Porous synthetic hectorite clay-alginate composite beads for effective adsorption of methylene blue dye from aqueous solution.

PubMed

Pawar, Radheshyam R; Lalhmunsiama; Gupta, Prabuddha; Sawant, Sandesh Y; Shahmoradi, B; Lee, Seung-Mok

2018-07-15

The present study deals with the preparation and characterization of mesoporous synthetic hectorite (MSH) clay which further encapsulated with Na-alginate for the preparation of mesoporous synthetic hectorite-alginate beads (MSH-AB) where Ca 2+ act as a cross-linking agent. The detail characterization of MSH and MSH-AB were carried out by various physicochemical techniques. The thermogravimetric analysis study showed better thermal stability results for MSH-AB. The textural properties results of MSH and MSH-AB showed the high surface area 468, 205m 2 /g, and the pore volume of 0.34, 0.29cm 3 /g respectively. The applicability of powder MSH and MSH-AB in wet (W) and dry (D) forms were assessed for the removal of cationic dye, methylene blue (MB) by optimizing various batch adsorption parameters. The Langmuir monolayer adsorption capacity obtained for MSH-AB-W showed significant high adsorption efficacy (i.e., 785.45mgMB/g) compared to the MSH-AB-D (357.14mgMB/g) and powder MSH materials (196.00mgMB/g). The adsorption isotherm studies showed that the Langmuir isotherm model was best suitable for MSH, whereas the Freundlich model was utilised to describe the adsorption behavior of organized hydrogel composite beads. The pseudo-second-order kinetics model was observed best for MB sorption onto MSH, whereas pseudo-first order useful to describe the kinetic behavior of MSH-AB. The regeneration experimental results revealed that MSH-AB-W could be recycled more than six cycles with high MB removal efficiency. Furthermore, the adsorption property of the MSH-AB-W was examined for the binary mixture of MB with other dye solutions such as Methyl Red (MR), Methyl Orange (MO), Alizarine Yellow (AY), and Remazol Brilliant Blue (RBB) to evaluate the selective adsorption efficiency. The MSH composite beads were found potentially suitable as an efficient, selective and recyclable adsorbent for the removal of MB from the aqueous solutions. Copyright © 2018 Elsevier B.V. All rights reserved.

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

PubMed

Kritayakornupong, Chinapong

2009-12-01

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

Bulky Polar Additives That Greatly Reduce the Viscosity of Concentrated Solutions of Therapeutic Monoclonal Antibodies.

PubMed

Larson, Alyssa M; Weight, Alisha K; Love, Kevin; Bonificio, Amanda; Wescott, Charles R; Klibanov, Alexander M

2017-05-01

The viscosity of concentrated aqueous solutions of 3 clinical monoclonal antibodies (mAbs), Erbitux®, Herceptin®, and Rituxan®, has been reduced up to over 10-fold by adding certain bulky polar additives instead of saline at isotonic levels. Because these additives are also found not to compromise mAbs' stability against aggregation induced by stresses, a drug-delivery modality switch from intravenous infusions to more convenient and inexpensive parenteral options like subcutaneous injections may become possible. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

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

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

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

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

Activated bauxite waste as an adsorbent for removal of Acid Blue 92 from aqueous solutions.

PubMed

Norouzi, Sh; Badii, Kh; Doulati Ardejani, F

2010-01-01

Bauxite waste, known as red mud, is produced in some industrial processes, such as aluminum production process. In this process, the waste material is produced from leached bauxite as a by product. In this research, the removal of Acid Blue 92 (AB92) dye was investigated from aqueous solution onto the activated bauxite waste (red mud) in a batch equilibration system. Besides, the influences of pH, adsorbent dosage, contact time, initial concentration of dye and temperature have been considered. It was found that the OH group is an effective functional group for the adsorption process. The intensity of the peaks correspond to OH group has been significantly climbed after the activation process. The adsorption kinetics of AB92 can be well described by the pseudo-second-order reaction model. Based on the isotherm data obtained from the fittings of the adsorption kinetics, the Langmuir model appears to fit the adsorption process better than the Freundlich and Brunauer-Emmett-Teller (BET) models.

Proton affinity of the histidine-tryptophan cluster motif from the influenza A virus from ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Bankura, Arindam; Klein, Michael L.; Carnevale, Vincenzo

2013-08-01

Ab initio molecular dynamics calculations have been used to compare and contrast the deprotonation reaction of a histidine residue in aqueous solution with the situation arising in a histidine-tryptophan cluster. The latter is used as a model of the proton storage unit present in the pore of the M2 proton conducting ion channel. We compute potentials of mean force for the dissociation of a proton from the Nδ and Nɛ positions of the imidazole group to estimate the pKas. Anticipating our results, we will see that the estimated pKa for the first protonation event of the M2 channel is in good agreement with experimental estimates. Surprisingly, despite the fact that the histidine is partially desolvated in the M2 channel, the affinity for protons is similar to that of a histidine in aqueous solution. Importantly, the electrostatic environment provided by the indoles is responsible for the stabilization of the charged imidazolium.

Structure and dynamics of the CrIII ion in aqueous solution: Ab initio QM/MM molecular dynamics simulation.

PubMed

Kritayakornupong, Chinapong; Plankensteiner, Kristof; Rode, Bernd M

2004-10-01

Structural and dynamical properties of the Cr(III) ion in aqueous solution have been investigated using a combined ab initio quantum mechanical/molecular mechanical (QM/MM) molecular dynamics simulation. The hydration structure of Cr(III) was determined in terms of radial distribution functions, coordination numbers, and angular distributions. The QM/MM simulation gives coordination numbers of 6 and 15.4 for the first and second hydration shell, respectively. The first hydration shell is kinetically very inert but by no means rigid and variations of the first hydration shell geometry lead to distinct splitting in the vibrational spectra of Cr(H(2)O)(6) (3+). A mean residence time of 22 ps was obtained for water ligands residing in the second hydration shell, which is remarkably shorter than the experimentally estimated value. The hydration energy of -1108 +/- 7 kcal/mol, obtained from the QM/MM simulation, corresponds well to the experimental hydration enthalpy value. Copyright 2004 Wiley Periodicals, Inc.

Hydrated Electron Transfer to Nucleobases in Aqueous Solutions Revealed by Ab Initio Molecular Dynamics Simulations.

PubMed

Zhao, Jing; Wang, Mei; Fu, Aiyun; Yang, Hongfang; Bu, Yuxiang

2015-08-03

We present an ab initio molecular dynamics (AIMD) simulation study into the transfer dynamics of an excess electron from its cavity-shaped hydrated electron state to a hydrated nucleobase (NB)-bound state. In contrast to the traditional view that electron localization at NBs (G/A/C/T), which is the first step for electron-induced DNA damage, is related only to dry or prehydrated electrons, and a fully hydrated electron no longer transfers to NBs, our AIMD simulations indicate that a fully hydrated electron can still transfer to NBs. We monitored the transfer dynamics of fully hydrated electrons towards hydrated NBs in aqueous solutions by using AIMD simulations and found that due to solution-structure fluctuation and attraction of NBs, a fully hydrated electron can transfer to a NB gradually over time. Concurrently, the hydrated electron cavity gradually reorganizes, distorts, and even breaks. The transfer could be completed in about 120-200 fs in four aqueous NB solutions, depending on the electron-binding ability of hydrated NBs and the structural fluctuation of the solution. The transferring electron resides in the π*-type lowest unoccupied molecular orbital of the NB, which leads to a hydrated NB anion. Clearly, the observed transfer of hydrated electrons can be attributed to the strong electron-binding ability of hydrated NBs over the hydrated electron cavity, which is the driving force, and the transfer dynamics is structure-fluctuation controlled. This work provides new insights into the evolution dynamics of hydrated electrons and provides some helpful information for understanding the DNA-damage mechanism in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method of forming grooves in the [011] crystalline direction

NASA Technical Reports Server (NTRS)

Marinelli, Donald Paul (Inventor)

1977-01-01

An A-B etchant is applied to a (100) surface of a body of semiconductor material, a portion of which along the (100) surface of the body is either gallium arsenide or gallium aluminum arsenide. The etchant is applied for at least 15 seconds at a temperature of approximately 80.degree. C. The A-B etchant is a solution by weight percent of 47.5%, water, 0.2% silver nitrate, 23.8% chromium trioxide and 28.5% of a 48% aqueous solution of hydrofluoric acid. As a result of the application of the A-B etchant a pattern of elongated etch pits form having their longitudinal axes along the [011] crystalline direction. Grooves are formed in the body at a surface opposite the (100) surface on which was applied the etchant. The grooves are formed along the [011] crystalline direction by aligning the longitudinal axes of the grooves with the longitudinal axes of the etch pits.

Three-dimensional printed acrylonitrile butadiene styrene framework coated with Cu-BTC metal-organic frameworks for the removal of methylene blue.

PubMed

Wang, Zongyuan; Wang, Jiajun; Li, Minyue; Sun, Kaihang; Liu, Chang-jun

2014-08-04

Three-dimensional (3D) printing was applied for the fabrication of acrylonitrile butadiene styrene (ABS) framework. Functionalization of the ABS framework was then performed by coating of porous Cu-BTC (BTC = benzene tricarboxylic acid) metal-organic frameworks on it using a step-by-step in-situ growth. The size of the Cu-BTC particles on ABS was ranged from 200 nm to 900 nm. The Cu-BTC/ABS framework can take up most of the space of the tubular reactor that makes the adsorption effective with no need of stirring. Methylene blue (MB) can be readily removed from aqueous solution by this Cu-BTC/ABS framework. The MB removal efficiency for solutions with concentrations of 10 and 5 mg/L was 93.3% and 98.3%, respectively, within 10 min. After MB adsorption, the Cu-BTC/ABS composite can easily be recovered without the need for centrifugation or filtration and the composite is reusable. In addition the ABS framework can be recovered for subsequent reuse. A significant advantage of 3D-printed frameworks is that different frameworks can be easily fabricated to meet the needs of different applications. This is a promising strategy to synthesize new frameworks using MOFs and polymers to develop materials for applications beyond adsorption.

Calculating Permittivity and Dielectric Loss Frequency Spectra for Aqueous Electrolyte Solutions

NASA Astrophysics Data System (ADS)

Odinaev, S.; Makhmadbegov, R. S.

2018-01-01

Analytic expressions for dielectric permittivity factor ɛ1(ω) and dielectric dissipation factor ɛ2(ω) of electrolyte solutions are obtained, based on the ratio between complex factors of dielectric permittivity and specific conductivity. The range of frequency dispersion of dynamic factors ɛ1(ω) and ɛ2(ω) for aqueous solutions of LiCl, NaCl, KCl, and CsCl is considered. Numerical calculations are performed for friction coefficients β a and β b ; relaxation times τ a , τ b , and τ ab ; and factors ɛ1(ω) and ɛ2(ω) in a wide range of variation for ρ; concentration c; temperature T; and frequencies ω. The resulting theoretically calculated ɛ1(ω) and ɛ2(ω) values and the Cole-Cole diagram are in quantitative agreement with experimental data.

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

PubMed

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

2002-06-10

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

A new force field including charge directionality for TMAO in aqueous solution

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

Usui, Kota; Nagata, Yuki, E-mail: sulpizi@uni-mainz.de, E-mail: nagata@mpip-mainz.mpg.de; Hunger, Johannes

We propose a new force field for trimethylamine N-oxide (TMAO), which is designed to reproduce the long-lived and highly directional hydrogen bond between the TMAO oxygen (O{sub TMAO}) atom and surrounding water molecules. Based on the data obtained by ab initio molecular dynamics simulations, we introduce three dummy sites around O{sub TMAO} to mimic the O{sub TMAO} lone pairs and we migrate the negative charge on the O{sub TMAO} to the dummy sites. The force field model developed here improves both structural and dynamical properties of aqueous TMAO solutions. Moreover, it reproduces the experimentally observed dependence of viscosity upon increasingmore » TMAO concentration quantitatively. The simple procedure of the force field construction makes it easy to implement in molecular dynamics simulation packages and makes it compatible with the existing biomolecular force fields. This paves the path for further investigation of protein-TMAO interaction in aqueous solutions.« less

Biosorption of Acid Black 172 and Congo Red from aqueous solution by nonviable Penicillium YW 01: kinetic study, equilibrium isotherm and artificial neural network modeling.

PubMed

Yang, Yuyi; Wang, Guan; Wang, Bing; Li, Zeli; Jia, Xiaoming; Zhou, Qifa; Zhao, Yuhua

2011-01-01

The main objective of this work was to investigate the biosorption performance of nonviable Penicillium YW 01 biomass for removal of Acid Black 172 metal-complex dye (AB) and Congo Red (CR) in solutions. Maximum biosorption capacities of 225.38 and 411.53 mg g(-1) under initial dye concentration of 800 mg L(-1), pH 3.0 and 40 °C conditions were observed for AB and CR, respectively. Biosorption data were successfully described with Langmuir isotherm and the pseudo-second-order kinetic model. The Weber-Morris model analysis indicated that intraparticle diffusion was the limiting step for biosorption of AB and CR onto biosorbent. Analysis based on the artificial neural network and genetic algorithms hybrid model indicated that initial dye concentration and temperature appeared to be the most influential parameters for biosorption process of AB and CR onto biosorbent, respectively. Characterization of the biosorbent and possible dye-biosorbent interaction were confirmed by Fourier transform infrared spectroscopy and scanning electron microscopy. Copyright © 2010 Elsevier Ltd. All rights reserved.

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study.

PubMed

Guo, Xugeng; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Zhang, Jinglai

2016-04-21

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solventwater has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in watersolution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.

Three-dimensional Printed Acrylonitrile Butadiene Styrene Framework Coated with Cu-BTC Metal-organic Frameworks for the Removal of Methylene Blue

PubMed Central

Wang, Zongyuan; Wang, Jiajun; Li, Minyue; Sun, Kaihang; Liu, Chang-jun

2014-01-01

Three-dimensional (3D) printing was applied for the fabrication of acrylonitrile butadiene styrene (ABS) framework. Functionalization of the ABS framework was then performed by coating of porous Cu-BTC (BTC = benzene tricarboxylic acid) metal-organic frameworks on it using a step-by-step in-situ growth. The size of the Cu-BTC particles on ABS was ranged from 200 nm to 900 nm. The Cu-BTC/ABS framework can take up most of the space of the tubular reactor that makes the adsorption effective with no need of stirring. Methylene blue (MB) can be readily removed from aqueous solution by this Cu-BTC/ABS framework. The MB removal efficiency for solutions with concentrations of 10 and 5 mg/L was 93.3% and 98.3%, respectively, within 10 min. After MB adsorption, the Cu-BTC/ABS composite can easily be recovered without the need for centrifugation or filtration and the composite is reusable. In addition the ABS framework can be recovered for subsequent reuse. A significant advantage of 3D-printed frameworks is that different frameworks can be easily fabricated to meet the needs of different applications. This is a promising strategy to synthesize new frameworks using MOFs and polymers to develop materials for applications beyond adsorption. PMID:25089616

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study

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

Guo, Xugeng, E-mail: xgguo@henu.edu.cn, E-mail: zhangjinglai@henu.edu.cn; Yuan, Huijuan; An, Beibei

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S{sub 1}more » state, which may undergo an ultrafast non-radiative deactivation to the S{sub 0} state. The lifetime of the S{sub 1} state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solvent water has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in water solution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.« less

Controlling the Formation of Ionic-Liquid-based Aqueous Biphasic Systems by Changing the Hydrogen-Bonding Ability of Polyethylene Glycol End Groups.

PubMed

Pereira, Jorge F B; Kurnia, Kiki A; Freire, Mara G; Coutinho, João A P; Rogers, Robin D

2015-07-20

The formation of aqueous biphasic systems (ABS) when mixing aqueous solutions of polyethylene glycol (PEG) and an ionic liquid (IL) can be controlled by modifying the hydrogen-bond-donating/-accepting ability of the polymer end groups. It is shown that the miscibility/immiscibility in these systems stems from both the solvation of the ether groups in the oxygen chain and the ability of the PEG terminal groups to preferably hydrogen bond with water or the anion of the salt. The removal of even one hydrogen bond in PEG can noticeably affect the phase behavior, especially in the region of the phase diagram in which all the ethylene oxide (EO) units of the polymeric chain are completely solvated. In this region, removing or weakening the hydrogen-bond-donating ability of PEG results in greater immiscibility, and thus, in a higher ability to form ABS, as a result of the much weaker interactions between the IL anion and the PEG end groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular dynamics simulations of aqueous solutions of ethanolamines.

PubMed

López-Rendón, Roberto; Mora, Marco A; Alejandre, José; Tuckerman, Mark E

2006-08-03

We report on molecular dynamics simulations performed at constant temperature and pressure to study ethanolamines as pure components and in aqueous solutions. A new geometric integration algorithm that preserves the correct phase space volume is employed to study molecules having up to three ethanol chains. The most stable geometry, rotational barriers, and atomic charges were obtained by ab initio calculations in the gas phase. The calculated dipole moments agree well with available experimental data. The most stable conformation, due to intramolecular hydrogen bonding interactions, has a ringlike structure in one of the ethanol chains, leading to high molecular stability. All molecular dynamics simulations were performed in the liquid phase. The interaction parameters are the same for the atoms in the ethanol chains, reducing the number of variables in the potential model. Intermolecular hydrogen bonding is also analyzed, and it is shown that water associates at low water mole fractions. The force field reproduced (within 1%) the experimental liquid densities at different temperatures of pure components and aqueous solutions at 313 K. The excess and partial molar volumes are analyzed as a function of ethanolamine concentration.

APTES Functionalized Iron Oxide-Silver Magnetic Hetero-Nanocomposites for Selective Capture and Rapid Removal of Salmonella enteritidis from Aqueous Solution

NASA Astrophysics Data System (ADS)

Trang, Vu Thi; Dinh, Ngo Xuan; Lan, Hoang; Tam, Le Thi; Huy, Tran Quang; Tuan, Pham Anh; Phan, Vu Ngoc; Le, Anh-Tuan

2018-02-01

Magnetic nanomaterials, as a promising platform for the fast and sensitive detection of bacterial pathogens, have attracted increasing interest from researchers in recent years. In this work, by utilizing a two-step synthetic technique consisting of co-precipitation and subsequent hydrothermal reaction, followed by functionalization steps with (3-aminopropyl)triethoxysilane (APTES) and the antibody against Salmonella enteritidis, antibody-conjugated Fe3O4-Ag@APTES hetero-nanocomposites were successfully prepared. Due to the specific antibody, the developed Fe3O4-Ag@APTES@SE-Ab conjugates are capable of selectively capturing S. enteritidis at a low concentration of about 101 CFU/mL. Moreover, the prepared magnetic conjugates also revealed that the S. enteritidis could be rapidly removed from water solution in 20 min by using an external magnetic field with a removal efficiency obtained of ˜ 91.36%. These results indicated that the Fe3O4-Ag@APTES@SE-Ab conjugates are promising for the rapid selective capture and removal of bacterial pathogens from aqueous environments, and can be used for improving the detection quality of pathogens in water samples using immunosensor-based diagnostic tests.

Structure and dynamics of phosphate ion in aqueous solution: an ab initio QMCF MD study.

PubMed

Pribil, Andreas B; Hofer, Thomas S; Randolf, Bernhard R; Rode, Bernd M

2008-11-15

A simulation of phosphate in aqueous solution was carried out employing the new QMCF MD approach which offers the possibility to investigate composite systems with the accuracy of a QMMM method but without the time consuming creation of solute-solvent potential functions. The data of the simulations give a clear picture of the hydration shells of the phosphate anion. The first shell consists of 13 water molecules and each oxygen of the phosphate forms in average three hydrogens bonds to different solvent molecules. Several structural parameters such as radial distribution functions and coordination number distributions allow to fully characterize the embedding of the highly charged phosphate ion in the solvent water. The dynamics of the hydration structure of phosphate are described by mean residence times of the solvent molecules in the first hydration shell and the water exchange rate. 2008 Wiley Periodicals, Inc.

Structure and dynamics of the UO(2)(2+) ion in aqueous solution: an ab initio QMCF MD study.

PubMed

Frick, Robert J; Hofer, Thomas S; Pribil, Andreas B; Randolf, Bernhard R; Rode, Bernd M

2009-11-12

A comprehensive theoretical investigation on the structure and dynamics of the UO(2)(2+) ion in aqueous solution using double-zeta HF level quantum mechanical charge field molecular dynamics is presented. The quantum mechanical region includes two full layers of hydration and is embedded in a large box of explicitly treated water to achieve a realistic environment. A number of different functions, including segmential, radial, and angular distribution functions, are employed together with tilt- and Theta-angle distribution functions to describe the complex structural properties of this ion. These data were compared to recent experimental data obtained from LAXS and EXAFS and results of various theoretical calculations. Some properties were explained with the aid of charge distribution plots for the solute. The solvent dynamics around the ion were investigated using distance plots and mean ligand residence times and the results compared to experimental and theoretical data of related ions.

Separation of acid blue 25 from aqueous solution using water lettuce and agro-wastes by batch adsorption studies

NASA Astrophysics Data System (ADS)

Kooh, Muhammad Raziq Rahimi; Dahri, Muhammad Khairud; Lim, Linda B. L.; Lim, Lee Hoon; Chan, Chin Mei

2018-05-01

Three plant-based materials, namely water lettuce (WL), tarap peel (TP) and cempedak peel (CP), were used to investigate their potentials as adsorbents using acid blue 25 (AB25) dye as a model for acidic dye. The adsorbents were characterised using Fourier transform infrared spectroscopy, X-ray fluorescence and scanning electron microscope. Batch experiments involving parameters such as pH, temperature, contact time, and initial dye concentration were done to investigate the optimal conditions for the adsorption of AB25 onto the adsorbents. Thermodynamics study showed that the uptake of AB25 by the three adsorbents was feasible and endothermic in nature. Both the Langmuir and Freundlich isotherm models can be used to describe the adsorption process of AB25 onto WL and CP while pseudo-second-order fitted the kinetics data, suggesting that chemisorptions were majorly involved. The use of 0.1 M of NaOH showed the best results in regenerating of the WL, TP and CP's adsorption ability after AB25 treatment.

Radiolytic Synthesis of Pt-Particle/ABS Catalysts for H₂O₂ Decomposition in Contact Lens Cleaning.

PubMed

Ohkubo, Yuji; Aoki, Tomonori; Seino, Satoshi; Mori, Osamu; Ito, Issaku; Endo, Katsuyoshi; Yamamura, Kazuya

2017-08-23

A container used in contact lens cleaning requires a Pt plating weight of 1.5 mg for H₂O₂ decomposition although Pt is an expensive material. Techniques that decrease the amount of Pt are therefore needed. In this study, Pt nanoparticles instead of Pt plating film were supported on a substrate of acrylonitrile-butadiene-styrene copolymer (ABS). This was achieved by the reduction of Pt ions in an aqueous solution containing the ABS substrate using high-energy electron-beam irradiation. Pt nanoparticles supported on the ABS substrate (Pt-particle/ABS) had a size of 4-10 nm. The amount of Pt required for Pt-particle/ABS was 250 times less than that required for an ABS substrate covered with Pt plating film (Pt-film/ABS). The catalytic activity for H₂O₂ decomposition was estimated by measuring the residual H₂O₂ concentration after immersing the catalyst for 360 min. The Pt-particle/ABS catalyst had a considerably higher specific catalytic activity for H₂O₂ decomposition than the Pt-film/ABS catalyst. In addition, sterilization performance was estimated from the initial rate of H₂O₂ decomposition over 60 min. The Pt-particle/ABS catalyst demonstrated a better sterilization performance than the Pt-film/ABS catalyst. The difference between Pt-particle/ABS and Pt-film/ABS was shown to reflect the size of the O₂ bubbles formed during H₂O₂ decomposition.

Ti-substituted tunnel-type Na 0.44MnO 2 oxide as a negative electrode for aqueous sodium-ion batteries

DOE PAGES

Wang, Yuesheng; Liu, Jue; Lee, Byungju; ...

2015-03-25

The aqueous sodium-ion battery system is a safe and low-cost solution for large-scale energy storage, due to the abundance of sodium and inexpensive aqueous electrolytes. Although several positive electrode materials, e.g., Na 0.44MnO 2, were proposed, few negative electrode materials, e.g., activated carbon and NaTi 2(PO 4) 3, are available. Here we show that Ti-substituted Na 0.44MnO 2 (Na 0.44[Mn 1-xTi x]O 2) with tunnel structure can be used as a negative electrode material for aqueous sodium-ion batteries. This material exhibits superior cyclability even without the special treatment of oxygen removal from the aqueous solution. Atomic-scale characterizations based on sphericalmore » aberration-corrected electron microscopy and ab initio calculations are utilized to accurately identify the Ti substitution sites and sodium storage mechanism. Ti substitution tunes the charge ordering property and reaction pathway, significantly smoothing the discharge/charge profiles and lowering the storage voltage. Both the fundamental understanding and practical demonstrations suggest that Na 0.44[Mn 1-xTi x]O 2 is a promising negative electrode material for aqueous sodium-ion batteries.« less

Transport behaviors of anionic azo dyes at interface between surfactant-modified flax shives and aqueous solution: Synchrotron infrared and adsorption studies

NASA Astrophysics Data System (ADS)

Wang, Wenxia; Huang, Guohe; An, Chunjiang; Xin, Xiaying; Zhang, Yan; Liu, Xia

2017-05-01

From the viewpoint of sustainability, biomass adsorbent has a high potential in pollution control and there is an emerging interest to investigate the behaviors of pollutants at the interface between biomass adsorbent and solution. This study investigated the performance of cetyltrimethylammonium bromide surfactant-modified flax shives (MFS) for removal of anionic azo dyes from aqueous solution. The equilibrium and kinetic analysis for the adsorption of Acid Orange 7 (AO-7), Acid Red 18 (AR-18) and Acid Black 1 (AB-1) on MFS were conducted. The surface of MFS was characterized by synchrotron infrared and SEM analysis. The absorbed amount of three anionic azo dyes varied with the change of adsorbent dosage, pH and ionic strength. The adsorption isotherm data well fit to the Langmuir model. The adsorption process followed the pseudo-second-order kinetics and the liquid film diffusion models. Thermodynamic studies indicated that the adsorption of three anionic azo dyes was spontaneous. The adsorption of AR-18 and AB-1 onto MFS was endothermic while the adsorption of AO-7 was exothermic. The results can help better understand the behaviors of organic pollutants at biomass adsorbent-water interface. They also present the potential of using MFS as a suitable adsorbent for the removal of anionic azo dyes from wastewater.

On the structure and dynamics of the hydrated sulfite ion in aqueous solution--an ab initio QMCF MD simulation and large angle X-ray scattering study.

PubMed

Eklund, Lars; Hofer, Thomas S; Pribil, Andreas B; Rode, Bernd M; Persson, Ingmar

2012-05-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) formalism has been applied in conjunction to experimental large angle X-ray scattering to study the structure and dynamics of the hydrated sulfite ion in aqueous solution. The results show that there is a considerable effect of the lone electron-pair on sulfur concerning structure and dynamics in comparison with the sulfate ion with higher oxidation number and symmetry of the hydration shell. The S-O bond distance in the hydrated sulfite ion has been determined to 1.53(1) Å by both methods. The hydrogen bonds between the three water molecules bound to each sulfite oxygen are only slightly stronger than those in bulk water. The sulfite ion can therefore be regarded as a weak structure maker. The water exchange rate is somewhat slower for the sulfite ion than for the sulfate ion, τ(0.5) = 3.2 and 2.6 ps, respectively. An even more striking observation in the angular radial distribution (ARD) functions is that the for sulfite ion the water exchange takes place in close vicinity of the lone electron-pair directed at its sides, while in principle no water exchange did take place of the water molecules hydrogen bound to sulfite oxygens during the simulation time. This is also confirmed when detailed pathway analysis is conducted. The simulation showed that the water molecules hydrogen bound to the sulfite oxygens can move inside the hydration shell to the area outside the lone electron-pair and there be exchanged. On the other hand, for the hydrated sulfate ion in aqueous solution one can clearly see from the ARD that the distribution of exchange events is symmetrical around the entire hydration sphere.

Preparation of surface modified zinc oxide nanoparticle with high capacity dye removal ability

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

Mahmoodi, Niyaz Mohammad, E-mail: nm_mahmoodi@yahoo.com; Najafi, Farhood

2012-07-15

Highlights: ► Amine-functionalized zinc oxide nanoparticle (AFZON) was synthesized. ► Isotherm and kinetics data followed Langmuir isotherm and pseudo-second order kinetic model, respectively. ► Q{sub 0} of ZON for AB25, DR23 and DR31 was 20, 12 and 15 mg/g, respectively. ► Q{sub 0} of AFZON for AB25, DR23 and DR31 was 1250, 1000 and 1429 mg/g, respectively. ► AFZON was regenerated at pH 12. -- Abstract: In this paper, the surface modification of zinc oxide nanoparticle (ZON) by amine functionalization was studied to prepare high capacity adsorbent. Dye removal ability of amine-functionalized zinc oxide nanoparticle (AFZON) and zinc oxide nanoparticlemore » (ZON) was also investigated. The physical characteristics of AFZON were studied using Fourier transform infrared (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Acid Blue 25 (AB25), Direct Red 23 (DR23) and Direct Red 31 (DR31) were used as model compounds. The effect of operational parameters such as dye concentration, adsorbent dosage, pH and salt on dye removal was evaluated. The isotherm and kinetic of dye adsorption were studied. The maximum dye adsorption capacity (Q{sub 0}) was 20 mg/g AB25, 12 mg/g DR23 and 15 mg/g DR31 for ZON and 1250 mg/g AB25, 1000 mg/g DR23 and 1429 mg/g DR31 for AFZON. It was found that dye adsorption followed Langmuir isotherm. Adsorption kinetic of dyes was found to conform to pseudo-second order kinetics. Dye desorption tests (adsorbent regeneration) showed that the maximum dye release of 90% AB25, 86% for DR23 and 90% for DR31 were achieved in aqueous solution at pH 12. Based on the data of the present investigation, it can be concluded that the AFZON being an adsorbent with high dye adsorption capacity might be a suitable alternative to remove dyes from colored aqueous solutions.« less

CO2 capture in amine solutions: modelling and simulations with non-empirical methods

NASA Astrophysics Data System (ADS)

Andreoni, Wanda; Pietrucci, Fabio

2016-12-01

Absorption in aqueous amine solutions is the most advanced technology for the capture of CO2, although suffering from drawbacks that do not allow exploitation on large scale. The search for optimum solvents has been pursued with empirical methods and has also motivated a number of computational approaches over the last decade. However, a deeper level of understanding of the relevant chemical reactions in solution is required so as to contribute to this effort. We present here a brief critical overview of the most recent applications of computer simulations using ab initio methods. Comparison of their outcome shows a strong dependence on the structural models employed to represent the molecular systems in solution and on the strategy used to simulate the reactions. In particular, the results of very recent ab initio molecular dynamics augmented with metadynamics are summarized, showing the crucial role of water, which has been so far strongly underestimated both in the calculations and in the interpretation of experimental data. Indications are given for advances in computational approaches that are necessary if meant to contribute to the rational design of new solvents.

Preparation of metallic nanoparticles by irradiation in starch aqueous solution

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

Nemţanu, Monica R., E-mail: monica.nemtanu@inflpr.ro; Braşoveanu, Mirela, E-mail: monica.nemtanu@inflpr.ro; Iacob, Nicuşor, E-mail: monica.nemtanu@inflpr.ro

Colloidal silver nanoparticles (AgNPs) were synthesized in a single step by electron beam irradiation reduction of silver ions in aqueous solution containing starch. The nanoparticles were characterized by spectrophotocolorimetry and compared with those obtained by chemical (thermal) reduction method. The results showed that the smaller sizes of AgNPs were prepared with higher yields as the irradiation dose increased. The broadening of particle size distribution occurred by increasing of irradiation dose and dose rate. Chromatic parameters such as b* (yellow-blue coordinate), C* (chroma) and ΔE{sub ab} (total color difference) could characterize the nanoparticles with respect of their concentration. Hue angle h{supmore » o} was correlated to the particle size distribution. Experimental data of the irradiated samples were also subjected to factor analysis using principal component extraction and varimax rotation in order to reveal the relation between dependent variables and independent variables and to reduce their number. The radiation-based method provided silver nanoparticles with higher concentration and narrower size distribution than those produced by chemical reduction method. Therefore, the electron beam irradiation is effective for preparation of silver nanoparticles using starch aqueous solution as dispersion medium.« less

Ab initio investigation of the surface properties of austenitic Fe-Ni-Cr alloys in aqueous environments

NASA Astrophysics Data System (ADS)

Rák, Zs.; Brenner, D. W.

2017-04-01

The surface energetics of two austenitic stainless steel alloys (Type 304 and 316) and three Ni-based alloys (Alloy 600, 690, and 800) are investigated using theoretical methods within the density functional theory. The relative stability of the low index surfaces display the same trend for all alloys; the most closely packed orientation and the most stable is the (111), followed by the (100) and the (110) surfaces. Calculations on the (111) surfaces using various surface chemical and magnetic configurations reveal that Ni has the tendency to segregate toward the surface and Cr has the tendency to segregate toward the bulk. The magnetic frustration present on the (111) surfaces plays an important role in the observed segregation tendencies of Ni and Cr. The stability of the (111) surfaces in contact with aqueous solution are evaluated as a function of temperature, pH, and concentration of aqueous species. The results indicate that the surface stability of the alloys decrease with temperature and pH, and increase slightly with concentration. Under conditions characteristic to an operating pressurized water reactor, the Ni-based alloy series appears to be of better quality than the stainless steel series with respect to corrosion resistance and release of aqueous species when in contact with aqueous solutions.

Enhanced removal of bisphenol-AF by activated carbon-alginate beads with cetyltrimethyl ammonium bromide.

PubMed

Tang, Zheng; Peng, Sha; Hu, Shuya; Hong, Song

2017-06-01

Adsorption removal of bisphenol-AF (BPAF) from aqueous solutions by synthesized activated carbon-alginate beads (AC-AB) with cetyltrimethyl ammonium bromide (CTAB) has been studied using two ways. The traditional method (two-step) first synthesized CTAB-modified AC-AB (AC-AB-CTAB), then used it to remove BPAF by adsorption. And one-step method dispersed AC-AB and CTAB in wastewater, followed by the removal of BPAF accompanied with the synthesis of AC-AB-CTAB. The one-step method showed a better performance than the two-step method, achieving a maximum removal of BPAF with 284.6mg/g. Kinetic studies and adsorption isotherms indicated that adsorption process of BPAF on AC-AB by the one-step method could be expressed by a pseudo-second-order model and a Dubinin-Ashtakhov (D-A) isotherm, respectively. The effects of pH, ionic strength, and inorganic ions on BPAF adsorption were also investigated. Furthermore, hydrophobic interactions, hydrogen bonds, and π-π electron donor-acceptor (EDA) interactions were discussed to explain the enhanced adsorption behavior of BPAF on AC-AB with CTAB. The findings verified the effectiveness of AC-AB for the removal of BPAF from wastewater and its high stability within five regeneration cycles. Copyright © 2017 Elsevier Inc. All rights reserved.

Tautomeric equilibria of 5-fluorouracil anionic species in water.

PubMed

Markova, Nadezhda; Enchev, Venelin; Ivanova, Galya

2010-12-23

It has long been postulated that rare tautomeric or ionized forms of nucleic acid bases may play a role in mispair formation. Therefore, ab initio quantum chemical investigations on the tautomeric equilibrium in 5-fluorouracil (5FU) and its anions (deprotonated from N1, AN1, and from N3, AN3) and their tautomeric forms in water were performed. The effect of the water as solvent was introduced using solute-solvent clusters (four water molecules). The influence of the water molecules on the tautomeric reactions between different forms was considered by multiple proton transfer mechanisms. We show that when a water dimer is located in the reaction site between the two pairs of N-H and C═O groups, the assistive effect of the water molecules is strengthened. All calculations of the solute-water complexes were carried out at an MP2 level of theory and supplemented with correction for higher order correlation terms at CCSD(T) level, using the 6-31+G(d,p) basis set. The ab initio calculated frequencies and Raman intensities of 5FU and its anions AN1, AN3, and dianion are in good agreement with the experimental Raman frequencies in aqueous solution at different pH. In order to establish the pH-induced structural transformation in the molecule of 5FU, further (1)H, (19)F, and (13)C NMR spectra in water solution for pH = 6.9-13.8 were acquired and the chemical shift alterations were determined as a function of pH. On the basis of NMR spectroscopic data obtained for 5FU in aqueous solution at alkaline pH, we suggest the existence of a mixture of the anionic tautomeric forms predicted by our theoretical calculations.

Bicanonical ab Initio Molecular Dynamics for Open Systems.

PubMed

Frenzel, Johannes; Meyer, Bernd; Marx, Dominik

2017-08-08

Performing ab initio molecular dynamics simulations of open systems, where the chemical potential rather than the number of both nuclei and electrons is fixed, still is a challenge. Here, drawing on bicanonical sampling ideas introduced two decades ago by Swope and Andersen [ J. Chem. Phys. 1995 , 102 , 2851 - 2863 ] to calculate chemical potentials of liquids and solids, an ab initio simulation technique is devised, which introduces a fictitious dynamics of two superimposed but otherwise independent periodic systems including full electronic structure, such that either the chemical potential or the average fractional particle number of a specific chemical species can be kept constant. As proof of concept, we demonstrate that solvation free energies can be computed from these bicanonical ab initio simulations upon directly superimposing pure bulk water and the respective aqueous solution being the two limiting systems. The method is useful in many circumstances, for instance for studying heterogeneous catalytic processes taking place on surfaces where the chemical potential of reactants rather than their number is controlled and opens a pathway toward ab initio simulations at constant electrochemical potential.

Nanostructured ZnO-TiO2 thin film oxide as anode material in electrooxidation of organic pollutants. Application to the removal of dye Amido black 10B from water.

PubMed

El-Kacemi, Sana; Zazou, Hicham; Oturan, Nihal; Dietze, Matthias; Hamdani, Mohamed; Es-Souni, Mohammed; Oturan, Mehmet A

2017-01-01

Electrochemical oxidative degradation of diazo dye Amido black 10B (AB10B) as model pollutant in water has been studied using nanostructured ZnO-TiO 2 thin films deposited on graphite felt (GrF) substrate as anode. The influence of various operating parameters, namely the current intensity, the nature and concentration of catalyst, the nature of electrode materials (anode/cathode), and the adsorption of dye and ambient light were investigated. It was found that the oxidative degradation of AB10B followed pseudo first-order kinetics. The optimal operating conditions for the degradation of 0.12 mM (74 mg L -1 ) dye concentration and mineralization of its aqueous solution were determined as GrF-ZnO-TiO 2 thin film anode, 100 mA current intensity, and 0.1 mM Fe 2+ (catalyst) concentration. Under these operating conditions, discoloration of AB10B solution was reached at 60 min while 6 h treatment needed for a mineralization degree of 91 %. Therefore, this study confirmed that the electrochemical process is effective for the degradation of AB10B in water using nanostructured ZnO-TiO 2 thin film anodes.

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

PubMed

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

2010-09-02

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

Solvation and Aggregation of Meta-Aminobenzoic Acid in Water: Density Functional Theory and Molecular Dynamics Study

PubMed Central

Gaines, Etienne

2018-01-01

Meta-aminobenzoic acid, an important model system in the study of polymorphism and crystallization of active pharmaceutical ingredients, exist in water in both the nonionic (mABA) and zwitterionic (mABA±) forms. However, the constituent molecules of the polymorph that crystallizes from aqueous solutions are zwitterionic. This study reports atomistic simulations of the events surrounding the early stage of crystal nucleation of meta-aminobenzoic acid from aqueous solutions. Ab initio molecular dynamics was used to simulate the hydration of mABA± and mABA and to quantify the interaction of these molecules with the surrounding water molecules. Density functional theory calculations were conducted to determine the low-lying energy conformers of meta-aminobenzoic acid dimers and to compute the Gibbs free energies in water of nonionic, (mABA)2, zwitterionic, (mABA±)2, and nonionic-zwitterionic, (mABA)(mABA±), species. Classical molecular dynamics simulations of mixed mABA–mABA± aqueous solutions were carried out to examine the aggregation of meta-aminobenzoic acid. According to these simulations, the selective crystallization of the polymorphs whose constituent molecules are zwitterionic is driven by the formation of zwitterionic dimers in solution, which are thermodynamically more stable than (mABA)2 and (mABA)(mABA±) pairs. This work represents a paradigm of the role of molecular processes during the early stages of crystal nucleation in affecting polymorph selection during crystallization from solution. PMID:29360788

Vibrational mode frequencies of silica species in SiO2-H2O liquids and glasses from ab initio molecular dynamics.

PubMed

Spiekermann, Georg; Steele-MacInnis, Matthew; Schmidt, Christian; Jahn, Sandro

2012-04-21

Vibrational spectroscopy techniques are commonly used to probe the atomic-scale structure of silica species in aqueous solution and hydrous silica glasses. However, unequivocal assignment of individual spectroscopic features to specific vibrational modes is challenging. In this contribution, we establish a connection between experimentally observed vibrational bands and ab initio molecular dynamics (MD) of silica species in solution and in hydrous silica glass. Using the mode-projection approach, we decompose the vibrations of silica species into subspectra resulting from several fundamental structural subunits: The SiO(4) tetrahedron of symmetry T(d), the bridging oxygen (BO) Si-O-Si of symmetry C(2v), the geminal oxygen O-Si-O of symmetry C(2v), the individual Si-OH stretching, and the specific ethane-like symmetric stretching contribution of the H(6)Si(2)O(7) dimer. This allows us to study relevant vibrations of these subunits in any degree of polymerization, from the Q(0) monomer up to the fully polymerized Q(4) tetrahedra. Demonstrating the potential of this approach for supplementing the interpretation of experimental spectra, we compare the calculated frequencies to those extracted from experimental Raman spectra of hydrous silica glasses and silica species in aqueous solution. We discuss observed features such as the double-peaked contribution of the Q(2) tetrahedral symmetric stretch, the individual Si-OH stretching vibrations, the origin of the experimentally observed band at 970 cm(-1) and the ethane-like vibrational contribution of the H(6)Si(2)O(7) dimer at 870 cm(-1).

Modeling the IR spectra of aqueous metal carboxylate complexes: correlation between bonding geometry and stretching mode wavenumber shifts.

PubMed

Sutton, Catherine C R; da Silva, Gabriel; Franks, George V

2015-04-27

A widely used principle is that shifts in the wavenumber of carboxylate stretching modes upon bonding with a metal center can be used to infer if the geometry of the bonding is monodentate or bidentate. We have tested this principle with ab initio modeling for aqueous metal carboxylate complexes and have shown that it does indeed hold. Modeling of the bonding of acetate and formate in aqueous solution to a range of cations was used to predict the infrared spectra of the metal-carboxylate complexes, and the wavenumbers of the symmetric and antisymmetric vibrational modes are reported. Furthermore, we have shown that these shifts in wavenumber occur primarily due to how bonding with the metal changes the carboxylate C-O bond lengths and O-C-O angle. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zero-field splitting in the isoelectronic aqueous Gd(III) and Eu(II) complexes from a first principles analysis

NASA Astrophysics Data System (ADS)

Khan, S.; Peters, V.; Kowalewski, J.; Odelius, M.

2018-03-01

The zero-field splitting (ZFS) of the ground state octet in aqueous Eu(II) and Gd(III) solutions was investigated through multi- configurational quantum chemical calculations and ab initio molecular dynamics (AIMD) simulations. Investigation of the ZFS of the lanthanide ions is essential to understand the electron spin dynamics and nuclear spin relaxation around paramagnetic ions and consequently the mechanisms underlying applications like magnetic resonance imaging. We found by comparing clusters at identical geometries but different metallic centres that there is not a simple relationship for their ZFS, in spite of the complexes being isoelectronic - each containing 7 unpaired f electrons. Through sampling it was established that inclusion of the first hydration shell has a dominant (over 90 %) influence on the ZFS. Extended sampling of aqueous Gd(III) showed that the 2 nd order spin Hamiltonian formalism is valid and that the rhombic ZFS component is decisive.

Aluminum speciation in aqueous fluids at deep crustal pressure and temperature

NASA Astrophysics Data System (ADS)

Mookherjee, Mainak; Keppler, Hans; Manning, Craig E.

2014-05-01

We investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 °C. We have studied aluminum species in (a) pure H2O, (b) 5.3 m KOH solution, and (c) 1 m KOH solution. In order to better understand the spectral features of the aqueous fluids, we used ab initio simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with 5.3 m and 1 m KOH solution in equilibrium with Al2O3 show a sharp band at ˜620 cm-1 which could be attributed to the [ species. The band grows in intensity with temperature along an isochore. A shoulder on the high-frequency side of this band may be due to a hydrated, charge neutral Al(OH)3·H2O species. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [ species to dimers [(OH)2-Al-(OH)2-Al(OH)2] or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. Upon cooling of Al-bearing solutions to room temperatures, Raman bands indicating the precipitation of diaspore (AlOOH) were observed in some experiments. The Raman spectra of the KOH solutions (with or without dissolved alumina) showed a sharp OH stretching band at ˜3614 cm-1 and an in-plane OH bending vibration at ˜1068 cm-1, likely related to an OH- ion with the oxygen atom attached to a water molecule by hydrogen bonding. A weak feature at ˜935 cm-1 may be related to the out-of-plane bending vibration of the same species or to an OH species with a different environment.

Labeling of monoclonal antibodies with a 67Ga-phenolic aminocarboxylic acid chelate. Part I. Chemistry and labeling technique.

PubMed

Schuhmacher, J; Matys, R; Hauser, H; Maier-Borst, W; Matzku, S

1986-01-01

As a chelating agent for labeling antibodies (Abs) with metallic radionuclides, a propionic acid substituted ethylenediamine N,N'-di-[(o-hydroxyphenyl) acetic acid] (P-EDDHA), which tightly complexes 67Ga, was synthesized. The 67Ga-P-EDDHA chelate was coupled in aqueous solution to IgG at a molar ratio of 1:1 via carbodiimide. The average coupling yield was 15%. A specific activity of 4 mCi/mg IgG could be obtained with commercially supplied 67Ga. In vitro stability was evaluated in human serum at 37 degrees C and showed a half-life of about 120 h for the release of 67Ga from the labeled Ab during the initial phase of incubation. This in vitro halflife is similar to that measured for 111In-DTPA labeled Abs. Because of the high stability of the 67Ga-P-EDDHA chelate, the in vivo formation of radioactive labeled transferrin by transchelation, as described for 111In-DTPA labeled Abs, should, however, be reduced by this labeling technique.

Stability of carbon electrodes for aqueous lithium-air secondary batteries

NASA Astrophysics Data System (ADS)

Ohkuma, Hirokazu; Uechi, Ichiro; Matsui, Masaki; Takeda, Yasuo; Yamamoto, Osamu; Imanishi, Nobuyuki

2014-01-01

The air electrode performance of various carbon materials, such as Ketjen black (KB), acetylene black (AB and AB-S), Vulcan XC-72R (VX), and vapor grown carbon fiber (VGCF) with and without La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) catalyst were examined in an aqueous solution of saturated LiOH with 10 M LiCl in the current density range 0.2-2.0 mA cm-2. The best performance for oxygen reduction and evolution reactions was observed for the KB electrode, which has the highest surface area among the carbon materials examined. A steady over-potential of 0.2 V was obtained for the oxygen reduction reaction using the KB electrode without the catalyst, while the over-potential was 0.15 V for KB with the LSCF catalyst at 2.0 mA cm-2. The over-potentials for the oxygen evolution reaction were slightly higher than those for the oxygen reduction reaction, and gradually increased with the polarization period. Analysis of the gas in the cell after polarization above 0.4 V revealed the evolution of a small amount of CO during the oxygen evolution reaction by the decomposition of carbon in the electrode. The amount of CO evolved was significantly decreased by the addition of LSCF to the carbon electrode.

Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

NASA Astrophysics Data System (ADS)

Watkins, James M.; DePaolo, Donald J.; Ryerson, Frederick J.; Peterson, Brook T.

2011-06-01

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl 2Si 2O 8; denoted AN), albite (NaAlSi 3O 8; denoted AB), and diopside (CaMgSi 2O 6; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D Ca/ D Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D Ca/ D Si ≈ 1. In the AB-DI experiment, D Ca/ D Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D Mg/ D Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids. The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation ( D Ca) to the diffusivity of silicon ( D Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D cation/ D Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and Dcation/D, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.

Two-state model based on the block-localized wave function method

NASA Astrophysics Data System (ADS)

Mo, Yirong

2007-06-01

The block-localized wave function (BLW) method is a variant of ab initio valence bond method but retains the efficiency of molecular orbital methods. It can derive the wave function for a diabatic (resonance) state self-consistently and is available at the Hartree-Fock (HF) and density functional theory (DFT) levels. In this work we present a two-state model based on the BLW method. Although numerous empirical and semiempirical two-state models, such as the Marcus-Hush two-state model, have been proposed to describe a chemical reaction process, the advantage of this BLW-based two-state model is that no empirical parameter is required. Important quantities such as the electronic coupling energy, structural weights of two diabatic states, and excitation energy can be uniquely derived from the energies of two diabatic states and the adiabatic state at the same HF or DFT level. Two simple examples of formamide and thioformamide in the gas phase and aqueous solution were presented and discussed. The solvation of formamide and thioformamide was studied with the combined ab initio quantum mechanical and molecular mechanical Monte Carlo simulations, together with the BLW-DFT calculations and analyses. Due to the favorable solute-solvent electrostatic interaction, the contribution of the ionic resonance structure to the ground state of formamide and thioformamide significantly increases, and for thioformamide the ionic form is even more stable than the covalent form. Thus, thioformamide in aqueous solution is essentially ionic rather than covalent. Although our two-state model in general underestimates the electronic excitation energies, it can predict relative solvatochromic shifts well. For instance, the intense π →π* transition for formamide upon solvation undergoes a redshift of 0.3eV, compared with the experimental data (0.40-0.5eV).

Evidence for the interactions occurring between ionic liquids and tetraethylene glycol in binary mixtures and aqueous biphasic systems.

PubMed

Tomé, Luciana I N; Pereira, Jorge F B; Rogers, Robin D; Freire, Mara G; Gomes, José R B; Coutinho, João A P

2014-05-01

The well-recognized advantageous properties of poly(ethylene glycol)s (PEGs) and ionic liquids (ILs) in the context of an increasing demand for safe and efficient biotechnological processes has led to a growing interest in the study of their combinations for a wide range of procedures within the framework of green chemistry. Recently, one of the most promising and attractive applications has been the novel IL/polymer-based aqueous biphasic systems (ABS) for the extraction and purification of biomolecules. There still lacks, however, a comprehensive picture of the molecular phenomena that control the phase behavior of these systems. In order to further delve into the interactions that govern the mutual solubilities between ILs and PEGs and the formation of PEG/IL-based ABS, (1)H NMR spectroscopy in combination with classical molecular dynamics (MD) simulations performed for binary mixtures of tetraethylene glycol (TEG) and 1-alkyl-3-methylimidazolium-chloride-based ILs and for the corresponding ternary TEG/IL/water solutions, at T = 298.15 K, were employed in this work. The results of the simulations show that the mutual solubilities of the ILs and TEG are mainly governed by the hydrogen bonds established between the chloride anion and the -OH group of the polymer in the binary systems. Additionally, the formation of IL/PEG-based ABS is shown to be controlled by a competition between water and chloride for the interactions with the hydroxyl group of TEG.

Synergic adsorption in the simultaneous removal of acid blue 25 and heavy metals from water using a Ca(PO3)2-modified carbon.

PubMed

Tovar-Gómez, R; Rivera-Ramírez, D A; Hernández-Montoya, V; Bonilla-Petriciolet, A; Durán-Valle, C J; Montes-Morán, M A

2012-01-15

We report the simultaneous adsorption of acid blue 25 dye (AB25) and heavy metals (Zn(2+), Ni(2+) and Cd(2+)) on a low-cost activated carbon, whose adsorption properties have been improved via a surface chemistry modification using a calcium solution extracted from egg shell wastes. Specifically, we have studied the removal performance of this adsorbent using the binary aqueous systems: AB25-Cd(2+), AB25-Ni(2+) and AB25-Zn(2+). Multi-component kinetic and equilibrium experiments have been performed and used to identify and characterize the synergic adsorption in the simultaneous removal of these pollutants. Our results show that the presence of AB25 significantly favors the removal of heavy metals and may increase the adsorption capacities up to six times with respect to the results obtained using the mono-cationic metallic systems, while the adsorption capacities of AB25 are not affected by the presence of metallic ions. It appears that this anionic dye favors the electrostatic interactions with heavy metals or may create new specific sites for adsorption process. In particular, heavy metals may interact with the -SO(3)(-) group of AB25 and to the hydroxyl and phosphoric groups of this adsorbent. A response surface methodology model has been successfully used for fitting multi-component adsorption data. Copyright © 2011 Elsevier B.V. All rights reserved.

Nucleation of metastable aragonite CaCO3 in seawater.

PubMed

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A; Ceder, Gerbrand

2015-03-17

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.

Nucleation of metastable aragonite CaCO 3 in seawater

DOE PAGES

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; ...

2015-03-04

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters ofmore » surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. The ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.« less

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

Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei

Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters ofmore » surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing “calcite–aragonite problem”––the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite––which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg–Ca ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. The ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.« less

Development of a Scaled Quantum Mechanical Force Field for Peptides in Aqueous Solution

DTIC Science & Technology

1996-03-01

differ. Raman and IR techniques are complimentary which helps in assignment of observed vibrational modes. As described in beginning organic ...1588 I NH, .i.sor(98) 2076 2100 24 CH3 55(95) 2125 2207 82 CH3 as’ (56), CH3 as’ (43) 2235 2253 18 CH3 as’(55), CH3 as’(41) 2888 COff .(100) 3155 NH...Application of self- consistent-field ab initio calculations to organic molecules I. Equilibrium struc- ture and force constants of hydrocarbons

A Simplified Model of Local Structure in Aqueous Proline Amino Acid Revealed by First-Principles Molecular Dynamics Simulations

PubMed Central

Troitzsch, Raphael Z.; Tulip, Paul R.; Crain, Jason; Martyna, Glenn J.

2008-01-01

Aqueous proline solutions are deceptively simple as they can take on complex roles such as protein chaperones, cryoprotectants, and hydrotropic agents in biological processes. Here, a molecular level picture of proline/water mixtures is developed. Car-Parrinello ab initio molecular dynamics (CPAIMD) simulations of aqueous proline amino acid at the B-LYP level of theory, performed using IBM's Blue Gene/L supercomputer and massively parallel software, reveal hydrogen-bonding propensities that are at odds with the predictions of the CHARMM22 empirical force field but are in better agreement with results of recent neutron diffraction experiments. In general, the CPAIMD (B-LYP) simulations predict a simplified structural model of proline/water mixtures consisting of fewer distinct local motifs. Comparisons of simulation results to experiment are made by direct evaluation of the neutron static structure factor S(Q) from CPAIMD (B-LYP) trajectories as well as to the results of the empirical potential structure refinement reverse Monte Carlo procedure applied to the neutron data. PMID:18790850

A simplified model of local structure in aqueous proline amino acid revealed by first-principles molecular dynamics simulations.

PubMed

Troitzsch, Raphael Z; Tulip, Paul R; Crain, Jason; Martyna, Glenn J

2008-12-01

Aqueous proline solutions are deceptively simple as they can take on complex roles such as protein chaperones, cryoprotectants, and hydrotropic agents in biological processes. Here, a molecular level picture of proline/water mixtures is developed. Car-Parrinello ab initio molecular dynamics (CPAIMD) simulations of aqueous proline amino acid at the B-LYP level of theory, performed using IBM's Blue Gene/L supercomputer and massively parallel software, reveal hydrogen-bonding propensities that are at odds with the predictions of the CHARMM22 empirical force field but are in better agreement with results of recent neutron diffraction experiments. In general, the CPAIMD (B-LYP) simulations predict a simplified structural model of proline/water mixtures consisting of fewer distinct local motifs. Comparisons of simulation results to experiment are made by direct evaluation of the neutron static structure factor S(Q) from CPAIMD (B-LYP) trajectories as well as to the results of the empirical potential structure refinement reverse Monte Carlo procedure applied to the neutron data.

Understanding THz spectra of aqueous solutions: glycine in light and heavy water.

PubMed

Sun, Jian; Niehues, Gudrun; Forbert, Harald; Decka, Dominique; Schwaab, Gerhard; Marx, Dominik; Havenith, Martina

2014-04-02

THz spectroscopy of aqueous solutions has been established as of recently to be a valuable and complementary experimental tool to provide direct insights into the solute-solvent coupling due to hydrogen-bond dynamics involving interfacial water. Despite much experimental progress, understanding THz spectra in terms of molecular motions, akin to mid-infrared spectra, still remains elusive. Here, using the osmoprotectant glycine as a showcase, we demonstrate how this can be achieved by combining THz absorption spectroscopy and ab initio molecular dynamics. The experimental THz spectrum is characterized by broad yet clearly discernible peaks. Based on substantial extensions of available mode-specific decomposition schemes, the experimental spectrum can be reproduced by theory and assigned on an essentially quantitative level. This joint effort reveals an unexpectedly clear picture of the individual contributions of molecular motion to the THz absorption spectrum in terms of distinct modes stemming from intramolecular vibrations, rigid-body-like hindered rotational and translational motion, and specific couplings to interfacial water molecules. The assignment is confirmed by the peak shifts observed in the THz spectrum of deuterated glycine in heavy water, which allow us to separate the distinct modes experimentally.

Interaction of Black Phosphorus with Oxygen and Water

DOE PAGES

Huang, Yuan; Qiao, Jingsi; He, Kai; ...

2016-10-24

Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. Chemical reactions with different ambient species, notably oxygen and water, are important as they govern key properties such as stability in air, electronic structure and charge transport, wetting by aqueous solutions, etc. Here, we report experiments combined with ab-initio calculations that address the effects of oxygen and water in contact with BP. Our results show that the reaction with oxygen is primarily responsible for changing properties of BP. Oxidation involving the dissociative chemisorption of O 2 causes the decomposition of BPmore » and continuously lowers the conductance of BP field-effect transistors (FETs). In contrast, BP is stable in contact with deaerated (i.e., O 2 depleted) water and the carrier mobility in BP FETs gated by H 2O increases significantly due to efficient dielectric screening of scattering centers by the high-k dielectric. Isotope labeling experiments, contact angle measurements and calculations show that the pristine BP surface is hydrophobic, but is turned progressively hydrophilic by oxidation. Lastly, our results open new avenues for exploring applications that require contact of BP with aqueous solutions including solution gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP.« less

The spectral properties of (-)-epigallocatechin 3-O-gallate (EGCG) fluorescence in different solvents: dependence on solvent polarity.

PubMed

Snitsarev, Vladislav; Young, Michael N; Miller, Ross M S; Rotella, David P

2013-01-01

(-)-Epigallocatechin 3-O-gallate (EGCG) a molecule found in green tea and known for a plethora of bioactive properties is an inhibitor of heat shock protein 90 (HSP90), a protein of interest as a target for cancer and neuroprotection. Determination of the spectral properties of EGCG fluorescence in environments similar to those of binding sites found in proteins provides an important tool to directly study protein-EGCG interactions. The goal of this study is to examine the spectral properties of EGCG fluorescence in an aqueous buffer (AB) at pH=7.0, acetonitrile (AN) (a polar aprotic solvent), dimethylsulfoxide (DMSO) (a polar aprotic solvent), and ethanol (EtOH) (a polar protic solvent). We demonstrate that EGCG is a highly fluorescent molecule when excited at approximately 275 nm with emission maxima between 350 and 400 nm depending on solvent. Another smaller excitation peak was found when EGCG is excited at approximately 235 nm with maximum emission between 340 and 400 nm. We found that the fluorescence intensity (FI) of EGCG in AB at pH=7.0 is significantly quenched, and that it is about 85 times higher in an aprotic solvent DMSO. The Stokes shifts of EGCG fluorescence were determined by solvent polarity. In addition, while the emission maxima of EGCG fluorescence in AB, DMSO, and EtOH follow the Lippert-Mataga equation, its fluorescence in AN points to non-specific solvent effects on EGCG fluorescence. We conclude that significant solvent-dependent changes in both fluorescence intensity and fluorescence emission shifts can be effectively used to distinguish EGCG in aqueous solutions from EGCG in environments of different polarity, and, thus, can be used to study specific EGCG binding to protein binding sites where the environment is often different from aqueous in terms of polarity.

Experimental and theoretical vibrational spectroscopy studies of acetohydroxamic acid and desferrioxamine B in aqueous solution: Effects of pH and iron complexation

NASA Astrophysics Data System (ADS)

Edwards, David C.; Nielsen, Steen B.; Jarzęcki, Andrzej A.; Spiro, Thomas G.; Myneni, Satish C. B.

2005-07-01

The deprotonation and iron complexation of the hydroxamate siderophore, desferrioxamine B (desB), and a model hydroxamate ligand, acetohydroxamic acid (aHa), were studied using infrared, resonance Raman and UV-vis spectroscopy. The experimental spectra were interpreted by a comparison with DFT calculated spectra of aHa (partly hydrated) and desB (reactive groups of unhydrated molecule) at the B3LYP/6-31G* level of theory. The ab initio models include three water molecules surrounding the deprotonation site of aHa to account for partial hydration. Experiments and calculations were also conducted in D 2O to verify spectral assignments. These studies of aHa suggest that the cis-keto-aHa is the dominant form, and its deprotonation occurs at the oxime oxygen atom in aqueous solutions. The stable form of iron-complexed aHa is identified as Fe(aHa) 3 for a wide range of pH conditions. The spectral information of aHa and an ab initio model of desB were used to interpret the chemical state of different functional groups in desB. Vibrational spectra of desB indicate that the oxime and amide carbonyl groups can be identified unambiguously. Vibrational spectral analysis of the oxime carbonyl after deprotonation and iron complexation of desB indicates that the conformational changes between anion and the iron-complexed anion are small. Enhanced electron delocalization in the oxime group of Fe-desB when compared to that of Fe(aHa) 3 may be responsible for higher stability constant of the former.

Modeling the absorption spectrum of the permanganate ion in vacuum and in aqueous solution

NASA Astrophysics Data System (ADS)

Olsen, Jógvan Magnus Haugaard; Hedegård, Erik Donovan

The absorption spectrum of the MnO$_{4}$$^{-}$ ion has been a test-bed for quantum-chemical methods over the last decades. Its correct description requires highly-correlated multiconfigurational methods, which are incompatible with the inclusion of finite-temperature and solvent effects due to their high computational demands. Therefore, implicit solvent models are usually employed. Here we show that implicit solvent models are not sufficiently accurate to model the solvent shift of MnO$_{4}$$^{-}$, and we analyze the origins of their failure. We obtain the correct solvent shift for MnO$_{4}$$^{-}$ in aqueous solution by employing the polarizable embedding (PE) model combined with a range-separated complete active space short-range density functional theory method (CAS-srDFT). Finite-temperature effects are taken into account by averaging over structures obtained from ab initio molecular dynamics simulations. The explicit treatment of finite-temperature and solvent effects facilitates the interpretation of the bands in the low-energy region of the MnO$_{4}$$^{-}$ absorption spectrum, whose assignment has been elusive.

Dispersion Interactions between Urea and Nucleobases Contribute to the Destabilization of RNA by Urea in Aqueous Solution

PubMed Central

Kasavajhala, Koushik; Bikkina, Swetha; Patil, Indrajit; MacKerell, Alexander D.; Priyakumar, U. Deva

2015-01-01

Urea has long been used to investigate protein folding and, more recently, RNA folding. Studies have proposed that urea denatures RNA by participating in stacking interactions and hydrogen bonds with nucleic acid bases. In this study, the ability of urea to form unconventional stacking interactions with RNA bases is investigated using ab initio calculations (RI-MP2 and CCSD(T) methods with the aug-cc-pVDZ basis set). A total of 29 stable nucleobase-urea stacked complexes are identified in which the intermolecular interaction energies (up to −14 kcal/mol) are dominated by dispersion effects. Natural bond orbital (NBO) and atoms in molecules (AIM) calculations further confirm strong interactions between urea and nucleobases. Calculations on model systems with multiple urea and water molecules interacting with a guanine base lead to a hypothesis that urea molecules along with water are able to form cage-like structures capable of trapping nucleic acid bases in extrahelical states by forming both hydrogen bonded and dispersion interactions, thereby contributing to the unfolding of RNA in the presence of urea in aqueous solution. PMID:25668757

Organic ion association in aqueous phase and ab initio-based force fields: The case of carboxylate/ammonium salts

NASA Astrophysics Data System (ADS)

Houriez, Céline; Vallet, Valérie; Réal, Florent; Meot-Ner Mautner, Michael; Masella, Michel

2017-10-01

We performed molecular dynamics simulations of carboxylate/methylated ammonium ion pairs solvated in bulk water and of carboxylate/methylated ammonium salt solutions at ambient conditions using an ab initio-based polarizable force field whose parameters are assigned to reproduce only high end quantum computations, at the Møller-Plesset second-order perturbation theory/complete basis set limit level, regarding single ions and ion pairs as isolated and micro-hydrated in gas phase. Our results agree with the available experimental results regarding carboxylate/ammonium salt solutions. For instance, our force field approach predicts the percentage of acetate associated with ammonium ions in CH3 COO-/CH3 NH3+ solutions at the 0.2-0.8M concentration scale to range from 14% to 35%, in line with the estimates computed from the experimental ion association constant in liquid water. Moreover our simulations predict the number of water molecules released from the ion first hydration shell to the bulk upon ion association to be about 2.0 ± 0.6 molecules for acetate/protonated amine ion pairs, 3.1 ± 1.5 molecules for the HCOO-/NH4+ pair and 3.3 ± 1.2 molecules for the CH3COO-/(CH3)4N+ pair. For protonated amine-based ion pairs, these values are in line with experiment for alkali/halide pairs solvated in bulk water. All these results demonstrate the promising feature of ab initio-based force fields, i.e., their capacity in accurately modeling chemical systems that cannot be readily investigated using available experimental techniques.

Aqueous biphasic systems in the separation of food colorants.

PubMed

Santos, João H P M; Capela, Emanuel V; Boal-Palheiros, Isabel; Coutinho, João A P; Freire, Mara G; Ventura, Sónia P M

2018-04-25

Aqueous biphasic systems (ABS) composed of polypropylene glycol and carbohydrates, two benign substances are proposed to separate two food colorants (E122 and E133). ABS are promising extractive platforms, particularly for biomolecules, due to their aqueous and mild nature (pH and temperature), reduced environmental impact and processing costs. Another major aspect considered, particularly useful in downstream processing, is the "tuning" ability for the extraction and purification of these systems by a proper choice of the ABS components. In this work, our intention is to show the concept of ABS as an alternative and volatile organic solvent-free tool to separate two different biomolecules in a simple way, so simple that teachers can effectively adopt it in their classes to explain the concept of bioseparation processes. Informative documents and general information about the preparation of binodal curves and their use in the partition of biomolecules is available in this work to be used by teachers in their classes. In this sense, the students use different carbohydrates to build ABS, then study the partition of two food color dyes (synthetic origin), thus evaluating their ability on the separation of both food colorants. Through these experiments, the students get acquainted with ABS, learn how to determine solubility curves and perform extraction procedures using colorant food additives, that can also be applied in the extraction of various (bio)molecules. © 2018 by The International Union of Biochemistry and Molecular Biology, 2018. © 2018 The International Union of Biochemistry and Molecular Biology.

Vibrational studies of phosphoryl transfer enzymes: ras- p21(*)magnesium-GTP and Myosin S1(*)magnesium-ADP- vanadate

NASA Astrophysics Data System (ADS)

Wang, Jianghua

1999-07-01

We have measured the Raman spectra of monophosphate compounds in aqueous solution. The measured frequencies were correlated with P••O valence bond order by using a modification of the Hardcastle- Wachs procedure. The P••O bond order and bond length in phosphates can be determined from vibrational spectra by using the derived bond order/stretching frequency correlation and the bond length/bond order correlation of Brown and Wu. The Raman and infrared spectra of guanosine 5'-diphosphate (GDP) and guanosine 5'-triphosphate (GTP) in aqueous solution were also examined. Frequency shifts were observed as Mg2+ complexes with GDP and GTP in aqueous solution. These results suggested that Mg2+ binds to GDP in a bidentate manner to the α,β P••O bonds and in a tridentate manner to the α,β and γ P••O bonds of Mg•GTP . We have analyzed the previously obtained isotope edited Raman difference spectra of 1:1 complexes of Mg•GDP and Mg•GTP in ras-p21. Frequency changes of the phosphate groups were observed when Mg•GDP , Mg•GTP bind to the protein. Employing both the previous empirical relationships between bond orders/lengths and frequencies as well as vibrational analysis from ab initio calculations, the spectral changes can be explained by the change of the Mg2+ binding sites and hydrogen-bonding. Implications of these structural results for the reaction mechanism of GTP hydrolysis catalyzed by the GTPase are discussed. We have analyzed previously obtained isotope edited Raman difference spectra of the non-bridging V••O bonds of vanadates, both in solution, and when bound to the myosin S1•MgADP complex. By use of ab initio calculations on a model of the vanadate binding site in myosin, the angles between the non-bridging V••O bonds and between these bonds and the apical bonds in the myosin S1•MgADP -Vi complex were determined. The summed bond order of the two apical bonds between the attacking and leaving group oxygens with the central vanadium ion in the S1•MgADP -Vi complex was found to increase only slightly compared with the bond order of the ester V-O bond of a monoester vanadate model compound in solution, suggesting an SN2 like mechanism for the phosphoryl transfer reaction catalyzed by myosin.

Internal force corrections with machine learning for quantum mechanics/molecular mechanics simulations.

PubMed

Wu, Jingheng; Shen, Lin; Yang, Weitao

2017-10-28

Ab initio quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulation is a useful tool to calculate thermodynamic properties such as potential of mean force for chemical reactions but intensely time consuming. In this paper, we developed a new method using the internal force correction for low-level semiempirical QM/MM molecular dynamics samplings with a predefined reaction coordinate. As a correction term, the internal force was predicted with a machine learning scheme, which provides a sophisticated force field, and added to the atomic forces on the reaction coordinate related atoms at each integration step. We applied this method to two reactions in aqueous solution and reproduced potentials of mean force at the ab initio QM/MM level. The saving in computational cost is about 2 orders of magnitude. The present work reveals great potentials for machine learning in QM/MM simulations to study complex chemical processes.

Mechanistic Insights into Radical-Mediated Oxidation of Tryptophan from ab Initio Quantum Chemistry Calculations and QM/MM Molecular Dynamics Simulations.

PubMed

Wood, Geoffrey P F; Sreedhara, Alavattam; Moore, Jamie M; Wang, John; Trout, Bernhardt L

2016-05-12

An assessment of the mechanisms of (•)OH and (•)OOH radical-mediated oxidation of tryptophan was performed using density functional theory calculations and ab initio plane-wave Quantum Mechanics/Molecular Mechanics (QM/MM) molecular dynamics simulations. For the (•)OH reactions, addition to the pyrrole ring at position 2 is the most favored site with a barrierless reaction in the gas phase. The subsequent degradation of this adduct through a H atom transfer to water was intermittently observed in aqueous-phase molecular dynamics simulations. For the (•)OOH reactions, addition to the pyrrole ring at position 2 is the most favored pathway, in contrast to the situation in the model system ethylene, where concerted addition to the double bond is preferred. From the (•)OOH position 2 adduct QM/MM simulations show that formation of oxy-3-indolanaline occurs readily in an aqueous environment. The observed transformation starts from an initial rupture of the O-O bond followed by a H atom transfer with the accompanying loss of an (•)OH radical to solution. Finally, classical molecular dynamics simulations were performed to equate observed differential oxidation rates of various tryptophan residues in monoclonal antibody fragments. It was found that simple parameters derived from simulation correlate well with the experimental data.

Hydrogen bond basicity of ionic liquids and molar entropy of hydration of salts as major descriptors in the formation of aqueous biphasic systems.

PubMed

Passos, Helena; Dinis, Teresa B V; Cláudio, Ana Filipa M; Freire, Mara G; Coutinho, João A P

2018-05-23

Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and conventional salts have been largely investigated and successfully used in separation processes, for which the determination of the corresponding ternary phase diagrams is a prerequisite. However, due the large number of ILs that can be prepared and their high structural versatility, it is impossible to experimentally cover and characterize all possible combinations of ILs and salts that may form ABS. The development of tools for the prediction and design of IL-based ABS is thus a crucial requirement. Based on a large compilation of experimental data, a correlation describing the formation of IL-based ABS is shown here, based on the hydrogen-bonding interaction energies of ILs (EHB) obtained by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) and the molar entropy of hydration of the salt ions. The ability of the proposed model to predict the formation of novel IL-based ABS is further ascertained.

Observation of small cluster formation in concentrated monoclonal antibody solutions and its implications to solution viscosity.

PubMed

Yearley, Eric J; Godfrin, Paul D; Perevozchikova, Tatiana; Zhang, Hailiang; Falus, Peter; Porcar, Lionel; Nagao, Michihiro; Curtis, Joseph E; Gawande, Pradad; Taing, Rosalynn; Zarraga, Isidro E; Wagner, Norman J; Liu, Yun

2014-04-15

Monoclonal antibodies (mAbs) are a major class of biopharmaceuticals. It is hypothesized that some concentrated mAb solutions exhibit formation of a solution phase consisting of reversibly self-associated aggregates (or reversible clusters), which is speculated to be responsible for their distinct solution properties. Here, we report direct observation of reversible clusters in concentrated solutions of mAbs using neutron spin echo. Specifically, a stable mAb solution is studied across a transition from dispersed monomers in dilute solution to clustered states at more concentrated conditions, where clusters of a preferred size are observed. Once mAb clusters have formed, their size, in contrast to that observed in typical globular protein solutions, is observed to remain nearly constant over a wide range of concentrations. Our results not only conclusively establish a clear relationship between the undesirable high viscosity of some mAb solutions and the formation of reversible clusters with extended open structures, but also directly observe self-assembled mAb protein clusters of preferred small finite size similar to that in micelle formation that dominate the properties of concentrated mAb solutions. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Correlation of Electron-Transfer Rates with the Surface Density of States of Native and Anodically Grown Oxide Films on Titanium

DTIC Science & Technology

1990-11-16

materials. v :67:RiB T7;N, AVAILA81UTY CF ABS-.RAC- 21. ABSTRAC7 SEC-RTY C .SSi~ CAT ;CN X NC_SSF:E- /UNL:MITE- : C SA.ME AS ;P’ C C jSE’S Unclassified i...value in ambient environments. Localized breakdown of the native film occurs in chemically aggresive environments (e.g., aqueous Br- solutions...oxide film, Fig. 1 (c), show highly rectifying behavior , in agreement with expectations for a large band gap semiconductor. The tunneling current at each

Quantum mechanical study of solvent effects in a prototype S{sub N}2 reaction in solution: Cl{sup −} attack on CH{sub 3}Cl

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

Kuechler, Erich R.; Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431; York, Darrin M., E-mail: york@biomaps.rutgers.edu

2014-02-07

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype S{sub N}2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resultingmore » free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.« less

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl

NASA Astrophysics Data System (ADS)

Kuechler, Erich R.; York, Darrin M.

2014-02-01

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.

Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl.

PubMed

Kuechler, Erich R; York, Darrin M

2014-02-07

The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.

Pesticide Removal from Aqueous Solutions by Adding Salting Out Agents

PubMed Central

Moscoso, Fátima; Deive, Francisco J.; Esperança, José M. S. S.; Rodríguez, Ana

2013-01-01

Phase segregation in aqueous biphasic systems (ABS) composed of four hydrophilic ionic liquids (ILs): 1-butyl-3-methylimidazolium methylsulfate and 1-ethyl-3-methylimidazolium methylsulfate (CnC1im C1SO4, n = 2 and 4), tributylmethyl phosphonium methylsulfate (P4441 C1SO4) and methylpyridinium methylsulfate (C1Py C1SO4) and two high charge density potassium inorganic salts (K2CO3 and K2HPO4) were determined by the cloud point method at 298.15 K. The influence of the addition of the selected inorganic salts to aqueous mixtures of ILs was discussed in the light of the Hofmeister series and in terms of molar Gibbs free energy of hydration. The effect of the alkyl chain length of the cation on the methylsulfate-based ILs has been investigated. All the solubility data were satisfactorily correlated to several empirical equations. A pesticide (pentachlorophenol, PCP) extraction process based on the inorganic salt providing a greater salting out effect was tackled. The viability of the proposed process was analyzed in terms of partition coefficients and extraction efficiencies. PMID:24145747

Characterization of corrosion products of AB{sub 5}-type hydrogen storage alloys for nickel-metal hydride batteries

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

Maurel, F.; Knosp, B.; Backhaus-Ricoult, M.

2000-01-01

To better understand the decrease in storage capacity of AB{sub 5}-type alloys in rechargeable Ni/MH batteries undergoing repeated charge/discharge cycles, the corrosion of a MnNi{sub 3.55}Co{sub 0.75}Mn{sub 0.4}Al{sub 0.3} alloy in aqueous KOH electrolyte was studied. The crystal structure, chemical composition, and distribution of corrosion products were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Hollow and filed needles of a mixed rare earth hydroxide Mn(OH){sub 3} were found to cover a continuous nanocrystalline corrosion scale composed of metal (Ni, Co) solid solution, oxide (Ni,Co)O solid solution and rare earth hydroxide, and a Mn-depleted alloy subscale. Corrosionmore » kinetics were measured for three different temperatures. Growth kinetics of the continuous corrosion scale and of the Mm(OH){sub 3} needles obeyed linear and parabolic rate laws, respectively. Models for the corrosion mechanism were developed on the basis of diffusional transport of Mn and OH through the hydroxide needles and subsequent diffusion along grain boundaries through the nanocrystalline scale.« less

Exploring Nuclear Photorelaxation of Pyranine in Aqueous Solution: an Integrated Ab-Initio Molecular Dynamics and Time Resolved Vibrational Analysis Approach.

PubMed

Chiariello, Maria Gabriella; Rega, Nadia

2018-03-22

Advances in time-resolved vibrational spectroscopy techniques provided a new stimulus for understanding the transient molecular dynamics triggered by the electronic excitation. The detailed interpretation of such time-dependent spectroscopic signals is a challenging task from both experimental and theoretical points of view. We simulated and analyzed the transient photorelaxation of the pyranine photoacid in aqueous solution, with special focus on structural parameters and low frequency skeleton modes that are possibly preparatory for the photoreaction occurring at later time, as suggested by experimental spectroscopic studies. To this aim, we adopted an accurate computational protocol that combines excited state ab initio molecular dynamics within an hybrid quantum mechanical/molecular mechanics framework and a time-resolved vibrational analysis based on the Wavelet transform. According to our results, the main nuclear relaxation on the excited potential energy surface is completed in about 500 fs, in agreement with experimental data. The rearrangement of C-C bonds occurs according to a complex vibrational dynamics, showing oscillatory patterns that are out of phase and modulated by modes below 200 cm -1 . We also analyzed in both the ground and the excited state the evolution of some structural parameters involved in excited state proton transfer reaction, namely, those involving the pyranine and the water molecule hydrogen bonded to the phenolic O-H group. Both the hydrogen bond distance and the intermolecular orientation are optimized in the excited state, resulting in a tighter proton donor-acceptor couple. Indeed, we found evidence that collective low frequency skeleton modes, such as the out of plane wagging at 108 cm -1 and the deformation at 280 cm -1 , are photoactivated by the ultrafast part of the relaxation and modulate the pyranine-water molecule rearrangement, favoring the preparatory step for the photoreactivity.

"Washing-out" ionic liquids from polyethylene glycol to form aqueous biphasic systems.

PubMed

Tomé, Luciana I N; Pereira, Jorge F B; Rogers, Robin D; Freire, Mara G; Gomes, José R B; Coutinho, João A P

2014-02-14

The molecular-level mechanisms behind the formation of aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and polymers are hitherto not completely understood. For the first time, it is herein shown that polymer-IL-based ABS are a result of a "washing-out" phenomenon, and not of a salting-out effect of the IL over the polymer as assumed in the past few years. Novel evidence is herein provided by experimental results combined with molecular dynamics (MD) simulations and density functional theory (DFT) calculations.

RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels.

PubMed

Hemp, Sean T; Smith, Adam E; Bunyard, W Clayton; Rubinstein, Michael H; Long, Timothy E

2014-05-13

Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG- b -DEG 95 TMA 5 ) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG 98 TMA 2 - b -OEG- b -DEG 98 TMA 2 ) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.

The accuracy of ab initio calculations without ab initio calculations for charged systems: Kriging predictions of atomistic properties for ions in aqueous solutions

NASA Astrophysics Data System (ADS)

Di Pasquale, Nicodemo; Davie, Stuart J.; Popelier, Paul L. A.

2018-06-01

Using the machine learning method kriging, we predict the energies of atoms in ion-water clusters, consisting of either Cl- or Na+ surrounded by a number of water molecules (i.e., without Na+Cl- interaction). These atomic energies are calculated following the topological energy partitioning method called Interacting Quantum Atoms (IQAs). Kriging predicts atomic properties (in this case IQA energies) by a model that has been trained over a small set of geometries with known property values. The results presented here are part of the development of an advanced type of force field, called FFLUX, which offers quantum mechanical information to molecular dynamics simulations without the limiting computational cost of ab initio calculations. The results reported for the prediction of the IQA components of the energy in the test set exhibit an accuracy of a few kJ/mol, corresponding to an average error of less than 5%, even when a large cluster of water molecules surrounding an ion is considered. Ions represent an important chemical system and this work shows that they can be correctly taken into account in the framework of the FFLUX force field.

Evaluating the Role of the Air-Solution Interface on the Mechanism of Subvisible Particle Formation Caused by Mechanical Agitation for an IgG1 mAb.

PubMed

Ghazvini, Saba; Kalonia, Cavan; Volkin, David B; Dhar, Prajnaparamita

2016-05-01

Mechanical agitation of monoclonal antibody (mAb) solutions often leads to protein particle formation. In this study, various formulations of an immunoglobulin G (IgG) 1 mAb were subjected to different controlled interfacial stresses using a Langmuir trough, and protein particles formed at the interface and measured in bulk solution were characterized using atomic force microscopy and flow digital imaging. Results were compared to mAb solutions agitated in glass vials and unstressed controls. At lower pH, mAb solutions exhibited larger hysteresis in their surface pressure versus area isotherms and increased number of particles in bulk solution, when subjected to interfacial stresses. mAb samples subjected to 750-1000 interfacial compression-expansion cycles in 6 h contained high particle numbers in bulk solution, and displayed similar particulation trends when agitated in vials. At compression rates of 50 cycles in 6 h, however, particle levels in mAb solutions were comparable to unstressed controls, despite protein aggregates being present at the air-solution interface. These results suggest that while the air-solution interface serves as a nucleation site for initiating protein aggregation, the number of protein particles measured in bulk mAb solutions depends on the total number of compression cycles that proteins at the air-solution interface are subjected to within a fixed time. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Effects of mushroom extract on textural properties and muscle protein degradation of bovine longissimus dorsi muscle.

PubMed

Lee, Kyung-Ha; Kim, Ho-Kyoung; Kim, Sae-Hun; Kim, Kyoung-Hwan; Choi, Young-Min; Jin, Hyun-Hee; Lee, Seung-Joo; Ryu, Youn-Chul

2017-03-01

We investigated the effects of Sarcodon aspratus, Agaricus bisporus, and Lentinula edodes aqueous extracts on the tenderization of bovine longissimus dorsi muscle. Meat quality and muscle protein degradation were examined as well. Beef chunks were marinated in distilled water (control), 5% S. aspratus (SA), 5% A. bisporus (AB), or 5% L. edodes (LE) extracts. SA was shown to have a higher enzymatic activity (p < 0.001) and water-holding capacity than LE (p < 0.01). SA and AB extracts exhibited lower shear force values compared with the control (p < 0.05). SA, AB, and LE showed superior muscle proteolytic effects compared with the control. SA demonstrated the ability to degrade myosin heavy chains and actin, which was not observed after AB and LE extract treatments. This suggests that SA extract may affect tenderization. Taken together, our results show that aqueous extract of S. aspratus affects the tenderness of the bovine longissimus dorsi muscle.

Separation and recovery of food coloring dyes using aqueous biphasic extraction chromatographic resins.

PubMed

Huddleston, J G; Willauer, H D; Boaz, K R; Rogers, R D

1998-06-26

Aqueous biphasic systems (ABS) and aqueous biphasic extraction chromatographic (ABEC) resins are currently under investigation for their utility in the removal of color from textile plant wastes. The structures of several widely used food colorings, suggest that these dyes would also be retained on the resins. In work currently in progress, we have begun to investigate the retention and resolution of several common food colorings including indigo carmine, amaranth, carminic acid. erythrosin B, tartrazine and quinoline yellow. The relationship between the uptake of these dyes on ABEC resins in terms of the binding strengths and capacities of the resins and their partitioning behavior in ABS is illustrated. Some possible theoretical and practical approaches to the prediction of the partitioning and retention behavior is discussed.

pH-sensitive wax emulsion copolymerization with acrylamide hydrogel using gamma irradiation for dye removal

NASA Astrophysics Data System (ADS)

Ghobashy, Mohamed Mohamady; Elhady, Mohamed., A.

2017-05-01

Emulsion polymerization is an efficient method for the production of new wax-hydrogel matrices of cetyl alcohol: stearic acid wax and acrylamide hydrogel using triethylamine (TEA) as an emulsifier. A cross-linking reaction occurred when a mixture of wax-hydrogel solution was irradiated with gamma rays at a dose of 20 kGy. The gelation percentage of the matrices (CtOH-StA/PAAm) was 86%, which indicates that a sufficiently high conversion occurred in these new wax-hydrogel matrices. The ability of PAAm and CtOH-StA/PAAm as an adsorbent for dye removal was investigated. The removal of three reactive dyes, namely Remazol Red (RR), Amido Black (AB), and Toluidine Blue (TB), from aqueous solutions depends on the pH of the dye solution. Removal efficiency was investigated by UV spectrophotometry, and the results showed the affinity of the wax hydrogel to adsorb TB was 98% after 320 min. Fourier transform infrared-attenuated total reflectance spectra confirmed the cross-linking process involved between the chains of wax and hydrogel; furthermore, scanning electron microscopy images showed that the wax and hydrogel were completely miscible to form a single matrix. Swelling measurements showed the high affinity of adsorbed dyes from aqueous solutions at different pH values to the wax-hydrogel network; the highest swelling values of 13.05 and 8.24 (g/g) were observed at pH 10 and 6, respectively

Ionic liquid-based aqueous biphasic systems as a versatile tool for the recovery of antioxidant compounds.

PubMed

Santos, João H; e Silva, Francisca A; Ventura, Sónia P M; Coutinho, João A P; de Souza, Ranyere L; Soares, Cleide M F; Lima, Álvaro S

2015-01-01

The comparative evaluation of distinct types of ionic liquid-based aqueous biphasic systems (IL-ABS) and more conventional polymer/salt-based ABS to the extraction of two antioxidants, eugenol and propyl gallate, is focused. In a first approach, IL-ABS composed of ILs and potassium citrate (C6H5K3O7/C6H8O7) buffer at pH 7 were applied to the extraction of two antioxidants, enabling the assessment of the impact of IL cation core on the extraction. The second approach uses ABS composed of polyethylene glycol (PEG) and potassium phosphate (K2HPO4/KH2PO4) buffer at pH 7 with imidazolium-based ILs as adjuvants. Their application to the extraction of the compounds allowed the investigation of the impact of the presence/absence of IL, the PEG molecular weight, and the alkyl side chain length of the imidazolium cation on the partition. It is possible to maximize the extractive performance of both antioxidants up to 100% using both types of IL-ABS. The IL enhances the performance of ABS technology. The data puts in evidence the pivotal role of the appropriate selection of the ABS components and design to develop a successful extractive process, from both environmental and performance points of view. © 2014 American Institute of Chemical Engineers.

Carbon Monoxide Is Involved in Hydrogen Gas-Induced Adventitious Root Development in Cucumber under Simulated Drought Stress

PubMed Central

Chen, Yue; Wang, Meng; Hu, Linli; Liao, Weibiao; Dawuda, Mohammed M.; Li, Chunlan

2017-01-01

Hydrogen gas (H2) and carbon monoxide (CO) are involved in plant growth and developmental processes and may induce plant tolerance to several stresses. However, the independent roles and interaction effect of H2 and CO in adventitious root development under drought conditions have still not received the needed research attention. We hypothesize that there exists crosstalk between H2 and CO during adventitious root development under drought stress. The results of our current study revealed that 50% (v/v) hydrogen-rich water (HRW), 500 μM Hemin (the CO donor) and 30% (w/v) CO aqueous solution apparently promoted the development of adventitious roots in cucumber explants (Cucumis Sativus L.) under drought stress. H2 and CO increased relative water content (RWC), leaf chlorophyll content (chlorophyll a, b, and a+b), and chlorophyll fluorescence parameters [photochemical efficiency of photosystem II (PSII), PSII actual photochemical efficiency and photochemical quench coefficient] under drought condition. When the CO scavenger hemoglobin (Hb) or zinc protoporphyrin IX (ZnPPIX) was added to HRW/CO aqueous solution, the positive effect of HRW/CO aqueous solution on RWC, leaf chlorophyll content, and chlorophyll fluorescence parameters were reversed. Additionally, superoxide dismutases, peroxidase, catalase, and ascorbate peroxidase was significantly increased in the explants treated with HRW and CO aqueous solution under drought stress, thus alleviating oxidative damage, as indicated by decreases in thiobarbituric acid reactive substances (TBARS), hydrogen peroxide (H2O2), and superoxide radical (O2-) levels. H2 and CO also improved the levels of water soluble carbohydrate, total soluble protein, and proline content. However, the above CO/H2-mediated effects were reversed by CO scavenger Hb or CO specific synthetic inhibitor ZnPPIX. Therefore, CO may be involved in H2-induced adventitious rooting under drought stress and alleviate oxidative damage by enhancing RWC, leaf chlorophyll content, chlorophyll fluorescence parameters, metabolic constituent content, activating anti-oxidant enzymes and reducing TBARS, O2-, and H2O2 levels. PMID:28223992

Protein denaturants at aqueous-hydrophobic interfaces: self-consistent correlation between induced interfacial fluctuations and denaturant stability at the interface.

PubMed

Cui, Di; Ou, Shu-Ching; Patel, Sandeep

2015-01-08

The notion of direct interaction between denaturing cosolvent and protein residues has been proposed in dialogue relevant to molecular mechanisms of protein denaturation. Here we consider the correlation between free energetic stability and induced fluctuations of an aqueous-hydrophobic interface between a model hydrophobically associating protein, HFBII, and two common protein denaturants, guanidinium cation (Gdm(+)) and urea. We compute potentials of mean force along an order parameter that brings the solute molecule close to the known hydrophobic region of the protein. We assess potentials of mean force for different relative orientations between the protein and denaturant molecule. We find that in both cases of guanidinium cation and urea relative orientations of the denaturant molecule that are parallel to the local protein-water interface exhibit greater stability compared to edge-on or perpendicular orientations. This behavior has been observed for guanidinium/methylguanidinium cations at the liquid-vapor interface of water, and thus the present results further corroborate earlier findings. Further analysis of the induced fluctuations of the aqueous-hydrophobic interface upon approach of the denaturant molecule indicates that the parallel orientation, displaying a greater stability at the interface, also induces larger fluctuations of the interface compared to the perpendicular orientations. The correlation of interfacial stability and induced interface fluctuation is a recurring theme for interface-stable solutes at hydrophobic interfaces. Moreover, observed correlations between interface stability and induced fluctuations recapitulate connections to local hydration structure and patterns around solutes as evidenced by experiment (Cooper et al., J. Phys. Chem. A 2014, 118, 5657.) and high-level ab initio/DFT calculations (Baer et al., Faraday Discuss 2013, 160, 89).

Chromium speciation in oxide-type compounds: application to minerals, gems, aqueous solutions and silicate glasses

NASA Astrophysics Data System (ADS)

Farges, François

2009-09-01

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO4 2- moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.

Theoretical studies of UO(2)(OH)(H(2)O)(n) (+), UO(2)(OH)(2)(H(2)O)(n), NpO(2)(OH)(H(2)O)(n), and PuO(2)(OH)(H(2)O)(n) (+) (n

PubMed

Cao, Zhiji; Balasubramanian, K

2009-10-28

Extensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO(2)(OH)(+), UO(2)(OH)(2), NpO(2)(OH), and PuO(2)(OH)(+) complexes that contain up to 21 water molecules both in first and second hydration spheres in both aqueous solution and the gas phase. The structures have been further optimized by considering long-range solvent effects through a polarizable continuum dielectric model. The hydrolysis reaction Gibbs free energy of UO(2)(H(2)O)(5) (2+) is computed to be 8.11 kcal/mol at the MP2 level in good agreement with experiments. Our results reveal that it is necessary to include water molecules bound to the complex in the first hydration sphere for proper treatment of the hydrated complex and the dielectric cavity although water molecules in the second hydration sphere do not change the coordination complex. Structural reoptimization of the complex in a dielectric cavity seems inevitable to seek subtle structural variations in the solvent and to correlate with the observed spectra and thermodynamic properties in the aqueous environment. Our computations reveal dramatically different equilibrium structures in the gas phase and solution and also confirm the observed facile exchanges between the complex and bulk solvent. Complete active space multiconfiguration self-consistent field followed by multireference singles+doubles CI (MRSDCI) computations on smaller complexes confirm predominantly single-configurational nature of these species and the validity of B3LYP and MP2 techniques for these complexes in their ground states.

On the constituents of aqueous polyselenide electrolytes: A combined theoretical and Raman spectroscopic study

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

Goldbach, A.; Johnson, J.; Meisel, D.

1999-05-12

The speciation of aqueous polyselenide solutions at high pH values has been investigated by Raman and Uv/vis absorption spectroscopy. Complementary, ab initio molecular orbital calculations at the HF/6-31+G{sup *} level of theory have been carried out on the vibrational frequencies of polyselenide dianions Se{sub x}{sup 2{minus}} (x = 2--4), polyselenide radical anions Se{sub x}{sup {minus}} (x = 2, 3), and protonated polyselenides HSe{sub x}{sup {minus}} (x = 1--3) in order to substantiate the assignment of the experimental Raman spectra. Although the optical spectra suggest the successive formation of Se{sub 2}{sup 2{minus}}, Se{sub 3}{sup 2{minus}}, and Se{sub 4}{sup 2{minus}} with progressivemore » oxidation of the solutions, only two characteristic Raman bands are observed at 269 and 324 cm{sup {minus}1}. A sequence of overtones of the 269 cm{sup {minus}1} band is observed after excitation with blue light. Likewise strong overtones of the 324 cm{sup {minus}1} band appear after excitation with green light. The 269 cm{sup {minus}1} features is assigned to Se{sub 4}{sup 2{minus}} while the 324 cm{sup {minus}1} band is attributed to the radical anion Se{sub 2}{sup {minus}}. The occurrence of polyselenide radicals in aqueous solution is without precedent, and the formation of Se{sub 2}{sup {minus}} is ascribed to a photolytic process in the electrolyte. The only protonated species observed in this study is HSe{sup {minus}}, which is characterized by a Raman band at 2,303 cm{sup {minus}1}.« less

Mobile Element Studies in Rocks (RAT) from Columbia Hills/West Spur at Gusev

NASA Technical Reports Server (NTRS)

Rao, M. N.; Nyquist, L. E.; Sutton, S. R.; Garrison, D. H.

2007-01-01

Using elemental abundances determined by SPIRIT APX spectrometer on rocks and soils at Gusev Plains and Columbia Hills/ West Spur regions, the Athena Team discussed the aqueous geochemical implications at these sites on Mars. They suggested that these rocks were exposed to variable degrees of aqueous alteration (low to high) at Gusev crater. Earlier, we developed analytical procedures for studying aqueous geochemical behavior of fluids on rocks at Meridiani. In the present study, we apply these methods to rocks at Columbia Hills/West Spur in order to understand the significance of the Gusev rock results in reference to aqueous geochemical processes on Mars . The data analysis procedure is based on treating SO3 ("a") and Cl ("b") as two variables and tracking the relationship between "a" and "b" when the fluids undergo evaporation. This process of evaporation leads to concentration changes in these two elements finally producing salt assemblages on Martian rocks. In some cases on plotting "a"/ "b" versus "b" in salt assemblages, they yield a hyperbolic distribution. The relationship is transformed into a straight line when "a"/"b" is again plotted against 1/"b" in the system. Earlier, we used this procedure in the case of Merdiani rock abrasion tool (RAT) rocks and in this study, we discuss the application of this procedure to Gusev rocks. This study shows that the Gusev Plains rocks were exposed to low SO3/Cl solutions (sulfate-poor) for short period of time (weak interaction), whereas solutions with high SO3/Cl ratios (sulfate-rich) seem to have pervasively interacted with Columbia Hills/ West Spur rocks (strong interaction) at Gusev crater. Our conclusions seem to be consistent with the Mossbauer results given for these rocks

Aqueous electrolytes for redox flow battery systems

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

Liu, Tianbiao; Li, Bin; Wei, Xiaoliang

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

Ultrasound-assisted extraction and preliminary purification of proanthocyanidins and chlorogenic acid from almond (Prunus dulcis) skin.

PubMed

Ma, Xue; Zhou, Xin-Yu; Qiang, Qian-Qian; Zhang, Zhi-Qi

2014-07-01

An aqueous solution of polyethylene glycol (PEG) as a green solvent was employed for the first time to develop the ultrasound-assisted extraction of proanthocyanidins (PA) and chlorogenic acid (CA) from almond skin. The optimized extraction parameters were determined based on response surface methodology, and corresponded to an ultrasound power of 120 W, a liquid-to-solid ratio of 20:1 (mL/g), and a PEG concentration of 50% (v/v). Under these optimized conditions, the extraction yields of PAs and CA from almond skin were 32.68 ± 0.22 and 16.01 ± 0.19 mg/g, respectively. Compared with organic solvent extraction, PEG solution extraction produced higher yields. Different macroporous resins were compared for their performance in purifying PAs and CA from almond skin extract. Static adsorption/desorption experimental results demonstrated that AB-8 resin exhibits excellent purification performance at pH 4. Under the optimized dynamic adsorption/desorption conditions on the AB-8 column, the total recovery of purification for PAs and CA was 80.67%. The total content of PAs and CA in the preliminarily purified extract was 89.17% (with respective contents of 60.90 and 28.27%). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine

NASA Astrophysics Data System (ADS)

Moynier, Frédéric; Fujii, Toshiyuki

2017-03-01

Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000 ppm for the 44Ca/40Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000 ppm. We show that the Ca isotopic fractionation between soil solutions and plant roots can be explained by the difference of isotopic fractionation between the different first shell hydration degree of Ca2+ and that the isotopic fractionation between roots and leaves is controlled by the precipitation of Ca-oxalates. The isotopic fractionation between blood and urine is due to the complexation of heavy Ca with citrate and oxalates in urine. Calculations are presented for additional Ca species that may be useful to interpret future Ca isotopic measurements.

Ion Association in AlCl3 Aqueous Solutions from Constrained First-Principles Molecular Dynamics

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

Cauet, Emilie L.; Bogatko, Stuart A.; Bylaska, Eric J.

2012-10-15

Ab initio molecular dynamics was used to investigate the ion pairing behavior between Cl- and the Al3+ ion in an aqueous AlCl3 solution containing 63 water molecules. A series of constrained simulations was carried out at 300 K for up to 16 ps each, by fixing the inter-nuclear separation (rAl-Cl) between the Al3+ ion and one of the Cl- ions. The calculated potential of mean force of the Al3+-Cl- ion pair shows a pronounced minimum at rAl-Cl = 2.3 Å corresponding to a contact ion pair (CIP). Two local minima assigned to solvent separated ion pairs (SSIP) are identified atmore » rAl-Cl= 4.4 and 6.0 Å. The positions of the free energy minima coincide with the hydration shell intervals of the Al3+ cation suggesting that the Cl- ion is inclined to reside in regions of low concentration of waters, i.e. between the 1st and 2nd shells of Al3+ and between the 2nd shell and bulk. A detailed analysis of solvent structure around the Al3+ and Cl- ions as a function of rAl-Cl is presented. The results are compared to structure data from X-ray measurements and unconstrained AIMD simulations of single ions Al3+ and Cl- and AlCl3 solutions. The dipole moment of the water molecules inside the 1st and 2nd hydration shells of Al3+ and in the bulk region and those of the Clion were calculated as a function of rAl-Cl. Major changes in the electronic structure of the system result from the removal of Cl- from the 1st hydration shell of the Al3+ cation. Finally, two unconstrained AIMD simulations of aqueous AlCl3 solutions corresponding to CIP and SSIP configurations were performed (17 ps, 300 K). Only minor structural changes are observed in these systems, confirming their stability.« less

Measurement of Biologically Available Naphthalene in Gas and Aqueous Phases by Use of a Pseudomonas putida Biosensor

PubMed Central

Werlen, Christoph; Jaspers, Marco C. M.; van der Meer, Jan Roelof

2004-01-01

Genetically constructed microbial biosensors for measuring organic pollutants are mostly applied in aqueous samples. Unfortunately, the detection limit of most biosensors is insufficient to detect pollutants at low but environmentally relevant concentrations. However, organic pollutants with low levels of water solubility often have significant gas-water partitioning coefficients, which in principle makes it possible to measure such compounds in the gas rather than the aqueous phase. Here we describe the first use of a microbial biosensor for measuring organic pollutants directly in the gas phase. For this purpose, we reconstructed a bioluminescent Pseudomonas putida naphthalene biosensor strain to carry the NAH7 plasmid and a chromosomally inserted gene fusion between the sal promoter and the luxAB genes. Specific calibration studies were performed with suspended and filter-immobilized biosensor cells, in aqueous solution and in the gas phase. Gas phase measurements with filter-immobilized biosensor cells in closed flasks, with a naphthalene-contaminated aqueous phase, showed that the biosensor cells can measure naphthalene effectively. The biosensor cells on the filter responded with increasing light output proportional to the naphthalene concentration added to the water phase, even though only a small proportion of the naphthalene was present in the gas phase. In fact, the biosensor cells could concentrate a larger proportion of naphthalene through the gas phase than in the aqueous suspension, probably due to faster transport of naphthalene to the cells in the gas phase. This led to a 10-fold lower detectable aqueous naphthalene concentration (50 nM instead of 0.5 μM). Thus, the use of bacterial biosensors for measuring organic pollutants in the gas phase is a valid method for increasing the sensitivity of these valuable biological devices. PMID:14711624

Iris reconstruction using autologous iris preserved in cold balanced salt solution for 8 hours in iatrogenic total iridodialysis during cataract surgery: a case report.

PubMed

Bang, Seung Pil; Jun, Jong Hwa

2017-04-04

A large iris defect or extensive iridodialysis can be an intractable cause of visual disturbance, photophobia, glare, monocular diplopia, or cosmetic deformity. The implantation of an artificial iris substitute could be an effective option, but this can cause a reduction in endothelial cell density. We succeeded in the anatomical restoration of iris tissue that was totally dialyzed out of the eye, and was preserved in cold balanced salt solution for 8 h. Engrafted iris tissue was maintained within the aqueous humor. A 71-year-old man was referred to our clinic for management of an iatrogenic total iridodialysis. The totally dialyzed iris tissue was immediately preserved in sterile cold balanced salt solution and packed in a sterile biopsy bottle that was surrounded with ice cubes. Under general anesthesia, a pars plana vitrectomy was performed to remove the remaining lens cortex and vitreous fiber anterior to the equator. A sulcus-positioned intraocular lens (IOL) was repositioned and fixed by ab externo scleral sutures. Preserved iris tissue was inserted and ironed using both iris spatula and ocular viscoelastic devices. Five-point ab interno scleral sutures were made 1.0 mm posterior to the limbus. The engrafted iris was successfully maintained for 6 months and did not undergo any atrophic change or depigmentation, which may be caused by primary implantation failure due to a blocked blood supply.

Improving the extraction of l-phenylalanine by the use of ionic liquids as adjuvants in aqueous biphasic systems.

PubMed

Yang, Hongpeng; Chen, Li; Zhou, Cunshan; Yu, Xiaojie; Yagoub, Abu ElGasim A; Ma, Haile

2018-04-15

Polyethylene glycol (PEG) is widely used in the polymer-salt systems. However, the low polarity of the PEG-rich phase limits the application of aqueous biphasic systems (ABS). To overcome this disadvantage, a small quantity of ionic liquid (IL) was used as an adjuvant in ABS to enlarge the polarity range. Therefore, an innovative study involving addition of 4wt% imidazolium-based ILs to the PEG 600/NaH 2 PO 4 ABS, aiming at controlling the phase behavior and extraction ability, was carried out. The phase diagrams, the tie-lines and the partitioning behavior of l-phenylalanine and ILs were studied in these systems. The results reveal that l-phenylalanine preferentially partitions for the PEG-rich phase. The addition of 4wt% IL to ABS controls the partitioning behavior of l-phenylalanine, which depends on the type of IL employed. Moreover, it is verified that increasing temperature lead to a decrease in the partition coefficient of l-phenylalanine. Copyright © 2017 Elsevier Ltd. All rights reserved.

Consistent integration of experimental and ab initio data into molecular and coarse-grained models

NASA Astrophysics Data System (ADS)

Vlcek, Lukas

As computer simulations are increasingly used to complement or replace experiments, highly accurate descriptions of physical systems at different time and length scales are required to achieve realistic predictions. The questions of how to objectively measure model quality in relation to reference experimental or ab initio data, and how to transition seamlessly between different levels of resolution are therefore of prime interest. To address these issues, we use the concept of statistical distance to define a measure of similarity between statistical mechanical systems, i.e., a model and its target, and show that its minimization leads to general convergence of the systems' measurable properties. Through systematic coarse-graining, we arrive at appropriate expressions for optimization loss functions consistently incorporating microscopic ab initio data as well as macroscopic experimental data. The design of coarse-grained and multiscale models is then based on factoring the model system partition function into terms describing the system at different resolution levels. The optimization algorithm takes advantage of thermodynamic perturbation expressions for fast exploration of the model parameter space, enabling us to scan millions of parameter combinations per hour on a single CPU. The robustness and generality of the new model optimization framework and its efficient implementation are illustrated on selected examples including aqueous solutions, magnetic systems, and metal alloys.

Excited States and Luminescent Properties of UO 2F 2 and Its Solvated Complexes in Aqueous Solution

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

Su, Jing; Wang, Zheming; Pan, Duoqiang

2014-07-21

The electronic absorption and emission spectra of free UO 2F 2 and its water solvated complexes below 32 000 cm –1 are investigated at the levels of ab initio CASPT2 and CCSD(T) with inclusion of scalar relativistic and spin–orbit coupling effects. The influence of the water coordination on the electronic spectra of UO 2F 2 is explored by investigating the excited states of solvated complexes (H 2O) nUO 2F 2 (n = 1–3). In these uranyl complexes, water coordination is found to have appreciable influence on the 3Δ (Ω = 1 g) character of the luminescent state and on themore » electronic spectral shape. The simulated luminescence spectral curves based on the calculated spectral parameters of (H 2O) nUO 2F 2 from CCSD(T) approach agree well with experimental spectra in aqueous solution at both near-liquid-helium temperature and room temperature. The possible luminescence spectra of free UO 2F 2 in gas phase are predicted on the basis of CASPT2 and CCSD(T) results, respectively, by considering three symmetric vibration modes. Finally, the effect of competition between spin–orbit coupling and ligand field repulsion on the luminescent state properties is discussed.« less

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

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

Trimerization Dictates Solution Opalescence of a Monoclonal Antibody.

PubMed

Yang, Teng-Chieh; Langford, Alex Jacob; Kumar, Sandeep; Ruesch, John Carl; Wang, Wei

2016-08-01

Opalescence, sometimes observed in antibody solutions, is thought to be mediated by light scattering of soluble oligomers or insoluble particulates. However, mechanistic features, such as stoichiometry and self-association affinity of oligomeric species related to opalescence, are poorly understood. Here, opalescence behavior of a monoclonal antibody (mAb-1) solution was studied over a wide range of solution conditions including different protein concentrations, pH, and in the presence or absence of salt. Hydrodynamic and thermodynamic properties of mAb-1 solutions were studied by analytical ultracentrifugation and dynamic light scattering. Opalescence in mAb-1 solutions is pH and concentration dependent. The degree of opalescence correlates with reversible monomer-trimer equilibrium detected by analytical ultracentrifugation. Increased trimer formation corresponds to increased opalescence in mAb-1 solutions at higher pH and protein concentrations. Addition of NaCl shifts this equilibrium toward monomer and reduces solution opalescence. This study demonstrates that opalescence in mAb-1 solutions does not arise from the light scattering of monomer or random molecular self-associations but is strongly correlated with a specific self-association stoichiometry and affinity. Importantly, at pH 5.5 (far below isoelectric point of mAb-1), the solution is not opalescent and with nonideal behavior. This study also dissects several parameters to describe the hydrodynamic and thermodynamic nonideality. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Ocular tissue distribution and pharmacokinetic study of a small 13kDa domain antibody after intravitreal, subconjuctival and eye drop administration in rabbits.

PubMed

Gough, Gerald; Szapacs, Matthew; Shah, Tejash; Clements, Peter; Struble, Craig; Wilson, Robert

2018-02-01

Domain antibodies (dAb's) comprise the smallest functional unit of human IgG and can be targeted to a range of different soluble cytokine and receptor targets in the eye. In particular their small size may offer advantage for ocular tissue penetration and distribution. To investigate this we used a 13kDa tool molecule to undertake a preliminary short term ocular tissue distribution and pharmacokinetic study in the rabbit eye. The dAb was administered by the intravitreal or subconjunctival route or, as topical eye drops for up to five days and dAb concentrations measured in vitreous, aqueous, conjunctiva, choroid-RPE, retina, iris, sclera, and ciliary body. The observed elimination half-live of the dAb (~3 days) in vitreous showed a similar elimination rate to that of a much larger (∼50kDa) Fab fragment whilst the half-life following subconjunctival administration was ∼24 h and, after eye drop dosing the dAb was detectable in aqueous and conjunctiva. These preliminary data show that the intravitreal half-life of dAb's are similar to much larger antibody fragments, offering the potential to deliver significantly more drug to target on a molar basis with a single intravitreal injection potentially enabling dosing frequencies of once a month or less. Subconjunctival injection may provide short duration therapeutic levels of dAb to the anterior and posterior chamber whilst topical eye drop delivery of dAbs may be useful in front-of-eye disease. These data indicate that small domain antibodies may have utility in ophthalmology. Further studies are warranted. Copyright © 2017 Elsevier Ltd. All rights reserved.

Development and application of ab initio QM/MM methods for mechanistic simulation of reactions in solution and in enzymes

PubMed Central

Hu, Hao; Yang, Weitao

2013-01-01

Determining the free energies and mechanisms of chemical reactions in solution and enzymes is a major challenge. For such complex reaction processes, combined quantum mechanics/molecular mechanics (QM/MM) method is the most effective simulation method to provide an accurate and efficient theoretical description of the molecular system. The computational costs of ab initio QM methods, however, have limited the application of ab initio QM/MM methods. Recent advances in ab initio QM/MM methods allowed the accurate simulation of the free energies for reactions in solution and in enzymes and thus paved the way for broader application of the ab initio QM/MM methods. We review here the theoretical developments and applications of the ab initio QM/MM methods, focusing on the determination of reaction path and the free energies of the reaction processes in solution and enzymes. PMID:24146439

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

DOEpatents

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

1957-10-29

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

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

DOE PAGES

Chen, Ying; Bylaska, Eric J.; Weare, John H.

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite (α-Fe(OOH). Ab-initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Here, several exchange correlation functionals were employed (PBE96, PBE96+Grimme, and PBE0) in the simulations of a (3 x 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a=30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

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

Chen, Ying; Bylaska, Eric J.; Weare, John H.

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite (α-Fe(OOH). Ab-initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Here, several exchange correlation functionals were employed (PBE96, PBE96+Grimme, and PBE0) in the simulations of a (3 x 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a=30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

New Dioxaborolane Chemistry Enables [18F]-Positron-Emitting, Fluorescent [18F]-Multimodality Biomolecule Generation from the Solid Phase

PubMed Central

Crisp, Jessica L.; Vera, David R.; Tsien, Roger Y.; Ting, Richard

2016-01-01

New protecting group chemistry is used to greatly simplify imaging probe production. Temperature and organic solvent-sensitive biomolecules are covalently attached to a biotin-bearing dioxaborolane, which facilitates antibody immobilization on a streptavidin-agarose solid-phase support. Treatment with aqueous fluoride triggers fluoride-labeled antibody release from the solid phase, separated from unlabeled antibody, and creates [18F]-trifluoroborate-antibody for positron emission tomography and near-infrared fluorescent (PET/NIRF) multimodality imaging. This dioxaborolane-fluoride reaction is bioorthogonal, does not inhibit antigen binding, and increases [18F]-specific activity relative to solution-based radiosyntheses. Two applications are investigated: an anti-epithelial cell adhesion molecule (EpCAM) monoclonal antibody (mAb) that labels prostate tumors and Cetuximab, an anti-epidermal growth factor receptor (EGFR) mAb (FDA approved) that labels lung adenocarcinoma tumors. Colocalized, tumor-specific NIRF and PET imaging confirm utility of the new technology. The described chemistry should allow labeling of many commercial systems, diabodies, nanoparticles, and small molecules for dual modality imaging of many diseases. PMID:27064381

New Dioxaborolane Chemistry Enables [(18)F]-Positron-Emitting, Fluorescent [(18)F]-Multimodality Biomolecule Generation from the Solid Phase.

PubMed

Rodriguez, Erik A; Wang, Ye; Crisp, Jessica L; Vera, David R; Tsien, Roger Y; Ting, Richard

2016-05-18

New protecting group chemistry is used to greatly simplify imaging probe production. Temperature and organic solvent-sensitive biomolecules are covalently attached to a biotin-bearing dioxaborolane, which facilitates antibody immobilization on a streptavidin-agarose solid-phase support. Treatment with aqueous fluoride triggers fluoride-labeled antibody release from the solid phase, separated from unlabeled antibody, and creates [(18)F]-trifluoroborate-antibody for positron emission tomography and near-infrared fluorescent (PET/NIRF) multimodality imaging. This dioxaborolane-fluoride reaction is bioorthogonal, does not inhibit antigen binding, and increases [(18)F]-specific activity relative to solution-based radiosyntheses. Two applications are investigated: an anti-epithelial cell adhesion molecule (EpCAM) monoclonal antibody (mAb) that labels prostate tumors and Cetuximab, an anti-epidermal growth factor receptor (EGFR) mAb (FDA approved) that labels lung adenocarcinoma tumors. Colocalized, tumor-specific NIRF and PET imaging confirm utility of the new technology. The described chemistry should allow labeling of many commercial systems, diabodies, nanoparticles, and small molecules for dual modality imaging of many diseases.

Simulation of water solutions of Ni 2+ at infinite dilution

NASA Astrophysics Data System (ADS)

Natália, M.; Cordeiro, D. S.; Ignaczak, Anna; Gomes, José A. N. F.

1993-10-01

A new ab initio pair potential is developed to describe the nickel—water interactions in Ni(II) aqueous solutions. Results of Monte Carlo simulations for the Ni(II)(H 2O) 200 system are presented for this pair potential with and without three-body classical polarization terms (the water—water interaction is described by the ab initio MCY potential). The structure of the solution around Ni(II) is discussed in terms of radial distribution functions, coordination numbers and thermal ellipsoids. The results show that the three-body terms have a non-negligible effect on the simulated solution. In fact, the experimental coordination number of six is reproduced with the full potential while a higher value is predicted when the simple pairwise-additive potential is used. The equilibrium NiO distance for the first hydration shell is also dependent on the use of the three-body terms. Comparison of our distribution functions with those obtained by neutron-diffraction experiments shows a reasonable quantitative agreement. Statistical pattern recognition analysis has also been applied to our simulations in order to better understand the local thermal motion of the water molecules around the metal ion. In this way, thermal ellipsoids have been computed (and graphically displayed) for each atom of the water molecules belonging to the Ni(II) first hydration shell. This analysis revealed that the twisting and bending motions are greater than the radial motion, and that the hydrogens have a higher mobility than the oxygens. In addition, a thermodynamic perturbation method has been incorporated in our Monte Carlo procedure in order to compute the free energy of hydration for the Ni(II) ion. Agreement between these results and the experimental ones is also sufficiently reasonable to demonstrate the feasibility of this new potential for the nickel—water interactions.

Molecular insights into the enhanced rate of CO2 absorption to produce bicarbonate in aqueous 2-amino-2-methyl-1-propanol.

PubMed

Stowe, Haley M; Hwang, Gyeong S

2017-12-06

2-Amino-2-methyl-1-propanol (AMP), a sterically hindered amine, exhibits a much higher CO 2 absorption rate relative to tertiary amine diethylethanolamine (DEEA), while both yield bicarbonate as a major product in aqueous solution, despite their similar basicity. We present molecular mechanisms underlying the significant difference of CO 2 absorption rate based on ab initio molecular dynamics simulations combined with metadynamics. Our calculations predict the free energy barrier for base-catalyzed CO 2 hydration to be lower in aqueous AMP compared to DEEA. Further molecular analysis suggests that the difference in free energy barrier is largely attributed to entropic effects associated with reorganization of H 2 O molecules adjacent to the basic N site. Stronger hydrogen bonding of H 2 O with N of DEEA than AMP, in addition to the presence of bulky ethyl groups, suppresses the thermal rearrangement of adjacent H 2 O molecules, thereby leading to lower stability of the transition state involving OH - creation and CO 2 polarization. Moreover, the hindered reorganization of adjacent H 2 O molecules is found to facilitate migration of OH - (created via proton abstraction by DEEA) away from the N site while suppressing CO 2 approach. This leads us to speculate that catalyzed CO 2 hydration in aqueous DEEA may involve OH - migration through multiple hydrogen-bonded H 2 O molecules prior to reaction with CO 2 , whereas in aqueous AMP it seems to preferentially follow the one H 2 O-mediated mechanism. This study highlights the importance of entropic effects in determining both mechanisms and rates of CO 2 absorption into aqueous sterically hindered amines.

Use of Foam to Reduce Gun Blast Noise Levels.

DTIC Science & Technology

1981-03-01

conclusively demonstrated that aqueous foam can effect significant (greater than 10 dB) reductions in gun muzzle blast peak sound pressure level...can yield large reductions in airblast noise level. In these experiments, the explosive charge was engulfed in aqueous foam such as that used in fire...within the foam was closely controlled. Coniguration "C" was also quite similar exc, -" !iat ab .. _ 1 gallon of aqueous foam , contained in a 1-mil

Exact PsTd invariant and PsTd symmetric breaking solutions, symmetry reductions and Bäcklund transformations for an AB-KdV system

NASA Astrophysics Data System (ADS)

Jia, Man; Lou, Sen Yue

2018-05-01

In natural and social science, many events happened at different space-times may be closely correlated. Two events, A (Alice) and B (Bob) are defined as correlated if one event is determined by another, say, B = f ˆ A for suitable f ˆ operators. A nonlocal AB-KdV system with shifted-parity (Ps, parity with a shift), delayed time reversal (Td, time reversal with a delay) symmetry where B =Ps ˆ Td ˆ A is constructed directly from the normal KdV equation to describe two-area physical event. The exact solutions of the AB-KdV system, including PsTd invariant and PsTd symmetric breaking solutions are shown by different methods. The PsTd invariant solution show that the event happened at A will happen also at B. These solutions, such as single soliton solutions, infinitely many singular soliton solutions, soliton-cnoidal wave interaction solutions, and symmetry reduction solutions etc., show the AB-KdV system possesses rich structures. Also, a special Bäcklund transformation related to residual symmetry is presented via the localization of the residual symmetry to find interaction solutions between the solitons and other types of the AB-KdV system.

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS.

PubMed

Eklund, Lars; Hofer, Tomas S; Persson, Ingmar

2015-01-28

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2(-), chlorate, ClO3(-), and perchlorate, ClO4(-). In addition, the structures of the hydrated hypochlorite, ClO(-), bromate, BrO3(-), iodate, IO3(-) and metaperiodate, IO4(-), ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO6(3-), ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01-0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

PubMed Central

Eklund, Lars; Hofer, Tomas S.

2014-01-01

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO2−, chlorate, ClO3−, and perchlorate, ClO4−. In addition, the structures of the hydrated hypochlorite, ClO−, bromate, BrO3−, iodate, IO3− and metaperiodate, IO4−, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H2IO63−, ions have been determined by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl-O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. The water exchange rate for the perchlorate ion is significantly faster, τ0.5=1.4 ps, compared to the hydrated sulfate ion and pure water, τ0.5=2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions. PMID:25473816

Structure and water exchange dynamics of hydrated oxo halo ions in aqueous solution using QMCF MD simulation, large angle X-ray scattering and EXAFS

DOE PAGES

Eklund, Lars; Hofer, Tomas S.; Persson, Ingmar

2014-11-26

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) and EXAFS measurements to study structure and dynamics of the hydrated oxo chloro anions chlorite, ClO 2 –, chlorate, ClO 3 –, and perchlorate, ClO 4 –. In addition, the structures of the hydrated hypochlorite, ClO –, bromate, BrO 3 –, iodate, IO 3 – and metaperiodate, IO 4 –, ions have been determined in aqueous solution by means of LAXS. The structures of the bromate, metaperiodate, and orthoperiodate, H 2IO 6 3–, ions have been determinedmore » by EXAFS as solid sodium salts and in aqueous solution as well. The results show clearly that the only form of periodate present in aqueous solution is metaperiodate. The Cl–O bond distances in the hydrated oxo chloro anions as determined by LAXS and obtained in the QMCF MD simulations are in excellent agreement, being 0.01–0.02 Å longer than in solid anhydrous salts due to hydration through hydrogen bonding to water molecules. The oxo halo anions, all with unit negative charge, have low charge density making them typical structure breakers, thus the hydrogen bonds formed to the hydrating water molecules are weaker and more short-lived than those between water molecules in pure water. The water exchange mechanism of the oxo chloro anions resembles those of the oxo sulfur anions with a direct exchange at the oxygen atoms for perchlorate and sulfate. Here, the water exchange rate for the perchlorate ion is significantly faster, τ 0.5 = 1.4 ps, compared to the hydrated sulfate ion and pure water, τ 0.5 = 2.6 and 1.7 ps, respectively. The angular radial distribution functions show that the chlorate and sulfite ions have a more complex water exchange mechanism. As the chlorite and chlorate ions are more weakly hydrated than the sulfite ion the spatial occupancy is less well-defined and it is not possible to follow any well-defined migration pattern as it is difficult to distinguish between hydrating water molecules and bulk water in the region close to the ions.« less

Fractionated-combustion analysis of carbonate-containing phases in composite materials of the hydroxyapatite-calcium carbonate system

NASA Astrophysics Data System (ADS)

Goldberg, M. A.; Shibaeva, T. V.; Smirnov, V. V.; Kutsev, S. V.; Barinov, S. M.; Grigorovich, K. V.

2012-12-01

Materials in the hydroxyapatite (HA)-calcium carbonate (CC) system were synthesized by a precipitation method from aqueous solutions. According to the data of X-ray phase analysis and IR spectroscopy, the powders consisted of CC and AB-type carbonate-substituted HA (CHA). In order to determine the content of carbonate-containing phases in materials, the temperature-temporal mode of fractionated-combustion analysis of carbon was developed. The quantitative phase ratios and the degree of substitution of carbonate groups in CHA were determined. It was shown that the degree of substitution of carbonate groups in CHA increased from 2.47 to 5.31 wt % as the CC content increased from 13.50 to 88.33 wt %.

Towards an ab initio theory for metal L-edge soft X-ray spectroscopy of molecular aggregates.

PubMed

Preuße, Marie; Bokarev, Sergey I; Aziz, Saadullah G; Kühn, Oliver

2016-11-01

The Frenkel exciton model was adapted to describe X-ray absorption and resonant inelastic scattering spectra of polynuclear transition metal complexes by means of the restricted active space self-consistent field method. The proposed approach allows to substantially decrease the requirements on computational resources if compared to a full supermolecular quantum chemical treatment. This holds true, in particular, in cases where the dipole approximation to the electronic transition charge density can be applied. The computational protocol was applied to the calculation of X-ray spectra of the hemin complex, which forms dimers in aqueous solution. The aggregation effects were found to be comparable to the spectral alterations due to the replacement of the axial ligand by solvent molecules.

The use of synthesized aqueous solutions for determining strontium sorption isotherms

USGS Publications Warehouse

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

1998-01-01

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

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

PubMed

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

2005-05-01

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

Membrane separation for non-aqueous solution

NASA Astrophysics Data System (ADS)

Widodo, S.; Khoiruddin; Ariono, D.; Subagjo; Wenten, I. G.

2018-01-01

Membrane technology has been widely used in a number of applications competing with conventional technologies in various ways. Despite the enormous applications, they are mainly used for the aqueous system. The use of membrane-based processes in a non-aqueous system is an emerging area. This is because developed membranes are still limited in separations involving aqueous solution which show several drawbacks when implemented in a non-aqueous system. The purpose of this paper is to provide a review of the current application of membrane processes in non-aqueous solutions, such as mineral oil treatment, vegetable oil processing, and organic solvent recovery. Developments of advanced membrane materials for the non-aqueous solutions such as super-hydrophobic and organic solvent resistant membranes are reviewed. In addition, challenges and future outlook of membrane separation for the non-aqueous solution are discussed.

Water-soluble polymers for recovery of metal ions from aqueous streams

DOEpatents

Smith, Barbara F.; Robison, Thomas W.

1998-01-01

A process of selectively separating a target metal contained in an aqueous solution by contacting the aqueous solution containing a target metal with an aqueous solution including a water-soluble polymer capable of binding with the target metal for sufficient time whereby a water-soluble polymer-target metal complex is formed, and, separating the solution including the water-soluble polymer-target metal complex from the solution is disclosed.

Generation and Characterization of a Bispecific Antibody Targeting Both PD-1 and c-MET.

PubMed

Wu, Yi; Yu, Min; Sun, Zujun; Hou, Weihua; Wang, Yuxiong; Yuan, Qingyun; Mo, Wei

2018-02-08

Bispecific antibodies, BsAbs, are molecules with the ability to bind to two different epitopes on the same or different antigens. c-MET, cellular-mesenchymal to epithelial transition factor, is deregulated in many types of human malignancies. Abnormal c-MET activation in cancer correlates with poor prognosis. PD-1, programmed death-1, is an additional inhibitory receptor expressed by T cells. Blocking the interactions between PD-1 and PD-L1 has emerged as a promising immunotherapy for treating cancer. The goal of this study was to identify a novel bispecific antibody targeting both c-MET and PD-1 as an anti-cancer therapeutic candidate. The BsAb was produced using 293E expression system and purified by Protein A affinity chromatography. Then the binding specificity and affinity of the BsAb was examined by FACS and biolayer light interferometry. The ability of the BsAb to inhibit the proliferation of tuman cells was measured using the CellTiter 96 Aqueous One Solution Cell Proliferation Assay kit; the potential signaling pathway involved was identified by Western Blot. Cytokine secreted by PHA-L stimulated PBMC was measured by ELISA. Effects of BsAb on PBMC-mediated lysis of MKN45 cells was measured by LDH cytotoxicity assay. Based on the original sequences of PD-1 and c-MET mAb, a BsAb gene was designed, cloned into pCEP4 vector for expression in 293E cells. The BsAb was obtained after purification of the cell culture supernatant. It can bind to PD-1 and c-MET simultaneously, the calculated affinity was 11.5 nM for PD-1 and 9.09 nM for c-MET. The BsAb enhanced IFN-γ production over control IgG by 2-3 folds. It also inhibit the c-MET pathway activation and the proliferation of tumor cells significantly, comparable to JnJ-38877605. The BsAb showed dose-dependent cytotoxic activity against MKN45 cells. Our results indicated that a novel BsAb recognizing PD-1 and c-MET was successfully generated. It could redirect T cells to kill tumor cells, while retaining its inherent ability to restore T cells and inhibit tumor cells. With this potential, this BsAb could be developed as a therapeutic candidate for the treatment of various solid tumors. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Weak Interactions Govern the Viscosity of Concentrated Antibody Solutions: High-Throughput Analysis Using the Diffusion Interaction Parameter

PubMed Central

Connolly, Brian D.; Petry, Chris; Yadav, Sandeep; Demeule, Barthélemy; Ciaccio, Natalie; Moore, Jamie M.R.; Shire, Steven J.; Gokarn, Yatin R.

2012-01-01

Weak protein-protein interactions are thought to modulate the viscoelastic properties of concentrated antibody solutions. Predicting the viscoelastic behavior of concentrated antibodies from their dilute solution behavior is of significant interest and remains a challenge. Here, we show that the diffusion interaction parameter (kD), a component of the osmotic second virial coefficient (B2) that is amenable to high-throughput measurement in dilute solutions, correlates well with the viscosity of concentrated monoclonal antibody (mAb) solutions. We measured the kD of 29 different mAbs (IgG1 and IgG4) in four different solvent conditions (low and high ion normality) and found a linear dependence between kD and the exponential coefficient that describes the viscosity concentration profiles (|R| ≥ 0.9). Through experimentally measured effective charge measurements, under low ion normality where the electroviscous effect can dominate, we show that the mAb solution viscosity is poorly correlated with the mAb net charge (|R| ≤ 0.6). With this large data set, our results provide compelling evidence in support of weak intermolecular interactions, in contrast to the notion that the electroviscous effect is important in governing the viscoelastic behavior of concentrated mAb solutions. Our approach is particularly applicable as a screening tool for selecting mAbs with desirable viscosity properties early during lead candidate selection. PMID:22828333

Hierarchical Cluster Formation in Concentrated Monoclonal Antibody Formulations

NASA Astrophysics Data System (ADS)

Godfrin, P. Douglas; Zarzar, Jonathan; Zarraga, Isidro Dan; Porcar, Lionel; Falus, Peter; Wagner, Norman; Liu, Yun

Reversible cluster formation has been identified as an underlying cause of large solution viscosities observed in some concentrated monoclonal antibody (mAb) formulations. As high solution viscosity prevents the use of subcutaneous injection as a delivery method for some mAbs, a fundamental understanding of the interactions responsible for high viscosities in concentrated mAb solutions is of significant relevance to mAb applications in human health care as well as of intellectual interest. Here, we present a detailed investigation of a well-studied IgG1 based mAb to relate the short time dynamics and microstructure to significant viscosity changes over a range of pharmaceutically relevant physiochemical conditions. Using a combination of experimental techniques, it is found that upon adding Na2SO4, these antibodies dimerize in solution. Proteins form strongly bounded reversible dimers at dilute concentrations that, when concentrated, interact with each other to form loosely bounded, large, transient clusters. The combined effect of forming strongly bounded dimers and a large transient network is a significant increase in the solution viscosity. Strongly bounded, reversible dimers may exist in many IgG1 based mAb systems such that these results contribute to a more comprehensive understanding of the physical mechanisms producing high viscosities in concentrated protein solutions.

Both Reversible Self-Association and Structural Changes Underpin Molecular Viscoelasticity of mAb Solutions.

PubMed

Sarangapani, Prasad S; Weaver, Justin; Parupudi, Arun; Besong, Tabot M D; Adams, Gary G; Harding, Stephen E; Manikwar, Prakash; Castellanos, Maria M; Bishop, Steven M; Pathak, Jai A

2016-12-01

The role of antibody structure (conformation) in solution rheology is probed. It is demonstrated here that pH-dependent changes in the tertiary structure of 2 mAb solutions lead to viscoelasticity and not merely a shear viscosity (η) increase. Steady shear flow curves on mAb solutions are reported over broad pH (3.0 ≤ pH ≤ 8.7) and concentration (2 mg/mL ≤ c ≤ 120 mg/mL) ranges to comprehensively characterize their rheology. Results are interpreted using size exclusion chromatography, differential scanning calorimetry, analytical ultracentrifugation, near-UV circular dichroism, and dynamic light scattering. Changes in tertiary structure with concentration lead to elastic yield stress and increased solution viscosity in solution of "mAb1." These findings are supported by dynamic light scattering and differential scanning calorimetry, which show increased hydrodynamic radius of mAb1 at low pH and a reduced melting temperature T m , respectively. Conversely, another molecule at 120 mg/mL solution concentration is a strong viscoelastic gel due to perturbed tertiary structure (seen in circular dichroism) at pH 3.0, but the same molecule responds as a viscous liquid due to reversible self-association at pH 7.4 (verified by analytical ultracentrifugation). Both protein-protein interactions and structural perturbations govern pH-dependent viscoelasticity of mAb solutions. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1998-01-01

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

Simultaneous Separation of Manganese, Cobalt, and Nickel by the Organic-Aqueous-Aqueous Three-Phase Solvent Extraction

NASA Astrophysics Data System (ADS)

Shirayama, Sakae; Uda, Tetsuya

2016-04-01

This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.

Natural additives to preserve quality and improve nutritional value of fresh-cut nectarine.

PubMed

Falagán, Natalia; Artés, Francisco; Aguayo, Encarna

2016-07-01

There is currently a high demand for natural and fresh-cut fruits. In this study, natural additives were applied to fresh-cut nectarines: (1) control, nontreated; (2) wedges were dipped in an antibrowning solution containing calcium ascorbate (AB); (3) and (4) wedges were dipped in an AB plus natural antimicrobial agents (vanillin or cinnamic acid, respectively). After these treatments, fresh-cut nectarines were packed and stored at 5 ℃ for eight days. The treatments AB+Vanillin and AB+Cinnamic inhibited microbial counts when compared with control and AB-only samples. The application of these solutions did not impart any aromas or off-flavors to nectarines and maintained firmness during the shelf-life period. AB solutions inhibited polyophenol oxidase action and reduced browning while stabilizing the soluble phenolic content, increasing consumer's acceptance. Nectarine wedges assimilated the ascorbic acid from the AB solution and retained it during the shelf-life period. The combination of an antibrowning agent and natural antimicrobials helped to control microbiological growth while maintaining high-quality parameters. They can be an attractive "green" alternative for organic fresh-cut products to other chemical sanitizers such as chlorine. © The Author(s) 2015.

EMERGING TECHNOLOGY BULLETIN: REMOVAL OF PHENOL FROM AQUEOUS SOLUTIONS USING HIGH ENERGY ELECTRON BEAM IRRADIATION

EPA Science Inventory

Irradiation of aqueous solutions with high-energy electrons results in the formation of the aqueous electron, hydrogen radical, H-, and the hydroxyl radical, OH-. These reactive transient species initiate chemical reactions capable of destroying organic compounds in aqueous solut...

REMOVAL OF CHLORIDE FROM AQUEOUS SOLUTIONS

DOEpatents

Schulz, W.W.

1959-08-01

The removal of chlorides from aqueons solutions is described. The process involves contacting the aqueous chloride containing solution with a benzene solution about 0.005 M in phenyl mercuric acetate whereby the chloride anions are taken up by the organic phase and separating the organic phase from the aqueous solutions.

Surf Zone Currents. Volume I. State of Knowledge.

DTIC Science & Technology

1982-09-01

elevation above an arbitrary datum a angle between wave crest and bottom contour a angle between wave crest and the shoreline . ab angle between breaking...b- Note that neglecting wave setup, refraction and for small ab , equation (74) reduces to that employed by Longuet-Higgins (eq. 48). These researchers...28. As ab o (Note that ab = o means theory reduces to original order (zero order) solution given by Longuet-Higgins, 1970, the triangular solution is

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1998-01-13

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.

Phase-separable aqueous amide solutions as a thermal history indicator.

PubMed

Kitsunai, Makoto; Miyajima, Kentaro; Mikami, Yuzuru; Kim, Shokaku; Hirasawa, Akira; Chiba, Kazuhiro

2008-12-01

Aqueous solutions of several new amide compounds for use as simple thermal history indicators in the low-temperature transport of food and other products were synthesized. The phase transition temperatures of the aqueous solutions can be freely adjusted by changing the amide-water ratio in solution, the sodium chloride concentration of the water, and the type of amide compound. It is expected that these aqueous solutions can be applied as new thermal history indicators.

Biological effects of an aqueous extract of Salix alba on the survival of Escherichia coli AB1157 cultures submitted to the action of stannous chloride.

PubMed

Souza, Raphael S S; Almeida, Marcela C; Manoel, Cristiano V; Santos-Filho, Sebastião D; Fonseca, Adenilson S; Bernardo Filho, Mario

2009-01-01

Stannous chloride (SnC12) is used in nuclear medicine as a reducing agent to obtain technetium-99m-radiopharmaceuticals. It have been reported that natural products might reduce the genotoxic and cytotoxic effects related to SnC12. This work evaluated the biological effects of an aqueous extract of Salix alba on the survival of Escherichia coli (E. coli) AB1157 (wild type) cultures submitted to the action of SnC12. E. coli AB1157 cultures (exponential growth phase) were collected by centrifugation, washed and resuspended in 0.9% NaCl. Samples were incubated in water bath shaker with: (a) SnC12 (25 microg/ml), (b) Salix alba extract(11.6 mg/ml) and (c) SnC12 (25 microg/ml) + Salix alba extract (11.6 mg/ml). Incubation with 0.9% NaCl was also carried out (control). At 60 min intervals, aliquots were withdrawn, diluted, spread onto Petri dishes with solid LB medium and incubated overnight. The colonies formed were counted and the survival fractions calculated. The extract was not able to protect the E. coli cultures against the lesive action of SnC12. The extract also did not interfere with the survival of the cultures. It suggested that the substances present in the Salix alba aqueous extract did not interfere strongly with cellular metabolism and did not alter the survival fractions of E. coli AB 1157. It is speculated that this extract cannot interfere with the generation of free radicals, the possible main agent responsible for SnC12 lesive action.

LASERS, ACTIVE MEDIA: The aqueous-polyelectrolyte dye solution as an active laser medium

NASA Astrophysics Data System (ADS)

Akimov, A. I.; Saletskii, A. M.

2000-11-01

The spectral, luminescent, and lasing properties of aqueous solutions of a cationic dye rhodamine 6G with additions of anion polyelectrolytes — polyacrylic and polymethacrylic acids — are studied. It is found that the energy and spectral properties of lasing of these solutions depend on the ratio of concentrations of polyelectrolyte and molecules. It is also found that the lasing parameters of aqueous-polyelectrolyte dye solutions can be controlled by changing the structure of the molecular system. The variation in the structure of aqueous-polyelectrolyte dye solutions of rhodamine 6G resulted in an almost five-fold increase in the lasing efficiency compared to that in aqueous dye solutions.

Nano and Mesoscale Ion and Water Transport in Perfluorosulfonic AcidMembranes

DTIC Science & Technology

2017-10-01

Nano- and Mesoscale Ion and Water Transport in Perfluorosulfonic-Acid Membranes A. R. Crothers a,b , C. J. Radke a,b , A. Z. Weber a a...Berkeley, CA 94720, USA Water and aqueous cations transport along multiple length scales in perfluorosulfonic-acid membranes. Molecular interactions...as a function of hydration. A resistor network upscales the nanoscale properties to predict effective membrane ion and water transport and their

Solution-phase electronegativity scale: insight into the chemical behaviors of metal ions in solution.

PubMed

Li, Keyan; Li, Min; Xue, Dongfeng

2012-04-26

By incorporating the solvent effect into the Born effective radius, we have proposed an electronegativity scale of metal ions in aqueous solution with the most common oxidation states and hydration coordination numbers in terms of the effective ionic electrostatic potential. It is found that the metal ions in aqueous solution are poorer electron acceptors compared to those in the gas phase. This solution-phase electronegativity scale shows its efficiency in predicting some important properties of metal ions in aqueous solution such as the aqueous acidities of the metal ions, the stability constants of metal complexes, and the solubility product constants of the metal hydroxides. We have elaborated that the standard reduction potential and the solution-phase electronegativity are two different quantities for describing the processes of metal ions in aqueous solution to soak up electrons with different final states. This work provides a new insight into the chemical behaviors of the metal ions in aqueous solution, indicating a potential application of this electronegativity scale to the design of solution reactions.

Method of precipitating uranium from an aqueous solution and/or sediment

DOEpatents

Tokunaga, Tetsu K; Kim, Yongman; Wan, Jiamin

2013-08-20

A method for precipitating uranium from an aqueous solution and/or sediment comprising uranium and/or vanadium is presented. The method includes precipitating uranium as a uranyl vanadate through mixing an aqueous solution and/or sediment comprising uranium and/or vanadium and a solution comprising a monovalent or divalent cation to form the corresponding cation uranyl vanadate precipitate. The method also provides a pathway for extraction of uranium and vanadium from an aqueous solution and/or sediment.

SEPARATION OF SCANDIUM VALUES FORM IRON VALUES BY SOLVENT EXTRACTION

DOEpatents

Kuhlman, C.W. Jr.; Lang, G.P.

1961-12-19

A process is given for separating scandium from trivalent iron values. In this process, an aqueous nitric acid solution is contacted with a water- immiscible alkyl phosphate solution, the aqueous solution containing the values to be separated, whereby the scandium is taken up by the alkyl phosphate. The aqueous so1ution is preferably saturated with magnesium nitrate to retain the iron in the aqueous solution. (AEC)

Method for the separation of high impact polystyrene (HIPS) and acrylonitrile butadiene styrene (ABS) plastics

DOEpatents

Jody, Bassam J.; Arman, Bayram; Karvelas, Dimitrios E.; Pomykala, Jr., Joseph A.; Daniels, Edward J.

1997-01-01

An improved method is provided for separating acrylonitrile butadiene styrene (ABS) and high impact polystyrene (HIPS) plastics from each other. The ABS and HIPS plastics are shredded to provide a selected particle size. The shredded particles of the ABS and HIPS plastics are applied to a solution having a solution density in a predefined range between 1.055 gm/cm.sup.3 and 1.07 gm/cm.sup.3, a predefined surface tension in a range between 22 dynes/cm to 40 dynes/cm and a pH in the range of 1.77 and 2.05. In accordance with a feature of the invention, the novel method is provided for separating ABS and HIPS, two solid thermoplastics which have similar densities by selectively modifying the effective density of the HIPS using a binary solution with the appropriate properties, such as pH, density and surface tension, such as a solution of acetic acid and water or a quaternary solution having the appropriate density, surface tension, and pH.

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Reversible cluster formation in concentrated monoclonal antibody solutions

NASA Astrophysics Data System (ADS)

Godfrin, P. Douglas; Porcar, Lionel; Falus, Peter; Zarraga, Isidro; Wagner, Norm; Liu, Yun

2015-03-01

Protein cluster formation in solution is of fundamental interest for both academic research and industrial applications. Recently, industrial scientists are also exploring the effect of reversible cluster formation on biopharmaceutical processing and delivery. However, despite of its importance, the understanding of protein clusters at concentrated solutions remains scientifically very challenging. Using the neutron spin echo technique to study the short time dynamics of proteins in solutions, we have recently systematically studied cluster formation in a few monoclonal antibody (mAb) solutions and their relation with solution viscosity. We show that the existence of anisotropic attraction can cause the formation of finite sized clusters, which increases the solution viscosity. Interestingly, once clusters form at relatively low concentrations, the average size of clusters in solutions remains almost constant over a wide range of concentrations similar to that of micelle formation. For a different mAb we have also investigated, the attraction is mostly induced by hydrophobic patches. As a result, these mAbs form large clusters with loosely linked proteins. In both cases, the formation of clusters all increases the solution viscosity substantially. However, due to different physics origins of cluster formation, solutions viscosities for these two different types of mAbs need to be controlled by different ways.

In-silico prediction of concentration-dependent viscosity curves for monoclonal antibody solutions

PubMed Central

Tomar, Dheeraj S.; Li, Li; Broulidakis, Matthew P.; Luksha, Nicholas G.; Burns, Christopher T.; Singh, Satish K.; Kumar, Sandeep

2017-01-01

ABSTRACT Early stage developability assessments of monoclonal antibody (mAb) candidates can help reduce risks and costs associated with their product development. Forecasting viscosity of highly concentrated mAb solutions is an important aspect of such developability assessments. Reliable predictions of concentration-dependent viscosity behaviors for mAb solutions in platform formulations can help screen or optimize drug candidates for flexible manufacturing and drug delivery options. Here, we present a computational method to predict concentration-dependent viscosity curves for mAbs solely from their sequence—structural attributes. This method was developed using experimental data on 16 different mAbs whose concentration-dependent viscosity curves were experimentally obtained under standardized conditions. Each concentration-dependent viscosity curve was fitted with a straight line, via logarithmic manipulations, and the values for intercept and slope were obtained. Intercept, which relates to antibody diffusivity, was found to be nearly constant. In contrast, slope, the rate of increase in solution viscosity with solute concentration, varied significantly across different mAbs, demonstrating the importance of intermolecular interactions toward viscosity. Next, several molecular descriptors for electrostatic and hydrophobic properties of the 16 mAbs derived using their full-length homology models were examined for potential correlations with the slope. An equation consisting of hydrophobic surface area of full-length antibody and charges on VH, VL, and hinge regions was found to be capable of predicting the concentration-dependent viscosity curves of the antibody solutions. Availability of this computational tool may facilitate material-free high-throughput screening of antibody candidates during early stages of drug discovery and development. PMID:28125318

In-silico prediction of concentration-dependent viscosity curves for monoclonal antibody solutions.

PubMed

Tomar, Dheeraj S; Li, Li; Broulidakis, Matthew P; Luksha, Nicholas G; Burns, Christopher T; Singh, Satish K; Kumar, Sandeep

2017-04-01

Early stage developability assessments of monoclonal antibody (mAb) candidates can help reduce risks and costs associated with their product development. Forecasting viscosity of highly concentrated mAb solutions is an important aspect of such developability assessments. Reliable predictions of concentration-dependent viscosity behaviors for mAb solutions in platform formulations can help screen or optimize drug candidates for flexible manufacturing and drug delivery options. Here, we present a computational method to predict concentration-dependent viscosity curves for mAbs solely from their sequence-structural attributes. This method was developed using experimental data on 16 different mAbs whose concentration-dependent viscosity curves were experimentally obtained under standardized conditions. Each concentration-dependent viscosity curve was fitted with a straight line, via logarithmic manipulations, and the values for intercept and slope were obtained. Intercept, which relates to antibody diffusivity, was found to be nearly constant. In contrast, slope, the rate of increase in solution viscosity with solute concentration, varied significantly across different mAbs, demonstrating the importance of intermolecular interactions toward viscosity. Next, several molecular descriptors for electrostatic and hydrophobic properties of the 16 mAbs derived using their full-length homology models were examined for potential correlations with the slope. An equation consisting of hydrophobic surface area of full-length antibody and charges on V H , V L , and hinge regions was found to be capable of predicting the concentration-dependent viscosity curves of the antibody solutions. Availability of this computational tool may facilitate material-free high-throughput screening of antibody candidates during early stages of drug discovery and development.

Hydrogen production by sodium borohydride in NaOH aqueous solution

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Assessment of Fenton's reagent and ozonation as pre-treatments for increasing the biodegradability of aqueous diethanolamine solutions from an oil refinery gas sweetening process.

PubMed

Durán-Moreno, A; García-González, S A; Gutiérrez-Lara, M R; Rigas, F; Ramírez-Zamora, R M

2011-02-28

The aim of this work was to evaluate the efficiency of three chemical oxidation processes for increasing the biodegradability of aqueous diethanolamine solutions (aqueous DEA solutions), to be used as pre-treatments before a biological process. The raw aqueous DEA solution, sourced from a sour gas sweetening plant at a Mexican oil refinery, was first characterized by standardized physico-chemical methods. Then experiments were conducted on diluted aqueous DEA solutions to test the effects of Fenton's reagent, ozone and ozone-hydrogen peroxide on the removal of some physicochemical parameters of these solutions. Lastly, biodegradability tests based on Dissolved Organic Carbon Die Away OECD301-A, were carried out on a dilution of the raw aqueous DEA solution and on the treated aqueous DEA solutions, produced by applying the best experimental conditions determined during the aforementioned oxidation tests. Experimental results showed that for aqueous DEA solutions treated with Fenton's reagent, the best degradation rate (70%) was obtained at pH 2.8, with Fe(2+) and H(2)O(2) at doses of 1000 and 10,000 mg/L respectively. In the ozone process, the best degradation (60%) was observed in aqueous DEA solution (100 mg COD/L), using 100 mg O(3)/L at pH 5. In the ozone-hydrogen peroxide process, no COD or DOC removals were observed. The diluted spent diethanolamine solution showed its greatest increase in biodegradability after a reaction period of 28 days when treated with Fenton's reagent, but after only 15 days in the case of ozonation. Copyright © 2011 Elsevier B.V. All rights reserved.

Cryo-irradiation as a terminal method for the sterilization of drug aqueous solutions.

PubMed

Maquille, Aubert; Habib Jiwan, Jean-Louis; Tilquin, Bernard

2008-05-01

The aim of this study is to evaluate the specificities of the irradiation of drugs in frozen aqueous solution. The structures of the degradation products were determined to gain insight into the radiolysis mechanisms occurring in frozen aqueous solutions. Metoclopramide hydrochloride and metoprolol tartrate were chosen as models. The frozen solutions were irradiated at dry ice temperature by high energy electrons at various doses. The drug purity (chemical potency) and the radiolysis products were quantified by HPLC-DAD. Characterization of the degradation products was performed by LC-APCI-MS-MS. The structures of the radiolysis products detected in irradiated frozen aqueous solutions were compared to those detected in solid-state and aqueous solutions (previous studies). For both metoclopramide and metoprolol, solute loss upon irradiation of frozen aqueous solutions was negligible. Five radiolysis products present in traces were identified in irradiated metoclopramide frozen solutions. Three of them were previously identified in solid-state irradiated metoclopramide crystals. The two others were formed following reactions with the hydroxyl radical (indirect effect). Only one fragmentation product was observed in irradiated metoprolol frozen solutions. For both drugs, radiosterilization of frozen solutions, even at high doses (25 kGy), was found to be possible.

Noble metal superparticles and methods of preparation thereof

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

Sun, Yugang; Hu, Yongxing

A method comprises heating an aqueous solution of colloidal silver particles. A soluble noble metal halide salt is added to the aqueous solution which undergoes a redox reaction on a surface of the silver particles to form noble metal/silver halide SPs, noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs on the surface of the silver particles. The heat is maintained for a predetermined time to consume the silver particles and release the noble metal/silver halide SPs, the noble metal halide/silver halide SPs or the noble metal oxide/silver halide SPs into the aqueous solution. The aqueous solution ismore » cooled. The noble metal/silver halide SPs, the noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs are separated from the aqueous solution. The method optionally includes adding a soluble halide salt to the aqueous solution.« less

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

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

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One systemmore » operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.« less

Hydrogen generation systems utilizing sodium silicide and sodium silica gel materials

DOEpatents

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

2015-07-14

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

Passive asymmetric transport of hesperetin across isolated rabbit cornea.

PubMed

Srirangam, Ramesh; Majumdar, Soumyajit

2010-07-15

Hesperetin, an aglycone of the flavanone hesperidin, is a potential candidate for the treatment of diabetic retinopathy and macular edema. The purpose of this investigation was to determine solubility, stability and in vitro permeability characteristics of hesperetin across excised rabbit corneas. Aqueous and pH dependent solubility was determined using standard shake flask method. Solution stability was evaluated as a function of pH (1.2-9) and temperature (25 and 40 degrees C). Permeability of hesperetin was determined across the isolated rabbit cornea utilizing a side-bi-side diffusion apparatus, in the apical to basolateral (A-B) and basolateral to apical (B-A) directions. Hesperetin displayed asymmetrical transcorneal transport with a 2.3-fold higher apparent permeability in the B-A direction compared to the A-B direction. The transport process was observed to be pH dependent. Surprisingly, however, the involvement of efflux transporters or proton-coupled carrier-systems was not evident in this asymmetric transcorneal diffusion process. The passive and pH dependent corneal transport of hesperetin could probably be attributable to corneal ultrastructure, physicochemical characteristics of hesperetin and the role of transport buffer components. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

PubMed

Wang, Zhijuan; Li, Bing; Ge, Xiaoming; Goh, F W Thomas; Zhang, Xiao; Du, Guojun; Wuu, Delvin; Liu, Zhaolin; Andy Hor, T S; Zhang, Hua; Zong, Yun

2016-05-01

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combined ab initio/empirical approach for optimization of Lennard-Jones parameters for polar-neutral compounds.

PubMed

Chen, I Jen; Yin, Daxu; MacKerell, Alexander D

2002-01-30

The study of small functionalized organic molecules in aqueous solution is a useful step toward gaining a basic understanding of the behavior of biomolecular systems in their native aqueous environment. Interest in studying amines and fluorine-substituted compounds has risen from their intrinsic physicochemical properties and their prevalence in biological and pharmaceutical compounds. In the present study, a previously developed approach which optimizes Lennard-Jones (LJ) parameters via the use of rare gas atoms combined with the reproduction of experimental condensed phase properties was extended to polar-neutral compounds. Compounds studied included four amines (ammonia, methylamine, dimethylamine, and trimethylamine) and three fluoroethanes (1-fluoroethane, 1,1-difluoroethane, and 1,1,1-trifluoroethane). The resulting force field yielded heats of vaporization and molecular volumes in excellent agreement with the experiment, with average differences less than 1%. The current amine CHARMM parameters successfully reproduced experimental aqueous solvation data where methylamine is more hydrophilic than ammonia, with hydrophobicity increasing with additional methylation on the nitrogen. For both the amines and fluoroethanes the parabolic relationship of the extent of methylation or fluorination, respectively, to the heats of vaporization were reproduced by the new parameters. The present results are also discussed with respect to the impact of parameterization approach to molecular details obtained from computer simulations and to the unique biological properties of fluorine in pharmaceutical compounds.

Adsorptive removal of dye using biochar derived from residual algae after in-situ transesterification: Alternate use of waste of biodiesel industry.

PubMed

Nautiyal, Piyushi; Subramanian, K A; Dastidar, M G

2016-11-01

The primary aim of this present study was to utilize the residual biomass (DB) of Spirulina platensis algae, left after in-situ transesterification, for biochar preparation. This is a solid waste residue of biodiesel industry. The biochar (BC) prepared was examined for its capacity to adsorb congo red dye from the aqueous solution. The results were compared with other adsorbents used in the study such as commercial activated carbon (AC), original algae biomass (AB) and DB. The results of proximate analysis of BC showed the decrease in the percentage of volatile matter and an increase in fixed carbon content compared to DB. The physico-chemical properties of BC were studied using elemental analysis, SEM, FTIR and XRD techniques. The AC and BC adsorbents showed better performance in removing 85.4% and 82.6% of dye respectively from solution compared to AB (76.6%) and DB (78.1%). The effect of initial dye concentration, adsorbent dosage and pH of solution on the adsorption phenomena was studied by conducting the batch adsorption experiments. The highest specific uptake for biochar was observed at acidic pH of 2 with 0.2 g/100 ml of adsorbent dosage and 90 mg/l of initial concentration. The equilibrium adsorption data were fitted to three isotherms, namely Langmuir, Freundlich and Temkin. Freundlich model proved to show the best suited results with value of correlation coefficient of 99.12%. Thus, the application of DB for production of biochar as potential adsorbent supports sustainability of algae biodiesel. Copyright © 2016 Elsevier Ltd. All rights reserved.

Small-scale screening method for low-viscosity antibody solutions using small-angle X-ray scattering.

PubMed

Fukuda, Masakazu; Watanabe, Atsushi; Hayasaka, Akira; Muraoka, Masaru; Hori, Yuji; Yamazaki, Tadao; Imaeda, Yoshimi; Koga, Akiko

2017-03-01

In this study, we investigated the concentration range in which self-association starts to form in humanized IgG monoclonal antibody (mAb) solutions. Furthermore, on the basis of the results, we developed a practical method of screening for low-viscosity antibody solutions by using small-angle X-ray scattering (SAXS) measurements utilizing small quantities of samples. With lower-viscosity mAb3, self-association was not detected in the range of 1-80mg/mL. With higher-viscosity mAb1, on the other hand, self-association was detected in the range of 10-20mg/mL and was clearly enhanced by a decrease in temperature. The viscosities of mAb solutions at 160, 180, and 200mg/mL at 25°C quantitatively correlated very well with the particle size parameters obtained by SAXS measurements of mAb solutions at 15mg/mL at 5°C. The quantity of mAb sample required for the SAXS measurements was only 0.15mg, which is about one-hundredth of that required for actual viscosity measurements at a high concentration, and such quantities could be available even at an early stage of development. In conclusion, the SAXS analysis method proposed in this study is a valuable tool for the development of concentrated mAb therapeutics with high manufacturability and high usability for subcutaneous injection. Copyright © 2016 Elsevier B.V. All rights reserved.

Conversion of depleted uranium hexafluoride to a solid uranium compound

DOEpatents

Rothman, Alan B.; Graczyk, Donald G.; Essling, Alice M.; Horwitz, E. Philip

2001-01-01

A process for converting UF.sub.6 to a solid uranium compound such as UO.sub.2 and CaF. The UF.sub.6 vapor form is contacted with an aqueous solution of NH.sub.4 OH at a pH greater than 7 to precipitate at least some solid uranium values as a solid leaving an aqueous solution containing NH.sub.4 OH and NH.sub.4 F and remaining uranium values. The solid uranium values are separated from the aqueous solution of NH.sub.4 OH and NH.sub.4 F and remaining uranium values which is then diluted with additional water precipitating more uranium values as a solid leaving trace quantities of uranium in a dilute aqueous solution. The dilute aqueous solution is contacted with an ion-exchange resin to remove substantially all the uranium values from the dilute aqueous solution. The dilute solution being contacted with Ca(OH).sub.2 to precipitate CaF.sub.2 leaving dilute NH.sub.4 OH.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Beederman, M.; Vogler, S.; Hyman, H.H.

1959-07-14

The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

SEPARATION OF POLONIUM, PROTACTINIUM OR MIXTURES THEREOF IN AQUEOUS SOLUTION FROM BISMUTH, LEAD, ZIRCONIUM AND/OR COLUMBIUM VALUES

DOEpatents

Van Winkle, Q.; Kraus, K.A.

1959-10-27

A process is presented for separating polonium, protactinium, or mixtures thereof in aqueous solution from bismuth, zirconium, lead, and niobium values contained in the solution. The method comprises providing hydrochloric acid in the solution in a concentration of at least 5N. contacting the aqueous solution with a substantially waterimmiscible organic solvent such as diisopropyl ketone, and separating the aqueous phase containing the bismuth, zirconium, lead, and niobium from the organic extract phase containing the polonium, protactinium, or mixture thereof.

Highly viscous antibody solutions are a consequence of network formation caused by domain-domain electrostatic complementarities: insights from coarse-grained simulations.

PubMed

Buck, Patrick M; Chaudhri, Anuj; Kumar, Sandeep; Singh, Satish K

2015-01-05

Therapeutic monoclonal antibody (mAb) candidates that form highly viscous solutions at concentrations above 100 mg/mL can lead to challenges in bioprocessing, formulation development, and subcutaneous drug delivery. Earlier studies of mAbs with concentration-dependent high viscosity have indicated that mAbs with negatively charged Fv regions have a dipole-like quality that increases the likelihood of reversible self-association. This suggests that weak electrostatic intermolecular interactions can form transient antibody networks that participate in resistance to solution deformation under shear stress. Here this hypothesis is explored by parametrizing a coarse-grained (CG) model of an antibody using the domain charges from four different mAbs that have had their concentration-dependent viscosity behaviors previously determined. Multicopy molecular dynamics simulations were performed for these four CG mAbs at several concentrations to understand the effect of surface charge on mass diffusivity, pairwise interactions, and electrostatic network formation. Diffusion coefficients computed from simulations were in qualitative agreement with experimentally determined viscosities for all four mAbs. Contact analysis revealed an overall greater number of pairwise interactions for the two mAbs in this study with high concentration viscosity issues. Further, using equilibrated solution trajectories, the two mAbs with high concentration viscosity issues quantitatively formed more features of an electrostatic network than the other mAbs. The change in the number of these network features as a function of concentration is related to the number of pairwise interactions formed by electrostatic complementarities between antibody domains. Thus, transient antibody network formation caused by domain-domain electrostatic complementarities is the most probable origin of high concentration viscosity for mAbs in this study.

Ionization energies of aqueous nucleic acids: photoelectron spectroscopy of pyrimidine nucleosides and ab initio calculations.

PubMed

Slavícek, Petr; Winter, Bernd; Faubel, Manfred; Bradforth, Stephen E; Jungwirth, Pavel

2009-05-13

Vertical ionization energies of the nucleosides cytidine and deoxythymidine in water, the lowest ones amounting in both cases to 8.3 eV, are obtained from photoelectron spectroscopy measurements in aqueous microjets. Ab initio calculations employing a nonequilibrium polarizable continuum model quantitatively reproduce the experimental spectra and provide molecular interpretation of the individual peaks of the photoelectron spectrum, showing also that lowest ionization originates from the base. Comparison of calculated vertical ionization potentials of pyrimidine bases, nucleosides, and nucleotides in water and in the gas phase underlines the dramatic effect of bulk hydration on the electronic structure. In the gas phase, the presence of sugar and, in particular, of phosphate has a strong effect on the energetics of ionization of the base. Upon bulk hydration, the ionization potential of the base in contrast becomes rather insensitive to the presence of the sugar and phosphate, which indicates a remarkable screening ability of the aqueous solvent. Accurate aqueous-phase vertical ionization potentials provide a significant improvement to the corrected gas-phase values used in the literature and represent important information in assessing the threshold energies for photooxidation and oxidation free energies of solvent-exposed DNA components. Likewise, such energetic data should allow improved assessment of delocalization and charge-hopping mechanisms in DNA ionized by radiation.

RECOVERY OF ACTINIDES FROM AQUEOUS NITRIC ACID SOLUTIONS

DOEpatents

Ader, M.

1963-11-19

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

Dark solitons, breathers, and rogue wave solutions of the coupled generalized nonlinear Schrödinger equations.

PubMed

Priya, N Vishnu; Senthilvelan, M; Lakshmanan, M

2014-06-01

We construct dark-dark soliton, general breather (GB), Akhmediev breather (AB), Ma soliton (MS), and rogue wave (RW) solutions of a coupled generalized nonlinear Schrödinger (CGNLS) equation. While dark-dark solitons are captured in the defocusing regime of the CGNLS system, the other solutions, namely, GB, AB, MS, and RW, are identified in the focusing regime. We also analyze the structures of GB, AB, MS, and RW profiles with respect to the four-wave mixing parameter. We show that when we increase the value of the real part of the four-wave mixing parameter, the number of peaks in the breather profile increases and the width of each peak shrinks. Interestingly, the direction of this profile also changes due to this change. As far as the RW profile is concerned the width of the peak becomes very thin when we increase the value of this parameter. Further, we consider the RW solution as the starting point, derive AB, MS, and GB in the reverse direction, and show that the solutions obtained in both directions match each other. In the course of the reverse analysis we also demonstrate how to capture the RW solutions directly from AB and MS.

ENGINEERING BULLETIN: AIR STRIPPING OF AQUEOUS SOLUTIONS

EPA Science Inventory

Air striding is a means to transfer contaminants from aqueous solutions to air. ontaminants are not destroyed by air stripping but are physically separated from the aqueous solutions. ontaminant vapors are transferred into the air stream and, if necessary, can be treated by incin...

Separation of no-carrier-added rhenium from bulk tantalum by the sodium malonate-PEG aqueous biphasic system.

PubMed

Dutta, Binita; Lahiri, Susanta; Tomar, B S

2014-02-01

The aqueous biphasic system (ABS) involving sodium malonate-polyethylene glycol (PEG) phases has been applied for the first time for separation of no-carrier-added (183)Re (T1/2=70 d) from α-particle irradiated bulk tantalum target. The various ABS conditions were applied for investigating the separation by varying pH, temperature, PEG-molecular weight, concentration of salt. The extraction pattern was hardly affected by change in pH and the molecular weight of PEG. One step separation of nca (183)Re from Ta was achieved at the optimal conditions of (i) 50% (w/w) PEG-4000-2 M sodium malonate, 40 °C and (ii) 50% (w/w) PEG-4000-3 M sodium malonate, room temperature (27 °C). © 2013 Published by Elsevier Ltd.

Aqueous two-phase extraction as a platform in the biomanufacturing industry: economical and environmental sustainability.

PubMed

Rosa, P A J; Azevedo, A M; Sommerfeld, S; Bäcker, W; Aires-Barros, M R

2011-01-01

The biotech industry is, nowadays, facing unparalleled challenges due to the enhanced demand for biotechnology-based human therapeutic products, such as monoclonal antibodies (mAbs). This has led companies to improve substantially their upstream processes, with the yield of monoclonals increasing to titers never seen before. The downstream processes have, however, been overlooked, leading to a production bottleneck. Although chromatography remains the workhorse of most purification processes, several limitations, such as low capacity, scale-related packing problems, low chemical and proteolytic stability and resins' high cost, have arisen. Aqueous two-phase extraction (ATPE) has been successfully revisited as a valuable alternative for the capture of antibodies. One of the important remaining questions for this technology to be adopted by the biotech industries is, now, how it compares to the currently established platforms in terms of costs and environmental impact. In this report, the economical and environmental sustainability of the aqueous two-phase extraction process is evaluated and compared to the currently established protein A affinity chromatography. Accordingly, the ATPE process was shown to be considerably advantageous in terms of process economics, especially when processing high titer cell culture supernatants. This alternative process is able to purify continuously the same amount of mAbs reducing the annual operating costs from 14.4 to 8.5 million (US$/kg) when cell culture supernatants with mAb titers higher than 2.5 g/L are processed. Copyright © 2011 Elsevier Inc. All rights reserved.

Metal separations using aqueous biphasic partitioning systems

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

Chaiko, D.J.; Zaslavsky, B.; Rollins, A.N.

1996-05-01

Aqueous biphasic extraction (ABE) processes offer the potential for low-cost, highly selective separations. This countercurrent extraction technique involves selective partitioning of either dissolved solutes or ultrafine particulates between two immiscible aqueous phases. The extraction systems that the authors have studied are generated by combining an aqueous salt solution with an aqueous polymer solution. They have examined a wide range of applications for ABE, including the treatment of solid and liquid nuclear wastes, decontamination of soils, and processing of mineral ores. They have also conducted fundamental studies of solution microstructure using small angle neutron scattering (SANS). In this report they reviewmore » the physicochemical fundamentals of aqueous biphase formation and discuss the development and scaleup of ABE processes for environmental remediation.« less

Raman spectroscopic study of the conformation of dicarboxylic acid salts in aqueous solutions

NASA Astrophysics Data System (ADS)

Fukushima, Kunio; Watanabe, Toshiaki; Umemura, Matome

1986-08-01

It is already known that the molecules of long chain monocarboxylic acid salts have a tendency to form micelles in aqueous solutions, the molecular chain taking the all- trans zigzag structure. However it is considered difficult for dicarboxylic acid salts to adopt the same structure as the monocarboxylic acid salts as they have two carboxyl groups, one on each end of the molecular chain. Therefore, a special structure is expected to exist for dicarboxylic acid salts in aqueous solution. In order to examine this, Raman spectra of suberic acid salt and azelaic acid salt in aqueous solution were measured and the normal vibrational calculation carried out, showing that dicarboxylic acid salts have a helical structure in aqueous solution.

SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES

DOEpatents

Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.

1962-08-14

A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)

Characterizing monoclonal antibody formulations in arginine glutamate solutions using 1H NMR spectroscopy

PubMed Central

Kheddo, Priscilla; Cliff, Matthew J.; Uddin, Shahid; van der Walle, Christopher F.; Golovanov, Alexander P.

2016-01-01

ABSTRACT Assessing how excipients affect the self-association of monoclonal antibodies (mAbs) requires informative and direct in situ measurements for highly concentrated solutions, without sample dilution or perturbation. This study explores the application of solution nuclear magnetic resonance (NMR) spectroscopy for characterization of typical mAb behavior in formulations containing arginine glutamate. The data show that the analysis of signal intensities in 1D 1H NMR spectra, when compensated for changes in buffer viscosity, is invaluable for identifying conditions where protein-protein interactions are minimized. NMR-derived molecular translational diffusion rates for concentrated solutions are less useful than transverse relaxation rates as parameters defining optimal formulation. Furthermore, NMR reports on the solution viscosity and mAb aggregation during accelerated stability study assessment, generating data consistent with that acquired by size-exclusion chromatography. The methodology developed here offers NMR spectroscopy as a new tool providing complementary information useful to formulation development of mAbs and other large therapeutic proteins. PMID:27589351

Characterizing monoclonal antibody formulations in arginine glutamate solutions using 1H NMR spectroscopy.

PubMed

Kheddo, Priscilla; Cliff, Matthew J; Uddin, Shahid; van der Walle, Christopher F; Golovanov, Alexander P

2016-10-01

Assessing how excipients affect the self-association of monoclonal antibodies (mAbs) requires informative and direct in situ measurements for highly concentrated solutions, without sample dilution or perturbation. This study explores the application of solution nuclear magnetic resonance (NMR) spectroscopy for characterization of typical mAb behavior in formulations containing arginine glutamate. The data show that the analysis of signal intensities in 1D 1 H NMR spectra, when compensated for changes in buffer viscosity, is invaluable for identifying conditions where protein-protein interactions are minimized. NMR-derived molecular translational diffusion rates for concentrated solutions are less useful than transverse relaxation rates as parameters defining optimal formulation. Furthermore, NMR reports on the solution viscosity and mAb aggregation during accelerated stability study assessment, generating data consistent with that acquired by size-exclusion chromatography. The methodology developed here offers NMR spectroscopy as a new tool providing complementary information useful to formulation development of mAbs and other large therapeutic proteins.

Ab initio theory and modeling of water.

PubMed

Chen, Mohan; Ko, Hsin-Yu; Remsing, Richard C; Calegari Andrade, Marcos F; Santra, Biswajit; Sun, Zhaoru; Selloni, Annabella; Car, Roberto; Klein, Michael L; Perdew, John P; Wu, Xifan

2017-10-10

Water is of the utmost importance for life and technology. However, a genuinely predictive ab initio model of water has eluded scientists. We demonstrate that a fully ab initio approach, relying on the strongly constrained and appropriately normed (SCAN) density functional, provides such a description of water. SCAN accurately describes the balance among covalent bonds, hydrogen bonds, and van der Waals interactions that dictates the structure and dynamics of liquid water. Notably, SCAN captures the density difference between water and ice I h at ambient conditions, as well as many important structural, electronic, and dynamic properties of liquid water. These successful predictions of the versatile SCAN functional open the gates to study complex processes in aqueous phase chemistry and the interactions of water with other materials in an efficient, accurate, and predictive, ab initio manner.

Ab initio theory and modeling of water

PubMed Central

Chen, Mohan; Ko, Hsin-Yu; Remsing, Richard C.; Calegari Andrade, Marcos F.; Santra, Biswajit; Sun, Zhaoru; Selloni, Annabella; Car, Roberto; Klein, Michael L.; Perdew, John P.; Wu, Xifan

2017-01-01

Water is of the utmost importance for life and technology. However, a genuinely predictive ab initio model of water has eluded scientists. We demonstrate that a fully ab initio approach, relying on the strongly constrained and appropriately normed (SCAN) density functional, provides such a description of water. SCAN accurately describes the balance among covalent bonds, hydrogen bonds, and van der Waals interactions that dictates the structure and dynamics of liquid water. Notably, SCAN captures the density difference between water and ice Ih at ambient conditions, as well as many important structural, electronic, and dynamic properties of liquid water. These successful predictions of the versatile SCAN functional open the gates to study complex processes in aqueous phase chemistry and the interactions of water with other materials in an efficient, accurate, and predictive, ab initio manner. PMID:28973868

Measuring the change in hydration of a polypeptide-based block polymer vesicle as a function of pH

NASA Astrophysics Data System (ADS)

Smith, Ian; Charlier, Alban; Shishlov, Alexander; Savin, Daniel

Amphiphilic AB2 star polymers undergo directed self-assembly into vesicles in aqueous solution. The overall structure of the assembly is responsive to a change in solution pH by incorporating an ionizable polypeptide as the A-block and two lipid-like tails for the B-blocks. Herein, we present some recent results in the solution characterization of polyglutamate-octadecanethiol2 (PE-DDT2) star polymers using static and dynamic light scattering, as well as transmission electron microscopy. An increase in pH will induce a transition in secondary structure of the PE block from an α-helix to an extended coil, thereby perturbing the morphological structure and resulting in an expansion of the vesicle. The magnitude of this response is much larger than what is expected based on the conformational transition of the peptide. The mechanism of this process can be probed by measuring the change in hydration at the surface of the hydrophobic bilayer. Towards this end, we utilize 2,4,6-trichloro-1,3,5-triazine (TCT) as a modular linker to install spin labels into the assembly as a mechanism to directly interrogate local hydrophobicity using electron paramagnetic resonance (EPR). NSF 1539347.

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.

Aqueous Plasma Pharmacy: Preparation Methods, Chemistry, and Therapeutic Applications

PubMed Central

Joslin, Jessica M.; McCall, James R.; Bzdek, Justin P.; Johnson, Derek C.; Hybertson, Brooks M.

2017-01-01

Plasma pharmacy is a subset of the broader field of plasma medicine. Although not strictly defined, the term aqueous plasma pharmacy (APP) is used to refer to the generation and distribution of reactive plasma-generated species in an aqueous solution followed by subsequent administration for therapeutic benefits. APP attempts to harness the therapeutic effects of plasma-generated oxidant species within aqueous solution in various applications, such as disinfectant solutions, cell proliferation related to wound healing, and cancer treatment. The subsequent use of plasma-generated solutions in the APP approach facilitates the delivery of reactive plasma species to internal locations within the body. Although significant efforts in the field of plasma medicine have concentrated on employing direct plasma plume exposure to cells or tissues, here we focus specifically on plasma discharge in aqueous solution to render the solution biologically active for subsequent application. Methods of plasma discharge in solution are reviewed, along with aqueous plasma chemistry and the applications for APP. The future of the field also is discussed regarding necessary research efforts that will enable commercialization for clinical deployment. PMID:28428835

Mechanistic insights for block copolymer morphologies: how do worms form vesicles?

PubMed

Blanazs, Adam; Madsen, Jeppe; Battaglia, Giuseppe; Ryan, Anthony J; Armes, Steven P

2011-10-19

Amphiphilic diblock copolymers composed of two covalently linked, chemically distinct chains can be considered to be biological mimics of cell membrane-forming lipid molecules, but with typically more than an order of magnitude increase in molecular weight. These macromolecular amphiphiles are known to form a wide range of nanostructures (spheres, worms, vesicles, etc.) in solvents that are selective for one of the blocks. However, such self-assembly is usually limited to dilute copolymer solutions (<1%), which is a significant disadvantage for potential commercial applications such as drug delivery and coatings. In principle, this problem can be circumvented by polymerization-induced block copolymer self-assembly. Here we detail the synthesis and subsequent in situ self-assembly of amphiphilic AB diblock copolymers in a one pot concentrated aqueous dispersion polymerization formulation. We show that spherical micelles, wormlike micelles, and vesicles can be predictably and efficiently obtained (within 2 h of polymerization, >99% monomer conversion) at relatively high solids in purely aqueous solution. Furthermore, careful monitoring of the in situ polymerization by transmission electron microscopy reveals various novel intermediate structures (including branched worms, partially coalesced worms, nascent bilayers, "octopi", "jellyfish", and finally pure vesicles) that provide important mechanistic insights regarding the evolution of the particle morphology during the sphere-to-worm and worm-to-vesicle transitions. This environmentally benign approach (which involves no toxic solvents, is conducted at relatively high solids, and requires no additional processing) is readily amenable to industrial scale-up, since it is based on commercially available starting materials.

Electronic properties of semiconductor-water interfaces: Predictions from ab-initio molecular dynamics and many-body perturbation theory

NASA Astrophysics Data System (ADS)

Pham, Tuan Anh

2015-03-01

Photoelectrochemical cells offer a promising avenue for hydrogen production from water and sunlight. The efficiency of these devices depends on the electronic structure of the interface between the photoelectrode and liquid water, including the alignment between the semiconductor band edges and the water redox potential. In this talk, we will present the results of first principles calculations of semiconductor-water interfaces that are obtained with a combination of density functional theory (DFT)-based molecular dynamics simulations and many-body perturbation theory (MBPT). First, we will discuss the development of an MBPT approach that is aimed at improving the efficiency and accuracy of existing methodologies while still being applicable to complex heterogeneous interfaces consisting of hundreds of atoms. We will then present studies of the electronic structure of liquid water and aqueous solutions using MBPT, which represent an essential step in establishing a quantitative framework for computing the energy alignment at semiconductor-water interfaces. Finally, using a combination of DFT-based molecular dynamics simulations and MBPT, we will describe the relationship between interfacial structure, electronic properties of semiconductors and their reactivity in aqueous solutions through a number of examples, including functionalized Si surfaces and GaP/InP surfaces in contact with liquid water. T.A.P was supported by the U.S. Department of Energy at the Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and by the Lawrence Fellowship Program.

Determination of the topological shape of integral membrane protein light-harvesting complex LH2 from photosynthetic bacteria in the detergent solution by small-angle X-ray scattering.

PubMed

Hong, Xinguo; Weng, Yu-Xiang; Li, Ming

2004-02-01

The topological shape of the integral membrane protein light-harvesting complex LH2 from photosynthetic bacteria Rhodobacter spheroides 2.4.1 in detergent solution has been determined from synchrotron small-angle X-ray scattering data using direct curve-fitting by the ellipsoid, ab initio shape determination methods of simulated annealing algorithm and multipole expansion, respectively. The results indicate that the LH2 protein in aqueous solution is encapsulated by a monolayered detergent shell. The detergent-stabilized structure has the shape of an oblate plate, with a thickness of 40 A, a long axis of 110 A, and a short axis of 85 A. After correction for the detergent shell, the shape of the LH2 core is also an oblate plate with a height of 40 A, a long axis of 80 A, and a short axis of 55 A. In contrast to the cylindrical crystal structure with a height of 40 A and a diameter of 68 A, the molecular shape of the LH2 complex in detergent solution clearly deviates from the ringlike crystal structure, with an eccentricity found to be 0.59-consistent with the result of single molecular spectroscopy study of the isolated single LH2 molecules.

Determination of the Topological Shape of Integral Membrane Protein Light-Harvesting Complex LH2 from Photosynthetic Bacteria in the Detergent Solution by Small-Angle X-Ray Scattering

PubMed Central

Hong, Xinguo; Weng, Yu-Xiang; Li, Ming

2004-01-01

The topological shape of the integral membrane protein light-harvesting complex LH2 from photosynthetic bacteria Rhodobacter spheroides 2.4.1 in detergent solution has been determined from synchrotron small-angle X-ray scattering data using direct curve-fitting by the ellipsoid, ab initio shape determination methods of simulated annealing algorithm and multipole expansion, respectively. The results indicate that the LH2 protein in aqueous solution is encapsulated by a monolayered detergent shell. The detergent-stabilized structure has the shape of an oblate plate, with a thickness of 40 Å, a long axis of 110 Å, and a short axis of 85 Å . After correction for the detergent shell, the shape of the LH2 core is also an oblate plate with a height of 40 Å, a long axis of 80 Å, and a short axis of 55 Å. In contrast to the cylindrical crystal structure with a height of 40 Å and a diameter of 68 Å, the molecular shape of the LH2 complex in detergent solution clearly deviates from the ringlike crystal structure, with an eccentricity found to be 0.59—consistent with the result of single molecular spectroscopy study of the isolated single LH2 molecules. PMID:14747343

Replica exchange with solute tempering: A method for sampling biological systems in explicit water

NASA Astrophysics Data System (ADS)

Liu, Pu; Kim, Byungchan; Friesner, Richard A.; Berne, B. J.

2005-09-01

An innovative replica exchange (parallel tempering) method called replica exchange with solute tempering (REST) for the efficient sampling of aqueous protein solutions is presented here. The method bypasses the poor scaling with system size of standard replica exchange and thus reduces the number of replicas (parallel processes) that must be used. This reduction is accomplished by deforming the Hamiltonian function for each replica in such a way that the acceptance probability for the exchange of replica configurations does not depend on the number of explicit water molecules in the system. For proof of concept, REST is compared with standard replica exchange for an alanine dipeptide molecule in water. The comparisons confirm that REST greatly reduces the number of CPUs required by regular replica exchange and increases the sampling efficiency. This method reduces the CPU time required for calculating thermodynamic averages and for the ab initio folding of proteins in explicit water. Author contributions: B.J.B. designed research; P.L. and B.K. performed research; P.L. and B.K. analyzed data; and P.L., B.K., R.A.F., and B.J.B. wrote the paper.Abbreviations: REST, replica exchange with solute tempering; REM, replica exchange method; MD, molecular dynamics.*P.L. and B.K. contributed equally to this work.

Ion adsorption at the rutile-water interface: linking molecular and macroscopic properties.

PubMed

Zhang, Z; Fenter, P; Cheng, L; Sturchio, N C; Bedzyk, M J; Predota, M; Bandura, A; Kubicki, J D; Lvov, S N; Cummings, P T; Chialvo, A A; Ridley, M K; Bénézeth, P; Anovitz, L; Palmer, D A; Machesky, M L; Wesolowski, D J

2004-06-08

A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength.

Beyond Simple AB Diblock Copolymers: Application of Bifunctional and Trifunctional RAFT Agents to PISA in Water.

PubMed

Mellot, Gaëlle; Beaunier, Patricia; Guigner, Jean-Michel; Bouteiller, Laurent; Rieger, Jutta; Stoffelbach, François

2018-06-20

The influence of the macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agent architecture on the morphology of the self-assemblies obtained by aqueous RAFT dispersion polymerization in polymerization-induced self-assembly (PISA) is studied by comparing amphiphilic AB diblock, (AB) 2 triblock, and triarm star-shaped (AB) 3 copolymers, constituted of N,N-dimethylacrylamide (DMAc = A) and diacetone acrylamide (DAAm = B). Symmetrical triarm (AB) 3 copolymers could be synthesized for the first time in a PISA process. Spheres and higher order morphologies, such as worms or vesicles, could be obtained for all types of architectures and the parameters that determine their formation have been studied. In particular, we found that the total DP n of the PDMAc and the PDAAm segments, i.e., the same overall molar mass, at the same M n (PDMAc)/M n (PDAAm) ratio, rather than the individual length of the arms determined the morphologies for the linear (AB) 2 and star shaped (AB) 3 copolymers obtained by using the bi- and trifunctional macro-RAFT agents. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

Liu, Xianli; Wu, Feng; Deng, Nansheng

2004-01-01

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

Ab initio study of the structural properties of ascorbic acid (vitamin C)

NASA Astrophysics Data System (ADS)

Allen, Reeshemah N.; Shukla, M. K.; Reed, Demarcio; Leszczynski, Jerzy

Geometries of the neutral and ionic tautomeric species of ascorbic acid were optimized at the density functional theory (DFT) level using the B3LYP functional. The radical species were evaluated using the unrestricted B3LYP method. Single-point energy calculations were also performed using the Møller-Plesset (MP2) and unrestricted MP2 (UMP2) methods for the closed-shell and open-shell systems, respectively. The effects of aqueous solution were evaluated using the conducting polarized continuum model (CPCM) and polarized continuum model (PCM). The geometries of most stable radicals in the respective groups were also optimized in the water solution using the CPCM model at the UB3LYP level. All calculation were performed using the 6-311++G(d,p) basis set. The nature of stationary points on the gas phase potential energy surfaces (PESs) was evaluated using vibrational frequency calculations; all geometries characterize local minima. The species obtained by the deprotonation of the O3 site is the most stable monoanion of ascorbic acid. For the radical species, the structure obtained by the dehydrogenation of the O3 site is the most stable monoradical. Among the radical anions, the species obtained by the deprotonation of the O3 site and subsequent dehydrogenation of the O2 site is the most stable in the gas phase and in an aqueous medium. The computed isotropic hyperfine coupling constants of this species were found to be in good agreement with the experimental data. Our investigation also supports the earlier findings that the oxidized species of ascorbic acid in water solution by the OH? radical is radical anion of the AAO?3O-2 form. The spin densities and molecular electrostatic potentials are also discussed.

Germanium films by polymer-assisted deposition

DOEpatents

Jia, Quanxi; Burrell, Anthony K.; Bauer, Eve; Ronning, Filip; McCleskey, Thomas Mark; Zou, Guifu

2013-01-15

Highly ordered Ge films are prepared directly on single crystal Si substrates by applying an aqueous coating solution having Ge-bound polymer onto the substrate and then heating in a hydrogen-containing atmosphere. A coating solution was prepared by mixing water, a germanium compound, ethylenediaminetetraacetic acid, and polyethyleneimine to form a first aqueous solution and then subjecting the first aqueous solution to ultrafiltration.

Tested Demonstrations. Color, Solubility, and Complex Ion Equilibria of Nickel (II) Species in Aqueous Solution.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.; And Others

1980-01-01

Presents three different procedures in which reagents are added in a specified order to a large beaker containing an aqueous solution of nickel sulfate. Complex ions of nickel (II) are prepared by using aqueous solutions of ammonia, ethylenediamine, dimethylglyoxime, and cyanide ion. (CS)

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1999-01-01

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1999-03-30

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

Method for Non-Invasive Determination of Chemical Properties of Aqueous Solutions

NASA Technical Reports Server (NTRS)

Jones, Alan (Inventor); Thomas, Nathan A. (Inventor); Todd, Paul W. (Inventor)

2016-01-01

A method for non-invasively determining a chemical property of an aqueous solution is provided. The method provides the steps of providing a colored solute having a light absorbance spectrum and transmitting light through the colored solute at two different wavelengths. The method further provides the steps of measuring light absorbance of the colored solute at the two different transmitted light wavelengths, and comparing the light absorbance of the colored solute at the two different wavelengths to determine a chemical property of an aqueous solution.

A simple and effective solution to the constrained QM/MM simulations

NASA Astrophysics Data System (ADS)

Takahashi, Hideaki; Kambe, Hiroyuki; Morita, Akihiro

2018-04-01

It is a promising extension of the quantum mechanical/molecular mechanical (QM/MM) approach to incorporate the solvent molecules surrounding the QM solute into the QM region to ensure the adequate description of the electronic polarization of the solute. However, the solvent molecules in the QM region inevitably diffuse into the MM bulk during the QM/MM simulation. In this article, we developed a simple and efficient method, referred to as the "boundary constraint with correction (BCC)," to prevent the diffusion of the solvent water molecules by means of a constraint potential. The point of the BCC method is to compensate the error in a statistical property due to the bias potential by adding a correction term obtained through a set of QM/MM simulations. The BCC method is designed so that the effect of the bias potential completely vanishes when the QM solvent is identical with the MM solvent. Furthermore, the desirable conditions, that is, the continuities of energy and force and the conservations of energy and momentum, are fulfilled in principle. We applied the QM/MM-BCC method to a hydronium ion(H3O+) in aqueous solution to construct the radial distribution function (RDF) of the solvent around the solute. It was demonstrated that the correction term fairly compensated the error and led the RDF in good agreement with the result given by an ab initio molecular dynamics simulation.

Dilution Confusion: Conventions for Defining a Dilution

ERIC Educational Resources Information Center

Fishel, Laurence A.

2010-01-01

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

ABS 3D printed solutions for cryogenic applications

NASA Astrophysics Data System (ADS)

Bartolomé, E.; Bozzo, B.; Sevilla, P.; Martínez-Pasarell, O.; Puig, T.; Granados, X.

2017-03-01

3D printing has become a common, inexpensive and rapid prototyping technique, enabling the ad hoc fabrication of complex shapes. In this paper, we demonstrate that 3D printed objects in ABS can be used at cryogenic temperatures, offering flexible solutions in different fields. Firstly, a thermo-mechanical characterization of ABS 3D printed specimens at 77 K is reported, which allowed us to delimit the type of cryogenic uses where 3D printed pieces may be implemented. Secondly, we present three different examples where ABS 3D printed objects working at low temperatures have provided specific solutions: (i) SQUID inserts for angular magnetometry (low temperature material characterization field); (ii) a cage support for a metamaterial ;magnetic concentrator; (superconductivity application), and (iii) dedicated tools for cryopreservation in assisted reproductive techniques (medicine field).

Characteristics of regenerated nanocellulosic fibers from cellulose dissolution in aqueous solutions for wood fiber/polypropylene composites

Treesearch

Sangyeob Lee; Hui Pan; Chung Y. Hse; Alfred R. Gunasekaran; Todd F. Shupe

2014-01-01

The effects of aqueous solutions were evaluated on the properties of regenerated cellulosic nanofibers prepared from pure cellulose fibers in various formulations of aqueous solutions. Thermoplastic composites were prepared with reinforcement of the regenerated cellulosic nanofibers. The regenerated cellulosic fibers from cellulosic woody biomass were obtained from...

URANIUM SEPARATION PROCESS

DOEpatents

McVey, W.H.; Reas, W.H.

1959-03-10

The separation of uranium from an aqueous solution containing a water soluble uranyl salt is described. The process involves adding an alkali thiocyanate to the aqueous solution, contacting the resulting solution with methyl isobutyl ketons and separating the resulting aqueous and organic phase. The uranium is extracted in the organic phase as UO/sub 2/(SCN)/sub/.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Callis, C.F.; Moore, R.L.

1959-09-01

>The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

SE-72/AS-72 generator system based on Se extraction/ As reextraction

DOEpatents

Fassbender, Michael Ernst; Ballard, Beau D

2013-09-10

The preparation of a .sup.72Se/.sup.72As radioisotope generator involves forming an acidic aqueous solution of an irradiated alkali bromide target such as a NaBr target, oxidizing soluble bromide in the solution to elemental bromine, removing the elemental bromine, evaporating the resulting solution to a residue, removing hydrogen chloride from the residue, forming an acidic aqueous solution of the residue, adding a chelator that selectively forms a chelation complex with selenium, and extracting the chelation complex from the acidic aqueous solution into an organic phase. As the .sup.72Se generates .sup.72As in the organic phase, the .sup.72As may be extracted repeatedly from the organic phase with an aqueous acid solution.

Methods and systems for utilizing carbide lime or slag

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

Devenney, Martin; Fernandez, Miguel; Chen, Irvin

Provided herein are methods comprising a) treating a slag solid or carbide lime suspension with an ammonium salt in water to produce an aqueous solution comprising calcium salt, ammonium salt, and solids; b) contacting the aqueous solution with carbon dioxide from an industrial process under one or more precipitation conditions to produce a precipitation material comprising calcium carbonate and a supernatant aqueous solution wherein the precipitation material and the supernatant aqueous solution comprise residual ammonium salt; and c) removing and optionally recovering ammonia and/or ammonium salt using one or more steps of (i) recovering a gas exhaust stream comprising ammoniamore » during the treating and/or the contacting step; (ii) recovering the residual ammonium salt from the supernatant aqueous solution; and (iii) removing and optionally recovering the residual ammonium salt from the precipitation material.« less

Unique role of ionic liquid [bmin][BF 4] during curcumin-surfactant association and micellization of cationic, anionic and non-ionic surfactant solutions

NASA Astrophysics Data System (ADS)

Patra, Digambara; Barakat, Christelle

2011-09-01

Hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroburate, modified the properties of aqueous surfactant solutions associated with curcumin. Because of potential pharmaceutical applications as an antioxidant, anti-inflammatory and anti-carcinogenic agent, curcumin has received ample attention as potential drug. The interaction of curcumin with various charged aqueous surfactant solutions showed it exists in deprotonated enol form in surfactant solutions. The nitro and hydroxyl groups of o-nitrophenol interact with the carbonyl and hydroxyl groups of the enol form of curcumin by forming ground state complex through hydrogen bonds and offered interesting information about the nature of the interactions between the aqueous surfactant solutions and curcumin depending on charge of head group of the surfactant. IL[bmin][BF 4] encouraged early formation of micelle in case of cationic and anionic aqueous surfactant solutions, but slightly prolonged micelle formation in the case of neutral aqueous surfactant solution. However, for curcumin IL [bmin][BF 4] favored strong association (7-fold increase) with neutral surfactant solution, marginally supported association with anionic surfactant solution and discouraged (˜2-fold decrease) association with cationic surfactant solution.

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

PubMed

Sekiya, S; Ohmori, K; Harii, K

1997-01-01

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

Preparing polymeric matrix composites using an aqueous slurry technique

NASA Technical Reports Server (NTRS)

Johnston, Norman J. (Inventor); Towell, Timothy W. (Inventor)

1993-01-01

An aqueous process was developed to prepare a consolidated composite laminate from an aqueous slurry. An aqueous poly(amic acid) surfactant solution was prepared by dissolving a poly(amic acid) powder in an aqueous ammonia solution. A polymeric powder was added to this solution to form a slurry. The slurry was deposited on carbon fiber to form a prepreg which was dried and stacked to form a composite laminate. The composite laminate was consolidated using pressure and was heated to form the polymeric matrix. The resulting composite laminate exhibited high fracture toughness and excellent consolidation.

Atomic scale behavior of oxygen-based radicals in water

NASA Astrophysics Data System (ADS)

Verlackt, C. C. W.; Neyts, E. C.; Bogaerts, A.

2017-03-01

Cold atmospheric pressure plasmas in and in contact with liquids represent a growing field of research for various applications. Understanding the interactions between the plasma generated species and the liquid is crucial. In this work we perform molecular dynamics (MD) simulations based on a quantum mechanical method, i.e. density-functional based tight-binding (DFTB), to examine the interactions of OH radicals and O atoms in bulk water. Our calculations reveal that the transport of OH radicals through water is not only governed by diffusion, but also by an equilibrium reaction of H-abstraction with water molecules. Furthermore, when two OH radicals encounter each other, they either form a stable cluster, or react, resulting in the formation of a new water molecule and an O atom. In addition, the O atoms form either oxywater (when in singlet configuration) or they remain stable in solution (when in triplet configuration), stressing the important role that O atoms can play in aqueous solution, and in contact with biomolecules. Our observations are in line with both experimental and ab initio results from the literature.

Glucose transformation to 5-hydroxymethylfurfural in acidic ionic liquid: A quantum mechanical study.

PubMed

Arifin; Puripat, Maneeporn; Yokogawa, Daisuke; Parasuk, Vudhichai; Irle, Stephan

2016-01-30

Isomerization and transformation of glucose and fructose to 5-hydroxymethylfurfural (HMF) in both ionic liquids (ILs) and water has been studied by the reference interaction site model self-consistent field spatial electron density distribution (RISM-SCF-SEDD) method coupled with ab initio electronic structure theory, namely coupled cluster single, double, and perturbative triple excitation (CCSD(T)). Glucose isomerization to fructose has been investigated via cyclic and open chain mechanisms. In water, the calculations support the cyclic mechanism of glucose isomerization; with the predicted activation free energy is 23.8 kcal mol(-1) at experimental condition. Conversely, open ring mechanism is more favorable in ILs with the energy barrier is 32.4 kcal mol(-1) . Moreover, the transformation of fructose into HMF via cyclic mechanism is reasonable; the calculated activation barriers are 16.0 and 21.5 kcal mol(-1) in aqueous and ILs solutions, respectively. The solvent effects of ILs could be explained by the decomposition of free energies and radial distribution functions of solute-solvent that are produced by RISM-SCF-SEDD. © 2015 Wiley Periodicals, Inc.

Scattering on two Aharonov-Bohm vortices

NASA Astrophysics Data System (ADS)

Bogomolny, E.

2016-12-01

The problem of two Aharonov-Bohm (AB) vortices for the Helmholtz equation is examined in detail. It is demonstrated that the method proposed by Myers (1963 J. Math. Phys. 6 1839) for slit diffraction can be generalised to obtain an explicit solution for AB vortices. Due to the singular nature of AB interaction the Green function and scattering amplitude for two AB vortices obey a series of partial differential equations. Coefficients entering these equations, fulfil ordinary non-linear differential equations whose solutions can be obtained by solving the Painlevé III equation. The asymptotics of necessary functions for very large and very small vortex separations are calculated explicitly. Taken together, this means that the problem of two AB vortices is exactly solvable.

A highly sensitive monoclonal antibody based biosensor for quantifying 3-5 ring polycyclic aromatic hydrocarbons (PAHs) in aqueous environmental samples.

PubMed

Li, Xin; Kaattari, Stephen L; Vogelbein, Mary A; Vadas, George G; Unger, Michael A

2016-03-01

Immunoassays based on monoclonal antibodies (mAbs) are highly sensitive for the detection of polycyclic aromatic hydrocarbons (PAHs) and can be employed to determine concentrations in near real-time. A sensitive generic mAb against PAHs, named as 2G8, was developed by a three-step screening procedure. It exhibited nearly uniformly high sensitivity against 3-ring to 5-ring unsubstituted PAHs and their common environmental methylated PAHs, with IC 50 values between 1.68-31 μg/L (ppb). 2G8 has been successfully applied on the KinExA Inline Biosensor system for quantifying 3-5 ring PAHs in aqueous environmental samples. PAHs were detected at a concentration as low as 0.2 μg/L. Furthermore, the analyses only required 10 min for each sample. To evaluate the accuracy of the 2G8-based biosensor, the total PAH concentrations in a series of environmental samples analyzed by biosensor and GC-MS were compared. In most cases, the results yielded a good correlation between methods. This indicates that generic antibody 2G8 based biosensor possesses significant promise for a low cost, rapid method for PAH determination in aqueous samples.

Evaluation of commercially available aqueous batch immersion cleaning products. Technical report

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

Bevilacqua, P.; Clark, K.G.

1996-01-10

With the production of Class I Ozone Depleting Substances scheduled to cease in January 1996, it has become necessary to identify suitable replacements for chlorofluorocarbon (CFC-113, Freon 113) vapor degreasing operations currently used to clean avionics components in Navy aircraft maintenance facilities. In this study, one potential option, the use of aqueous cleaning agents, was explored. Commercially available industrial aqueous cleaning agents were evaluated for cleaning capability on simulated operational soils and effects on aircraft materials. Two cleaning agents, Armakleen 2001 and Crest ABS 901, were recommended as a result of this work, and a Military Specification was drafted outliningmore » performance requirements.« less

[Analysis of parameters of serum concentration and pharmacokinetic of liposome and aqueous solution of toatal ginsenoside of ginseng stems and leaves in rats].

PubMed

Zha, Lin; Zhao, Yan; Zhu, Hong-Yan; Cai, En-Bo; Liu, Shuang-Li; Yang, He; Zhao, Ying; Gao, Yu-Gang; Zhang, Lian-Xue

2017-05-01

The experiment was aimed to investigate the difference of plasma concentration and pharmacokinetic parameters between liposome and aqueous solution of toatal ginsenoside of ginseng stems and leaves in rats, such as ginsenosides Rg₁, Re, Rf, Rb₁, Rg₂, Rc, Rb₂, Rb₃, Rd. After intravenous injection of liposome and aqueous solution in rats, the blood was taken from the femoral vein to detect the plasma concentration of the above 9 ginsenoside monomers in different time points by using HPLC. The concentration-time curve was obtained and 3p97 pharmacokinetic software was used to get the pharmacokinetic parameters. After the intravenous injection of ginsenosides to rats, nine ginsenosides were detected in plasma. In general, among these ginsenosides, the peak time of the aqueous solution was between 0.05 to 0.083 3 h, and the serum concentration peak of liposome usually appeared after 0.5 h. After software fitting, the aqueous solution of ginsenoside monomers Rg₁, Re, Rf, Rg₂, Rc, Rd, Rb₃ was two-compartment model, and the liposomes were one-compartment model; aqueous solution and liposome of ginsenoside monomers Rb₁ were three-compartment model; aqueous solution of ginsenoside monomers Rb₂ was three-compartment model, and its liposome was one-compartment model. Area under the drug time curve (AUC) of these 9 kinds of saponin liposomes was larger than that of aqueous solution, and the retention time of the liposomes was longer than that of the aqueous solution; the removal rate was slower than that of the aqueous solution, and the half-life was longer than that of the water solution. The results from the experiment showed that by intravenous administration, the pharmacokinetic parameters of two formulations were significantly different from each other; the liposomes could not only remain the drug for a longer time in vivo, but also reduce the elimination rate and increase the treatment efficacy. As compared with the traditional dosage forms, the total ginsenoside of ginseng stems and leaves can improve the sustained release of the drug, which is of great significance for the research and development of new dosage forms of ginsenosides in the future. Copyright© by the Chinese Pharmaceutical Association.

Thermodynamic properties of potassium chloride aqueous solutions

NASA Astrophysics Data System (ADS)

Zezin, Denis; Driesner, Thomas

2017-04-01

Potassium chloride is a ubiquitous salt in natural fluids, being the second most abundant dissolved salt in many geological aqueous solutions after sodium chloride. It is a simple solute and strong electrolyte easily dissociating in water, however the thermodynamic properties of KCl aqueous solutions were never correlated with sufficient accuracy for a wide range of physicochemical conditions. In this communication we propose a set of parameters for a Pitzer-type model which allows calculation of all necessary thermodynamic properties of KCl solution, namely excess Gibbs free energy and derived activity coefficient, apparent molar enthalpy, heat capacity and volume, as well as osmotic coefficient and activity of water in solutions. The system KCl-water is one of the best studied aqueous systems containing electrolytes. Although extensive experimental data were collected for thermodynamic properties of these solutions over the years, the accurate volumetric data became available only recently, thus making possible a complete thermodynamic formulation including a pressure dependence of excess Gibbs free energy and derived properties of the KCl-water liquids. Our proposed model is intended for calculation of major thermodynamic properties of KCl aqueous solutions at temperatures ranging from freezing point of a solution to 623 K, pressures ranging from saturated water vapor up to 150 MPa, and concentrations up to the salt saturation. This parameterized model will be further implemented in geochemical software packages and can facilitate the calculation of aqueous equilibrium for reactive transport codes.

Extracting alcohols from aqueous solutions. [USDOE patent application

DOEpatents

Compere, A.L.; Googin, J.M.; Griffith, W.L.

1981-12-02

The objective is to provide an efficient process for extracting alcohols in aqueous solutions into hydrocarbon fuel mixtures, such as gasoline, diesel fuel and fuel oil. This is done by contacting an aqueous fermentation liquor with a hydrocarbon or hydrocarbon mixture containing carbon compounds having 5-18 carbon atoms, which may include gasoline, diesel fuel or fuel oil. The hydrocarbon-aqueous alcohol solution is then mixed with one or more of a group of polyoxyalkylene polymers to extract the alcohol into the hydrocarbon fuel-polyoxyalkylene polymer mixture.

Exploratory studies on some electrochemical cell systems

NASA Astrophysics Data System (ADS)

Chaudhuri, Srikumar; Guha, D.

Exploratory studies were conducted on cell systems with different metal anodes, and iodine and sulphur mixed with graphite powder in a polymer matrix as cathodes, using different electrolytes in non-aqueous and aqueous media as ionic charge carriers. The electrical conductance of the electrolyte solutions in aqueous and non-aqueous solvents, the open circuit voltage (OCV) and short circuit current (SCC) for the different cell systems were measured. To date, the non-aqueous solvents used in our studies were dimethylformamide, formamide, dioxan, and nitrobenzene, and the electrolytes used were potassium iodide, caustic potash, cetyltrimethylammonium bromide (CTAB), sodium lauryl sulphate (SLS) and calcium chloride. These electrolytes were used in both non-aqueous and aqueous media. In general, aqueous electrolyte solutions gave a better performance than non-aqueous electrolyte solutions. Of the aqueous electrolytes, the highest conductance was shown by potassium chloride solution in water (conductance=0.0334 mho). However, the best OCV and SCC were shown by aluminium as anode and iodine as cathode with a saturated solution of caustic potash in water. The OCV was 1.85 V and the SCC was 290 mA cm -2. The highest conductance among the non-aqueous systems was shown by caustic potash in formamide. (Conductance=0.013 mho.) The best OCV and SCC, however, were shown by a zinc anode and iodine cathode with saturated potassium chloride in formamide, having an OCV of 1.55 V and an SCC of 150 mA cm -2. Further studies are in progress to obtain detailed performance data and recharging characteristics of some of the more promising systems reported here.

SEPARATION OF PLUTONIUM FROM AQUEOUS SOLUTIONS BY ION-EXCHANGE

DOEpatents

Schubert, J.

1958-06-01

A process is described for the separation of plutonium from an aqueous solution of a plutonium salt, which comprises adding to the solution an acid of the group consisting of sulfuric acid, phosphoric acid, and oxalic acid, and mixtures thereof to provide an acid concentration between 0.0001 and 1 M, contacting the resultant solution with a synthetic organic anion exchange resin, and separating the aqueous phase and the resin which contains the plutonium.

A study on lithium/air secondary batteries-Stability of the NASICON-type lithium ion conducting solid electrolyte in alkaline aqueous solutions

NASA Astrophysics Data System (ADS)

Shimonishi, Yuta; Zhang, Tao; Imanishi, Nobuyuki; Im, Dongmin; Lee, Dong Joon; Hirano, Atsushi; Takeda, Yasuo; Yamamoto, Osamu; Sammes, Nigel

The stability of the high lithium ion conducting glass ceramics, Li 1+ x+ yTi 2- xAl xSi yP 3- yO 12 (LTAP) in alkaline aqueous solutions with and without LiCl has been examined. A significant conductivity decrease of the LTAP plate immersed in 0.057 M LiOH aqueous solution at 50 °C for 3 weeks was observed. However, no conductivity change of the LTAP plate immersed in LiCl saturated LiOH aqueous solutions at 50 °C for 3 weeks was observed. The pH value of the LiCl-LiOH-H 2O solution with saturated LiCl was in a range of 7-9. The molarity of LiOH and LiCl in the LiOH and LiCl saturated aqueous solution were estimated to be 5.12 and 11.57 M, respectively, by analysis of Li + and OH -. The high concentration of LiOH and the low pH value of 8.14 in this solution suggested that the dissociation of LiOH into Li + and OH - is too low in the solution with a high concentration of Li +. These results suggest that the water stable LTAP could be used as a protect layer of the lithium metal anode in the lithium/air cell with LiCl saturated aqueous solution as the electrolyte, because the content of OH - ions in the LiCl saturated aqueous solution does not increase via the cell reaction of Li + 1/2O 2 + H 2O → 2LiOH, and LTAP is stable under a deep discharge state.

N-Sulfonyl-β-lactam hapten as an effective labeling reagent for aldolase mAb.

PubMed

Inokuma, Tsubasa; Fuller, Roberta P; Barbas, Carlos F

2015-04-15

Utilization of chemically programmed antibodies (cpAbs) is regarded to be one of the most efficient methods for the development of therapeutic systems. cpAbs can extend the half-life of programming reagents, activate immune systems via the Fc region of antibodies and achieve universal vaccination by attaching varieties of small, programmed molecules. In the current study, we aimed to develop a novel labeling reagent for the preparation of cpAbs and found that N-sulfonyl-β-lactams (NSBLs) were optimal. NSBL can be synthesized from readily available 4-(bromomethyl)benzenesulfonyl chloride via few simple manipulations and can label the aldolase monoclonal antibody (mAb) 84G3, which could not be labeled effectively by the conventional labeling reagent, N-acyl-β-lactam (NABL). We also demonstrated that the conjugate, which consists of mAb 84G3 and an NSBL bearing a biotin moiety, maintained strong binding activity to streptavidin. In addition, the stability assay of NSBL revealed that NSBLs can tolerate aqueous media without significant decomposition over 24h. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

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

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactantmore » fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.« less

Environment-Friendly Post-Treatment of PEDOT-Tos Films by Aqueous Vitamin C Solutions for Tuning of Thermoelectric Properties

NASA Astrophysics Data System (ADS)

Khan, Ezaz Hasan; Thota, Sammaiah; Wang, Yiwen; Li, Lian; Wilusz, Eugene; Osgood, Richard; Kumar, Jayant

2018-04-01

Aqueous vitamin C solution has been used as an environment-friendly reducing agent for tuning the thermoelectric properties of p-toluenesulfonate-doped poly(3,4-ethylenedioxythiophene) (PEDOT-Tos) films. The de-doping of the PEDOT-Tos films by aqueous vitamin C solutions led to a decrease in the electrical conductivity of the films. The measured ultraviolet-visible-near-infrared and x-ray photoelectron spectra clearly indicated the reduction in the oxidation level from 37 to 23% when the PEDOT-Tos films were treated with 5% (w/v) aqueous vitamin C solutions. An increase in the Seebeck coefficient was measured, resulting in an increase in the figure-of-merit (ZT). A 42% increase in ZT was determined for the 5% aqueous vitamin C solution-treated PEDOT-Tos films with respect to that of the untreated films.

Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials

DOEpatents

Wallace, Andrew P.; Melack, John M.; Lefenfeld, Michael

2015-08-11

Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactant fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.

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

PubMed Central

Wang, Junmei; Hou, Tingjun

2011-01-01

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

Large-Scale Hybrid Density Functional Theory Calculations in the Condensed-Phase: Ab Initio Molecular Dynamics in the Isobaric-Isothermal Ensemble

NASA Astrophysics Data System (ADS)

Ko, Hsin-Yu; Santra, Biswajit; Distasio, Robert A., Jr.; Wu, Xifan; Car, Roberto

Hybrid functionals are known to alleviate the self-interaction error in density functional theory (DFT) and provide a more accurate description of the electronic structure of molecules and materials. However, hybrid DFT in the condensed-phase has a prohibitively high associated computational cost which limits their applicability to large systems of interest. In this work, we present a general-purpose order(N) implementation of hybrid DFT in the condensed-phase using Maximally localized Wannier function; this implementation is optimized for massively parallel computing architectures. This algorithm is used to perform large-scale ab initio molecular dynamics simulations of liquid water, ice, and aqueous ionic solutions. We have performed simulations in the isothermal-isobaric ensemble to quantify the effects of exact exchange on the equilibrium density properties of water at different thermodynamic conditions. We find that the anomalous density difference between ice I h and liquid water at ambient conditions as well as the enthalpy differences between ice I h, II, and III phases at the experimental triple point (238 K and 20 Kbar) are significantly improved using hybrid DFT over previous estimates using the lower rungs of DFT This work has been supported by the Department of Energy under Grants No. DE-FG02-05ER46201 and DE-SC0008626.

Ab Initio Molecular Dynamics Study on the Interactions between Carboxylate Ions and Metal Ions in Water.

PubMed

Mehandzhiyski, Aleksandar Y; Riccardi, Enrico; van Erp, Titus S; Trinh, Thuat T; Grimes, Brian A

2015-08-20

The interaction between a carboxylate anion (deprotonated propanoic acid) and the divalent Mg(2+), Ca(2+), Sr(2+), Ba(2+) metal ions is studied via ab initio molecular dynamics. The main focus of the study is the selectivity of the carboxylate-metal ion interaction in aqueous solution. The interaction is modeled by explicitly accounting for the solvent molecules on a DFT level. The hydration energies of the metal ions along with their diffusion and mobility coefficients are determined and a trend correlated with their ionic radius is found. Subsequently, a series of 16 constrained molecular dynamics simulations for every ion is performed, and the interaction free energy is obtained from thermodynamic integration of the forces between the metal ion and the carboxylate ion. The results indicate that the magnesium ion interacts most strongly with the carboxylate, followed by calcium, strontium, and barium. Because the interaction free energy is not enough to explain the selectivity of the reaction observed experimentally, more detailed analysis is performed on the simulation trajectories to understand the steric changes in the reaction complex during dissociation. The solvent dynamics appear to play an important role during the dissociation of the complex and also in the observed selectivity behavior of the divalent ions.

Born-Oppenheimer ab initio QM/MM Molecular Dynamics Simulations of Enzyme Reactions

PubMed Central

Zhou, Yanzi; Wang, Shenglong; Li, Yongle; Zhang, Yingkai

2016-01-01

There are two key requirements for reliably simulating enzyme reactions: one is a reasonably accurate potential energy surface to describe the bond forming/breaking process as well as to adequately model the heterogeneous enzyme environment; the other is to perform extensive sampling since an enzyme system consists of at least thousands of atoms and its energy landscape is very complex. One attractive approach to meet both daunting tasks is Born-Oppenheimer ab initio QM/MM molecular dynamics simulation (aiQM/MM-MD) with umbrella sampling. In this chapter, we describe our recently developed pseudobond Q-Chem–Amber interface, which employs a combined electrostatic-mechanical embedding scheme with periodic boundary condition and the particle mesh Ewald method for long-range electrostatics interactions. In our implementation, Q-Chem and the sander module of Amber are combined at the source code level without using system calls, and all necessary data communications between QM and MM calculations are achieved via computer memory. We demonstrate the applicability of this pseudobond Q-Chem–Amber interface by presenting two examples, one reaction in aqueous solution and one enzyme reaction. Finally, we describe our established aiQM/MM-MD enzyme simulation protocol, which has been successfully applied to study more than a dozen enzymes. PMID:27498636

Thioether-Bearing Hyperbranched Polyether Polyols with Methionine-Like Side-Chains: A Versatile Platform for Orthogonal Functionalization.

PubMed

Seiwert, Jan; Herzberger, Jana; Leibig, Daniel; Frey, Holger

2017-01-01

The synthesis of thioether-bearing hyperbranched polyether polyols based on an AB/AB 2 type copolymerization (cyclic latent monomers) is introduced. The polymers are prepared by anionic ring-opening multibranching copolymerization of glycidol and 2-(methylthio)ethyl glycidyl ether (MTEGE), which is conveniently accessible in a single etherification step. Slow monomer addition provides control over molecular weights. Moderate dispersities (Đ = 1.48-1.85) are obtained, given the hyperbranched structure. In situ 1 H NMR copolymerization kinetics reveal reactivity ratios of r G = 3.7 and r MTEGE = 0.27. Using slow monomer addition, copolymer composition can be systematically varied, allowing for the adjustment of the hydroxyl/thioether ratio, the degree of branching (DB = 0.36-0.48), thermal properties, and cloud point temperatures in aqueous solution in the range of 29-75 °C. Thioether oxidation to sulfoxides enables to tailor the copolymers' solubility profile. Use of these copolymers as a versatile, multifunctional platform for orthogonal modification is highlighted. The methyl sulfide groups can be selectively alkoxylated, using propylene oxide, allyl glycidyl ether, or furfuryl glycidyl ether, resulting in functional hyperbranched polyelectrolytes. Reaction of the alcohol groups with benzyl isocyanate demonstrates successful orthogonal functionalization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tandem Aldol-Michael Reactions in Aqueous Diethylamine Medium: A Greener and Efficient Approach to Bis-Pyrimidine Derivatives

PubMed Central

Al-Majid, Abdullah M.; Barakat, Assem; AL-Najjar, Hany J.; Mabkhot, Yahia N.; Ghabbour, Hazem A.; Fun, Hoong-Kun

2013-01-01

A simple protocol, involving the green synthesis for the construction of novel bis-pyrimidine derivatives, 3a–i and 4a–e are accomplished by the aqueous diethylamine media promoted tandem Aldol-Michael reaction between two molecules of barbituric acid derivatives 1a,b with various aldehydes. This efficient synthetic protocol using an economic and environmentally friendly reaction media with versatility and shorter reaction time provides bis-pyrimidine derivatives with high yields (88%–99%). PMID:24317435

Electrophotolysis oxidation system for measurement of organic concentration in water

NASA Technical Reports Server (NTRS)

Winkler, H. E. (Inventor)

1981-01-01

Methods and apparatus for determining organic carbon in aqueous solution are described. The method comprises subjecting the aqueous solution to electrolysis, for generating oxygen from water, and simultaneously to ultraviolet radiation, for oxidation of substantially all organic carbon to carbon dioxide. The carbon dioxide is measured and the value is related to the concentration of organic carbon in the aqueous solution.

RECOVERY AND SEPARATION OF LITHIUM VALUES FROM SALVAGE SOLUTIONS

DOEpatents

Hansford, D.L.; Raabe, E.W.

1963-08-20

Lithium values can be recovered from an aqueous basic solution by reacting the values with a phosphate salt soluble in the solution, forming an aqueous slurry of the resultant aqueous insoluble lithium phosphate, contacting the slurry with an organic cation exchange resin in the acid form until the slurry has been clarified, and thereafter recovering lithium values from the resin. (AEC)

Prediction of the glass transition in aqueous solutions of simple amides by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Kreck, Cara A.; Mandumpal, Jestin B.; Mancera, Ricardo L.

2011-01-01

Some simple amides in aqueous solution are used in the cryopreservation of biological tissues as they are believed to promote the vitrification of water, inhibiting its crystallisation and the ensuing damage from ice formation. Molecular dynamics annealing simulations reveal a broadening in the glass transition of aqueous acetamide and N-methylacetamide solutions, suggesting a thermodynamic stabilisation of the glassy state, which may be responsible for their increased tendency of vitrification and their cryoprotective ability. By contrast, aqueous formamide solutions do not exhibit broadening of the glass transition; instead, it is shifted to lower temperatures, which explains their lack of vitrification properties.

Study of thermodynamic and acoustic behaviour of nicotinic acid in binary aqueous mixtures of D-lactose

NASA Astrophysics Data System (ADS)

Sharma, Ravi; Thakur, R. C.

2017-07-01

In the present study, the thermodynamic properties such as partial molar volumes, partial molar expansibilities, partial molar compressibilities, partial molar heat capacities and isobaric thermal expansion coefficient of different solutions of nicotinic acid in binary aqueous mixtures of D-lactose have been determined at different temperatures (298.15, 303.15, 308.15, 313.15) K. Masson's equation is used to interpret the data in terms of solute-solute and solute-solvent interactions. In the present study it has been found that nicotinic acid behaves as structure maker in aqueous and binary aqueous mixtures of D-lactose.

Ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine and N-acetyltryptophan in aqueous solution: proton-coupled electron transfer versus electron transfer.

PubMed

Zhang, Ying; Yuan, Shuwei; Lu, Rong; Yu, Anchi

2013-06-20

We studied the ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine (AcTyr) and N-acetyltryptophan (AcTrp) in aqueous solution with femtosecond transient absorption spectroscopy. We found that the charge-transfer rate between Atto655 and AcTyr is about 240 times smaller than that between Atto655 and AcTrp. The pH value and D2O dependences of the excited-state decay kinetics of Atto655 in the presence of AcTyr and AcTrp reveal that the quenching of Atto655 fluorescence by AcTyr in aqueous solution is via a proton-coupled electron-transfer (PCET) process and that the quenching of Atto655 fluorescence by AcTrp in aqueous solution is via an electron-transfer process. With the version of the semiclassical Marcus ET theory, we derived that the electronic coupling constant for the PCET reaction between Atto655 and AcTyr in aqueous solution is 8.3 cm(-1), indicating that the PCET reaction between Atto655 and AcTyr in aqueous solution is nonadiabatic.

Method and apparatus for synthesizing anhydrous HNO.sub.3

DOEpatents

Coon, Clifford L.; Harrar, Jackson E.; Pearson, Richard K.; McGuire, Raymond R.

1984-01-01

A method and apparatus for electrochemically synthesizing anhydrous HNO.sub.3 from an aqueous solution of HNO.sub.3 includes oxidizing a solution of N.sub.2 O.sub.4 /aqueous HNO.sub.3 at an anode, while maintaining a controlled potential between the N.sub.2 O.sub.4 /aqueous HNO.sub.3 solution and the anode. A potential of about 1.80V vs. SCE is preferred. Anhydrous or aqueous HNO.sub.3 may be disposed at the cathode within the electrochemical cell. Aqueous HNO.sub.3 having a water content of up to about 12% by weight is utilized to synthesize anhydrous HNO.sub.3.

Method and apparatus for synthesizing anhydrous HNO/sub 3/. [Patent application

DOEpatents

Coon, C.L.; Harrar, J.E.; Pearson, R.K.; McGuire, R.R.

1982-07-20

A method and apparatus for electrochemically synthesizing anhydrous HNO/sub 3/ from an aqueous solution of HNO/sub 3/- includes oxidizing a solution of N/sub 2/O/sub 4//aqueous HNO/sub 3/ at an anode, while maintaining a controlled potential between the N/sub 2/O/sub 4//aqueous HNO/sub 3/ solution and the anode. A potential of about 1.80V vs. SCE is preferred. Anhydrous or aqueous HNO/sub 3/ may be disposed at the cathode within the electrochemical cell. Aqueous HNO/sub 3/ having a water content of up to about 12% by weight is utilized to synthesize anhydrous HNO/sub 3/.

Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water

PubMed Central

Zhao, Li-Shan; Cao, Ze-Xian; Wang, Qiang

2015-01-01

Liquid-liquid transition of water is an important concept in condensed-matter physics. Recently, it was claimed to have been confirmed in aqueous solutions based on annealing-induced upshift of glass-liquid transition temperature, . Here we report a universal water-content, , dependence of for aqueous solutions. Solutions with vitrify/devitrify at a constant temperature, , referring to freeze-concentrated phase with left behind ice crystallization. Those solutions with totally vitrify at under conventional cooling/heating process though, of the samples annealed at temperatures   to effectively evoke ice recrystallization is stabilized at . Experiments on aqueous glycerol and 1,2,4-butanetriol solutions in literature were repeated, and the same samples subject to other annealing treatments equally reproduce the result. The upshift of by annealing is attributable to freeze-concentrated phase of solutions instead of ‘liquid II phase of water’. Our work also provides a reliable method to determine hydration formula and to scrutinize solute-solvent interaction in solution. PMID:26503911

Physico-chemical properties of aqueous drug solutions: From the basic thermodynamics to the advanced experimental and simulation results.

PubMed

Bellich, Barbara; Gamini, Amelia; Brady, John W; Cesàro, Attilio

2018-04-05

The physical chemical properties of aqueous solutions of model compounds are illustrated in relation to hydration and solubility issues by using three perspectives: thermodynamic, spectroscopic and molecular dynamics simulations. The thermodynamic survey of the fundamental backgrounds of concentration dependence and experimental solubility results show some peculiar behavior of aqueous solutions with several types of similar solutes. Secondly, the use of a variety of experimental spectroscopic devices, operating under different experimental conditions of dimension and frequency, has produced a large amount of structural and dynamic data on aqueous solutions showing the richness of the information produced, depending on where and how the experiment is carried out. Finally, the use of molecular dynamics computational work is presented to highlight how the different types of solute functional groups and surface topologies organize adjacent water molecules differently. The highly valuable contribution of computer simulation studies in providing molecular explanations for experimental deductions, either of a thermodynamic or spectroscopic nature, is shown to have changed the current knowledge of many aqueous solution processes. While this paper is intended to provide a collective view on the latest literature results, still the presentation aims at a tutorial explanation of the potentials of the three methodologies in the field of aqueous solutions of pharmaceutical molecules. Copyright © 2018. Published by Elsevier B.V.

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

The effect of calcination temperature on the formation and magnetic properties of ZnMn2O4 spinel

NASA Astrophysics Data System (ADS)

Hermanto, B.; Ciswandi; Afriani, F.; Aryanto, D.; Sudiro, T.

2018-03-01

The spinel based on transition-metal oxides has a typical composition of AB2O4. In this study, the ZnMn2O4 spinel was synthesized using a powder metallurgy technique. The Zn and Mn metallic powders with an atomic ratio of 1:2 were mechanically alloyed for 3 hours in aqueous solution. The mixed powder was then calcined in a muffle furnace at elevated temperature of 400, 500 and 600 °C. The X-ray Diffractometer (XRD) was used to evaluate the formation of a ZnMn2O4 spinel structure. The magnetic properties of the sample at varying calcination temperatures were characterized by a Vibrating Sample Magnetometer (VSM). The results show that the fraction of ZnMn2O4 spinel formation increases with the increase of calcination temperature. The calcination temperature also affects the magnetic properties of the samples.

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

In Situ Cross-Linking of Polyvinyl Alcohol Films

NASA Technical Reports Server (NTRS)

Philipp, W. H.; Shu, L. C.; May, C. E.

1984-01-01

Films or impregnated matrices readily made from aqueous polyvinyl alcohol solution. Controlled thickness films made by casting precise quantities of aqueous polymer solution on smooth surface, allowing water to evaporate and then removing film. Composite separators formed in similar fashion by impregnating cloth matrix with polyvinyl alcohol solution and drying composite. Insoluble thin hydrophilic membranes made from aqueous systems, and use of undesirable organic solvents not required.

Sediment Ecosystem Assessment Protocol (SEAP): An Accurate and Integrated Weight-of-Evidence Based System

DTIC Science & Technology

2011-01-01

polychaete Neanthes arenaceodentata from exposures to copper in aqueous solutions ...involved 96 h exposures in aqueous solutions , followed by a 1-2 hour (depending on size) feeding period on Artemia (brine shrimp) nauplii in clean seawater...EC50) based on post- exposure feeding of the polychaete Neanthes arenaceodentata from exposures to copper in aqueous solutions . Metric (µg/L) Worm age

Synthesis and Characterization of Functional Mesostructures Using Colloidal Crystal Templating

DTIC Science & Technology

2004-01-01

fluorescent probes in aqueous polymer solutions . Khoury and co-workers measured the diffusion coefficient of several fluorescein-labeled proteins in...diffraction naq refractive index of the aqueous solution phase xvii ni refractive index of component i ngel refractive index of the hydrogel...phase Tg glass transition temperature α angle of diffraction φaq volume fraction of the aqueous solution phase φi volume fraction of

SOLVENT EXTRACTION OF THORIUM VALUES FROM AQUEOUS SOLUTIONS

DOEpatents

Warf, J.C.

1959-04-21

The separation of thorium values from rare earth metals contained ln aqueous solutions by means of extraction with a water immiscible alkyl phosphate diluted with a hydrocarbon such as hexane is described. While the extraction according to this invention may be carried out from any aqueous salt solution, it is preferred to use solutions containing free mineral acid. Hydrochloric acid and in particular nitric acid are sultable in a concentration ranging from 0.1 to 7 normal. The higher acid concentration results in higher extraction values.

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

PubMed

Kameda, Tsunenori

2015-01-01

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

Aspheric Solute Ions Modulate Gold Nanoparticle Interactions in an Aqueous Solution: An Optimal Way to Reversibly Concentrate Functionalized Nanoparticles

PubMed Central

Villarreal, Oscar D; Chen, Liao Y; Whetten, Robert L; Demeler, Borries

2015-01-01

Nanometer-sized gold particles (AuNPs) are of peculiar interest because their behaviors in an aqueous solution are sensitive to changes in environmental factors including the size and shape of the solute ions. In order to determine these important characteristics, we performed all-atom molecular dynamics simulations on the icosahedral Au144 nanoparticles each coated with a homogeneous set of 60 thiolates (4-mercapto-benzoate, pMBA) in eight aqueous solutions having ions of varying sizes and shapes (Na+, K+, tetramethylamonium cation TMA+, trisamonium cation TRS+, Cl−, and OH−). For each solution, we computed the reversible work (potential of mean of force) to bring two nanoparticles together as a function of their separation distance. We found that the behavior of pMBA protected Au144 nanoparticles can be readily modulated by tuning their aqueous environmental factors (pH and solute ion combinations). We examined the atomistic details on how the sizes and shapes of solute ions quantitatively factor in the definitive characteristics of nanoparticle-environment and nanoparticle-nanoparticle interactions. We predict that tuning the concentrations of non-spherical composite ions such as TRS+ in an aqueous solution of AuNPs be an effective means to modulate the aggregation propensity desired in biomedical and other applications of small charged nanoparticles. PMID:26581232

Aspheric Solute Ions Modulate Gold Nanoparticle Interactions in an Aqueous Solution: An Optimal Way To Reversibly Concentrate Functionalized Nanoparticles.

PubMed

Villarreal, Oscar D; Chen, Liao Y; Whetten, Robert L; Demeler, Borries

2015-12-17

Nanometer-sized gold particles (AuNPs) are of peculiar interest because their behaviors in an aqueous solution are sensitive to changes in environmental factors including the size and shape of the solute ions. In order to determine these important characteristics, we performed all-atom molecular dynamics simulations on the icosahedral Au144 nanoparticles each coated with a homogeneous set of 60 thiolates (4-mercaptobenzoate, pMBA) in eight aqueous solutions having ions of varying sizes and shapes (Na(+), K(+), tetramethylamonium cation TMA(+), tris-ammonium cation TRS(+), Cl(-), and OH(-)). For each solution, we computed the reversible work (potential of mean of force) to bring two nanoparticles together as a function of their separation distance. We found that the behavior of pMBA protected Au144 nanoparticles can be readily modulated by tuning their aqueous environmental factors (pH and solute ion combinations). We examined the atomistic details on how the sizes and shapes of solute ions quantitatively factor in the definitive characteristics of nanoparticle-environment and nanoparticle-nanoparticle interactions. We predict that tuning the concentrations of nonspherical composite ions such as TRS(+) in an aqueous solution of AuNPs be an effective means to modulate the aggregation propensity desired in biomedical and other applications of small charged nanoparticles.

Modified resins for solid-phase extraction

DOEpatents

Fritz, James S.; Sun, Jeffrey J.

1993-07-27

A process of treating aqueous solutions to remove organic solute contaminants by contacting an aqueous solution containing polar organic solute contaminants with a functionalized polystyrene-divinyl benzene adsorbent resin, with the functionalization of said resin being accomplished by organic hydrophilic groups such as hydroxymethyl, acetyl and cyanomethyl.

Modified resins for solid-phase extraction

DOEpatents

Fritz, James S.; Sun, Jeffrey J.

1991-12-10

A process of treating aqueous solutions to remove organic solute contaminants by contacting an aqueous solution containing polar organic solute contaminants with a functionalized polystyrene-divinyl benzene adsorbent resin, with the functionalization of said resin being accomplished by organic hydrophilic groups such as hydroxymethyl, acetyl and cyanomethyl.

URANIUM RECOVERY PROCESS

DOEpatents

Hyman, H.H.; Dreher, J.L.

1959-07-01

The recovery of uranium from the acidic aqueous metal waste solutions resulting from the bismuth phosphate carrier precipitation of plutonium from solutions of neutron irradiated uranium is described. The waste solutions consist of phosphoric acid, sulfuric acid, and uranium as a uranyl salt, together with salts of the fission products normally associated with neutron irradiated uranium. Generally, the process of the invention involves the partial neutralization of the waste solution with sodium hydroxide, followed by conversion of the solution to a pH 11 by mixing therewith sufficient sodium carbonate. The resultant carbonate-complexed waste is contacted with a titanated silica gel and the adsorbent separated from the aqueous medium. The aqueous solution is then mixed with sufficient acetic acid to bring the pH of the aqueous medium to between 4 and 5, whereby sodium uranyl acetate is precipitated. The precipitate is dissolved in nitric acid and the resulting solution preferably provided with salting out agents. Uranyl nitrate is recovered from the solution by extraction with an ether such as diethyl ether.

Diffusion of aqueous solutions of ionic, zwitterionic, and polar solutes

NASA Astrophysics Data System (ADS)

Teng, Xiaojing; Huang, Qi; Dharmawardhana, Chamila Chathuranga; Ichiye, Toshiko

2018-06-01

The properties of aqueous solutions of ionic, zwitterionic, and polar solutes are of interest to many fields. For instance, one of the many anomalous properties of aqueous solutions is the behavior of water diffusion in different monovalent salt solutions. In addition, solutes can affect the stabilities of macromolecules such as proteins in aqueous solution. Here, the diffusivities of aqueous solutions of sodium chloride, potassium chloride, tri-methylamine oxide (TMAO), urea, and TMAO-urea are examined in molecular dynamics simulations. The decrease in the diffusivity of water with the concentration of simple ions and urea can be described by a simple model in which the water molecules hydrogen bonded to the solutes are considered to diffuse at the same rate as the solutes, while the remainder of the water molecules are considered to be bulk and diffuse at almost the same rate as pure water. On the other hand, the decrease in the diffusivity of water with the concentration of TMAO is apparently affected by a decrease in the diffusion rate of the bulk water molecules in addition to the decrease due to the water molecules hydrogen bonded to TMAO. In other words, TMAO enhances the viscosity of water, while urea barely affects it. Overall, this separation of water molecules into those that are hydrogen bonded to solute and those that are bulk can provide a useful means of understanding the short- and long-range effects of solutes on water.

Method and apparatus for measuring volatile compounds in an aqueous solution

DOEpatents

Gilmore, Tyler J [Pasco, WA; Cantrell, Kirk J [West Richland, WA

2002-07-16

The present invention is an improvement to the method and apparatus for measuring volatile compounds in an aqueous solution. The apparatus is a chamber with sides and two ends, where the first end is closed. The chamber contains a solution volume of the aqueous solution and a gas that is trapped within the first end of the chamber above the solution volume. The gas defines a head space within the chamber above the solution volume. The chamber may also be a cup with the second end. open and facing down and submerged in the aqueous solution so that the gas defines the head space within the cup above the solution volume. The cup can also be entirely submerged in the aqueous solution. The second end of the. chamber may be closed such that the chamber can be used while resting on a flat surface such as a bench. The improvement is a sparger for mixing the gas with the solution volume. The sparger can be a rotating element such as a propeller on a shaft or a cavitating impeller. The sparger can also be a pump and nozzle where the pump is a liquid pump and the nozzle is a liquid spray nozzle open, to the head space for spraying the solution volume into the head space of gas. The pump could also be a gas pump and the nozzle a gas nozzle submerged in the solution volume for spraying the head space gas into the solution volume.

Comparison of cytotoxicity in vitro and irritation in vivo for aqueous and oily solutions of surfactants.

PubMed

Czajkowska-Kośnik, Anna; Wolska, Eliza; Chorążewicz, Juliusz; Sznitowska, Małgorzata

2015-01-01

The in vivo model on rabbit eyes and the in vitro cytotoxicity on fibroblasts were used to compare irritation effect of aqueous and oily (Miglyol 812) solutions of surfactants. Tween 20, Tween 80 and Cremophor EL were tested in different concentrations (0.1, 1 or 5%) and the in vitro test demonstrated that surfactants in oil are less cytotoxic than in aqueous solutions. In the in vivo study, the aqueous solutions of surfactants were characterized as non-irritant while small changes in conjunctiva were observed after application the oily solutions of surfactants and the preparations were classified as slightly irritant, however this effect was similar when Miglyol was applied alone. In conclusion, it is reported that the MTT assay does not correlate well with the Draize scores.

Dielectric study of aqueous solutions of sodium dodecyl sulfate in the frequency span 20 Hz to 2 MHz

NASA Astrophysics Data System (ADS)

Kadve, A. M.; Vankar, H. P.; Rana, V. A.

2017-05-01

Dielectric measurements were carried out for aqueous solutions of Sodium Dodecyl Sulfate (SDS) in the frequency span of 20 Hz to 2 MHz at 300.15 K temperature using precision LCR meter. Also the refractive indices were measured for the solutions at 300.15 K temperature using Abbe's refractometer. The measurements were done for ten different concentrations of SDS in distilled water. Determined values of complex permittivity as a function of frequency were used to evaluate other parameters like loss tangent and electric modulus for the liquid samples. The permittivity at optical frequency were also calculated from the measured refractive indices for the aqueous solutions. The effect of concentration variation of SDS in the aqueous solutions on the determined parameters is discussed.

Effective adsorption and collection of cesium from aqueous solution using graphene oxide grown on porous alumina

NASA Astrophysics Data System (ADS)

Entani, Shiro; Honda, Mitsunori; Shimoyama, Iwao; Li, Songtian; Naramoto, Hiroshi; Yaita, Tsuyoshi; Sakai, Seiji

2018-04-01

Graphene oxide (GO) with a large surface area was synthesized by the direct growth of GO on porous alumina using chemical vapor deposition to study the Cs adsorption mechanism in aqueous solutions. Electronic structure analysis employing in situ near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy measurements clarifies the Cs atoms bond via oxygen functional groups on GO in the aqueous solution. The Cs adsorption capacity was found to be as high as 650-850 mg g-1, which indicates that the GO/porous alumina acts as an effective adsorbent with high adsorption efficiency for radioactive nuclides in aqueous solutions.

RECOVERY OF PROTACTINIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Elson, R.E.

1959-07-14

The recovery of fluoride complexed protactinium from aqueous acidic solutions by solvent extraction is described. Generally the prccess of the invention com rises mixing an aqueous solution containing protactinium in a complexed form with an organic solvent which is specific for protactinium, such as diisopropyl carbinol, then decomposing the protactinium complex by adjusting the acidity of the aqueous solution to between 0-3 to 0-9 M in hydrogen ion concentration, and introducing a source of aluminum ions in sufficient quantity to establish a concentration of 0.5 to 1.2 M aluminum ion, whereupon decomposition of the protactinium fluoride complex takes place and the protactinium ion is taken up by the organic solvent phase.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1997-01-01

A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Method for selectively reducing plutonium values by a photochemical process

DOEpatents

Friedman, Horace A.; Toth, Louis M.; Bell, Jimmy T.

1978-01-01

The rate of reduction of Pu(IV) to Pu(III) in nitric acid solution containing a reducing agent is enhanced by exposing the solution to 200-500 nm electromagnetic radiation. Pu values are recovered from an organic extractant solution containing Pu(IV) values and U(VI) values by the method of contacting the extractant solution with an aqueous nitric acid solution in the presence of a reducing agent and exposing the aqueous solution to electromagnetic radiation having a wavelength of 200-500 nm. Under these conditions, Pu values preferentially distribute to the aqueous phase and U values preferentially distribute to the organic phase.

Thermodynamic characteristics of protolytic equilibria of L-serine in aqueous solutions

NASA Astrophysics Data System (ADS)

Kochergina, L. A.; Volkov, A. V.; Khokhlova, E. A.; Krutova, O. N.

2011-05-01

The heat effects of the reaction of aqueous solution of L-serine with aqueous solutions of HNO3 and KOH were determined by calorimetry at temperatures of 288.15, 298.15, and 308.15 K, and ionic strength values of 0.2, 0.5, and 1.0 (background electrolyte, KNO3). Standard thermodynamic characteristics (Δr H o, Δr G o, Δr S o, Δ C {/p o}) of the acid-base reactions in aqueous solutions of L-serine were calculated. The effect of the concentration of background electrolyte and temperature on the heats of dissociation of amino acid was considered. The combustion energy of L-serine by bomb calorimetry in the medium of oxygen was determined. The standard combustion and formation enthalpies of crystalline L-serine were calculated. The heats of dissolution of crystalline L-serine in water and solutions of potassium hydroxide at 298.15 K were measured by direct calorimetry. The standard enthalpies of formation of L-serine and products of its dissociation in aqueous solution were calculated.

Biodegradation of Azure-B dye by Serratia liquefaciens and its validation by phytotoxicity, genotoxicity and cytotoxicity studies.

PubMed

Haq, Izharul; Raj, Abhay; Markandeya

2018-04-01

The azo dyes in textile industry are a major source of environmental pollution and cause serious threat to aquatic flora and fauna. The present study aims to evaluate the potential of previously isolated lignin peroxidase (LiP) enzyme producing Serratia liquefaciens in degradation of Azure-B (AB) dye. S. liquefaciens showed rapid decolourisation of AB dye (100 mg L -1 ) in mineral salt medium (MSM) supplemented with 0.2% glucose and yeast extract, and more than 90% dye decolourisation was observed at 48 h when incubated at 30 °C. Decolourisation conditions were optimized by Response Surface Methodology (RSM) using Box-Behnken Designs (BBD). The dye degradation was further confirmed by ATR-FTIR and GC-MS analysis. Toxicological studies of untreated (UT) and bacterial treated (BT) AB dye solutions were studied by using phytotoxicity, genotoxicity and cytotoxicity endpoints. Phytotoxicity assay using Vigna radiata indicated that bacterial treatment led to detoxification of AB dye. Genotoxicity assay with Allium cepa showed that pure AB dye solutions significantly reduced mitotic index (MI) and induced various chromosomal abnormalities (CAs) like c-mitosis, stickiness, chromosome break, anaphase bridges, vagrant chromosomes and binucleated and micronucleated cell in the root tip cells, whereas, bacterial treated solutions induced relatively less genotoxicity in nature. Improved cell survivability (%) was also noted in kidney cell line (NRK-52E) after S. liquefaciens treated dye solutions than the pure dye solutions. The findings suggest that S. liquefaciens could be a potential bacterium for azo dye degradation, as it is effective in lowering of toxic effects of AB dye. Copyright © 2018 Elsevier Ltd. All rights reserved.

Stabilization of diketo tautomer of curcumin by premicellar anionic surfactants: UV-Visible, fluorescence, tensiometric and TD-DFT evidences

NASA Astrophysics Data System (ADS)

Dutta, Anisha; Boruah, Bornali; Manna, Arun K.; Gohain, Biren; Saikia, Palash M.; Dutta, Robin K.

2013-03-01

A newly observed UV band of aqueous curcumin, a biologically important molecule, in presence of anionic surfactants, viz., sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and sodium dodecylsulfonate (SDSN) in buffered aqueous solutions has been studied experimentally and theoretically. The 425 nm absorption band of curcumin disappears and a new UV-band is observed at 355 nm on addition of the surfactants in the submicellar concentration range which is reversed as the surfactant concentration approaches the critical micelle concentration (CMC). The observed spectral absorption, fluorescence intensity and surface tension behavior, under optimal experimental conditions of submicellar concentration ranges of the surfactants in the pH range of 2.00-7.00, indicate that the new band is due to the β-diketo tautomer of curcumin stabilized by interactions between curcumin and the anionic surfactants. The stabilization of the diketo tautomer by submicellar anionic surfactants described here as well as by submicellar cationic surfactant, reported recently, is unique as this is the only such behavior observed in presence of submicellar surfactants of both charge types. The experimental results are in good agreement with the theoretical calculations using ab initio density functional theory combined with time dependent density functional theory (TD-DFT) calculations.

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, W.Y.

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

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

PubMed

Jung, Kwan Ho; Lee, Keun-Hyeung

2015-09-15

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

Process for extracting technetium from alkaline solutions

DOEpatents

Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.

1995-01-01

A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

Bidentate organophosphorus solvent extraction process for actinide recovery and partition

DOEpatents

Schulz, Wallace W.

1976-01-01

A liquid-liquid extraction process for the recovery and partitioning of actinide values from acidic nuclear waste aqueous solutions, the actinide values including trivalent, tetravalent and hexavalent oxidation states is provided and includes the steps of contacting the aqueous solution with a bidentate organophosphorous extractant to extract essentially all of the actinide values into the organic phase. Thereafter the respective actinide fractions are selectively partitioned into separate aqueous solutions by contact with dilute nitric or nitric-hydrofluoric acid solutions. The hexavalent uranium is finally removed from the organic phase by contact with a dilute sodium carbonate solution.

Adsorption of Cu(II) from aqueous solution on sulfuric acid treated palygorskite

NASA Astrophysics Data System (ADS)

Niu, Yan-Ning; Yuan, Yuan; Gao, Wei-Xin; Qian, Sheng; Sun, Wen

2018-03-01

The absorption behavior of Cu2+ from aqueous solution on sulfuric acid treated palygorskite were investigated, the results showed that palygorskite had high absorption ability for Cu2+ from aqueous solution. Effects of the shaking time, pH and the copper ion concentration on the removal rate were discussed. The absorption behavior of Cu2+ could be well imitated by the Langmuir isothermal equation.

Water purification using organic salts

DOEpatents

Currier, Robert P.

2004-11-23

Water purification using organic salts. Feed water is mixed with at least one organic salt at a temperature sufficiently low to form organic salt hydrate crystals and brine. The crystals are separated from the brine, rinsed, and melted to form an aqueous solution of organic salt. Some of the water is removed from the aqueous organic salt solution. The purified water is collected, and the remaining more concentrated aqueous organic salt solution is reused.

Structural and spectroscopic studies of a rare non-oxido V(v) complex crystallized from aqueous solution

DOE PAGES

Leggett, Christina J.; Parker, Bernard F.; Teat, Simon J.; ...

2016-01-14

A “bare” V 5+ complex with glutaroimide-dioxime (H 3L), a ligand for uranium recovery from seawater, was synthesized from aqueous solution as Na[V(L) 2]2H 2O and the structure determined by x-ray diffraction. It is the first non-oxo V(v) complex that has been directly synthesized in and crystallized from aqueous solution.

Measurement of Surface Forces

DTIC Science & Technology

1990-11-16

creating an electrical double-layer whenever a bare mica surface is in contact with an aqueous solution . The mica/electrolyte double-layer...between mica in aqueous solutions containing 10-5 to I M KNO 3 (From Reference 44. Copyright 0 1985 Royal Swedish Academy. Reprinted with permission of...can be observed in aqueous KNO 3 solutions at close separations and at high ion concentrations. For example, if the force curves in Figure 8 (top) for

Structural and spectroscopic studies of a rare non-oxido V(v) complex crystallized from aqueous solution

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

Leggett, Christina J.; Parker, Bernard F.; Teat, Simon J.

A “bare” V 5+ complex with glutaroimide-dioxime (H 3L), a ligand for uranium recovery from seawater, was synthesized from aqueous solution as Na[V(L) 2]2H 2O and the structure determined by x-ray diffraction. It is the first non-oxo V(v) complex that has been directly synthesized in and crystallized from aqueous solution.

Sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on the surface of porous graphitized carbon

NASA Astrophysics Data System (ADS)

Savchenkova, A. S.; Buryak, A. K.; Kurbatova, S. V.

2015-09-01

The sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on porous graphitized carbon was studied. The effect of the structure of analyte molecules and the eluent composition on the characteristics of retention under the conditions of RP HPLC was analyzed. The effect of pH of the eluent on the shift of equilibrium in aqueous acetonitrile solutions was investigated.

ADSORPTION PROCEDURE IN PREPARING U$sup 23$$sup 3$

DOEpatents

Stoughton, R.W.

1958-10-14

A process is presented for the separation of protoactinium and thorium from an aqueous nitric acid solution containing these metals. It comprises contacting the solution with a cation exchange phenol-formaldehyde resin containing sulfonic acid groups, and eluting the adsorbed thorium from the resin by means of aqueous nitric acid. Thereafter the adsorbed protoactinium is eluted from the resin by means of an aqueous solution of ammonium fluoride.

KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal

PubMed Central

Dong, Hui; Wang, Lili; Gao, Wei; Li, Xiaoyuan; Wang, Chao; Ji, Fang; Pan, Jinlong; Wang, Baorui

2017-01-01

A novel functional KH2PO4 (KDP) aqueous solution-in-oil (KDP aq/O) microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP) was prepared. The system, which consisted of decanol, Triton X-100, and KH2PO4 aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations (cKDP) were applied to replace water in the traditional water-in-oil (W/O) microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR) with the increasing of the cKDP. As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion (cKDP was changed from 10 mM to 100 mM) as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR. PMID:28772632

KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal.

PubMed

Dong, Hui; Wang, Lili; Gao, Wei; Li, Xiaoyuan; Wang, Chao; Ji, Fang; Pan, Jinlong; Wang, Baorui

2017-03-09

A novel functional KH₂PO₄ (KDP) aqueous solution-in-oil (KDP aq/O) microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP) was prepared. The system, which consisted of decanol, Triton X-100, and KH₂PO₄ aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations ( c KDP ) were applied to replace water in the traditional water-in-oil (W/O) microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR) with the increasing of the c KDP . As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion ( c KDP was changed from 10 mM to 100 mM) as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR.

Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

2016-09-01

Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

Ceramic porous material and method of making same

DOEpatents

Liu, Jun; Kim, Anthony Y.; Virden, Jud W.

1997-01-01

The invention is a mesoporous ceramic membrane having substantially uniform pore size. Additionally, the invention includes aqueous and non-aqueous processing routes to making the mesoporous ceramic membranes. According to one aspect of the present invention, inserting a substrate into a reaction chamber at pressure results in reaction products collecting on the substrate and forming a membrane thereon. According to another aspect of the present invention, a second aqueous solution that is sufficiently immiscible in the aqueous solution provides an interface between the two solutions whereon the mesoporous membrane is formed. According to a further aspect of the present invention, a porous substrate is placed at the interface between the two solutions permitting formation of a membrane on the surface or within the pores of the porous substrate. According to yet another aspect of the present invention, mesoporous ceramic materials are formed using a non-aqueous solvent and water-sensitive precursors.

Ceramic porous material and method of making same

DOEpatents

Liu, J.; Kim, A.Y.; Virden, J.W.

1997-07-08

The invention is a mesoporous ceramic membrane having substantially uniform pore size. Additionally, the invention includes aqueous and non-aqueous processing routes to making the mesoporous ceramic membranes. According to one aspect of the present invention, inserting a substrate into a reaction chamber at pressure results in reaction products collecting on the substrate and forming a membrane thereon. According to another aspect of the present invention, a second aqueous solution that is sufficiently immiscible in the aqueous solution provides an interface between the two solutions whereon the mesoporous membrane is formed. According to a further aspect of the present invention, a porous substrate is placed at the interface between the two solutions permitting formation of a membrane on the surface or within the pores of the porous substrate. According to yet another aspect of the present invention, mesoporous ceramic materials are formed using a non-aqueous solvent and water-sensitive precursors. 21 figs.

High-throughput ab-initio dilute solute diffusion database.

PubMed

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-07-19

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world.

Brown carbon formation by aqueous-phase carbonyl compound reactions with amines and ammonium sulfate.

PubMed

Powelson, Michelle H; Espelien, Brenna M; Hawkins, Lelia N; Galloway, Melissa M; De Haan, David O

2014-01-21

Reactions between small water-soluble carbonyl compounds, ammonium sulfate (AS), and/or amines were evaluated for their ability to form light-absorbing species in aqueous aerosol. Aerosol chemistry was simulated with bulk phase reactions at pH 4, 275 K, initial concentrations of 0.05 to 0.25 M, and UV-vis and fluorescence spectroscopy monitoring. Glycolaldehyde-glycine mixtures produced the most intense absorbance. In carbonyl compound reactions with AS, methylamine, or AS/glycine mixtures, product absorbance followed the order methylglyoxal > glyoxal > glycolaldehyde > hydroxyacetone. Absorbance extended into the visible, with a wavelength dependence fit by absorption Ångstrom coefficients (Å(abs)) of 2 to 11, overlapping the Å(abs) range of atmospheric, water-soluble brown carbon. Many reaction products absorbing between 300 and 400 nm were strongly fluorescent. On a per mole basis, amines are much more effective than AS at producing brown carbon. In addition, methylglyoxal and glyoxal produced more light-absorbing products in reactions with a 5:1 AS-glycine mixture than with AS or glycine alone, illustrating the importance of both organic and inorganic nitrogen in brown carbon formation. Through comparison to biomass burning aerosol, we place an upper limit on the contribution of these aqueous carbonyl-AS-amine reactions of ≤ 10% of global light absorption by brown carbon.

A highly sensitive monoclonal antibody based biosensor for quantifying 3-5 ring polycyclic aromatic hydrocarbons (PAHs) in aqueous environmental samples

PubMed Central

Li, Xin; Kaattari, Stephen L.; Vogelbein, Mary A.; Vadas, George G.; Unger, Michael A.

2016-01-01

Immunoassays based on monoclonal antibodies (mAbs) are highly sensitive for the detection of polycyclic aromatic hydrocarbons (PAHs) and can be employed to determine concentrations in near real-time. A sensitive generic mAb against PAHs, named as 2G8, was developed by a three-step screening procedure. It exhibited nearly uniformly high sensitivity against 3-ring to 5-ring unsubstituted PAHs and their common environmental methylated PAHs, with IC50 values between 1.68–31 μg/L (ppb). 2G8 has been successfully applied on the KinExA Inline Biosensor system for quantifying 3-5 ring PAHs in aqueous environmental samples. PAHs were detected at a concentration as low as 0.2 μg/L. Furthermore, the analyses only required 10 min for each sample. To evaluate the accuracy of the 2G8-based biosensor, the total PAH concentrations in a series of environmental samples analyzed by biosensor and GC-MS were compared. In most cases, the results yielded a good correlation between methods. This indicates that generic antibody 2G8 based biosensor possesses significant promise for a low cost, rapid method for PAH determination in aqueous samples. PMID:26925369

Antiscalant properties of Spergularia rubra and Parietaria officinalis aqueous solutions

NASA Astrophysics Data System (ADS)

Cheap-Charpentier, Hélène; Gelus, Dominique; Pécoul, Nathalie; Perrot, Hubert; Lédion, Jean; Horner, Olivier; Sadoun, Jonathan; Cachet, Xavier; Litaudon, Marc; Roussi, Fanny

2016-06-01

The formation of calcium carbonate in water has important implications in industry. Chemical antiscalant is usually used to control scale depositions. Plant extracts have been recently used as new green antiscalant agents, as they can be easily prepared and are environmentally friendly. In this study, stock aqueous solutions of Spergularia rubra and Parietaria officinalis, two plants used in traditional medicine to treat or prevent urolithiasis, were obtained by infusion. The antiscaling properties of these extracts towards CaCO3 formation were tested by using chronoamperometry and Fast Controlled Precipitation methods. The aqueous solution of S. rubra was further fractionated to isolate compounds of lower polarity. Their efficiency towards CaCO3 precipitation was characterized by Fast Controlled Precipitation method. The inhibiting efficiency of this fractionated solution was greater than that of the stock aqueous solution.

SEPARATION PROCESS FOR TRANSURANIC ELEMENT AND COMPOUNDS THEREOF

DOEpatents

Magnusson, L.B.

1958-04-01

A process is described for the separation of neptunium, from aqueous solutions of neptunium, plutonium, uraniunn, and fission prcducts. This separation from an acidic aqueous solution of a tetravalent neptuniunn can be made by contacting the solution with a certain type of chelating,; agent, preferably dissolved in an organic solvent, to form a neptunium chelate compound. When the organic solvent is present, the neptunium chelate compound is extracted; otherwise, it precipitates from the aqueous solution and is separated by any suitable means. The chelating agent is a fluorinated BETA -diketone. such as trifluoroacetyl acetone.

Radiolysis of aqueous solutions of thiamine

NASA Astrophysics Data System (ADS)

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

1998-06-01

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

ION EXCHANGE PROCESS FOR THE RECOVERY AND PURIFICATION OF MATERIALS

DOEpatents

Long, R.S.; Bailes, R.H.

1958-04-15

A process for the recovery of certain metallic ions from aqueous solutions by ion exchange techniques is described. It is applicable to elements such as vanadium, chromium, nnanganese, and the like, which are capable of forming lower valent cations soluble in aqueous solutions and which also form ldgher valent anions soluble in aqueous acidic solutions. For example, small amounts of vanadium occurring in phosphoric acid prepared from phosphate rock may be recovered by reducing the vanadium to a trivalent cation adsorbing; the vanadium in a cationic exchange resin, then treating the resin with a suitable oxidizing agent to convert the adsorbed vanadium to a higher valent state, and finally eluting; the vanadium as an anion from the resin by means of an aqueous acidic solution.

Removal of copper ions from aqueous solutions by a steel-making by-product.

PubMed

López, F A; Martín, M I; Pérez, C; López-Delgado, A; Alguacil, F J

2003-09-01

A study is made of the use of a steel-making by-product (rolling mill scale) as a material for removing Cu(2+) ions from aqueous solutions. The influence of contact time, initial copper ion concentration and temperature on removal capability is considered. The removal of Cu(2+) ions from an aqueous solution involves two processes: on the one hand, the adsorption of Cu(2+) ions on the surface of mill scale due to the iron oxides present in the latter; and on the other hand, the cementation of Cu(2+) onto metallic iron contained in the mill scale. Rolling mill scale is seen to be an effective material for the removal of copper ions from aqueous solutions.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1997-02-18

A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures.

PubMed

Kanno, H; Kajiwara, K; Miyata, K

2010-05-21

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for T(H) (homogeneous ice nucleation temperature) and T(m) (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the T(H) curve for a DMSO solution of R=20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at P(c2)= approximately 200 MPa and at T(c2)<-100 degrees C (P(c2): pressure of SCP, T(c2): temperature of SCP). The presence of two T(H) peaks for DMSO solutions (R=15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

NASA Astrophysics Data System (ADS)

Kanno, H.; Kajiwara, K.; Miyata, K.

2010-05-01

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2<-100 °C (Pc2: pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (<-90 °C). The pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

Enthalpic parameters of interaction between diglycylglycine and polyatomic alcohols in aqueous solutions

NASA Astrophysics Data System (ADS)

Mezhevoi, I. N.; Badelin, V. G.

2015-12-01

Integral enthalpies of solution Δsol H m of diglycylglycine in aqueous solutions of glycerol, ethylene glycol, and 1,2-propylene glycol are measured via solution calorimetry. The experimental data are used to calculate the standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of the tripeptide from water to aqueous solutions of polyatomic alcohols. The enthalpic pairwise coefficients h xy of interactions between the tripeptide and polyatomic alcohol molecules are calculated using the McMillan-Mayer solution theory and are found to have positive values. The findings are discussed using the theory of estimating various types of interactions in ternary systems and the effect the structural features of interacting biomolecules have on the thermochemical parameters of diglycylglycine dissolution.

PROCESS FOR SEPARATING PLUTONIUM BY REPEATED PRECIPITATION WITH AMPHOTERIC HYDROXIDE CARRIERS

DOEpatents

Faris, B.F.

1960-04-01

A multiple carrier precipitation method is described for separating and recovering plutonium from an aqueous solution. The hydroxide of an amphoteric metal is precipitated in an aqueous plutonium-containing solution. This precipitate, which carries plutonium, is then separated from the supernatant liquid and dissolved in an aqueous hydroxide solution, forming a second plutonium- containing solution. lons of an amphoteric metal which forms an insoluble hydroxide under the conditions existing in this second solution are added to the second solution. The precipitate which forms and which carries plutonium is separated from the supernatant liquid. Amphoteric metals which may be employed are aluminum, bibmuth, copper, cobalt, iron, lanthanum, nickel, and zirconium.

Mechanistic roles of soil humus and minerals in the sorption of nonionic organic compounds from aqueous and organic solutions

USGS Publications Warehouse

Chiou, C.T.; Shoup, T.D.; Porter, P.E.

1985-01-01

Mechanistic roles of soil humus and soil minerals and their contributions to soil sorption of nonionic organic compounds from aqueous and organic solutions are illustrated. Parathion and lindane are used as model solutes on two soils that differ greatly in their humic and mineral contents. In aqueous systems, observed sorptive characteristics suggest that solute partitioning into the soil-humic phase is the primary mechanism of soil uptake. By contrast, data obtained from organic solutions on dehydrated soil partitioning into humic phase and adsorption by soil minerals is influenced by the soil-moisture content and by the solvent medium from which the solute is sorbed. ?? 1985.

Nanobeads-based assays. The case of gluten detection

NASA Astrophysics Data System (ADS)

Venditti, Iole; Fratoddi, Ilaria; Vittoria Russo, Maria; Bellucci, Stefano; Crescenzo, Roberta; Iozzino, Luisa; Staiano, Maria; Aurilia, Vincenzo; Varriale, Antonio; Rossi, Mosè; D'Auria, Sabato

2008-11-01

In order to verify if the use of nanobeads of poly[phenylacetylene-(co-acrylic acid)] (PPA/AA) in the ELISA test would affect the immune-activity of the antibodies (Ab) and/or the activity of the enzymes used to label the Ab anti-rabbit IGg, in this work we immobilized the horse liver peroxidase labelled Ab anti-rabbit IGg onto PPA/AA nanobeads. The gluten test was chosen as the model to demonstrate the usefulness of these nanobeads in immunoassays. The synthesis of PPA/AA nanobeads was performed by a modified emulsion polymerization. Self-assembly of nanospheres with mean diameter equal to 200 nm was achieved by casting aqueous suspensions. The materials were characterized by traditional spectroscopic techniques, while the size and dispersion of the particles were analysed by scanning electron microscopy (SEM) measurements. The obtained results show that the immobilization process of the Abs onto PPA/AA did not affect either the immune-response of the Abs or the functional activity of the peroxidase suggesting the usefulness of PPA/AA for the design of advanced nanobeads-based assays for the simultaneous screening of several analytes in complex media.

How Does a Hydrophobic Macromolecule Respond to Mixed Osmolyte Environment?

PubMed

Tah, Indrajit; Mondal, Jagannath

2016-10-04

The role of the protecting osmolyte Trimethyl N-oxide (TMAO) in counteracting the denaturing effect of urea on a protein is quite well established. However, the mechanistic role of osmolytes on the hydrophobic interaction underlying protein folding is a topic of contention and is emerging as a key area of biophysical interest. Although recent experiment and computer simulation have established that individual aqueous solution of TMAO and urea respectively stabilizes and destabilizes the collapsed conformation of a hydrophobic polymer, it remains to be explored how a mixed aqueous solution of protecting and denaturing osmolytes influences the conformations of the polymer. In order to bridge the gap, we have simulated the conformational behavior of both a model hydrophobic polymer and a synthetic polymer polystyrene in an aqueous mixture of TMAO and urea. Intriguingly, our free energy based simulations on both the systems show that even though a pure aqueous solution of TMAO stabilizes the collapsed or globular conformation of the hydrophobic polymer, addition of TMAO to an aqueous solution of urea further destabilizes the collapsed conformation of the hydrophobic polymer. We also observe that the extent of destabilization in a mixed osmolyte solution is relatively higher than that in pure aqueous urea solution. The reinforcement of the denaturation effect of the hydrophobic macromolecule in a mixed osmolyte solution is in stark contrast to the well-known counteracting role of TMAO in proteins under denaturing condition of urea. In both model and realistic systems, our results show that in a mixed aqueous solution, greater number of cosolutes preferentially bind to the extended conformation of the polymer relative to that in the collapsed conformation, thereby complying with Tanford-Wyman preferential solvation theory disfavoring the collapsed conformation. The results are robust across a range of osmolyte concentrations and multiple cosolute forcefields. Our findings unequivocally imply that the action of mixed osmolyte solution on hydrophobic polymer is significantly distinct from that of proteins.

Simple introduction of carboxyl head group with alkyl spacer onto multiwalled carbon nanotubes by solution plasma process

NASA Astrophysics Data System (ADS)

Nemoto, Shimpei; Ueno, Tomonaga; Watthanaphanit, Anyarat; Hieda, Junko; Bratescu, Maria Antoaneta; Saito, Nagahiro

2017-09-01

A simple method of fabricating carboxyl-terminated multiwalled carbon nanotubes (MWCNTs) with alkyl spacers was developed to improve the dispersion quality of MWCNTs in aqueous solutions using solution plasma (SP) in a 6-aminocaproic acid solution. The formation of SP in the solution led to better dispersion of MWCNTs in aqueous solutions. Fourier transform infrared spectroscopy (FT-IR) results indicate that a carboxyl group with an alkyl spacer can be introduced by SP treatment in the 6-aminocaproic acid solution. Sedimentation tests show that the SP-treated MWCNTs in the 6-aminocaproic acid solution retained their good dispersion quality in aqueous solutions of pHs 5, 6, and 9. The alkyl spacer plays an important role in the preservation of dispersion states particularly at pH 6.

Aqueous penetration and biological activity of moxifloxacin 0.5% ophthalmic solution and gatifloxacin 0.3% solution in cataract surgery patients.

PubMed

Kim, Dianne H; Stark, Walter J; O'Brien, Terrence P; Dick, James D

2005-11-01

To measure the achievable perioperative aqueous concentration of the commercially available topically administered fourth generation fluoroquinolones, moxifloxacin 0.5% ophthalmic solution, and gatifloxacin 0.3% ophthalmic solution, and to correlate this concentration with the agents' biological efficacy in the aqueous humor of patients undergoing routine cataract surgery. Prospective, randomized, parallel, double-masked, clinical trial. Fifty patients undergoing cataract extraction. Patients (n = 25) were given perioperative topical moxifloxacin 0.5% or topical gatifloxacin 0.3% (n = 25). One drop of antibiotic was administered every 10 minutes for 4 doses beginning 1 hour prior to surgery. Aqueous humor was sampled via paracentesis and antibiotic concentrations were determined using validated high performance liquid chromatography (HPLC) procedures. Dilution analyses were performed to determine the biological efficacy of the agents in the aqueous against Staphylococcus epidermidis, the most common cause of postcataract endophthalmitis. Aqueous humor antibiotic concentrations were measured using HPLC and microdilution bioassay techniques. Biological activity was measured as minimal inhibitory dilution and minimal bactericidal dilution. Aqueous humor concentrations for moxifloxacin via HPLC analysis were 1.80 (+/-1.21) microg/ml, whereas those for gatifloxacin were 0.48 (+/-0.34) microg/ml. This 3.8-fold difference in aqueous humor antibiotic concentrations was statistically significant (P = 0.00003). Similarly, the biological dilution analysis of the aqueous humor samples showed that moxifloxacin attained an estimated activity of 2.1 microg/ml, whereas the gatifloxacin activity was approximately 0.4 mug/ml, which represented a 4.9-fold difference. This study demonstrated that after topically administered perioperative antibiotics with cataract surgery, moxifloxacin 0.5% ophthalmic solution achieved a statistically significantly higher concentration in aqueous humor compared with gatifloxacin (P = 0.00003). Results from the broth dilution analysis showed that moxifloxacin 0.5% was biologically more active against S. epidermidis than gatifloxacin 0.3% in aqueous humor after topical application. There were no adverse events reported, and incision wounds healed quickly and as expected.

Electromarking solution

DOEpatents

Bullock, Jonathan S.; Harper, William L.; Peck, Charles G.

1976-06-22

This invention is directed to an aqueous halogen-free electromarking solution which possesses the capacity for marking a broad spectrum of metals and alloys selected from different classes. The aqueous solution comprises basically the nitrate salt of an amphoteric metal, a chelating agent, and a corrosion-inhibiting agent.

SEPARATION OF TECHNETIUM FROM AQUEOUS SOLUTIONS BY COPRECIPITATION WITH MAGNETITE

DOEpatents

Rimshaw, S.J.

1961-10-24

A method of separating technetium in the 4+ oxidation state from an aqueous basic solution containing products of uranium fission is described. The method consists of contacting the solution with finely divided magnetite and recovering a technetium-bearing precipitate. (AEC)

Ice growth from supercooled aqueous solutions of benzene, naphthalene, and phenanthrene.

PubMed

Liyana-Arachchi, Thilanga P; Valsaraj, Kalliat T; Hung, Francisco R

2012-08-23

Classical molecular dynamics (MD) were performed to investigate the growth of ice from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene. The main objective of this study is to explore the fate of those aromatic molecules after freezing of the supercooled aqueous solutions, i.e., if these molecules become trapped inside the ice lattice or if they are displaced to the QLL or to the interface with air. Ice growth from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene result in the formation of quasi-liquid layers (QLLs) at the air/ice interface that are thicker than those observed when pure supercooled water freezes. Naphthalene and phenanthrene molecules in the supercooled aqueous solutions are displaced to the air/ice interface during the freezing process at both 270 and 260 K; no incorporation of these aromatics into the ice lattice is observed throughout the freezing process. Similar trends were observed during freezing of supercooled aqueous solutions of benzene at 270 K. In contrast, a fraction of the benzene molecules become trapped inside the ice lattice during the freezing process at 260 K, with the rest of the benzene molecules being displaced to the air/ice interface. These results suggest that the size of the aromatic molecule in the supercooled aqueous solution is an important parameter in determining whether these molecules become trapped inside the ice crystals. Finally, we also report potential of mean force (PMF) calculations aimed at studying the adsorption of gas-phase benzene and phenanthrene on atmospheric air/ice interfaces. Our PMF calculations indicate the presence of deep free energy minima for both benzene and phenanthrene at the air/ice interface, with these molecules adopting a flat orientation at the air/ice interface.

Polymer-assisted aqueous deposition of metal oxide films

DOEpatents

Li, DeQuan [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM

2003-07-08

An organic solvent-free process for deposition of metal oxide thin films is presented. The process includes aqueous solutions of necessary metal precursors and an aqueous solution of a water-soluble polymer. After a coating operation, the resultant coating is fired at high temperatures to yield optical quality metal oxide thin films.

Recovering oil by injecting aqueous alkali, cosurfactant and gas

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

Reisberg, J.; Bielmowicz, L. J.; Thigpen, D. R.

1985-01-15

A process of recovering oil from a subterranean reservoir in which the oil is acidic but forms monovalent cation soaps of only relatively low interfacial activity when reacted with aqueous alkaline solutions, comprises displacing the oil toward a production location with a mixture of gas and cosurfactant-containing aqueous alkaline solution.

Membrane Treatment of Aqueous Film Forming Foam (AFFF) Wastes for Recovery of Its Active Ingredients

DTIC Science & Technology

1980-10-01

T ME1MBRANE TREATMENT OF AQUEOUS FILM FORMING FOAM~ (AFFF) WASTES FOR RECOVERY OFI Fts ACTIVE INGREDIENTS FINAL REPORT October 1980 by Edward S. K...OF THIS PAGEOPMn Date AVntr* d)__ ---- Ultrafiltration (UF) and Reverse Osmosis (RO) treatment of Aqueous Film Forming Foam (AFFF) solutions was...of Aqueous Film Forming Foam (AFFF) solutions was investigated to determine the feasibility of employing membrane processes to separate and recover

Method for producing oxygen from lunar materials

NASA Technical Reports Server (NTRS)

Sullivan, Thomas A. (Inventor)

1993-01-01

This invention is related to producing oxygen from lunar or Martian materials, particularly from lunar ilmenite in situ. The process includes producing a slurry of the minerals and hot sulfuric acid, the acid and minerals reacting to form sulfates of the metal. Water is added to the slurry to dissolve the minerals into an aqueous solution, the first aqueous solution is separated from unreacted minerals from the slurry, and the aqueous solution is electrolyzed to produce the metal and oxygen.

A fluorescent sensor for selective detection of cyanide using mesoporous graphitic carbon(IV) nitride.

PubMed

Lee, Eun Zoo; Lee, Sun Uk; Heo, Nam-Su; Stucky, Galen D; Jun, Young-Si; Hong, Won Hi

2012-04-25

A turn-on fluorescence sensor, Cu(2+)-c-mpg-C(3)N(4), was developed for detection of CN(-) in aqueous solution by simply mixing cubic mesoporous graphitic carbon nitride (c-mpg-C(3)N(4)) and aqueous solution of Cu(NO(3))(2). The highly sensitive detection of CN(-) with a detection limit of 80 nM is not only possible in aqueous solution but also in human blood serum.

Stiffness-independent highly efficient on-chip extraction of cell-laden hydrogel microcapsules from oil emulsion into aqueous solution by dielectrophoresis

PubMed Central

Huang, Haishui; Sun, Mingrui; Heisler-Taylor, Tyler; Kiourti, Asimina; Volakis, John; Lafyatis, Gregory

2015-01-01

A dielectrophoresis (DEP)-based method is reported to achieve highly efficient on-chip extraction of cell-laden microcapsules of any stiffness from oil into aqueous solution. The hydrogel microcapsules can be extracted into the aqueous solution by DEP and interfacial tension (IFT) forces with no trapped oil while the encapsulated cells are free from the electrical damages due to the Faraday cage effect. PMID:26297051

SALICYLATE PROCESS FOR THORIUM SEPARATION FROM RARE EARTHS

DOEpatents

Cowan, G.A.

1959-08-25

The separation of thorium from rare earths is accomplished by forming an aqueous solution of salts of thorium and rare earths and sufficient acetate buffer to provide a pH of between 2 and 5, adding an ammonium salicylate to the aqueous buffered solution, contacting the resultant solution with a substantially water-immiscible organic solvent mixture of an ether and an ester, and separating the solvent extract phase containing thorium salicylate from the aqueous phase containing the rare earths.

Surface chemical analysis and ab initio investigations of CsI coated C fiber cathodes for high power microwave sources

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios; Morgan, Dane; LaCour, Matthew; Golby, Ken; Shiffler, Don; Booske, John H.

2010-02-01

CsI coated C fiber cathodes are promising electron emitters utilized in field emission applications. Ab initio calculations, in conjunction with experimental investigations on CsI-spray coated C fiber cathodes, were performed in order to better understand the origin of the low turn-on E-field obtained, as compared to uncoated C fibers. One possible mechanism for lowering the turn-on E-field is surface dipole layers reducing the work function. Ab initio modeling revealed that surface monolayers of Cs, CsI, Cs2O, and CsO are all capable of producing low work function C fiber cathodes (1 eV<Φ<1.5 eV), yielding a reduction in the turn-on E-field by as much as ten times, when compared to the bare fiber. Although a CsI-containing aqueous solution is spray deposited on the C fiber surface, energy dispersive x-ray spectroscopy and scanning auger microscopy measurements show coabsorption of Cs and I into the fiber interior and Cs and O on the fiber surface, with no surface I. It is therefore proposed that a cesium oxide (CsxOy) surface coating is responsible, at least in part, for the low turn E-field and superior emission characteristics of this type of fiber cathode. This CsxOy layer could be formed during preconditioning heating. CsxOy surface layers cannot only lower the fiber work function by the formation of surface dipoles (if they are thin enough) but may also enhance surface emission through their ability to emit secondary electrons due to a process of grazing electron impact. These multiple electron emission processes may explain the reported 10-100 fold reduction in the turn-on E-field of coated C fibers.

Stability of GO Modified by Different Dispersants in Cement Paste and Its Related Mechanism.

PubMed

Long, Wu-Jian; Fang, Changle; Wei, Jingjie; Li, Haodao

2018-05-18

Graphene oxide (GO) is a potential material to be used as a nano-reinforcement in cement matrix. However, a prerequisite for GO to fulfill its function in the cement matrix is homogeneous dispersion. In this study, the effects of three different dispersing agents (DAs), including polycarboxylate-based high range water reducer (P-HRWR), naphthalene-based high range water reducer (N-HRWR), and air entraining agent (AEA) on the dispersion of GO in aqueous solution, simulated concrete pore solution (SCPS), and suspension of cement pastes were sequentially investigated. Results showed that the dispersion effect of GO in aqueous solutions was improved with different DAs. However, the homogeneous dispersion of GO in aqueous solution re-agglomerated in SCPS and suspension of cement pastes. It was concluded that as the cement content and pH of aqueous solutions increased, GOs re-agglomerated and precipitated in an alkaline solution. A possible mechanism was proposed in this study and it was believed that electrostatic interactions and steric hindrance provided by the P-HRWR further made GOs stable in aqueous solutions. The ions and pH of cement pastes increased with the increasing amount of cement, which caused the separation of P-HRWR from GOs. Therefore, GOs were re-agglomerated and absorbed on the surface of the cement particles, resulting in GOs sedimentation.

Ultrasonic accelerates asparagine-glucose non-enzymatic browning reaction without acrylamide formation.

PubMed

Gao, Zhiqiang; Zheng, Junfeng; Chen, Lian

2017-01-01

Ultrasonic accelerated the asparagine-glucose non-enzymatic browning reaction with significant decrease of glucose and asparagine concentrations, and marked increase of intermediate products (UV-absorbance value at 294nm, Abs 294 ), melanoidins (UV-absorbance value at 420nm, Abs 420 ) and in vitro antioxidant activity (DPPH free radical scavenging activity). As the ultrasonic intensity was 17.83W/cm 2 , the asparagine-glucose solution's Abs 294 , Abs 420 and antioxidant activity increased from 0 to 1.26, 0.88 and 21.56%, respectively, and the glucose and asparagine concentrations of the asparagine-glucose solution reduced 58.97 and 12.57%, respectively. The high performance liquid chromatography (HPLC)-Diode Array Detector (DAD) analyses showed that no acrylamide was detected after 50-min ultrasonic reaction. This study suggested that ultrasonic at higher intensity was a potential method to accelerate the non-enzymatic browning reaction in the asparagine-glucose solution without acrylamide production. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption of arsenic from aqueous solution using magnetic graphene oxide

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Defining microchannels and valves on a hydrophobic paper by low-cost inkjet printing of aqueous or weak organic solutions.

PubMed

Cai, Longfei; Zhong, Minghua; Li, Huolin; Xu, Chunxiu; Yuan, Biyu

2015-07-01

We describe a simple and cost-effective strategy for rapid fabrication of microfluidic paper-based analytical devices and valves by inkjet printing. NaOH aqueous solution was printed onto a hydrophobic filter paper, which was previously obtained by soaking in a trimethoxyoctadecylsilane-heptane solution, allowing selective wet etching of hydrophobic cellulose to create hydrophilic-hydrophobic contrast with a relatively good resolution. Hexadecyltrimethylammonium bromide (CTMAB)-ethanol solution was printed onto hydrophobic paper to fabricate temperature-controlled valves. At low temperature, CTMAB deposited on the paper is insoluble in aqueous fluid, thus the paper remains hydrophobic. At high temperature, CTMAB becomes soluble so the CTMAB-deposited channel becomes hydrophilic, allowing the wicking of aqueous solution through the valve. We believe that this strategy will be very attractive for the development of simple micro analytical devices for point-of-care applications, including diagnostic testing, food safety control, and environmental monitoring.

Adsorptive removal of antibiotics from aqueous solution using carbon materials.

PubMed

Yu, Fei; Li, Yong; Han, Sheng; Ma, Jie

2016-06-01

Antibiotics, an important type of environmental contamination, have attracted many researchers to the study of their removal from aqueous solutions. Adsorption technology is a fast, efficient, and economical physicochemical method that is extensively used in wastewater treatment. From original activated carbon and carbon nanotubes to the latest graphene-based materials, carbon-based materials have been widely used as highly effective adsorbents for contaminant removal from aqueous solution because of their large specific surface area, high porosity, and high reaction activity. In this article, adsorption removal methods for four major types of antibiotic (tetracyclines, sulfonamides, macrolides, and quinolones) are reviewed. We also provide an overview of the application development of carbon materials as adsorbents for antibiotic removal from aqueous solution. The most promising works are discussed, and the main challenges in preparing high-performance adsorbents and the development tendency of adsorbents are also analyzed. This work provides theoretical guidance for subsequent research in the design and modification of carbon materials for applications in the adsorption removal of antibiotics from aqueous solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

Removal of chromium(III) from aqueous waste solution by liquid-liquid extraction in a circular microchannel.

PubMed

Luo, Jian Hong; Li, Jun; Guo, Lei; Zhu, Xin Hua; Dai, Shuang; Li, Xing

2017-11-01

A new circular microchannel device has been proposed for the removal of chromium(III) from aqueous waste solution by using kerosene as a diluent and (2-ethylhexyl) 2-ethylhexyl phosphonate as an extractant. The proposed device has several advantages such as a flexible and easily adaptable design, easy maintenance, and cheap setup without the requirement of microfabrication. To study the extraction efficiency and advantages of the circular microchannel device in the removal of chromium(III), the effects of various operating conditions such as the inner diameter of the channel, the total flow velocity, the phase ratio, the initial pH of aqueous waste solution, the reaction temperature and the initial concentration of extractant on the extraction efficiency are investigated and the optimal process conditions are obtained. The results show that chromium(III) in aqueous waste solution can be effectively removed with (2-ethylhexyl) 2-ethylhexyl phosphonate in the circular microchannel. Under optimized conditions, an extraction efficiency of chromium(III) of more than 99% can be attained and the aqueous waste solution can be discharged directly, which can meet the Chinese national emission standards.

Thermodynamic and structure-property study of liquid-vapor equilibrium for aroma compounds.

PubMed

Tromelin, Anne; Andriot, Isabelle; Kopjar, Mirela; Guichard, Elisabeth

2010-04-14

Thermodynamic parameters (T, DeltaH degrees , DeltaS degrees , K) were collected from the literature and/or calculated for five esters, four ketones, two aldehydes, and three alcohols, pure compounds and compounds in aqueous solution. Examination of correlations between these parameters and the range values of DeltaH degrees and DeltaS degrees puts forward the key roles of enthalpy for vaporization of pure compounds and of entropy in liquid-vapor equilibrium of compounds in aqueous solution. A structure-property relationship (SPR) study was performed using molecular descriptors on aroma compounds to better understand their vaporization behavior. In addition to the role of polarity for vapor-liquid equilibrium of compounds in aqueous solution, the structure-property study points out the role of chain length and branching, illustrated by the correlation between the connectivity index CHI-V-1 and the difference between T and log K for vaporization of pure compounds and compounds in aqueous solution. Moreover, examination of the esters' enthalpy values allowed a probable conformation adopted by ethyl octanoate in aqueous solution to be proposed.

Surface tensions of inorganic multicomponent aqueous electrolyte solutions and melts.

PubMed

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

2010-11-25

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

A graphene oxide based smart drug delivery system for tumor mitochondria-targeting photodynamic therapy

NASA Astrophysics Data System (ADS)

Wei, Yanchun; Zhou, Feifan; Zhang, Da; Chen, Qun; Xing, Da

2016-02-01

Subcellular organelles play critical roles in cell survival. In this work, a novel photodynamic therapy (PDT) drug delivery and phototoxicity on/off nano-system based on graphene oxide (NGO) as the carrier is developed to implement subcellular targeting and attacking. To construct the nanodrug (PPa-NGO-mAb), NGO is modified with the integrin αvβ3 monoclonal antibody (mAb) for tumor targeting. Pyropheophorbide-a (PPa) conjugated with polyethylene-glycol is used to cover the surface of the NGO to induce phototoxicity. Polyethylene-glycol phospholipid is loaded to enhance water solubility. The results show that the phototoxicity of PPa on NGO can be switched on and off in organic and aqueous environments, respectively. The PPa-NGO-mAb assembly is able to effectively target the αvβ3-positive tumor cells with surface ligand and receptor recognition; once endocytosized by the cells, they are observed escaping from lysosomes and subsequently transferring to the mitochondria. In the mitochondria, the `on' state PPa-NGO-mAb performs its effective phototoxicity to kill cells. The biological and physical dual selections and on/off control of PPa-NGO-mAb significantly enhance mitochondria-mediated apoptosis of PDT. This smart system offers a potential alternative to drug delivery systems for cancer therapy.Subcellular organelles play critical roles in cell survival. In this work, a novel photodynamic therapy (PDT) drug delivery and phototoxicity on/off nano-system based on graphene oxide (NGO) as the carrier is developed to implement subcellular targeting and attacking. To construct the nanodrug (PPa-NGO-mAb), NGO is modified with the integrin αvβ3 monoclonal antibody (mAb) for tumor targeting. Pyropheophorbide-a (PPa) conjugated with polyethylene-glycol is used to cover the surface of the NGO to induce phototoxicity. Polyethylene-glycol phospholipid is loaded to enhance water solubility. The results show that the phototoxicity of PPa on NGO can be switched on and off in organic and aqueous environments, respectively. The PPa-NGO-mAb assembly is able to effectively target the αvβ3-positive tumor cells with surface ligand and receptor recognition; once endocytosized by the cells, they are observed escaping from lysosomes and subsequently transferring to the mitochondria. In the mitochondria, the `on' state PPa-NGO-mAb performs its effective phototoxicity to kill cells. The biological and physical dual selections and on/off control of PPa-NGO-mAb significantly enhance mitochondria-mediated apoptosis of PDT. This smart system offers a potential alternative to drug delivery systems for cancer therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07785k

EXTRACTION METHOD FOR SEPARATING URANIUM, PLUTONIUM, AND FISSION PRODUCTS FROM COMPOSITIONS CONTAINING SAME

DOEpatents

Seaborg, G.T.

1957-10-29

Methods for separating plutonium from the fission products present in masses of neutron irradiated uranium are reported. The neutron irradiated uranium is first dissolved in an aqueous solution of nitric acid. The plutonium in this solution is present as plutonous nitrate. The aqueous solution is then agitated with an organic solvent, which is not miscible with water, such as diethyl ether. The ether extracts 90% of the uraryl nitrate leaving, substantially all of the plutonium in the aqueous phase. The aqueous solution of plutonous nitrate is then oxidized to the hexavalent state, and agitated with diethyl ether again. In the ether phase there is then obtained 90% of plutonium as a solution of plutonyl nitrate. The ether solution of plutonyl nitrate is then agitated with water containing a reducing agent such as sulfur dioxide, and the plutonium dissolves in the water and is reduced to the plutonous state. The uranyl nitrate remains in the ether. The plutonous nitrate in the water may be recovered by precipitation.

The relative viscosity of NaNO 3 and NaNO 2 aqueous solutions

DOE PAGES

Reynolds, Jacob G.; Mauss, Billie M.; Daniel, Richard C.

2018-05-09

In aqueous solution, both nitrate and nitrite are planar, monovalent, and have the same elements but different sizes and charge densities. Comparing the viscosity of NaNO 2 and NaNO 3 aqueous solutions provides an opportunity to determine the relative importance of anion size versus strength of anion interaction with water. The viscosity of aqueous NaNO 2 and NaNO 3 were measured over a temperature and concentration range relevant to nuclear waste processing. The viscosity of NaNO 2 solutions was consistently larger than NaNO 3 under all conditions, even though nitrate is larger than nitrite. This was interpreted in terms ofmore » quantum mechanical charge field molecular dynamics calculations that indicate that nitrite forms more and stronger hydrogen bonds with water per oxygen atom than nitrate. Furthermore, these hydrogen bonds inhibit rotational motion required for fluid flow, thus increasing the nitrite solution viscosity relative to that of an equivalent nitrate solution.« less

The relative viscosity of NaNO 3 and NaNO 2 aqueous solutions

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

Reynolds, Jacob G.; Mauss, Billie M.; Daniel, Richard C.

In aqueous solution, both nitrate and nitrite are planar, monovalent, and have the same elements but different sizes and charge densities. Comparing the viscosity of NaNO 2 and NaNO 3 aqueous solutions provides an opportunity to determine the relative importance of anion size versus strength of anion interaction with water. The viscosity of aqueous NaNO 2 and NaNO 3 were measured over a temperature and concentration range relevant to nuclear waste processing. The viscosity of NaNO 2 solutions was consistently larger than NaNO 3 under all conditions, even though nitrate is larger than nitrite. This was interpreted in terms ofmore » quantum mechanical charge field molecular dynamics calculations that indicate that nitrite forms more and stronger hydrogen bonds with water per oxygen atom than nitrate. Furthermore, these hydrogen bonds inhibit rotational motion required for fluid flow, thus increasing the nitrite solution viscosity relative to that of an equivalent nitrate solution.« less

Recovery of alkali metal constituents from catalytic coal conversion residues

DOEpatents

Soung, Wen Y.

1984-01-01

In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them (46, 53, 61, 69) with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide (63) to precipitate silicon constituents, the pH of the resultant solution is increased (81), preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated (84) to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process (86, 18, 17) where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

Freeze-thawing behaviour of highly concentrated aqueous alkali chloride-glucose systems.

PubMed

Kajiwara, K; Motegi, A; Murase, N

2001-01-01

The freeze-thawing behaviour of highly concentrated aqueous alkali chloride-glucose systems was investigated by differential scanning calorimetry (DSC). In the aqueous NaCl-glucose solution system, single or double glass transitions followed by the corresponding devitrification exotherms were observed during rewarming. In the aqueous KCl-glucose solution system, on the other hand, a single glass transition followed by an exotherm was observed during rewarming. The presence of double glass transitions observed for a certain composition of the aqueous NaCl-glucose solution was taken as an evidence for the liquid-liquid immiscibility at low temperatures. Two kinds of crystallisation accompanied by exotherms during rewarming were identified by X-ray diffraction as ice and ice/NaCl x 2H(2)O, or ice/KCl eutectic component.

Exploring Solute-Solvent Interactions of -Amino Acids in Aqueous [] Arrangements by Volumetric, Viscometric, Refractometric, and Acoustic Approach

NASA Astrophysics Data System (ADS)

Roy, Mahendra Nath; Roy, Milan Chandra; Basak, Saptarshi

2014-05-01

Qualitative and quantitative analysis of molecular interaction prevailing in glycine, l-alanine, l-valine, and aqueous solution of ionic liquid (IL) [1-ethylpyridinium tetrafluoroborate (] have been investigated by thermophysical properties. The apparent molar volume (), viscosity -coefficient, molal refraction (), and adiabatic compressibility ( of glycine, l-alanine, and l-valine have been studied in 0.001 mol , 0.003 mol , and 0.005 mol aqueous 1-ethylpyridinium tetrafluoroborate [] solutions at 298.15 K from the values of densities , viscosities (), refractive index (, and speed of sound , respectively. The extent of interaction, i.e., the solute-solvent interaction is expressed in terms of the limiting apparent molar volume (, viscosity -coefficient, and limiting apparent molar adiabatic compressibility (. The limiting apparent molar volumes (, experimental slopes ( derived from the Masson equation, and viscosity - and -coefficients using the Jones-Dole equation have been interpreted in terms of ion-ion and ion-solvent interactions, respectively. Molal refractions ( have been calculated with the help of the Lorentz-Lorenz equation. The role of the solvent (aqueous IL solution) and the contribution of solute-solute and solute-solvent interactions to the solution complexes have also been analyzed through the derived properties.

High-throughput ab-initio dilute solute diffusion database

PubMed Central

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-01-01

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world. PMID:27434308

Selected specific rates of reactions of transients from water in aqueous solution. Hydrated electron, supplemental data. [Reactions with transients from water, with inorganic solutes, and with solutes

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

Ross, A.B.

1975-06-01

A compilation of rates of reactions of hydrated electrons with other transients and with organic and inorganic solutes in aqueous solution appeared in NSRDS-NBS 43, and covered the literature up to early 1971. This supplement includes additional rates which have been published through July 1973.

Options for refractive index and viscosity matching to study variable density flows

NASA Astrophysics Data System (ADS)

Clément, Simon A.; Guillemain, Anaïs; McCleney, Amy B.; Bardet, Philippe M.

2018-02-01

Variable density flows are often studied by mixing two miscible aqueous solutions of different densities. To perform optical diagnostics in such environments, the refractive index of the fluids must be matched, which can be achieved by carefully choosing the two solutes and the concentration of the solutions. To separate the effects of buoyancy forces and viscosity variations, it is desirable to match the viscosity of the two solutions in addition to their refractive index. In this manuscript, several pairs of index matched fluids are compared in terms of viscosity matching, monetary cost, and practical use. Two fluid pairs are studied in detail, with two aqueous solutions (binary solutions of water and a salt or alcohol) mixed into a ternary solution. In each case: an aqueous solution of isopropanol mixed with an aqueous solution of sodium chloride (NaCl) and an aqueous solution of glycerol mixed with an aqueous solution of sodium sulfate (Na_2SO_4). The first fluid pair allows reaching high-density differences at low cost, but brings a large difference in dynamic viscosity. The second allows matching dynamic viscosity and refractive index simultaneously, at reasonable cost. For each of these four solutes, the density, kinematic viscosity, and refractive index are measured versus concentration and temperature, as well as wavelength for the refractive index. To investigate non-linear effects when two index-matched, binary solutions are mixed, the ternary solutions formed are also analyzed. Results show that density and refractive index follow a linear variation with concentration. However, the viscosity of the isopropanol and NaCl pair deviates from the linear law and has to be considered. Empirical correlations and their coefficients are given to create index-matched fluids at a chosen temperature and wavelength. Finally, the effectiveness of the refractive index matching is illustrated with particle image velocimetry measurements performed for a buoyant jet in a linearly stratified environment. The creation of the index-matched solutions and linear stratification in a large-scale experimental facility are detailed, as well as the practical challenges to obtain precise refractive index matching.

Method for loading resin beds

DOEpatents

Notz, Karl J.; Rainey, Robert H.; Greene, Charles W.; Shockley, William E.

1978-01-01

An improved method of preparing nuclear reactor fuel by carbonizing a uranium loaded cation exchange resin provided by contacting a H.sup.+ loaded resin with a uranyl nitrate solution deficient in nitrate, comprises providing the nitrate deficient solution by a method comprising the steps of reacting in a reaction zone maintained between about 145.degree.-200.degree. C, a first aqueous component comprising a uranyl nitrate solution having a boiling point of at least 145.degree. C with a second aqueous component to provide a gaseous phase containing HNO.sub.3 and a reaction product comprising an aqueous uranyl nitrate solution deficient in nitrate.

Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

NASA Technical Reports Server (NTRS)

T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor); Huang, Cunping (Inventor)

2014-01-01

Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

SEPARATION OF HAFNIUM FROM ZIRCONIUM

DOEpatents

Overholser, L.B.; Barton, C.J. Sr.; Ramsey, J.W.

1960-05-31

The separation of hafnium impurities from zirconium can be accomplished by means of organic solvent extraction. The hafnium-containing zirconium feed material is dissolved in an aqueous chloride solution and the resulting solution is contacted with an organic hexone phase, with at least one of the phases containing thiocyanate. The hafnium is extracted into the organic phase while zirconium remains in the aqueous phase. Further recovery of zirconium is effected by stripping the onganic phase with a hydrochloric acid solution and commingling the resulting strip solution with the aqueous feed solution. Hexone is recovered and recycled by means of scrubbing the onganic phase with a sulfuric acid solution to remove the hafnium, and thiocyanate is recovered and recycled by means of neutralizing the effluent streams to obtain ammonium thiocyanate.

RECOVERY OF PROTACTINIUM

DOEpatents

Kraus, K.A.; Moore, G.E.

1959-02-01

A process is presented for the separation of protactinium values from an aqueous solution containing Pa and Th values comprising establishing in the solution a HCl concentration of from 4 to 11 molar, contacting the resulting solution with an anion-exchange adsorbent, such as a polystyrene divinyl benzene polymer with quatenary amines as the active exchange group, to effect the adsorption of Pa values upon the adsorbent while leaving Th values in the solution, and then washlng the separated Pa bearing adsorbent with an aqueous solution of HCl of less than 4M to exclusively elute Pa values from the adsorbent. If hexavalent U values are contained in the original solution thcy are adsorbed on the resin together with Pa. A separation is offected chromatographically by percolating the resin with aqueous HCl.

Data files for ab initio calculations of the lattice parameter and elastic stiffness coefficients of bcc Fe with solutes

DOE PAGES

Fellinger, Michael R.; Hector, Jr., Louis G.; Trinkle, Dallas R.

2016-11-29

Here, we present computed datasets on changes in the lattice parameter and elastic stiffness coefficients of BCC Fe due to substitutional Al, B, Cu, Mn, and Si solutes, and octahedral interstitial C and N solutes. The data is calculated using the methodology based on density functional theory (DFT). All the DFT calculations were performed using the Vienna Ab initio Simulations Package (VASP). The data is stored in the NIST dSpace repository.

Singlet Oxygen in Aqueous Solution: A Lecture Demonstration

ERIC Educational Resources Information Center

Shakhashiri, Bassam Z.; Williams, Lloyd G.

1976-01-01

Describes a demonstration that illustrates the red chemiluminescence due to singlet molecular oxygen that can be observed when aqueous solutions of hypochlorite ion and hydrogen peroxide are mixed. (MLH)

pH-Dependent Surface Chemistry from First Principles: Application to the BiVO4(010)-Water Interface.

PubMed

Ambrosio, Francesco; Wiktor, Julia; Pasquarello, Alfredo

2018-03-28

We present a theoretical formulation for studying the pH-dependent interfacial coverage of semiconductor-water interfaces through ab initio electronic structure calculations, molecular dynamics simulations, and the thermodynamic integration method. This general methodology allows one to calculate the acidity of the individual adsorption sites on the surface and consequently the pH at the point of zero charge, pH PZC , and the preferential adsorption mode of water molecules, either molecular or dissociative, at the semiconductor-water interface. The proposed method is applied to study the BiVO 4 (010)-water interface, yields a pH PZC in excellent agreement with the experimental characterization. Furthermore, from the calculated p K a values of the individual adsorption sites, we construct an ab initio concentration diagram of all adsorbed species at the interface as a function of the pH of the aqueous solution. The diagram clearly illustrates the pH-dependent coverage of the surface and indicates that protons are found to be significantly adsorbed (∼1% of available sites) only in highly acidic conditions. The surface is found to be mostly covered by molecularly adsorbed water molecules in a wide interval of pH values ranging from 2 to 8. Hydroxyl ions are identified as the dominant adsorbed species at pH larger than 8.2.

Raman scattering tensors of tyrosine.

PubMed

Tsuboi, M; Ezaki, Y; Aida, M; Suzuki, M; Yimit, A; Ushizawa, K; Ueda, T

1998-01-01

Polarized Raman scattering measurements have been made of a single crystal of L-tyrosine by the use of a Raman microscope with the 488.0-nm exciting beam from an argon ion laser. The L-tyrosine crystal belongs to the space group P2(1)2(1)2(1) (orthorhombic), and Raman scattering intensities corresponding to the aa, bb, cc, ab and ac components of the crystal Raman tensor have been determined for each prominent Raman band. A similar set of measurements has been made of L-tyrosine-d4, in which four hydrogen atoms on the benzene ring are replaced by deuterium atoms. The effects of NH3-->ND3 and OH-->OD on the Raman spectrum have also been examined. In addition, depolarization ratios of some bands of L-tyrosine in aqueous solutions of pH 13 and pH 1 were examined. For comparison with these experimental results, on the other hand, ab initio molecular orbital calculations have been made of the normal modes of vibration and their associated polarizability oscillations of the L-tyrosine molecule. On the basis of these experimental data and by referring to the results of the calculations, discussions have been presented on the Raman tensors associated to some Raman bands, including those at 829 cm-1 (benzene ring breathing), 642 cm-1 (benzene ring deformation), and 432 cm-1 (C alpha-C beta-C gamma bending).

Molecular Modeling of Water Interfaces: From Molecular Spectroscopy to Thermodynamics.

PubMed

Nagata, Yuki; Ohto, Tatsuhiko; Backus, Ellen H G; Bonn, Mischa

2016-04-28

Understanding aqueous interfaces at the molecular level is not only fundamentally important, but also highly relevant for a variety of disciplines. For instance, electrode-water interfaces are relevant for electrochemistry, as are mineral-water interfaces for geochemistry and air-water interfaces for environmental chemistry; water-lipid interfaces constitute the boundaries of the cell membrane, and are thus relevant for biochemistry. One of the major challenges in these fields is to link macroscopic properties such as interfacial reactivity, solubility, and permeability as well as macroscopic thermodynamic and spectroscopic observables to the structure, structural changes, and dynamics of molecules at these interfaces. Simulations, by themselves, or in conjunction with appropriate experiments, can provide such molecular-level insights into aqueous interfaces. In this contribution, we review the current state-of-the-art of three levels of molecular dynamics (MD) simulation: ab initio, force field, and coarse-grained. We discuss the advantages, the potential, and the limitations of each approach for studying aqueous interfaces, by assessing computations of the sum-frequency generation spectra and surface tension. The comparison of experimental and simulation data provides information on the challenges of future MD simulations, such as improving the force field models and the van der Waals corrections in ab initio MD simulations. Once good agreement between experimental observables and simulation can be established, the simulation can be used to provide insights into the processes at a level of detail that is generally inaccessible to experiments. As an example we discuss the mechanism of the evaporation of water. We finish by presenting an outlook outlining four future challenges for molecular dynamics simulations of aqueous interfacial systems.

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

PubMed

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

2007-07-05

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

Stiffness-Independent Highly Efficient On-Chip Extraction of Cell-Laden Hydrogel Microcapsules from Oil Emulsion into Aqueous Solution by Dielectrophoresis.

PubMed

Huang, Haishui; Sun, Mingrui; Heisler-Taylor, Tyler; Kiourti, Asimina; Volakis, John; Lafyatis, Gregory; He, Xiaoming

2015-10-28

A dielectrophoresis (DEP)-based method achieves highly efficient on-chip extraction of cell-laden microcapsules of any stiffness from oil into aqueous solution. The hydrogel microcapsules can be extracted into the aqueous solution by DEP and interfacial tension forces with no trapped oil, while the encapsulated cells are free from electrical damage due to the Faraday cage effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SOLVENT EXTRACTION PROCESS FOR PLUTONIUM

DOEpatents

Seaborg, G.T.

1959-04-14

The separation of plutonium from aqueous inorganic acid solutions by the use of a water immiscible organic extractant liquid is described. The plutonium must be in the oxidized state, and the solvents covered by the patent include nitromethane, nitroethane, nitropropane, and nitrobenzene. The use of a salting out agents such as ammonium nitrate in the case of an aqueous nitric acid solution is advantageous. After contacting the aqueous solution with the organic extractant, the resulting extract and raffinate phases are separated. The plutonium may be recovered by any suitable method.

Aqueous solution-chemical derived Nisbnd Al2O3 solar selective absorbing coatings. 2. Wetting agents and spreading of aqueous solutions on aluminum substrate

NASA Astrophysics Data System (ADS)

Li, Zhenxiang; Zhao, Jianxi

2013-03-01

Wettability of aluminum substrate by the aqueous solutions containing ethoxylated alcohol nonionic surfactants C12En- or Triton X-series was studied using dynamic contact angle measurements. The efficiency of wetting was found to strongly depend on the length of polyoxyethylene (POE) chain of C12En- or Triton X surfactants. For C12E4 that has a very short POE chain, it hardly made the aqueous solution spreading over aluminum. The others with a long POE chain were indeed very efficient in promoting the solution spreading. Moreover, all the spreading process could be completed within 10 s. The single-layer Nisbnd Al2O3 coatings were fabricated from the precursor solutions containing C12En- or Triton X surfactants and the reflectance spectra were measured by a UV/vis spectrophotometer equipped with an integrating sphere. The results indicated that the precursor solution with a long POE chain surfactant as wetting agent favored to fabricate a uniform film on the aluminum substrate and therefore to get a high solar absorptance.

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

PubMed

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

2000-02-01

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

Process for the extraction of technetium from uranium

DOEpatents

Gong, Cynthia-May S.; Poineau, Frederic; Czerwinski, Kenneth R.

2010-12-21

A spent fuel reprocessing method contacts an aqueous solution containing Technetium(V) and uranyl with an acidic solution comprising hydroxylamine hydrochloride or acetohydroxamic acid to reduce Tc(V) to Tc(II, and then extracts the uranyl with an organic phase, leaving technetium(II) in aqueous solution.

ADSORPTION OF CERIUM VALUES FROM AQUEOUS SOLUTIONS

DOEpatents

Roberts, F.P.

1963-08-13

Cerium can be removed from aqueous nitric acid (2 to 13 M) solutions by passing the latter over a PbO/sub 2/-containing anion exchange resin. The cerium is taken up by the resin, while any lanthanides, yttrium, and strontium present remain in the solution. (AEC)

Method for separating water soluble organics from a process stream by aqueous biphasic extraction

DOEpatents

Chaiko, David J.; Mego, William A.

1999-01-01

A method for separating water-miscible organic species from a process stream by aqueous biphasic extraction is provided. An aqueous biphase system is generated by contacting a process stream comprised of water, salt, and organic species with an aqueous polymer solution. The organic species transfer from the salt-rich phase to the polymer-rich phase, and the phases are separated. Next, the polymer is recovered from the loaded polymer phase by selectively extracting the polymer into an organic phase at an elevated temperature, while the organic species remain in a substantially salt-free aqueous solution. Alternatively, the polymer is recovered from the loaded polymer by a temperature induced phase separation (cloud point extraction), whereby the polymer and the organic species separate into two distinct solutions. The method for separating water-miscible organic species is applicable to the treatment of industrial wastewater streams, including the extraction and recovery of complexed metal ions from salt solutions, organic contaminants from mineral processing streams, and colorants from spent dye baths.

Thermodynamic Parameters of the Dissolution of 4-Hydroxy-L-Proline and L-Phenylalanine in Mixed Aqueous Solvents at 298 K

NASA Astrophysics Data System (ADS)

Smirnov, V. I.; Badelin, V. G.

2018-01-01

The enthalpies of solution of 4-hydroxy-L-proline and L-phenylalanine in binary mixed aqueous solvents containing acetonitrile (AN), 1,4-dioxane (1,4-DO), or acetone (AC) at mole fractions of 0 to 0.25 are determined at T = 298.15 K via isothermal calorimetry. The standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of 4-hydroxy-L-proline and L-phenylalanine from water to mixed aqueous solvents are calculated using the experimental calorimetric data, as are the enthalpy coefficients of paired interactions ( h xy ) between the molecules of the investigated amino acids and the organic solvents. The effects the mixed aqueous solvent composition and the structure of the organic solvent molecules have on the enthalpies of solution and transfer for the investigated amino acids are considered. The correlation between the enthalpy of solution of the amino acids and the electron-donating properties of the organic solvents in the mixed aqueous solvent systems is established.

Soliton solutions for ABS lattice equations: I. Cauchy matrix approach

NASA Astrophysics Data System (ADS)

Nijhoff, Frank; Atkinson, James; Hietarinta, Jarmo

2009-10-01

In recent years there have been new insights into the integrability of quadrilateral lattice equations, i.e. partial difference equations which are the natural discrete analogues of integrable partial differential equations in 1+1 dimensions. In the scalar (i.e. single-field) case, there now exist classification results by Adler, Bobenko and Suris (ABS) leading to some new examples in addition to the lattice equations 'of KdV type' that were known since the late 1970s and early 1980s. In this paper, we review the construction of soliton solutions for the KdV-type lattice equations and use those results to construct N-soliton solutions for all lattice equations in the ABS list except for the elliptic case of Q4, which is left to a separate treatment.

Rb + adsorption at the quartz(101)-aqueous interface: comparison of resonant anomalous x-ray reflectivity with ab initio calculations

DOE PAGES

Bellucci, Francesco; Lee, Sang Soo; Kubicki, James D.; ...

2015-01-29

We study adsorption of Rb + to the quartz(101)–aqueous interface at room temperature with specular X-ray reflectivity, resonant anomalous X-ray reflectivity, and density functional theory. The interfacial water structures observed in deionized water and 10 mM RbCl solution at pH 9.8 were similar, having a first water layer at height of 1.7 ± 0.1 Å above the quartz surface and a second layer at 4.8 ± 0.1 Å and 3.9 ± 0.8 Å for the water and RbCl solutions, respectively. The adsorbed Rb + distribution is broad and consists of presumed inner-sphere (IS) and outer-sphere (OS) complexes at heights ofmore » 1.8 ± 0.1 and 6.4 ± 1.0 Å, respectively. Projector-augmented planewave density functional theory (DFT) calculations of potential configurations for neutral and negatively charged quartz(101) surfaces at pH 7 and 12, respectively, reveal a water structure in agreement with experimental results. These DFT calculations also show differences in adsorbed speciation of Rb + between these two conditions. At pH 7, the lowest energy structure shows that Rb + adsorbs dominantly as an IS complex, whereas at pH 12 IS and OS complexes have equivalent energies. The DFT results at pH 12 are generally consistent with the two site Rb distribution observed from the X-ray data at pH 9.8, albeit with some differences that are discussed. In conclusion, surface charge estimated on the basis of the measured total Rb + coverage was -0.11 C/m 2, in good agreement with the range of the surface charge magnitudes reported in the literature.« less

Theoretical investigation on the mechanism and dynamics of oxo exchange of neptunyl(VI) hydroxide in aqueous solution.

PubMed

Yang, Xia; Chai, Zhifang; Wang, Dongqi

2015-03-21

Four types of reaction mechanisms for the oxo ligand exchange of monomeric and dimeric neptunyl(VI) hydroxide in aqueous solution were explored computationally using density functional theory (DFT) and ab initio classical molecular dynamics. The obtained results were compared with previous studies on the oxo exchange of uranyl hydroxide, as well as with experiments. It is found that the stable T-shaped [NpO3(OH)3](3-) intermediate is a key species for oxo exchange in the proton transfer in mononuclear Path I and binuclear Path IV, similar to the case of uranyl(VI) hydroxide. Path I is thought to be the preferred oxo exchange mechanism for neptunyl(VI) hydroxide in our calculations, due to the lower activation energy (22.7 and 13.1 kcal mol(-1) for ΔG(‡) and ΔH(‡), respectively) of the overall reaction. Path II via a cis-neptunyl structure assisted by a water molecule might be a competitive channel against Path I with a mononuclear mechanism, owing to a rapid dynamical process occurring in Path II. In Path IV with the binuclear mechanism, oxo exchange is accomplished via the interaction between [NpO2(OH)4](2-) and T-shaped [NpO3(OH)3](3-) with a low activation energy for the rate-determining step, however, the overall energy required to fulfill the reaction is slightly higher than that in mononuclear Path I, suggesting a possible binuclear process in the higher energy region. The chemical bonding evolution along the reaction pathways was discussed by using topological methodologies of the electron localization function (ELF).

Use of solid phase extraction (SPE) to evaluate in vitro skin permeation of aescin.

PubMed

Montenegro, L; Carbone, C; Giannone, I; Puglisi, G

2007-05-01

The aim of this work was to evaluate the feasibility of assessing aescin in vitro permeation through human skin by determining the amount of aescin permeated using conventional HPLC procedures after extraction of skin permeation samples by means of solid phase extraction (SPE). Aescin in vitro skin permeation was assessed from aqueous solutions and gels using both Franz-type diffusion cells and flow-through diffusion cells. The SPE method used was highly accurate (mean accuracy 99.66%), highly reproducible (intra-day and inter-day variations lower than 2.3% and 2.2%, respectively) and aescin recovery from normal saline was greater than 99%. The use of Franz-type diffusion cells did not allow us to determine aescin flux values through excised human skin, therefore aescin skin permeation parameters could be calculated only using flow-through diffusion cells. Plotting the cumulative amount of aescin permeated as a function of time, linear relationships were obtained from both aqueous solution and gel using flow-through diffusion cells. Aescin flux values through excised human skin from aqueous gel were significantly lower than those observed from aqueous solution (p < 0.05). Calculating aescin percutaneous absorption parameters we evidenced that aescin partition coefficient was lower from the aqueous gel with respect to the aqueous solution. Therefore, the SPE method used in this study was suitable to determine aescin in vitro skin permeation parameters from aqueous solutions and gels using a conventional HPLC method for the analysis of the skin permeation samples.

21 CFR 163.112 - Breakfast cocoa.

Code of Federal Regulations, 2012 CFR

2012-04-01

... oxide, used as such, or in aqueous solution; (2) Neutralizing agents. Phosphoric acid, citric acid and L-tartaric acid, used as such, or in aqueous solution; (3) Spices, natural and artificial flavorings, and...

21 CFR 163.112 - Breakfast cocoa.

Code of Federal Regulations, 2014 CFR

2014-04-01

... oxide, used as such, or in aqueous solution; (2) Neutralizing agents. Phosphoric acid, citric acid and L-tartaric acid, used as such, or in aqueous solution; (3) Spices, natural and artificial flavorings, and...

21 CFR 163.112 - Breakfast cocoa.

Code of Federal Regulations, 2013 CFR

2013-04-01

... oxide, used as such, or in aqueous solution; (2) Neutralizing agents. Phosphoric acid, citric acid and L-tartaric acid, used as such, or in aqueous solution; (3) Spices, natural and artificial flavorings, and...

Process for treating ab5 nickel-metal hydride battery scrap

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

Lyman, J.W.; Palmer, G.R.

1994-12-31

A process for treating an AB5 Ni-MH battery to recover purified positive and negative electrode components of the battery is disclosed. An AB5 Ni-MH battery is placed in a mineral acid leach solution to cause the positive and negative electrode components of the battery to separate.

Method for gettering organic, inorganic and elemental iodine in aqueous solutions

DOEpatents

Beahm, Edward C.; Shockley, William E.

1990-07-03

A process for the removal of iodine from aqueous solutions, particularly the trapping of radioactive iodine to mitigate damage resulting from accidents or spills associated with nuclear reactors, by exposing the solution to well dispersed silver carbonate which reacts with the iodine and iodides, thereby gettering iodine and iodine compounds from solution. The iodine is not only removed from solution but also from the contiguous vapor.

Method for gettering organic, inorganic and elemental iodine in aqueous solutions

DOEpatents

Beahm, Edward C.; Shockley, William E.

1990-01-01

A process for the removal of iodine from aqueous solutions, particularly the trapping of radioactive iodine to mitigate damage resulting from accidents or spills associated with nuclear reactors, by exposing the solution to well dispersed silver carbonate which reacts with the iodine and iodides, thereby gettering iodine and iodine compounds from solution. The iodine is not only removed from solution but also from the contiguous vapor.

Crystal growth in fused solvent systems

NASA Technical Reports Server (NTRS)

Ulrich, D. R.; Noone, M. J.; Spear, K. E.; White, W. B.; Henry, E. C.

1973-01-01

Research is reported on the growth of electronic ceramic single crystals from solution for the future growth of crystals in a microgravity environment. Work included growth from fused or glass solvents and aqueous solutions. Topics discussed include: crystal identification and selection; aqueous solution growth of triglycine sulphate (TGS); and characterization of TGS.

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

EPA Science Inventory

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

Rheological characterization of solutions and thin films made from amylose-hexadecylammonium chloride inclusion complexes and polyvinyl alcohol

USDA-ARS?s Scientific Manuscript database

The rheological properties of aqueous solutions and films made from blends of polyvinyl alcohol (PVOH) and amylose-hexadecylammonium chloride inclusion complexes (Hex-Am) were investigated to better understand the polymer interactions and processing parameters. Aqueous solutions of Hex-Am displayed ...

Study on Latent Heat of Fusion of Ice in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Kumano, Hiroyuki; Asaoka, Tatsunori; Saito, Akio; Okawa, Seiji

In this study, latent heat of fusion of ice in aqueous solutions was measured to understand latent heat of fusion of ice slurries. Propylene glycol, ethylene glycol, ethanol, NaCl and NaNO3 solutions were examined as the aqueous solutions. In the measurement, pure ice was put into the solution, and the temperature variation of the solution due to the melting of the ice was measured. Then, the effective latent heat of fusion was calculated from energy balance equation. When ice melts in solution, the concentration of the solution varies due to the melting of the ice, and dilution heat must be considered. Therefore, the latent heat of fusion of ice in aqueous solutions was predicted by considering the effects of dilution and freezing-point depression. The latent heat of fusion was also measured by differential scanning calorimetry(DSC) to compare the results obtained from the experiments with that obtained by DSC. As the result, it was found that the effective latent heat of fusion of ice decreased with the increase of the concentration of solution, and the effective latent heat of fusion was calculated from latent heat of fusion of pure ice and the effects of freezing-point depression and the dilution heat.

Selective modification of NMR relaxation time in human colorectal carcinoma by using gadolinium-diethylenetriaminepentaacetic acid conjugated with monoclonal antibody 19-9.

PubMed Central

Curtet, C; Tellier, C; Bohy, J; Conti, M L; Saccavini, J C; Thedrez, P; Douillard, J Y; Chatal, J F; Koprowski, H

1986-01-01

Monoclonal antibody 19-9 (mAb 19-9) against human colon adenocarcinoma was conjugated with gadolinium X diethylenetriaminepentaacetic acid (Gd X DTPA) and used as a contrast agent in nuclear magnetic resonance (NMR) in an effort to improve tumor target selectivity in nude mice. The data indicate that Gd X DTPA-mAb 19-9 in solution decreased the T1 relaxation of water protons at 90 MHz in direct proportion to the gadolinium concentration, and this effect was greater than in Gd X DTPA solutions. T1 relaxation time at 90 MHz, measured in tumors removed from nude mice 24 hr after injection of Gd X DTPA-mAb 19-9 (Gd, 20 mumol/kg; 16 DTPA molecules per mAb molecule), was significantly decreased (by 15%) as compared with the control group. Similar results were obtained in tumors from mice injected with Gd X DTPA-mAb 19-9 solutions in which Gd was used at 2, 6, or 10 mumol/kg (16 DTPA molecules per mAb molecule). These doses are lower than those commonly used for Gd X DTPA (10-100 mumol/kg) as contrast agent. Tumor localization by the Gd X DTPA-mAb 19-9 complex containing radioactive Gd (0.3 microCi/microgram of 153Gd) to confirm scintigraphy revealed significant concentrations of the complex (5% of the injected dose per gram of tissue) in the tumor. Scan images recorded in planar scintigraphy at day 5 showed good visualization of tumors. Images PMID:3459174

Direct Detection of Aqueous CO2 by Infrared Waveguide Spectroscopy with an Amorphous Fluoropolymer Coating Rod.

PubMed

Hotta, Hiroki; Miki, Yuko; Kawaguchi, Yukiko; Tsunoda, Kin-Ichi; Nakaoka, Atsuko; Ko, Sho; Kimoto, Takashi

2017-01-01

Infrared waveguide spectroscopy using a sapphire rod coated with an amorphous fluoropolymer (Cytop, Asahi Glass Co., ltd, Japan) has been developed in order to directly observe CO 2 in aqueous solutions. Since the amorphous fluoropolymer has a relatively high gas-permeability and hydrophobic feature, the aqueous CO 2 transmits into the amorphous fluoropolymer coating film, but water cannot penetrate into the film. Good linearity of calibration curves for CO 2 in the gas and the aqueous solution were obtained.

POLONIUM SEPARATION PROCESS

DOEpatents

Karraker, D.G.

1959-07-14

A liquid-liquid extraction process is presented for the recovery of polonium from lead and bismuth. According to the invention an acidic aqueous chloride phase containing the polonium, lead, and bismuth values is contacted with a tributyl phosphate ether phase. The polonium preferentially enters the organic phase which is then separated and washed with an aqueous hydrochloric solution to remove any lead or bismuth which may also have been extracted. The now highly purified polonium in the organic phase may be transferred to an aqueous solution by extraction with aqueous nitric acid.

Microbial solubilization of phosphate

DOEpatents

Rogers, R.D.; Wolfram, J.H.

1993-10-26

A process is provided for solubilizing phosphate from phosphate containing ore by treatment with microorganisms which comprises forming an aqueous mixture of phosphate ore, microorganisms operable for solubilizing phosphate from the phosphate ore and maintaining the aqueous mixture for a period of time and under conditions operable to effect the microbial solubilization process. An aqueous solution containing soluble phosphorus can be separated from the reacted mixture by precipitation, solvent extraction, selective membrane, exchange resin or gravity methods to recover phosphate from the aqueous solution. 6 figures.

Microbial solubilization of phosphate

DOEpatents

Rogers, Robert D.; Wolfram, James H.

1993-01-01

A process is provided for solubilizing phosphate from phosphate containing ore by treatment with microorganisms which comprises forming an aqueous mixture of phosphate ore, microorganisms operable for solubilizing phosphate from the phosphate ore and maintaining the aqueous mixture for a period of time and under conditions operable to effect the microbial solubilization process. An aqueous solution containing soluble phosphorous can be separated from the reacted mixture by precipitation, solvent extraction, selective membrane, exchange resin or gravity methods to recover phosphate from the aqueous solution.

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

PubMed

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

2012-01-01

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

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

PubMed Central

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

2012-01-01

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

Viscosity-Lowering Effect of Amino Acids and Salts on Highly Concentrated Solutions of Two IgG1 Monoclonal Antibodies.

PubMed

Wang, Shujing; Zhang, Ning; Hu, Tao; Dai, Weiguo; Feng, Xiuying; Zhang, Xinyi; Qian, Feng

2015-12-07

Monoclonal antibodies display complicated solution properties in highly concentrated (>100 mg/mL) formulations, such as high viscosity, high aggregation propensity, and low stability, among others, originating from protein-protein interactions within the colloidal protein solution. These properties severely hinder the successful development of high-concentration mAb solution for subcutaneous injection. We hereby investigated the effects of several small-molecule excipients with diverse biophysical-chemical properties on the viscosity, aggregation propensity, and stability on two model IgG1 (JM1 and JM2) mAb formulations. These excipients include nine amino acids or their salt forms (Ala, Pro, Val, Gly, Ser, HisHCl, LysHCl, ArgHCl, and NaGlu), four representative salts (NaCl, NaAc, Na2SO4, and NH4Cl), and two chaotropic reagents (urea and GdnHCl). With only salts or amino acids in their salt-forms, significant decrease in viscosity was observed for JM1 (by up to 30-40%) and JM2 (by up to 50-80%) formulations, suggesting charge-charge interaction between the mAbs dictates the high viscosity of these mAbs formulations. Most of these viscosity-lowering excipients did not induce substantial protein aggregation or changes in the secondary structure of the mAbs, as evidenced by HPLC-SEC, DSC, and FT-IR analysis, even in the absence of common protein stabilizers such as sugars and surfactants. Therefore, amino acids in their salt-forms and several common salts, such as ArgHCl, HisHCl, LysHCl, NaCl, Na2SO4, and NaAc, could potentially serve as viscosity-lowering excipients during high-concentration mAb formulation development.

An enzyme-chromogenic surface plasmon resonance biosensor probe for hydrogen peroxide determination using a modified Trinder's reagent.

PubMed

Nakamura, Hideaki; Mogi, Yotaro; Akimoto, Takuo; Naemura, Kiyoshi; Kato, Teru; Yano, Kazuyoshi; Karube, Isao

2008-11-15

An absorption-based surface plasmon resonance (SPR(Abs)) biosensor probe has been developed for simple and reproducible measurements of hydrogen peroxide using a modified Trinder's reagent (a chromogenic reagent). The reagent enabled the determination of the hydrogen peroxide concentration by the development of deep color dyes (lambda(max)=630 nm) through the oxidative coupling reaction with N-ethyl-N-(2-hydroxy-3-sulfopropyl)-3,5-dimethylaniline sodium salt monohydrate (MAOS; C(13)H(20)NNaO(4)S.H(2)O) and 4-aminoantipyrine (4-AA) in the presence of hydrogen peroxide and horseradish peroxidase (HRP). In the present study, urea as an adduct of hydrogen peroxide for color development could be omitted from the measurement solution. The measurement solution containing 5mM hydrogen peroxide was deeply colored at a high absorbance value calculated as 46.7cm(-1) and was directly applied to the SPR(Abs) biosensing without dilution. The measurement was simply performed by dropping the measurement solution onto the surface of the SPR sensor probe, and the SPR(Abs) biosensor response to hydrogen peroxide was obtained as a reflectivity change in the SPR spectrum. After investigation of the pH profiles in the SPR(Abs) biosensor probe, a linear calibration curve was obtained between 1.0 and 50mM hydrogen peroxide (r=0.991, six points, average of relative standard deviation; 0.152%, n=3) with a detection limit of 0.5mM. To examine the applicability of this SPR(Abs) biosensor probe, 20mM glucose detection using glucose oxidase was also confirmed without influence of the refractive index in the measurement solution. Thus, the SPR(Abs) biosensor probe employing the modified Trinder's reagent demonstrated applicability to other analyte biosensing tools.

75 FR 30844 - General Mills, Inc.; Withdrawal of Food Additive Petition

Federal Register 2010, 2011, 2012, 2013, 2014

2010-06-02

... for the reduction of pathogens and other microorganisms in aqueous sugar solutions and potable water... reduction of pathogens and other microorganisms in aqueous sugar solutions and potable water intended for...

Structural characterization of metal complexes in aqueous solutions: a XAS study of stannous fluoride

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

Alsina, Marco A.; Gaillard, Jean-François

The identity and structure of tin(ii)-fluoride complexes formed in aqueous solutions are determined by combining X-ray absorption spectroscopy, thermodynamic modeling and quantum mechanical calculations.

Sorption of ochratoxin A from aqueous solutions using β-cyclodextrin-polyurethane polymer.

PubMed

Appell, Michael; Jackson, Michael A

2012-02-01

The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions was examined by batch rebinding assays. The results from the aqueous binding studies were fit to two parameter models to gain insight into the interaction of ochratoxin A with the nanosponge material. The ochratoxin A sorption data fit well to the heterogeneous Freundlich isotherm model. The polymer was less effective at binding ochratoxin A in high pH buffer (9.5) under conditions where ochratoxin A exists predominantly in the dianionic state. Batch rebinding assays in red wine indicate the polymer is able to remove significant levels of ochratoxin A from spiked solutions between 1-10 μg·L(-1). These results suggest cyclodextrin nanosponge materials are suitable to reduce levels of ochratoxin A from spiked aqueous solutions and red wine samples.

Superlubricity of a Mixed Aqueous Solution

NASA Astrophysics Data System (ADS)

Ma, Zhi-Zuo; Zhang, Chen-Hui; Luo, Jian-Bin; Lu, Xin-Chun; Wen, Shi-Zhu

2011-05-01

A super-low friction coefficient of 0.0028 is measured under a pressure of 300 MPa when the friction pair (the silicon nitride ball sliding on the silicate glass) is lubricated by the mixed aqueous solution of glycerol and boric acid. The morphorlogies of the hydroxylated glass plate are observed by an atomic force microscope (AFM) in deionized water, glycerol, boric acid and their mixed aqueous solution. Bonding peaks of the retained liquids adhered on the surface of the sliding track are detected by an infrared spectrum apparatus and a Raman spectrum apparatus. The mechanism of the superlubricity of the glycerol and boric acid mixed aqueous solution is discussed. It is deduced that the formation of the lubricant film has enough strength to support higher loads, the hydration effect offering the super lower shear resistance. Key words: superlubricity, water based lubricant, ultra-low friction

Separation and concentration of lower alcohols from dilute aqueous solutions

DOEpatents

Moore, Raymond H.; Eakin, David E.; Baker, Eddie G.; Hallen, Richard T.

1991-01-01

A process for producing, from a dilute aqueous solution of a lower (C.sub.1 -C.sub.5) alcohol, a concentrated liquid solution of the alcohol in an aromatic organic solvent is disclosed. Most of the water is removed from the dilute aqueous solution of alcohol by chilling sufficiently to form ice crystals. Simultaneously, the remaining liquid is extracted at substantially the same low temperature with a liquid organic solvent that is substantially immiscible in aqueous liquids and has an affinity for the alcohol at that temperature, causing the alcohol to transfer to the organic phase. After separating the organic liquid from the ice crystals, the organic liquid can be distilled to enrich the concentration of alcohol therein. Ethanol so separated from water and concentrated in an organic solvent such as toluene is useful as an anti-knock additive for gasoline.

Methods for separating medical isotopes using ionic liquids

DOEpatents

Luo, Huimin; Boll, Rose Ann; Bell, Jason Richard; Dai, Sheng

2014-10-21

A method for extracting a radioisotope from an aqueous solution, the method comprising: a) intimately mixing a non-chelating ionic liquid with the aqueous solution to transfer at least a portion of said radioisotope to said non-chelating ionic liquid; and b) separating the non-chelating ionic liquid from the aqueous solution. In preferred embodiments, the method achieves an extraction efficiency of at least 80%, or a separation factor of at least 1.times.10.sup.4 when more than one radioisotope is included in the aqueous solution. In particular embodiments, the method is applied to the separation of medical isotopes pairs, such as Th from Ac (Th-229/Ac-225, Ac-227/Th-227), or Ra from Ac (Ac-225 and Ra-225, Ac-227 and Ra-223), or Ra from Th (Th-227 and Ra-223, Th-229 and Ra-225).

Green Silver Nanoparticles Based Dual Sensor for Toxic Hg (II) Ions.

PubMed

Sebastian, Maria; Aravind, Archana; Mathew, Beena

2018-06-11

The present study focuses on the utilization of green silver nanoparticles as they are more preferred for sensing applications due to their environment friendly nature. We have examined the optical and electrochemical sensing behavior of silver nanoparticles from Agaricus Bispores (AgNP-AB) towards Hg(II) ions. AgNP-AB was prepared by microwave reactor. The synthesized AgNPs have been used for the sensing of Hg(II) ions without the use of modifiers or further sophisticated instrumentation. The synthesized nanoparticles were successfully characterized by different techniques. AgNP-AB leads to aggregation with addition of Hg(II) ions in aqueous medium and developed a color change from brown to black which leads to the formation of AgNP-AB-Hg(II) complex. Moreover, the metal sensing ability of AgNPs has been explored using electrochemical studies. AgNP-AB modified platinum electrode (AgNP-AB/PE) was developed for the fast sensing of toxic Hg(II) ions. The sensor exhibits good limit of detection at 2.1x10-6M. The sensitivity of AgNP-AB/PE towards Hg(II) ion was analyzed with various metal ions. The sensing skill of developed system was successfully checked with real water sample from Vembanade Lake, Kumarakom, Kerala. The silver nanoparticles from Agaricus Bispoes are highly versatile and promising for different environmental applications. © 2018 IOP Publishing Ltd.

Densities of L-Glutamic Acid HCl Drug in Aqueous NaCl and KCl Solutions at Different Temperatures

NASA Astrophysics Data System (ADS)

Ryshetti, Suresh; Raghuram, Noothi; Rani, Emmadi Jayanthi; Tangeda, Savitha Jyostna

2016-04-01

Densities (ρ ) of (0.01 to 0.07) {mol}{\\cdot } {kg}^{-1} L-Glutamic acid HCl (L-HCl) drug in water, and in aqueous NaCl and KCl (0.5 and 1.0) {mol}{\\cdot } {kg}^{-1} solutions have been reported as a function of temperature at T = (298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure. The accurate density (ρ ) values are used to estimate the various parameters such as the apparent molar volume (V_{2,{\\upphi }}), the partial molar volume (V2^{∞}), the isobaric thermal expansion coefficient (α 2), the partial molar expansion (E2^{∞}), and Hepler's constant (partial 2V2^{∞}/partial T2)P. The Cosphere overlap model is used to understand the solute-solvent interactions in a ternary mixture (L-HCl drug + NaCl or KCl + water). Hepler's constant (partial 2V2^{∞}/partial T2)_P is utilized to interpret the structure-making or -breaking ability of L-HCl drug in aqueous NaCl and KCl solutions, and the results are inferred that L-HCl drug acts as a structure maker, i.e., kosmotrope in aqueous NaCl solutions and performs as a structure breaker, i.e., chaotrope in aqueous KCl solutions.

Heat capacity of alkanolamine aqueous solutions

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

Chiu, L.F.; Li, M.H.

1999-12-01

Heat capacities of monoethanoloamine, diglycolamine, diethanolamine, di-w propanolamine, triethanolamine, N-methyldiethanolamine, 2-amino-2-methyl-l-propanol, and 2-piperidineethanol aqueous solutions were measured from 30 to 80 C with a differential scanning calorimeter (DSC). The mole fractions of alkanolamines studied are 0.2, 0.4, 0.6, and 0.8. Heat capacities of N-methyldiethanolamine aqueous solutions have been measured to verify the validity of C{sub p} measurements for alkanolamine aqueous solutions. The estimated uncertainty of the measured heat capacities is {plus{underscore}minus}3%, including the effect of up to 5% impurities in a substance. An excess molar heat capacity expression using the Redlich-Kister equation for the composition dependence is used to representmore » the measured C{sub p} of alkanolamine aqueous solutions. For a total of 374 data points, the calculation results for eight alkanolamine solutions give the overall average absolute deviations of 11.9% and 0.29% for the excess molar heat capacity and the heat capacity, respectively. The heat capacities presented in this study are, in general, of sufficient accuracy for most engineering-design calculations. Solutions of alkanolamines are industrially important mixtures used in the natural gas industry, oil refineries, petroleum chemical plants, and synthetic ammonia plants for the removal of acidic components such as CO{sub 2} and H{sub 2}S from gas streams.« less

METHOD OF APPLYING COPPER COATINGS TO URANIUM

DOEpatents

Gray, A.G.

1959-07-14

A method is presented for protecting metallic uranium, which comprises anodic etching of the uranium in an aqueous phosphoric acid solution containing chloride ions, cleaning the etched uranium in aqueous nitric acid solution, promptly electro-plating the cleaned uranium in a copper electro-plating bath, and then electro-plating thereupon lead, tin, zinc, cadmium, chromium or nickel from an aqueous electro-plating bath.

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

PubMed

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

2012-01-01

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

Desorption of CO{sub 2} from MDEA and activated MDEA solutions

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

Xu, G.W.; Zhang, C.F.; Qin, S.J.

1995-03-01

A packed column was used for investigating the desorption rate of CO{sub 2} from aqueous methyldiethanolamine (MDEA) and activated MDEA solutions. Experiments were conducted within the temperature range 30--70 C, the concentration of MDEA was 4.28 kmol/m{sup 3}, and the concentration of piperazine (PZ) was 0.10 kmol/m{sup 3} for aqueous activated MDEA solutions. Experimental data confirmed that the kinetics model of absorption CO{sub 2} into aqueous MDEA and activated MDEA solutions can be applicable to the situations in which desorption occurs, and the desorption rate of model predictions agree well with that of experimental determination.

Separation of metal ions from aqueous solutions

DOEpatents

Almon, Amy C.

1994-01-01

A process and apparatus for quantitatively and selectively separating metal ions from mixtures thereof in aqueous solution. The apparatus includes, in combination, a horizontal electrochemical flow cell containing flow bulk electrolyte solution and an aqueous, metal ion-containing solution, the cell containing a metal mesh working electrode, a counter electrode positioned downstream from the working electrode, an independent variable power supply/potentiostat positioned outside of the flow cell and connected to the electrodes, and optionally a detector such as a chromatographic detector, positioned outside the flow cell. This apparatus and its operation has significant application where trace amounts of metal ions are to be separated.

Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.; Zhukova, T. V.

2014-06-01

A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.

A Modified Robinson-Stokes equation for describing the thermodynamic properties of aqueous solutions of 1-1 electrolytes

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.

2008-05-01

Equations relating osmotic, mean ionic activity, and water activity coefficients to electrolyte concentrations in binary aqueous solutions were substantiated within the framework of cluster concepts. The model includes the contribution to solution nonideality of electrostatic interactions in terms of the Debye-Hückel theory along with hydration and association of salts via relations containing hydration and association numbers in the standard states. According to the description of data on 54 aqueous solutions of 1-1 electrolytes, this model should be given preference compared with the most extensively used NRTL, NRTL-NRF, Wilson, and Pitzer models.

Heat-induced morphological transformation of gold nanodumbbells in ionic surfactant solutions

NASA Astrophysics Data System (ADS)

Wen, Ting-Chun; Lu, Chung-Wen; Hsieh, Wei-Chi; Chang, Sheng-Te; Yang, Ya-Ting; Deng, Jin-Pei

2018-01-01

The thermal stability of gold nanodumbbells (NDs) is studied in aqueous solution of ionic surfactants. It is found in aqueous solution of cetyltrimethylammonium bromide that the blue-shift of longitudinal surface plasmon resonance band of gold NDs occurs at 75 °C and the new gold nanorods (NRs) with shortened aspect ratio are formed at the same time. The aspect ratio of the generated gold NRs gradually decreases and finally approaches ∼1.7 after repeated processing. Similarly, the same results are also obtained in aqueous solution of sodium dodecyl sulfate at room temperature. Mechanism is proposed for the shape transformation of gold NDs.

Laboratory studies of aqueous-phase oxidation of polyols in submicron particles

NASA Astrophysics Data System (ADS)

Daumit, K. E.; Carrasquillo, A. J.; Hunter, J. F.; Kroll, J. H.

2013-12-01

Aqueous-phase oxidation has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. However most aqueous oxidation studies are performed in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation is carried out within submicron particles, allowing for gas-particle partitioning of reactants, intermediates, and products. Using Fenton chemistry as a source of hydroxyl radicals, and a high-resolution aerosol mass spectrometer (AMS) for online characterization of particle composition, we find that aqueous oxidation can be quite rapid. The formation of high concentrations of oxalic acid is observed in the particle phase with some loss of carbon to the gas phase, indicating the formation of volatile products. We see a rapid degradation of condensed-phase oxidation products upon exposure to ultraviolet lights (centered at 350 nm) suggesting that these products may exist as iron(III)-oxalate complexes. Similar results are also seen when oxidation is carried out in bulk solution (with AMS analysis of the atomized solution); however in some cases the mass loss is less than is observed for submicron particles, likely due to differences in partitioning of early-generation products. Such products can partition out of the aqueous phase at the low liquid water contents in the chamber but remain in solution for further aqueous processing in bulk oxidation experiments. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different than those in bulk oxidation, pointing to the need to carry out aqueous oxidation studies under atmospherically relevant partitioning conditions (with liquid water contents mimicking those of cloud droplets or wet aerosol).

An ex vivo human aqueous humor-concentration comparison of two commercial bromfenac formulations

PubMed Central

Walters, Thomas R; Smyth-Medina, Robert J; Cockrum, Paul C

2018-01-01

Purpose The purpose of this study was to quantify the concentration of bromfenac in the aqueous humor utilizing high-performance liquid chromatography mass spectrometry between two commercial nonsteroidal anti-inflammatory drugs, using aqueous humor concentrations to characterize pharmacokinetic proportional differences between 0.075% bromfenac ophthalmic solution in DuraSite (BromSite®) and 0.09% bromfenac ophthalmic solution (Bromday®). Methods In this multicenter, randomized, double-masked, two-arm, parallel-group, comparative, Phase II clinical trial, subjects were assigned to receive bromfenac in DuraSite or bromfenac ophthalmic solution in a 1:1 ratio. One drop of the masked test article was instilled into the study eye once a day for 2 days prior to and 3 hours prior (last instillation) to the subject’s cataract surgery. Aqueous humor samples were collected upon initial cataract incision for analysis of bromfenac levels. The primary end point was aqueous humor concentration of bromfenac at Day 3, at the initiation of cataract surgery. Aqueous humor samples were collected and analyzed for bromfenac levels. Results A total of 60 subjects completed the study, 30 in each group. The mean bromfenac aqueous humor concentration in subjects who received bromfenac in DuraSite was more than twice (49.33±41.87 ng/mL, P=0.004) that of subjects who received bromfenac ophthalmic solution (23.65±16.31 ng/mL) after three doses. Conclusion Mean bromfenac aqueous humor concentration in subjects receiving the DuraSite-containing bromfenac in DuraSite (0.075%) was significantly higher compared to subjects receiving bromfenac ophthalmic solution (0.09%) after 3 days of dosing. PMID:29849449

Design principles for high-pressure force fields: Aqueous TMAO solutions from ambient to kilobar pressures.

PubMed

Hölzl, Christoph; Kibies, Patrick; Imoto, Sho; Frach, Roland; Suladze, Saba; Winter, Roland; Marx, Dominik; Horinek, Dominik; Kast, Stefan M

2016-04-14

Accurate force fields are one of the major pillars on which successful molecular dynamics simulations of complex biomolecular processes rest. They have been optimized for ambient conditions, whereas high-pressure simulations become increasingly important in pressure perturbation studies, using pressure as an independent thermodynamic variable. Here, we explore the design of non-polarizable force fields tailored to work well in the realm of kilobar pressures--while avoiding complete reparameterization. Our key is to first compute the pressure-induced electronic and structural response of a solute by combining an integral equation approach to include pressure effects on solvent structure with a quantum-chemical treatment of the solute within the embedded cluster reference interaction site model (EC-RISM) framework. Next, the solute's response to compression is taken into account by introducing pressure-dependence into selected parameters of a well-established force field. In our proof-of-principle study, the full machinery is applied to N,N,N-trimethylamine-N-oxide (TMAO) in water being a potent osmolyte that counteracts pressure denaturation. EC-RISM theory is shown to describe well the charge redistribution upon compression of TMAO(aq) to 10 kbar, which is then embodied in force field molecular dynamics by pressure-dependent partial charges. The performance of the high pressure force field is assessed by comparing to experimental and ab initio molecular dynamics data. Beyond its broad usefulness for designing non-polarizable force fields for extreme thermodynamic conditions, a good description of the pressure-response of solutions is highly recommended when constructing and validating polarizable force fields.

Theoretic Study on Dispersion Mechanism of Boron Nitride Nanotubes by Polynucleotides

PubMed Central

Liang, Lijun; Hu, Wei; Zhang, Zhisen; Shen, Jia-Wei

2016-01-01

Due to the unique electrical and mechanical properties of boron nitride nanotubes (BNNT), BNNT has been a promising material for many potential applications, especially in biomedical field. Understanding the dispersion of BNNT in aqueous solution by biomolecules is essential for its use in biomedical applications. In this study, BNNT wrapped by polynucleotides in aqueous solution was investigated by molecular dynamics (MD) simulations. Our results demonstrated that the BNNT wrapped by polynucleotides could greatly hinder the aggregation of BNNTs and improve the dispersion of BNNTs in aqueous solution. Dispersion of BNNTs with the assistance of polynucleotides is greatly affected by the wrapping manner of polynucleotides on BNNT, which mainly depends on two factors: the type of polynucleotides and the radius of BNNT. The interaction between polynucleotides and BNNT(9, 9) is larger than that between polynucleotides and BNNT(5, 5), which leads to the fact that dispersion of BNNT(9, 9) is better than that of BNNT(5, 5) with the assistance of polynucleotides in aqueous solution. Our study revealed the molecular-level dispersion mechanism of BNNT with the assistance of polynucleotides in aqueous solution. It shades a light on the understanding of dispersion of single wall nanotubes by biomolecules. PMID:28004832

Photolysis of Diazo Dye in Aqueous Solutions of Metal Nitrates

NASA Astrophysics Data System (ADS)

Volkova, N. A.; Evstrop'ev, S. K.; Istomina, O. V.; Kolobkova, E. V.

2018-04-01

The photolysis of Chicago Blue Sky diazo dye is studied. It is experimentally shown that the presence of metal nitrates in aqueous solutions changes the photolysis mechanism and sharply increases the photolysis rate.

Mussel-inspired one-pot synthesis of transition metal and nitrogen co-doped carbon (M/N-C) as efficient oxygen catalysts for Zn-air batteries

NASA Astrophysics Data System (ADS)

Li, Bing; Chen, Ye; Ge, Xiaoming; Chai, Jianwei; Zhang, Xiao; Hor, T. S. Andy; Du, Guojun; Liu, Zhaolin; Zhang, Hua; Zong, Yun

2016-02-01

Transition metal and nitrogen co-doping into carbon is an effective approach to promote the catalytic activities towards the oxygen reduction reaction (ORR) and/or oxygen evolution reaction (OER) in the resultant electrocatalysts, M/N-C. The preparation of such catalysts, however, is often complicated and in low yield. Herein we report a robust approach for easy synthesis of M/N-C hybrids in high yield, which includes a mussel-inspired polymerization reaction at room temperature and a subsequent carbonization process. With the introduction of selected transition metal salts into an aqueous solution of dopamine (DA), the obtained mixture self-polymerizes to form metal-containing polydopamine (M-PDA) composites, e.g. Co-PDA, Ni-PDA and Fe-PDA. Upon carbonization at elevated temperatures, these metal-containing composites were converted into M/N-C, i.e. Co-PDA-C, Ni-PDA-C and Fe-PDA-C, respectively, whose morphologies, chemical compositions, and electrochemical performances were fully studied. Enhanced ORR activities were found in all the obtained hybrids, with Co-PDA-C standing out as the most promising catalyst with excellent stability and catalytic activities towards both ORR and OER. This was further proven in Zn-air batteries (ZnABs) in terms of discharge voltage stability and cycling performance. At a discharge-charge current density of 2 mA cm-2 and 1 h per cycle, the Co-PDA-C based ZnABs were able to steadily cycle up to 500 cycles with only a small increase in the discharge-charge voltage gap which notably outperformed Pt/C; at a discharge current density of 5 mA cm-2, the battery continuously discharged for more than 540 h with the discharge voltage above 1 V and a voltage drop rate of merely 0.37 mV h-1. With the simplicity and scalability of the synthetic approach and remarkable battery performances, the Co-PDA-C hybrid catalyst is anticipated to play an important role in practical ZnABs.Transition metal and nitrogen co-doping into carbon is an effective approach to promote the catalytic activities towards the oxygen reduction reaction (ORR) and/or oxygen evolution reaction (OER) in the resultant electrocatalysts, M/N-C. The preparation of such catalysts, however, is often complicated and in low yield. Herein we report a robust approach for easy synthesis of M/N-C hybrids in high yield, which includes a mussel-inspired polymerization reaction at room temperature and a subsequent carbonization process. With the introduction of selected transition metal salts into an aqueous solution of dopamine (DA), the obtained mixture self-polymerizes to form metal-containing polydopamine (M-PDA) composites, e.g. Co-PDA, Ni-PDA and Fe-PDA. Upon carbonization at elevated temperatures, these metal-containing composites were converted into M/N-C, i.e. Co-PDA-C, Ni-PDA-C and Fe-PDA-C, respectively, whose morphologies, chemical compositions, and electrochemical performances were fully studied. Enhanced ORR activities were found in all the obtained hybrids, with Co-PDA-C standing out as the most promising catalyst with excellent stability and catalytic activities towards both ORR and OER. This was further proven in Zn-air batteries (ZnABs) in terms of discharge voltage stability and cycling performance. At a discharge-charge current density of 2 mA cm-2 and 1 h per cycle, the Co-PDA-C based ZnABs were able to steadily cycle up to 500 cycles with only a small increase in the discharge-charge voltage gap which notably outperformed Pt/C; at a discharge current density of 5 mA cm-2, the battery continuously discharged for more than 540 h with the discharge voltage above 1 V and a voltage drop rate of merely 0.37 mV h-1. With the simplicity and scalability of the synthetic approach and remarkable battery performances, the Co-PDA-C hybrid catalyst is anticipated to play an important role in practical ZnABs. Electronic supplementary information (ESI) available: Schematic structure of ZnAB; photos of home-made ZnABs; EDX spectra and elemental mapping of M-PDA-C; N2 adsorption/desorption isotherms, high magnification TEM images of M-PDA-C, and RDE data of M-PDA-C, etc. See DOI: 10.1039/c5nr06538k

Antidiabetic Bis-Maltolato-OxoVanadium(IV): Conversion of inactive trans- to bioactive cis-BMOV for possible binding to target PTP-1B

PubMed Central

Scior, Thomas; Mack, Hans-Georg; García, José Antonio Guevara; Koch, Wolfhard

2008-01-01

The postulated transition of Bis-Maltolato-OxoVanadium(IV) (BMOV) from its inactive trans- into its cis-aquo-BMOV isomeric form in solution was simulated by means of computational molecular modeling. The rotational barrier was calculated with DFT – B3LYP under a stepwise optimization protocol with STO-3G, 3-21G, 3-21G*, and 6-31G ab initio basis sets. Our computed results are consistent with reports on the putative molecular mechanism of BMOV triggering the insulin-like cellular response (insulin mimetic) as a potent inhibitor of the protein tyrosine phosphatase-1B (PTP-1B). Initially, trans-BMOV is present in its solid dosage form but in aqueous solution, and during oral administration, it is readily converted into a mixture of “open-type” and “closed-type” complexes of cis-aquo-BMOV under equilibrium conditions. However, in the same measure as the “closed-type” complex binds to the cytosolic PTP-1B, it disappears from solution, and the equilibrium shifts towards the “closed-type” species. In full accordance, the computed binding mode of cis-BMOV is energetically favored over sterically hindered trans-BMOV. In view of our earlier report on prodrug hypothesis of vanadium organic compounds the present results suggest that cis-BMOV is the bioactive species. PMID:19920909

Multiple stimulus reversible hydrogels

DOEpatents

Gutowska, Anna; Krzyminski, Karol J.

2003-12-09

A polymeric solution capable of gelling upon exposure to a critical minimum value of a plurality of environmental stimuli is disclosed. The polymeric solution may be an aqueous solution utilized in vivo and capable of having the gelation reversed if at least one of the stimuli fall below, or outside the range of, the critical minimum value. The aqueous polymeric solution can be used either in industrial or pharmaceutical environments. In the medical environment, the aqueous polymeric solution is provided with either a chemical or radioisotopic therapeutic agent for delivery to a specific body part. The primary advantage of the process is that exposure to one environmental stimuli alone will not cause gelation, thereby enabling the therapeutic agent to be conducted through the body for relatively long distances without gelation occurring.

Multiple stimulus reversible hydrogels

DOEpatents

Gutowska, Anna; Krzyminski, Karol J.

2006-04-25

A polymeric solution capable of gelling upon exposure to a critical minimum value of a plurality of environmental stimuli is disclosed. The polymeric solution may be an aqueous solution utilized in vivo and capable of having the gelation reversed if at least one of the stimuli fall below, or outside the range of, the critical minimum value. The aqueous polymeric solution can be used either in industrial or pharmaceutical environments. In the medical environment, the aqueous polymeric solution is provided with either a chemical or radioisotopic therapeutic agent for delivery to a specific body part. The primary advantage of the process is that exposure to one environmental stimuli alone will not cause gelation, thereby enabling the therapeutic agent to be conducted through the body for relatively long distances without gelation occurring.

Removal of metal ions from aqueous solution

DOEpatents

Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

1990-01-01

A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form.

Removal of metal ions from aqueous solution

DOEpatents

Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

1990-11-13

A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat unit for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heayv metals from solution. This also results in the removal of the metals from the column in a concentrated form.

Long-term results of treatment with diquafosol ophthalmic solution for aqueous-deficient dry eye.

PubMed

Koh, Shizuka; Ikeda, Chikako; Takai, Yoshihiro; Watanabe, Hitoshi; Maeda, Naoyuki; Nishida, Kohji

2013-09-01

To evaluate the preliminary long-term efficacy of diquafosol ophthalmic solution for aqueous-deficient dry eye. Fifteen patients with mild-to-moderate aqueous-deficient dry eye were enrolled. After a washout period, the patients were treated with 3 % diquafosol ophthalmic solution for 6 months. We assessed 12 subjective dry eye symptoms, corneal and conjunctival staining with fluorescein, tear film break-up time (BUT), lower tear meniscus height measured with anterior-segment optical coherence tomography, Schirmer's testing, and adverse reactions at baseline and 1, 3, and 6 months after the start of treatment. Treatment with diquafosol ophthalmic solution significantly improved dry eye symptoms, corneal staining, BUT, and tear meniscus height at 1 month and maintained the effectiveness for 6 months. Conjunctival staining significantly improved 3 and 6 months after treatment. No significant adverse reactions developed. Prolonged use of diquafosol ophthalmic solution for 6 months produced significant improvement both subjectively (dry eye symptom score) and objectively (ocular staining score and tear function tests) for aqueous-deficient dry eye.

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

METHOD FOR SEPARATION OF PLUTONIUM FROM URANIUM AND FISSION PRODUCTS BY SOLVENT EXTRACTION

DOEpatents

Seaborg, G.T.; Blaedel, W.J.; Walling, M.T. Jr.

1960-08-23

A process is given for separating from each other uranium, plutonium, and fission products in an aqueous nitric acid solution by the so-called Redox process. The plutonium is first oxidized to the hexavalent state, e.g., with a water-soluble dichromate or sodium bismuthate, preferably together with a holding oxidant such as potassium bromate. potassium permanganate, or an excess of the oxidizing agent. The solution is then contacted with a water-immiscible organic solvent, preferably hexone. whereby uranium and plutonium are extracted while the fission products remain in the aqueous solution. The separated organic phase is then contacted with an aqueous solution of a reducing agent, with or without a holding reductant (e.g., with a ferrous salt plus hydrazine or with ferrous sulfamate), whereby plutonium is reduced to the trivalent state and back- extracted into the aqueous solution. The uranium may finally be back-extracted from the organic solvent (e.g., with a 0.1 N nitric acid).

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments.

PubMed

Pham, Tuan Anh; Govoni, Marco; Seidel, Robert; Bradforth, Stephen E; Schwegler, Eric; Galli, Giulia

2017-06-01

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum mechanical methods. However, it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. We propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, on the basis of the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results of the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecular dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of the electronic properties of the solvent and solutes, including excitation energies. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies.

Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

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

Pham, Tuan Anh; Govoni, Marco; Seidel, Robert

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum mechanical methods. However, it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. We propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, on the basis of the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results of the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecularmore » dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of the electronic properties of the solvent and solutes, including excitation energies. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies.« less

Mercury removal from aqueous solutions by zinc cementation.

PubMed

Ku, Young; Wu, Ming-Huan; Shen, Yung-Shen

2002-01-01

The main purpose of this research is to study the addition effect of the surfactant and other operating factors on the treatment of wastewater containing mercury ions in aqueous solution by cementation with sacrificing metal, zinc. The removal of mercury ions from aqueous solutions by cementation of zinc powder was found to be a function of solution pH and temperature, amount of zinc, concentration of mercury ion, contact time and the addition of several organic surfactants. Cementation of mercury was shown to be a feasible process to achieve a very high degree of mercury removal over a broad operational range within a fairly reasonable contact time. The reaction rate is approximately first order with respect to the concentration of mercury ion in aqueous solution. Among the surfactants used in this study, only the presence of SDS, an anionic surfactant, slightly enhanced the cementation rate of mercury. The presence of CTAB and Triton-X100 retarded the cementation of mercury by zinc.

Self-Assembly of Porphyrin J-Aggregates

NASA Astrophysics Data System (ADS)

Snitka, Valentinas; Rackaitis, Mindaugas; Navickaite, Gintare

2006-03-01

The porphyrin nanotubes were built by ionic self-assembly of two oppositely charged porphyrins in aqueous solution. The porphyrins in the acid aqueous solution self-assemble into J-aggregates, wheels or other structures. The electrostatic forces between these porphyrin blocks contribute to the formation of porphyrin aggregates in the form of nanotubes, enhance the structural stability of these nanostructures. The nanotubes were composed mixing aqueous solutions of the two porphyrins - anionic Meso-tetra(4- sulfonatophrnyl)porhine dihydrochloride (TPPS4) and cationic Meso-tetra(4-pyridyl)porphine (T4MPyP). The porphyrin nanotubes obtained are hollow structures with the length of 300 nm and diameter 50 nm. Photocatalytic porphyrins are used to reduce metal complexes from aqueous solution and to control the deposition of Au from AuHCl4 and Au nanoparticles colloid solutions onto porphyrin nanotubes. Porphyrin nanotubes are shown to reduce metal complexes and deposit the metal selectively onto the inner or outer surface of the tubes, leading to nanotube-metal composite structures.

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

PubMed

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

2014-01-01

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

Final product analysis in the e-beam and gamma radiolysis of aqueous solutions of metoprolol tartrate

NASA Astrophysics Data System (ADS)

Slegers, Catherine; Tilquin, Bernard

2006-09-01

The radiostability of metoprolol tartrate aqueous solutions and the influence of the absorbed dose (0-50 kGy), dose rate (e-beam (EB) vs. gamma ( γ)) and radioprotectors (pharmaceutical excipients) are investigated by HPLC-UV analyses and through computer simulations. The use of radioprotecting excipients is more promising than an increase in the dose rate to lower the degradation of metoprolol tartrate aqueous solutions for applications such as radiosterilization. The decontamination of metoprolol tartrate from waste waters by EB processing appears highly feasible.

Vibrational spectroscopic study of nickel (II) formate, Ni(HCO 2) 2, and its aqueous solution

NASA Astrophysics Data System (ADS)

Edwards, H. G. M.; Knowles, A.

1992-04-01

A vibrational spectroscopic study of nickel (II) formate and its aqueous solution has been made. The vibrations characteristic of a formato—nickel complex have been assigned and it is concluded that the species Ni(HCO 2) +(HCO 2) - exists in the solid state, with monodentate ligand-to-metal bonding. The Raman spectrum of an aqueous solution of nickel (II) formate indicates that complete dissociation of the formato—nickel (II) species occurs to formate ions and nickel (II) hexa-aquo ions. Comparisons are made with other nickel (II) carboxylates.

Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxyl radical and perhydroxyl radical and their radical ions

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

Ross, F; Ross, A B

1977-01-01

Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.

Measurements of Atmospheric Aerosols: Experimental Methods and Results of Measurements off the East Coast of the United States.

DTIC Science & Technology

1983-07-19

Pruppacher and Klett, 1978) 2(rl ’. r R 1 F5S = a,, e (5) where a. is the water activity of the aqueous solution , (r is the surface tension of the droplet...desorption) of ions by the insoluble portion of the particle, which is assumed to be totally submerged in the aqueous solution . We denote the coefficient ...between the saturation ratio S (relative humidity/100) of the air and the equili- brium radius r of an aqueous solution droplet may be expressed as

Exploring the speed and performance of molecular replacement with AMPLE using QUARK ab initio protein models.

PubMed

Keegan, Ronan M; Bibby, Jaclyn; Thomas, Jens; Xu, Dong; Zhang, Yang; Mayans, Olga; Winn, Martyn D; Rigden, Daniel J

2015-02-01

AMPLE clusters and truncates ab initio protein structure predictions, producing search models for molecular replacement. Here, an interesting degree of complementarity is shown between targets solved using the different ab initio modelling programs QUARK and ROSETTA. Search models derived from either program collectively solve almost all of the all-helical targets in the test set. Initial solutions produced by Phaser after only 5 min perform surprisingly well, improving the prospects for in situ structure solution by AMPLE during synchrotron visits. Taken together, the results show the potential for AMPLE to run more quickly and successfully solve more targets than previously suspected.

Patents – Melvin Calvin

Science.gov Websites

plutonium from uranium and fission products in an aqueous acidic solution by use of a chelating agent. The concentration is adjusted to about 1 N bar. The aqueous solution is then contacted with a water-immiscible organic solvent solution and the chelating agent. The chelating agents covered by this invention comprise

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

Bunkin, N F; Shkirin, A V; Burkhanov, I S

Aqueous NaCl solutions with different concentrations have been investigated by dynamic scattering of laser radiation. It is experimentally shown that these solutions contain scattering particles with a wide size distribution in a range of ∼10 – 100 nm. The experimental results indirectly confirm the existence of quasi-stable gas nanobubbles in the bulk of aqueous ionic solutions. (light scattering)

NMR studies of water dynamics during sol-to-gel transition of poly (N-isopropylacrylamide) in concentrated aqueous solution

USDA-ARS?s Scientific Manuscript database

The thermo-sensitive polymer, poly(N-isopropylacrylamide) (PNIPAM) undergoes a coil-to-globule transition in an aqueous solution as the temperature is raised through the lower critical solution temperature. Thus far, little is known about the dynamical states of the water molecules that contribute ...

METHOD FOR ELECTRODEPOSITING POLONIUM

DOEpatents

Wehrmann, R.F.

1960-08-30

The deposition of a thick uniform layer of polonium metal from aqueous solutions can be carried out by electrolyzing an aqueous solution of 1 N hydrofluoric acid containing about 0.13 curie of polonium per cubic centimeter of solution with platinum electrodes and a current density of about 1.2 ma/cm/sup 2/ of cathode surface.

MECHANISTIC ROLES OF SOIL HUMUS AND MINERALS IN THE SORPTION OF NONIONIC ORGANIC COMPOUNDS FROM AQUEOUS AND ORGANIC SOLUTIONS

EPA Science Inventory

Mechanistic roles of soil humus and soil minerals and their contributions to soil sorption of nonionic organic compounds from aqueous and organic solutions are illustrated. Parathion and lindane are used as model solutes on two soils that differ greatly in their humic and mineral...

CO2 as a smart gelator for Pluronic aqueous solutions.

PubMed

Liu, Chengcheng; Mei, Qingqing; Zhang, Jianling; Kang, Xinchen; Peng, Li; Han, Buxing; Xue, Zhimin; Sang, Xinxin; Yang, Xiaogan; Wu, Zhonghua; Li, Zhihong; Mo, Guang

2014-11-25

It was found that CO2 could induce the gelation of Pluronic aqueous solutions, during which the microstructure of the solution transforms from randomly dispersed spherical micelles to cubic close packed micelles. The gelation switched by compressed CO2 has many advantages and can be applied in the synthesis of porous materials.

Method for aqueous radioactive waste treatment

DOEpatents

Bray, L.A.; Burger, L.L.

1994-03-29

Plutonium, strontium, and cesium found in aqueous waste solutions resulting from nuclear fuel processing are removed by contacting the waste solutions with synthetic zeolite incorporating up to about 5 wt % titanium as sodium titanate in an ion exchange system. More than 99.9% of the plutonium, strontium, and cesium are removed from the waste solutions. 3 figures.

Method for aqueous radioactive waste treatment

DOEpatents

Bray, Lane A.; Burger, Leland L.

1994-01-01

Plutonium, strontium, and cesium found in aqueous waste solutions resulting from nuclear fuel processing are removed by contacting the waste solutions with synthetic zeolite incorporating up to about 5 wt % titanium as sodium titanate in an ion exchange system. More than 99.9% of the plutonium, strontium, and cesium are removed from the waste solutions.

Direct evidence on the existence of [Mo132]Keplerate-type species in aqueous solution.

PubMed

Roy, Soumyajit; Planken, Karel L; Kim, Robbert; Mandele, Dexx v d; Kegel, Willem K

2007-10-15

We demonstrate the existence of discrete single molecular [Mo(132)] Keplerate-type clusters in aqueous solution. Starting from a discrete spherical [Mo(132)] cluster, the formation of an open-basket-type [Mo(116)] defect structure is shown for the first time in solution using analytical ultracentrifugation sedimentation velocity experiments.

Solubilization of polycyclic aromatic hydrocarbons in micellar nonionic surfactant solutions

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

Edwards, D.A.; Luthy, R.G.; Liu, Zhongbao

1991-01-01

Experimental data are presented on the enhanced apparent solubilities of naphthalene, phenanthrene, and pyrene resulting from solubilization in aqueous solutions of four commercial, nonionic surfactants: an alkyl polyoxyethylene (POE) type, two octylphenol POE types, and a nonylphenol POE type. Apparent solubilities of the polycyclic aromatic hydrocarbon (PAH) compounds in surfactant solutions were determined by radiolabeled techniques. Solubilization of each PAH compound commenced at the surfactant critical micelle concentration and was proportional to the concentration of surfactant in micelle form. The partitioning of organic compounds between surfactant micelles and aqueous solution is characterized by a mole fraction micelle-phase/aqueous-phase partition coefficient, K{submore » m}. Values of log K{sub m} for PAH compounds in surfactant solutions of this study range from 4.57 to 6.53. Log K{sub m} appears to be a linear function of log K{sub ow} for a given surfactant solution. A knowledge of partitioning in aqueous surfactant systems is a prerequisite to understanding mechanisms affecting the behavior of hydrophobic organic compounds in soil-water systems in which surfactants play a role in contaminant remediation or facilitated transport.« less

Raman spectra of amino acids and their aqueous solutions

NASA Astrophysics Data System (ADS)

Zhu, Guangyong; Zhu, Xian; Fan, Qi; Wan, Xueliang

2011-03-01

Amino acids are the basic "building blocks" that combine to form proteins and play an important physiological role in all life-forms. Amino acids can be used as models for the examination of the importance of intermolecular bonding in life processes. Raman spectra serve to obtain information regarding molecular conformation, giving valuable insights into the topology of more complex molecules (peptides and proteins). In this paper, amino acids and their aqueous solution have been studied by Raman spectroscopy. Comparisons of certain values for these frequencies in amino acids and their aqueous solutions are given. Spectra of solids when compared to those of the solute in solution are invariably much more complex and almost always sharper. We present a collection of Raman spectra of 18 kinds of amino acids ( L-alanine, L-arginine, L-aspartic acid, cystine, L-glutamic acid, L-glycine, L-histidine, L-isoluecine, L-leucine, L-lysine, L-phenylalanine, L-methionone, L-proline, L-serine, L-threonine, L-tryptophan, L-tyrosine, L-valine) and their aqueous solutions that can serve as references for the interpretation of Raman spectra of proteins and biological materials.

STRIPPING OF URANIUM FROM ORGANIC EXTRACTANTS

DOEpatents

Crouse, D.J. Jr.

1962-09-01

A liquid-liquid extraction method is given for recovering uranium values from uranium-containing solutions. Uranium is removed from a uranium-containing organic solution by contacting said organic solution with an aqueous ammonium carbonate solution substantially saturated in uranium values. A uranium- containing precipitate is thereby formed which is separated from the organic and aqueous phases. Uranium values are recovered from this separated precipitate. (AE C)

PROCESS OF ELIMINATING HYDROGEN PEROXIDE IN SOLUTIONS CONTAINING PLUTONIUM VALUES

DOEpatents

Barrick, J.G.; Fries, B.A.

1960-09-27

A procedure is given for peroxide precipitation processes for separating and recovering plutonium values contained in an aqueous solution. When plutonium peroxide is precipitated from an aqueous solution, the supernatant contains appreciable quantities of plutonium and peroxide. It is desirable to process this solution further to recover plutonium contained therein, but the presence of the peroxide introduces difficulties; residual hydrogen peroxide contained in the supernatant solution is eliminated by adding a nitrite or a sulfite to this solution.

Application of regular associated solution model to the liquidus curves of the Sn-Te and Sn-SnS systems

NASA Astrophysics Data System (ADS)

Eric, H.

1982-12-01

The liquidus curves of the Sn-Te and Sn-SnS systems were evaluated by the regular associated solution model (RAS). The main assumption of this theory is the existence of species A, B and associated complexes AB in the liquid phase. Thermodynamic properties of the binary A-B system are derived by ternary regular solution equations. Calculations based on this model for the Sn-Te and Sn-SnS systems are in agreement with published data.

Piezoelectric Resonance Defined High Performance Sensors and Modulators

DTIC Science & Technology

2016-05-30

Lopez-Ribot, Amar S. Bhalla, Melissa Montes, Ruyan Guo. Properties of Silver and Copper Nanoparticle Containing Aqueous Suspensions and Evaluation of...Amar S. Bhalla, Ruyan Guo, “Properties of Silver and Copper Nanoparticle - Containing Aqueous Solutions and Their Anti-Biofilm Effects," (2015)Symposium...Properties of Silver and Copper Nanoparticle -Containing AqueousSolutions and Evaluation of their In Vitro Activity againstCandida albicans and

Kinetics of photobleaching of aqueous solutions of ricin agglutinin in the presence of guanidine chloride

NASA Astrophysics Data System (ADS)

Brandt, Nikolai N.; Chikishev, Andrey Y.

2002-05-01

Kinetics of background decay in Raman spectra of aqueous solutions of ricin agglutinin in the presence of guanidine chloride were measured. The differences in the kinetics of photobleaching are discussed.

Small-angle neutron scattering study of a monoclonal antibody using free-energy constraints.

PubMed

Clark, Nicholas J; Zhang, Hailiang; Krueger, Susan; Lee, Hyo Jin; Ketchem, Randal R; Kerwin, Bruce; Kanapuram, Sekhar R; Treuheit, Michael J; McAuley, Arnold; Curtis, Joseph E

2013-11-14

Monoclonal antibodies (mAbs) contain hinge-like regions that enable structural flexibility of globular domains that have a direct effect on biological function. A subclass of mAbs, IgG2, have several interchain disulfide bonds in the hinge region that could potentially limit structural flexibility of the globular domains and affect the overall configuration space available to the mAb. We have characterized human IgG2 mAb in solution via small-angle neutron scattering (SANS) and interpreted the scattering data using atomistic models. Molecular Monte Carlo combined with molecular dynamics simulations of a model mAb indicate that a wide range of structural configurations are plausible, spanning radius of gyration values from ∼39 to ∼55 Å. Structural ensembles and representative single structure solutions were derived by comparison of theoretical SANS profiles of mAb models to experimental SANS data. Additionally, molecular mechanical and solvation free-energy calculations were carried out on the ensemble of best-fitting mAb structures. The results of this study indicate that low-resolution techniques like small-angle scattering combined with atomistic molecular simulations with free-energy analysis may be helpful to determine the types of intramolecular interactions that influence function and could lead to deleterious changes to mAb structure. This methodology will be useful to analyze small-angle scattering data of many macromolecular systems.

Sorption of Ochratoxin A from Aqueous Solutions Using β-Cyclodextrin-Polyurethane Polymer

PubMed Central

Appell, Michael; Jackson, Michael A.

2012-01-01

The ability of a cyclodextrin-polyurethane polymer to remove ochratoxin A from aqueous solutions was examined by batch rebinding assays. The results from the aqueous binding studies were fit to two parameter models to gain insight into the interaction of ochratoxin A with the nanosponge material. The ochratoxin A sorption data fit well to the heterogeneous Freundlich isotherm model. The polymer was less effective at binding ochratoxin A in high pH buffer (9.5) under conditions where ochratoxin A exists predominantly in the dianionic state. Batch rebinding assays in red wine indicate the polymer is able to remove significant levels of ochratoxin A from spiked solutions between 1–10 μg·L−1. These results suggest cyclodextrin nanosponge materials are suitable to reduce levels of ochratoxin A from spiked aqueous solutions and red wine samples. PMID:22474569

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-interactive Chemicals Contained in Boundary Layer-targeted Emulsions

NASA Technical Reports Server (NTRS)

Richmond, Robert Chafee (Inventor); Schramm, Jr., Harry F. (Inventor); Defalco, Francis G. (Inventor)

2013-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

NASA Technical Reports Server (NTRS)

Defalco, Francis G. (Inventor); Richmond, Robert Chaffee (Inventor); Schramm, Jr., Harry F. (Inventor)

2017-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, water, or a water-based lubricant. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

NASA Technical Reports Server (NTRS)

Defalco, Francis G. (Inventor); Richmond, Robert Chaffee (Inventor); Schramm, Harry F., Jr. (Inventor)

2016-01-01

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Direct NMR Monitoring of Phase Separation Behavior of Highly Supersaturated Nifedipine Solution Stabilized with Hypromellose Derivatives.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2017-07-03

We investigated the phase separation behavior and maintenance mechanism of the supersaturated state of poorly water-soluble nifedipine (NIF) in hypromellose (HPMC) derivative solutions. Highly supersaturated NIF formed NIF-rich nanodroplets through phase separation from aqueous solution containing HPMC derivative. Dissolvable NIF concentration in the bulk water phase was limited by the phase separation of NIF from the aqueous solution. HPMC derivatives stabilized the NIF-rich nanodroplets and maintained the NIF supersaturation with phase-separated NIF for several hours. The size of the NIF-rich phase was different depending on the HPMC derivatives dissolved in aqueous solution, although the droplet size had no correlation with the time for which NIF supersaturation was maintained without NIF crystallization. HPMC acetate and HPMC acetate succinate (HPMC-AS) effectively maintained the NIF supersaturation containing phase-separated NIF compared with HPMC. Furthermore, HPMC-AS stabilized NIF supersaturation more effectively in acidic conditions. Solution 1 H NMR measurements of NIF-supersaturated solution revealed that HPMC derivatives distributed into the NIF-rich phase during the phase separation of NIF from the aqueous solution. The hydrophobicity of HPMC derivative strongly affected its distribution into the NIF-rich phase. Moreover, the distribution of HPMC-AS into the NIF-rich phase was promoted at lower pH due to the lower aqueous solubility of HPMC-AS. The distribution of a large amount of HPMC derivatives into NIF-rich phase induced the strong inhibition of NIF crystallization from the NIF-rich phase. Polymer distribution into the drug-rich phase directly monitored by solution NMR technique can be a useful index for the stabilization efficiency of drug-supersaturated solution containing a drug-rich phase.

Rotational dynamics of trehalose in aqueous solutions studied by depolarized light scattering

NASA Astrophysics Data System (ADS)

Gallina, M. E.; Comez, L.; Morresi, A.; Paolantoni, M.; Perticaroli, S.; Sassi, P.; Fioretto, D.

2010-06-01

High resolution depolarized light scattering spectra, extended from 0.5 to 2×104 GHz by the combined used of a dispersive and an interferometric setup, give evidence of separated solute and solvent dynamics in diluted trehalose aqueous solutions. The slow relaxation process, located in the gigahertz frequency region, is analyzed as a function of temperature and concentration and assigned to the rotational diffusion of the sugar molecule. The results are discussed in comparison with the data obtained on glucose solutions and they are used to clarify the molecular origin of some among the several relaxation processes reported in literature for oligosaccharides solutions. The concentration dependence of relaxation time and of shear viscosity are also discussed, suggesting that the main effect of carbohydrate molecules on the structural relaxation of diluted aqueous solutions is the perturbation induced on the dynamics of the first hydration shell of each solute molecule.

Immunohistochemistry for the detection of neural and inflammatory cells in equine brain tissue

PubMed Central

Liu, Junjie; Herrington, Jenna M.; Vallario, Kelsey

2016-01-01

Phenotypic characterization of cellular responses in equine infectious encephalitides has had limited description of both peripheral and resident cell populations in central nervous system (CNS) tissues due to limited species-specific reagents that react with formalin-fixed, paraffin embedded tissue (FFPE). This study identified a set of antibodies for investigating the immunopathology of infectious CNS diseases in horses. Multiple commercially available staining reagents and antibodies derived from antigens of various species for manual immunohistochemistry (IHC) were screened. Several techniques and reagents for heat-induced antigen retrieval, non-specific protein blocking, endogenous peroxidase blocking, and visualization-detection systems were tested during IHC protocol development. Boiling of slides in a low pH, citrate-based buffer solution in a double-boiler system was most consistent for epitope retrieval. Pressure-cooking, microwaving, high pH buffers, and proteinase K solutions often resulted in tissue disruption or no reactivity. Optimal blocking reagents and concentrations of each working antibody were determined. Ultimately, a set of monoclonal (mAb) and polyclonal antibodies (pAb) were identified for CD3+ (pAb A0452, Dako) T-lymphocytes, CD79αcy+ B-lymphocytes (mAb HM57, Dako), macrophages (mAb MAC387, Leica), NF-H+ neurons (mAb NAP4, EnCor Biotechnology), microglia/macrophage (pAb Iba-1, Wako), and GFAP+ astrocytes (mAb 5C10, EnCor Biotechnology). In paraffin embedded tissues, mAbs and pAbs derived from human and swine antigens were very successful at binding equine tissue targets. Individual, optimized protocols are provided for each positively reactive antibody for analyzing equine neuroinflammatory disease histopathology. PMID:26855862

The effect of arginine glutamate on the stability of monoclonal antibodies in solution.

PubMed

Kheddo, Priscilla; Tracka, Malgorzata; Armer, Jonathan; Dearman, Rebecca J; Uddin, Shahid; van der Walle, Christopher F; Golovanov, Alexander P

2014-10-01

Finding excipients which mitigate protein self-association and aggregation is an important task during formulation. Here, the effect of an equimolar mixture of l-Arg and l-Glu (Arg·Glu) on colloidal and conformational stability of four monoclonal antibodies (mAb1-mAb4) at different pH is explored, with the temperatures of the on-set of aggregation (Tagg) and unfolding (Tm1) measured by static light scattering and intrinsic fluorescence, respectively. Arg·Glu increased the Tagg of all four mAbs in concentration-dependent manner, especially as pH increased to neutral. Arg·Glu also increased Tm1 of the least thermally stable mAb3, but without similar direct effect on the Tm1 of other mAbs. Raising pH itself from 5 to 7 increased Tm1 for all four mAbs. Selected mAb formulations were assessed under accelerated stability conditions for the monomer fraction remaining in solution after storage. The aggregation of mAb3 was suppressed to a greater extent by Arg·Glu than by Arg·HCl. Furthermore, Arg·Glu suppressed the aggregation of mAb1 at neutral pH such that the fraction monomer was near to that at the more typical formulation pH of 5.5. We conclude that Arg·Glu can suppress mAb aggregation with increasing temperature/pH and, importantly, under accelerated stability conditions at weakly acidic to neutral pH. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

Aggregation of concentrated monoclonal antibody solutions studied by rheology and neutron scattering

NASA Astrophysics Data System (ADS)

Castellanos, Maria Monica; Pathak, Jai; Colby, Ralph

2013-03-01

Protein solutions are studied using rheology and scattering techniques to investigate aggregation. Here we present a monoclonal antibody (mAb) that aggregates after incubation at 40 °C (below its unfolding temperature), with a decrease in monomer purity of 6% in 10 days. The mAb solution contains surfactant and behaves as a Newtonian fluid when reconstituted into solution from the lyophilized form (before incubation at 40 °C). In contrast, mAb solutions incubated at 40 °C for 1 month exhibit shear yielding in torsional bulk rheometers. Interfacial rheology reveals that interfacial properties are controlled by the surfactant, producing a negligible surface contribution to the bulk yield stress. These results provide evidence that protein aggregates formed in the bulk are responsible for the yield stress. Small-angle neutron scattering (SANS) measurements show an increase in intensity at low wavevectors (q < 4*10-2 nm-1) that we attribute to protein aggregation, and is not observed in solutions stored at 4 °C for 3 days before the measurement. This work suggests a correlation between the aggregated state of the protein (stability) and the yield stress from rheology. Research funded by MedImmune

Structure and water exchange of the hydrated thiosulfate ion in aqueous solution using QMCF MD simulation and large angle X-ray scattering.

PubMed

Eklund, Lars; Hofer, Tomas S; Weiss, Alexander K H; Tirler, Andreas O; Persson, Ingmar

2014-09-07

Theoretical ab initio quantum mechanical charge field molecular dynamics (QMCF MD) has been applied in conjunction with experimental large angle X-ray scattering (LAXS) to study the structure and dynamics of the hydrated thiosulfate ion, S2O3(2-), in aqueous solution. The S-O and SC-ST bond distances have been determined to be 1.479(5) and 2.020(6) Å by LAXS and to be 1.478 and 2.017 Å by QMCF MD simulations, which are slightly longer than the mean values found in the solid state, 1.467 and 2.002 Å, respectively. This is due to the hydrogen bonds formed at hydration. The water dynamics show that water molecules are exchanged at the hydrated oxygen and sulfur atoms, and that the water exchange is ca. 50% faster at the sulfur atom than at the oxygen atoms with mean residence times, τ0.5, of 2.4 and 3.6 ps, respectively. From this point of view the water exchange dynamics mechanism resembles the sulfate ion, while it is significantly different from the sulfite ion. This shows that the lone electron-pair in the sulfite ion has a much larger impact on the water exchange dynamics than a substitution of an oxygen atom for a sulfur one. The LAXS data did give mean SCOaq1 and SCOaq2 distances of 3.66(2) and 4.36(10) Å, respectively, and SC-Othio and OthioOaq1, SC-ST and STOaq2 distances of 1.479(5), 2.845(10), 2.020(6) and 3.24(5) Å, respectively, giving SC-OthioOaq1 and SC-STOaq2 angles close to 110°, strongly indicating a tetrahedral geometry around the terminal thiosulfate sulfur and the oxygens, and thereby, three water molecules are hydrogen bound to each of them. The hydrogen bonds between thiosulfate oxygens and the hydrating water molecules are stronger and with longer mean residence times than those between water molecules in the aqueous bulk, while the opposite is true for the hydrogen bonds between the terminal thiosulfate sulfur and the hydrating water molecules. The hydration of all oxo sulfur ions is discussed using the detailed observations for the sulfate, thiosulfate and sulfite ions, and the structure of the hydrated peroxodisulfate ion, S2O8(2-), in aqueous solution has been determined by means of LAXS to support the general observations. The mean S-O bond distances are 1.448(2) and 1.675(5) Å to the oxo and peroxo oxygens, respectively.

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

DOEpatents

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

1988-01-01

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

Molecular dynamics simulation studies of the interactions between ionic liquids and amino acids in aqueous solution.

PubMed

Tomé, Luciana I N; Jorge, Miguel; Gomes, José R B; Coutinho, João A P

2012-02-16

Although the understanding of the influence of ionic liquids (ILs) on the solubility behavior of biomolecules in aqueous solutions is relevant for the design and optimization of novel biotechnological processes, the underlying molecular-level mechanisms are not yet consensual or clearly elucidated. In order to contribute to the understanding of the molecular interactions established between amino acids and ILs in aqueous media, classical molecular dynamics (MD) simulations were performed for aqueous solutions of five amino acids with different structural characteristics (glycine, alanine, valine, isoleucine, and glutamic acid) in the presence of 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonyl imide. The results from MD simulations enable to relate the properties of the amino acids, namely their hydrophobicity, to the type and strength of their interactions with ILs in aqueous solutions and provide an explanation for the direction and magnitude of the solubility phenomena observed in [IL + amino acid + water] systems by a mechanism governed by a balance between competitive interactions of the IL cation, IL anion, and water with the amino acids.

DISSOLUTION OF LANTHANUM FLUORIDE PRECIPITATES

DOEpatents

Fries, B.A.

1959-11-10

A plutonium separatory ore concentration procedure involving the use of a fluoride type of carrier is presented. An improvement is given in the derivation step in the process for plutonium recovery by carrier precipitation of plutonium values from solution with a lanthanum fluoride carrier precipitate and subsequent derivation from the resulting plutonium bearing carrier precipitate of an aqueous acidic plutonium-containing solution. The carrier precipitate is contacted with a concentrated aqueous solution of potassium carbonate to effect dissolution therein of at least a part of the precipitate, including the plutonium values. Any remaining precipitate is separated from the resulting solution and dissolves in an aqueous solution containing at least 20% by weight of potassium carbonate. The reacting solutions are combined, and an alkali metal hydroxide added to a concentration of at least 2N to precipitate lanthanum hydroxide concomitantly carrying plutonium values.

Sorption of tetracycline antibiotics on hyper-crosslinked polystyrene from aqueous and aqueous-organic media

NASA Astrophysics Data System (ADS)

Udalova, A. Yu.; Dmitrienko, S. G.; Apyari, V. V.

2015-06-01

The sorption of tetracycline, oxytetracycline, chlortetracycline, and doxycycline on hyper-cross-linked polystyrene from aqueous and aqueous-organic solutions is studied under static and dynamic conditions in order to extend the range of the sorbents suitable for sorption isolation and the preconcentration of tetracycline antibiotics. Features of tetracycline sorption depending on the acidity of a solution and the nature and concentration of the compounds are explained. It is shown that hyper-crosslinked polystyrene can be used for the group sorption preconcentration of these compounds.

Solvation and thermal effects on the optical properties of naturaldyes: a case study on the flavylium cyanin

NASA Astrophysics Data System (ADS)

Calzolari, Arrigo; Malcioglu, Baris; Gebauer, Ralph; Varsano, Daniele; Baroni, Stefano

2011-03-01

We present a first-principles study of the effects of both hydration and thermal dynamics on the optical properties of a natural anthocyanin dye, namely, cyanin (Cya), in aqueous solution. We combine Car-Parrinello molecular dynamics and time-dependent density functional theory (TDDFT) approaches to simulate the time evolution of UV-vis spectrum of the hydrated Cya molecule at room temperature [2,3]. The spectrum of the dye calculated in the gas phase is characterized by two peaks in the red and in the blue, which would bring about a greenish hue incompatible with the dark purple coloration observed in nature. Describing the effect of the water solvent through a polarizable continuum model does not modify qualitatively the resulting picture. An explicit simulation of both solvent and thermal effects using ab-initio molecular dynamics results instead in a spectrum that is compatible with the observed coloration. This result is analyzed in terms of the spectroscopic effects of molecular distortions, induced by thermal fluctuations.

NEPTUNIUM SOLVENT EXTRACTION PROCESS

DOEpatents

Dawson, L.R.; Fields, P.R.

1959-10-01

The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

The effect of deep eutectic solvents on catalytic function and structure of bovine liver catalase.

PubMed

Harifi-Mood, Ali Reza; Ghobadi, Roohollah; Divsalar, Adeleh

2017-02-01

Aqueous solutions of reline and glyceline, the most common deep eutectic solvents, were used as a medium for Catalase reaction. By some spectroscopic methods such as UV-vis, fluorescence and circular dichroism (CD) function and structure of Catalase were investigated in aqueous solutions of reline and glyceline. These studies showed that the binding affinity of the substrate to the enzyme increased in the presence of 100mM glyceline solution, which contrasts with reline solution that probably relates to instructive changes in secondary structure of protein. Meanwhile, enzyme remained nearly 70% and 80% active in this concentration of glyceline and reline solutions respectively. In the high concentration of DES solutions, enzyme became mainly inactive but surprisingly stayed in nearly 40% active in choline chloride solution, which is the common ion species in reline and glyceline solvents. It is proposed that the chaotropic nature of choline cation might stop the reducing trend of activity in concentrated choline chloride solutions but this instructive effect is lost in aqueous deep eutectic solvents. In this regard, the presence of various concentrations of deep eutectic solvents in the aqueous media of human cells would be an activity adjuster for this important enzyme in its different operation conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydration and dielectrical properties of aqueous pyrrolidinium trifluoroacetate solutions

NASA Astrophysics Data System (ADS)

Lyashchenko, A. K.; Balakaeva, I. V.; Simonova, Yu. A.; Timofeeva, L. M.

2017-10-01

Results from microwave measurements of the dielectrical properties of aqueous pyrrolidinium trifluoroacetate solutions at maximum water dispersion frequencies (13-25 GHz) and temperatures of 288, 298, and 308 K are given. The static dielectrical constants, times, and activation parameters of the dielectrical relaxation of solutions are calculated. The enthalpy and time of dielectrical relaxation activation are increased by deceleration of the motion of water molecules in the hydrate shells of ions. The changes in dielectrical parameters are in this case minimal in a series of aqueous solutions of diallylammonium salts with cations of different structures and degrees of substitution. It is shown that pyrrolidinium ions are characterized by weak hydrophobic hydration.

Marangoni Flow Induced Evaporation Enhancement on Binary Sessile Drops.

PubMed

Chen, Pin; Harmand, Souad; Ouenzerfi, Safouene; Schiffler, Jesse

2017-06-15

The evaporation processes of pure water, pure 1-butanol, and 5% 1-butanol aqueous solution drops on heated hydrophobic substrates are investigated to determine the effect of temperature on the drop evaporation behavior. The evolution of the parameters (contact angle, diameter, and volume) during evaporation measured using a drop shape analyzer and the infrared thermal mapping of the drop surface recorded by an infrared camera were used in investigating the evaporation process. The pure 1-butanol drop does not show any thermal instability at different substrate temperatures, while the convection cells created by the thermal Marangoni effect appear on the surface of the pure water drop from 50 °C. Because 1-butanol and water have different surface tensions, the infrared video of the 5% 1-butanol aqueous solution drop shows that the convection cells are generated by the solutal Marangoni effect at any substrate temperature. Furthermore, when the substrate temperature exceeds 50 °C, coexistence of the thermal and solutal Marangoni flows is observed. By analyzing the relation between the ratio of the evaporation rate of pure water and 1-butanol aqueous solution drops and the Marangoni number, a series of empirical equations for predicting the evaporation rates of pure water and 1-butanol aqueous solution drops at the initial time as well as the equations for the evaporation rate of 1-butanol aqueous solution drop before the depletion of alcohol are derived. The results of these equations correspond fairly well to the experimental data.

METHOD OF SEPARATING PLUTONIUM

DOEpatents

Heal, H.G.

1960-02-16

BS>A method of separating plutonium from aqueous nitrate solutions of plutonium, uranium. and high beta activity fission products is given. The pH of the aqueous solution is adjusted between 3.0 to 6.0 with ammonium acetate, ferric nitrate is added, and the solution is heated to 80 to 100 deg C to selectively form a basic ferric plutonium-carrying precipitate.

Cesium recovery from aqueous solutions

DOEpatents

Goodhall, C. A.

1960-09-13

A process for recovering cesium from aqueous solutions is given in which precipitation on zinc ferricyanide is used. The precipitation is preferably carried out in solutions containing at least 0.0004M zinc ferricyanide, an acidity ranging from 0.2N mineral acid to 0.61N acid deficiency, and 1 to 2.5M aluminum nitrate. (D.L.C.)

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

PubMed

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

2013-12-19

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

Separations by supported liquid membrane cascades

DOEpatents

Danesi, P.R.

1983-09-01

The invention describes a new separation technique which leads to multi-stage operations by the use of a series (a cascade) of alternated carrier-containing supported-liquid cation exchanger extractant and a liquid anion exchanger extractant (or a neutral extractant) as carrier. The membranes are spaced between alternated aqueous electrolytic solutions of different composition which alternatively provide positively charged extractable species and negatively charged (or zero charged) extractable species, of the chemical species to be separated. The alternated aqueous electrolytic solutions in addition to providing the driving force to the process, simultaneously function as a stripping solution from one type of membrane and as an extraction-promoting solution for the other type of membrane. The aqueous electrolytic solution and the supported liquid membranes are arranged to provide a continuous process.

Quenching characteristics of bathocuproinedisulfonic acid, disodium salt in aqueous solution and copper sulfate plating solution

NASA Astrophysics Data System (ADS)

Koga, Toshiaki; Hirakawa, Chieko; Takeshita, Michinori; Terasaki, Nao

2018-04-01

Bathocuproinedisulfonic acid, disodium salt (BCS) is generally used to detect Cu(I) through a color reaction. We newly found BCS fluorescence in the visible blue region in an aqueous solution. However, the fluorescence mechanism of BCS is not well known, so we should investigate its fundamental information. We confirmed that the characteristics of fluorescence are highly dependent on the molecular concentration and solvent properties. In particular, owing to the presence of the copper compound, the fluorescence intensity extremely decreases. By fluorescence quenching, we observed that a copper compound concentration of 10-6 mol/L or less could easily be measured in an aqueous solution. We also observed BCS fluorescence in copper sulfate plating solution and the possibility of detecting monovalent copper by fluorescence reabsorption.

DISTRIBUTION OF URANIUM, ZIRCONIUM, NIOBIUM, RUTHENIUM AND CERIUM BETWEEN NITRIC ACID SOLUTIONS AND 10% TLA-5% OCTYL ALCOHOL/SHELL SOL-T

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

Lopez-Menchero, E.; Centeno, J.; Magni, G.

1962-03-01

The extraction of traces of Ru, Zr, Nb, Ce, and U at low concentrations (5 mg/l in aqueous solution) from nitric acid solutions using trilauryl amine (TLA) has been experimentally studied. TLA will eventually be used for final purification of plutonium. Room-temperature data on plutonium contaminant distribution between aqueous solutions of varying nitric acid concentrations and a Shellsol-T solution containing l0% TlA and 5% octyl alcohol are presented. Within the temperature and nitric acid concentration ranges tested, the extractability of uranium increased with increased acid concentrations, although acid concentration in the aqueous phase had no effect on the decontamination factorsmore » for the main fission products. (H.G.G.)« less

End-Member Formulation of Solid Solutions and Reactive Transport

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

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

First-principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase

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

Yoon, Yeohoon; Rousseau, Roger J.; Weber, Robert S.

2014-07-23

The effects of aqueous phase on the reactivity of phenol hydrogenation over Pt and Ni catalysts were investigated using density functional theory based ab initio molecular dynamics (AIMD) calculations. The adsorption of phenol and the first hydrogenation steps via three carbon positions (ortho, meta and para) with respect to the phenolic OH group were studied in both vacuum and liquid phase conditions. To gain insight into how the aqueous phase affects the metal catalyst surface, increasing water environments including singly adsorbed water molecule, mono- (9 water molecules), double layers (24 water molecules), and the bulk liquid water which (52 watermore » molecules) on the Pt(111) and the Ni(111) surfaces were modeled. Compared to the vacuum/metal interfaces, AIMD simulation results suggest that the aqueous Pt(111) and Ni(111) interfaces have a lower metal work function in the order of 0.8 - 0.9 eV, thus, making the metals in aqueous phase stronger reducing agents and poorer oxidizing agents. Phenol adsorption from the aqueous phase is found to be slightly weaker that from the vapor phase. The first hydrogenation step of phenol at the ortho position of the phenolic ring is slightly favored over the other two positions. The polarization induced by the surrounding water molecules and the solvation effect play important roles in stabilizing the transition states associated with phenol hydrogenation by lowering the barriers of 0.1 - 0.4 eV. The detailed discussion on the basis of the interfacial electrostatics from the current study is very useful to understand the nature of a broader class of metal catalyzed reactions in liquid solution phase. This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences and Office of Energy Efficiency and Renewable Energy. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.« less

Thin film superconductors and process for making same

DOEpatents

Nigrey, P.J.

1988-01-21

A process for the preparation of oxide superconductors from high-viscosity non-aqueous solution is described. Solutions of lanthanide nitrates, alkaline earth nitrates and copper nitrates in a 1:2:3 stoichiometric ratio, when added to ethylene glycol containing citric acid solutions, have been used to prepare highly viscous non-aqueous solutions of metal mixed nitrates-citrates. Thin films of these compositions are produced when a layer of the viscous solution is formed on a substrate and subjected to thermal decomposition.

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

DOEpatents

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

1959-12-01

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

METHOD OF REDUCING PLUTONIUM COMPOUNDS

DOEpatents

Johns, I.B.

1958-06-01

A method is described for reducing plutonium compounds in aqueous solution from a higher to a lower valence state. This reduction of valence is achieved by treating the aqueous solution of higher valence plutonium compounds with hydrogen in contact with an activated platinum catalyst.

SURFACE TREATMENT OF MOLYBDENUM METAL

DOEpatents

Coffer, C.O.

1961-12-01

A process of descaling molybdenum articles comprises first immersing them in an aqueous sodium hydroxide-potassium permanganate solution of between 60 and 85 deg C, rinsing, and then immersing them in an aqueous solution containing a mixture of sulfuric, hydrochloric, and chromic acids.

PHOTOREACTION OF VALEROPHENONE IN AQUEOUS SOLUTION

EPA Science Inventory

Kinetics and products of the photoreaction of the phenyl ketone valerophenone were investigated as a function of temperature, pH, and wavelength in aqueous solution. Under these conditions (<10-4M), the photoreactions are pseudo-first-order with respect to valerophenone concentra...

Investigation into the temporal stability of aqueous standard solutions of psilocin and psilocybin using high performance liquid chromatography.

PubMed

Anastos, N; Barnett, N W; Pfeffer, F M; Lewis, S W

2006-01-01

This paper reports an investigation into the temporal stability of aqueous solutions of psilocin and psilocybin reference drug standards over a period of fourteen days. This study was performed using high performance liquid chromatography utilising a (95:5% v/v) methanol: 10 mM ammonium formate, pH 3.5 mobile phase and absorption detection at 269 nm. It was found that the exclusion of light significantly prolonged the useful life of standards, with aqueous solutions of both psilocin and psilocybin being stable over a period of seven days.

Fabrication of metal nanoshells

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo (Inventor); King, Glen C. (Inventor); Lillehei, Peter T. (Inventor); Park, Yeonjoon (Inventor); Elliott, Jr., James R. (Inventor); Choi, Sang H. (Inventor); Chu, Sang-Hyon (Inventor)

2012-01-01

Metal nanoshells are fabricated by admixing an aqueous solution of metal ions with an aqueous solution of apoferritin protein molecules, followed by admixing an aqueous solution containing an excess of an oxidizing agent for the metal ions. The apoferritin molecules serve as bio-templates for the formation of metal nanoshells, which form on and are bonded to the inside walls of the hollow cores of the individual apoferritin molecules. Control of the number of metal atoms which enter the hollow core of each individual apoferritin molecule provides a hollow metal nonparticle, or nanoshell, instead of a solid spherical metal nanoparticle.

Enthalpies of Dissolution of Crystalline Naproxen Sodium in Water and Potassium Hydroxide Aqueous Solutions at 298 K

NASA Astrophysics Data System (ADS)

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

2018-03-01

The enthalpies of dissolution of crystalline naproxen sodium in water and aqueous solutions of KOH at 298.15 K are measured by direct calorimetric means in a wide range of concentrations. The acid-base properties of naproxen sodium at ionic strength I 0 and I = 0.1 (KNO3) and a temperature of 298.15 K are studied by spectrophotometric means. The concentration and thermodynamic dissociation constants are determined. The standard enthalpies of the formation of naproxen sodium and the products of its dissociation in aqueous solution are calculated.

Solubility of mixtures of hydrogen sulfide and carbon dioxide in aqueous N-methyldiethanolamine solutions

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

Jou, Fang Yuan; Carroll, J.J.; Mather, A.E.

1993-01-01

Aqueous solutions of alkanolamines are commonly used to strip acid gases (H[sub 2]S and CO[sub 2]) from streams contaminated with these components. The two most widely used amines are monoethanolamine (MEA) and diethanolamine (DEA). The solubilities of mixtures of hydrogen sulfide and carbon dioxide in a 35 wt% (3.04 kmol/m[sup 3]) aqueous solution of N-methyldiethanolamine at 40 and 100C have been measured. Partial pressures of the acid gases ranged from 0.006 to 101 kPa at 40C and from 4 to 530 kPa at 100C.

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

PubMed

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

2013-09-11

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

Simplified Production of Organic Compounds Containing High Enantiomer Excesses

NASA Technical Reports Server (NTRS)

Cooper, George W. (Inventor)

2015-01-01

The present invention is directed to a method for making an enantiomeric organic compound having a high amount of enantiomer excesses including the steps of a) providing an aqueous solution including an initial reactant and a catalyst; and b) subjecting said aqueous solution simultaneously to a magnetic field and photolysis radiation such that said photolysis radiation produces light rays that run substantially parallel or anti-parallel to the magnetic field passing through said aqueous solution, wherein said catalyst reacts with said initial reactant to form the enantiomeric organic compound having a high amount of enantiomer excesses.

Quantum Chemical Simulation of the Interaction of Functional Groups in Polyurethanes with 3 d-Metal Ions During Their Extraction from Aqueous Solutions

NASA Astrophysics Data System (ADS)

Ksenofontov, M. A.; Bobkova, E. Yu.; Shundalau, M. B.; Ostrovskaya, L. E.; Vasil'eva, V. S.

2017-11-01

The interaction of the functional groups in the polyurethane foam adsorbent Penopurm® with the cations of some 3d-metals upon their extraction from aqueous solutions has been studied by atomic emission spectroscopy, UV/Vis and vibrational IR spectroscopy, and quantum chemical simulation using density functional theory. Penopurm® absorbs 3d-metal cations from aqueous solutions in the pH range 5-7. Some spectral criteria have been found indicating a predominant interaction of Ni2+ ions with various fragments of the polyurethane foam structure.

Micelle formation of nonionic surfactants in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate: surfactant chain length dependence of the critical micelle concentration.

PubMed

Inoue, Tohru; Yamakawa, Haruka

2011-04-15

Micellization behavior was investigated for polyoxyethylene-type nonionic surfactants with varying chain length (C(n)E(m)) in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)). Critical micelle concentration (cmc) was determined from the variation of (1)H NMR chemical shift with the surfactant concentration. The logarithmic value of cmc decreased linearly with the number of carbon atoms in the surfactant hydrocarbon chain, similarly to the case observed in aqueous surfactant solutions. However, the slope of the straight line is much smaller in bmimBF(4) than in aqueous solution. Thermodynamic parameters for micelle formation estimated from the temperature dependence of cmc showed that the micellization in bmimBF(4) is an entropy-driven process around room temperature. This behavior is also similar to the case in aqueous solution. However, the magnitude of the entropic contribution to the overall micellization free energy in bmimBF(4) is much smaller compared with that in aqueous solution. These results suggest that the micellization in bmimBF(4) proceeds through a mechanism similar to the hydrophobic interaction in aqueous surfactant solutions, although the solvophobic effect in bmimBF(4) is much weaker than the hydrophobic effect. Copyright © 2011 Elsevier Inc. All rights reserved.

Hierarchical viscosity of aqueous solution of tilapia scale collagen investigated via dielectric spectroscopy between 500 MHz and 2.5 THz

PubMed Central

Kawamata, H.; Kuwaki, S.; Mishina, T.; Ikoma, T.; Tanaka, J.; Nozaki, R.

2017-01-01

Aqueous solutions of biomolecules such as proteins are very important model systems for understanding the functions of biomolecules in actual life processes because interactions between biomolecules and the surrounding water molecules are considered to be important determinants of biomolecules’ functions. Globule proteins have been extensively studied via dielectric spectroscopy; the results indicate three relaxation processes originating from fluctuations in the protein molecule, the bound water and the bulk water. However, the characteristics of aqueous solutions of collagens have rarely been investigated. In this work, based on broadband dielectric measurements between 500 MHz and 2.5 THz, we demonstrate that the high viscosity of a collagen aqueous solution is due to the network structure being constructed of rod-like collagen molecules surrounding free water molecules and that the water molecules are not responsible for the viscosity. We determine that the macroscopic viscosity is related to the mean lifetime of the collagen-collagen interactions supporting the networks and that the local viscosity of the water surrounded by the networks is governed by the viscosity of free water as in the bulk. This hierarchical structure in the dynamics of the aqueous solution of biomolecules has been revealed for the first time. PMID:28345664

Exploring the speed and performance of molecular replacement with AMPLE using QUARK ab initio protein models

PubMed Central

Keegan, Ronan M.; Bibby, Jaclyn; Thomas, Jens; Xu, Dong; Zhang, Yang; Mayans, Olga; Winn, Martyn D.; Rigden, Daniel J.

2015-01-01

AMPLE clusters and truncates ab initio protein structure predictions, producing search models for molecular replacement. Here, an interesting degree of complementarity is shown between targets solved using the different ab initio modelling programs QUARK and ROSETTA. Search models derived from either program collectively solve almost all of the all-helical targets in the test set. Initial solutions produced by Phaser after only 5 min perform surprisingly well, improving the prospects for in situ structure solution by AMPLE during synchrotron visits. Taken together, the results show the potential for AMPLE to run more quickly and successfully solve more targets than previously suspected. PMID:25664744

Approaches to ab initio molecular replacement of α-helical transmembrane proteins.

PubMed

Thomas, Jens M H; Simkovic, Felix; Keegan, Ronan; Mayans, Olga; Zhang, Chengxin; Zhang, Yang; Rigden, Daniel J

2017-12-01

α-Helical transmembrane proteins are a ubiquitous and important class of proteins, but present difficulties for crystallographic structure solution. Here, the effectiveness of the AMPLE molecular replacement pipeline in solving α-helical transmembrane-protein structures is assessed using a small library of eight ideal helices, as well as search models derived from ab initio models generated both with and without evolutionary contact information. The ideal helices prove to be surprisingly effective at solving higher resolution structures, but ab initio-derived search models are able to solve structures that could not be solved with the ideal helices. The addition of evolutionary contact information results in a marked improvement in the modelling and makes additional solutions possible.

SEPARATION OF PLUTONIUM VALUES FROM OTHER METAL VALUES IN AQUEOUS SOLUTIONS BY SELECTIVE COMPLEXING AND ADSORPTION

DOEpatents

Beaton, R.H.

1960-06-28

A process is given for separating tri- or tetravalent plutonium from fission products in an aqueous solution by complexing the fission products with oxalate, tannate, citrate, or tartrate anions at a pH value of at least 2.4 (preferably between 2.4 and 4), and contacting a cation exchange resin with the solution whereby the plutonium is adsorbed while the complexed fission products remain in solution.

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

PubMed

Liaw, Horng-Jang; Chiu, Yi-Yu

2003-07-18

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

Structure of Agaricus spp. fucogalactans and their anti-inflammatory and antinociceptive properties.

PubMed

Komura, Dirce L; Carbonero, Elaine R; Gracher, Ana Helena P; Baggio, Cristiane H; Freitas, Cristina S; Marcon, Rodrigo; Santos, Adair R S; Gorin, Philip A J; Iacomini, Marcello

2010-08-01

Fucogalactans from Agaricus brasiliensis (EPF-Ab) and A. bisporus var. hortensis (EPF-Ah) were prepared via by aqueous extraction and a purification procedure. EPF-Ab had M(w) 19.4 x 10(3)g/mol and EPF-Ah M(w) 31.1 x 10(3)g/mol. EPF-Ab had a (1-->6)-linked alpha-D-Galp main-chain partially substituted in O-2 by non-reducing end-units of alpha-L-Fucp. EPF-Ah had a similar main-chain with O-2 substitution, but was partially methylated at HO-3, as well as having 2.5% non-reducing end-units of beta-D-Gal. In mice, EPF-Ab gave 39% antinociceptive inhibition (ID(50)>100mg/kg) and no anti-inflammatory activity. EPF-Ah also gave an inhibition of 39% at ID(50) 0.33 mg/kg and also inhibited by 61% (ID(50) 5.0mg/kg) total cell migration and by 32% peritoneal capillary permeability, which is related to the anti-inflammatory effect. The small differences in chemical structure in these polysaccharides thus modified their biological activities. (c) 2010. Published by Elsevier Ltd.

Topical drug delivery to the eye: dorzolamide.

PubMed

Loftsson, Thorsteinn; Jansook, Phatsawee; Stefánsson, Einar

2012-11-01

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

Acidities of Water and Methanol in Aqueous Solution and DMSO

ERIC Educational Resources Information Center

Gao, Daqing

2009-01-01

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

Effects of Metal Ions on Viscosity of Aqueous Sodium Carboxylmethylcellulose Solution and Development of Dropping Ball Method on Viscosity

ERIC Educational Resources Information Center

Set, Seng; Ford, David; Kita, Masakazu

2015-01-01

This research revealed that metal ions with different charges could significantly affect the viscosity of aqueous sodium carboxylmethylcellulose (CMC) solution. On the basis of an Ostwald viscometer, an improvised apparatus using a dropping ball for examining the viscosity of liquids/solutions has been developed. The results indicate that the…

Evaluation of the antibacterial activity of a cationic polymer in aqueous solution with a convenient electrochemical method.

PubMed

Wang, Yihong; Guo, Qing; Wang, Huafu; Qian, Kun; Tian, Liang; Yao, Chen; Song, Wei; Shu, Weixia; Chen, Ping; Qi, Jinxu

2017-02-01

Quaternized chitosan is a cationic biopolymer with good antibacterial activity, biocompatibility, and biodegradability, and it has been widely applied in many fields. We have developed a convenient method to evaluate the antibacterial activity of hydroxypropyltrimethylammonium chloride chitosan (HACC) with a nonionic surfactant poloxamer in aqueous solution by monitoring the change of the oxidation peak current in cyclic voltammetry. Increasing values of the oxidation peak current were positively correlated with the antibacterial activity of HACC-poloxamer solutions. Optical microscope images, the zeta potential, and fluorescence spectroscopy showed that the aggregation state of HACC-poloxamer was related to the ratio of the two polymers and also to the antibacterial activity and oxidation peak current. At an HACC-to-poloxamer ratio of 1:0.75, the maximum surface charge density and the smooth edge of HACC-poloxamer aggregates can accelerate diffusion in aqueous solution. It is expected that this convenient method can be applied for a quick evaluation of the antibacterial activity of cationic biopolymers in aqueous solution. Graphical Abstract The cyclic voltammograms of MB in HACC/poloxamer solution, and the antibacterial efficiency against S. aureus after incubated with HACC (a) and 1/0.75 of HACC/poloxamer (b).

Radiosterilization of drugs in aqueous solutions may be achieved by the use of radioprotective excipients.

PubMed

Maquille, Aubert; Jiwan, Jean-Louis Habib; Tilquin, Bernard

2008-02-12

The aim of this study was to assess the feasibility of radiosterilization of drugs aqueous solutions and to evaluate the effects of some additives, such as mannitol, nicotinamide and pyridoxine, which might protect the drug from degradation. Metoclopramide was selected as a model drug. The structures of the degradation products were determined to gain insight on the radiolysis mechanisms in aqueous solution in order to design strategies to lower the drug degradation. Metoclopramide hydrochloride aqueous solutions with and without excipients were irradiated either with gamma rays or high-energy electrons. HPLC-DAD was used to measure the loss of chemical potency and to quantify the degradation products which were also characterized by LC-APCI-MS-MS. Metoclopramide recovery for gamma and electron beam-irradiated solutions containing either mannitol, pyridoxine or nicotinamide meets the pharmacopoeial specifications for metoclopramide content up to a 15 kGy irradiation so that metoclopramide solutions containing these excipients might be radiosterilized at 15 kGy either with gamma rays or high-energy electrons. Structures are proposed for the majority of radiolysis products. Similar radiolysis products were detected for gamma and electron beam irradiations but the chromatographic profiles were different (differences in the distribution of radiolysis products).

Aqueous pathways dominate permeation of solutes across Pisum sativum seed coats and mediate solute transport via diffusion and bulk flow of water.

PubMed

Niemann, Sylvia; Burghardt, Markus; Popp, Christian; Riederer, Markus

2013-05-01

The permeability of seed coats to solutes either of biological or anthropogenic origin plays a major role in germination, seedling growth and seed treatment by pesticides. An experimental set-up was designed for investigating the mechanisms of seed coat permeation, which allows steady-state experiments with isolated seed coats of Pisum sativum. Permeances were measured for a set of organic model compounds with different physicochemical properties and sizes. The results show that narrow aqueous pathways dominate the diffusion of solutes across pea seed coats, as indicated by a correlation of permeances with the molecular sizes of the compounds instead of their lipophilicity. Further indicators for an aqueous pathway are small size selectivity and a small effect of temperature on permeation. The application of an osmotic water potential gradient across isolated seed coats leads to an increase in solute transfer, indicating that the aqueous pathways form a water-filled continuum across the seed coat allowing the bulk flow of water. Thus, the uptake of organic solutes across pea testae has two components: (1) by diffusion and (2) by bulk water inflow, which, however, is relevant only during imbibition. © 2012 Blackwell Publishing Ltd.

Development of a Compact and Efficient Ice Thermal Energy Storage Vessel

NASA Astrophysics Data System (ADS)

Sasaguchi, Kengo; Ishikawa, Masatoshi; Muta, Kenji; Yoshino, Kiyotaka; Hayashi, Hiroko; Baba, Yoshiyuki

In the present study, the authors propose the use of a low concentration aqueous solution as phase change material for static-type ice-storage-vessels, instead of pure water commonly used today. If an aqueous solution with low concentration is used, even when a large amount of solution (aqueous ethylene glycol in this study) is solidified and bridging of ice developed around cold tubes occurs, the pressure increase could be prevented by the existence of a continuous liquid phase in the solid-liquid two-phase layer (mushy layer) which opens to an air gap at the top of a vessel. Therefore, one can continue to solidify an aqueous solution after bridging, achieving a high ice packing factor (IPF). First, experiments using small-scale test cells have been conducted to confirm the present idea, and then we have performed experiments using a large vessel with an early practical size. It was seen that a large pressure increase is prevented for the initial concentration of the solution C0 of 1.0%, and IPF obtained using the solution is much greater than 0.65 using pure water for which the solidification must be stopped before the bridging.

Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains

PubMed Central

2017-01-01

The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer’s side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics. PMID:28979937

Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains.

PubMed

Schmatz, Brian; Yuan, Zhibo; Lang, Augustus W; Hernandez, Jeff L; Reichmanis, Elsa; Reynolds, John R

2017-09-27

The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer's side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics.

Predicting the electronic properties of aqueous solutions from first-principles

NASA Astrophysics Data System (ADS)

Schwegler, Eric; Pham, Tuan Anh; Govoni, Marco; Seidel, Robert; Bradforth, Stephen; Galli, Giulia

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum-mechanical methods. Yet it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. Here we propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, based on the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results for the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecular dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of their electronic properties, including excitation energies, of the solvent and solutes. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies. Part of this work was performed under the auspices of the U.S. Department of Energy at LLNL under Contract DE-AC52-07A27344.

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

NASA Astrophysics Data System (ADS)

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

2014-07-01

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

REMOVAL OF CESIUM FROM AQUEOUS SOLUTIONS BY ADSORPTION

DOEpatents

Knoll, K.C.

1963-07-16

A process of removing microquantities of cesium from aqueous solutions also containing macroquantities of other ions by adsorption on clinoptilolite is described. The invention resides in the pretreatment of the clinoptilolite by heating at 400 deg C and cooling prior to use. (AEC)

Highly efficient conductivity modulation of cinnamate-based light-responsive ionic liquids in aqueous solutions.

PubMed

Yang, Jie; Wang, Huiyong; Wang, Jianji; Zhang, Yue; Guo, Zhongjia

2014-12-11

A new class of cinnamate-based light-responsive ionic liquids was synthesized and characterized, and these ionic liquids with longer alkyl chains showed a remarkable increase in ionic conductivity under UV light irradiation in aqueous solutions.

EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

DOEpatents

Furman, N.H.; Mundy, R.J.

1957-12-10

An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

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

PubMed

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

2004-03-01

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

Cr(III) solubility in aqueous fluids at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Watenphul, Anke; Schmidt, Christian; Jahn, Sandro

2014-02-01

Trivalent chromium is generally considered relatively insoluble in aqueous fluids and melts. However, numerous counterexamples in nature indicate Cr(III) mobilization by aqueous fluids during metamorphism or hydrothermal alteration of chromite-bearing rocks, or by pegmatite melts. So far, very little is known about the chromium concentrations and speciation in such fluids. In this study, the solubility of eskolaite (Cr2O3) in 1.6-4.2 m aqueous HCl solutions was determined in situ at elevated pressures up to 1 GPa and temperatures ranging between 400 and 700 °C using synchrotron micro-X-ray fluorescence spectroscopy (μ-XRF). Determined concentrations of dissolved Cr ranged between about 900-18,000 ppm, with the highest concentrations found at 500 °C and 861 MPa. The Cr(III) solubility in aqueous HCl fluids is retrograde in the studied temperature range and increases with pressure. In addition, Cr(III) complexation in these fluids was explored by Raman spectroscopy on a 12.3 mass% HCl fluid in equilibrium with eskolaite at 400 and 600 °C, 0.3-1.6 GPa. All spectra show two prominent Cr-Cl stretching bands at about 275 and 325 cm-1, which display some fine structure, and in some spectra weak bands in the region between 380 and 500 cm-1. The sum of the integrated intensities of the two dominant bands reveals qualitatively the same changes with temperature along an isochore, with pressure at constant temperature, and with the time required for equilibration as the Cr(III) concentrations in the fluid determined by μ-XRF. Complementary ab initio molecular dynamics simulations of a 4 m HCl solution at two different densities (0.8 and 0.97 g/cm3) and temperatures (427 and 727 °C) were performed to investigate the vibrational properties of various(O)y3-x and (O)y(OH)z3-x-z complexes with 3⩽x+z⩽4 and 0⩽y⩽2. Quasi-normal mode analysis reveals that both the tetrahedral symmetric and antisymmetric Cr-Cl stretching vibrations of CrCl4(H2O)0-2- have characteristic frequencies in the range of the two strongest experimentally observed Raman bands, whereas Cr-O stretching vibrations of hydroxy-chloride complexes occur at wavenumbers above 400 cm-1. Solubility and complexation of Cr(III) depend strongly on the activities of Cl- and H+. At high H+ and Cl- activity, the results are consistent with CrCl(H2O)0-2-1-0 complexes as major Cr(III) species, the Cr coordination number of which increases with pressure by becoming more aquated. At low Cl- activity, i.e. in our study at high-temperature low-pressure conditions, the data indicate mixed CrClx((OH)z3-x-z complexes with Cl-Cr ratios less than three. In situ μ-XRF solubility experiments conducted with eskolaite + (H2O + 29 mass% Na2CO3) and kosmochlor + (H2O + 44 mass% Na2Si3O7) resulted in dissolved Cr concentrations at or below the detection limit of 500 ppm. Thus, acidic chloridic fluids seem to be more efficient agents for Cr(III) mobilization and transport at crustal conditions than aqueous alkali carbonate or silicate solutions.

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

Popa, C. L.; Ciobanu, C. S.; Predoi, D., E-mail: dpredoi@gmail.com

The aim of this study was to synthetize new nanoparticles based on methyltrimethoxysilane coated hydroxyapatite (MTHAp) for lead removal in aqueous solutions. The morphological and compositional analysis of MTHAp was investigated by scanning electron microscopy (SEM) equipped with an energy dispersive X-ray spectrometer (EDS). Removal experiments of Pb{sup 2+} ions were carried out in aqueous solutions with controlled concentration of Pb{sup 2+} and at fixed pH of 5. After the removal experiment of Pb{sup 2+} ions from solutions, porous hydroxyapatite nanoparticles were transformed into PbMTHAp-5 via the adsorption of Pb{sup 2+} ions followed by a cation exchange reaction. Our resultsmore » demonstrate that the porous hydroxyapatite nanoparticles can be used as an adsorbent for removing Pb{sup 2+} ions from aqueous solution.« less

Thermochemical analysis of intermolecular interactions between N-acetylglycine and polyols in aqueous solutions

NASA Astrophysics Data System (ADS)

Mezhevoi, I. N.; Badelin, V. G.

2017-05-01

The integral enthalpies of dissolution Δsol H m for N-acetylglycine in aqueous solutions of glycerol, ethylene glycol and 1,2-propylene glycol are measured via solution calorimetry. The standard enthalpies of dissolution (Δsol H 0) and transfer (Δtr H 0) for N-acetylglycine from water to aqueous solutions of polyhydric alcohols are calculated from experimental data. Positive values of enthalpy coefficients of pair interactions h xy for amino acids and polyol molecules are calculated using the McMillan-Mayer theory. The results are discussed using an approach for evaluating different types of interactions in ternary systems and the effect the structural features of interacting biomolecules have on the thermochemical characteristics of N-acetylglycine dissolution.

Osmotic potential calculations of inorganic and organic aqueous solutions over wide solute concentration levels and temperatures.

PubMed

Cochrane, T T; Cochrane, T A

2016-01-01

To demonstrate that the authors' new "aqueous solution vs pure water" equation to calculate osmotic potential may be used to calculate the osmotic potentials of inorganic and organic aqueous solutions over wide ranges of solute concentrations and temperatures. Currently, the osmotic potentials of solutions used for medical purposes are calculated from equations based on the thermodynamics of the gas laws which are only accurate at low temperature and solute concentration levels. Some solutions used in medicine may need their osmotic potentials calculated more accurately to take into account solute concentrations and temperatures. The authors experimented with their new equation for calculating the osmotic potentials of inorganic and organic aqueous solutions up to and beyond body temperatures by adjusting three of its factors; (a) the volume property of pure water, (b) the number of "free" water molecules per unit volume of solution, "Nf," and (c) the "t" factor expressing the cooperative structural relaxation time of pure water at given temperatures. Adequate information on the volume property of pure water at different temperatures is available in the literature. However, as little information on the relative densities of inorganic and organic solutions, respectively, at varying temperatures needed to calculate Nf was available, provisional equations were formulated to approximate values. Those values together with tentative t values for different temperatures chosen from values calculated by different workers were substituted into the authors' equation to demonstrate how osmotic potentials could be estimated over temperatures up to and beyond bodily temperatures. The provisional equations formulated to calculate Nf, the number of free water molecules per unit volume of inorganic and organic solute solutions, respectively, over wide concentration ranges compared well with the calculations of Nf using recorded relative density data at 20 °C. They were subsequently used to estimate Nf values at temperatures up to and excess of body temperatures. Those values, together with t values at temperatures up to and in excess of body temperatures recorded in the literature, were substituted in the authors' equation for the provisional calculation of osmotic potentials. The calculations indicated that solution temperatures and solute concentrations have a marked effect on osmotic potentials. Following work to measure the relative densities of aqueous solutions for the calculation of Nf values and the determination of definitive t values up to and beyond bodily temperatures, the authors' equation would enable the accurate estimations of the osmotic potentials of wide concentrations of aqueous solutions of inorganic and organic solutes over the temperature range. The study illustrates that not only solute concentrations but also temperatures have a marked effect on osmotic potentials, an observation of medical and biological significance.

The effect of nanoparticles and humic acid on technology critical element concentrations in aqueous solutions with soil and sand.

PubMed

Stepka, Zane; Dror, Ishai; Berkowitz, Brian

2018-01-01

As a consequence of their growing use in electronic and industrial products, increasing amounts of technology critical elements (TCEs) are being released to the environment. Currently little is known about the fate of many of these elements. Initial research on their potential environmental impact identifies TCEs as emerging contaminants. TCE movement in the environment is often governed by water systems. Research on "natural" waters so far demonstrates that TCEs tend to be associated with suspended particulate matter (SPM), which influences TCE aqueous concentrations (here: concentration of TCEs in dissolved form and attached to SPM) and transport. However, the relative potential of different types of SPM to interact with TCEs is unknown. Here we examine the potential of various types of particulate matter, namely different nanoparticles (NPs; Al 2 O 3, SiO 2 , CeO 2 , ZnO, montmorillonite, Ag, Au and carbon dots) and humic acid (HA), to impact TCE aqueous concentrations in aqueous solutions with soil and sand, and thus influence TCE transport in soil-water environments. We show that a combination of NPs and HA, and not NPs or HA individually, increases the aqueous concentrations of TCEs in soil solutions, for all tested NPs regardless of their type. TCEs retained on SPM, however, settle with time. In solutions with sand, HA alone is as influential as NPs+HA in keeping TCEs in the aqueous phase. Among NPs, Ag-NPs and Au-NPs demonstrate the highest potential for TCE transport. These results suggest that in natural soil-water environments, once TCEs are retained by soil, their partitioning to the aqueous phase by through-flowing water is unlikely. However, if TCEs are introduced to soil-water environments as part of solutions rich in NPs and HA, it is likely that NP and HA combinations can increase TCE stability in the aqueous phase and prevent their retention on soil and sand, thus facilitating TCE transport. Copyright © 2017 Elsevier B.V. All rights reserved.

The use of poly(vinyl phosphonic acid) microgels for the preparation of inherently magnetic Co metal catalyst particles in hydrogen production

NASA Astrophysics Data System (ADS)

Sahiner, Nurettin; Sagbas, Selin

2014-01-01

Novel poly(vinyl phosphonic acid) (p(VPA)) micro particle and composite p(VPA)-silica micro particle hydrogels are synthesized using a micro-emulsion polymerization technique. Porous p(VPA) particles are generated after removal of silica particles upon treatment of composite p(VPA) with 0.5 M NaOH solution. Bare, composite with silica, and porous p(VPA) micro particle hydrogels are used as templates and as reactors. Metal nanoparticles, Co, Ni, and Cu are generated in situ inside these hydrogels by chemical reduction of the absorbed metal ions with a reducing agent such as sodium boron hydride (NaBH4), and are used as catalyst in hydrogen production by hydrolysis of NaBH4 in a basic medium and ammonia borane (AB). The effects of reloaded metal ions, the reaction temperature, the porosity, the reusability, and the type of metal (Co, Ni, Cu) are investigated. The activation energy for hydrolysis of NaBH4, and AB by p(VPA)-Co is 28.02 and 25.51 kJ mol-1, respectively. The mass susceptibility measurements of composite p(VPA)-Co microgel is found as ferromagnetic. It is found that p(VPA) microgels provided better catalytic performance in comparison to macro p(VPA) hydrogels due to improved properties such as higher surface area, pore structure, and inherently magnetic behavior after multiple loadings-reduction of Co(II) from aqueous medium.

Method of repressing the precipitation of calcium fluozirconate

DOEpatents

Newby, B.J.; Rhodes, D.W.

1973-12-25

Boric acid or a borate salt is added to aqueous solutions of fluoride containing radioactive wastes generated during the reprocessing of zirconium alloy nuclear fuels which are to be converted to solid form by calcining in a fluidized bed. The addition of calcium nitrate to the aqueous waste solutions to prevent fluoride volatility during calcination, causes the precipitation of calcium fluozirconate, which tends to form a gel at fluoride concentrations of 3.0 M or greater. The boron containing species introduced into the solution by the addition of the boric acid or borate salt retard the formation of the calcium fluozirconate precipitate and prevent formation of the gel. These boron containing species can be introduced into the solution by the addition of a borate salt but preferably are introduced by the addition of an aqueous solution of boric acid. (Official Gazette)