geochemical interest is the demonstration that simple stable equilibrium models fail in nearly every case to predict compositions of water yielded by the wells studied. Only one stable phase (calcite) was found to exhibit behavior approximately predictable from stable equilibrium considerations. No other stable phase was found to behave as would be predicted from equilibrium considerations. All the solids found to precipitate (except calcite) are metastable in that they are not the least soluble phases possible in the systems studied. In terms of metastable equilibrium, siderite and ferric hydroxide behave approximately as would be predicted from equilibrium considerations, but both are metastable and the presence of neither would be anticipated if only the most stable phases were considered. The behaviors of none of the other solids would be predictable from either stable or metastable equilibrium considerations. An unanswered problem raised by the study reported here is how, or by what paths, truly stable phases form if first precipitates are generally metastable.The utility of the findings in well design and operation is in no way impaired by the general lack of equilibrium. Conditions leading to either corrosion (which is related to lack of supersaturation with protective phases), or encrustation (supersaturation with phases that were found to precipitate), or both, apparently can be identified. The application of the methods described can be of great importance in developing unexploited ground-water resources in that certain practical problems can be identified before extensive well construction and unnecessary well failure.

Improvements in Ionized Cluster-Beam Deposition

NASA Technical Reports Server (NTRS)

Fitzgerald, D. J.; Compton, L. E.; Pawlik, E. V.

1986-01-01

Lower temperatures result in higher purity and fewer equipment problems. In cluster-beam deposition, clusters of atoms formed by adiabatic expansion nozzle and with proper nozzle design, expanding vapor cools sufficiently to become supersaturated and form clusters of material deposited. Clusters are ionized and accelerated in electric field and then impacted on substrate where films form. Improved cluster-beam technique useful for deposition of refractory metals.

Growth and dissolution kinetics of tetragonal lysozyme

NASA Technical Reports Server (NTRS)

Monaco, L. A.; Rosenberger, F.

1993-01-01

The growth and dissolution kinetics of lysozyme in a 25 ml solution bridge inside a closed growth cell was investigated. It was found that, under all growth conditions, the growth habit forming (110) and (101) faces grew through layer spreading with different growth rate dependence on supersaturation/temperature. On the other hand, (100) faces which formed only at low temperatures underwent a thermal roughening transition around 12 C.

Method for fabricating apatite crystals and ceramics

DOEpatents

Soules, Thomas F.; Schaffers, Kathleen I.; Tassano, Jr., John B.; Hollingsworth, Joel P.

2013-09-10

The present invention provides a method of crystallizing Yb:C-FAP [Yb.sup.3+:Ca.sub.5(PO.sub.4).sub.3F], by dissolving the Yb:C-FAP in an acidic solution, following by neutralizing the solution. The present invention also provides a method of forming crystalline Yb:C-FAP by dissolving the component ingredients in an acidic solution, followed by forming a supersaturated solution.

Struvite scale formation and control.

PubMed

Parsons, S A; Doyle, J D

2004-01-01

Struvite scale formation is a major operational issue at both conventional and biological nutrient removal wastewater treatment plants. Factors affecting the formation of struvite scales were investigated including supersaturation, pH and pipe material and roughness. A range of control methods have been investigated including low fouling materials, pH control, inhibitor and chemical dosing. Control methods exist to reduce scale formation although each has its advantages and disadvantages.

Supersaturation of Dissolved Hydrogen and Methane in Rumen of Tibetan Sheep

PubMed Central

Wang, Min; Ungerfeld, Emilio M.; Wang, Rong; Zhou, Chuan She; Basang, Zhu Zha; Ao, Si Man; Tan, Zhi Liang

2016-01-01

Hydrogen (H2) is an essential substrate for methanogens to produce methane (CH4), and also influences pathways of volatile fatty acids (VFA) production in the rumen. Dissolved H2 (H2 (aq)) is the form of H2 available to microbes, and dissolved CH4 (CH4 (aq)) is important for indicating methanogens activity. Rumen H2 (aq) concentration has been estimated by assuming equilibrium with headspace gaseous H2 (H2 (g)) concentration using Henry's law, and has also been directly measured in the liquid phase in some in vitro and in vivo experiments. In this in vivo study, H2 (aq) and CH4 (aq) concentration measured directly in rumen fluid and their corresponding concentrations estimated from their gaseous phase concentrations, were compared to investigate the existence of equilibrium between the gas and liquid phases. Twenty-four Tibetan sheep were randomly assigned to two mixed diets containing the same concentrate mixed with oat grass (OG diet) or barley straw (BS diet). Rumen gaseous phase and contents were sampled using rumenocentesis and oral stomach tubing, respectively. Rumen H2 (aq) and CH4 (aq) concentration and VFA profile differed between sheep fed OG and BS diets. Measured H2 (aq) and CH4 (aq) concentration were greater than H2 (aq) and CH4 (aq) concentrations estimated using gas concentrations, indicating lack of equilibrium between gas and liquid phase and supersaturation of H2 and CH4 in rumen fluid. As a consequence, Gibbs energy changes (ΔG) estimated for various metabolic pathways were different when calculated using dissolved gases concentrations directly measured and when using dissolved gases concentrations assuming equilibrium with the gaseous phase. Dissolved CH4, but not CH4 (g), was positively correlated with H2 (aq). Both H2 (aq) and H2 (g) concentrations were positively correlated with the molar percentage of butyrate and negatively correlated with the molar percentage of acetate. In summary, rumen fluid was supersaturated with both H2 and CH4, and H2 (aq) was closely associated with the VFA profile and CH4 (aq) concentration. The assumption of equilibrium between dissolved gases and gaseous phase affected ΔG estimation. PMID:27379028

Development of a continuous flow thermal gradient diffusion chamber for ice nucleation studies

NASA Astrophysics Data System (ADS)

Rogers, David C.

A supercooled continuous flow, thermal gradient diffusion chamber has been developed to study the ice nucleating properties of natural or artificial aerosols. The chamber has concentric cylinder geometry with the cylinder axis alignment and airflow vertically downward. Sample airflow is 1 l min -1 and occupies the central 10% of the annular lamina; it is separated from the ice-covered walls by filtered sheath air. The wall temperatures are independently controlled over the range from about -4°C to -25°C, so that the vapor concentration at the location of the sample lamina can be set to a well defined value between ice saturation and a few percent water supersaturation. There is a range of temperature and supersaturation values across the sample region; for lamina center conditions of -15°C and +1% with respect to water, the range is -14.6 to -15.4°C and +0.53 to +1.31%. Errors in temperature control produce variations estimated as ±0.1°C and ±0.23%. Typical sample residence time is about 10 s. Ice crystals which form on active nuclei are detected optically at the outlet end of the chamber. To enhance the size difference between ice crystals and cloud droplets, the downstream 25% of the warm ice wall is covered with a thermally insulating vapor barrier which reduces the vapor concentration to ice saturation at the cold wall temperature, so cloud droplets evaporate. A mathematical model was developed to describe the temperature and vapor fields and to calculate the growth, evaporation, and sedimentation of water and ice particles. At 1% water supersaturation, the model predicts that ice particles will grow to about 5 μm diameter, and cloud droplets will achieve about 1 μm before they reach the evaporation section of the chamber. A different model was developed to describe the steady state airflow profile and location of the sample lamina. Experimental tests of the chamber were performed to characterize the airflow, to assess the ability of the technique to detect silver iodide ice nucleating aerosols and to distinguish ice crystals from water droplets.

Grain formation around carbon stars. 1: Stationary outflow models

NASA Technical Reports Server (NTRS)

Egan, Michael P.; Leung, Chun Ming

1995-01-01

Asymptotic giant branch (AGB) stars are known to be sites of dust formation and undergo significant mass loss. The outflow is believed to be driven by radiation pressure on grains and momentum coupling between the grains and gas. While the physics of shell dynamics and grain formation are closely coupled, most previous models of circumstellar shells have treated the problem separately. Studies of shell dynamics typically assume the existence of grains needed to drive the outflow, while most grain formation models assume a constant veolcity wind in which grains form. Furthermore, models of grain formation have relied primarily on classical nucleation theory instead of using a more realistic approach based on chemical kinetics. To model grain formation in carbon-rich AGB stars, we have coupled the kinetic equations governing small cluster growth to moment equations which determine the growth of large particles. Phenomenological models assuming stationary outflow are presented to demonstrate the differences between the classical nucleation approach and the kinetic equation method. It is found that classical nucleation theory predicts nucleation at a lower supersaturation ratio than is predicted by the kinetic equations, resulting in significant differences in grain properties. Coagulation of clusters larger than monomers is unimportant for grain formation in high mass-loss models but becomes more important to grain growth in low mass-loss situations. The properties of the dust grains are altered considerably if differential drift velocities are ignored in modeling grain formation. The effect of stellar temperature, stellar luminosity, and different outflow velocities are investigated. The models indicate that changing the stellar temperature while keeping the stellar luminosity constant has little effect on the physical parameters of the dust shell formed. Increasing the stellar luminosity while keeping the stellar temperature constant results in large differences in grain properties. For small outflow velocities, grains form at lower supersaturation ratios and close to the stellar photosphere, resulting in larger but fewer grains. The reverse is true when grains form under high outflow velocities, i.e., they form at higher supersaturation ratios, farther from the star, and are much smaller but at larger quantities.

Biomass Burning Organic Aerosol as a Modulator of Droplet Number in the Southern Atlantic

NASA Astrophysics Data System (ADS)

Kacarab, M.; Howell, S. G.; Small Griswold, J. D.; Thornhill, K. L., II; Wood, R.; Redemann, J.; Nenes, A.

2017-12-01

Aerosols play a significant yet highly variable role in local and global air quality and climate. They act as cloud condensation nuclei (CCN) and both scatter and absorb radiation, lending a large source of uncertainty to climate predictions. Biomass burning organic aerosol (BBOA) can drastically elevate CCN concentrations, but the response in cloud droplet number may be suppressed or even reversed due to low supersaturations that develop from strong competition for water vapor. Constraining droplet response to BBOA is a key factor to understanding aerosol-cloud interactions. The southeastern Atlantic (SEA) cloud deck off the west coast of central Africa is a prime opportunity to study these cloud-BBOA interactions for marine stratocumulus as during winter in the southern hemisphere the SEA cloud deck is overlain by a large, optically thick BBOA plume. The NASA ObseRvations of Aerosols above Clouds and their intEractionS (ORACLES) study focuses on increasing the understanding of how these BBOA affect the SEA cloud deck. Measurements of CCN concentration, aerosol size distribution and composition, updraft velocities, and cloud droplet number in and around the SEA cloud deck and associated BBOA plume were taken aboard the NASA P-3 aircraft during the first two years of the ORACLES campaign in September 2016 and August 2017. Here we evaluate the predicted and observed droplet number sensitivity to the aerosol fluctuations and quantify, using the data, the drivers of droplet number variability (vertical velocity or aerosol properties) as a function of biomass burning plume characteristics. Over the course of the campaign, different levels of BBOA influence in the marine boundary layer (MBL) were observed, allowing for comparison of cloud droplet number, hygroscopicity parameter (κ), and maximum in-cloud supersaturation over a range of "clean" and "dirty" conditions. Droplet number sensitivity to aerosol concentration, κ, and vertical updraft velocities are also evaluated. Generally, an increase in BBOA led to increased droplet number along with decreased κ and maximum in-cloud supersaturation (leading to an increase in competition for water vapor). This work seeks to contribute to an increased understanding of how CCN and aerosol properties affect the radiative and hydrological properties and impact of the cloud.

Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy.

PubMed

Choi, Man Yee; Chan, Chak K

2005-02-17

The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets.

Explicit Cloud Nucleation from Arbitrary Mixtures of Aerosol Types and Sizes Using an Ultra-Efficient In-Line Aerosol Bin Model in High-Resolution Simulations of Hurricanes

NASA Astrophysics Data System (ADS)

Walko, R. L.; Ashby, T.; Cotton, W. R.

2017-12-01

The fundamental role of atmospheric aerosols in the process of cloud droplet nucleation is well known, and there is ample evidence that the concentration, size, and chemistry of aerosols can strongly influence microphysical, thermodynamic, and ultimately dynamic properties and evolution of clouds and convective systems. With the increasing availability of observation- and model-based environmental representations of different types of anthropogenic and natural aerosols, there is increasing need for models to be able to represent which aerosols nucleate and which do not in supersaturated conditions. However, this is a very complex process that involves competition for water vapor between multiple aerosol species (chemistries) and different aerosol sizes within each species. Attempts have been made to parameterize the nucleation properties of mixtures of different aerosol species, but it is very difficult or impossible to represent all possible mixtures that may occur in practice. As part of a modeling study of the impact of anthropogenic and natural aerosols on hurricanes, we developed an ultra-efficient aerosol bin model to represent nucleation in a high-resolution atmospheric model that explicitly represents cloud- and subcloud-scale vertical motion. The bin model is activated at any time and location in a simulation where supersaturation occurs and is potentially capable of activating new cloud droplets. The bins are populated from the aerosol species that are present at the given time and location and by multiple sizes from each aerosol species according to a characteristic size distribution, and the chemistry of each species is represented by its absorption or adsorption characteristics. The bin model is integrated in time increments that are smaller than that of the atmospheric model in order to temporally resolve the peak supersaturation, which determines the total nucleated number. Even though on the order of 100 bins are typically utilized, this leads only to a 10 or 20% increase in overall computational cost due to the efficiency of the bin model. This method is highly versatile in that it automatically accommodates any possible number and mixture of different aerosol species. Applications of this model to simulations of Typhoon Nuri will be presented.

Estimation of critical supersaturation solubility ratio for predicting diameters of dry particles prepared by air-jet atomization of solutions.

PubMed

Sapra, Mahak; Ugrani, Suraj; Mayya, Y S; Venkataraman, Chandra

2017-08-15

Air-jet atomization of solution into droplets followed by controlled drying is increasingly being used for producing nanoparticles for drug delivery applications. Nanoparticle size is an important parameter that influences the stability, bioavailability and efficacy of the drug. In air-jet atomization technique, dry particle diameters are generally predicted by using solute diffusion models involving the key concept of critical supersaturation solubility ratio (Sc) that dictates the point of crust formation within the droplet. As no reliable method exists to determine this quantity, the present study proposes an aerosol based method to determine Sc for a given solute-solvent system and process conditions. The feasibility has been demonstrated by conducting experiments for stearic acid in ethanol and chloroform as well as for anti-tubercular drug isoniazid in ethanol. Sc values were estimated by combining the experimentally observed particle and droplet diameters with simulations from a solute diffusion model. Important findings of the study were: (i) the measured droplet diameters systematically decreased with increasing precursor concentration (ii) estimated Sc values were 9.3±0.7, 13.3±2.4 and 18±0.8 for stearic acid in chloroform, stearic acid and isoniazid in ethanol respectively (iii) experimental results pointed at the correct interfacial tension pre-factor to be used in theoretical estimates of Sc and (iv) results showed a consistent evidence for the existence of induction time delay between the attainment of theoretical Sc and crust formation. The proposed approach has been validated by testing its predictive power for a challenge concentration against experimental data. The study not only advances spray-drying technique by establishing an aerosol based approach to determine Sc, but also throws considerable light on the interfacial processes responsible for solid-phase formation in a rapidly supersaturating system. Until satisfactory theoretical formulae for predicting CSS are developed, the present approach appears to offer the best option for engineering nanoparticle size through solute diffusion models. Copyright © 2017 Elsevier Inc. All rights reserved.

Water-mineral relations of Quaternary deposits in the Lower Platte River drainage area in eastern Nebraska

USGS Publications Warehouse

Barnes, Ivan; Bentall, Ray

1968-01-01

The partial pressure of carbon dioxide (PCO2), the degree of saturation with respect to calcite (IAP/K calcite), the pH, and the concentrations of selected constituents in solution were determined for water from 52 wells and the Platte River. Compared to the PCO2 in the atmosphere, the average PCO2 in the ground water was many times greater and that in .the river water was about twice as great. The high PCO2 in the ground water probably results from the absorption, by infiltrating precipitation, of carbon dioxide produced in the soil by respiration of plant roots ,and microorganisms. The values for IAP/K calcite for the ground water ranged from 0.141 to 1.29 and for the river water the average was 9.6. Water from each of the 10 sampled wells on the terrace plain in southeastern Saunders County was unsaturated with respect to calcite, whereas water from seven of the 42 wells on the Platte River flood plain was nearly saturated or supersaturated. Of the ,seven, two were in the Lincoln city well field where hydrologic relations indicate that a large fraction of the water yielded by the wells is induced seepage from the .river. That more of the city wells did not yield supersaturated water is surprising in view of the high IAP/K calcite values for the river water. Supersaturation of water from five of nine sampled wells downvalley from the well field probably is due to the presence of numerous limestone fragments in the Quaternary deposits in that part of the area. also surprising was the finding that the average pH of the water from the city wells was 1 unit lower than that of the river water. The presence of both dissolved iron and dissolved oxygen in the water from several of the city wells probably reflects derivation of the water from two distinct sources : ground water naturally in the aquifer and induced seepage from the river.

A review on the kinetics of microbially induced calcium carbonate precipitation by urea hydrolysis

NASA Astrophysics Data System (ADS)

van Paassen, L. A.

2017-12-01

In this study the kinetics of calcium carbonate precipitation induced by the ureolytic bacteria are reviewed based on experiments and mathematical modelling. The study shows how urea hydrolysis rate depends on the amount of bacteria and the conditions during growth, storage, hydrolysis and precipitation. The dynamics of Microbially Induced Carbonate Precipitation has been monitored in non-seeded liquid batch experiments. Results show that particulary for a fast hydrolysis of urea (>1 M-urea day-1) in a highly concentrated equimolar solution with calcium chloride (>0.25 M) the solubility product of CaCO3 is exceeded within a short period (less than 30 minutes), the supersaturation remains high for an exended period, resulting in prolonged periods of nucleation and crystal growth and extended growth of metastable precursor mineral phases. The pH, being a result of the speciation, quickly rises until critical supersaturation is reached and precipitation is initiated. Then pH drops (sometimes showing oscillating behaviour) to about neutral where it stays until all substrates are depleted. Higher hydrolysis rates lead to higher supersaturation and pH and relatively many small crystals, whereas higher concentrations of urea and calcium chloride mainly lead to lower pH values. The conversion can be reasonably monitored by electrical conductivity and reasonably predicted, using a simplified model based on a single reaction as long as the urea hydrolysis rate is known. Complex geochemical models, which include chemical speciciation through acid-base equilibria and kinetic equations to describe mineral precipitation, do not show significant difference from the simplified model regarding the bulk chemistry and the total amount of precipitates. However, experiments show that ureolytic MICP can result in a highly variable crystal morphologies with large variation in the affected hydraulic properties when applied in a porous medium. In order to calculate the number, size and type of crystals, use of these more complex models is essential. Quantitative prediction to a level at which the pH and conductivity are simulated accurately is not yet possible as experimental data regarding the interaction between existing mineral surfaces are the surface interaction between ions and micro-organisms is still lacking.

Water uptake of clay and desert dust aerosol particles at sub- and supersaturated water vapor conditions

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

Herich, Hanna; Tritscher, Torsten; Wiacek, Aldona

2009-11-01

Airborne mineral dust particles serve as cloud condensation nuclei (CCN), thereby influencing the formation and properties of warm clouds. It is therefore of particular interest how dust aerosols with different mineralogy behave when exposed to high relative humidity (RH) or supersaturation with respect to liquid water similar to atmospheric conditions. In this study the sub-saturated hygroscopic growth and the supersaturated cloud condensation nucleus activity of pure clays and real desert dust aerosols was determined using a hygroscopicity tandem differential mobility analyzer (HTDMA) and a cloud condensation nuclei counter (CCNC), respectively. Five different illite, montmorillonite and kaolinite clay samples as wellmore » as three desert dust samples (Saharan dust (SD), Chinese dust (CD) and Arizona test dust (ATD)) were used. Aerosols were generated both with a wet and a dry disperser and the water uptake was parameterized via the hygroscopicity parameter, κ. The hygroscopicity of dry generated dust aerosols was found to be negligible when compared to processed atmospheric aerosols, with CCNC derived κ values between 0.00 and 0.02. The latter value can be idealized as a particle consisting of 96.7% (by volume) insoluble material and ~3.3% ammonium sulfate. Pure clay aerosols were found to be generally less hygroscopic than real desert dust particles. All illite and montmorillonite samples had κ~0.003, kaolinites were least hygroscopic and had κ=0.001. SD (κ=0.023) was found to be the most hygroscopic dry-generated desert dust followed by CD (κ=0.007) and ATD (κ=0.003). Wet-generated dust showed an increased water uptake when compared to dry-generated samples. This is considered to be an artifact introduced by redistribution of soluble material between the particles while immersed in an aqueous medium during atomization, thus indicating that specification of the generation method is critically important when presenting such data. Any atmospheric processing of fresh mineral dust which leads to the addition of more than ~3% soluble material is expected to significantly enhance hygroscopicity and CCN activity.« less

Theoretical and experimental investigation of drug-polymer interaction and miscibility and its impact on drug supersaturation in aqueous medium.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2016-10-01

Amorphous solid dispersions (ASDs) have the potential to offer higher apparent solubility and bioavailability of BCS class II drugs. Knowledge of the solid state drug-polymer solubility/miscibility and their mutual interaction are fundamental requirements for the effective design and development of such systems. To this end, we have carried out a comprehensive investigation of various ASD systems of dipyridamole and cinnarizine in polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) at different drug loadings. Theoretical and experimental examinations (by implementing binary and ternary Flory-Huggins (F-H) theory) related to drug-polymer interaction/miscibility including solubility parameter approach, melting point depression method, phase diagram, drug-polymer interaction in the presence of moisture and the effect of drug loading on interaction parameter were performed. The information obtained from this study was used to predict the stability of ASDs at different drug loadings and under different thermal and moisture conditions. Thermal and moisture sorption analysis not only provided the composition-dependent interaction parameter but also predicted the composition dependent miscibility. DPM-PVP, DPM-PAA and CNZ-PAA systems have shown molecular level mixing over the complete range of drug loading. For CNZ-PVP, the presence of a single Tg at lower drug loadings (10, 20 and 35%w/w) indicates the formation of solid solution. However, drug recrystallization was observed for samples with higher drug weight fractions (50 and 65%w/w). Finally, the role of polymer in maintaining drug supersaturation has also been explored. It has been found that drug-polymer combinations capable of hydrogen-bonding in the solution state (DPM-PVP, DPM-PAA and CNZ-PAA) are more effective in preventing drug crystallization compared to the drug-polymer systems without such interaction (CNZ-PVP). The DPM-PAA system outperformed all other ASDs in various stability conditions (dry-state, in the presence of moisture and in solution state), which was attributed to the drug's low crystallization tendency, the strong DPM-PAA interaction, the robustness of this interaction against moisture or water and the ability of PAA in maintaining DPM supersaturation. Copyright © 2016 Elsevier B.V. All rights reserved.

Controllable synthesis and electrochemical hydrogen storage properties of Bi2Se3 architectural structures.

PubMed

Sun, Zhengliang; Liufu, Shengcong; Chen, Xihong; Chen, Lidong

2010-05-14

Two kinds of Bi2Se3 nanostructures, 3D rose-like hierarchitectures and monodisperse nanospheres, have been synthesized through adjusting the supersaturation of the precursor solution. Noticeable hydrogen storage capacity, amounting to 185 mA h g-1, has been found for the 3D rose-like hierarchitectures, which arises from the special micro/nano-hierarchitectures with highly crystallized flake-substructures.

The solubility of quartz in water in the temperature interval from 25° to 300° C

USGS Publications Warehouse

Morey, G.W.; Fournier, R.O.; Rowe, J.J.

1962-01-01

the very slow rate at which dissolved silica polymerizes to species appropriate to act as nuclei for quartz growth. At the termination of the runs rotated at 75 rev/min, spikelike projections were present on many of the quartz grains. These are interpreted as indicating that abrasion was not the dominant cause for the great supersaturations which were obtained.  

The Fundamentals of Dislocation Transport of Hydrogen in BCC Iron.

DTIC Science & Technology

1984-10-01

4.2.1. Single Crystal Material 24 4.2.2. Polycrystalline Material 25 4.3. Single Crystal Orientation Determination 25 4.4. Straining Permeation Test 27...Test 45 4.6. Supersaturation Study 47 S. RESULTS AND DISCUSSION 50 5.1. Single Crystal Orientation Determination 50 5.1.1. Slip System Determination 58...Orientation 162 Determination B.1. Dislocation Line Direction Determination 162 B.2. Burgers Vector Determination 164

Photosynthesis as a Possible Source of Gas Bubbles in Shallow Sandy Coastal Sediments

DTIC Science & Technology

2011-09-30

bubbles can be formed when photosynthesis by benthic microalgae causes pore water to become supersaturated with oxygen. OBJECTIVES The next...reflectivity. We also collected sediment samples from the upper few mm of sand to identify the dominant taxa of benthic microalgae present. After...Graduate School of Oceanography / University of Rhode Island (GSO/URI) to identify the benthic microalgae in the samples. Following the untimely death of

Photosynthesis as a Possible Source of Gas Bubbles in Shallow Sandy Coastal Sediments

DTIC Science & Technology

2012-09-30

clearly demonstrates that gas bubbles can be formed when photosynthesis by benthic microalgae causes pore water to become supersaturated with oxygen...We also collected sediment samples from the upper few mm of sand to identify the dominant taxa of benthic microalgae present. Although benthic...Jan Rines (Graduate School of Oceanography / University of Rhode Island = GSO/URI) to identify the benthic microalgae in the samples. Following the

Nucleation of Crystals From Solution in Microgravity (USML-1 Glovebox (GBX) Investigation)

NASA Technical Reports Server (NTRS)

Kroes, Roger L.; Reiss, Donald A.; Lehoczky, Sandor L.

1994-01-01

A new method for initiating nucleation from solutions in microgravity which avoids nucleation on container walls and other surfaces is described. This method consists of injecting a small quantity of highly concentrated, heated solution into the interior of a lightly supersaturated, cooler host gowth solution. It was tested successfully on USML-I, producing a large number of LAP crystals whose longest dimension averaged 1 mm.

Water system microbial check valve development

NASA Technical Reports Server (NTRS)

Colombo, G. V.; Greenley, D. R.; Putnam, D. F.

1978-01-01

A residual iodine microbial check valve (RIMCV) assembly was developed and tested. The assembly is designed to be used in the space shuttle potable water system. The RIMCV is based on an anion exchange resin that is supersaturated with an iodine solution. This system causes a residual to be present in the effluent water which provides continuing bactericidal action. A flight prototype design was finalized and five units were manufactured and delivered.

Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid

PubMed Central

Tavafoghi, M.; Brodusch, N.; Gauvin, R.; Cerruti, M.

2016-01-01

Hydroxyapatite (HA, Ca5(PO4)3OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca2+ and PO43− ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca2+ and PO43− ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca2+ and PO43− ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only. PMID:26791001

Pathology of ocular lesions associated with gas supersaturation in white seabass.

PubMed

Smiley, Jeffrey E; Okihiro, Mark S; Drawbridge, Mark A; Kaufmann, Ronald S

2012-03-01

Cultured juvenile white seabass Atractoscion nobilis (WSB) can suffer from intraocular emphysemas and exophthalmia in the hatchery environment. To identify the cause, two size-groups of WSB were exposed to five gas saturation levels, ranging from 98% to 122% total gas pressure (TGP), over a 96-h exposure period in 18 degrees C and 23 degrees C seawater. Histological examination revealed that the gross and subgross lesions associated with gas supersaturation included corneal and orbital emphysema, along with subretinal, optic nerve, and iridial hemorrhage. Corneal emphysema was the most prominent gross lesion, with the severity and prevalence increasing between size-groups and water temperatures as TGP increased. Following the same pattern was orbital emphysema, which affected more than 93% of the fish examined and caused hemorrhage in the subretinal space, around the optic nerve, in the iris, or a combination thereof. Iridial hemorrhage occurred in 91% of the fish examined and decreased significantly with fish size. The prevalence and severity of hemorrhage in the subretinal space increased significantly with TGP and fish size but not with temperature. Optic nerve hemorrhage was absent in small fish exposed at 18 degrees C but increased significantly with temperature and fish size. The reverse was true for the large fish.

Towards a Model Climatology of Relative Humidity in the Upper Troposphere for Estimation of Contrail and Contrail-Induced Cirrus

NASA Technical Reports Server (NTRS)

Selkirk, Henry B.; Manyin, M.; Ott, L.; Oman, L.; Benson, C.; Pawson, S.; Douglass, A. R.; Stolarski, R. S.

2011-01-01

The formation of contrails and contrail cirrus is very sensitive to the relative humidity of the upper troposphere. To reduce uncertainty in an estimate of the radiative impact of aviation-induced cirrus, a model must therefore be able to reproduce the observed background moisture fields with reasonable and quantifiable fidelity. Here we present an upper tropospheric moisture climatology from a 26-year ensemble of simulations using the GEOS CCM. We compare this free-running model's moisture fields to those obtained from the MLS and AIRS satellite instruments, our most comprehensive observational databases for upper tropospheric water vapor. Published comparisons have shown a substantial wet bias in GEOS-5 assimilated fields with respect to MLS water vapor and ice water content. This tendency is clear as well in the GEOS CCM simulations. The GEOS-5 moist physics in the GEOS CCM uses a saturation adjustment that prevents supersaturation, which is unrealistic when compared to in situ moisture observations from MOZAIC aircraft and balloon sondes as we will show. Further, the large-scale satellite datasets also consistently underestimate super-saturation when compared to the in-situ observations. We place these results in the context of estimates of contrail and contrail cirrus frequency.

A new in vitro lipid digestion - in vivo absorption model to evaluate the mechanisms of drug absorption from lipid-based formulations.

PubMed

Crum, Matthew F; Trevaskis, Natalie L; Williams, Hywel D; Pouton, Colin W; Porter, Christopher J H

2016-04-01

In vitro lipid digestion models are commonly used to screen lipid-based formulations (LBF), but in vitro-in vivo correlations are in some cases unsuccessful. Here we enhance the scope of the lipid digestion test by incorporating an absorption 'sink' into the experimental model. An in vitro model of lipid digestion was coupled directly to a single pass in situ intestinal perfusion experiment in an anaesthetised rat. The model allowed simultaneous real-time analysis of the digestion and absorption of LBFs of fenofibrate and was employed to evaluate the influence of formulation digestion, supersaturation and precipitation on drug absorption. Formulations containing higher quantities of co-solvent and surfactant resulted in higher supersaturation and more rapid drug precipitation in vitro when compared to those containing higher quantities of lipid. In contrast, when the same formulations were examined using the coupled in vitro lipid digestion - in vivo absorption model, drug flux into the mesenteric vein was similar regardless of in vitro formulation performance. For some drugs, simple in vitro lipid digestion models may underestimate the potential for absorption from LBFs. Consistent with recent in vivo studies, drug absorption for rapidly absorbed drugs such as fenofibrate may occur even when drug precipitation is apparent during in vitro digestion.

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.

Magnetic properties of mechanically alloyed Mn-Al-C powders

NASA Astrophysics Data System (ADS)

Kohmoto, O.; Kageyama, N.; Kageyama, Y.; Haji, H.; Uchida, M.; Matsushima, Y.

2011-01-01

We have prepared supersaturated-solution Mn-Al-C alloy powders by mechanical alloying using a planetary high-energy mill. The starting materials were pure Mn, Al and C powers. The mechanically-alloyed powders were subjected to a two-step heating. Although starting particles are Al and Mn with additive C, the Al peak disappears with MA time. With increasing MA time, transition from α-Mn to β-Mn does not occur; the α-Mn structure maintains. At 100 h, a single phase of supersaturated-solution α-Mn is obtained. The lattice constant of α-Mn decreases with increasing MA time. From the Scherrer formula, the crystallite size at 500 h is obtained as 200Å, which does not mean amorphous state. By two-step heating, high magnetization (66 emu/g) was obtained from short-time-milled powders (t=10 h). The precursor of the as-milled powder is not a single phase α-Mn but contains small amount of fcc Al. After two-step heating, the powder changes to τ-phase. Although the saturation magnetization increases, the value is less than that by conventional bulk MnAl (88 emu/g). Meanwhile, long-time-milled powder of single α-Mn phase results in low magnetization (5.2 emu/g) after two-step heating.

Use of In Situ Cloud Condensation Nuclei, Extinction, and Aerosol Size Distribution Measurements to Test a Method for Retrieving Cloud Condensation Nuclei Profiles From Surface Measurements

NASA Technical Reports Server (NTRS)

Ghan, Stephen J.; Rissman, Tracey A.; Ellman, Robert; Ferrare, Richard A.; Turner, David; Flynn, Connor; Wang, Jian; Ogren, John; Hudson, James; Jonsson, Haflidi H.;

Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid.

PubMed

Tavafoghi, M; Brodusch, N; Gauvin, R; Cerruti, M

2016-01-01

Hydroxyapatite (HA, Ca5(PO4)3OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca(2+) and PO4(3-) ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca(2+) and PO4(3-) ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca(2+) and PO4(3-) ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only. © 2016 The Author(s).

Carbon, oxygen and their interaction with intrinsic point defects in solar silicon ribbon material: A speculative approach

NASA Technical Reports Server (NTRS)

Goesele, U.; Ast, D. G.

1983-01-01

Some background information on intrinsic point defects is provided and on carbon and oxygen in silicon in so far as it may be relevant for the efficiency of solar cells fabricated from EFG ribbon material. The co-precipitation of carbon and oxygen and especially of carbon and silicon self interstitials are discussed. A simple model for the electrical activity of carbon-self-interstitial agglomerates is presented. The self-interstitial content of these agglomerates is assumed to determine their electrical activity and that both compressive stresses (high self-interstitial content) and tensile stresses (low self-interstitial content) give rise to electrical activity of the agglomerates. The self-interstitial content of these carbon-related agglomerates may be reduced by an appropriate high temperature treatment and enhanced by a supersaturation of self-interstitials generated during formation of the p-n junction of solar cells. Oxygen present in supersaturation in carbon-rich silicon may be induced to form SiO, precipitates by self-interstitials generated during phosphorus diffusion. It is proposed that the SiO2-Si interface of the precipates gives rise to a continuum of donor stables and that these interface states are responsible for at least part of the light inhancement effects observed in oxygen containing EFG silicon after phosphorus diffusion.

Polydopamine-induced tooth remineralization.

PubMed

Zhou, Yun-Zhi; Cao, Ying; Liu, Wei; Chu, Chun Hung; Li, Quan-Li

2012-12-01

Inspired by mussel bioadhesion in nature, dopamine is extensively used for biomaterial surface modification. In this study, we coated dopamine on demineralized enamel and dentin surfaces to evaluate the effect of polydopamine coating on dental remineralization. Dental slices containing enamel and dentin were first etched with 37% phosphoric acid for 2 min, followed by immersion in a 2 mg/mL freshly prepared solution of dopamine (10 mM Tris buffer, pH 8.5) for approximately 24 h at room temperature in the dark to obtain polydopamine coating. Then, the dental slices with and without polydopamine coating were immersed in the supersaturated solution of calcium and phosphate at 37 °C for 2 and 7 days. The supersaturated solution of calcium and phosphate was refreshed each day. The precipitates were characterized by SEM, XRD, FTIR, microhardness, and nanoscratch analyses. No significant difference was observed in the remineralization of enamel whether it was coated with polydopamine or not. However, a significant difference was found in dentin remineralization between dentin with and without polydopamine coating. Polydopamine coating remarkably promoted demineralized dentin remineralization, and all dentin tubules were occluded by densely packed hydroxyapatite crystals. Thus, coating polydopamine on dental tissue surface may be a simple universal technique to induce enamel and dentin remineralization simultaneously.

Molecular hydrogen alleviates motor deficits and muscle degeneration in mdx mice.

PubMed

Hasegawa, Satoru; Ito, Mikako; Fukami, Mayu; Hashimoto, Miki; Hirayama, Masaaki; Ohno, Kinji

2017-01-01

Duchenne muscular dystrophy (DMD) is a devastating muscle disease caused by a mutation in DMD encoding dystrophin. Oxidative stress accounts for dystrophic muscle pathologies in DMD. We examined the effects of molecular hydrogen in mdx mice, a model animal for DMD. The pregnant mother started to take supersaturated hydrogen water (>5 ppm) ad libitum from E15.5 up to weaning of the offspring. The mdx mice took supersaturated hydrogen water from weaning until age 10 or 24 weeks when they were sacrificed. Hydrogen water prevented abnormal body mass gain that is commonly observed in mdx mice. Hydrogen improved the spontaneous running distance that was estimated by a counter-equipped running-wheel, and extended the duration on the rota-rod. Plasma creatine kinase activities were decreased by hydrogen at ages 10 and 24 weeks. Hydrogen also decreased the number of central nuclei of muscle fibers at ages 10 and 24 weeks, and immunostaining for nitrotyrosine in gastrocnemius muscle at age 24 weeks. Additionally, hydrogen tended to increase protein expressions of antioxidant glutathione peroxidase 1, as well as anti-apoptotic Bcl-2, in skeletal muscle at age 10 weeks. Although molecular mechanisms of the diverse effects of hydrogen remain to be elucidated, hydrogen potentially improves muscular dystrophy in DMD patients.

Nucleation and strain-stabilization during organic semiconductor thin film deposition.

PubMed

Li, Yang; Wan, Jing; Smilgies, Detlef-M; Bouffard, Nicole; Sun, Richard; Headrick, Randall L

2016-09-07

The nucleation mechanisms during solution deposition of organic semiconductor thin films determine the grain morphology and may influence the crystalline packing in some cases. Here, in-situ optical spectromicroscopy in reflection mode is used to study the growth mechanisms and thermal stability of 6,13-bis(trisopropylsilylethynyl)-pentacene thin films. The results show that the films form in a supersaturated state before transforming to a solid film. Molecular aggregates corresponding to subcritical nuclei in the crystallization process are inferred from optical spectroscopy measurements of the supersaturated region. Strain-free solid films exhibit a temperature-dependent blue shift of optical absorption peaks due to a continuous thermally driven change of the crystalline packing. As crystalline films are cooled to ambient temperature they become strained although cracking of thicker films is observed, which allows the strain to partially relax. Below a critical thickness, cracking is not observed and grazing incidence X-ray diffraction measurements confirm that the thinnest films are constrained to the lattice constants corresponding to the temperature at which they were deposited. Optical spectroscopy results show that the transition temperature between Form I (room temperature phase) and Form II (high temperature phase) depends on the film thickness, and that Form I can also be strain-stabilized up to 135 °C.

Investigations of the hygroscopic properties of ammonium sulfate and mixed ammonium sulfate and glutaric acid micro droplets by means of optical levitation and Raman spectroscopy.

PubMed

Jordanov, N; Zellner, R

2006-06-21

In the presented work an optical levitation technique performed by means of a focused laser beam, Mie and Raman spectroscopy have been utilized for measuring hygroscopic growth curves and composition of laboratory generated single ammonium sulfate (AS) and internally mixed ammonium sulfate-glutaric acid (GA) droplets in the micrometer range. The generated particles have been found to immediately supersaturate (above 45wt% for AS) at 297 K after capturing in the laser beam. Further increase of the relative humidity (RH) up to 85% does not dilute the droplets under the saturation point. A spontaneous hygroscopic growth takes place at 73.5-78% RH for pure AS. The particle grows with an average factor of 1.62 at the deliquescence relative humidity (DRH). Efflorescence of AS occurs at 43% RH with a corresponding concentration of more than 85wt%. Independent of the mixing ratios in ranges 25/75, 50/50, 75/25% AS/GA mixed particles don't exist as a metastable supersaturated solution droplets in the 35-85% RH range. Instead of growing with increasing relative humidity internally mixed particles build up a solid crystalline layer on the surface. This crystalline phase is not further influenced by ambient relative humidities.

Nanosecond-laser induced crosstalk of CMOS image sensor

NASA Astrophysics Data System (ADS)

Zhu, Rongzhen; Wang, Yanbin; Chen, Qianrong; Zhou, Xuanfeng; Ren, Guangsen; Cui, Longfei; Li, Hua; Hao, Daoliang

2018-02-01

The CMOS Image Sensor (CIS) is photoelectricity image device which focused the photosensitive array, amplifier, A/D transfer, storage, DSP, computer interface circuit on the same silicon substrate[1]. It has low power consumption, high integration,low cost etc. With large scale integrated circuit technology progress, the noise suppression level of CIS is enhanced unceasingly, and its image quality is getting better and better. It has been in the security monitoring, biometrice, detection and imaging and even military reconnaissance and other field is widely used. CIS is easily disturbed and damaged while it is irradiated by laser. It is of great significance to study the effect of laser irradiation on optoelectronic countermeasure and device for the laser strengthening resistance is of great significance. There are some researchers have studied the laser induced disturbed and damaged of CIS. They focused on the saturation, supersaturated effects, and they observed different effects as for unsaturation, saturation, supersaturated, allsaturated and pixel flip etc. This paper research 1064nm laser interference effect in a typical before type CMOS, and observring the saturated crosstalk and half the crosstalk line. This paper extracted from cmos devices working principle and signal detection methods such as the Angle of the formation mechanism of the crosstalk line phenomenon are analyzed.

Perlwapin, an Abalone Nacre Protein with Three Four-Disulfide Core (Whey Acidic Protein) Domains, Inhibits the Growth of Calcium Carbonate Crystals

PubMed Central

Treccani, Laura; Mann, Karlheinz; Heinemann, Fabian; Fritz, Monika

2006-01-01

We have isolated a new protein from the nacreous layer of the shell of the sea snail Haliotis laevigata (abalone). Amino acid sequence analysis showed the protein to consist of 134 amino acids and to contain three sequence repeats of ∼40 amino acids which were very similar to the well-known whey acidic protein domains of other proteins. The new protein was therefore named perlwapin. In addition to the major sequence, we identified several minor variants. Atomic force microscopy was used to explore the interaction of perlwapin with calcite crystals. Monomolecular layers of calcite crystals dissolve very slowly in deionized water and recrystallize in supersaturated calcium carbonate solution. When perlwapin was dissolved in the supersaturated calcium carbonate solution, growth of the crystal was inhibited immediately. Perlwapin molecules bound tightly to distinct step edges, preventing the crystal layers from growing. Using lower concentrations of perlwapin in a saturated calcium carbonate solution, we could distinguish native, active perlwapin molecules from denaturated ones. These observations showed that perlwapin can act as a growth inhibitor for calcium carbonate crystals in saturated calcium carbonate solution. The function of perlwapin in nacre growth may be to inhibit the growth of certain crystallographic planes in the mineral phase of the polymer/mineral composite nacre. PMID:16861275

Kinetics of the cellular decomposition of supersaturated solid solutions

NASA Astrophysics Data System (ADS)

Ivanov, M. A.; Naumuk, A. Yu.

2014-09-01

A consistent description of the kinetics of the cellular decomposition of supersaturated solid solutions with the development of a spatially periodic structure of lamellar (platelike) type, which consists of alternating phases of precipitates on the basis of the impurity component and depleted initial solid solution, is given. One of the equations, which determines the relationship between the parameters that describe the process of decomposition, has been obtained from a comparison of two approaches in order to determine the rate of change in the free energy of the system. The other kinetic parameters can be described with the use of a variational method, namely, by the maximum velocity of motion of the decomposition boundary at a given temperature. It is shown that the mutual directions of growth of the lamellae of different phases are determined by the minimum value of the interphase surface energy. To determine the parameters of the decomposition, a simple thermodynamic model of states with a parabolic dependence of the free energy on the concentrations has been used. As a result, expressions that describe the decomposition rate, interlamellar distance, and the concentration of impurities in the phase that remain after the decomposition have been derived. This concentration proves to be equal to the half-sum of the initial concentration and the equilibrium concentration corresponding to the decomposition temperature.

The effect of CO2 at low temperature and pressure on solutions supersaturated with silica in the presence of limestone and dolomite

USGS Publications Warehouse

Lovering, T.G.; Patten, L.E.

1962-01-01

The effect of 1 atm of CO2 over initially neutral solutions supersaturated with silica, at room temperature, as contrasted with 1 atm of air was determined over a period of 5 months, together with changes brought about by the introduction of calcite and dolomite to these solutions in the form of either chips or finely ground powder. In the absence of CO2 all solutions quickly reached equilibrium and no silica precipitated. In the presence of CO2 approximately two-thirds of the silica precipitated as silica gel within the first 2 months; the amount of silica precipitated was not affected by the presence of limestone or dolomite. Silica gel precipitated as a fine powder in the presence of finely ground calcite and dolomite, but as a cloudy gelatinous mass in the presence of coarse chips of dolomite and calcite, and in the absence of either calcite or dolomite. Preferential leaching of calcium from dolomite took place, both in the presence of air and in the presence of CO2, but was more pronounced in the presence of air. There was no evidence of physical replacement of either limestone or dolomite by precipitated silica. ?? 1962.

Kinetic theory of heterogeneous nucleation; effect of nonuniform density in the nuclei.

PubMed

Berim, Gersh O; Ruckenstein, Eli

2011-03-01

The heterogeneous nucleation of a liquid from a vapor in contact with a planar solid surface or a solid surface with cavities is examined on the basis of the kinetic theory of nucleation developed by Nowakowski and Ruckenstein [J. Phys. Chem. 96 (1992) 2313] which is extended to nonuniform fluid density distribution (FDD) in the nucleus. The latter is determined under the assumption that at each moment the FDD in the nucleus is provided by the density functional theory (DFT) for a nanodrop. As a result of this assumption, the theory does not require to consider that the contact angle which the nucleus makes with the solid surface and the density of the nucleus are independent parameters since they are provided by the DFT. For all considered cases, the nucleation rate is higher in the cavities than on a planar surface and increases with increasing strength of the fluid-solid interactions and decreasing cavity radius. The difference is small at high supersaturations (small critical nuclei), but becomes larger at low supersaturations when the critical nucleus has a size comparable with the size of the cavity. The nonuniformity of the FDD in the nucleus decreases the nucleation rate when compared to the uniform FDD. Copyright © 2010 Elsevier Inc. All rights reserved.

A reduced theoretical model for estimating condensation effects in combustion-heated hypersonic tunnel

NASA Astrophysics Data System (ADS)

Lin, L.; Luo, X.; Qin, F.; Yang, J.

2018-03-01

As one of the combustion products of hydrocarbon fuels in a combustion-heated wind tunnel, water vapor may condense during the rapid expansion process, which will lead to a complex two-phase flow inside the wind tunnel and even change the design flow conditions at the nozzle exit. The coupling of the phase transition and the compressible flow makes the estimation of the condensation effects in such wind tunnels very difficult and time-consuming. In this work, a reduced theoretical model is developed to approximately compute the nozzle-exit conditions of a flow including real-gas and homogeneous condensation effects. Specifically, the conservation equations of the axisymmetric flow are first approximated in the quasi-one-dimensional way. Then, the complex process is split into two steps, i.e., a real-gas nozzle flow but excluding condensation, resulting in supersaturated nozzle-exit conditions, and a discontinuous jump at the end of the nozzle from the supersaturated state to a saturated state. Compared with two-dimensional numerical simulations implemented with a detailed condensation model, the reduced model predicts the flow parameters with good accuracy except for some deviations caused by the two-dimensional effect. Therefore, this reduced theoretical model can provide a fast, simple but also accurate estimation of the condensation effect in combustion-heated hypersonic tunnels.

Deuterium supersaturation in low-energy plasma-loaded tungsten surfaces

NASA Astrophysics Data System (ADS)

Gao, L.; Jacob, W.; von Toussaint, U.; Manhard, A.; Balden, M.; Schmid, K.; Schwarz-Selinger, T.

2017-01-01

Fundamental understanding of hydrogen-metal interactions is challenging due to a lack of knowledge on defect production and/or evolution upon hydrogen ingression, especially for metals undergoing hydrogen irradiation with ion energy below the displacement thresholds reported in literature. Here, applying a novel low-energy argon-sputter depth profiling method with significantly improved depth resolution for tungsten (W) surfaces exposed to deuterium (D) plasma at 300 K, we show the existence of a 10 nm thick D-supersaturated surface layer (DSSL) with an unexpectedly high D concentration of ~10 at.% after irradiation with ion energy of 215 eV. Electron back-scatter diffraction reveals that the W lattice within this DSSL is highly distorted, thus strongly blurring the Kikuchi pattern. We explain this strong damage by the synergistic interaction of energetic D ions and solute D atoms with the W lattice. Solute D atoms prevent the recombination of vacancies with interstitial W atoms, which are produced by collisions of energetic D ions with W lattice atoms (Frenkel pairs). This proposed damaging mechanism could also be active on other hydrogen-irradiated metal surfaces. The present work provides deep insight into hydrogen-induced lattice distortion at plasma-metal interfaces and sheds light on its modelling work.

Effects of different operating parameters on the particle size of silver chloride nanoparticles prepared in a spinning disk reactor

NASA Astrophysics Data System (ADS)

Dabir, Hossein; Davarpanah, Morteza; Ahmadpour, Ali

2015-07-01

The aim of this research was to present an experimental method for large-scale production of silver chloride nanoparticles using spinning disk reactor. Silver nitrate and sodium chloride were used as the reactants, and the protecting agent was gelatin. The experiments were carried out in a continuous mode by injecting the reactants onto the surface of the spinning disk, where a chemical precipitation reaction took place to form AgCl particles. The effects of various operating variables, including supersaturation, disk rotational speed, reactants flow rate, disk diameter, and excess ions, on the particle size of products were investigated. In addition, the AgCl nanoparticles were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction. According to the results, smaller AgCl particles are obtained under higher supersaturations and also higher disk rotation speeds. Moreover, in the range of our investigation, the use of lower reactants flow rates and larger disk diameter can reduce the particle size of products. The non-stoichiometric condition of reactants has a significant influence on the reduction in particle aggregation. It was also found that by optimizing the operating conditions, uniform AgCl nanoparticles with the mean size of around 37 nm can be produced.

Model for capping of membrane receptors based on boundary surface effects

PubMed Central

Gershon, N. D.

1978-01-01

Crosslinking of membrane surface receptors may lead to their segregation into patches and then into a single large aggregate at one pole of the cell. This process is called capping. Here, a novel explanation of such a process is presented in which the membrane is viewed as a supersaturated solution of receptors in the lipid bilayer and the adjacent two aqueous layers. Without a crosslinking agent, a patch of receptors that is less than a certain size cannot stay in equilibrium with the solution and thus should dissolve. Patches greater than a certain size are stable and can, in principle, grow by the precipitation of the remaining dissolved receptors from the supersaturated solution. The task of the crosslinking molecules is to form such stable patches. These considerations are based on a qualitative thermodynamic calculation that takes into account the existence of a boundary tension in a patch (in analogy to the surface tension of a droplet). Thermodynamically, these systems should cap spontaneously after the patches have reached a certain size. But, in practice, such a process can be very slow. A suspension of patches may stay practically stable. The ways in which a cell may abolish this metastable equilibrium and thus achieve capping are considered and possible effects of capping inhibitors are discussed. PMID:274724

Efficacy of Mixtures of Magnesium, Citrate and Phytate as Calcium Oxalate Crystallization Inhibitors in Urine.

PubMed

Grases, Felix; Rodriguez, Adrian; Costa-Bauza, Antonia

2015-09-01

The main aim of the current study was to evaluate the effectiveness of mixtures of magnesium, citrate and phytate as calcium oxalate crystallization inhibitors. A turbidimetric assay in synthetic urine was performed to obtain induction times for calcium oxalate crystallization in the absence and presence of different mixtures of inhibitors. The morphology of calcium oxalate crystals in the absence or presence of inhibitors and mixtures of the inhibitors was evaluated in 2 crystallization experiments at low and high calcium oxalate supersaturation. The crystals formed were examined using scanning electron microscopy. Examination of crystallization induction times revealed clear inhibitory effects of magnesium, citrate and phytate on calcium oxalate crystallization, supporting usefulness in the treatment and prevention of calcium oxalate nephrolithiasis. Significant synergistic effects between magnesium and phytate were observed. Scanning electron microscopy images revealed that phytate is a powerful crystal growth inhibitor of calcium oxalate, totally preventing the formation of trihydrate and monohydrate. In addition to crystallization inhibition capacity, citrate and magnesium avoided calcium oxalate crystallization by decreasing its supersaturation. The synergistic effect between magnesium and phytate on calcium oxalate crystallization suggests that a combination of these 2 compounds may be highly useful as antilithiasis therapy. Copyright © 2015 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

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

Li, Jincheng; Kim, Tong-Ho; Jiao, Wenyuan

Recent work has shown that Bi incorporation increases during molecular beam epitaxy (MBE) when surface processes are kinetically limited through increased growth rate. Herein we explore how the structural and optical properties of GaAs{sub 1−x}Bi{sub x} films are modified when grown under conditions with varying degrees of kinetic limitations realized through growth temperature and growth rate changes. Within the typical window of MBE growth conditions for GaAs{sub 1−x}Bi{sub x}, we compare films with similar (∼3%) compositions grown under conditions of reduced kinetic limitations, i.e., relatively low gallium supersaturation achieved at higher temperatures (∼350 °C) and lower growth rates (∼0.5 μm/h), tomore » those grown farther from equilibrium, specifically, higher supersaturation achieved at lower growth temperatures (∼290 °C) and higher growth rates (∼1.4 μm/h). Both the x-ray diffraction full width at half maximum of the omega-2theta scan and the 300 K photoluminescence intensity increase when samples are grown under less kinetically limited conditions. We interpret these findings in relation to the incorporation of Bi-related microstructural defects that are more readily formed during less kinetically limited growth. These defects lead to enhanced luminescence efficiency due to the spatial localization of carriers.« less

Estimation of the growth kinetics for the cooling crystallisation of paracetamol and ethanol solutions

NASA Astrophysics Data System (ADS)

Mitchell, Niall A.; Ó'Ciardhá, Clifford T.; Frawley, Patrick J.

2011-08-01

This work details the estimation of the growth kinetics of paracetamol in ethanol solutions for cooling crystallisation processes, by means of isothermal seeded batch experiments. The growth kinetics of paracetamol crystals were evaluated in isolation, with the growth rate assumed to be size independent. Prior knowledge of the Metastable Zone Width (MSZW) was required, so that supersaturation ratios of 1.7-1.1 could be induced in solution without the occurrence of nucleation. The technique involved the utilisation of two in-situ Process Analytical Techniques (PATs), with a Focused Beam Reflectance Measurement (FBRM ®) utilised to ensure that negligible nucleation occurred and an Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) probe employed for online monitoring of solute concentration. Initial Particle Size Distributions (PSDs) were used in conjunction with desupersaturation profiles to determine the growth rate as a function of temperature and supersaturation. Furthermore, the effects of seed loading and size on the crystal growth rate were investigated. A numerical model, incorporating the population balance equation and the method of moments, was utilised to describe the crystal growth process. Experimental parameters were compared to the model simulation, with the accuracy of the model validated by means of the final product PSDs and solute concentration.

The Effect of Temperature and Solution pH on Tetragonal Lysozyme Nucleation Kinetics

NASA Technical Reports Server (NTRS)

Judge, Russell A.; Jacobs, Randolph S.; Frazier, Tyralynn; Snell, Edward H.; Pusey, Marc L.

1998-01-01

Part of the challenge of macromolecular crystal growth for structure determination is obtaining an appropriate number of crystals with a crystal volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over one week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions, Duplicate experiments indicate the reproducibility of the technique, Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable however, was pH, where crystal numbers changed by two orders of magnitude over the pH range 4.0 to 5.2. Crystal size varied also with solution conditions, with the largest crystals being obtained at pH 5.2. Having optimized the crystallization conditions, a batch of crystals were prepared under exactly the same conditions and fifty of these crystals were analyzed by x-ray techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.

Molecular Dynamics Study of the Solubility Curve of Polyglutamine for the PLUM Model.

NASA Astrophysics Data System (ADS)

Kutlu, Songul; Haaga, Jason; Gunton, James D.

A recent study by Crick et al determined the saturation (solubility) curve for polyglutamine (PolyQ) for several different repeat lengths, n, of Qn, and for different flanking sequences, such as K2. The degree of supersaturation S, (S =ln(Co/Ce), where Co and Ce are the metastable and equilibrium saturation monomer concentrations, respectively) plays a crucial role in the kinetics of aggregation of misfolded proteins containing polyQ. Thus the degree of supersaturation is an important factor in diseases such as Huntington's disease for which polyQ is a major component. We present here preliminary results of a molecular dynamics study for the solubility curve for a PLUM model of Q10. (An extensive study of the kinetics of aggregation for this model is being carried out in a separate study) Our results display a normal solubility curve behavior, with the saturation concentration increasing with increasing temperature. This is only in partial qualitative agreement with the experimental results, which show a retrograde behavior at low temperatures. We are extending this study to other repeat lengths, including Q40. ∖ ∖ ∖ ∖ This work is supported by the G. Harold and Leila Y. Mathers Foundation and used an allocation of time from XSEDE.

Air Sparging Versus Gas Saturated Water Injection for Remediation of Volatile LNAPL in the Borden Aquifer

NASA Astrophysics Data System (ADS)

Barker, J.; Nelson, L.; Doughty, C.; Thomson, N.; Lambert, J.

2009-05-01

In the shallow, rather homogeneous, unconfined Borden sand aquifer, field trials of air sparging (Tomlinson et al., 2003) and pulsed air sparging (Lambert et al., 2009) have been conducted, the latter to remediate a residual gasoline source emplaced below the water table. As well, a supersaturated (with CO2) water injection (SWI) technology, using the inVentures inFusion system, has been trialed in two phases: 1. in the uncontaminated sand aquifer to evaluate the radius of influence, extent of lateral gas movement and gas saturation below the water table, and 2. in a sheet pile cell in the Borden aquifer to evaluate the recovery of volatile hydrocarbon components (pentane and hexane) of an LNAPL emplaced below the water table (Nelson et al., 2008). The SWI injects water supersaturated with CO2. The supersaturated injected water moves laterally away from the sparge point, releasing CO2 over a wider area than does gas sparging from a single well screen. This presentation compares these two techniques in terms of their potential for remediating volatile NAPL components occurring below the water table in a rather homogeneous sand aquifer. Air sparging created a significantly greater air saturation in the vicinity of the sparge well than did the CO2 system (60 percent versus 16 percent) in the uncontaminated Borden aquifer. However, SWI pushed water, still supersaturated with CO2, up to about 2.5 m from the injection well. This would seem to provide a considerable advantage over air sparging from a point, in that gas bubbles are generated at a much larger radius from the point of injection with SWI and so should involve additional gas pathways through a residual NAPL. Overall, air sparging created a greater area of influence, defined by measurable air saturation in the aquifer, but air sparging also injected about 12 times more gas than was injected in the SWI trials. The pulsed air sparging at Borden (Lambert et al.) removed about 20 percent (4.6 kg) of gasoline hydrocarbons, mainly pentane and hexane, from the residual gasoline via sparging. A similar mass was estimated to have been removed by aerobic biodegradation. The extent of volatile recovery needs to be better defined and so post-sparging coring and analysis of residual LNAPL is underway. Impressively, the second SWI trial recovered more than 60 percent of the pentane-hexane from the NAPL. In both field experiments there was potential for minor additional recovery if the system had been operated longer. Comparison of efficiency of the pulsed air sparging and SWI systems is difficult in that the initial LNAPL residuals have different chemistry, but similar distribution, different volumes of gas were used, and biodegradation accounted for a significant removal of hydrocarbons only in the air sparging system. The SWI trial recovered an impressive portion of the volatile LNAPL, while using considerably less gas than the air sparging system, but the SWI delivery system was both more complex and more expensive than the air sparging system. Additional trials are underway in more complex aquifers to further assess the performance of the SWI technology, including costs and practical limitations.

A Systems Biology Approach to Heat Stress, Heat Injury and Heat Stroke

DTIC Science & Technology

2015-01-01

Winkler et al., “Computational lipidology: predicting lipoprotein density profiles in human blood plasma,” PLoS Comput Biol, 4(5), e1000079 (2008). [74...other organs at high risk for injury, such as liver and kidney [24, 25]. 2.1 Utility of the computational model Molecular indicators of heat...induced heart injury had a large shift in relative abundance of proteins with high supersaturation scores, suggesting increased abundance of

Liesegang-Like Rings in Lactational Changes in the Breast

PubMed Central

Islam, Mohd T.; Ou, Joyce J.; Hansen, Katrine; Simon, Rochelle A.; Quddus, M. Ruhul

2012-01-01

Liesagang-like rings (LR) are periodic structures with equally spaced radial striations formed by a process that involves diffusion, nucleation, flocculation or precipitation, and supersaturation. Being more common in vitro, on rare occasions also reported in vivo in association with inflammatory or cystic lesions and confused with parasites or calcification on needle aspirates. The current paper documents that LRs may be seen in noncystic and noninflammatory changes of the breast. PMID:23094171

Laterally Overgrown Structures as Substrates for Lattice Mismatched Epitaxy

DTIC Science & Technology

2002-06-03

low supersaturation substrate [3]. Therefore, equilibrium growth techniques as liquid buffer with TD phase epitaxy (LPE) or vapour phase epitaxy (VPE...phase diffusion during MBE growth, so lateral over- low cost semiconductor devices. Therefore, vapour growth must rely on the surface mobility of...is replaced by graphite film not wetted For the GaAs on GaAs ELO system we attributed by the gallium melt [35]. Similarly, tungsten has been broadening

Initiating Growth Of Crystals Away From Container Walls

NASA Technical Reports Server (NTRS)

Kroes, Roger L.; Reiss, Donald A.; Lehoczky, Sandor L.

1991-01-01

Nucleation controlled to obtain better crystals. In technique proposed specifically for growing large protein crystals in microgravity (where no thermal convection), small region of high supersaturation created by injection of hot concentrated solution or by use of cold probe. Crystals nucleate preferably in this small region. Also conceivable technique applied on Earth to crystallizations in melts and solutions sufficiently viscous to suppress convection to extent necessary to prevent cooling-induced nucleation in undesired sites.

Photosynthesis as a Possible Source of Gas Bubbles in Shallow Sandy Coastal Sediments

DTIC Science & Technology

2010-09-30

gas bubbles can be formed when photosynthesis by benthic microalgae causes pore water to become supersaturated with oxygen. OBJECTIVES The...acoustic reflectivity. We also collected sediment samples from the upper few mm of sand to identify the dominant taxa of benthic microalgae present... microalgae in the samples. Following the untimely death of Dr. D.V. Holliday, the remaining team members are sharing the responsibility of analyzing data and