Non-aqueous liquid compositions comprising ion exchange polymers reference to related application

DOEpatents

Kim,; Yu Seung, Lee [Los Alamos, NM; Kwan-Soo, Rockward [Los Alamos, NM; T, Tommy Q [Rio Rancho, NM

2012-08-07

Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.

Methods for preparing colloidal nanocrystal-based thin films

DOEpatents

Kagan, Cherie R.; Fafarman, Aaron T.; Choi, Ji-Hyuk; Koh, Weon-kyu; Kim, David K.; Oh, Soong Ju; Lai, Yuming; Hong, Sung-Hoon; Saudari, Sangameshwar Rao; Murray, Christopher B.

2016-05-10

Methods of exchanging ligands to form colloidal nanocrystals (NCs) with chalcogenocyanate (xCN)-based ligands and apparatuses using the same are disclosed. The ligands may be exchanged by assembling NCs into a thin film and immersing the thin film in a solution containing xCN-based ligands. The ligands may also be exchanged by mixing a xCN-based solution with a dispersion of NCs, flocculating the mixture, centrifuging the mixture, discarding the supernatant, adding a solvent to the pellet, and dispersing the solvent and pellet to form dispersed NCs with exchanged xCN-ligands. The NCs with xCN-based ligands may be used to form thin film devices and/or other electronic, optoelectronic, and photonic devices. Devices comprising nanocrystal-based thin films and methods for forming such devices are also disclosed. These devices may be constructed by depositing NCs on to a substrate to form an NC thin film and then doping the thin film by evaporation and thermal diffusion.

Activation of porous MOF materials

DOEpatents

Hupp, Joseph T; Farha, Omar K

2013-04-23

A method for the treatment of solvent-containing MOF material to increase its internal surface area involves introducing a liquid into the MOF in which liquid the solvent is miscible, subjecting the MOF to supercritical conditions for a time to form supercritical fluid, and releasing the supercritical conditions to remove the supercritical fluid from the MOF. Prior to introducing the liquid into the MOF, occluded reaction solvent, such as DEF or DMF, in the MOF can be exchanged for the miscible solvent.

Activation of porous MOF materials

DOEpatents

Hupp, Joseph T; Farha, Omar K

2014-04-01

A method for the treatment of solvent-containing MOF material to increase its internal surface area involves introducing a liquid into the MOF in which liquid the solvent is miscible, subjecting the MOF to supercritical conditions for a time to form supercritical fluid, and releasing the supercritical conditions to remove the supercritcal fluid from the MOF. Prior to introducing the liquid into the MOF, occluded reaction solvent, such as DEF or DMF, in the MOF can be exchanged for the miscible solvent.

A review on methods of regeneration of spent pickling solutions from steel processing.

PubMed

Regel-Rosocka, Magdalena

2010-05-15

The review presents various techniques of regeneration of spent pickling solutions, including the methods with acid recovery, such as diffusion dialysis, electrodialysis, membrane electrolysis and membrane distillation, evaporation, precipitation and spray roasting as well as those with acid and metal recovery: ion exchange, retardation, crystallization solvent and membrane extraction. Advantages and disadvantages of the techniques are presented, discussed and confronted with the best available techniques requirements. Most of the methods presented meet the BAT requirements. The best available techniques are electrodialysis, diffusion dialysis and crystallization; however, in practice spray roasting and retardation/ion-exchange are applied most frequently for spent pickling solution regeneration. As "waiting for their chance" solvent extraction, non-dispersive solvent extraction and membrane distillation should be indicated because they are well investigated and developed. Environmental and economic benefits of the methods presented in the review depend on the cost of chemicals and wastewater treatment, legislative regulations and cost of modernization of existing technologies or implementation of new ones. Copyright (c) 2009 Elsevier B.V. All rights reserved.

Scalable free energy calculation of proteins via multiscale essential sampling

NASA Astrophysics Data System (ADS)

Moritsugu, Kei; Terada, Tohru; Kidera, Akinori

2010-12-01

A multiscale simulation method, "multiscale essential sampling (MSES)," is proposed for calculating free energy surface of proteins in a sizable dimensional space with good scalability. In MSES, the configurational sampling of a full-dimensional model is enhanced by coupling with the accelerated dynamics of the essential degrees of freedom. Applying the Hamiltonian exchange method to MSES can remove the biasing potential from the coupling term, deriving the free energy surface of the essential degrees of freedom. The form of the coupling term ensures good scalability in the Hamiltonian exchange. As a test application, the free energy surface of the folding process of a miniprotein, chignolin, was calculated in the continuum solvent model. Results agreed with the free energy surface derived from the multicanonical simulation. Significantly improved scalability with the MSES method was clearly shown in the free energy calculation of chignolin in explicit solvent, which was achieved without increasing the number of replicas in the Hamiltonian exchange.

Enhanced conformational sampling of carbohydrates by Hamiltonian replica-exchange simulation.

PubMed

Mishra, Sushil Kumar; Kara, Mahmut; Zacharias, Martin; Koca, Jaroslav

2014-01-01

Knowledge of the structure and conformational flexibility of carbohydrates in an aqueous solvent is important to improving our understanding of how carbohydrates function in biological systems. In this study, we extend a variant of the Hamiltonian replica-exchange molecular dynamics (MD) simulation to improve the conformational sampling of saccharides in an explicit solvent. During the simulations, a biasing potential along the glycosidic-dihedral linkage between the saccharide monomer units in an oligomer is applied at various levels along the replica runs to enable effective transitions between various conformations. One reference replica runs under the control of the original force field. The method was tested on disaccharide structures and further validated on biologically relevant blood group B, Lewis X and Lewis A trisaccharides. The biasing potential-based replica-exchange molecular dynamics (BP-REMD) method provided a significantly improved sampling of relevant conformational states compared with standard continuous MD simulations, with modest computational costs. Thus, the proposed BP-REMD approach adds a new dimension to existing carbohydrate conformational sampling approaches by enhancing conformational sampling in the presence of solvent molecules explicitly at relatively low computational cost.

Coulomb replica-exchange method: handling electrostatic attractive and repulsive forces for biomolecules.

PubMed

Itoh, Satoru G; Okumura, Hisashi

2013-03-30

We propose a new type of the Hamiltonian replica-exchange method (REM) for molecular dynamics (MD) and Monte Carlo simulations, which we refer to as the Coulomb REM (CREM). In this method, electrostatic charge parameters in the Coulomb interactions are exchanged among replicas while temperatures are exchanged in the usual REM. By varying the atom charges, the CREM overcomes free-energy barriers and realizes more efficient sampling in the conformational space than the REM. Furthermore, this method requires only a smaller number of replicas because only the atom charges of solute molecules are used as exchanged parameters. We performed Coulomb replica-exchange MD simulations of an alanine dipeptide in explicit water solvent and compared the results with those of the conventional canonical, replica exchange, and van der Waals REMs. Two force fields of AMBER parm99 and AMBER parm99SB were used. As a result, the CREM sampled all local-minimum free-energy states more frequently than the other methods for both force fields. Moreover, the Coulomb, van der Waals, and usual REMs were applied to a fragment of an amyloid-β peptide (Aβ) in explicit water solvent to compare the sampling efficiency of these methods for a larger system. The CREM sampled structures of the Aβ fragment more efficiently than the other methods. We obtained β-helix, α-helix, 3(10)-helix, β-hairpin, and β-sheet structures as stable structures and deduced pathways of conformational transitions among these structures from a free-energy landscape. Copyright © 2012 Wiley Periodicals, Inc.

Development of novel purifiers with appropriate functional groups based on solvent polarities at bulk filtration

NASA Astrophysics Data System (ADS)

Kohyama, Tetsu; Kaneko, Fumiya; Ly, Saksatha; Hamzik, James; Jaber, Jad; Yamada, Yoshiaki

2017-03-01

Weak-polar solvents like PGMEA (Propylene Glycol Monomethyl Ether Acetate) or CHN (Cyclohexanone) are used to dissolve hydrophobic photo-resist polymers, which are challenging for traditional cleaning methods such as distillation, ion-exchange resins service or water-washing processes. This paper investigated two novel surface modifications to see their effectiveness at metal removal and to understand the mechanism. The experiments yielded effective purification methods for metal reduction, focusing on solvent polarities based on HSP (Hansen Solubility Parameters), and developing optimal purification strategies.

Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

PubMed

Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

2017-08-22

Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

Unlocking Chain Exchange in Highly Amphiphilic Block Polymer Micellar Systems: Influence of Agitation.

PubMed

Murphy, Ryan P; Kelley, Elizabeth G; Rogers, Simon A; Sullivan, Millicent O; Epps, Thomas H

2014-11-18

Chain exchange between block polymer micelles in highly selective solvents, such as water, is well-known to be arrested under quiescent conditions, yet this work demonstrates that simple agitation methods can induce rapid chain exchange in these solvents. Aqueous solutions containing either pure poly(butadiene- b -ethylene oxide) or pure poly(butadiene- b -ethylene oxide- d 4 ) micelles were combined and then subjected to agitation by vortex mixing, concentric cylinder Couette flow, or nitrogen gas sparging. Subsequently, the extent of chain exchange between micelles was quantified using small angle neutron scattering. Rapid vortex mixing induced chain exchange within minutes, as evidenced by a monotonic decrease in scattered intensity, whereas Couette flow and sparging did not lead to measurable chain exchange over the examined time scale of hours. The linear kinetics with respect to agitation time suggested a surface-limited exchange process at the air-water interface. These findings demonstrate the strong influence of processing conditions on block polymer solution assemblies.

Exploring Hamiltonian dielectric solvent molecular dynamics

NASA Astrophysics Data System (ADS)

Bauer, Sebastian; Tavan, Paul; Mathias, Gerald

2014-09-01

Hamiltonian dielectric solvent (HADES) is a recent method [7,25], which enables Hamiltonian molecular dynamics (MD) simulations of peptides and proteins in dielectric continua. Sample simulations of an α-helical decapeptide with and without explicit solvent demonstrate the high efficiency of HADES-MD. Addressing the folding of this peptide by replica exchange MD we study the properties of HADES by comparing melting curves, secondary structure motifs and salt bridges with explicit solvent results. Despite the unoptimized ad hoc parametrization of HADES, calculated reaction field energies correlate well with numerical grid solutions of the dielectric Poisson equation.

Development of multicomponent hybrid density functional theory with polarizable continuum model for the analysis of nuclear quantum effect and solvent effect on NMR chemical shift.

PubMed

Kanematsu, Yusuke; Tachikawa, Masanori

2014-04-28

We have developed the multicomponent hybrid density functional theory [MC_(HF+DFT)] method with polarizable continuum model (PCM) for the analysis of molecular properties including both nuclear quantum effect and solvent effect. The chemical shifts and H/D isotope shifts of the picolinic acid N-oxide (PANO) molecule in chloroform and acetonitrile solvents are applied by B3LYP electron exchange-correlation functional for our MC_(HF+DFT) method with PCM (MC_B3LYP/PCM). Our MC_B3LYP/PCM results for PANO are in reasonable agreement with the corresponding experimental chemical shifts and isotope shifts. We further investigated the applicability of our method for acetylacetone in several solvents.

Reliable oligonucleotide conformational ensemble generation in explicit solvent for force field assessment using reservoir replica exchange molecular dynamics simulations

PubMed Central

Henriksen, Niel M.; Roe, Daniel R.; Cheatham, Thomas E.

2013-01-01

Molecular dynamics force field development and assessment requires a reliable means for obtaining a well-converged conformational ensemble of a molecule in both a time-efficient and cost-effective manner. This remains a challenge for RNA because its rugged energy landscape results in slow conformational sampling and accurate results typically require explicit solvent which increases computational cost. To address this, we performed both traditional and modified replica exchange molecular dynamics simulations on a test system (alanine dipeptide) and an RNA tetramer known to populate A-form-like conformations in solution (single-stranded rGACC). A key focus is on providing the means to demonstrate that convergence is obtained, for example by investigating replica RMSD profiles and/or detailed ensemble analysis through clustering. We found that traditional replica exchange simulations still require prohibitive time and resource expenditures, even when using GPU accelerated hardware, and our results are not well converged even at 2 microseconds of simulation time per replica. In contrast, a modified version of replica exchange, reservoir replica exchange in explicit solvent, showed much better convergence and proved to be both a cost-effective and reliable alternative to the traditional approach. We expect this method will be attractive for future research that requires quantitative conformational analysis from explicitly solvated simulations. PMID:23477537

Reliable oligonucleotide conformational ensemble generation in explicit solvent for force field assessment using reservoir replica exchange molecular dynamics simulations.

PubMed

Henriksen, Niel M; Roe, Daniel R; Cheatham, Thomas E

2013-04-18

Molecular dynamics force field development and assessment requires a reliable means for obtaining a well-converged conformational ensemble of a molecule in both a time-efficient and cost-effective manner. This remains a challenge for RNA because its rugged energy landscape results in slow conformational sampling and accurate results typically require explicit solvent which increases computational cost. To address this, we performed both traditional and modified replica exchange molecular dynamics simulations on a test system (alanine dipeptide) and an RNA tetramer known to populate A-form-like conformations in solution (single-stranded rGACC). A key focus is on providing the means to demonstrate that convergence is obtained, for example, by investigating replica RMSD profiles and/or detailed ensemble analysis through clustering. We found that traditional replica exchange simulations still require prohibitive time and resource expenditures, even when using GPU accelerated hardware, and our results are not well converged even at 2 μs of simulation time per replica. In contrast, a modified version of replica exchange, reservoir replica exchange in explicit solvent, showed much better convergence and proved to be both a cost-effective and reliable alternative to the traditional approach. We expect this method will be attractive for future research that requires quantitative conformational analysis from explicitly solvated simulations.

On the Helix Propensity in Generalized Born Solvent Descriptions of Modeling the Dark Proteome

PubMed Central

Olson, Mark A.

2017-01-01

Intrinsically disordered proteins that populate the so-called “Dark Proteome” offer challenging benchmarks of atomistic simulation methods to accurately model conformational transitions on a multidimensional energy landscape. This work explores the application of parallel tempering with implicit solvent models as a computational framework to capture the conformational ensemble of an intrinsically disordered peptide derived from the Ebola virus protein VP35. A recent X-ray crystallographic study reported a protein-peptide interface where the VP35 peptide underwent a folding transition from a disordered form to a helix-β-turn-helix topological fold upon molecular association with the Ebola protein NP. An assessment is provided of the accuracy of two generalized Born solvent models (GBMV2 and GBSW2) using the CHARMM force field and applied with temperature-based replica exchange dynamics to calculate the disorder propensity of the peptide and its probability density of states in a continuum solvent. A further comparison is presented of applying an explicit/implicit solvent hybrid replica exchange simulation of the peptide to determine the effect of modeling water interactions at the all-atom resolution. PMID:28197405

On the Helix Propensity in Generalized Born Solvent Descriptions of Modeling the Dark Proteome.

PubMed

Olson, Mark A

2017-01-01

Intrinsically disordered proteins that populate the so-called "Dark Proteome" offer challenging benchmarks of atomistic simulation methods to accurately model conformational transitions on a multidimensional energy landscape. This work explores the application of parallel tempering with implicit solvent models as a computational framework to capture the conformational ensemble of an intrinsically disordered peptide derived from the Ebola virus protein VP35. A recent X-ray crystallographic study reported a protein-peptide interface where the VP35 peptide underwent a folding transition from a disordered form to a helix-β-turn-helix topological fold upon molecular association with the Ebola protein NP. An assessment is provided of the accuracy of two generalized Born solvent models (GBMV2 and GBSW2) using the CHARMM force field and applied with temperature-based replica exchange dynamics to calculate the disorder propensity of the peptide and its probability density of states in a continuum solvent. A further comparison is presented of applying an explicit/implicit solvent hybrid replica exchange simulation of the peptide to determine the effect of modeling water interactions at the all-atom resolution.

Different ligand exchange solvents effect on the densification of CuIn0.7Ga0.3Se2 prepared using the heating-up method

NASA Astrophysics Data System (ADS)

Yang, Chang-Ting; Hsiang, Hsing-I.

2017-12-01

The effects of different ligand exchange solvents and heat treatment conditions on the densification and microstructure development of CuIn0.7Ga0.3Se2 (CIGS) crystallites synthesized using the heating-up method were studied in this work. The heat treatment effects on the organic molecules and crystalline structure were investigated using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was observed that oleylamine (OLA) adsorbed onto the CIGS surface was difficult to remove during sintering. Ligand-exchange with m-xylene or 1-hexanethiol can promote the removal of oleylamine adsorbed onto the CIGS surface and prevent the residual carbon from forming during sintering, which leads to grain growth and densification. A dense CuIn0.7Ga0.3Se2 can be obtained using the precursor powders after ligand-exchange with 1-hexanethiol and m-xylene to remove organic molecules and sintering at 600 °C for 2 h under Se atmosphere.

Vibrational energy transfer between carbon nanotubes and nonaqueous solvents: a molecular dynamics study.

PubMed

Nelson, Tammie R; Chaban, Vitaly V; Prezhdo, Victor V; Prezhdo, Oleg V

2011-05-12

We report molecular dynamics (MD) simulation of energy exchange between single-walled carbon nanotubes (CNTs) and two aprotic solvents, acetonitrile and cyclohexane. Following our earlier study of hydrated CNTs, we find that the time scales and molecular mechanisms of the energy transfer are largely independent of the nature of the surrounding medium, and therefore, should hold for other media including polymer matrices and DNA. The vibrational energy exchange between CNT and solvents exhibits two time-scales. Over half of the energy is transferred in less than one picosecond, indicating that the dominant exchange mechanism is inertial relaxation. It occurs by collisions of solvent molecules with CNT walls, facilitated by the short-range Lennard-Jones interaction. Additional several picoseconds are required for the remainder of the vibrational energy exchange, corresponding to the diffusive relaxation mechanism and involving collective molecular motions. The faster stage of the CNT-solvent energy exchange occurs on the same time-scale, and therefore, competes with the vibrational energy relaxation inside CNTs. The energy exchange time-scales are significantly influenced by the arrangement of solvent molecules inside CNTs. Generally, the effects of confinement on the dynamics can be rationalized by analysis of the solvent structure. For the same CNT diameter, the extent of the confinement effect strongly depends on the size of the solvent molecules. Icelike properties in water seen in small CNTs disappear in CNTs with intermediate diameters. In acetonitrile and cyclohexane, medium size CNTs still show strong confinement effects. Rotational motions of acetonitrile molecules are inhibited, and the cyclohexane density is dramatically decreased. The disbalance between the local temperatures of the inside and outside regions of the solvent equilibrates through a tube-mediated interaction, rather than by a direct coupling between the two solvent subsystems. In all cases, the CNT-solvent energy transfer is mediated by slow motions in the frequency range of CNT radial breathing modes.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

PubMed Central

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-01-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level. PMID:28272396

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

NASA Astrophysics Data System (ADS)

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion...carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery.

PubMed

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-08

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Method of forming a foamed thermoplastic polymer

DOEpatents

Duchane, David V.; Cash, David L.

1986-01-01

A method of forming a foamed thermoplastic polymer. A solid thermoplastic lymer is immersed in an immersant solution comprising a compatible carrier solvent and an infusant solution containing an incompatible liquid blowing agent for a time sufficient for the immersant solution to infuse into the polymer. The carrier solvent is then selectively extracted, preferably by a solvent exchange process in which the immersant solution is gradually diluted with and replaced by the infusant solution, so as to selectively leave behind the infusant solution permanently entrapped in the polymer. The polymer is then heated to volatilize the blowing agent and expand the polymer into a foamed state.

Application of a Permethrin Immunosorbent Assay Method to Residential Soil and Dust Samples

EPA Science Inventory

A low-cost, high throughput bioanalytical screening method was developed for monitoring cis/trans-permethrin in dust and soil samples. The method consisted of a simple sample preparation procedure [sonication with dichloromethane followed by a solvent exchange into methanol:wate...

Nuclear spin hyperpolarization of the solvent using signal amplification by reversible exchange (SABRE).

PubMed

Moreno, Karlos X; Nasr, Khaled; Milne, Mark; Sherry, A Dean; Goux, Warren J

2015-08-01

Here we report the polarization of the solvent OH protons by SABRE using standard iridium-based catalysts under slightly acidic conditions. Solvent polarization was observed in the presence of a variety of structurally similar N-donor substrates while no solvent enhancement was observed in the absence of substrate or para-hydrogen (p-H2). Solvent polarization was sensitive to the polarizing field and catalyst:substrate ratio in a manner similar to that of substrate protons. SABRE experiments with pyridine-d5 suggest a mechanism where hyperpolarization is transferred from the free substrate to the solvent by chemical exchange while measured hyperpolarization decay times suggest a complimentary mechanism which occurs by direct coordination of the solvent to the catalytic complex. We found the solvent hyperpolarization to decay nearly 3 times more slowly than its characteristic spin-lattice relaxation time suggesting that the hyperpolarized state of the solvent may be sufficiently long lived (∼20s) to hyperpolarize biomolecules having exchangeable protons. This route may offer future opportunities for SABRE to impact metabolic imaging. Copyright © 2015 Elsevier Inc. All rights reserved.

Nuclear spin hyperpolarization of the solvent using signal amplification by reversible exchange (SABRE)

NASA Astrophysics Data System (ADS)

Moreno, Karlos X.; Nasr, Khaled; Milne, Mark; Sherry, A. Dean; Goux, Warren J.

2015-08-01

Here we report the polarization of the solvent OH protons by SABRE using standard iridium-based catalysts under slightly acidic conditions. Solvent polarization was observed in the presence of a variety of structurally similar N-donor substrates while no solvent enhancement was observed in the absence of substrate or para-hydrogen (p-H2). Solvent polarization was sensitive to the polarizing field and catalyst:substrate ratio in a manner similar to that of substrate protons. SABRE experiments with pyridine-d5 suggest a mechanism where hyperpolarization is transferred from the free substrate to the solvent by chemical exchange while measured hyperpolarization decay times suggest a complimentary mechanism which occurs by direct coordination of the solvent to the catalytic complex. We found the solvent hyperpolarization to decay nearly 3 times more slowly than its characteristic spin-lattice relaxation time suggesting that the hyperpolarized state of the solvent may be sufficiently long lived (∼20 s) to hyperpolarize biomolecules having exchangeable protons. This route may offer future opportunities for SABRE to impact metabolic imaging.

NMR based solvent exchange experiments to understand the conformational preference of intrinsically disordered proteins using FG-nucleoporin peptide as a model

PubMed Central

Heisel, Kurt A.; Krishnan, V. V.

2014-01-01

The conformational preference of a peptide with three phenylalanine-glycine (FG) repeats from the intrinsically disordered domain of nucleoporin 159 (nup159) from the yeast nucleopore complex (NPC) is studied. Conformational states of this FG-peptide in dimethyl sulfoxide (DMSO), a non-native solvent are first studied. A solvent exchange scheme is designed and performed to understand how the conformational preferences of the peptide are altered as the solvent shifts from DMSO to water. An ensemble of structures of a 19-residue peptide is determined based on 13Cα, 1Hα, and 1HN chemical shifts and with inter-proton distances. An experimental model is then presented where chemical shifts and amide-proton temperature dependence is probed at changing DMSO to water ratios. These co-solvent experiments provide evidence of a conformational change as the fraction of water increases by the stark change in the behavior of amide protons under varied temperature. This investigation provides a NMR based experimental method in the field of intrinsically disordered proteins to realize conformational transitions from a non-native set of structures (in DMSO) to a native set of disordered conformers (in water). PMID:24037535

Hot melt extrusion of ion-exchange resin for taste masking.

PubMed

Tan, David Cheng Thiam; Ong, Jeremy Jianming; Gokhale, Rajeev; Heng, Paul Wan Sia

2018-05-30

Taste masking is important for some unpleasant tasting bioactives in oral dosage forms. Among many methods available for taste-masking, use of ion-exchange resin (IER) holds promise. IER combined with hot melt extrusion (HME) may offer additional advantages over solvent methods. IER provides taste masking by complexing with the drug ions and preventing drug dissolution in the mouth. Drug-IER complexation approaches described in literatures are mainly based either on batch processing or column eluting. These methods of drug-IER complexation have obvious limitations such as high solvent volume requirements, multiprocessing steps and extended processing time. Thus, the objective of this study was to develop a single-step, solvent-free, continuous HME process for complexation of drug-IER. The screening study evaluated drug to IER ratio, types of IER and drug complexation methods. In the screening study, a potassium salt of a weakly acidic carboxylate-based cationic IER was found suitable for the HME method. Thereafter, optimization study was conducted by varying HME process parameters such as screw speed, extrusion temperature and drug to IER ratio. It was observed that extrusion temperature and drug to IER ratio are imperative in drug-IER complexation through HME. In summary, this study has established the feasibility of a continuous complexation method for drug to IER using HME for taste masking. Copyright © 2018 Elsevier B.V. All rights reserved.

Method of forming a foamed thermoplastic polymer

DOEpatents

Duchane, D.V.; Cash, D.L.

1984-11-21

A solid thermoplastic polymer is immersed in an immersant solution comprising a compatible carrier solvent and an infusant solution containing an incompatible liquid blowing agent for a time sufficient for the immersant solution to infuse into the polymer. The carrier solvent is then selectively extracted, preferably by a solvent exchange process in which the immersant solution is gradually diluted with and replaced by the infusant solution, so as to selectively leave behind the infustant solution permanently entrapped in the polymer. The polymer is then heated to volatilize the blowing agent and expand the polymer into a foamed state.

Accessibility of Nitroxide Side Chains: Absolute Heisenberg Exchange Rates from Power Saturation EPR

PubMed Central

Altenbach, Christian; Froncisz, Wojciech; Hemker, Roy; Mchaourab, Hassane; Hubbell, Wayne L.

2005-01-01

In site-directed spin labeling, the relative solvent accessibility of spin-labeled side chains is taken to be proportional to the Heisenberg exchange rate (Wex) of the nitroxide with a paramagnetic reagent in solution. In turn, relative values of Wex are determined by continuous wave power saturation methods and expressed as a proportional and dimensionless parameter Π. In the experiments presented here, NiEDDA is characterized as a paramagnetic reagent for solvent accessibility studies, and it is shown that absolute values of Wex can be determined from Π, and that the proportionality constant relating them is independent of the paramagnetic reagent and mobility of the nitroxide. Based on absolute exchange rates, an accessibility factor is defined (0 < ρ < 1) that serves as a quantitative measure of side-chain solvent accessibility. The accessibility factors for a nitroxide side chain at 14 different sites in T4 lysozyme are shown to correlate with a structure-based accessibility parameter derived from the crystal structure of the protein. These results provide a useful means for relating crystallographic and site-directed spin labeling data, and hence comparing crystal and solution structures. PMID:15994891

A General Method for Predicting Amino Acid Residues Experiencing Hydrogen Exchange

PubMed Central

Wang, Boshen; Perez-Rathke, Alan; Li, Renhao; Liang, Jie

2018-01-01

Information on protein hydrogen exchange can help delineate key regions involved in protein-protein interactions and provides important insight towards determining functional roles of genetic variants and their possible mechanisms in disease processes. Previous studies have shown that the degree of hydrogen exchange is affected by hydrogen bond formations, solvent accessibility, proximity to other residues, and experimental conditions. However, a general predictive method for identifying residues capable of hydrogen exchange transferable to a broad set of proteins is lacking. We have developed a machine learning method based on random forest that can predict whether a residue experiences hydrogen exchange. Using data from the Start2Fold database, which contains information on 13,306 residues (3,790 of which experience hydrogen exchange and 9,516 which do not exchange), our method achieves good performance. Specifically, we achieve an overall out-of-bag (OOB) error, an unbiased estimate of the test set error, of 20.3 percent. Using a randomly selected test data set consisting of 500 residues experiencing hydrogen exchange and 500 which do not, our method achieves an accuracy of 0.79, a recall of 0.74, a precision of 0.82, and an F1 score of 0.78.

Density functional theory studies on the solvent effects in Al(H2O)63+ water-exchange reactions: the number and arrangement of outer-sphere water molecules.

PubMed

Liu, Li; Zhang, Jing; Dong, Shaonan; Zhang, Fuping; Wang, Ye; Bi, Shuping

2018-03-07

Density functional theory (DFT) calculations combined with cluster models are performed at the B3LYP/6-311+G(d,p) level for investigating the solvent effects in Al(H 2 O) 6 3+ water-exchange reactions. A "One-by-one" method is proposed to obtain the most representative number and arrangement of explicit H 2 Os in the second hydration sphere. First, all the possible ways to locate one explicit H 2 O in second sphere (N m ' = 1) based on the gas phase structure (N m ' = 0) are examined, and the optimal pathway (with the lowest energy barrier) for N m ' = 1 is determined. Next, more explicit H 2 Os are added one by one until the inner-sphere is fully hydrogen bonded. Finally, the optimal pathways with N m ' = 0-7 are obtained. The structural and energetic parameters as well as the lifetimes of the transition states are compared with the results obtained with the "Independent-minimum" method and the "Independent-average" method, and all three methods show that the pathway with N m ' = 6 may be representative. Our results give a new idea for finding the representative pathway for water-exchange reactions in other hydrated metal ion systems.

The Ionic Atmosphere around A-RNA: Poisson-Boltzmann and Molecular Dynamics Simulations

PubMed Central

Kirmizialtin, Serdal; Silalahi, Alexander R.J.; Elber, Ron; Fenley, Marcia O.

2012-01-01

The distributions of different cations around A-RNA are computed by Poisson-Boltzmann (PB) equation and replica exchange molecular dynamics (MD). Both the nonlinear PB and size-modified PB theories are considered. The number of ions bound to A-RNA, which can be measured experimentally, is well reproduced in all methods. On the other hand, the radial ion distribution profiles show differences between MD and PB. We showed that PB results are sensitive to ion size and functional form of the solvent dielectric region but not the solvent dielectric boundary definition. Size-modified PB agrees with replica exchange molecular dynamics much better than nonlinear PB when the ion sizes are chosen from atomistic simulations. The distribution of ions 14 Å away from the RNA central axis are reasonably well reproduced by size-modified PB for all ion types with a uniform solvent dielectric model and a sharp dielectric boundary between solvent and RNA. However, this model does not agree with MD for shorter distances from the A-RNA. A distance-dependent solvent dielectric function proposed by another research group improves the agreement for sodium and strontium ions, even for shorter distances from the A-RNA. However, Mg2+ distributions are still at significant variances for shorter distances. PMID:22385854

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, Arnold R.

1987-01-01

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer (11) at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer (11) to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator (10) to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, Arnold R.

1987-01-01

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer (11) at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer (11) to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator (10) to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing he evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, A.R.

1987-06-23

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator. 5 figs.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, A.R.

1987-11-24

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator. 5 figs.

Thermal regeneration of an electrochemical concentration cell

DOEpatents

Krumpelt, Michael; Bates, John K.

1981-01-01

A system and method for thermally regenerating an electrochemical concentration cell having first and second aluminum electrodes respectively positioned in contact with first and second electrolytes separated by an ion exchange member, the first and second electrolytes being composed of different concentrations of an ionic solvent and a salt, preferably an aluminum halide. The ionic solvent may be either organic or inorganic with a relatively low melting point, the ionic solvent and the salt form a complex wherein the free energy of formation of said complex is less than about -5 Kcal/mole. A distillation column using solar heat or low grade industrial waste heat receives the first and second electrolytes and thermally decomposes the salt-solvent complex to provide feed material for the two half cells.

Quantifying NMR relaxation correlation and exchange in articular cartilage with time domain analysis

NASA Astrophysics Data System (ADS)

Mailhiot, Sarah E.; Zong, Fangrong; Maneval, James E.; June, Ronald K.; Galvosas, Petrik; Seymour, Joseph D.

2018-02-01

Measured nuclear magnetic resonance (NMR) transverse relaxation data in articular cartilage has been shown to be multi-exponential and correlated to the health of the tissue. The observed relaxation rates are dependent on experimental parameters such as solvent, data acquisition methods, data analysis methods, and alignment to the magnetic field. In this study, we show that diffusive exchange occurs in porcine articular cartilage and impacts the observed relaxation rates in T1-T2 correlation experiments. By using time domain analysis of T2-T2 exchange spectroscopy, the diffusive exchange time can be quantified by measurements that use a single mixing time. Measured characteristic times for exchange are commensurate with T1 in this material and so impacts the observed T1 behavior. The approach used here allows for reliable quantification of NMR relaxation behavior in cartilage in the presence of diffusive fluid exchange between two environments.

Aqueous-Processed, High-Capacity Electrodes for Membrane Capacitive Deionization.

PubMed

Jain, Amit; Kim, Jun; Owoseni, Oluwaseye M; Weathers, Cierra; Caña, Daniel; Zuo, Kuichang; Walker, W Shane; Li, Qilin; Verduzco, Rafael

2018-05-15

Membrane capacitive deionization (MCDI) is a low-cost technology for desalination. Typically, MCDI electrodes are fabricated using a slurry of nanoparticles in an organic solvent along with polyvinylidene fluoride (PVDF) polymeric binder. Recent studies of the environmental impact of CDI have pointed to the organic solvents used in the fabrication of CDI electrodes as key contributors to the overall environmental impact of the technology. Here, we report a scalable, aqueous processing approach to prepare MCDI electrodes using water-soluble polymer poly(vinyl alcohol) (PVA) as a binder and ion-exchange polymer. Electrodes are prepared by depositing aqueous slurry of activated carbon and PVA binder followed by coating with a thin layer of PVA-based cation- or anion-exchange polymer. When coated with ion-exchange layers, the PVA-bound electrodes exhibit salt adsorption capacities up to 14.4 mg/g and charge efficiencies up to 86.3%, higher than typically achieved for activated carbon electrodes with a hydrophobic polymer binder and ion-exchange membranes (5-13 mg/g). Furthermore, when paired with low-resistance commercial ion-exchange membranes, salt adsorption capacities exceed 18 mg/g. Our overall approach demonstrates a simple, environmentally friendly, cost-effective, and scalable method for the fabrication of high-capacity MCDI electrodes.

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

Estimation of the outer-sphere contribution to the activation volume for electron exchange reactions using the mean spherical approximation

NASA Astrophysics Data System (ADS)

Takagi, Hideo D.; Swaddle, Thomas W.

1996-01-01

The outer-sphere contribution to the volume of activation of homogeneous electron exchange reactions is estimated for selected solvents on the basis of the mean spherical approximation (MSA), and the calculated values are compared with those estimated by the Strank-Hush-Marcus (SHM) theory and with activation volumes obtained experimentally for the electron exchange reaction between tris(hexafluoroacetylacetonato)ruthenium(III) and -(II) in acetone, acetonitrile, methanol and chloroform. The MSA treatment, which recognizes the molecular nature of the solvent, does not improve significantly upon the continuous-dielectric SHM theory, which represents the experimental data adequately for the more polar solvents.

In-pore exchange and diffusion of carbonate solvent mixtures in nanoporous carbon

DOE PAGES

Alam, Todd M.; Osborn Popp, Thomas M.

2016-06-04

High resolution magic angle spinning (HRMAS) 1H NMR spectroscopy has been used to resolve different surface and in-pore solvent environments of ethylene carbonate (EC) and dimethyl carbonate (DMC) mixtures absorbed within nanoporous carbon (NPC). Two dimensional (2D) 1H HRMAS NMR exchange measurements revealed that the inhomogeneous broadened in-pore resonances have pore-to-pore exchange rates on the millisecond timescale. Pulsed-field gradient (PFG) NMR diffusometry revealed the in-pore self-diffusion constants for both EC and DMC were reduced by up to a factor of five with respect to the diffusion in the non-absorbed solvent mixtures.

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

NASA Astrophysics Data System (ADS)

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; Mundy, Christopher J.

2018-01-01

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus' philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

Extraction of acidic degradation products of organophosphorus chemical warfare agents. Comparison between silica and mixed-mode strong anion-exchange cartridges.

PubMed

Kanaujia, Pankaj K; Pardasani, Deepak; Gupta, A K; Kumar, Rajesh; Srivastava, R K; Dubey, D K

2007-08-17

The analysis of alkyl alkylphosphonic acids (AAPAs) and alkylphosphonic acids (APAs), the hydrolyzed products of nerve agents, constitutes an important aspect for verifying the compliance to the Chemical weapons convention (CWC). This work devotes on the development of solid-phase extraction method using polymeric mixed-mode strong anion-exchange (Oasis MAX) cartridges for extraction of AAPAs and APAs from water. The extracted analytes were analyzed by GC-MS under full scan and selected ion monitoring mode. The extraction efficiencies of MAX and silica-based anion-exchange cartridges were compared, and results revealed that MAX sorbents yielded better recoveries. Extraction parameters, such as loading capacity, extraction solvent, its volume, and washing solvent were optimized. Best recoveries were obtained using 1 mL of acidic methanol (0.1 M), and limits of detection could be achieved up to 5 x 10(-4) microg mL(-1) (in SIM) and 0.05 microg mL(-1) in full scan mode. The method was successfully employed for the detection and identification of alkylphosphonic acids present in soil sample sent by the Organization for Prohibition of Chemical Weapons (OPCW) in the official proficiency tests.

Thermal regeneration of an electrochemical concentration cell

DOEpatents

Krumpelt, M.; Bates, J.K.

1980-05-09

A system and method are described for thermally regenerating an electrochemical concentration cell having first and second aluminum electrodes respectively positioned in contact with first and second electrolytes separated by an ion exchange member, the first and second electrolytes being composed of different concentrations of an ionic solvent and a salt, preferably an aluminum halide. The ionic solvent may be either organic or inorganic with a relatively low melting point, the ionic solvent and the salt form a complex wherein the free energy of formation of said complex is less than about -5 kcal/mole. A distillation column using solar heat or low grade industrial waste heat receives the first and second electrolytes and thermally decomposes the salt-solvent complex to provide feed material for the two half cells.

Fabrication and characterization of poly(L-lactic acid) gels induced by fibrous complex crystallization with solvents

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

Matsuda, Yasuhiro; Fukatsu, Akinobu; Wang, Yangyang

2014-01-01

Complex crystal induced gelation of poly(L-lactic acid) (PLLA) solutions was studied for a series of solvents, including N,N-dimethylformamide (DMF). By cooling the solutions prepared at elevated temperatures, PLLA gels were produced in solvents that induced complex crystals ( -crystals) with PLLA. Fibrous structure of PLLA in the gel with DMF was observed by polarizing optical microscopy, field emission electron microscopy, and atomic force microscopy. Upon heating, the crystal form of PLLA in the DMF gel changed from -crystal to a-crystal, the major crystal form in common untreated PLLA films, but the morphology and high elastic modulus of the gel remainedmore » until the a-crystal dissolved at higher temperature. In addition, a solvent exchanging method was developed, which allowed PLLA gels to be prepared in other useful solvents that do not induce -crystals without losing the morphology and mechanical properties.« less

Increasing the sampling efficiency of protein conformational transition using velocity-scaling optimized hybrid explicit/implicit solvent REMD simulation

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

Yu, Yuqi; Wang, Jinan; Shao, Qiang, E-mail: qshao@mail.shcnc.ac.cn, E-mail: Jiye.Shi@ucb.com, E-mail: wlzhu@mail.shcnc.ac.cn

2015-03-28

The application of temperature replica exchange molecular dynamics (REMD) simulation on protein motion is limited by its huge requirement of computational resource, particularly when explicit solvent model is implemented. In the previous study, we developed a velocity-scaling optimized hybrid explicit/implicit solvent REMD method with the hope to reduce the temperature (replica) number on the premise of maintaining high sampling efficiency. In this study, we utilized this method to characterize and energetically identify the conformational transition pathway of a protein model, the N-terminal domain of calmodulin. In comparison to the standard explicit solvent REMD simulation, the hybrid REMD is much lessmore » computationally expensive but, meanwhile, gives accurate evaluation of the structural and thermodynamic properties of the conformational transition which are in well agreement with the standard REMD simulation. Therefore, the hybrid REMD could highly increase the computational efficiency and thus expand the application of REMD simulation to larger-size protein systems.« less

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

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

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, here we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF 4 --water system is then computed using ab initio molecular dynamics and Marcus theory, and is foundmore » to be in excellent agreement with the 2DIR measurement.« less

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

DOE PAGES

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; ...

2017-12-24

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, here we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF 4 --water system is then computed using ab initio molecular dynamics and Marcus theory, and is foundmore » to be in excellent agreement with the 2DIR measurement.« less

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

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

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4- water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be inmore » excellent agreement with the 2DIR measurement.« less

Evaluation of a heat exchanger for use in the Integrated Equipment Test facility solvent-extraction system

NASA Astrophysics Data System (ADS)

Lewis, B. E.

1982-12-01

The primary decontamination extraction section product (HAP) heat exchanger will be located between the extracting section (HA) and scrubbing section (HS) of centrifugal solvent extraction contactors in the Integrated Equipment Test (IET) facility. The heat exchanger is required to raise the temperature of the organic product stream from the HA contactor from 40 to 500 C. Tests were conducted under prototypic IET operating conditions to determine the head requirements for gravity flow and the overall heat transfer coefficient for the heat exchanger. Results from the tests indicated that the specified heat exchanger would perform satisfactorily under normal operating conditions.

Organic-inorganic hybrid perovskite quantum dots with high PLQY and enhanced carrier mobility through crystallinity control by solvent engineering and solid-state ligand exchange.

PubMed

Woo Choi, Jin; Woo, Hee Chul; Huang, Xiaoguang; Jung, Wan-Gil; Kim, Bong-Joong; Jeon, Sie-Wook; Yim, Sang-Youp; Lee, Jae-Suk; Lee, Chang-Lyoul

2018-05-22

The photoluminescence quantum yield (PLQY) and charge carrier mobility of organic-inorganic perovskite QDs were enhanced by the optimization of crystallinity and surface passivation as well as solid-state ligand exchange. The crystallinity of perovskite QDs was determined by the Effective solvent field (Esol) of various solvents for precipitation. The solvent with high Esol could more quickly countervail the localized field generated by the polar solvent, and it causes fast crystallization of the dissolved precursor, which results in poor crystallinity. The post-ligand adding process (PLAP) and post-ligand exchange process (PLEP) increase the PLQY of perovskite QDs by reducing non-radiative recombination and the density of surface defect states through surface passivation. Particularly, the post ligand exchange process (PLEP) in the solid-state improved the charge carrier mobility of perovskite QDs in addition to the PLQY enhancement. The ligand exchange with short alkyl chain length ligands could improve the packing density of perovskite QDs in films by reducing the inter-particle distance between perovskite QDs. The maximum hole mobility of 6.2 × 10-3 cm2 V-1 s-1, one order higher than that of pristine QDs without the PLEP, is obtained at perovskite QDs with hexyl ligands. By using PLEP treatment, compared to the pristine device, a 2.5 times higher current efficiency in perovskite QD-LEDs was achieved due to the improved charge carrier mobility and PLQY.

Individual breathing reactions measured in hemoglobin by hydrogen exchange methods.

PubMed Central

Englander, S W; Calhoun, D B; Englander, J J; Kallenbach, N R; Liem, R K; Malin, E L; Mandal, C; Rogero, J R

1980-01-01

Protein hydrogen exchange is generally believed to register some aspects of internal protein dynamics, but the kind of motion at work is not clear. Experiments are being done to identify the determinants of protein hydrogen exchange and to distinguish between local unfolding and accessibility-penetration mechanisms. Results with small molecules, polynucleotides, and proteins demonstrate that solvent accessibility is by no means sufficient for fast exchange. H-exchange slowing is quite generally connected with intramolecular H-bonding, and the exchange process depends pivotally on transient H-bond cleavage. At least in alpha-helical structures, the cooperative aspect of H-bond cleavage must be expressed in local unfolding reactions. Results obtained by use of a difference hydrogen exchange method appear to provide a direct measurement of transient, cooperative, local unfolding reactions in hemoglobin. The reality of these supposed coherent breathing units is being tested by using the difference H-exchange approach to tritium label the units one at a time and then attempting to locate the tritium by fragmenting the protein, separating the fragments, and testing them for label. Early results demonstrate the feasibility of this approach. PMID:7248462

Computational study of the free energy landscape of the miniprotein CLN025 in explicit and implicit solvent.

PubMed

Rodriguez, Alex; Mokoema, Pol; Corcho, Francesc; Bisetty, Khrisna; Perez, Juan J

2011-02-17

The prediction capabilities of atomistic simulations of peptides are hampered by different difficulties, including the reliability of force fields, the treatment of the solvent or the adequate sampling of the conformational space. In this work, we have studied the conformational profile of the 10 residue miniprotein CLN025 known to exhibit a β-hairpin in its native state to understand the limitations of implicit methods to describe solvent effects and how these may be compensated by using different force fields. For this purpose, we carried out a thorough sampling of the conformational space of CLN025 in explicit solvent using the replica exchange molecular dynamics method as a sampling technique and compared the results with simulations of the system modeled using the analytical linearized Poisson-Boltzmann (ALPB) method with three different AMBER force fields: parm94, parm96, and parm99SB. The results show the peptide to exhibit a funnel-like free energy landscape with two minima in explicit solvent. In contrast, the higher minimum nearly disappears from the energy surface when the system is studied with an implicit representation of the solvent. Moreover, the different force fields used in combination with the ALPB method do not describe the system in the same manner. The results of this work suggest that the balance between intra- and intermolecular interactions is the cause of the differences between implicit and explicit solvent simulations in this system, stressing the role of the environment to define properly the conformational profile of a peptide in solution.

Probing chemical transformation in picolitre volume aerosol droplets

NASA Astrophysics Data System (ADS)

Miloserdov, Anatolij; Day, Calum P. F.; Rosario, Gabriela L.; Horrocks, Benjamin R.; Carruthers, Antonia E.

2017-08-01

We have demonstrated chemical transformation in single microscopic-sized aerosol droplets localised in optical tweezers. Droplets in situ are measured during chemical transformation processes of solvent exchange and solute transformation through an ion exchange reaction. Solvent exchange between deionised water and heavy water in aerosol droplets is monitored through observation of the OH and OD Raman stretches. A change in solute chemistry of aerosol is achieved through droplet coalescence events between calcium chloride and sodium carbonate to promote ion exchange. The transformation forming meta-stable and stable states of CaCO3 is observed and analysed using Gaussian peak decomposition to reveal polymorphs.

Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture

DOEpatents

Roelofs, Mark Gerrit; Yang, Zhen-Yu; Han, Amy Qi

2010-06-15

A fluorinated ion exchange polymer is prepared by grafting at least one grafting monomer derived from trifluorostyrene on to at least one base polymer in a organic solvent/water mixture. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

Using Asymmetric Flow Field-Flow Fractionation (AF4) to Determine C60 Colloidal Size Distributions

EPA Science Inventory

The formation of aqueous fullerene suspensions by solvent exchange, sonication, or extended mixing in water is widely reported. Commonly used methods for determining the size of these aggregates rely on static and dynamic light scattering, electron microscopy (EM), or atomic forc...

Method for the production of fabricated hollow microspheroids

DOEpatents

Wickramanayake, Shan; Luebke, David R.

2015-06-09

The method relates to the fabrication of a polymer microspheres comprised of an asymmetric layer surrounding a hollow interior. The fabricated hollow microsphere is generated from a nascent hollow microsphere comprised of an inner core of core fluid surrounded by a dope layer of polymer dope, where the thickness of the dope layer is at least 10% and less than 50% of the diameter of the inner core. The nascent hollow microsphere is exposed to a gaseous environment, generating a vitrified hollow microsphere, which is subsequently immersed in a coagulation bath. Solvent exchange produces a fabricated hollow microsphere comprised of a densified outer skin surrounding a macroporous inner layer, which surrounds a hollow interior. In an embodiment, the polymer is a polyimide or a polyamide-imide, and the non-solvent in the core fluid and the coagulation bath is water. The fabricated hollow microspheres are particularly suited as solvent supports for gas separation processes.

Polar Aprotic Modifiers for Chromatographic Separation and Back-Exchange Reduction for Protein Hydrogen/Deuterium Exchange Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

NASA Astrophysics Data System (ADS)

Valeja, Santosh G.; Emmett, Mark R.; Marshall, Alan G.

2012-04-01

Hydrogen/deuterium exchange monitored by mass spectrometry is an important non-perturbing tool to study protein structure and protein-protein interactions. However, water in the reversed-phase liquid chromatography mobile phase leads to back-exchange of D for H during chromatographic separation of proteolytic peptides following H/D exchange, resulting in incorrect identification of fast-exchanging hydrogens as unexchanged hydrogens. Previously, fast high-performance liquid chromatography (HPLC) and supercritical fluid chromatography have been shown to decrease back-exchange. Here, we show that replacement of up to 40% of the water in the LC mobile phase by the modifiers, dimethylformamide (DMF) and N-methylpyrrolidone (NMP) (i.e., polar organic modifiers that lack rapid exchanging hydrogens), significantly reduces back-exchange. On-line LC micro-ESI FT-ICR MS resolves overlapped proteolytic peptide isotopic distributions, allowing for quantitative determination of the extent of back-exchange. The DMF modified solvent composition also improves chromatographic separation while reducing back-exchange relative to conventional solvent.

Understanding the influence of solvent field and fluctuations on the stability of photo-induced charge-separated state in molecular triad

NASA Astrophysics Data System (ADS)

Balamurugan, D.; Aquino, Adelia; Lischka, Hans; Dios, Francis; Flores, Lionel; Cheung, Margaret

2013-03-01

Molecular triad composed of fullerene, porphyrin, and carotene is an artificial analogue of natural photosynthetic system and is considered for applications in solar energy conversion because of its ability to produce long-lived photo-induced charge separated state. The goal of the present multiscale simulation is to understand how the stability of photo-induced charge-separated state in molecular triad is influenced by a polar organic solvent, namely tetrahydrofuran (THF). The multiscale approach is based on combined quantum, classical molecular dynamics, and statistical physics calculations. The quantum chemical calculations were performed on the triad using the second order algebraic diagrammatic perturbation and time-dependent density functional theory. Molecular dynamics simulations were performed on triad in a box of THF solvent with the replica exchange method. The two methods on different length and time scales are bridged through an important sampling technique. We have analyzed the free energy landscape, structural fluctuations, and the long- range electrostatic interactions between triad and solvent molecules. The results suggest that the polarity and re-organization of the solvent is critical in stabilization of charge-separated state in triad. Supported by DOE (DE-FG02-10ER16175)

A Hydrogen Exchange Method Using Tritium and Sephadex: Its Application to Ribonuclease*

PubMed Central

Englander, S. Walter

2012-01-01

A new method for measuring the hydrogen exchange of macromolecules in solution is described. The method uses tritium to trace the movement of hydrogen, and utilizes Sephadex columns to effect, in about 2 minutes, a separation between tritiated macromolecule and tritiated solvent great enough to allow the measurement of bound tritium. High sensitivity and freedom from artifact is demonstrated and the possible value of the technique for investigation of other kinds of colloid-small molecule interaction is indicated. Competition experiments involving tritium, hydrogen, and deuterium indicate the absence of any equilibrium isotope effect in the ribonuclease-hydrogen isotope system, though a secondary kinetic isotope effect is apparent when ribonuclease is largely deuterated. Ribonuclease shows four clearly distinguishable kinetic classes of exchangeable hydrogens. Evidence is marshaled to suggest the independently measurable classes II, III, and IV (in order of decreasing rate of exchange) to represent “random-chain” peptides, peptides involved in α-helix, and otherwise shielded side-chain and peptide hydrogens, respectively. PMID:14075117

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.

Constant pH Molecular Dynamics in Explicit Solvent with Enveloping Distribution Sampling and Hamiltonian Exchange

PubMed Central

2015-01-01

We present a new computational approach for constant pH simulations in explicit solvent based on the combination of the enveloping distribution sampling (EDS) and Hamiltonian replica exchange (HREX) methods. Unlike constant pH methods based on variable and continuous charge models, our method is based on discrete protonation states. EDS generates a hybrid Hamiltonian of different protonation states. A smoothness parameter s is used to control the heights of energy barriers of the hybrid-state energy landscape. A small s value facilitates state transitions by lowering energy barriers. Replica exchange between EDS potentials with different s values allows us to readily obtain a thermodynamically accurate ensemble of multiple protonation states with frequent state transitions. The analysis is performed with an ensemble obtained from an EDS Hamiltonian without smoothing, s = ∞, which strictly follows the minimum energy surface of the end states. The accuracy and efficiency of this method is tested on aspartic acid, lysine, and glutamic acid, which have two protonation states, a histidine with three states, a four-residue peptide with four states, and snake cardiotoxin with eight states. The pKa values estimated with the EDS-HREX method agree well with the experimental pKa values. The mean absolute errors of small benchmark systems range from 0.03 to 0.17 pKa units, and those of three titratable groups of snake cardiotoxin range from 0.2 to 1.6 pKa units. This study demonstrates that EDS-HREX is a potent theoretical framework, which gives the correct description of multiple protonation states and good calculated pKa values. PMID:25061443

Rate theory of solvent exchange and kinetics of Li(+) - BF4 (-)/PF6 (-) ion pairs in acetonitrile.

PubMed

Dang, Liem X; Chang, Tsun-Mei

2016-09-07

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li(+) and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li(+) in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li(+)-[BF4] and Li(+)-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li(+). We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li(+)-[BF4] and Li(+)-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

Rate theory of solvent exchange and kinetics of Li+ - BF4-/PF6- ion pairs in acetonitrile

NASA Astrophysics Data System (ADS)

Dang, Liem X.; Chang, Tsun-Mei

2016-09-01

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li+ and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li+ in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li+-[BF4] and Li+-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li+. We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li+-[BF4] and Li+-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.

Longitudinal relaxation properties of 1HN and 1Hα determined by direct-detected 13C NMR experiments to study intrinsically disordered proteins (IDPs)

NASA Astrophysics Data System (ADS)

Hošek, Tomáš; Gil-Caballero, Sergi; Pierattelli, Roberta; Brutscher, Bernhard; Felli, Isabella C.

2015-05-01

Intrinsically disordered proteins (IDPs) are functional proteins containing large fragments characterized by high local mobility. Bioinformatic studies have suggested that a significant fraction (more than 30%) of eukaryotic proteins has disordered regions of more than 50 amino acids in length. Hence, NMR methods for the characterization of local compactness and solvent accessibility in such highly disordered proteins are of high importance. Among the available approaches, the HET-SOFAST/BEST experiments (Schanda et al., 2006, Rennella et al., 2014) provide semi-quantitative information by monitoring longitudinal 1H relaxation of amide protons under different initial conditions. However, when approaching physiological sample conditions, the potential of these amide 1H detected experiments is reduced due to rapid amide proton solvent exchange. 13C direct detection methods therefore provide a valuable alternative thanks to a higher chemical shift dispersion and their intrinsic insensitivity toward solvent exchange. Here we present two sets of 13C-detected experiments, which indirectly measure 1HN and 1Hα inversion recovery profiles. The experiments consist of an initial spin inversion-recovery block optimized for selective manipulation of different types of proton spins followed by a CON read-out scheme. The proposed experiments were tested on human α-synuclein and ubiquitin, two representative examples of unfolded and folded proteins.

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

Kleinheinz, G.T.; St. John, W.P.

A study was conducted to develop a rapid and reliable method for the collection and incorporation of biofiltration air samples containing volatile organic compounds (VOCs) into the Microtox toxicity testing system. To date, no method exists for this type of assay. A constant stream of VOCs was generated by air stripping compounds from a complex mixture of petroleum hydrocarbons (PHCs). Samples were collected on coconut charcoal ORBO tubes and the VOCs extracted with methylene chloride. The compounds extracted were then solvent exchanged into dimethyl sulfoxide (DMSO) under gaseous nitrogen. The resulting DMSO extract was directly incorporated into the Microtox toxicitymore » testing system. In order to determine the efficiency of the solvent exchange, the VOCs in the DMSO extract were then extracted into hexane and subsequently analyzed using gas chromatography (GC) with a flame ionization detector (FID). It was determined that all but the most volatile VOCs could be effectively transferred from the ORBO tubes to DMSO for Microtox testing. Potential trace amounts of residual methylene chloride in the DMSO extracts showed no adverse effects in the Microtox system when compared to control samples.« less

Precise determination of water exchanges on a mineral surface

DOE PAGES

Stack, Andrew G.; Borreguero, Jose M.; Prisk, Timothy R.; ...

2016-10-03

Solvent exchanges on solid surfaces and dissolved ions are a fundamental property important for understanding chemical reactions, but the rates of fast exchanges are poorly constrained. In this paper, we probed the diffusional motions of water adsorbed onto nanoparticles of the mineral barite (BaSO 4) using quasi-elastic neutron scattering (QENS) and classical molecular dynamics (MD) to reveal the complex dynamics of water exchange along mineral surfaces. QENS data as a function of temperature and momentum transfer (Q) were fit using scattering functions derived from MD trajectories. The simulations reproduce the dynamics measured in the experiments at ambient temperatures, but asmore » temperature is lowered the simulations overestimate slower motions. Decomposition of the MD-computed QENS intensity into contributions from adsorbed and unbound water shows that the majority of the signal arises from adsorbed species, although the dynamics of unbound water cannot be dismissed. The mean residence times of water on each of the four surface sites present on the barite {001} were calculated using MD: at room temperature the low barium site is 194 ps, whereas the high barium site contains two distributions of motions at 84 and 2.5 ps. These contrast to 13 ps residence time on both sulfate sites, with an additional surface diffusion exchange of 66 ps. Surface exchanges are similar to those of the aqueous ions calculated using the same force field: Ba aq 2+ is 208 ps and SO 4aq 2- is 5.8 ps. Finally, this work demonstrates how MD can be a reliable method to deconvolute solvent exchange reactions when quantitatively validated by QENS measurements.« less

Identification of protein–protein interfaces by decreased amide proton solvent accessibility

PubMed Central

Mandell, Jeffrey G.; Falick, Arnold M.; Komives, Elizabeth A.

1998-01-01

Matrix-assisted laser desorption ionization–time-of-flight mass spectrometry was used to identify peptic fragments from protein complexes that retained deuterium under hydrogen exchange conditions due to decreased solvent accessibility at the interface of the complex. Short deuteration times allowed preferential labeling of rapidly exchanging surface amides so that primarily solvent accessibility changes and not conformational changes were detected. A single mass spectrum of the peptic digest mixture was analyzed to determine the deuterium content of all proteolytic fragments of the protein. The protein–protein interface was reliably indicated by those peptides that retained more deuterons in the complex compared with control experiments in which only one protein was present. The method was used to identify the kinase inhibitor [PKI(5–24)] and ATP-binding sites in the cyclic-AMP-dependent protein kinase. Three overlapping peptides identified the ATP-binding site, three overlapping peptides identified the glycine-rich loop, and two peptides identified the PKI(5–24)-binding site. A complex of unknown structure also was analyzed, human α-thrombin bound to an 83-aa fragment of human thrombomodulin [TMEGF(4–5)]. Five peptides from thrombin showed significantly decreased solvent accessibility in the complex. Three peptides identified the anion-binding exosite I, confirming ligand competition experiments. Two peptides identified a new region of thrombin near the active site providing a potential mechanism of how thrombomodulin alters thrombin substrate specificity. PMID:9843953

Communication: Self-assembly of a model supramolecular polymer studied by replica exchange with solute tempering

NASA Astrophysics Data System (ADS)

Arefi, Hadi H.; Yamamoto, Takeshi

2017-12-01

Conventional molecular-dynamics (cMD) simulation has a well-known limitation in accessible time and length scales, and thus various enhanced sampling techniques have been proposed to alleviate the problem. In this paper, we explore the utility of replica exchange with solute tempering (REST) (i.e., a variant of Hamiltonian replica exchange methods) to simulate the self-assembly of a supramolecular polymer in explicit solvent and compare the performance with temperature-based replica exchange MD (T-REMD) as well as cMD. As a test system, we consider a relatively simple all-atom model of supramolecular polymerization (namely, benzene-1,3,5-tricarboxamides in methylcyclohexane solvent). Our results show that both REST and T-REMD are able to predict highly ordered polymer structures with helical H-bonding patterns, in contrast to cMD which completely fails to obtain such a structure for the present model. At the same time, we have also experienced some technical challenge (i.e., aggregation-dispersion transition and the resulting bottleneck for replica traversal), which is illustrated numerically. Since the computational cost of REST scales more moderately than T-REMD, we expect that REST will be useful for studying the self-assembly of larger systems in solution with enhanced rearrangement of monomers.

Batch extracting process using magneticparticle held solvents

DOEpatents

Nunez, Luis; Vandergrift, George F.

1995-01-01

A process for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents.

Application of cation-exchange solid-phase extraction for the analysis of amino alcohols from water and human plasma for verification of Chemical Weapons Convention.

PubMed

Kanaujia, Pankaj K; Tak, Vijay; Pardasani, Deepak; Gupta, A K; Dubey, D K

2008-03-28

The analysis of nitrogen containing amino alcohols, which are the precursors and degradation products of nitrogen mustards and nerve agent VX, constitutes an important aspect for verifying the compliance to the CWC (Chemical Weapons Convention). This work devotes on the development of solid-phase extraction method using silica- and polymer-based SCX (strong cation-exchange) and MCX (mixed-mode strong cation-exchange) cartridges for N,N-dialkylaminoethane-2-ols and alkyl N,N-diethanolamines, from water. The extracted analytes were analyzed by GC-MS (gas chromatography-mass spectrometry) in the full scan and selected ion monitoring modes. The extraction efficiencies of SCX and MCX cartridges were compared, and results revealed that SCX performed better. Extraction parameters, such as loading capacity, extraction solvent, its volume, and washing solvent were optimized. Best recoveries were obtained using 2 mL methanol containing 10% NH(4)OH and limits of detection could be achieved up to 5 x 10(-3) microg mL(-1) in the selected ion monitoring mode and 0.01 microg mL(-1) in full scan mode. The method was successfully employed for the detection and identification of amino alcohol present in water sample sent by Organization for Prohibition of Chemical Weapons (OPCW) in the official proficiency tests. The method was also applied to extract the analytes from human plasma. The SCX cartridge showed good recoveries of amino alcohols from human plasma after protein precipitation.

Method of separating and recovering uranium and related cations from spent Purex-type systems

DOEpatents

Mailen, J.C.; Tallent, O.K.

1987-02-25

A process for separating uranium and related cations from a spent Purex-type solvent extraction system which contains degradation complexes of tributylphosphate wherein the system is subjected to an ion-exchange process prior to a sodium carbonate scrubbing step. A further embodiment comprises recovery of the separated uranium and related cations. 5 figs.

Solvent dependence of the activation energy of attachment determined by single molecule observations of surfactant adsorption.

PubMed

Honciuc, Andrei; Baptiste, Denver Jn; Campbell, Ian P; Schwartz, Daniel K

2009-07-07

Single-molecule total internal reflection fluorescence microscopy was used to obtain real-time images of fluorescently labeled hexadecanoic (palmitic) acid molecules as they adsorbed at the interface between fused silica and three different solvents: hexadecane (HD), tetrahydrofuran (THF), and water. These solvents were chosen to explore the effect of solvent polarity on the activation energy associated with the attachment rate, i.e., the rate at which molecules were transferred to the surface from the near-surface layer. Direct counting of single-molecule events, made under steady-state conditions at extremely low coverage, provided direct, model-independent measurements of this attachment rate, in contrast with conventional ensemble-averaged methods, which are influenced by bulk transport and competing detachment processes. We found that the attachment rate increased with increasing temperature for all solvents. Arrhenius analyses gave activation energies of 5+/-2 kJ/mol for adsorption from HD, 10+/-2 kJ/mol for adsorption from THF, and 19+/-2 kJ/mol for adsorption from water. These energies increased systematically with the solvent polarity and, therefore, with the expected strength of the solvent-substrate interaction. We hypothesize that the adsorption of amphiphilic solute molecules from solution can be regarded as a competitive exchange between solute molecules and surface-bound solvent. In this scenario, adsorption is an activated process, and the activation energy for attachment is associated with the solvent-substrate interaction energy.

Surface nanodroplets for highly efficient liquid-liquid microextraction

NASA Astrophysics Data System (ADS)

Li, Miaosi; Lu, Ziyang; Yu, Haitao; Zhang, Xuehua

2016-11-01

Nanoscale droplets on a substrate are an essential element for a wide range of applications, such as laboratory-on-chip devices, simple and highly efficient miniaturized reactors for concentrating products, high-throughput single-bacteria or single-biomolecular analysis, encapsulation, and high-resolution imaging techniques. The solvent exchange process is a simple bottom-up approach for producing droplets at solid-liquid interfaces that are only several tens to hundreds of nanometers in height, or a few femtoliters in volume Oil nanodroplets can be produced on a substrate by solvent exchange in which a good solvent of oil is displaced by a poor solvent. Our previous work has significantly advanced understanding of the principle of solvent exchange, and the droplet size can be well-controlled by several parameters, including flow rates, flow geometry, gravitational effect and composition of solutions. In this work, we studied the microextraction effect of surface nanodroplets. Oil nanodroplets have been demonstrated to provide highly-efficient liquid-liquid microextraction of hydrophobic solute in a highly diluted solution. This effect proved the feasibility of nanodroplets as a platform for preconcentrating compounds for in situ highly sensitive microanalysis without further separation. Also the long lifetime and temporal stability of surface nanodroplets allow for some long-term extraction process and extraction without addition of stabilisers.

Droplet-Based Production of Liposomes

NASA Technical Reports Server (NTRS)

Ackley, Donald E.; Forster, Anita

2009-01-01

A process for making monodisperse liposomes having lipid bilayer membranes involves fewer, simpler process steps than do related prior methods. First, a microfluidic, cross junction droplet generator is used to produce vesicles comprising aqueous solution droplets contained in single layer lipid membranes. The vesicles are collected in a lipid-solvent mix that is at most partially soluble in water and is less dense than is water. A layer of water is dispensed on top of the solvent. By virtue of the difference in densities, the water sinks to the bottom and the solvent floats to the top. The vesicles, which have almost the same density as that of water, become exchanged into the water instead of floating to the top. As there are excess lipids in the solvent solution, in order for the vesicles to remain in the water, the addition of a second lipid layer to each vesicle is energetically favored. The resulting lipid bilayers present the hydrophilic ends of the lipid molecules to both the inner and outer membrane surfaces. If lipids of a second kind are dissolved in the solvent in sufficient excess before use, then asymmetric liposomes may be formed.

Taking the plunge: chemical reaction dynamics in liquids.

PubMed

Orr-Ewing, Andrew J

2017-12-11

The dynamics of chemical reactions in liquid solutions are now amenable to direct study using ultrafast laser spectroscopy techniques and advances in computer simulation methods. The surrounding solvent affects the chemical reaction dynamics in numerous ways, which include: (i) formation of complexes between reactants and solvent molecules; (ii) modifications to transition state energies and structures relative to the reactants and products; (iii) coupling between the motions of the reacting molecules and the solvent modes, and exchange of energy; (iv) solvent caging of reactants and products; and (v) structural changes to the solvation shells in response to the changing chemical identity of the solutes, on timescales which may be slower than the reactive events. This article reviews progress in the study of bimolecular chemical reaction dynamics in solution, concentrating on reactions which occur on ground electronic states. It illustrates this progress with reference to recent experimental and computational studies, and considers how the various ways in which a solvent affects the chemical reaction dynamics can be unravelled. Implications are considered for research in fields such as mechanistic synthetic chemistry.

Batch extracting process using magnetic particle held solvents

DOEpatents

Nunez, L.; Vandergrift, G.F.

1995-11-21

A process is described for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents. 5 figs.

Economic Methods of Ginger Protease'sextraction and Purification

NASA Astrophysics Data System (ADS)

Qiao, Yuanyuan; Tong, Junfeng; Wei, Siqing; Du, Xinyong; Tang, Xiaozhen

This article reports the ginger protease extraction and purification methods from fresh ginger rhizome. As to ginger protease extraction, we adapt the steps of organic solvent dissolving, ammonium sulfate depositing and freeze-drying, and this method can attain crude enzyme powder 0.6% weight of fresh ginger rhizome. The purification part in this study includes two steps: cellulose ion exchange (DEAE-52) and SP-Sephadex 50 chromatography, which can purify crude ginger protease through ion and molecular weight differences respectively.

Sampling the multiple folding mechanisms of Trp-cage in explicit solvent

PubMed Central

Juraszek, J.; Bolhuis, P. G.

2006-01-01

We investigate the kinetic pathways of folding and unfolding of the designed miniprotein Trp- cage in explicit solvent. Straightforward molecular dynamics and replica exchange methods both have severe convergence problems, whereas transition path sampling allows us to sample unbiased dynamical pathways between folded and unfolded states and leads to deeper understanding of the mechanisms of (un)folding. In contrast to previous predictions employing an implicit solvent, we find that Trp-cage folds primarily (80% of the paths) via a pathway forming the tertiary contacts and the salt bridge, before helix formation. The remaining 20% of the paths occur in the opposite order, by first forming the helix. The transition states of the rate-limiting steps are solvated native-like structures. Water expulsion is found to be the last step upon folding for each route. Committor analysis suggests that the dynamics of the solvent is not part of the reaction coordinate. Nevertheless, during the transition, specific water molecules are strongly bound and can play a structural role in the folding. PMID:17035504

Freezing polystyrene-b-poly(2-vinylpyridine) micelle nanoparticles with different nanostructures and sizes.

PubMed

Fan, Hailong; Jin, Zhaoxia

2014-04-28

Herein we report how to control the nanostructures and sizes of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) nanoparticles via manipulating freezing in solvent-exchange. By characterizing and analyzing the distinct structural features of the obtained nanoparticles, we recognized that micelle self-assembly happens in the precipitation of PS-b-P2VP when water is added into the block copolymer (BCP) solution. Solvent properties significantly influence micelle types that are vesicles in acetone/H2O and spherical micelles in tetrahydrofuran/H2O, respectively, thus further inducing different frozen nanostructures of the obtained nanoparticles, onion-like in acetone/H2O and large compound micelles in tetrahydrofuran/H2O. By changing the concentration of the block copolymers and the Vsolvent/VH2O ratio to modify the freezing stage at which block copolymer micelles are frozen, we can further control the size of the nanoparticles. Moreover, small molecules (phosphotungstic acid, pyrene, 1-pyrenebutyric acid) can be trapped into the block copolymer nanoparticles via the freezing process. Their distribution in the nanoparticles relies not only on the solvent property, but also on their interactions with block copolymers. The hybrid nanoparticles with ordered distribution of small molecules can be further changed to partially-void nanoparticles. Our study demonstrated that manipulating the freezing of block copolymers in the solvent exchange process is a simple and controllable fabrication method to generate BCP nanoparticles with different architectures.

Solvent-Assisted Linker Exchange: An Alternative to the De Novo Synthesis of Unattainable Metal-Organic Frameworks

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

Karagiaridi, Olga; Bury, Wojciech; Mondloch, Joseph E.

Metal-organic frameworks (MOFs) have gained considerable attention as hybrid materials—in part because of a multitude of potential useful applications, ranging from gas separation to catalysis and light harvesting. Unfortunately, de novo synthesis of MOFs with desirable function–property combinations is not always reliable and may suffer from vagaries such as formation of undesirable topologies, low solubility of precursors, and loss of functionality of the sensitive network components. The recently discovered synthetic approach coined solvent-assisted linker exchange (SALE) constitutes a simple to implement strategy for circumventing these setbacks; its use has already led to the generation of a variety of MOF materialsmore » previously unobtainable by direct synthesis methods. This Review provides a perspective of the achievements in MOF research that have been made possible with SALE and examines the studies that have facilitated the understanding and broadened the scope of use of this invaluable synthetic tool.« less

Characterization of Antimicrobial Agent Loaded Eudragit RS Solvent Exchange-Induced In Situ Forming Gels for Periodontitis Treatment.

PubMed

Phaechamud, Thawatchai; Jantadee, Takron; Mahadlek, Jongjan; Charoensuksai, Purin; Pichayakorn, Wiwat

2017-02-01

Eudragit RS (ERS), a quaternary polyacrylate positively charged polymer, exhibits a very low permeability and swells in aqueous media independently of pH without dissolving. Owing to its high solubility in N-methyl pyrrolidone (NMP), it was interesting to apply as polymer matrix for solvent-exchanged in situ forming gel. The aim of this research was to prepare in situ forming gels from ERS to deliver the antimicrobial agents (doxycycline hyclate, metronidazole, and benzoyl peroxide) for periodontitis treatment. They were evaluated for viscosity and rheology, gel formation, syringeability, drug release, and antimicrobial activities. The solvent exchange between NMP and an external aqueous simulated gingival crevicular fluid stimulated the dissolved ERS transforming into the opaque rigid gel. Antimicrobial agent loaded ERS systems exhibited Newtonian flow with acceptable syringeability. The higher-loaded ERS promoted the more prolongation of drug release because of the retardation of water diffusion into the precipitated matrix. Antimicrobial activities against Staphylococcus aureus, Escherichia coli, Candida albicans, Streptococcus mutans, and Porphyromonas gingivalis depended on type of drugs and test microorganisms. Doxycycline hyclate loaded ERS systems showed these activities greater than the others; however, all of them could inhibit all test microorganisms. Thus, the solvent exchange-induced in situ forming gels comprising ERS-antimicrobial drugs exhibited potential use as localized delivery systems for periodontitis treatment.

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

DOE PAGES

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

2016-11-25

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

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

Dang, Liem X.; Schenter, Gregory K.

To enhance our understanding of the solvent exchange mechanism in liquid methanol, we report a systematic study of this process using molecular dynamics simulations. We use transition state theory, the Impey-Madden-McDonald method, the reactive flux method, and Grote-Hynes theory to compute the rate constants for this process. Solvent coupling was found to dominate, resulting in a significantly small transmission coefficient. We predict a positive activation volume for the methanol exchange process. The essential features of the dynamics of the system as well as the pressure dependence are recovered from a Generalized Langevin Equation description of the dynamics. We find thatmore » the dynamics and response to anharmonicity can be decomposed into two time regimes, one corresponding to short time response (< 0.1 ps) and long time response (> 5 ps). An effective characterization of the process results from launching dynamics from the planar hypersurface corresponding to Grote-Hynes theory. This results in improved numerical convergence of correlation functions. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less

Pressure-assisted cold denaturation of hen egg white lysozyme: the influence of co-solvents probed by hydrogen exchange nuclear magnetic resonance.

PubMed

Vogtt, K; Winter, R

2005-08-01

COSY proton nuclear magnetic resonance was used to measure the exchange rates of amide protons of hen egg white lysozyme (HEWL) in the pressure-assisted cold-denatured state and in the heat-denatured state. After dissolving lysozyme in deuterium oxide buffer, labile protons exchange for deuterons in such a way that exposed protons are substituted rapidly, whereas "protected" protons within structured parts of the protein are substituted slowly. The exchange rates k obs were determined for HEWL under heat treatment (80 degrees C) and under high pressure conditions at low temperature (3.75 kbar, -13 degrees C). Moreover, the influence of co-solvents (sorbitol, urea) on the exchange rate was examined under pressure-assisted cold denaturation conditions, and the corresponding protection factors, P, were determined. The exchange kinetics upon heat treatment was found to be a two-step process with initial slow exchange followed by a fast one, showing residual protection in the slow-exchange state and P-factors in the random-coil-like range for the final temperature-denatured state. Addition of sorbitol (500 mM) led to an increase of P-factors for the pressure-assisted cold denatured state, but not for the heat-denatured state. The presence of 2 M urea resulted in a drastic decrease of the P-factors of the pressure-assisted cold denatured state. For both types of co-solvents, the effect they exert appears to be cooperative, i.e., no particular regions within the protein can be identified with significantly diverse changes of P-factors.

Nanobubbles do not sit alone at the solid-liquid interface.

PubMed

Peng, Hong; Hampton, Marc A; Nguyen, Anh V

2013-05-21

The unexpected stability and anomalous contact angle of gaseous nanobubbles at the hydrophobic solid-liquid interface has been an issue of debate for almost two decades. In this work silicon-nitride tipped AFM cantilevers are used to probe the highly ordered pyrolytic graphite (HOPG)-water interface with and without solvent-exchange (a common nanobubble production method). Without solvent-exchange the force obtained by the single force and force mapping techniques is consistent over the HOPG atomic layers and described by DLVO theory (strong EDL repulsion). With solvent-exchange the force is non-DLVO (no EDL repulsion) and the range of the attractive jump-in (>10 nm) over the surface is grouped into circular areas of longer range, consistent with nanobubbles, and the area of shorter range. The non-DLVO nature of the area between nanobubbles suggests that the interaction is no longer between a silicon-nitride tip and HOPG. Interfacial gas enrichment (IGE) covering the entire area between nanobubbles is suggested to be responsible for the non-DLVO forces. The absence of EDL repulsion suggests that both IGE and nanobubbles are not charged. The coexistence of nanobubbles and IGE provides further evidence of nanobubble stability by dynamic equilibrium. The IGE cannot be removed by contact mode scanning of a cantilever tip in pure water, but in a surfactant (SDS) solution the mechanical action of the tip and the chemical action of the surfactant molecules can successfully remove the enrichment. Strong EDL repulsion between the tip and nanobubbles/IGE in surfactant solutions is due to the polar heads of the adsorbed surfactant molecules.

Observation of Solvent Penetration during Cold Denaturation of E. coli Phosphofructokinase-2

PubMed Central

Ramírez-Sarmiento, César A.; Baez, Mauricio; Wilson, Christian A.M.; Babul, Jorge; Komives, Elizabeth A.; Guixé, Victoria

2013-01-01

Phosphofructokinase-2 is a dimeric enzyme that undergoes cold denaturation following a highly cooperative N2 2I mechanism with dimer dissociation and formation of an expanded monomeric intermediate. Here, we use intrinsic fluorescence of a tryptophan located at the dimer interface to show that dimer dissociation occurs slowly, over several hours. We then use hydrogen-deuterium exchange mass spectrometry experiments, performed by taking time points over the cold denaturation process, to measure amide exchange throughout the protein during approach to the cold denatured state. As expected, a peptide corresponding to the dimer interface became more solvent exposed over time at 3°C; unexpectedly, amide exchange increased throughout the protein over time at 3°C. The rate of increase in amide exchange over time at 3°C was the same for each region and equaled the rate of dimer dissociation measured by tryptophan fluorescence, suggesting that dimer dissociation and formation of the cold denatured intermediate occur without appreciable buildup of folded monomer. The observation that throughout the protein amide exchange increases as phosphofructokinase-2 cold denatures provides experimental evidence for theoretical predictions that cold denaturation primarily occurs by solvent penetration into the hydrophobic core of proteins in a sequence-independent manner. PMID:23708365

Observation of solvent penetration during cold denaturation of E. coli phosphofructokinase-2.

PubMed

Ramírez-Sarmiento, César A; Baez, Mauricio; Wilson, Christian A M; Babul, Jorge; Komives, Elizabeth A; Guixé, Victoria

2013-05-21

Phosphofructokinase-2 is a dimeric enzyme that undergoes cold denaturation following a highly cooperative N2 2I mechanism with dimer dissociation and formation of an expanded monomeric intermediate. Here, we use intrinsic fluorescence of a tryptophan located at the dimer interface to show that dimer dissociation occurs slowly, over several hours. We then use hydrogen-deuterium exchange mass spectrometry experiments, performed by taking time points over the cold denaturation process, to measure amide exchange throughout the protein during approach to the cold denatured state. As expected, a peptide corresponding to the dimer interface became more solvent exposed over time at 3°C; unexpectedly, amide exchange increased throughout the protein over time at 3°C. The rate of increase in amide exchange over time at 3°C was the same for each region and equaled the rate of dimer dissociation measured by tryptophan fluorescence, suggesting that dimer dissociation and formation of the cold denatured intermediate occur without appreciable buildup of folded monomer. The observation that throughout the protein amide exchange increases as phosphofructokinase-2 cold denatures provides experimental evidence for theoretical predictions that cold denaturation primarily occurs by solvent penetration into the hydrophobic core of proteins in a sequence-independent manner. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Systematic Assessment of Seven Solvent and Solid-Phase Extraction Methods for Metabolomics Analysis of Human Plasma by LC-MS

NASA Astrophysics Data System (ADS)

Sitnikov, Dmitri G.; Monnin, Cian S.; Vuckovic, Dajana

2016-12-01

The comparison of extraction methods for global metabolomics is usually executed in biofluids only and focuses on metabolite coverage and method repeatability. This limits our detailed understanding of extraction parameters such as recovery and matrix effects and prevents side-by-side comparison of different sample preparation strategies. To address this gap in knowledge, seven solvent-based and solid-phase extraction methods were systematically evaluated using standard analytes spiked into both buffer and human plasma. We compared recovery, coverage, repeatability, matrix effects, selectivity and orthogonality of all methods tested for non-lipid metabolome in combination with reversed-phased and mixed-mode liquid chromatography mass spectrometry analysis (LC-MS). Our results confirmed wide selectivity and excellent precision of solvent precipitations, but revealed their high susceptibility to matrix effects. The use of all seven methods showed high overlap and redundancy which resulted in metabolite coverage increases of 34-80% depending on LC-MS method employed as compared to the best single extraction protocol (methanol/ethanol precipitation) despite 7x increase in MS analysis time and sample consumption. The most orthogonal methods to methanol-based precipitation were ion-exchange solid-phase extraction and liquid-liquid extraction using methyl-tertbutyl ether. Our results help facilitate rational design and selection of sample preparation methods and internal standards for global metabolomics.

Systematic Assessment of Seven Solvent and Solid-Phase Extraction Methods for Metabolomics Analysis of Human Plasma by LC-MS

PubMed Central

Sitnikov, Dmitri G.; Monnin, Cian S.; Vuckovic, Dajana

2016-01-01

The comparison of extraction methods for global metabolomics is usually executed in biofluids only and focuses on metabolite coverage and method repeatability. This limits our detailed understanding of extraction parameters such as recovery and matrix effects and prevents side-by-side comparison of different sample preparation strategies. To address this gap in knowledge, seven solvent-based and solid-phase extraction methods were systematically evaluated using standard analytes spiked into both buffer and human plasma. We compared recovery, coverage, repeatability, matrix effects, selectivity and orthogonality of all methods tested for non-lipid metabolome in combination with reversed-phased and mixed-mode liquid chromatography mass spectrometry analysis (LC-MS). Our results confirmed wide selectivity and excellent precision of solvent precipitations, but revealed their high susceptibility to matrix effects. The use of all seven methods showed high overlap and redundancy which resulted in metabolite coverage increases of 34–80% depending on LC-MS method employed as compared to the best single extraction protocol (methanol/ethanol precipitation) despite 7x increase in MS analysis time and sample consumption. The most orthogonal methods to methanol-based precipitation were ion-exchange solid-phase extraction and liquid-liquid extraction using methyl-tertbutyl ether. Our results help facilitate rational design and selection of sample preparation methods and internal standards for global metabolomics. PMID:28000704

Impact of drying on pore structures in ettringite-rich cements

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

Galan, I., E-mail: isabelgalan@abdn.ac.uk; Beltagui, H.; García-Maté, M.

Drying techniques affect the properties of cement pastes to varying extents. The effect of different drying techniques on calcium sulfoaluminate-based (C$A) cements and their constituent phases is reported for a range of simulated and commercial C$A pastes which are benchmarked against an OPC paste. The recommended methodologies used to dry samples were identified from the literature and include D-drying and solvent exchange. These methods were used in conjunction with mercury intrusion porosimetry (MIP) and X-ray powder diffraction (XRPD) measurements to assess the changes in pore structure and the damage to crystalline phases, respectively. D-drying and isopropanol exchange are the mostmore » satisfactory and least damaging methods for drying C$A based pastes.« less

Atomistic understanding of cation exchange in PbS nanocrystals using simulations with pseudoligands

PubMed Central

Fan, Zhaochuan; Lin, Li-Chiang; Buijs, Wim; Vlugt, Thijs J. H.; van Huis, Marijn A.

2016-01-01

Cation exchange is a powerful tool for the synthesis of nanostructures such as core–shell nanocrystals, however, the underlying mechanism is poorly understood. Interactions of cations with ligands and solvent molecules are systematically ignored in simulations. Here, we introduce the concept of pseudoligands to incorporate cation-ligand-solvent interactions in molecular dynamics. This leads to excellent agreement with experimental data on cation exchange of PbS nanocrystals, whereby Pb ions are partially replaced by Cd ions from solution. The temperature and the ligand-type control the exchange rate and equilibrium composition of cations in the nanocrystal. Our simulations reveal that Pb ions are kicked out by exchanged Cd interstitials and migrate through interstitial sites, aided by local relaxations at core–shell interfaces and point defects. We also predict that high-pressure conditions facilitate strongly enhanced cation exchange reactions at elevated temperatures. Our approach is easily extendable to other semiconductor compounds and to other families of nanocrystals. PMID:27160371

Molecular dynamics simulations of biological membranes and membrane proteins using enhanced conformational sampling algorithms☆

PubMed Central

Mori, Takaharu; Miyashita, Naoyuki; Im, Wonpil; Feig, Michael; Sugita, Yuji

2016-01-01

This paper reviews various enhanced conformational sampling methods and explicit/implicit solvent/membrane models, as well as their recent applications to the exploration of the structure and dynamics of membranes and membrane proteins. Molecular dynamics simulations have become an essential tool to investigate biological problems, and their success relies on proper molecular models together with efficient conformational sampling methods. The implicit representation of solvent/membrane environments is reasonable approximation to the explicit all-atom models, considering the balance between computational cost and simulation accuracy. Implicit models can be easily combined with replica-exchange molecular dynamics methods to explore a wider conformational space of a protein. Other molecular models and enhanced conformational sampling methods are also briefly discussed. As application examples, we introduce recent simulation studies of glycophorin A, phospholamban, amyloid precursor protein, and mixed lipid bilayers and discuss the accuracy and efficiency of each simulation model and method. This article is part of a Special Issue entitled: Membrane Proteins. Guest Editors: J.C. Gumbart and Sergei Noskov. PMID:26766517

Interlaboratory comparison of mutagenesis testing of coal fly ash derived from differenct coal conversion technologies

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

Chrisp, C.; Hobbs, C.; Clark, R.

1979-01-01

This experiment showed that mutagenicity of fly ash derived from different coal conversion technologies, as determined by the Ames plate incorporation test, was similar in all three laboratories. The differences in mutagenic activity of each fly ash between laboratories with different solvent extraction methods were no greater than one order of magnitude. In addition, there were much smaller, but still significant differences in mutagenic activity between laboratories when the same solvent extract of a particular fly ash was tested in each laboratory. There were also significant differences in mutagenicity of the positive control mutagen (maximum of fivefold) between laboratories. Becausemore » of this difference in Ames test sensitivity between laboratories, the influence of the solvent extraction methods on differences in mutagenicity was not clear. However, the data suggested that either there were significant differences in the degree of sensitivity of Ames tests for different complex mixtures within each laboratory, or else there were differences in mutagen extraction efficiency between different solvent extraction methods. Both Ames test sensitivity and solvent extraction may be important. Further work would be necessary to separate the contribution of these two factors. An important aspect of further work would be to separate the contribution of the innate sensitivity of substrains of Ames tester strains in each laboratory from the possible effects of differences in Ames testing methodology. This could be done by testing the same extracts of fly ash and positive control mutagens with substrains of tester strains exchanged between laboratories. This work also implies that caution should be exercised in assuming that the same solvent would have the same efficiency for extraction of mutagens from different fly ashes even within the same laboratory.« less

Chiral ligand exchange high-speed countercurrent chromatography: mechanism, application and comparison with conventional liquid chromatography in enantioseparation of aromatic α-hydroxyl acids

PubMed Central

Tong, Shengqiang; Shen, Mangmang; Cheng, Dongping; Ito, Yoichiro; Yan, Jizhong

2014-01-01

This work concentrates on the separation mechanism and application of chiral ligand exchange high-speed countercurrent chromatography (HSCCC) in enantioseparations, and comparison with traditional chiral ligand exchange high performance liquid chromatography (HPLC). The enantioseparation of ten aromatic α-hydroxyl acids were performed by these two chromatographic methods. Results showed that five of the racemates were successfully enantioseparated by HSCCC while only three of the racemates could be enantioseparated by HPLC using a suitable chiral ligand mobile phase additive. For HSCCC, the two-phase solvent system was composed of butanol-water (1:1, v/v), to which N-n-dodecyl-L-proline was added in the organic phase as chiral ligand and cupric acetate was added in the aqueous phase as a transition metal ion. Various operation parameters in HSCCC were optimized by enantioselective liquid-liquid extraction. Based on the results of the present studies the separation mechanism for HSCCC was proposed. For HPLC, the optimized mobile phase composed of aqueous solution containing 6 mmol L−1 L-phenylalanine and 3 mmol L−1 cupric sulfate and methanol was used for enantioseparation. Among three ligands tested on a conventional reverse stationary phase column, only one was found to be effective. In the present studies HSCCC presented unique advantages due to its high versatility of two-phase solvent systems and it could be used as an alternative method for enantioseparations. PMID:25087742

Photothermal Activation of Metal-Organic Frameworks Using a UV-Vis Light Source.

PubMed

Espín, Jordi; Garzón-Tovar, Luis; Carné-Sánchez, Arnau; Imaz, Inhar; Maspoch, Daniel

2018-03-21

Metal-organic frameworks (MOFs) usually require meticulous removal of the solvent molecules to unlock their potential porosity. Herein, we report a novel one-step method for activating MOFs based on the photothermal effect induced by directly irradiating them with a UV-vis lamp. The localized light-to-heat conversion produced in the MOF crystals upon irradiation enables a very fast solvent removal, thereby significantly reducing the activation time to as low as 30 min and suppressing the need for time-consuming solvent-exchange procedures and vacuum conditions. This approach is successful for a broad range of MOFs, including HKUST-1, UiO-66-NH 2 , ZIF-67, CPO-27-M (M = Zn, Ni, and Mg), Fe-MIL-101-NH 2 , and IRMOF-3, all of which exhibit absorption bands in the light emission range. In addition, we anticipate that this photothermal activation can also be used to activate covalent organic frameworks (COFs).

On-line comprehensive two-dimensional normal-phase liquid chromatography×reversed-phase liquid chromatography for preparative isolation of toad venom.

PubMed

Li, Jia-Fu; Fang, Hua; Yan, Xia; Chang, Fang-Rong; Wu, Zhen; Wu, Yun-Long; Qiu, Ying-Kun

2016-07-22

An on-line comprehensive preparative two-dimensional normal-phase liquid chromatography×reversed-phase liquid chromatography (2D NPLC×RPLC) system was constructed with a newly developed vacuum evaporation assisted adsorption (VEAA) interface, allowing fast removal of NPLC solvent in the vacuum condition and successfully solving the solvent incompatibility problem between NPLC and RPLC. The system achieved on-line solvent exchange within the two dimensions and its performance was illustrated by gram-scale isolation of crude extract from the venom of Bufo bufo gargarizans. Within separation time of ∼20h, 19 compounds were obtained with high purity in a single run. With the VEAA interface, the 2D system exhibited apparent advantages in separation efficiency and automation compared with conventional methods, indicating its promising application in the routine separation process for complicated natural products. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of molecular geometry, exchange-correlation functional, and solvent effects in the modeling of vertical excitation energies in phthalocyanines using time-dependent density functional theory (TDDFT) and polarized continuum model TDDFT methods: can modern computational chemistry methods explain experimental controversies?

PubMed

Nemykin, Victor N; Hadt, Ryan G; Belosludov, Rodion V; Mizuseki, Hiroshi; Kawazoe, Yoshiyuki

2007-12-20

A time-dependent density functional theory (TDDFT) approach coupled with 14 different exchange-correlation functionals was used for the prediction of vertical excitation energies in zinc phthalocyanine (PcZn). In general, the TDDFT approach provides a more accurate description of both visible and ultraviolet regions of the UV-vis and magnetic circular dichroism (MCD) spectra of PcZn in comparison to the more popular semiempirical ZINDO/S and PM3 methods. It was found that the calculated vertical excitation energies of PcZn correlate with the amount of Hartree-Fock exchange involved in the exchange-correlation functional. The correlation was explained on the basis of the calculated difference in energy between occupied and unoccupied molecular orbitals. The influence of PcZn geometry, optimized using different exchange-correlation functionals, on the calculated vertical excitation energies in PcZn was found to be relatively small. The influence of solvents on the calculated vertical excitation energies in PcZn was considered for the first time using a polarized continuum model TDDFT (PCM-TDDFT) method and was found to be relatively small in excellent agreement with the experimental data. For all tested TDDFT and PCM-TDDFT cases, an assignment of the Q-band as an almost pure a1u (HOMO)-->eg (LUMO) transition, initially suggested by Gouterman, was confirmed. Pure exchange-correlation functionals indicate the presence of six 1Eu states in the B-band region of the UV-vis spectrum of PcZn, while hybrid exchange-correlation functionals predict only five 1Eu states for the same energy envelope. The first two symmetry-forbidden n-->pi* transitions were predicted in the Q0-2 region and in the low-energy tail of the B-band, while the first two symmetry-allowed n-->pi* transitions were found within the B-band energy envelope when pure exchange-correlation functionals were used for TDDFT calculations. The presence of a symmetry-forbidden but vibronically allowed n-->pi* transition in the Q0-2 spectral envelope explains the long-time controversy between the experimentally observed low-intensity transition in the Q0-2 region and previous semiempirical and TDDFT calculations, which were unable to predict any electronic transitions in this area. To prove the conceptual possibility of the presence of several degenerate 1Eu states in the B-band region of PcZn, room-temperature UV-vis and MCD spectra of zinc tetra-tert-butylphthalocyanine (PctZn) in non-coordinating solvents were recorded and analyzed using band deconvolution analysis. It was found that the B-band region of the UV-vis and MCD spectra of PctZn can be easily deconvoluted using six MCD Faraday A-terms and two MCD Faraday B-terms with energies close to those predicted by TDDFT calculations for 1Eu and 1A2u excited states, respectively. Such a good agreement between theory and experiment clearly indicates the possibility of employing a TDDFT approach for the accurate prediction of vertical excitation energies in phthalocyanines within a large energy range.

Stability of the solid electrolyte Li{sub 3}OBr to common battery solvents

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

Schroeder, D.J.; Hubaud, A.A.; Vaughey, J.T., E-mail: vaughey@anl.gov

2014-01-01

Graphical abstract: The stability of the anti-perovskite phase Li{sub 3}OBr has been assessed in a variety of battery solvents. - Highlights: • Lithium stable solid electrolyte Li{sub 3}OBr unstable to polar organic solvents. • Solvation with no dissolution destroys long-range structure. • Ion exchange with protons observed. - Abstract: Recently a new class of solid lithium ion conductors was reported based on the anti-perovskite structure, notably Li{sub 3}OCl and Li{sub 3}OBr. For many beyond lithium-ion battery uses, the solid electrolyte is envisioned to be in direct contact with liquid electrolytes and lithium metal. In this study we evaluated the stabilitymore » of the Li{sub 3}OBr phase against common battery solvents electrolytes, including diethylcarbonate (DEC) and dimethylcarbonate (DMC), as well as a LiPF{sub 6} containing commercial electrolyte. In contact with battery-grade organic solvents, Li{sub 3}OBr was typically found to be insoluble but lost its crystallinity and reacted with available protons and in some cases with the solvent. A low temperature heat treatment was able to restore crystallinity of the samples; however evidence of proton ion exchange was conserved.« less

Short communication: separation and quantification of caseins and casein macropeptide using ion-exchange chromatography.

PubMed

Holland, B; Rahimi Yazdi, S; Ion Titapiccolo, G; Corredig, M

2010-03-01

The aim of this work was to improve an existing method to separate and quantify the 4 major caseins from milk samples (i.e., containing whey proteins) using ion-exchange chromatography. The separation process was carried out using a mini-preparative cation exchange column (1 or 5mL of column volume), using urea acetate as elution buffer at pH 3.5 with a NaCl gradient. All 4 major caseins were separated, and the purity of each peak was assessed using sodium dodecyl sulfate-PAGE. Purified casein fractions were also added to raw milk to confirm their elution volumes. The quantification was carried out using purified caseins in buffer as well as added directly to fresh skim milk. This method can also be employed to determine the decrease in kappa-casein and the release of the casein-macropeptide during enzymatic hydrolysis using rennet. In this case, the main advantage of using this method is the lack of organic solvents compared with the conventional method for separation of macropeptide (using reversed phase HPLC).

Synthesis and characterization of sulfonated poly ether ether ketone (sPEEK) membranes for low temperature fuel cells

NASA Astrophysics Data System (ADS)

Ali, Mawlood Maajal; Rizvi, S. J. A.; Azam, Ameer

2018-05-01

Poly ether ether ketone (PEEK) was sulfonated with 1.0 M sulphuric acid for varying durations to have various degrees of sulfonation (DS) from 43 to 55%. The FT-IR spectra confirmed the successful sulfonation of PEEK. The sulfonated PEEK (sPEEK) membranes were prepared by a solvent casting method using dimethylacetamide (DMAc) as solvent and upon drying the membranes were characterized. The DS% and ion exchange capacity (IEC) were determined by a back titration method. The IEC and DS of sPEEK was found to increase with the increment of sulfonation reaction time. Water uptake also increased with increase in the DS. The Thermogravimetric (TGA) curves revealed poor thermal stability of sPEEK. The proton conductivity of sPEEK membrane was found to considerably better with degree of sulfonation for fuel cell application.

Development of an 19F NMR method for the analysis of fluorinated acids in environmental water samples.

PubMed

Ellis, D A; Martin, J W; Muir, D C; Mabury, S A

2000-02-15

This investigation was carried out to evaluate 19F NMR as an analytical tool for the measurement of trifluoroacetic acid (TFA) and other fluorinated acids in the aquatic environment. A method based upon strong anionic exchange (SAX) chromatography was also optimized for the concentration of the fluoro acids prior to NMR analysis. Extraction of the analyte from the SAX column was carried out directly in the NMR solvent in the presence of the strong organic base, DBU. The method allowed the analysis of the acid without any prior cleanup steps being involved. Optimal NMR sensitivity based upon T1 relaxation times was investigated for seven fluorinated compounds in four different NMR solvents. The use of the relaxation agent chromium acetylacetonate, Cr(acac)3, within these solvent systems was also evaluated. Results show that the optimal NMR solvent differs for each fluorinated analyte. Cr(acac)3 was shown to have pronounced effects on the limits of detection of the analyte. Generally, the optimal sensitivity condition appears to be methanol-d4/2M DBU in the presence of 4 mg/mL of Cr-(acac)3. The method was validated through spike and recovery for five fluoro acids from environmentally relevant waters. Results are presented for the analysis of TFA in Toronto rainwater, which ranged from < 16 to 850 ng/L. The NMR results were confirmed by GC-MS selected-ion monitoring of the fluoroanalide derivative.

Density functional theory studies on the structures and water-exchange reactions of aqueous Al(III)-oxalate complexes.

PubMed

Jin, Xiaoyan; Yan, Yu; Shi, Wenjing; Bi, Shuping

2011-12-01

The structures and water-exchange reactions of aqueous aluminum-oxalate complexes are investigated using density functional theory. The present work includes (1) The structures of Al(C(2)O(4))(H(2)O)(4)(+) and Al(C(2)O(4))(2)(H(2)O)(2)(-) were optimized at the level of B3LYP/6-311+G(d,p). The geometries obtained suggest that the Al-OH(2) bond lengths trans to C(2)O(4)(2-) ligand in Al(C(2)O(4))(H(2)O)(4)(+) are much longer than the Al-OH(2) bond lengths cis to C(2)O(4)(2-). For Al(C(2)O(4))(2)(H(2)O)(2)(-), the close energies between cis and trans isomers imply the coexistence in aqueous solution. The (27)Al NMR and (13)C NMR chemical shifts computed with the consideration of sufficient solvent effect using HF GIAO method and 6-311+G(d,p) basis set are in agreement with the experimental values available, indicating the appropriateness of the applied models; (2) The water-exchange reactions of Al(III)-oxalate complexes were simulated at the same computational level. The results show that water exchange proceeds via dissociative pathway and the activation energy barriers are sensitive to the solvent effect. The energy barriers obtained indicate that the coordinated H(2)O cis to C(2)O(4)(2-) in Al(C(2)O(4))(H(2)O)(4)(+) is more labile than trans H(2)O. The water-exchange rate constants (k(ex)) of trans- and cis-Al(C(2)O(4))(2)(H(2)O)(2)(-) were estimated by four methods and their respective characteristics were explored; (3) The significance of the study on the aqueous aluminum-oxalate complexes to environmental chemistry is discussed. The influences of ubiquitous organic ligands in environment on aluminum chemistry behavior can be elucidated by extending this study to a series of Al(III)-organic system.

Absorption and fluorescence spectra of heterocyclic isomers from long-range-corrected density functional theory in polarizable continuum approach.

PubMed

Kityk, Andriy V

2012-03-22

Long-range-corrected (LC) DFT/TDDFT methods may provide adequate description of ground and excited state properties; however, accuracy of such an approach depends much on a range separation (exchange screening) representing adjustable model parameter. Its relation to a size or specific of molecular systems has been explored in numerous studies, whereas the effect of solvent environment is usually ignored during the evaluation of state properties. To benchmark and assess the quality of the LC-DFT/TDDFT formalism, we report the optical absorption and fluorescence emission energies of organic heterocyclic isomers, DPIPQ and PTNA, calculated by LC-BLYP DFT/TDDFT method in the polarizable continuum (PCM) approach. The calculations are compared with the optical absorption and fluorescence spectra measured in organic solvents of different polarity. Despite a considerable structural difference, both dyes exhibit quite similar range separations being somewhat different for the optical absorption and fluorescence emission processes. Properly parametrized LC-BLYP xc-potential well reproduces basic features of the optical absorption spectra including the electronic transitions to higher excited states. The DFT/TDDFT/PCM analysis correctly predicts the solvation trends although solvatochromic shifts of the electronic transition energies appear to be evidently underestimated in most cases, especially for the fluorescence emission. Considering the discrepancy between the experiment and theory, evaluated state dipole moments and solvation corrections to the exchange screening are analyzed. The results of the present study emphasize the importance of a solvent-dependent range separation in DFT/TDDFT/PCM calculations for investigating excited state properties. © 2012 American Chemical Society

Theoretical prediction of pKa in methanol: testing SM8 and SMD models for carboxylic acids, phenols, and amines.

PubMed

Miguel, Elizabeth L M; Silva, Poliana L; Pliego, Josefredo R

2014-05-29

Methanol is a widely used solvent for chemical reactions and has solvation properties similar to those of water. However, the performance of continuum solvation models in this solvent has not been tested yet. In this report, we have investigated the performance of the SM8 and SMD models for pKa prediction of 26 carboxylic acids, 24 phenols, and 23 amines in methanol. The gas phase contribution was included at the X3LYP/TZVPP+diff//X3LYP/DZV+P(d) level. Using the proton exchange reaction with acetic acid, phenol, and ammonia as reference species leads to RMS error in the range of 1.4 to 3.6 pKa units. This finding suggests that the performance of the continuum models for methanol is similar to that found for aqueous solvent. Application of simple empirical correction through a linear equation leads to accurate pKa prediction, with uncertainty less than 0.8 units with the SM8 method. Testing with the less expensive PBE1PBE/6-311+G** method results in a slight improvement in the results.

Elucidating the Key Role of a Lewis Base Solvent in the Formation of Perovskite Films Fabricated from the Lewis Adduct Approach.

PubMed

Cao, Xiaobing; Zhi, Lili; Li, Yahui; Fang, Fei; Cui, Xian; Yao, Youwei; Ci, Lijie; Ding, Kongxian; Wei, Jinquan

2017-09-27

High-quality perovskite films can be fabricated from Lewis acid-base adducts through molecule exchange. Substantial work is needed to fully understand the formation mechanism of the perovskite films, which helps to further improve their quality. Here, we study the formation of CH 3 NH 3 PbI 3 perovskite films by introducing some dimethylacetamide into the PbI 2 /N,N-dimethylformamide solution. We reveal that there are three key processes during the formation of perovskite films through the Lewis acid-base adduct approach: molecule intercalation of solvent into the PbI 2 lattice, molecule exchange between the solvent and CH 3 NH 3 I, and dissolution-recrystallization of the perovskite grains during annealing. The Lewis base solvents play multiple functions in the above processes. The properties of the solvent, including Lewis basicity and boiling point, play key roles in forming smooth perovskite films with large grains. We also provide some rules for choosing Lewis base additives to prepare high-quality perovskite films through the Lewis adduct approach.

Kinetic Methods for Understanding Linker Exchange in Metal-Organic Frameworks

NASA Astrophysics Data System (ADS)

Morabito, Joseph V.

Exchange reactions have enabled a new level of control in the rational, stepwise preparation of metal-organic framework (MOF) materials. However, their full potential is limited by a lack of understanding of the molecular mechanisms by which they occur. This dissertation describes our efforts to understand this important class of reactions in two parts. The first reports our use of a linker exchange process to encapsulate guest molecules larger than the limiting pore aperture of the MOF. The concept is demonstrated, along with evidence for guest encapsulation and its relation to a dissociative linker exchange process. The second part describes our development of the first quantitative kinetic method for studying MOF linker exchange reactions and our application of this method to understand the solvent dependence of the reaction of ZIF-8 with imidazole. This project involved the collection of the largest set of rate data available on any MOF linker exchange reaction. The combination of this dataset with small molecule encapsulation experiments allowed us to formulate a mechanistic model that could account for all the observed kinetic and structural data. By comparison with the kinetic behavior of complexes in solution, we were able to fit the kinetic behavior of ZIF-8 into the broader family of coordination compounds. Aside from the specific use that our kinetic data may have in predicting the reactivity of ZIF linker exchange, we hope that the conceptual bridges made between MOFs and related metal?organic compounds can help reveal underlying patterns in behavior and advance the field.

Can a continuum solvent model reproduce the free energy landscape of a -hairpin folding in water?

NASA Astrophysics Data System (ADS)

Zhou, Ruhong; Berne, Bruce J.

2002-10-01

The folding free energy landscape of the C-terminal -hairpin of protein G is explored using the surface-generalized Born (SGB) implicit solvent model, and the results are compared with the landscape from an earlier study with explicit solvent model. The OPLSAA force field is used for the -hairpin in both implicit and explicit solvent simulations, and the conformational space sampling is carried out with a highly parallel replica-exchange method. Surprisingly, we find from exhaustive conformation space sampling that the free energy landscape from the implicit solvent model is quite different from that of the explicit solvent model. In the implicit solvent model some nonnative states are heavily overweighted, and more importantly, the lowest free energy state is no longer the native -strand structure. An overly strong salt-bridge effect between charged residues (E42, D46, D47, E56, and K50) is found to be responsible for this behavior in the implicit solvent model. Despite this, we find that the OPLSAA/SGB energies of all the nonnative structures are higher than that of the native structure; thus the OPLSAA/SGB energy is still a good scoring function for structure prediction for this -hairpin. Furthermore, the -hairpin population at 282 K is found to be less than 40% from the implicit solvent model, which is much smaller than the 72% from the explicit solvent model and 80% from experiment. On the other hand, both implicit and explicit solvent simulations with the OPLSAA force field exhibit no meaningful helical content during the folding process, which is in contrast to some very recent studies using other force fields.

Can a continuum solvent model reproduce the free energy landscape of a β-hairpin folding in water?

PubMed Central

Zhou, Ruhong; Berne, Bruce J.

2002-01-01

The folding free energy landscape of the C-terminal β-hairpin of protein G is explored using the surface-generalized Born (SGB) implicit solvent model, and the results are compared with the landscape from an earlier study with explicit solvent model. The OPLSAA force field is used for the β-hairpin in both implicit and explicit solvent simulations, and the conformational space sampling is carried out with a highly parallel replica-exchange method. Surprisingly, we find from exhaustive conformation space sampling that the free energy landscape from the implicit solvent model is quite different from that of the explicit solvent model. In the implicit solvent model some nonnative states are heavily overweighted, and more importantly, the lowest free energy state is no longer the native β-strand structure. An overly strong salt-bridge effect between charged residues (E42, D46, D47, E56, and K50) is found to be responsible for this behavior in the implicit solvent model. Despite this, we find that the OPLSAA/SGB energies of all the nonnative structures are higher than that of the native structure; thus the OPLSAA/SGB energy is still a good scoring function for structure prediction for this β-hairpin. Furthermore, the β-hairpin population at 282 K is found to be less than 40% from the implicit solvent model, which is much smaller than the 72% from the explicit solvent model and ≈80% from experiment. On the other hand, both implicit and explicit solvent simulations with the OPLSAA force field exhibit no meaningful helical content during the folding process, which is in contrast to some very recent studies using other force fields. PMID:12242327

Can a continuum solvent model reproduce the free energy landscape of a beta -hairpin folding in water?

PubMed

Zhou, Ruhong; Berne, Bruce J

2002-10-01

The folding free energy landscape of the C-terminal beta-hairpin of protein G is explored using the surface-generalized Born (SGB) implicit solvent model, and the results are compared with the landscape from an earlier study with explicit solvent model. The OPLSAA force field is used for the beta-hairpin in both implicit and explicit solvent simulations, and the conformational space sampling is carried out with a highly parallel replica-exchange method. Surprisingly, we find from exhaustive conformation space sampling that the free energy landscape from the implicit solvent model is quite different from that of the explicit solvent model. In the implicit solvent model some nonnative states are heavily overweighted, and more importantly, the lowest free energy state is no longer the native beta-strand structure. An overly strong salt-bridge effect between charged residues (E42, D46, D47, E56, and K50) is found to be responsible for this behavior in the implicit solvent model. Despite this, we find that the OPLSAA/SGB energies of all the nonnative structures are higher than that of the native structure; thus the OPLSAA/SGB energy is still a good scoring function for structure prediction for this beta-hairpin. Furthermore, the beta-hairpin population at 282 K is found to be less than 40% from the implicit solvent model, which is much smaller than the 72% from the explicit solvent model and approximately equal 80% from experiment. On the other hand, both implicit and explicit solvent simulations with the OPLSAA force field exhibit no meaningful helical content during the folding process, which is in contrast to some very recent studies using other force fields.

Cardio-pulmonary effects of inhaled solvents: computer-assisted measurement and analysis

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

Engwall, M.J.

The physiological effects of the inhalation of three solvent vapors were measured on anesthetized dogs. The tested solvents were: acetone, ethanol, and toluene. Measurements of respiratory mechanics, pulmonary and systemic hemodynamics, cardiac output, and gas-exchange were taken while exposing the animals to the vaporized solvents. After the exposures, the animals were terminated and lung tissue and alveolar lining material (ALM) were collected. The ALM was analyzed by high performance liquid chromatography for the amounts of component phospholipids. The tissues were inspected under light microscopy for evidence of acute damage associated with the solvent exposures.

Apparatus and methods for regeneration of precipitating solvent

DOEpatents

Liu, Guohai; Vimalchand, Pannalal; Peng, Wan Wang; Bonsu, Alexander

2015-08-25

A regenerator that can handle rich loaded chemical solvent containing precipitated absorption reaction products is disclosed. The invention is particularly suitable for separating CO.sub.2 from large gas streams that are typical of power plant processes. The internally circulating liquid stream in the regenerator (ICLS regenerator) rapidly heats-up the in-coming rich solvent stream in a downcomer standpipe as well as decreases the overall concentration of CO.sub.2 in the mixed stream. Both these actions lead to dissolution of precipitates. Any remaining precipitate further dissolves as heat is transferred to the mixed solution with an inverted bayonet tube heat exchanger in the riser portion of the regenerator. The evolving CO.sub.2 bubbles in the riser portion of the regenerator lead to substantial gas hold-up and the large density difference between the solutions in the downcomer standpipe and riser portions promotes internal circulation of the liquid stream in the regenerator. As minor amounts of solvent components present in the exit gas stream are condensed and returned back to the regenerator, pure CO.sub.2 gas stream exits the disclosed regenerator and condenser system.

Postassembly Transformation of a Catalytically Active Composite Material, Pt@ZIF-8, via Solvent-Assisted Linker Exchange.

PubMed

Stephenson, Casey J; Hupp, Joseph T; Farha, Omar K

2016-02-15

2-Methylimidazolate linkers of Pt@ZIF-8 are exchanged with imidazolate using solvent-assisted linker exchange (SALE) to expand the apertures of the parent material and create Pt@SALEM-2. Characterization of the material before and after SALE was performed. Both materials are active as catalysts for the hydrogenation of 1-octene, whereas the hydrogenation of cis-cyclohexene occurred only with Pt@SALEM-2, consistent with larger apertures for the daughter material. The largest substrate, β-pinene, proved to be unreactive with H2 when either material was employed as a candidate catalyst, supporting the contention that substrate molecules, for both composites, must traverse the metal-organic framework component in order to reach the catalytic nanoparticles.

Proton exchange membrane based on chitosan and solvent-free carbon nanotube fluids for fuel cells applications.

PubMed

Wang, Jie; Gong, Chunli; Wen, Sheng; Liu, Hai; Qin, Caiqin; Xiong, Chuanxi; Dong, Lijie

2018-04-15

Poor dispersion and inert ionic conduction are two major obstacles towards using carbon nanotubes (CNTs) to modify polymer electrolyte membranes (PEMs) in energy conversion devices. In this work, solvent-free carbon nanotube fluids (CNT fluids) with liquid-like behavior are prepared through an ion exchange method and incorporated into a chitosan (CS) matrix to fabricate composite membranes. The electrostatic interactions between SO 3 - groups in the CNT fluids and NH 2 groups in the CS matrix, in addition to the unique flow properties of the CNT fluids, promote the uniform dispersion of CNT fluids in the CS matrix. Markedly, the CS/CNT fluid-3 composite membrane is simultaneously reinforced and toughened by 180% and 300% compared to pure CS membrane, respectively. Moreover, the SO 3 - groups in the CNT fluids facilitate the proton transfer such that the proton conductivity of CS/CNT fluid-3 composite membrane reaches a maximum value of 0.044 S cm -1 at 80 °C. Copyright © 2018 Elsevier Ltd. All rights reserved.

Preparation of a Highly Fluorophilic Phosphonium Salt and its Use in a Fluorous Anion-Exchanger Membrane with High Selectivity for Perfluorinated Acids

PubMed Central

Boswell, Paul G.; Anfang, Alyce C.; Bühlmann, Philippe

2008-01-01

Fluorous solvents are the most nonpolar, nonpolarizable phases known, whereas ions are inherently polar. This makes it difficult to create salts that are soluble in a fluorous solvent. Here we present the synthesis and characterization of a new fluorophilic phosphonium salt, tris{3,5-bis[(perfluorooctyl)propyl]phenyl}methylphosphonium methyl sulfate. The salt has a solubility of at least 14 mM in perfluoro(perhydrophenanthrene), perfluoro(methylcyclohexane), and perfluorohexanes. It also shows immediate potential for use as a phase-transfer catalyst in fluorous biphasic catalysis, but in this work it is used as an anion exchanger site in the first potentiometric fluorous-membrane anion-selective electrode. The membrane sensor exhibited the exceptional selectivity of 3.9 × 1010 to 1 for perfluorooctanesulfonate over chloride, and of 2.5 × 107 to 1 for perfluorooctanoate over chloride. With improvements to the sensor’s detection limit and lifetime, it has the potential to be an attractive alternative to the expensive, time-consuming methods currently employed for measurement of perfluorinated acids. PMID:22072222

Design and Validation of In-Source Atmospheric Pressure Photoionization Hydrogen/Deuterium Exchange Mass Spectrometry with Continuous Feeding of D2O.

PubMed

Acter, Thamina; Lee, Seulgidaun; Cho, Eunji; Jung, Maeng-Joon; Kim, Sunghwan

2018-01-01

In this study, continuous in-source hydrogen/deuterium exchange (HDX) atmospheric pressure photoionization (APPI) mass spectrometry (MS) with continuous feeding of D 2 O was developed and validated. D 2 O was continuously fed using a capillary line placed on the center of a metal plate positioned between the UV lamp and nebulizer. The proposed system overcomes the limitations of previously reported APPI HDX-MS approaches where deuterated solvents were premixed with sample solutions before ionization. This is particularly important for APPI because solvent composition can greatly influence ionization efficiency as well as the solubility of analytes. The experimental parameters for APPI HDX-MS with continuous feeding of D 2 O were optimized, and the optimized conditions were applied for the analysis of nitrogen-, oxygen-, and sulfur-containing compounds. The developed method was also applied for the analysis of the polar fraction of a petroleum sample. Thus, the data presented in this study clearly show that the proposed HDX approach can serve as an effective analytical tool for the structural analysis of complex mixtures. Graphical abstract ᅟ.

Chain exchange in triblock copolymer micelles

NASA Astrophysics Data System (ADS)

Lu, Jie; Lodge, Timothy; Bates, Frank

2015-03-01

Block polymer micelles offer a host of technological applications including drug delivery, viscosity modification, toughening of plastics, and colloidal stabilization. Molecular exchange between micelles directly influences the stability, structure and access to an equilibrium state in such systems and this property recently has been shown to be extraordinarily sensitive to the core block molecular weight in diblock copolymers. The dependence of micelle chain exchange dynamics on molecular architecture has not been reported. The present work conclusively addresses this issue using time-resolved small-angle neutron scattering (TR-SANS) applied to complimentary S-EP-S and EP-S-EP triblock copolymers dissolved in squalane, a selective solvent for the EP blocks, where S and EP refer to poly(styrene) and poly(ethylenepropylene), respectively. Following the overall SANS intensity as a function of time from judiciously deuterium labelled polymer and solvent mixtures directly probes the rate of molecular exchange. Remarkably, the two triblocks display exchange rates that differ by approximately ten orders of magnitude, even though the solvophobic S blocks are of comparable size. This discovery is considered in the context of a model that successfully explains S-EP diblock exchange dynamics.

Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

PubMed

Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

2016-08-01

The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ.

Microcalorimetric study of thermal unfolding of lysozyme in water/glycerol mixtures: An analysis by solvent exchange model

NASA Astrophysics Data System (ADS)

Spinozzi, Francesco; Ortore, Maria Grazia; Sinibaldi, Raffaele; Mariani, Paolo; Esposito, Alessandro; Cinelli, Stefania; Onori, Giuseppe

2008-07-01

Folded protein stabilization or destabilization induced by cosolvent in mixed aqueous solutions has been studied by differential scanning microcalorimetry and related to difference in preferential solvation of native and denatured states. In particular, the thermal denaturation of a model system formed by lysozyme dissolved in water in the presence of the stabilizing cosolvent glycerol has been considered. Transition temperatures and enthalpies, heat capacity, and standard free energy changes have been determined when applying a two-state denaturation model to microcalorimetric data. Thermodynamic parameters show an unexpected, not linear, trend as a function of solvent composition; in particular, the lysozyme thermodynamic stability shows a maximum centered at water molar fraction of about 0.6. Using a thermodynamic hydration model based on the exchange equilibrium between glycerol and water molecules from the protein solvation layer to the bulk, the contribution of protein-solvent interactions to the unfolding free energy and the changes of this contribution with solvent composition have been derived. The preferential solvation data indicate that lysozyme unfolding involves an increase in the solvation surface, with a small reduction of the protein-preferential hydration. Moreover, the derived changes in the excess solvation numbers at denaturation show that only few solvent molecules are responsible for the variation of lysozyme stability in relation to the solvent composition.

Enhanced picture of protein-folding intermediates using organic solvents in H/D exchange and quench-flow experiments

PubMed Central

Nishimura, Chiaki; Dyson, H. Jane; Wright, Peter E.

2005-01-01

Hydrogen/deuterium exchange followed by trapping of the labeled species in the aprotic solvent DMSO has been used to elucidate structure in both the burst-phase molten globule-folding intermediate of apomyoglobin and in an equilibrium intermediate that models the kinetic intermediate. Precise estimates can be made of exchange times in an interrupted exchange-out experiment at pH 4 followed by analysis in DMSO solution, giving extensive sequence-specific information about the structure of the equilibrium intermediate. In addition, the use of DMSO as a solvent for NMR measurements after quench-flow pH-pulse labeling experiments gives a greatly increased data set for the elucidation of the kinetic folding pathway. Interestingly, differences are observed in some regions of apomyoglobin between the equilibrium and kinetic intermediates. These differences are quantitative rather than qualitative; that is, the overall patterns of labeling and secondary structure formation remain similar between the two species. However, local differences are observed, which probably reflect the difference in the solution conditions for the equilibrium experiment (pH 4) vs. the kinetic experiment (pH 6) and the change in the status of the stabilizing hydrogen bond between the side chains of His-24 and His-119. PMID:15769860

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

Dang, Liem X.; Chang, Tsun-Mei

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li +(aq) and the kinetics of ion pairings in lithium-ion batteries (LIB). We report one of the first computer simulations of the exchange dynamics around hydrated Li + in acetonitrile (ACN), which is common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li +-[BF 4] and Li +-[PF 6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells aroundmore » Li +(aq). We calculate exchange rates using transition state theory and weighted them with transmission coefficients determined by the reactive flux and Impey, Madden, and McDonald approaches and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li +-[BF 4] and Li +-[PF 6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.« less

Optimization of instantaneous solvent exchange/surface modification process for ambient synthesis of monolithic silica aerogels.

PubMed

Hwang, Sung-Woo; Kim, Tae-Youn; Hyun, Sang-Hoon

2008-06-01

The instantaneous solvent exchange/surface modification (ISE/SM) process for the ambient synthesis of crack-free silica aerogel monoliths with a high production yield was optimized. Monolithic forms of silica wet gels were obtained from aqueous colloidal silica sols prepared via the ion exchange of sodium silicate solutions. Crack-free silica aerogel monoliths were synthesized via an ISE/SM process using isopropyl alcohol/trimethylchlorosilane as a modification agent and n-hexane as a main solvent, followed by ambient drying. The optimum process conditions of the ISE/SM process were investigated by clarifying the reaction mechanism and phenomena. Most effective ranges of process variables on the ISE/SM stage were determined as 0.2500-0.3567 of TMCS/H2O (pore water) in molar ratio and 15-30 of n-hexane/TMCS in volumetric ratio, with a reaction temperature below 283 K. Crack-free silica aerogel monoliths synthesized via these conditions had a well-developed mesoporous structure and excellent properties (bulk density of 0.12-0.14 g/cm3, specific surface area of 724 m2/g), and a high yield (nearly 80%).

Conformational free energies of methyl-α-L-iduronic and methyl-β-D-glucuronic acids in water

NASA Astrophysics Data System (ADS)

Babin, Volodymyr; Sagui, Celeste

2010-03-01

We present a simulation protocol that allows for efficient sampling of the degrees of freedom of a solute in explicit solvent. The protocol involves using a nonequilibrium umbrella sampling method, in this case, the recently developed adaptively biased molecular dynamics method, to compute an approximate free energy for the slow modes of the solute in explicit solvent. This approximate free energy is then used to set up a Hamiltonian replica exchange scheme that samples both from biased and unbiased distributions. The final accurate free energy is recovered via the weighted histogram analysis technique applied to all the replicas, and equilibrium properties of the solute are computed from the unbiased trajectory. We illustrate the approach by applying it to the study of the puckering landscapes of the methyl glycosides of α-L-iduronic acid and its C5 epimer β-D-glucuronic acid in water. Big savings in computational resources are gained in comparison to the standard parallel tempering method.

Conformational free energies of methyl-alpha-L-iduronic and methyl-beta-D-glucuronic acids in water.

PubMed

Babin, Volodymyr; Sagui, Celeste

2010-03-14

We present a simulation protocol that allows for efficient sampling of the degrees of freedom of a solute in explicit solvent. The protocol involves using a nonequilibrium umbrella sampling method, in this case, the recently developed adaptively biased molecular dynamics method, to compute an approximate free energy for the slow modes of the solute in explicit solvent. This approximate free energy is then used to set up a Hamiltonian replica exchange scheme that samples both from biased and unbiased distributions. The final accurate free energy is recovered via the weighted histogram analysis technique applied to all the replicas, and equilibrium properties of the solute are computed from the unbiased trajectory. We illustrate the approach by applying it to the study of the puckering landscapes of the methyl glycosides of alpha-L-iduronic acid and its C5 epimer beta-D-glucuronic acid in water. Big savings in computational resources are gained in comparison to the standard parallel tempering method.

Molecular dynamics simulations of biological membranes and membrane proteins using enhanced conformational sampling algorithms.

PubMed

Mori, Takaharu; Miyashita, Naoyuki; Im, Wonpil; Feig, Michael; Sugita, Yuji

2016-07-01

This paper reviews various enhanced conformational sampling methods and explicit/implicit solvent/membrane models, as well as their recent applications to the exploration of the structure and dynamics of membranes and membrane proteins. Molecular dynamics simulations have become an essential tool to investigate biological problems, and their success relies on proper molecular models together with efficient conformational sampling methods. The implicit representation of solvent/membrane environments is reasonable approximation to the explicit all-atom models, considering the balance between computational cost and simulation accuracy. Implicit models can be easily combined with replica-exchange molecular dynamics methods to explore a wider conformational space of a protein. Other molecular models and enhanced conformational sampling methods are also briefly discussed. As application examples, we introduce recent simulation studies of glycophorin A, phospholamban, amyloid precursor protein, and mixed lipid bilayers and discuss the accuracy and efficiency of each simulation model and method. This article is part of a Special Issue entitled: Membrane Proteins edited by J.C. Gumbart and Sergei Noskov. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Conformation transitions of a single polyelectrolyte chain in a poor solvent: a replica-exchange lattice Monte-Carlo study.

PubMed

Wang, Lang; Wang, Zheng; Jiang, Run; Yin, Yuhua; Li, Baohui

2017-03-15

The thermodynamic behaviors of a strongly charged polyelectrolyte chain in a poor solvent are studied using replica-exchange Monte-Carlo simulations on a lattice model, focusing on the effects of finite chain length and the solvent quality on the chain conformation and conformation transitions. The neutralizing counterions and solvent molecules are considered explicitly. The thermodynamic quantities that vary continuously with temperature over a wide range are computed using the multiple histogram reweighting method. Our results suggest that the strength of the short-range hydrophobic interaction, the chain length, and the temperature of the system, characterized by ε, N, and T, respectively, are important parameters that control the conformations of a charged chain. When ε is moderate, the competition between the electrostatic energy and the short-range hydrophobic interaction leads to rich conformations and conformation transitions for a longer chain with a fixed length. Our results have unambiguously demonstrated the stability of the n-pearl-necklace structures, where n has a maximum value and decreases with decreasing temperature. The maximum n value increases with increasing chain length. Our results have also demonstrated the first-order nature of the conformation transitions between the m-pearl and the (m-1)-pearl necklaces. With the increase of ε, the transition temperature increases and the first-order feature becomes more pronounced. It is deduced that at the thermodynamic limit of infinitely long chain length, the conformational transitions between the m-pearl and the (m-1)-pearl necklaces may remain first order when ε > 0 and m = 2 or 3. Pearl-necklace conformations cannot be observed when either ε is too large or N is too small. To observe a pearl-necklace conformation, the T value needs to be carefully chosen for simulations performed at only a single temperature.

Modeling the oxidation of ebselen and other organoselenium compounds using explicit solvent networks.

PubMed

Bayse, Craig A; Antony, Sonia

2009-05-14

The oxidation of dimethylselenide, dimethyldiselenide, S-methylselenenyl-methylmercaptan, and truncated and full models of ebselen (N-phenyl-1,2-benzisoselenazol-3(2H)-one) by methyl hydrogen peroxide has been modeled using density functional theory (DFT) and solvent-assisted proton exchange (SAPE), a method of microsolvation that employs explicit solvent networks to facilitate proton transfer reactions. The calculated activation barriers for these systems were substantially lower in energy (DeltaG(double dagger) + DeltaG(solv) = 13 to 26 kcal/mol) than models that neglect the participation of solvent in proton exchange. The comparison of two- and three-water SAPE networks showed a reduction in the strain in the model system but without a substantial reduction in the activation barriers. Truncating the ebselen model to N-methylisoselenazol-3(2H)-one gave a larger activation barrier than ebselen or N-methyl-1,2-benzisoselenazol-3(2H)-one but provided an efficient means of determining an initial guess for larger transition-state models. The similar barriers obtained for ebselen and Me(2)Se(2) (DeltaG(double dagger) + DeltaG(solv) = 20.65 and 20.40 kcal/mol, respectively) were consistent with experimentally determined rate constants. The activation barrier for MeSeSMe (DeltaG(double dagger) + DeltaG(solv) = 21.25 kcal/mol) was similar to that of ebselen and Me(2)Se(2) despite its significantly lower experimental rate for oxidation of an ebselen selenenyl sulfide by hydrogen peroxide relative to ebselen and ebselen diselenide. The disparity is attributed to intramolecular Se-O interactions, which decrease the nucleophilicity of the selenium center of the selenenyl sulfide.

Coupling solid-phase extraction and enzyme-linked immunosorbent assay for ultratrace determination of herbicides in pristine water

USGS Publications Warehouse

Aga, D.S.; Thurman, E.M.

1993-01-01

Solid-phase extraction (SPE) and enzyme-linked immunosorbent assay (ELISA) were coupled for automated trace analysis of pristine water samples containing 2-chloro-4-ethylamino-6-isopropylamine-s-triazine (atrazine) and 2-chloro-2???,6???-diethyl-N-(methoxymethyl)acetanilide (alachlor). The isolation of the two herbicides on a C18-resin involved the selection of an elution solvent that both removes interfering substances and is compatible with ELISA. Ethyl acetate was selected as the elution solvent followed by a solvent exchange with methanol/water (20/80, % v/v). The SPE-ELISA method has a detection limit of 5.0 ng/L (5 ppt), >90% recovery, and a relative standard deviation of ??10%. The performance of a microtiter plate-based ELISA and a magnetic particle-based ELISA coupled to SPE was also evaluated. Although the sensitivity of the two ELISA methods was comparable, the precision using magnetic particles was improved considerably (??10% versus ??20%) because of the faster reaction kinetics provided by the magnetic particles. Finally, SPE-ELISA and isotope dilution gas chromatography/ mass spectrometry correlated well (correlation coefficient of 0.96) for lake-water samples. The SPE-ELISA method is simple and may have broader applications for the inexpensive automated analysis of other contaminants in water at trace levels.

Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

PubMed

Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

2016-04-29

An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. Copyright © 2016 Elsevier B.V. All rights reserved.

Solvent exchange-induced in situ forming gel comprising ethyl cellulose-antimicrobial drugs.

PubMed

Phaechamud, Thawatchai; Mahadlek, Jongjan

2015-10-15

Solvent-exchanged in situ forming gel is a drug delivery system which is in sol form before administration. When it contacts with the body fluid, then the water miscible organic solvent dissipates and water penetrates into the system, leading the polymer precipitation as in situ gel at the site of injection. The aim of this research was to study the parameters affecting the gel properties, drug release and antimicrobial activities of the in situ forming gels prepared from ethyl cellulose (EC) dissolved in N-methyl pyrrolidone (NMP) to deliver the antimicrobial agents (doxycycline hyclate, metronidazole and benzyl peroxide) for periodontitis treatment. The gel appearance, pH, viscosity, rheology, syringeability, gel formation, rate of water diffusion into the gels, in vitro degradation, drug release behavior and antimicrobial activities against Staphylococcus aureus, Escherichia coli, Candida albicans, Streptococcus mutans and Porphyrommonas gingivalis were determined. Increasing the amount of EC increased the viscosity of system while still exhibiting Newtonian flow and increased the work of syringeability whereas decreased the releasing of drug. The system transformed into the rigid gel formation after being injected into the simulated gingival crevicular fluid. The developed systems containing 5% w/w antimicrobial agent showed the antimicrobial activities against all test bacteria. Thus the developed solvent exchange-induced in situ forming gels comprising EC-antimicrobial drugs exhibited potential use for periodontitis treatment. Copyright © 2015 Elsevier B.V. All rights reserved.

Regeneration of strong-base anion-exchange resins by sequential chemical displacement

DOEpatents

Brown, Gilbert M.; Gu, Baohua; Moyer, Bruce A.; Bonnesen, Peter V.

2002-01-01

A method for regenerating strong-base anion exchange resins utilizing a sequential chemical displacement technique with new regenerant formulation. The new first regenerant solution is composed of a mixture of ferric chloride, a water-miscible organic solvent, hydrochloric acid, and water in which tetrachloroferrate anion is formed and used to displace the target anions on the resin. The second regenerant is composed of a dilute hydrochloric acid and is used to decompose tetrachloroferrate and elute ferric ions, thereby regenerating the resin. Alternative chemical displacement methods include: (1) displacement of target anions with fluoroborate followed by nitrate or salicylate and (2) displacement of target anions with salicylate followed by dilute hydrochloric acid. The methodology offers an improved regeneration efficiency, recovery, and waste minimization over the conventional displacement technique using sodium chloride (or a brine) or alkali metal hydroxide.

Exploring the protein folding free energy landscape: coupling replica exchange method with P3ME/RESPA algorithm.

PubMed

Zhou, Ruhong

2004-05-01

A highly parallel replica exchange method (REM) that couples with a newly developed molecular dynamics algorithm particle-particle particle-mesh Ewald (P3ME)/RESPA has been proposed for efficient sampling of protein folding free energy landscape. The algorithm is then applied to two separate protein systems, beta-hairpin and a designed protein Trp-cage. The all-atom OPLSAA force field with an explicit solvent model is used for both protein folding simulations. Up to 64 replicas of solvated protein systems are simulated in parallel over a wide range of temperatures. The combined trajectories in temperature and configurational space allow a replica to overcome free energy barriers present at low temperatures. These large scale simulations reveal detailed results on folding mechanisms, intermediate state structures, thermodynamic properties and the temperature dependences for both protein systems.

Sensitivity-enhanced detection of non-labile proton and carbon NMR spectra on water resonances.

PubMed

Novakovic, Mihajlo; Martinho, Ricardo P; Olsen, Gregory L; Lustig, Michael S; Frydman, Lucio

2017-12-20

Chemical exchange saturation transfer (CEST) experiments enhance the NMR signals of labile protons by continuously transferring these protons' saturation to an abundant solvent pool like water. The present study expands these principles by fusing into these experiments homonuclear isotropic mixing sequences, enabling the water-enhanced detection of non-exchangeable species. Further opportunities are opened by the addition of coupling-mediated heteronuclear polarization transfers, which then impose on the water resonance a saturation stemming from non-labile heteronuclear species like 13 C. To multiplex the ensuing experiments, these relayed approaches are combined with time-domain schemes involving multiple Ramsey-labeling experiments imparting the frequencies of the non-labile sites on the water resonance, via chemical exchange. 13 C and 1 H NMR spectra were detected in this fashion with about two-fold SNR amplification vis-à-vis conventionally detected spectroscopies. When combined with non-uniform sampling principles, this methodology thus becomes a sensitive alternative to detect non-exchangeable species in biomolecules. Still, multiple parameters including the scalar couplings and solvent exchange rates, will affect the efficiency and consequently the practicality of the overall experiment.

Comparison of the structures of free and ribosome-bound tRNAPhe by using slow tritium exchange.

PubMed Central

Farber, N; Cantor, C R

1980-01-01

The rate of incorporation of tritium from the solvent into the C-8 position of purines in RNA is markedly sensitive to the microenvironment. This slow tritium exchange reaction has been used to study the structure and interactions of yeast tRNAPhe bound to poly(U)-programed tight-couple 70S ribosomes of Escherichia coli. The tritium incorporation into specific sites of the tRNA was determined by enzymatic digestion and measurement of the specific activity of each of the isolated radioactive fragments. Ribosome binding leads to marked suppression in the exchange rate of a number of fragments. This delineates extensive regions of tRNA-ribosome contact. No change in exchange rates is seen for fragments from the corner of the molecule, indicating that this region of bound tRNA is readily accessible to the solvent. Ribosome binding results in an enhanced exchange rate at the T loop. This appears to be the result of a conformational change that is most likely an unfolding of the T and D loops. Additional tritium exchange reactions suggest this conformational change is induced by ribosomes and not by messenger. PMID:7001473

From nicotinate-containing layered double hydroxides (LDHs) to NAD coenzyme-LDH nanocomposites - Syntheses and structural characterization by various spectroscopic methods

NASA Astrophysics Data System (ADS)

Muráth, Szabolcs; Dudás, Csilla; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

2017-07-01

The syntheses of nicotinate anion- and NAD coenzyme-layered double hydroxide (LDH) composites were performed with the aim of having the organic component among the layers. In-house prepared CaAl-LDHs were the host materials. Intercalation was attempted by direct ion exchange or by the dehydration-rehydration method applying aqueous solvent mixtures (containing ethanol, propanol, acetone, N,N-dimethylformamide). For structural characterization, beside X-ray diffractometry, X-ray photoelectron and IR spectroscopies, transmission and scanning electron microscopies as well as energy-dispersive X-ray analysis were used. Molecular modelling served for the visualization of the arrangements of the intercalated ions among the layers of the LDH samples. Although not all the intercalation methods and solvent mixtures led to intercalated composite materials, successful ones could be identified. The combination of spectroscopic methods helped in proposing sensible spatial arrangements for the intercalated anions. The NAD-CaAl-LDH composite proved to be an active catalyst in the oxidation of hydroquinone to 1,4-bezoquinoe in the presence of H2O2.

Solvent effect on post-irradiation grafting of styrene onto poly(ethylene-alt-tetrafluoroethylene) (ETFE) films

NASA Astrophysics Data System (ADS)

Napoleão Geraldes, Adriana; Augusto Zen, Heloísa; Ribeiro, Geise; Fernandes Parra, Duclerc; Benévolo Lugão, Ademar

2013-03-01

Radiation-induced grafting of styrene onto ETFE films in different solvent was investigated after simultaneous irradiation (in post-irradiation condition) using a 60Co source. Grafting of styrene followed by sulfonation onto poly(ethylene-alt-tetrafluoroethylene) (ETFE) are currently studied for synthesis of ion exchange membranes. The ETFE films were immersed in styrene/toluene, styrene/methanol and styrene/isopropyl alcohol and irradiated at 20 and 100 kGy doses at room temperature. The post-irradiation time was established at 14 day and the grafting degree was evaluated. The grafted films were sulfonated using chlorosulfonic acid and 1,2-dichloroethane 20:80 (v/v) at room temperature for 5 h. The degree of grafting (DOG) was determined gravimetrically and physical or chemical changes were evaluated by differential scanning calorimeter analysis (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The ion exchange capacity (IEC) values showed the best performance of sulfonation for ETFE membranes grafted in toluene solvent. Surface images of the grafted films by SEM technique have presented a strong effect of the solvents on the films morphology.

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

Dang, Liem X.; Chang, Tsun-Mei

In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li{sup +} and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li{sup +} in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li{sup +}-[BF{sub 4}] and Li{sup +}-[PF{sub 6}] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shellsmore » around Li{sup +}. We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li{sup +}-[BF{sub 4}] and Li{sup +}-[PF{sub 6}] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.« less

Solid-phase extraction sorbent consisting of alkyltrimethylammonium surfactants immobilized onto strong cation-exchange polystyrene resin.

PubMed

Reid, Kendra R; Kennedy, Lonnie J; Crick, Eric W; Conte, Eric D

2002-10-25

Presented is a solid-phase extraction sorbent material composed of cationic alkyltrimethylammonium surfactants attached to a strong cation-exchange resin via ion-exchange. The original hydrophilic cation-exchange resin is made hydrophobic by covering the surface with alkyl chains from the hydrophobic portion of the surfactant. The sorbent material now has a better ability to extract hydrophobic molecules from aqueous samples. The entire stationary phase (alkyltrimethylammonium surfactant) is removed along with the analyte during the elution step. The elution step requires a mild elution solvent consisting of 0.25 M Mg2+ in a 50% 2-propanol solution. The main advantage of using a removable stationary phase is that traditionally utilized toxic elution solvents such as methylene chloride, which are necessary to efficiently release strongly hydrophobic species from SPE stationary phases, may now be avoided. Also, the final extract is directly compatible with reversed-phase liquid chromatography. The performance of this procedure is presented using pyrene as a test molecule.

Graphene/Ionic Liquid Composite Films and Ion Exchange

PubMed Central

Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

2014-01-01

Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force. PMID:24970602

Mapping transiently formed and sparsely populated conformations on a complex energy landscape.

PubMed

Wang, Yong; Papaleo, Elena; Lindorff-Larsen, Kresten

2016-08-23

Determining the structures, kinetics, thermodynamics and mechanisms that underlie conformational exchange processes in proteins remains extremely difficult. Only in favourable cases is it possible to provide atomic-level descriptions of sparsely populated and transiently formed alternative conformations. Here we benchmark the ability of enhanced-sampling molecular dynamics simulations to determine the free energy landscape of the L99A cavity mutant of T4 lysozyme. We find that the simulations capture key properties previously measured by NMR relaxation dispersion methods including the structure of a minor conformation, the kinetics and thermodynamics of conformational exchange, and the effect of mutations. We discover a new tunnel that involves the transient exposure towards the solvent of an internal cavity, and show it to be relevant for ligand escape. Together, our results provide a comprehensive view of the structural landscape of a protein, and point forward to studies of conformational exchange in systems that are less characterized experimentally.

Solid phase monofunctionalization of gold nanoparticles using ionic exchange resin as polymer support.

PubMed

Zou, Jianhua; Dai, Qiu; Wang, Jinhai; Liu, Xiong; Huo, Qun

2007-07-01

A solid phase modification method using anionic exchange resin as polymer support was developed for the synthesis of monofunctional gold nanoparticles. Based on a "catch and release" mechanism to control the number of functional groups attached to the nanoparticle surface, bifunctional thiol ligands with a carboxylic acid end group were first immobilized at a controlled density on anionic exchange resin through electrostatic interactions. Gold nanoparticles were then immobilized to the anionic exchange resin by a one-to-one place exchange reaction between resin-bound thiol ligands and butanethiol-protected gold nanoparticles in solution. After cleaving off from the resin under mild conditions, gold nanoparticles with a single carboxyl group attached to the surface were obtained as the major product. Experimental conditions such as the solvents used for ligand loading and solid phase place exchange reaction, and the loading density of the ligands, were found to play a critical role towards the successful synthesis of monofunctional nanoparticles. Overall, the noncovalent bond-based ligand immobilization technique reported here greatly simplified the process of solid phase monofunctionalization of nanoparticles compared to a previously reported covalent bond-based ligand immobilization technique.

Investigating Block-Copolymer Micelle Dynamics for Tunable Cargo Delivery

NASA Astrophysics Data System (ADS)

Li, Xiuli; Kidd, Bryce; Cooksey, Tyler; Robertson, Megan; Madsen, Louis

Block-copolymer micelles (BCPMs) can carry molecular cargo in a nanoscopic package that is tunable using polymer structure in combination with cargo properties, as well as with external stimuli such as temperature or pH. For example, BCPMs can be used in targeted anticancer drug delivery due to their biocompatibility, in vivo degradability and prolonged circulation time. We are using NMR spectroscopy and diffusometry as well as SANS to investigate BCPMs. Here we study a diblock poly(ethylene oxide)-b-(caprolactone) (PEO-PCL) that forms spherical micelles at 1% (w/v) in the mixed solvent D2O/THF-d8. We quantify the populations and diffusion coefficients of coexisting micelles and free unimers over a range of temperatures and solvent compositions. We use temperature as a stimulus to enhance unimer exchange and hence trigger cargo release, in some cases at a few degrees above body temperature. We present evidence for dominance of the insertion-expulsion mechanism of unimer exchange in these systems, and we map phase diagrams versus temperature and solvent composition. This study sheds light on how intermolecular interactions fundamentally affect cargo release, unimer exchange, and overall micelle tunability.

Ionic Liquids as Extraction Media for Metal Ions

NASA Astrophysics Data System (ADS)

Hirayama, Naoki

In solvent extraction separation of metal ions, recently, many researchers have investigated possible use of hydrophobic ionic liquids as extraction media instead of organic solvents. Ionic liquids are salts of liquid state around room temperature and can act not only as solvents but also as ion-exchangers. Therefore, the extraction mechanism of metal ions into ionic liquids is complicated. This review presents current overview and perspective on evaluation of nature of hydrophobic ionic liquids as extraction media for metal ions.

Ultrafast Multi-Dimentional Infrared Vibrational Echo Spectroscopy of Molecular Dynamics on Surfaces and in Bulk Systems

DTIC Science & Technology

2012-02-28

dimethylsulfoxide ( DMSO ). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO , both types of hydrogen bonded complexes exist. The...transition (negative) in the 2D IR spectrum. Also, line shape distortions caused by solvent background absorption and finite pulse durations do not affect...conditions as  = 7  1 ps. This is the first direct measurement of hydrogen bond exchange. b. Solute- Solvent Complex Switching Dynamics3 Hydrogen

Ultrafast Multi-Dimensional Infrared Vibrational Echo Spectroscopy of Molecular Dynamics on Surfaces and in Bulk Systems

DTIC Science & Technology

2012-02-28

dimethylsulfoxide ( DMSO ). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO , both types of hydrogen bonded complexes exist. The...transition (negative) in the 2D IR spectrum. Also, line shape distortions caused by solvent background absorption and finite pulse durations do not affect...conditions as  = 7  1 ps. This is the first direct measurement of hydrogen bond exchange. b. Solute- Solvent Complex Switching Dynamics3 Hydrogen

Design and Validation of In-Source Atmospheric Pressure Photoionization Hydrogen/Deuterium Exchange Mass Spectrometry with Continuous Feeding of D2O

NASA Astrophysics Data System (ADS)

Acter, Thamina; Lee, Seulgidaun; Cho, Eunji; Jung, Maeng-Joon; Kim, Sunghwan

2018-01-01

In this study, continuous in-source hydrogen/deuterium exchange (HDX) atmospheric pressure photoionization (APPI) mass spectrometry (MS) with continuous feeding of D2O was developed and validated. D2O was continuously fed using a capillary line placed on the center of a metal plate positioned between the UV lamp and nebulizer. The proposed system overcomes the limitations of previously reported APPI HDX-MS approaches where deuterated solvents were premixed with sample solutions before ionization. This is particularly important for APPI because solvent composition can greatly influence ionization efficiency as well as the solubility of analytes. The experimental parameters for APPI HDX-MS with continuous feeding of D2O were optimized, and the optimized conditions were applied for the analysis of nitrogen-, oxygen-, and sulfur-containing compounds. The developed method was also applied for the analysis of the polar fraction of a petroleum sample. Thus, the data presented in this study clearly show that the proposed HDX approach can serve as an effective analytical tool for the structural analysis of complex mixtures. [Figure not available: see fulltext.

Two-dimensional free-energy surface on the exchange reaction of alkyl chloride/chloride using the QM/MM-MC method

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

Ohisa, M.; Yamataka, H.; Dupuis, Michel

2007-12-05

Two-dimensional free-energy surfaces are calculated for alkyl chloride/chloride exchange/inversion reactions: Cl- + RCl (R = Me and t-Bu) surrounded by one hundred H2O molecules as a model of solvent. The methodology of free-energy calculation by perturbation theory based on a mixed-Hamiltonian model (QM/MM) combined with Monte Carlo sampling of the solvent configurations was used to obtain the changes in solvation free energy. We devised a special procedure to analyze the two-dimensional free-energy surfaces to gain unique insight into the differences in the reaction mechanisms between the two systems. The inversion reaction path for R = t-Bu on the free-energy surfacemore » is found to proceed in an asynchronous way within a concerted framework via the ion-pair region. This is in contrast to the R = Me system that proceeds as a typical SN2 reaction. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.« less

Thermodynamics of solvent interaction with the metal-organic framework MOF-5.

PubMed

Akimbekov, Zamirbek; Wu, Di; Brozek, Carl K; Dincă, Mircea; Navrotsky, Alexandra

2016-01-14

The inclusion of solvent in metal-organic framework (MOF) materials is a highly specific form of guest-host interaction. In this work, the energetics of solvent MOF-5 interactions has been investigated by solution calorimetry in 5 M sodium hydroxide (NaOH) at room temperature. Solution calorimetric measurement of enthalpy of formation (ΔH(f)) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)(-1), respectively. The enthalpies of interaction (ΔH(int)) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)(-1) and -89.28 ± 3.05 kJ (mol DEF)(-1), respectively. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quantitative thermodynamic basis to investigate transmetallation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.

Bifunctional anion-exchange resins with improved selectivity and exchange kinetics

DOEpatents

Alexandratos, Spiro D.; Brown, Gilbert M.; Bonnesen, Peter V.; Moyer, Bruce A.

2000-01-01

Disclosed herein are a class of anion exchange resins containing two different exchange sites with improved selectivity and sorptive capability for chemical species in solution, such as heptavalent technetium (as pertechnetate anion, TcO.sub.4.sup.-). The resins are prepared by first reacting haloalkylated crosslinked copolymer beads with a large tertiary amine in a solvent in which the resin beads can swell, followed by reaction with a second, smaller, tertiary amine to more fully complete the functionalization of the resin. The resins have enhanced selectivity, capacity, and exchange kinetics.

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

NASA Astrophysics Data System (ADS)

Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

2011-12-01

The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

Combining Coarse-Grained Protein Models with Replica-Exchange All-Atom Molecular Dynamics

PubMed Central

Wabik, Jacek; Kmiecik, Sebastian; Gront, Dominik; Kouza, Maksim; Koliński, Andrzej

2013-01-01

We describe a combination of all-atom simulations with CABS, a well-established coarse-grained protein modeling tool, into a single multiscale protocol. The simulation method has been tested on the C-terminal beta hairpin of protein G, a model system of protein folding. After reconstructing atomistic details, conformations derived from the CABS simulation were subjected to replica-exchange molecular dynamics simulations with OPLS-AA and AMBER99sb force fields in explicit solvent. Such a combination accelerates system convergence several times in comparison with all-atom simulations starting from the extended chain conformation, demonstrated by the analysis of melting curves, the number of native-like conformations as a function of time and secondary structure propagation. The results strongly suggest that the proposed multiscale method could be an efficient and accurate tool for high-resolution studies of protein folding dynamics in larger systems. PMID:23665897

Overview of the SAMPL5 host–guest challenge: Are we doing better?

PubMed Central

Yin, Jian; Henriksen, Niel M.; Slochower, David R.; Shirts, Michael R.; Chiu, Michael W.; Mobley, David L.; Gilson, Michael K.

2016-01-01

The ability to computationally predict protein-small molecule binding affinities with high accuracy would accelerate drug discovery and reduce its cost by eliminating rounds of trial-and-error synthesis and experimental evaluation of candidate ligands. As academic and industrial groups work toward this capability, there is an ongoing need for datasets that can be used to rigorously test new computational methods. Although protein–ligand data are clearly important for this purpose, their size and complexity make it difficult to obtain well-converged results and to troubleshoot computational methods. Host–guest systems offer a valuable alternative class of test cases, as they exemplify noncovalent molecular recognition but are far smaller and simpler. As a consequence, host–guest systems have been part of the prior two rounds of SAMPL prediction exercises, and they also figure in the present SAMPL5 round. In addition to being blinded, and thus avoiding biases that may arise in retrospective studies, the SAMPL challenges have the merit of focusing multiple researchers on a common set of molecular systems, so that methods may be compared and ideas exchanged. The present paper provides an overview of the host–guest component of SAMPL5, which centers on three different hosts, two octa-acids and a glycoluril-based molecular clip, and two different sets of guest molecules, in aqueous solution. A range of methods were applied, including electronic structure calculations with implicit solvent models; methods that combine empirical force fields with implicit solvent models; and explicit solvent free energy simulations. The most reliable methods tend to fall in the latter class, consistent with results in prior SAMPL rounds, but the level of accuracy is still below that sought for reliable computer-aided drug design. Advances in force field accuracy, modeling of protonation equilibria, electronic structure methods, and solvent models, hold promise for future improvements. PMID:27658802

Overview of the SAMPL5 host-guest challenge: Are we doing better?

PubMed

Yin, Jian; Henriksen, Niel M; Slochower, David R; Shirts, Michael R; Chiu, Michael W; Mobley, David L; Gilson, Michael K

2017-01-01

The ability to computationally predict protein-small molecule binding affinities with high accuracy would accelerate drug discovery and reduce its cost by eliminating rounds of trial-and-error synthesis and experimental evaluation of candidate ligands. As academic and industrial groups work toward this capability, there is an ongoing need for datasets that can be used to rigorously test new computational methods. Although protein-ligand data are clearly important for this purpose, their size and complexity make it difficult to obtain well-converged results and to troubleshoot computational methods. Host-guest systems offer a valuable alternative class of test cases, as they exemplify noncovalent molecular recognition but are far smaller and simpler. As a consequence, host-guest systems have been part of the prior two rounds of SAMPL prediction exercises, and they also figure in the present SAMPL5 round. In addition to being blinded, and thus avoiding biases that may arise in retrospective studies, the SAMPL challenges have the merit of focusing multiple researchers on a common set of molecular systems, so that methods may be compared and ideas exchanged. The present paper provides an overview of the host-guest component of SAMPL5, which centers on three different hosts, two octa-acids and a glycoluril-based molecular clip, and two different sets of guest molecules, in aqueous solution. A range of methods were applied, including electronic structure calculations with implicit solvent models; methods that combine empirical force fields with implicit solvent models; and explicit solvent free energy simulations. The most reliable methods tend to fall in the latter class, consistent with results in prior SAMPL rounds, but the level of accuracy is still below that sought for reliable computer-aided drug design. Advances in force field accuracy, modeling of protonation equilibria, electronic structure methods, and solvent models, hold promise for future improvements.

Transient rheology of stimuli responsive hydrogels: Integrating microrheology and microfluidics

NASA Astrophysics Data System (ADS)

Sato, Jun

Stimuli-responsive hydrogels have diverse potential applications in the field of drug delivery, tissue engineering, agriculture, cosmetics, gene therapy, and as sensors and actuators due to their unique responsiveness to external signals, such as pH, temperature, and ionic strength. Understanding the responsiveness of hydrogel structure and rheology to these stimuli is essential for designing materials with desirable performance. However, no instrumentation and well-defined methodology are available to characterize the structural and rheological responses to rapid solvent changes. In this thesis, a new microrheology set-up is described, which allows us to quantitatively measure the transient rheological properties and microstructure of a variety of solvent-responsive complex fluids. The device was constructed by integrating particle tracking microrheology and microfluidics and offers unique experimental capabilities for performing solvent-reponse measurements on soft fragile materials without applying external shear forces. Transient analysis methods to quantitatively obtain rheological properties were also constructed, and guidelines for the trade-off between statistical validity and temporal resolution were developed to accurately capture physical transitions. Employing the new device and methodology, we successfully quantified the transient rheological and microstructural responses during gel formation and break-up, and viscosity changes of solvent-responsive complex fluids. The analysis method was expanded for heterogeneous samples, incorporating methods to quantify the microrheology of samples with broad distributions of individual particle dynamics. Transient microrheology measurements of fragile, heterogeneous, self-assembled block copolypeptide hydrogels revealed that solvent exchange via convective mixing and dialysis can lead to significantly different gel properties and that commonly applied sample preparation protocols for the characterization of soft biomaterials could lead to erroneous conclusions about microstructural dynamics. Systematic investigations by varying key parameters, like molecular structure, gel concentration, salt concentration, and tracer particle size for microrheology, revealed that subtle variations in molecular architecture can cause major changes in response dynamics. Moreover, the results showed that the method can be applied for studying gel formation and breakup kinetics. The research in this thesis facilitates the design of solvent-responsive soft materials with appropriate microstructural dynamics for in vivo applications like tissue engineering and drug delivery, and can also be applied to study the effect of solvents on self-assembly mechanisms in other responsive soft materials, such as polymer solutions and colloidal dispersions.

Lanthanide-organic complexes based on polyoxometalates: Solvent effect on the luminescence properties

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

Tang Qun; Liu Shuxia, E-mail: liusx@nenu.edu.cn; Liang Dadong

2012-06-15

A series of lanthanide-organic complexes based on polyoxometalates (POMs) [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}][W{sub 6}O{sub 19}] (Ln=La(1), Ce(2), Sm(3), Eu(4), Gd(5); DNBA=3,5-dinitrobenzoate; DMF=N,N-dimethylformamide) has been synthesized. These complexes consist of [W{sub 6}O{sub 19}]{sup 2-} and dimeric [Ln{sub 2}(DNBA){sub 4}(DMF){sub 8}]{sup 2+} cations. The luminescence properties of 4 are measured in solid state and different solutions, respectively. Notably, the emission intensity increases gradually with the increase of solvent permittivity, and this solvent effect can be directly observed by electrospray mass spectrometry (ESI-MS). The analyses of ESI-MS show that the eight coordinated solvent DMF units of dimeric cation are active. They can movemore » away from dimeric cations and exchange with solvent molecules. Although the POM anions escape from 3D supramolecular network, the dimeric state structure of [Ln{sub 2}(DNBA){sub 4}]{sup 2+} remains unchanged in solution. The conservation of red luminescence is attributed to the maintenance of the aggregated state structures of dimeric cations. - Graphical abstract: 3D POMs-based lanthanide-organic complexes performed the solvent effect on the luminescence property. The origin of such solvent effect can be understood and explained on the basis of the existence of coordinated active sites by the studies of ESI-MS. Highlights: Black-Right-Pointing-Pointer The solvent effect on the luminescence property of POMs-based lanthanide-organic complexes. Black-Right-Pointing-Pointer ESI-MS analyses illuminate the correlation between the structure and luminescence property. Black-Right-Pointing-Pointer The dimeric cations have eight active sites of solvent coordination. Black-Right-Pointing-Pointer The aggregated state structure of dimer cation remains unchanged in solution. Black-Right-Pointing-Pointer Luminescence associating with ESI-MS is a new method for investigating the interaction of complex and solvent.« less

Imidazole C-2 Hydrogen/Deuterium Exchange Reaction at Histidine for Probing Protein Structure and Function with MALDI Mass Spectrometry

PubMed Central

Hayashi, Naoka; Kuyama, Hiroki; Nakajima, Chihiro; Kawahara, Kazuki; Miyagi, Masaru; Nishimura, Osamu; Matsuo, Hisayuki; Nakazawa, Takashi

2015-01-01

We present a mass spectrometric method for analyzing protein structure and function, based on the imidazole C-2 or histidine Cε1 hydrogen/deuterium (H/D) exchange reaction, which is intrinsically second order with respect to the concentrations of the imidazolium cation and OD− in D2O. The second-order rate constant (k2) of this reaction was calculated from the pH-dependency of the pseudo-first-order rate constant (kφ) obtained from the change of average mass ΔMr (0 ≤ ΔMr < 1) of a peptide fragment containing a defined histidine residue at incubation time (t) such that kφ = − [ln(1−ΔMr)]/t. We preferred using k2 rather than kφ because k2max (maximal value of k2) was empirically related to pKa as illustrated with a Brønsted plot: logk2max=-0.7pKa+α (α is an arbitrary constant), so that we could analyze the effect of structure on the H/D-exchange rate in terms of log(k2max/k2) representing the deviation of k2 from k2max. In the catalytic site of bovine ribonuclease A, His12 showed much larger change in log(k2max/k2) compared with His119 upon binding with cytidine 3′-monophosphate, as anticipated from the X-ray structures and the possible change in solvent accessibility. However, there is a need of considering the hydrogen bonds of the imidazole group with non-dissociable groups to interpret an extremely slow H/D exchange rate of His48 in partially solvent-exposed situation. PMID:24606199

Thermally Cross-Linked Anion Exchange Membranes from Solvent Processable Isoprene Containing Ionomers

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

Tsai, Tsung-Han; Ertem, S. Piril; Maes, Ashley M.

2015-01-28

Random copolymers of isoprene and 4-vinylbenzyl chloride (VBCl) with varying compositions were synthesized via nitroxide-mediated polymerization. Subsequent quaternization afforded solvent processable and cross-linkable ionomers with a wide range of ion exchange capacities (IECs). Solution cast membranes were thermally cross-linked to form anion exchange membranes. Cross-linking was achieved by taking advantage of the unsaturations on the polyisoprene backbone, without added cross-linkers. A strong correlation was found between water uptake and ion conductivity of the membranes: conductivities of the membranes with IECs beyond a critical value were found to be constant related to their high water absorption. Environmentally controlled small-angle X-ray scatteringmore » experiments revealed a correlation between the average distance between ionic clusters and the ion conductivity, indicating that a well-connected network of ion clusters is necessary for efficient ion conduction and high ion conductivity.« less

High-yield synthesis of brookite TiO.sub.2 nanoparticles

DOEpatents

Huber, Dale L [Albuquerque, NM; Monson, Todd C [Albuquerque, NM

2011-05-17

A method for forming non-agglomerated brookite TiO.sub.2 nanoparticles without the use of expensive organic surfactants or high temperature processing. Embodiments of this invention use titanium isopropoxide as the titanium precursor and isopropanol as both the solvent and ligand for ligand-stabilized brookite-phase titania. Isopropanol molecules serve as the ligands interacting with the titania surfaces that stabilize the titania nanoparticles. The isopropanol ligands can be exchanged with other alcohols and other ligands during or after the nanoparticle formation reaction.

Refractory concentrate gold leaching: Cyanide vs. bromine

NASA Astrophysics Data System (ADS)

Dadgar, Ahmad

1989-12-01

Gold extraction, recovery and economics for two refractory concentrates were investigated using cyanide and bromine reagents. Gold extractions for cyanide leaching (24-48 hours) and bromine leaching (six hours) were the same and ranged from 94 to 96%. Gold recoveries from bromine pregnant solutions using carbon adsorption, ion exchange, solvent extraction, and zinc and aluminum precipitation methods were better than 99.9%. A preliminary economic analysis indicates that chemical costs for cyanidation and bromine process are 11.70 and 11.60 respectively, per tonne of calcine processed.

Calculation of Protein Heat Capacity from Replica-Exchange Molecular Dynamics Simulations with Different Implicit Solvent Models

DTIC Science & Technology

2008-10-30

rigorous Poisson-based methods generally apply a Lee-Richards mo- lecular surface.9 This surface is considered the de facto description for continuum...definition and calculation of the Born radii. To evaluate the Born radii, two approximations are invoked. The first is the Coulomb field approximation (CFA...energy term, and depending on the particular GB formulation, higher-order non- Coulomb correction terms may be added to the Born radii to account for the

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.

Hydrogen/deuterium (H/D) exchange of gelatinized starch studied by two-dimensional (2D) near-infrared (NIR) correlation spectroscopy

NASA Astrophysics Data System (ADS)

Shinzawa, Hideyuki; Mizukado, Junji

2018-05-01

Hydrogen/deuterium (H/D) exchange of gelatinized starch was probed by in-situ near-infrared (NIR) monitoring coupled with two-dimensional (2D) correlation spectroscopy. Gelatinized starch undergoes spontaneous H/D exchange in D2O. During the substitution, the exchange rate essentially becomes different depending on solvent accessibility of various parts of the molecule. Thus, by analyzing the change in the NIR feature observed during the substitution, it becomes possible to sort out local structure and dynamics of the system. 2D correlation analysis of the time-dependent NIR spectra reveals the presence of different local structure of the starch, each having different solvent accessibility. For example, during the H/D exchange, the D2O is first absorbed by starch molecules especially around the surface area between the starch and water, where the water molecules are weakly interacted with the starch molecules. This absorption is quickly followed by the development of HDO species. Further absorption of the D2O results in the penetration of the molecules inside the starch and eventually develops the relatively strong interaction between the HDO and starch molecules because of the presence of dominant starch molecules.

Ab Initio Modeling of the Electronic Absorption Spectrum of Previtamin D in Solution

NASA Astrophysics Data System (ADS)

Zhu, Tianyang

To study the solvent effects of water on the previtamin D absorption spectrum, we use the quantum mechanics (QM)/molecular mechanics (MM) method combined with replica-exchange molecular dynamics (REMD). The QM method is applied for the previtamin D molecule and the MM method is used for the water molecules. To enhance conformational sampling of the flexible previtamin D molecule we apply REMD. Based on the REMD structures, we calculate the macroscopic ensemble of the absorption spectrum in solution by time-dependent density functional theory (TDDFT). Comparison between the calculated spectrum in the gas phase and in the solution reveals minor influences of the solvent on the absorption spectrum. In the conventional molecule dynamics simulation, the previtamin D molecule can be trapped by local minimum and cannot overcome energetics barriers when it is calculated at the room temperature. In addition, the higher temperature calculation for the molecule in REMD allows to overcome energetics barriers and to change the structure to other rotational isomers, then switch to the lower temperature and gives a more complete result in the configuration space for the lower temperature.

Inhibition of cyclooxygenase and nitric oxide synthase in hypoxic vasoconstriction and oleic acid-induced lung injury.

PubMed

Leeman, M; de Beyl, V Z; Biarent, D; Maggiorini, M; Mélot, C; Naeije, R

1999-05-01

Cyclooxygenase (COX) products and nitric oxide (NO) inhibit hypoxic pulmonary vasoconstriction (HPV), and their release could contribute to alterations in gas exchange in lung injury. We tested the hypothesis that combined blockade of COX and NO synthase (NOS) could further increase HPV and better protect gas exchange in lung injury than could blockade of either COX or NOS alone. We determined pulmonary vascular pressure-flow relationships in pentobarbital-anesthetized and ventilated dogs submitted to hypoxic challenges before and after administration of solvent (n = 4), indomethacin alone (2 mg/kg intravenously, n = 8), Nomega-nitro-L-arginine (L-NA) alone (10 mg/kg intravenoulsy, n = 8), indomethacin followed by L-NA (n = 8), and L-NA followed by indomethacin (n = 8). All of the dogs so treated then received oleic acid (0.06 ml/kg intravenously) to induce lung injury. Blood flow was manipulated by establishing a femoral arteriovenous bypass or by inflating an inferior vena caval balloon. Gas exchange was evaluated by measuring arterial PO2 and intrapulmonary shunt (using the inert gas sulfur hexafluoride) at identical cardiac outputs. The magnitude of HPV was not affected by solvent. Indomethacin and L-NA given separately enhanced HPV. L-NA added to indomethacin further enhanced HPV, as did indomethacin added to L-NA. After oleic acid-induced lung injury, gas exchange deteriorated less in dogs pretreated with indomethacin than in dogs pretreated with solvent or with L-NA alone. These results suggest that in pentobarbital-anesthetized dogs: (1) the magnitude of HPV is limited by the corelease of COX metabolites and of NO; and (2) inhibition of COX, but not of NOS, attenuates the deterioration of gas exchange in oleic acid-induced lung injury.

Separation of the rare earths by anion-exchange in the presence of lactic acid

NASA Technical Reports Server (NTRS)

Faris, J. P.

1969-01-01

Investigation of adsorption of rare earths and a few other elements to an anion-exchange resin from mixed solvents containing lactic acid shows that the lanthanides are absorbed more strongly than from the alpha-hydroxyisobutryric acid system, but with less separation between adjacent members of the series.

How amide hydrogens exchange in native proteins.

PubMed

Persson, Filip; Halle, Bertil

2015-08-18

Amide hydrogen exchange (HX) is widely used in protein biophysics even though our ignorance about the HX mechanism makes data interpretation imprecise. Notably, the open exchange-competent conformational state has not been identified. Based on analysis of an ultralong molecular dynamics trajectory of the protein BPTI, we propose that the open (O) states for amides that exchange by subglobal fluctuations are locally distorted conformations with two water molecules directly coordinated to the N-H group. The HX protection factors computed from the relative O-state populations agree well with experiment. The O states of different amides show little or no temporal correlation, even if adjacent residues unfold cooperatively. The mean residence time of the O state is ∼100 ps for all examined amides, so the large variation in measured HX rate must be attributed to the opening frequency. A few amides gain solvent access via tunnels or pores penetrated by water chains including native internal water molecules, but most amides access solvent by more local structural distortions. In either case, we argue that an overcoordinated N-H group is necessary for efficient proton transfer by Grotthuss-type structural diffusion.

How amide hydrogens exchange in native proteins

PubMed Central

Persson, Filip; Halle, Bertil

2015-01-01

Amide hydrogen exchange (HX) is widely used in protein biophysics even though our ignorance about the HX mechanism makes data interpretation imprecise. Notably, the open exchange-competent conformational state has not been identified. Based on analysis of an ultralong molecular dynamics trajectory of the protein BPTI, we propose that the open (O) states for amides that exchange by subglobal fluctuations are locally distorted conformations with two water molecules directly coordinated to the N–H group. The HX protection factors computed from the relative O-state populations agree well with experiment. The O states of different amides show little or no temporal correlation, even if adjacent residues unfold cooperatively. The mean residence time of the O state is ∼100 ps for all examined amides, so the large variation in measured HX rate must be attributed to the opening frequency. A few amides gain solvent access via tunnels or pores penetrated by water chains including native internal water molecules, but most amides access solvent by more local structural distortions. In either case, we argue that an overcoordinated N–H group is necessary for efficient proton transfer by Grotthuss-type structural diffusion. PMID:26195754

Protein hydrogen exchange: Testing current models

PubMed Central

Skinner, John J; Lim, Woon K; Bédard, Sabrina; Black, Ben E; Englander, S Walter

2012-01-01

To investigate the determinants of protein hydrogen exchange (HX), HX rates of most of the backbone amide hydrogens of Staphylococcal nuclease were measured by NMR methods. A modified analysis was used to improve accuracy for the faster hydrogens. HX rates of both near surface and well buried hydrogens are spread over more than 7 orders of magnitude. These results were compared with previous hypotheses for HX rate determination. Contrary to a common assumption, proximity to the surface of the native protein does not usually produce fast exchange. The slow HX rates for unprotected surface hydrogens are not well explained by local electrostatic field. The ability of buried hydrogens to exchange is not explained by a solvent penetration mechanism. The exchange rates of structurally protected hydrogens are not well predicted by algorithms that depend only on local interactions or only on transient unfolding reactions. These observations identify some of the present difficulties of HX rate prediction and suggest the need for returning to a detailed hydrogen by hydrogen analysis to examine the bases of structure-rate relationships, as described in the companion paper (Skinner et al., Protein Sci 2012;21:996–1005). PMID:22544567

Solvent-induced controllable synthesis, single-crystal to single-crystal transformation and encapsulation of Alq3 for modulated luminescence in (4,8)-connected metal-organic frameworks.

PubMed

Lan, Ya-Qian; Jiang, Hai-Long; Li, Shun-Li; Xu, Qiang

2012-07-16

In this work, for the first time, we have systematically demonstrated that solvent plays crucial roles in both controllable synthesis of metal-organic frameworks (MOFs) and their structural transformation process. With solvent as the only variable, five new MOFs with different structures have been constructed, in which one MOF undergoes solvent-induced single-crystal to single-crystal (SCSC) transformation that involves not only solvent exchange but also the cleavage and formation of coordination bonds. Particularly, a significant crystallographic change has been realized through an unprecedented three-step SCSC transformation process. Furthermore, we have demonstrated that the obtained MOF could be an excellent host for chromophores such as Alq3 for modulated luminescent properties.

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

Roy, Santanu; Dang, Liem X.

In this paper, we present the first computer simulation of methanol exchange dynamics between the first and second solvation shells around different cations and anions. After water, methanol is the most frequently used solvent for ions. Methanol has different structural and dynamical properties than water, so its ion solvation process is different. To this end, we performed molecular dynamics simulations using polarizable potential models to describe methanol-methanol and ion-methanol interactions. In particular, we computed methanol exchange rates by employing the transition state theory, the Impey-Madden-McDonald method, the reactive flux approach, and the Grote-Hynes theory. We observed that methanol exchange occursmore » at a nanosecond time scale for Na+ and at a picosecond time scale for other ions. We also observed a trend in which, for like charges, the exchange rate is slower for smaller ions because they are more strongly bound to methanol. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less

Understanding perovskite formation through the intramolecular exchange method in ambient conditions

NASA Astrophysics Data System (ADS)

Szostak, Rodrigo; Castro, Jhon A. P.; Marques, Adriano S.; Nogueira, Ana F.

2017-04-01

Among the methods to prepare hybrid organic-inorganic perovskite films, the intramolecular exchange method was the first one that made possible to prepare perovskite solar cells with efficiencies higher than 20%. However, perovskite formation by this method is not completely understood, especially in ambient conditions. In this work, perovskite films were prepared by the intramolecular exchange method in ambient conditions. The spin coating speed and the frequency of the MAI solution dripping onto PbI2(DMSO) were varied during the deposition steps. With the combination of these two parameters, a rigid control of the solvent drying was possible. Thus, depending on the chosen conditions, the intermediate MAPb3I8·2DMSO was formed with residual PbI2. Otherwise, direct formation of perovskite film was attained. A mechanism for the direct formation of bulk perovskite was proposed. We also investigated how the posterior thermal annealing affects the crystallinity and defects in perovskite films. With prolonged thermal annealing, the excess of MAI can be avoided, increasing the efficiency and decreasing the hysteresis of the solar cells. The best perovskite solar cell achieved a stabilized power output of 12.9%. The findings of this work pave the way for realizing the fabrication of efficient perovskite solar cells in ambient atmosphere, a very desirable condition for cost-efficient large scale manufacturing of this technology.

Effect of a magnetic field on molecule-solvent angular momentum transfer

NASA Astrophysics Data System (ADS)

Rzadkowski, Wojciech; Lemeshko, Mikhail

2018-03-01

Recently it was shown that a molecule rotating in a quantum solvent can be described in terms of the "angulon" quasiparticle [M. Lemeshko, Phys. Rev. Lett. 118, 095301 (2017)]. Here we extend the angulon theory to the case of molecules possessing an additional spin-1/2 degree of freedom and study the behavior of the system in the presence of a static magnetic field. We show that exchange of angular momentum between the molecule and the solvent can be altered by the field, even though the solvent itself is non-magnetic. In particular, we demonstrate a possibility to control resonant emission of phonons with a given angular momentum using a magnetic field.

Direct and Quantitative Characterization of Dynamic Ligand Exchange between Coordination-Driven Self-Assembled Supramolecular Polygons

PubMed Central

Zheng, Yao-Rong; Stang, Peter J.

2009-01-01

The direct observation of dynamic ligand exchange beween Pt-N coordination-driven self-assembled supramolecular polygons (triangles and rectangles) has been achieved using stable isotope labeling (1H/2D) of the pyridyl donors and electrospray ionization mass spectrometry (ESI-MS) together with NMR spectroscopy. Both the thermodynamic and kinetic aspects of such exchange processes have been established based on quantitative mass spectral results. Further investigation showed that the exchange is highly dependent on experimental conditions such as temperature, solvent, and the counter anions. PMID:19243144

Direct and quantitative characterization of dynamic ligand exchange between coordination-driven self-assembled supramolecular polygons.

PubMed

Zheng, Yao-Rong; Stang, Peter J

2009-03-18

The direct observation of dynamic ligand exchange between Pt-N coordination-driven self-assembled supramolecular polygons (triangles and rectangles) has been achieved using stable (1)H/(2)D isotope labeling of the pyridyl donors and electrospray ionization mass spectrometry combined with NMR spectroscopy. Both the thermodynamic and kinetic aspects of such exchange processes have been established on the basis of quantitative mass spectral results. Further investigation has shown that the exchange is highly dependent on experimental conditions such as temperature, solvent, and the counteranions.

Enhanced conformational sampling using replica exchange with concurrent solute scaling and hamiltonian biasing realized in one dimension.

PubMed

Yang, Mingjun; Huang, Jing; MacKerell, Alexander D

2015-06-09

Replica exchange (REX) is a powerful computational tool for overcoming the quasi-ergodic sampling problem of complex molecular systems. Recently, several multidimensional extensions of this method have been developed to realize exchanges in both temperature and biasing potential space or the use of multiple biasing potentials to improve sampling efficiency. However, increased computational cost due to the multidimensionality of exchanges becomes challenging for use on complex systems under explicit solvent conditions. In this study, we develop a one-dimensional (1D) REX algorithm to concurrently combine the advantages of overall enhanced sampling from Hamiltonian solute scaling and the specific enhancement of collective variables using Hamiltonian biasing potentials. In the present Hamiltonian replica exchange method, termed HREST-BP, Hamiltonian solute scaling is applied to the solute subsystem, and its interactions with the environment to enhance overall conformational transitions and biasing potentials are added along selected collective variables associated with specific conformational transitions, thereby balancing the sampling of different hierarchical degrees of freedom. The two enhanced sampling approaches are implemented concurrently allowing for the use of a small number of replicas (e.g., 6 to 8) in 1D, thus greatly reducing the computational cost in complex system simulations. The present method is applied to conformational sampling of two nitrogen-linked glycans (N-glycans) found on the HIV gp120 envelope protein. Considering the general importance of the conformational sampling problem, HREST-BP represents an efficient procedure for the study of complex saccharides, and, more generally, the method is anticipated to be of general utility for the conformational sampling in a wide range of macromolecular systems.

Trace elements retained in washed nuclear fuel reprocessing solvents

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

Gray, L.W.; MacMurdo, K.W.

1979-09-01

Analysis of purified TBP extractant from solvent extraction processes at Savannah River Plant showed several stable elements and several long-lived radioisotopes. Stable elements Al, Na, Br, Ce, Hg, and Sm are found in trace quantities in the solvent. The only stable metallic element consistently found in the solvent was Al, with a concentration which varies from about 30 ppM to about 10 ppM. The halogens Br and Cl appear to be found in the solvent systems as organo halides. Radionuclides found were principally /sup 106/Ru, /sup 129/I, /sup 3/H, /sup 235/U, and /sup 239/Pu. The /sup 129/I concentration was aboutmore » 1 ppM in the first solvent extraction cycle of each facility. In the other cycles, /sup 129/I concentration varied from about 0.1 to 0.5 ppM. Both /sup 129/I and /sup 3/H appear to be in the organic solvent as a result of exchange with hydrogen.« less

Structural and thermodynamic properties of the Cm III ion solvated by water and methanol

DOE PAGES

Kelley, Morgan P.; Yang, Ping; Clark, Sue B.; ...

2016-04-27

The geometric and electronic structures of the 9-coordinate Cm 3+ ion solvated with both water and methanol are systematically investigated in the gas phase at each possible solvent-shell composition and configuration using density functional theory and second-order Møller–Plesset perturbation theory. Ab initio molecular dynamics simulations are employed to assess the effects of second and third solvent shells on the gas-phase structure. The ion–solvent dissociation energy for methanol is greater than that of water, potentially because of increased charge donation to the ion made possible by the electron-rich methyl group. Further, the ion–solvent dissociation energy and the ion–solvent distance are shownmore » to be dependent on the solvent-shell composition. Furthermore, this has implications for solvent exchange, which is generally the rate-limiting step in complexation reactions utilized in the separation of curium from complex metal mixtures that derive from the advanced nuclear fuel cycle.« less

Ligand exchange in ionic systems and its effect on silver nucleation and growth.

PubMed

Abbott, Andrew P; Azam, Muhammad; Frisch, Gero; Hartley, Jennifer; Ryder, Karl S; Saleem, Saima

2013-10-28

The electrodeposition of metals from ionic solutions is intrinsically linked to the reactivity of the solute ions. When metal salts dissolve, the exchange of the anion with the molecular and ionic components from solution affects the speciation and therefore the characteristics of metal reduction. This study investigates the nucleation mechanism, deposition kinetics, metal speciation and diffusion coefficients of silver salts dissolved in Deep Eutectic Solvents. The electrochemical reduction of AgCl, AgNO3 and Ag2O is studied in 1 : 2 choline chloride : ethylene glycol and 1 : 2 choline chloride : urea. Cyclic voltammetry is used to evaluate electrochemical kinetics. Detailed analysis of chronoamperometric data shows that silver deposits form via multiple 3D nucleation with mass transport controlled hemispherical growth. The nucleation mechanism was found to be potential dependent, varying from progressive to instantaneous as the reduction potential becomes more cathodic. Diffusion coefficients are determined using three different methods. Trends are rationalised in terms of solvent viscosity and silver speciation analysis with EXAFS. The morphology of electroreduced silver is investigated with scanning electron microscopy and shows that deposits from the urea based liquid form more dense morphologies than those from the ethylene glycol based liquid.

Thermal Stability of Oil Palm Empty Fruit Bunch (OPEFB) Nanocrystalline Cellulose: Effects of post-treatment of oven drying and solvent exchange techniques

NASA Astrophysics Data System (ADS)

Indarti, E.; Marwan; Wanrosli, W. D.

2015-06-01

Nanocrystallinecellulose (NCC) from biomass is a promising material with huge potentials in various applications. A big challenge in its utilization is the agglomeration of the NCC's during processing due to hydrogen bonding among the cellulose chains when in close proximity to each other. Obtaining NCC's in a non-agglomerated and non-aqueous condition is challenging. In the present work NCC's was isolated from oil palm empty fruit bunch (OPEFB) using TEMPO-oxidation reaction method. To obtain non-agglomerated and non-aqueous products, the NCC's underwent post-treatment using oven drying (OD) and solvent exchanged (SE) techniques. The thermal stability of all samples was determined from TGA and DTG profiles whilst FTIR was used to analyzethe chemical modifications that occurred under these conditions. NCC-SE has better thermal stability than the NCC-OD and its on-set degradation temperature and residue are also higher. FTIR analysis shows that NCC-SE has a slightly different chemical composition whereby the absorption band at 1300 cm-1 (due to C-O symmetric stretching) is absent as compared to NCC-OD indicating that in NCC-SE the carboxylate group is in acid form which contribute to its thermal stability

Detection and measurement of organic lampricide residues

USGS Publications Warehouse

Daniels, Stacy L.; Kempe, Lloyd L.; Billy, Thomas J.; Beeton, Alfred M.

1965-01-01

The selective lampricide, 3-trifluoromethyl-4-nitrophenol (TFM), and its synergist, 5,2'-dichloro-4'-nitrosalicylanilide (DCN), are separable from natural waters by anion exchange. The adsorbed compounds can then be recovered from the resin as concentrates by elution with selective solvent mixtures. Measurements of the amounts of lampricides in the final concentrates can be made colorimetrically at 395 mI? for TFM and at 530 mI? for the safranin complex of DCN. TFM has also been separated for quantitative determination from homogenates of whole fish. The fish is first macerated in a blender and then hydrolyzed in hot, 3 N hydrochloric acid. The amount of background color, due to certain components of the fish in the hydrolysate, is reduced by one or a combination of three methods: (1) a series of three extractions with ether, methylene chloride, and benzene; (2) cation exchange followed by methylene chloride extraction; or (3) ether extraction followed by anion exchange and subsequent desorption with amyl acetate-acetic acid.

Mapping transiently formed and sparsely populated conformations on a complex energy landscape

PubMed Central

Wang, Yong; Papaleo, Elena; Lindorff-Larsen, Kresten

2016-01-01

Determining the structures, kinetics, thermodynamics and mechanisms that underlie conformational exchange processes in proteins remains extremely difficult. Only in favourable cases is it possible to provide atomic-level descriptions of sparsely populated and transiently formed alternative conformations. Here we benchmark the ability of enhanced-sampling molecular dynamics simulations to determine the free energy landscape of the L99A cavity mutant of T4 lysozyme. We find that the simulations capture key properties previously measured by NMR relaxation dispersion methods including the structure of a minor conformation, the kinetics and thermodynamics of conformational exchange, and the effect of mutations. We discover a new tunnel that involves the transient exposure towards the solvent of an internal cavity, and show it to be relevant for ligand escape. Together, our results provide a comprehensive view of the structural landscape of a protein, and point forward to studies of conformational exchange in systems that are less characterized experimentally. DOI: http://dx.doi.org/10.7554/eLife.17505.001 PMID:27552057

Combined DFT and BS study on the exchange coupling of dinuclear sandwich-type POM: comparison of different functionals and reliability of structure modeling.

PubMed

Yin, Bing; Xue, GangLin; Li, JianLi; Bai, Lu; Huang, YuanHe; Wen, ZhenYi; Jiang, ZhenYi

2012-05-01

The exchange coupling of a group of three dinuclear sandwich-type polyoxomolybdates [MM'(AsMo7O27)2](12-) with MM' = CrCr, FeFe, FeCr are theoretically predicted from combined DFT and broken-symmetry (BS) approach. Eight different XC functionals are utilized to calculate the exchange-coupling constant J from both the full crystalline structures and model structures of smaller size. The comparison between theoretical values and accurate experimental results supports the applicability of DFT-BS method in this new type of sandwich-type dinuclear polyoxomolybdates. However, a careful choice of functionals is necessary to achieve the desired accuracy. The encouraging results obtained from calculations on model structures highlight the great potential of application of structure modeling in theoretical study of POM. Structural modeling may not only reduce the computational cost of large POM species but also be able to take into account the external field effect arising from solvent molecules in solution or counterions in crystal.

Polymer blend of PLA/PHBV based bionanocomposites reinforced with nanocrystalline cellulose for potential application as packaging material.

PubMed

Dasan, Y K; Bhat, A H; Ahmad, Faiz

2017-02-10

The current research discusses the development of poly (lactic acid) (PLA) and poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) reinforced nanocrystalline cellulose bionanocomposites. The nanocrystalline cellulose was derived from waste oil palm empty fruit bunch fiber by acid hydrolysis process. The resulting nanocrystalline cellulose suspension was then surface functionalized by TEMPO-mediated oxidation and solvent exchange process. Furthermore, the PLA/PHBV/nanocrystalline cellulose bionanocomposites were produced by solvent casting method. The effect of the addition of nanocrystalline cellulose on structural, morphology, mechanical and barrier properties of bionanocomposites was investigated. The results revealed that the developed bionanocomposites showed improved mechanical properties and decrease in oxygen permeability rate. Therefore, the developed bio-based composite incorporated with an optimal composition of nanocrystalline cellulose exhibits properties as compared to the polymer blend. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of sequence and stereochemistry reversal on p53 peptide mimicry.

PubMed

Atzori, Alessio; Baker, Audrey E; Chiu, Mark; Bryce, Richard A; Bonnet, Pascal

2013-01-01

Peptidomimetics effective in modulating protein-protein interactions and resistant to proteolysis have potential in therapeutic applications. An appealing yet underperforming peptidomimetic strategy is to employ D-amino acids and reversed sequences to mimic a lead peptide conformation, either separately or as the combined retro-inverso peptide. In this work, we examine the conformations of inverse, reverse and retro-inverso peptides of p53(15-29) using implicit solvent molecular dynamics simulation and circular dichroism spectroscopy. In order to obtain converged ensembles for the peptides, we find enhanced sampling is required via the replica exchange molecular dynamics method. From these replica exchange simulations, the D-peptide analogues of p53(15-29) result in a predominantly left-handed helical conformation. When the parent sequence is reversed sequence as either the L-peptide and D-peptide, these peptides display a greater helical propensity, feature reflected by NMR and CD studies in TFE/water solvent. The simulations also indicate that, while approximately similar orientations of the side-chains are possible by the peptide analogues, their ability to mimic the parent peptide is severely compromised by backbone orientation (for D-amino acids) and side-chain orientation (for reversed sequences). A retro-inverso peptide is disadvantaged as a mimic in both aspects, and further chemical modification is required to enable this concept to be used fruitfully in peptidomimetic design. The replica exchange molecular simulation approach adopted here, with its ability to provide detailed conformational insights into modified peptides, has potential as a tool to guide structure-based design of new improved peptidomimetics.

Refinement of NMR structures using implicit solvent and advanced sampling techniques.

PubMed

Chen, Jianhan; Im, Wonpil; Brooks, Charles L

2004-12-15

NMR biomolecular structure calculations exploit simulated annealing methods for conformational sampling and require a relatively high level of redundancy in the experimental restraints to determine quality three-dimensional structures. Recent advances in generalized Born (GB) implicit solvent models should make it possible to combine information from both experimental measurements and accurate empirical force fields to improve the quality of NMR-derived structures. In this paper, we study the influence of implicit solvent on the refinement of protein NMR structures and identify an optimal protocol of utilizing these improved force fields. To do so, we carry out structure refinement experiments for model proteins with published NMR structures using full NMR restraints and subsets of them. We also investigate the application of advanced sampling techniques to NMR structure refinement. Similar to the observations of Xia et al. (J.Biomol. NMR 2002, 22, 317-331), we find that the impact of implicit solvent is rather small when there is a sufficient number of experimental restraints (such as in the final stage of NMR structure determination), whether implicit solvent is used throughout the calculation or only in the final refinement step. The application of advanced sampling techniques also seems to have minimal impact in this case. However, when the experimental data are limited, we demonstrate that refinement with implicit solvent can substantially improve the quality of the structures. In particular, when combined with an advanced sampling technique, the replica exchange (REX) method, near-native structures can be rapidly moved toward the native basin. The REX method provides both enhanced sampling and automatic selection of the most native-like (lowest energy) structures. An optimal protocol based on our studies first generates an ensemble of initial structures that maximally satisfy the available experimental data with conventional NMR software using a simplified force field and then refines these structures with implicit solvent using the REX method. We systematically examine the reliability and efficacy of this protocol using four proteins of various sizes ranging from the 56-residue B1 domain of Streptococcal protein G to the 370-residue Maltose-binding protein. Significant improvement in the structures was observed in all cases when refinement was based on low-redundancy restraint data. The proposed protocol is anticipated to be particularly useful in early stages of NMR structure determination where a reliable estimate of the native fold from limited data can significantly expedite the overall process. This refinement procedure is also expected to be useful when redundant experimental data are not readily available, such as for large multidomain biomolecules and in solid-state NMR structure determination.

Enhanced conformational sampling of nucleic acids by a new Hamiltonian replica exchange molecular dynamics approach.

PubMed

Curuksu, Jeremy; Zacharias, Martin

2009-03-14

Although molecular dynamics (MD) simulations have been applied frequently to study flexible molecules, the sampling of conformational states separated by barriers is limited due to currently possible simulation time scales. Replica-exchange (Rex)MD simulations that allow for exchanges between simulations performed at different temperatures (T-RexMD) can achieve improved conformational sampling. However, in the case of T-RexMD the computational demand grows rapidly with system size. A Hamiltonian RexMD method that specifically enhances coupled dihedral angle transitions has been developed. The method employs added biasing potentials as replica parameters that destabilize available dihedral substates and was applied to study coupled dihedral transitions in nucleic acid molecules. The biasing potentials can be either fixed at the beginning of the simulation or optimized during an equilibration phase. The method was extensively tested and compared to conventional MD simulations and T-RexMD simulations on an adenine dinucleotide system and on a DNA abasic site. The biasing potential RexMD method showed improved sampling of conformational substates compared to conventional MD simulations similar to T-RexMD simulations but at a fraction of the computational demand. It is well suited to study systematically the fine structure and dynamics of large nucleic acids under realistic conditions including explicit solvent and ions and can be easily extended to other types of molecules.

Preferential solvation of Brooker's merocyanine in binary solvent mixtures composed of formamides and hydroxylic solvents.

PubMed

Bevilaqua, Tharly; da Silva, Domingas C; Machado, Vanderlei G

2004-03-01

The ET polarity values of 4-[(1-methyl-4(1H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (Brooker's merocyanine) were collected in mixed-solvent systems comprising a formamide [N,N-dimethylformamide (DMF), N-methylformamide (NMF) or formamide (FA)] and a hydroxylic (water, methanol, ethanol, propan-2-ol or butan-1-ol) solvent. Binary mixtures involving DMF and the other formamides (NMF and FA) as well as NMF and FA were also studied. These data were employed in the investigation of the preferential solvation (PS) of the probe. Each solvent system was analyzed in terms of both solute-solvent and solvent-solvent interactions. These latter interactions were responsible for the synergism observed in many binary mixtures. This synergistic behaviour was observed for DMF-propan-2-ol, DMF-butan-1-ol, FA-methanol, FA-ethanol and for the mixtures of the alcohols with NMF. All data were successfully fitted to a model based on solvent-exchange equilibria, which allowed the separation of the different contributions of the solvent species in the solvation shell of the dye. The results suggest that both hydrogen bonding and solvophobic interactions contribute to the formation of the solvent complexes responsible for the observed synergistic effects in the PS of the dye.

TEMPO addition into pre-irradiated fluoropolymers and living-radical graft polymerization of styrene for preparation of polymer electrolyte membranes

NASA Astrophysics Data System (ADS)

Sawada, Shin-ichi; Suzuki, Akihiro; Terai, Takayuki; Maekawa, Yasunari

2010-04-01

We prepared proton exchange membranes (PEMs) by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated living-radical graft polymerization (LRGP) of styrene into fluoropolymer films and subsequent sulfonation. Poly(vinylidene fluoride) (PVDF) and poly(ethylene- co-tetrafluoroethylene) (ETFE) films were first irradiated and then treated with TEMPO solutions in various solvents. TEMPO addition was confirmed by the test of styrene grafting into TEMPO-treated films at 60 °C, at which the LRGP never proceeds. This test enabled us to differentiate the LRGP from the conventional graft polymerization. In order to gain a deep insight about TEMPO-addition reaction, the TEMPO-penetration behavior into the base polymer films was examined by a permeation experiment and computer simulation. Xylene and dioxane were appropriate solvents for the complete introduction of TEMPO into PVDF and ETFE films, respectively. Then, the LRGP of styrene was performed based on the fully TEMPO-capped films at 125 °C with various solvents. By using an alcoholic solvent, the degree of grafting was enhanced and it reached a maximum of 38%. This grafted film was sulfonated to prepare a PEM showing an ion exchange capacity of 2.2 meq/g and proton conductivity of 1.6×10 -1 S/cm.

Propensity of bond exchange as a window into the mechanical properties of metallic glasses

NASA Astrophysics Data System (ADS)

Jiao, W.; Wang, X. L.; Lan, S.; Pan, S. P.; Lu, Z. P.

2015-02-01

We investigated the mechanical properties of Zr-Cu-Al bulk metallic glasses, by compression experiment and molecular dynamics simulations. From the simulation, we found that the large, solvent atom, Zr, has high propensity of bond exchange compared to those of the smaller solute atoms. The difference in bond exchange is consistent with the observed disparity in mechanical behaviors: Zr-rich metallic glass exhibits low elastic modulus and large plastic strain. X-ray photoelectron spectroscopy measurements suggest that the increased propensity in bond exchange is related to the softening of Zr bonds with increasing Zr content.

Membrane-Based Technologies in the Pharmaceutical Industry and Continuous Production of Polymer-Coated Crystals/Particles.

PubMed

Chen, Dengyue; Sirkar, Kamalesh K; Jin, Chi; Singh, Dhananjay; Pfeffer, Robert

2017-01-01

Membrane technologies are of increasing importance in a variety of separation and purification applications involving liquid phases and gaseous mixtures. Although the most widely used applications at this time are in water treatment including desalination, there are many applications in chemical, food, healthcare, paper and petrochemical industries. This brief review is concerned with existing and emerging applications of various membrane technologies in the pharmaceutical and biopharmaceutical industry. The goal of this review article is to identify important membrane processes and techniques which are being used or proposed to be used in the pharmaceutical and biopharmaceutical operations. How novel membrane processes can be useful for delivery of crystalline/particulate drugs is also of interest. Membrane separation technologies are extensively used in downstream processes for bio-pharmaceutical separation and purification operations via microfiltration, ultrafiltration and diafiltration. Also the new technique of membrane chromatography allows efficient purification of monoclonal antibodies. Membrane filtration techniques of reverse osmosis and nanofiltration are being combined with bioreactors and advanced oxidation processes to treat wastewaters from pharmaceutical plants. Nanofiltration with organic solvent-stable membranes can implement solvent exchange and catalyst recovery during organic solvent-based drug synthesis of pharmaceutical compounds/intermediates. Membranes in the form of hollow fibers can be conveniently used to implement crystallization of pharmaceutical compounds. The novel crystallization methods of solid hollow fiber cooling crystallizer (SHFCC) and porous hollow fiber anti-solvent crystallization (PHFAC) are being developed to provide efficient methods for continuous production of polymer-coated drug crystals in the area of drug delivery. This brief review provides a general introduction to various applications of membrane technologies in the pharmaceutical/biopharmaceutical industry with special emphasis on novel membrane techniques for pharmaceutical applications. The method of coating a drug particle with a polymer using the SHFCC method is stable and ready for scale-up for operation over an extended period. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Modeling the chelation of As(III) in lewisite by dithiols using density functional theory and solvent-assisted proton exchange.

PubMed

Harper, Lenora K; Bayse, Craig A

2015-12-01

Dithiols such as British anti-lewisite (BAL, rac-2,3-dimercaptopropanol) are an important class of antidotes for the blister agent lewisite (trans-2-chlorovinyldichloroarsine) and, more generally, are chelating agents for arsenic and other toxic metals. The reaction of the vicinal thiols of BAL with lewisite through the chelation of the As(III) center has been modeled using density functional theory (DFT) and solvent-assisted proton exchange (SAPE), a microsolvation method that uses a network of water molecules to mimic the role of bulk solvent in models of aqueous phase chemical reactions. The small activation barriers for the stepwise SN2-type nucleophilic attack of BAL on lewisite (0.7-4.9kcal/mol) are consistent with the favorable leaving group properties of the chloride and the affinity of As(III) for soft sulfur nucleophiles. Small, but insignificant, differences in activation barriers were found for the initial attack of the primary versus secondary thiol of BAL and the R vs S enantiomer. An examination of the relative stability of various dithiol-lewisite complexes shows that ethanedithiols like BAL form the most favorable chelation complexes because the angles formed in five-membered ring are most consistent with the hybridization of As(III). More obtuse S-As-S angles are required for larger chelate rings, but internal As⋯N or As⋯O interactions can enhance the stability of moderate-sized rings. The low barriers for lewisite detoxification by BAL and the greater stability of the chelation complexes of small dithiols are consistent with the rapid reversal of toxicity demonstrated in previously reported animal models. Copyright © 2015 Elsevier Inc. All rights reserved.

Microfluidic chemical reaction circuits

DOEpatents

Lee, Chung-cheng [Irvine, CA; Sui, Guodong [Los Angeles, CA; Elizarov, Arkadij [Valley Village, CA; Kolb, Hartmuth C [Playa del Rey, CA; Huang, Jiang [San Jose, CA; Heath, James R [South Pasadena, CA; Phelps, Michael E [Los Angeles, CA; Quake, Stephen R [Stanford, CA; Tseng, Hsian-rong [Los Angeles, CA; Wyatt, Paul [Tipperary, IE; Daridon, Antoine [Mont-Sur-Rolle, CH

2012-06-26

New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

Mass spectrometry-based carboxyl footprinting of proteins: Method evaluation

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

Zhang, Hao; Wen, Jianzhong; Huang, Richard Y-C.

2012-02-01

Protein structure determines function in biology, and a variety of approaches have been employed to obtain structural information about proteins. Mass spectrometry-based protein footprinting is one fast-growing approach. One labeling-based footprinting approach is the use of a water-soluble carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) and glycine ethyl ester (GEE) to modify solvent-accessible carboxyl groups on glutamate (E) and aspartate (D). This paper describes method development of carboxyl-group modification in protein footprinting. The modification protocol was evaluated by using the protein calmodulin as a model. Because carboxyl-group modification is a slow reaction relative to protein folding and unfolding, there is an issue that modificationsmore » at certain sites may induce protein unfolding and lead to additional modification at sites that are not solvent-accessible in the wild-type protein. We investigated this possibility by using hydrogen deuterium amide exchange (H/DX). The study demonstrated that application of carboxyl group modification in probing conformational changes in calmodulin induced by Ca{sup 2+} binding provides useful information that is not compromised by modification-induced protein unfolding.« less

Terminal base pairs of oligodeoxynucleotides: imino proton exchange and fraying.

PubMed

Nonin, S; Leroy, J L; Guéron, M

1995-08-22

We have estimated the dissociation constant of the terminal base pairs of the B-DNA duplexes formed by 5'-d(CGCGATCGCG) and 5'-d(TAGCGCTA) by two methods, one based on the change in imino proton chemical shift with temperature and the other on the apparent pK shift of the imino proton, as monitored by the change in chemical shift of aromatic protons. These methods do not rely on imino proton exchange, whose rate was also measured. (1) The effect of ammonia on the imino proton exchange rate of the terminal pair of the 5'-d(CGCGATCGCG) duplex is 67 times less than on the isolated nucleoside. This provides an upper limit on the exchange rate from the closed pair. In fact, the effect is just as predicted from the dissociation constant, assuming that there is no exchange at all from the closed pair and that, as has been argued previously, external catalysts act on the open state as they do on the isolated nucleoside. The inhibition of catalyzed proton exchange in the closed pair, despite exposure of one face of the pair to solvent, is a new feature of the exchange process. It will allow determination of the dissociation constant of terminal pairs from the exchange rate. (2) Intrinsic catalysis of proton exchange is less efficient for the terminal pair than for an internal one. A possible explanation is that proton transfer across the water bridge responsible for intrinsic catalysis is slower, as expected if the open-state separation of the bases is larger in a terminal pair. This observation may lead to a direct method for the study of fraying. (3) At 0 degrees C, the dissociation constant of the second pair of the 5'-d(CGCGATCGCG) duplex is close to the square of the constant for the terminal pair, as predicted from a simple model of fraying. The enthalpy and entropy of opening of the terminal pairs may be compared with those of nearest neighbor interactions derived from calorimetry [Breslauer, K. J., et al. (1986) Proc. Natl. Acad. Sci. U.S.A. 83, 3746-3750].

Free energy landscape of protein folding in water: explicit vs. implicit solvent.

PubMed

Zhou, Ruhong

2003-11-01

The Generalized Born (GB) continuum solvent model is arguably the most widely used implicit solvent model in protein folding and protein structure prediction simulations; however, it still remains an open question on how well the model behaves in these large-scale simulations. The current study uses the beta-hairpin from C-terminus of protein G as an example to explore the folding free energy landscape with various GB models, and the results are compared to the explicit solvent simulations and experiments. All free energy landscapes are obtained from extensive conformation space sampling with a highly parallel replica exchange method. Because solvation model parameters are strongly coupled with force fields, five different force field/solvation model combinations are examined and compared in this study, namely the explicit solvent model: OPLSAA/SPC model, and the implicit solvent models: OPLSAA/SGB (Surface GB), AMBER94/GBSA (GB with Solvent Accessible Surface Area), AMBER96/GBSA, and AMBER99/GBSA. Surprisingly, we find that the free energy landscapes from implicit solvent models are quite different from that of the explicit solvent model. Except for AMBER96/GBSA, all other implicit solvent models find the lowest free energy state not the native state. All implicit solvent models show erroneous salt-bridge effects between charged residues, particularly in OPLSAA/SGB model, where the overly strong salt-bridge effect results in an overweighting of a non-native structure with one hydrophobic residue F52 expelled from the hydrophobic core in order to make better salt bridges. On the other hand, both AMBER94/GBSA and AMBER99/GBSA models turn the beta-hairpin in to an alpha-helix, and the alpha-helical content is much higher than the previously reported alpha-helices in an explicit solvent simulation with AMBER94 (AMBER94/TIP3P). Only AMBER96/GBSA shows a reasonable free energy landscape with the lowest free energy structure the native one despite an erroneous salt-bridge between D47 and K50. Detailed results on free energy contour maps, lowest free energy structures, distribution of native contacts, alpha-helical content during the folding process, NOE comparison with NMR, and temperature dependences are reported and discussed for all five models. Copyright 2003 Wiley-Liss, Inc.

NIR photocleavage of the Si-C bond in axial Si-phthalocyanines.

PubMed

Doane, Tennyson; Cheng, Yu; Sodhi, Nipun; Burda, Clemens

2014-11-13

The use of light-triggered photolysis provides a powerful tool for unique syntheses and for applications that require remote operation such as drug delivery or molecular switches. Here, we describe the photochemistry of a recently developed alkylsilicon phthalocyanine Pc 227, which undergoes an exchange of the alkyl ligand for a ligand derived from the solvent when the axial Si-C bond is photolyzed in a solvent with low-energy visible light. In this work with methanol as the solvent, we investigate the formation of the methoxy analogue of the therapeutic drug Pc 4, (termed Pc 233) upon irradiation. Using steady-state spectroscopy and characterization of the photoproducts, the competing pathways between direct ligand exchange on the central silicon atom and delocalization of the radical produced by homolysis on the phthalocyanine ring is observed. The delocalized radical intermediate is quite long-lived. At long times this intermediate decomposes without significant formation of Pc 233. The results of this investigation provide insights into recent work utilizing Pc 227 for drug delivery applications and for future work on the use of phthalocyanines as long-wavelength phototriggers.

Alternative stripper configurations for CO{sub 2} capture by aqueous amines

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

Oyenekan, B.A.; Rochelle, G.T.

2007-12-15

Aqueous absorption/stripping is a promising technology for the capture of CO{sub 2} from existing or new coal-fired power plants. Four new stripper configurations (matrix, internal exchange, flashing feed, and multipressure with split feed) have been evaluated with seven model solvents that approximate the thermodynamic and rate properties of 7m (30 wt %) monoethanolamine (MEA), potassium carbonate promoted bypiperazine (PZ), promoted MEA, methyldiethanolamine (MDEA) promoted by PZ, and hindered amines. The results show that solvents with high heats of absorption (MEA, MEA/PZ) favor operation at normal pressure. The relative performance of the alternative configurations is matrix > internal exchange > multipressuremore » with split feed > flashing feed. MEA/PZ and MDEA/PZ are attractive alternatives to 7m MEA. The best solvent and process configuration, matrix with MDEA/PZ, offers 22 and 15% energy savings over the baseline and improved baseline, respectively,with stripping and compression to 10 MPa. The energy requirement for stripping and compression to 10 MPa is about 20% of the power output from a 500 MW power plant with 90% CO{sub 2} removal.« less

Effects of Conjugation in Length and Dimension on Spectroscopic Properties of Fluorene-Based Chromophores from Experiment and Theory (Preprint)

DTIC Science & Technology

2006-07-01

catalyzed iodo-bromo exchange reaction and (b) condensation of the resulting iodo-aldehyde precursor with 2-aminothiophenol in dimethylsulfoxide ( DMSO ). The...when compared to results from measurements carried out in a nonpolar solvent , which were available for some molecules. The computed oscillator... solvent , which were available for some molecules. The computed oscillator strengths may resolve discordant experimental values in some cases, for example

Synthesis, characterization and analytical application of hybrid; acrylamide zirconium (IV) arsenate a cation exchanger, effect of dielectric constant on distribution coefficient of metal ions.

PubMed

Nabi, Syed A; Shalla, Aabid H

2009-04-30

A new hybrid inorganic-organic cation exchanger acrylamide zirconium (IV) arsenate has been synthesized, characterized and its analytical application explored. The effect of experimental parameters such as mixing ratio of reagents, temperature, and pH on the properties of material has been studied. FTIR, TGA, X-ray, UV-vis spectrophotometry, SEM and elemental analysis were used to determine the physiochemical properties of this hybrid ion exchanger. The material behaves as a monofunctional acid with ion-exchange capacity of 1.65 meq/g for Na(+) ions. The chemical stability data reveals that the exchanger is quite stable in mineral acids, bases and fairly stable in organic solvents, while as thermal analysis shows that the material retain 84% of its ion-exchange capacity up to 600 degrees C. Adsorption behavior of metal ions in solvents with increasing dielectric constant has also been explored. The sorption studies reveal that the material is selective for Pb(2+) ions. The analytical utility of the material has been explored by achieving some binary separations of metal ions on its column. Pb(2+) has been selectively removed from synthetic mixtures containing Mg(2+), Ca(2+), Sr(2+), Zn(2+) and Cu(2+), Al(3+), Ni(2+), Fe(3+). In order to demonstrate practical utility of the material quantitative separation of the Cu(2+) and Zn(2+) in brass sample has been achieved on its columns.

Evaluation of advanced silica packings for the separation of biopolymers by high-performance liquid chromatography. VI. Design, chromatographic performance and application of non-porous silica-based anion exchangers.

PubMed

Jilge, G; Unger, K K; Esser, U; Schäfer, H J; Rathgeber, G; Müller, W

1989-08-04

The linear solvent strength model of Snyder was applied to describe fast protein separations on 2.1-micron non-porous, silica-based strong anion exchangers. It was demonstrated on short columns packed with these anion exchangers that (i) a substantially higher resolution of proteins and nucleotides was obtained at gradient times of less than 5 min than on porous anion exchangers; (ii) the low external surface area of the non-porous anion exchanger is not a critical parameter in analytical separations and (iii) microgram-amounts of enzymes of high purity and full biological activity were isolated.

Parallel Tempering of Dark Matter from the Ebola Virus Proteome: Comparison of CHARMM36m and CHARMM22 Force Fields with Implicit Solvent.

PubMed

Olson, Mark A

2018-01-22

Intrinsically disordered proteins are characterized by their large manifold of thermally accessible conformations and their related statistical weights, making them an interesting target of simulation studies. To assess the development of a computational framework for modeling this distinct class of proteins, this work examines temperature-based replica-exchange simulations to generate a conformational ensemble of a 28-residue peptide from the Ebola virus protein VP35. Starting from a prefolded helix-β-turn-helix topology observed in a crystallographic assembly, the simulation strategy tested is the recently refined CHARMM36m force field combined with a generalized Born solvent model. A comparison of two replica-exchange methods is provided, where one is a traditional approach with a fixed set of temperatures and the other is an adaptive scheme in which the thermal windows are allowed to move in temperature space. The assessment is further extended to include a comparison with equivalent CHARMM22 simulation data sets. The analysis finds CHARMM36m to shift the minimum in the potential of mean force (PMF) to a lower fractional helicity compared with CHARMM22, while the latter showed greater conformational plasticity along the helix-forming reaction coordinate. Among the simulation models, only the adaptive tempering method with CHARMM36m found an ensemble of conformational heterogeneity consisting of transitions between α-helix-β-hairpin folds and unstructured states that produced a PMF of fractional fold propensity in qualitative agreement with circular dichroism experiments reporting a disordered peptide.

Porous polymer media

DOEpatents

Shepodd, Timothy J.

2002-01-01

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

Surface Nanobubbles in Nonaqueous Media: Looking for Nanobubbles in DMSO, Formamide, Propylene Carbonate, Ethylammonium Nitrate, and Propylammonium Nitrate.

PubMed

An, Hongjie; Liu, Guangming; Atkin, Rob; Craig, Vincent S J

2015-07-28

Surface nanobubbles produced by supersaturation during the exchange of ethanol for water are routinely observed on hydrophobic surfaces, are stable for days, and have contact angles that are very much greater than observed macroscopically. Here, we test the hypothesis that nanobubbles can also be observed in nonaqueous solvents in order to ascertain if their anomalous lifetimes and contact angles are related to properties of the solvent. Nanobubbles were seen in the protic solvents formamide, ethylammonium nitrate, and propylammonium nitrate, but not in propylene carbonate or dimethyl sulfoxide. Solvents in which nanobubbles were observed exhibit a three-dimensional hydrogen-bonding network. Like in aqueous systems, the nanobubbles were stable for days and exhibited high contact angles (∼165°).

Semiautomated solid-phase extraction manifold with a solvent-level sensor.

PubMed

Orlando, R M; Rath, S; Rohwedder, J J R

2013-11-15

A semiautomated solid-phase extraction manifold for multiple extractions is presented. The manifold utilizes commercial solid-phase syringe cartridges and automatically introduces and elutes all the solvents during the extraction, reducing the typical workload and stress of the analyst. The manifold consists of a peristaltic pump with solenoid valves in a flow circuit that contains transmissive photomicrosensors. The photomicrosensors were used to control the solvent dispenser and the solvent level inside the cartridge. As solvent-level sensors, the photomicrosensors determined the exact time the solvent reached the top frit to avoid sorbent drying and accurately perform the solvent exchange. The repeatability of the manifold to introduce a particular volume of solvent into the cartridges was measured, and the precisions were between 0.05 and 2.89% (RSD). To evaluate the manifold, the amount of two fluoroquinolones in a fortified blank milk sample was determined. The results of the intra- and inter-day precision of multiple extractions from the fortified milk samples resulted in precisions better than 9.0% (RSD) and confirmed that the arrangement of the semiautomated manifold could adequately be used in solid-phase extraction with commercial cartridges. Copyright © 2013 Elsevier B.V. All rights reserved.

Two-Dimensional Self-Assembly and Chemical Synthesis of Charged Gold Nanoparticles in Non-Polar Solvents

NASA Astrophysics Data System (ADS)

Martin, Matthew Nichols

Gold nanoparticles between 1 and 10 nm in diameter exhibit size-dependent electronic and optical properties that cannot be explained by molecular science and which deviate significantly from their bulk counterparts. For example, the melting temperature of gold nanoparticles less than 5 nm in diameter is around 300 °C [1], whereas bulk gold melts at over 1000 °C [2]. Gold nanoparticles require precise control over particle diameter in order to exploit and tailor their unique properties; however, tuning the size reproducibly and predictably has proved to be a challenge. One of the most difficult obstacles to overcome is nanoparticle aggregation, since nanoparticles flocculate at room temperature quite readily. In 1994, Brust et al. solved the aggregation problem by introducing monolayer protection coatings on gold nanoparticles, in which organic ligand molecules are attached to the nanoparticle surface and create a physical barrier between the gold core and solvent. This was a definitive solution to size stability, since nanoparticles never aggregate, however the synthesis method does not generate monodisperse nanoparticles and has poor size-tuning capabilities. We developed a synthesis method for gold nanoparticles that improves greatly upon the Brust method. Starting from scratch, we discovered a "sweet zone" for aqueous gold nanoparticles, revealing how to make "naked" (stabilizer-free) gold nanoparticles which are continuously and precisely controlled between 3.2 and 5.2 nm in diameter, both reproducibly and predictably. Naked nanoparticles are then coated with organic 1-dodecanethiol ligand molecules, and transferred to hexane. Since all reaction byproducts remain in the water-phase, no postsynthesis cleaning or size-filtering is necessary, reducing the total synthesis time from ~24 hours in the Brust method, to less than 10 minutes. Surprisingly, our nanoparticles are highly negatively charged in nonpolar solvents. This unexpectedly caused nanoparticles to be unstable in toluene but stable in hexane. Consequently, nanoparticles float to the air-toluene interface, and after evaporation of toluene, form large 2D monolayer films of nanoparticle that are uniform at nanometer, micrometer, and millimeter length scales. This facile 2D self-assembly method also displays extremely size-dependent features in the 3.2 -- 5.2 nm range. Additionally, we managed to expand our synthesis method to include smaller gold nanoparticles. Since small gold clusters less than 2 nm in diameter are exponentially more efficient than other conventional catalysts, we labored to synthesize nanoclusters with diameters less than 2 nm, and fortunately, reduced the synthesis time to 2 minutes. With complete size control of gold nanoparticles between 1 and 5 nm, we have developed a truly novel synthesis method that forms a strong basis for many interesting studies. We have also discovered a novel method for place exchange reactions of organic molecular coatings. Ligand exchange of water-soluble thiols for alkylamines was performed at room temperature and occurred in less than 10 seconds, and allowed for the phase-transfer of nanoparticles from nonpolar solvents back to water. This method is extremely useful for the biological nanoparticle community as they are already using nanoparticles for drug delivery, DNA sensing, and molecular recognition.

NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

Rapid Flow-Based Peptide Synthesis

PubMed Central

Simon, Mark D.; Heider, Patrick L.; Adamo, Andrea; Vinogradov, Alexander A.; Mong, Surin K.; Li, Xiyuan; Berger, Tatiana; Policarpo, Rocco L.; Zhang, Chi; Zou, Yekui; Liao, Xiaoli; Spokoyny, Alexander M.; Jensen, Klavs F.

2014-01-01

A flow-based solid phase peptide synthesis methodology that enables the incorporation of an amino acid residue every 1.8 minutes under automatic control, or every three minutes under manual control, is described. This is accomplished by passing a stream of reagent through a heat exchanger, into a low volume, low backpressure reaction vessel, and through a UV detector. These features enable the continuous delivery of heated solvents and reagents to the solid support at high flow rate, maintaining a maximal concentration of reagents in the reaction vessel, quickly exchanging reagents, and eliminating the need to rapidly heat reagents after they have been added to the vessel. The UV detector enables continuous monitoring of the process. To demonstrate the broad applicability and reliability of this method, it was employed in the total synthesis of a small protein, as well as dozens of peptides. The quality of the material obtained with this method is comparable to traditional batch methods, and, in all cases, the desired material was readily purifiable via RP-HPLC. The application of this method to the synthesis of the 113 residue B. amyloliquefaciens RNase and the 130 residue pE59 DARPin is described in the accompanying manuscript. PMID:24616230

Impact of D2O/H2O Solvent Exchange on the Emission of HgTe and CdTe Quantum Dots: Polaron and Energy Transfer Effects.

PubMed

Wen, Qiannan; Kershaw, Stephen V; Kalytchuk, Sergii; Zhovtiuk, Olga; Reckmeier, Claas; Vasilevskiy, Mikhail I; Rogach, Andrey L

2016-04-26

We have studied light emission kinetics and analyzed carrier recombination channels in HgTe quantum dots that were initially grown in H2O. When the solvent is replaced by D2O, the nonradiative recombination rate changes highlight the role of the vibrational degrees of freedom in the medium surrounding the dots, including both solvent and ligands. The contributing energy loss mechanisms have been evaluated by developing quantitative models for the nonradiative recombination via (i) polaron states formed by strong coupling of ligand vibration modes to a surface trap state (nonresonant channel) and (ii) resonant energy transfer to vibration modes in the solvent. We conclude that channel (i) is more important than (ii) for HgTe dots in either solution. When some of these modes are removed from the relevant spectral range by the H2O to D2O replacement, the polaron effect becomes weaker and the nonradiative lifetime increases. Comparisons with CdTe quantum dots (QDs) served as a reference where the resonant energy loss (ii) a priori was not a factor, also confirmed by our experiments. The solvent exchange (H2O to D2O), however, is found to slightly increase the overall quantum yield of CdTe samples, probably by increasing the fraction of bright dots in the ensemble. The fundamental study reported here can serve as the foundation for the design and optimization principles of narrow bandgap quantum dots aimed at applications in long wavelength colloidal materials for infrared light emitting diodes and photodetectors.

Heterofunctionality interaction with donor solvent coal liquefaction. Final progress report, August 1982-April 1984

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

Cronauer, D.C.

1984-05-01

This project was undertaken to understand the role of the coal liquefaction solvent through a study of the interaction between the hydrogen donor solvent characteristics and the heterofunctionality of the solvent. Specifically, hydroxyl- and nitrogen-containing solvents were studied and characterized. A series of coal liquefaction experiments were carried out at 450/sup 0/C in a continuous feed stirred-tank reactor (CSTR) to observe the effect of adding phenolics to anthracene oil (AO) and SRC-II recycle solvents. The addition of phenol to AO at a ratio of 5/65 resulted in a nominal increase in coal conversion to THF solubles, but the amount ofmore » asphaltenes more than doubled resulting in a sizable net loss of solvent. The addition of m-cresol to both AO and SRC-II solvents had a positive effect on coal conversion to both THF and pentane solubles (oils). The partial removal of an OH-concentrate from SRC-II solvent was carried out using Amberlyst IRA-904 ion exchange resin. The resin-treated oil was only marginally better than raw SRC-II recycle solvent for coal liquefaction. Hydroaromatics having nitrogen functionality should be good solvents for coal liquefaction considering their effective solvent power, ability to penetrate and swell coal, and their ability to readily transfer hydrogen, particularly in the presence of oxygen functionality. However, these benefits are overshadowed by the strong tendency of the nitrogen-containing species to adduct with themselves and coal-derived materials.« less

Vibrational energy transfer between carbon nanotubes and liquid water: a molecular dynamics study.

PubMed

Nelson, Tammie R; Chaban, Vitaly V; Kalugin, Oleg N; Prezhdo, Oleg V

2010-04-08

The rates and magnitudes of vibrational energy transfer between single-wall carbon nanotubes (CNTs) and water are investigated by classical molecular dynamics. The interactions between the CNT and solvent confined inside of the tube, the CNT and solvent surrounding the tube, as well as the solvent inside and outside of the tube are considered for the (11,11), (15,15), and (19,19) armchair CNTs. The vibrational energy transfer exhibits two time scales, subpicosecond and picosecond, of roughly equal importance. Solvent molecules confined within CNTs are more strongly coupled to the tubes than the outside molecules. The energy exchange is facilitated by slow collective motions, including CNT radial breathing modes (RBM). The transfer rate between CNTs and the inside solvent shows strong dependence on the CNT diameter. In smaller tubes, the transfer is faster and the solvent coupling to RBMs is stronger. The magnitude of the CNT-outside solvent interaction scales with the CNT surface area, while that of the CNT-inside solvent exhibits scaling that is intermediate between the CNT volume and surface. The Coulomb interaction between the solvent molecules inside and outside of the CNTs is much weaker than the CNT-solvent interactions. The results indicate that the excitation energy supplied to CNTs in chemical and biological applications is rapidly deposited to the active molecular agents and should remain localized sufficiently long in order to perform the desired function.

Coarse kMC-based replica exchange algorithms for the accelerated simulation of protein folding in explicit solvent.

PubMed

Peter, Emanuel K; Shea, Joan-Emma; Pivkin, Igor V

2016-05-14

In this paper, we present a coarse replica exchange molecular dynamics (REMD) approach, based on kinetic Monte Carlo (kMC). The new development significantly can reduce the amount of replicas and the computational cost needed to enhance sampling in protein simulations. We introduce 2 different methods which primarily differ in the exchange scheme between the parallel ensembles. We apply this approach on folding of 2 different β-stranded peptides: the C-terminal β-hairpin fragment of GB1 and TrpZip4. Additionally, we use the new simulation technique to study the folding of TrpCage, a small fast folding α-helical peptide. Subsequently, we apply the new methodology on conformation changes in signaling of the light-oxygen voltage (LOV) sensitive domain from Avena sativa (AsLOV2). Our results agree well with data reported in the literature. In simulations of dialanine, we compare the statistical sampling of the 2 techniques with conventional REMD and analyze their performance. The new techniques can reduce the computational cost of REMD significantly and can be used in enhanced sampling simulations of biomolecules.

Gelation-driven selection in dynamic covalent C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C/CN exchange.

PubMed

Liang, Chunshuang; Kulchat, Sirinan; Jiang, Shimei; Lehn, Jean-Marie

2017-10-01

Knoevenagel barbiturate derivatives bearing long alkyl chains were proven to form organogels in suitable solvents based on supramolecular interactions. Their reaction with imines allows for component exchange through CC/CN recombination. The effect of various parameters (solvents, chain length, and temperature) on the CC/CN exchange reaction has been studied. Mixing Knoevenagel compound K and imine I-16 in a 1 : 1 ratio generated a constitutional dynamic library containing the four constituents K , I-16 , K'-16 , and I' . The reversible exchange reaction was monitored by 1 H-NMR, showing marked changes in the fractions of the four constituents on sol-gel interconversion as a function of temperature. The library composition changed from statistical distribution of the four constituents in the sol state to selective amplification of the gel forming K'-16 constituent together with that of its agonist I' . The process amounts to self-organization driven component selection in a constitutional dynamic organogel system undergoing gelation. This process displays up-regulation of the gel-forming constituent by component redistribution through reversible covalent connections.

Through-plane conductivities of membranes for nonaqueous redox flow batteries

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

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Through-plane conductivities of membranes for nonaqueous redox flow batteries

DOE PAGES

Anderson, Travis Mark; Small, Leo J.; Pratt, III, Harry D.; ...

2015-08-13

In this study, nonaqueous redox flow batteries (RFB) leverage nonaqueous solvents to enable higher operating voltages compared to their aqueous counterparts. Most commercial components for flow batteries, however, are designed for aqueous use. One critical component, the ion-selective membrane, provides ionic conductance between electrodes while preventing crossover of electroactive species. Here we evaluate the area-specific conductances and through-plane conductivities of commercially available microporous separators (Celgard 2400, 2500) and anion exchange membranes (Neosepta AFX, Neosepta AHA, Fumasep FAP-450, Fumasep FAP-PK) soaked in acetonitrile, propylene carbonate, or two imidazolium-based ionic liquids. Fumasep membranes combined with acetonitrile-based electrolyte solutions provided the highest conductancemore » values and conductivities by far. When tested in ionic liquids, all anion exchange membranes displayed conductivities greater than those of the Celgard microporous separators, though the separators’ decreased thickness-enabled conductances on par with the most conductive anion exchange membranes. Ionic conductivity is not the only consideration when choosing an anion exchange membrane; testing of FAP-450 and FAP-PK membranes in a nonaqueous RFB demonstrated that the increased mechanical stability of PEEK-supported FAP-PK minimized swelling, in turn decreasing solvent mediated crossover and enabling greater electrochemical yields (40% vs. 4%) and Coulombic efficiencies (94% vs. 90%) compared to the unsupported, higher conductance FAP-450.« less

Comparison of extraction methods for quantifying vitamin E from animal tissues.

PubMed

Xu, Zhimin

2008-12-01

Four extraction methods: (1) solvent (SOL), (2) ultrasound assisted solvent (UA), (3) saponification and solvent (SP), and (4) saponification and ultrasound assisted solvent (SP-UA), were used in sample preparation for quantifying vitamin E (tocopherols) in chicken liver and plasma samples. The extraction yields of SOL, UA, SP, and SP-UA methods obtained by adding delta-tocopherol as internal reference were 95%, 104%, 65%, and 62% for liver and 98%, 103%, 97%, and 94% for plasma, respectively. The methods with saponification significantly affected the stabilities of tocopherols in liver samples. The measured values of alpha- and gamma-tocopherols using the solvent only extraction (SOL) method were much lower than that using any of the other extraction methods. This indicated that less of the tocopherols in those samples were in a form that could be extracted directly by solvent. The measured value of alpha-tocopherol in the liver sample using the ultrasound assisted solvent (UA) method was 1.5-2.5 times of that obtained from the saponification and solvent (SP) method. The differences in measured values of tocopherols in the plasma samples by using the two methods were not significant. However, the measured value of the saponification and ultrasound assisted solvent (SP-UA) method was lower than either the saponification and solvent (SP) or the ultrasound assisted solvent (UA) method. Also, the reproducibility of the ultrasound assisted solvent (UA) method was greater than any of the saponification methods. Compared with the traditional saponification method, the ultrasound assisted solvent method could effectively extract tocopherols from sample matrix without any chemical degradation reactions, especially for complex animal tissue such as liver.

Dispersive micro solid phase extraction (DMSPE) using polymer anion exchange (PAX) as the sorbent followed by UPLC-MS/MS for the rapid determination of four bisphenols in commercial edible oils.

PubMed

Xian, Yanping; Wu, Yuluan; Dong, Hao; Guo, Xindong; Wang, Bin; Wang, Li

2017-09-29

The present work presents a novel and rapid analytical method for the simultaneous analysis of bisphenol A (BPA), bisphenol B (BPB), bisphenol F (BPF) and bisphenol S (BPS) in edible oil based on dispersive micro solid phase extraction (DMSPE) for the first time followed by isotope dilution-ultra high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). The edible oil sample was dispersed by n-hexane and extracted with ammoniated methanol-water solution. Then the target analytes were dispersedly absorbed using the polymer anion exchange (PAX) as the sorbent and eluted by acidic methanol. After that, four bisphenols were separated on a C18 column by gradient elution with methanol and 0.05% ammonium hydroxide in water as mobile phase, detected by MS/MS under multiple reactions monitoring (MRM) mode and quantified by internal standard method. The PAX amounts, adsorption time, concentrations of formic acid in the elution solvent and volume of elution solvent for the DMSPE technique were optimized. The limit of detection and quantitation (LOD and LOQ), matrix effect, recovery and precision of the developed method were investigated. Results indicated that BPS and the rest three bisphenols displayed excellent linearity in the concentration ranges of 0.1-50μg/L and 0.5-250μg/L, respectively, with correlation coefficients (R 2 ) all larger than 0.998. Achieved MLODs (S/N=3) varied between 0.1-0.4μg/kg for all bisphenols. The mean recoveries at three spiked levels in edible oil were in the range of 87.3-108%. Intra-day precision (n=6) and inter-day precision (n=5) were <9% and <11%, respectively. This method is of rapid-and-simple pretreatment, accurate and sensitive, and suitable for the simultaneous determination of bisphenols in edible oil. Copyright © 2017. Published by Elsevier B.V.

Process for producing an activated carbon adsorbent with integral heat transfer apparatus

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor); Yavrouian, Andre H. (Inventor)

1996-01-01

A process for producing an integral adsorbent-heat exchanger apparatus useful in ammonia refrigerant heat pump systems. In one embodiment, the process wets an activated carbon particles-solvent mixture with a binder-solvent mixture, presses the binder wetted activated carbon mixture on a metal tube surface and thereafter pyrolyzes the mixture to form a bonded activated carbon matrix adjoined to the tube surface. The integral apparatus can be easily and inexpensively produced by the process in large quantities.

Multiscale simulation of molecular processes in cellular environments.

PubMed

Chiricotto, Mara; Sterpone, Fabio; Derreumaux, Philippe; Melchionna, Simone

2016-11-13

We describe the recent advances in studying biological systems via multiscale simulations. Our scheme is based on a coarse-grained representation of the macromolecules and a mesoscopic description of the solvent. The dual technique handles particles, the aqueous solvent and their mutual exchange of forces resulting in a stable and accurate methodology allowing biosystems of unprecedented size to be simulated.This article is part of the themed issue 'Multiscale modelling at the physics-chemistry-biology interface'. © 2016 The Author(s).

The Role of Solvent Reorganization Dynamics in Electron-Transfer Processes. Theory-Experiment Comparisons for Electrochemical and Homogeneous Electron Exchange Involving Metallocene Redox Couples

DTIC Science & Technology

1985-08-01

Kodak) by crystallization from acetone; it was recrystallized twice from ethanol and dried in a vacuum oven. Tetraethylamonium perchlorate (TEAP) (G...the electrooxidation of in(Cp’) 2 , which yielded significantly smaller reverse (cathodic) currents in the most strongly coordinating solvents (DMX...DM50) at slower scan rates (< 0.5 V sec-1). Nevertheless, satisfactory a.c. polarograms were obtained for each of these system=. 5 4 Temperature

Characterizing Fullerene Nanoparticles in Aqueous Suspensions

EPA Science Inventory

Studies have indicated that fullerenes can form stable colloidal suspensions in water when introduced to the aqueous phase through solvent exchange, sonication, or extended mixing. The colloidal suspensions created using these techniques have effective aqueous phase concentratio...

Electronic Excitations in Solution: The Interplay between State Specific Approaches and a Time-Dependent Density Functional Theory Description.

PubMed

Guido, Ciro A; Jacquemin, Denis; Adamo, Carlo; Mennucci, Benedetta

2015-12-08

We critically analyze the performances of continuum solvation models when coupled to time-dependent density functional theory (TD-DFT) to predict solvent effects on both absorption and emission energies of chromophores in solution. Different polarization schemes of the polarizable continuum model (PCM), such as linear response (LR) and three different state specific (SS) approaches, are considered and compared. We show the necessity of introducing a SS model in cases where large electron density rearrangements are involved in the excitations, such as charge-transfer transitions in both twisted and quadrupolar compounds, and underline the very delicate interplay between the selected polarization method and the chosen exchange-correlation functional. This interplay originates in the different descriptions of the transition and ground/excited state multipolar moments by the different functionals. As a result, the choice of both the DFT functional and the solvent polarization scheme has to be consistent with the nature of the studied electronic excitation.

Clean amine solvents economically and online

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

Price, J.; Burns, D.

1995-08-01

Using electrodialysis technology to clean amine solvents is economically competitive with traditional change-out or ``bleed and feed`` methods, even for small systems, because a unit shutdown is not necessary to perform the process. Electrodialysis also has advantages over other online cleanup processes like ion exchange and vacuum reclamation. Off gases and olefinic and saturate liquefied petroleum gas (LPG) streams generated during operation of fluid catalytic crackers (FCC), cokers and other refinery processing equipment must be treated to remove undesirable components like hydrogen sulfide and carbon dioxide before they can be sold or used in downstream processes. At an Arkansas City,more » Kansas, refinery, a classic amine-based chemical absorbent system is used for this purpose. It comprises two absorbing contacts for gas and two for liquids. The system is charged with an N-methyldiethanolamine (MDEA)-based product that selectively absorbs contaminants. Amine is regenerated by removing contaminants with steam stripping. Lean amine is then recirculated to the absorbers. This case history demonstrates the effectiveness of electrodialysis technology for contaminant removal.« less

Super strong dopamine hydrogels with shape memory and bioinspired actuating behaviours modulated by solvent exchange.

PubMed

Huang, Jiahe; Liao, Jiexin; Wang, Tao; Sun, Weixiang; Tong, Zhen

2018-03-28

Dopamine-containing hydrogels were synthesized by copolymerization of dopamine methacrylamide (DMA), N,N-dimethylacrylamide (DMAA), and an N,N'-methylenebisacrylamide (BIS) crosslinker in a mixed solvent of water and DMSO. The association of DMA was formed by simply immersing in water to facilely reinforce the hydrogel due to the introduction of the second physical crosslinking. The tensile strength of the hydrogels was increased greatly and regulated in a wide range from 200 kPa to over 2 MPa. The association of DMA was destroyed upon immersing in DMSO. This reversible formation and dissociation of the association structure endowed the hydrogel with shape memory and actuating capabilities. Rapid shape fixing in water and complete shape recovery in DMSO was realized within several minutes. Bioinspired functional soft actuators were designed based on the reversible association and metal ion coordination of DMA, including fast responsive hydrogel tentacles, programable multiple shape change, reversible and versatile painting and writing "hydrogel paper". The facile preparation and strength regulation provide a new way to design novel soft actuators through solvent exchange, and will inspire more complex applications upon combining the association with other properties of mussel inspired dopamine derivatives.

Solvatochromism and preferential solvation of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone by UV-vis absorption and laser-induced fluorescence measurements

NASA Astrophysics Data System (ADS)

Sasirekha, V.; Vanelle, P.; Terme, T.; Ramakrishnan, V.

2008-12-01

Solvation characteristics of 1,4-dihydroxy-2,3-dimethyl-9,10-anthraquinone ( 1) in pure and binary solvent mixtures have been studied by UV-vis absorption spectroscopy and laser-induced fluorescence techniques. The binary solvent mixtures used as CCl 4 (tetrachloromethane)-DMF ( N, N-dimethylformamide), AN (acetonitrile)-DMSO (dimethylsulfoxide), CHCl 3 (chloroform)-DMSO, CHCl 3-MeOH (methanol), and MeOH-DMSO. The longest wavelength band of 1 has been studied in pure solvents as well as in binary solvent mixtures as a function of the bulk mole fraction. The Vis absorption band maxima show an unusual blue shift with increasing solvent polarity. The emission maxima of 1 show changes with varying the pure solvents and the composition in the case of binary solvent mixtures. Non-ideal solvation characteristics are observed in all binary solvent mixtures. It has been observed that the quantity [ ν-(Xν+Xν)] serves as a measure of the extent of preferential solvation, where ν˜ and X are the position of band maximum in wavenumbers (cm -1) and the bulk mole fraction values, respectively. The preferential solvation parameters local mole fraction ( X2L), solvation index ( δs2), and exchange constant ( k12) are evaluated.

Magnetic self-assembly for the synthesis of magnetically exchange coupled MnBi/Fe–Co composites

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

Xu, Xia; Hong, Yang-Ki, E-mail: ykhong@eng.ua.edu; Park, Jihoon

2015-11-15

Exchange coupled hard/soft MnBi/Fe–Co core/shell structured composites were synthesized using a magnetic self-assembly process. MnBi particles were prepared by arc-melting, and Fe–Co nanoparticles were synthesized by an oleic acid assisted chemical reduction method. Grinding a mixture of micron-sized MnBi and Fe–Co nanoparticles in hexane resulted in MnBi/Fe–Co core/shell structured composites. The MnBi/Fe–Co (95/5 wt%) composites showed smooth magnetic hysteresis loops, enhanced remanent magnetization, and positive values in the ΔM curve, indicating exchange coupling between MnBi and Fe–Co particles. - Graphical abstract: Both MnBi and Fe–Co particles were dispersed in hexane for grinding. Because of the oleic acid used during themore » Fe–Co nanoparticle synthesis, they could be well dispersed in hexane. During the grinding, the size of MnBi particles was decreased, hexane was evaporated, and the Fe–Co nanoparticles were concentrated in the solvent and magnetically attracted by MnBi particles, forming a core/shell structure. - Highlights: • Exchange coupled MnBi/Fe–Co composites are synthesized through magnetic selfassembly. • Magnetic exchange coupling is demonstrated by smooth magnetic hysteresis loops, enhanced remanent magnetization, and dominant positive peak in the ΔM curve. • The experimental results in magnetic properties are close to the theoretical calculation results.« less

Analysis of N-Nitrosodimethylamine and N-Nitrodimethylamine in Groundwater

NASA Technical Reports Server (NTRS)

Greene, Ben; Mast, Dion; Baker, David L.

2006-01-01

A method for the analytical determination of N-nitrosodimethylamine (NDMA) and N-nitrodimethylamine (DMN) at parts-per-trillion (ppt) concentrations in groundwater is reported. The method uses a solid phase extraction (SPE) cartridge containing 2 g of activated coconut charcoal to extract a 500-mL water sample. NDMA and DMN are eluted from the SPE cartridge using acetone. The acetone is concentrated and brought to a final volume of 1.0 mL, which results in a theoretical 500-fold concentration of the analytes. The extracts are analyzed by gas chromatography (GC) with a nitrogenphosphorous detector (NPD), which is a highly sensitive and relatively inexpensive technique. The measured extraction efficiencies averaged 61 percent for NDMA and 74 percent for DMN. Extraction efficiencies were independent of NDMA and DMN concentrations from 40 to 2000 ppt. Several samples could be extracted then analyzed in a single day with the use of an extraction manifold and GC autosampler. A reporting limit of 10 ppt for NDMA and DMN was achieved. The MDLs for NDMA and DMN were 6.4 and 5.8 ppt, respectively. A typical turn-around time from beginning of extraction to reporting was 4 h. The method avoids the use of halogenated solvents, such as dichloromethane, and subsequent solvent exchange procedures necessary for use of the NPD detector.

A New Method to Grow SiC: Solvent-Laser Heated Floating Zone

NASA Technical Reports Server (NTRS)

Woodworth, Andrew A.; Neudeck, Philip G.; Sayir, Ali

2012-01-01

The solvent-laser heated floating zone (solvent-LHFZ) growth method is being developed to grow long single crystal SiC fibers. The technique combines the single crystal fiber growth ability of laser heated floating zone with solvent based growth techniques (e.g. traveling solvent method) ability to grow SiC from the liquid phase. Initial investigations reported in this paper show that the solvent-LHFZ method readily grows single crystal SiC (retains polytype and orientation), but has a significant amount of inhomogeneous strain and solvent rich inclusions.

Equilibrium Passive Sampling of POP in Lipid-Rich and Lean Fish Tissue: Quality Control Using Performance Reference Compounds.

PubMed

Rusina, Tatsiana P; Carlsson, Pernilla; Vrana, Branislav; Smedes, Foppe

2017-10-03

Passive sampling is widely used to measure levels of contaminants in various environmental matrices, including fish tissue. Equilibrium passive sampling (EPS) of persistent organic pollutants (POP) in fish tissue has been hitherto limited to application in lipid-rich tissue. We tested several exposure methods to extend EPS applicability to lean tissue. Thin-film polydimethylsiloxane (PDMS) passive samplers were exposed statically to intact fillet and fish homogenate and dynamically by rolling with cut fillet cubes. The release of performance reference compounds (PRC) dosed to passive samplers prior to exposure was used to monitor the exchange process. The sampler-tissue exchange was isotropic, and PRC were shown to be good indicators of sampler-tissue equilibration status. The dynamic exposures demonstrated equilibrium attainment in less than 2 days for all three tested fish species, including lean fish containing 1% lipid. Lipid-based concentrations derived from EPS were in good agreement with lipid-normalized concentrations obtained using conventional solvent extraction. The developed in-tissue EPS method is robust and has potential for application in chemical monitoring of biota and bioaccumulation studies.

Quantitative description of proton exchange processes between water and endogenous and exogenous agents for WEX, CEST, and APT experiments.

PubMed

Zhou, Jinyuan; Wilson, David A; Sun, Phillip Zhe; Klaus, Judith A; Van Zijl, Peter C M

2004-05-01

The proton exchange processes between water and solutes containing exchangeable protons have recently become of interest for monitoring pH effects, detecting cellular mobile proteins and peptides, and enhancing the detection sensitivity of various low-concentration endogenous and exogenous species. In this work, the analytic expressions for water exchange (WEX) filter spectroscopy, chemical exchange-dependent saturation transfer (CEST), and amide proton transfer (APT) experiments are derived by the use of Bloch equations with exchange terms. The effects of the initial states for the system, the difference between a steady state and a saturation state, and the relative contributions of the forward and backward exchange processes are discussed. The theory, in combination with numerical calculations, provides a useful tool for designing experimental schemes and assessing magnetization transfer (MT) processes between water protons and solvent-exchangeable protons. As an example, the case of endogenous amide proton exchange in the rat brain at 4.7 T is analyzed in detail. Copyright 2004 Wiley-Liss, Inc.

Ultra-high performance liquid chromatography tandem mass spectrometry for the determination of five glycopeptide antibiotics in food and biological samples using solid-phase extraction.

PubMed

Deng, Fenfang; Yu, Hong; Pan, Xinhong; Hu, Guoyuan; Wang, Qiqin; Peng, Rongfei; Tan, Lei; Yang, Zhicong

2018-02-23

This paper demonstrated the development and validation of an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method for simultaneous determination of five glycopeptide antibiotics in food and biological samples. The target glycopeptide antibiotics were isolated from the samples by solvent extraction, and the extracts were cleaned with a tandem solid-phase extraction step using mixed strong cation exchange and hydrophilic/lipophilic balance cartridges. Subsequently, the analytes were eluted with different solvents, and then quantified by UHPLC-MS/MS in the positive ionization mode with multiple reaction monitoring. Under optimal conditions, good linear correlations were obtained for the five glycopeptide antibiotics in the concentration range of 1.0 μg/L to 20.0 μg/L, and with linear correlation coefficients >0.998. Employing this method, the target glycopeptide antibiotics in food and biological samples were identified with a recovery of 83.0-102%, and a low quantitation limit of 1.0 μg/kg in food and 2.0 μg/L in biological samples with low matrix effects. Copyright © 2018 Elsevier B.V. All rights reserved.

Hydrogen Bond Lifetimes and Energetics for Solute-Solvent Complexes Studied with 2D-IR Vibrational Echo Spectroscopy

PubMed Central

Zheng, Junrong; Fayer, Michael D.

2008-01-01

Weak π hydrogen bonded solute-solvent complexes are studied with ultrafast two dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy, temperature dependent IR absorption spectroscopy, and density functional theory calculations. Eight solute-solvent complexes composed of a number of phenol derivatives and various benzene derivatives are investigated. The complexes are formed between the phenol derivative (solute) in a mixed solvent of the benzene derivative and CCl4. The time dependence of the 2D-IR vibrational echo spectra of the phenol hydroxyl stretch is used to directly determine the dissociation and formation rates of the hydrogen bonded complexes. The dissociation rates of the weak hydrogen bonds are found to be strongly correlated with their formation enthalpies. The correlation can be described with an equation similar to the Arrhenius equation. The results are discussed in terms of transition state theory. PMID:17373792

Interactions of solvent with the heme region of methemoglobin and fluoro-methemoglobin.

PubMed

Koenig, S H; Brown, R D; Lindstrom, T R

1981-06-01

It is now more than 20 years since Davidson and collaborators (1957, Biochim. Biophys, Acta. 26:370-373; J. Mol. Biol. 1:190-191) applied the theoretical ideas of Bloembergen et al. (1948. Phys. Rev. 73:679-712) on outer sphere magnetic relaxation of solvent protons to studies of solutions of methemoglobin. From then on, there has been debate regarding the relative contributions to paramagnetic solvent proton relaxation by inner sphere (ligand-exchange) effects and by outer sphere (diffusional) effects in methemoglobin solutions. Gupta and Mildvan (1975. J. Biol. Chem 250:146-253) extended the early measurements, attributed the relatively small paramagnetic effects to exchange with solvent of the water ligand of the heme-Fe3+ ion, and interpreted their data to indicate cooperativity and an alkaline Bohr effect in the presence of inositol hexaphosphate. They neglected the earlier discussions entirely, and made no reference to outer sphere effects. We have measured the relaxation rate of solvent protons as a function of magnetic field for solutions of methemoglobin, under a variety of conditions of pH and temperature, and have given careful consideration to the relatively large diamagnetic corrections that are necessary by making analogous measurements on oxyhemoglobin, carbonmonoxyhemoglobin, and cyano- and azide-methemoglobin. (The latter two, because of their short electronic relaxation times, behave as though diamagnetic). We show that the paramagnetic contribution to solvent relaxation can be dominated by outer sphere effects, a result implying that many conclusions, including those of Gupta and Mildvan, require reexamination. Finally, we present data for fluoro-methemoglobin, which relaxes solvent protons an order of magnitude better than does methemoglobin. Here one has a startling breakdown of the dogma that has been the basis for interpreting many ligand-replacement studies; in contrast to the prevailing view that replacement of a water ligand of a protein-bound paramagnetic ion by another ligand should decrease relaxation rates, replacement of H2O by F- increases the relaxation rate drastically. The data can all be reconciled, however, with what is anticipated from knowledge of ligand interactions in the heme region.

Radiolabeling of DOTA-like conjugated peptides with generator-produced 68Ga and using NaCl-based cationic elution method

PubMed Central

Mueller, Dirk; Breeman, Wouter A P; Klette, Ingo; Gottschaldt, Michael; Odparlik, Andreas; Baehre, Manfred; Tworowska, Izabela; Schultz, Michael K

2017-01-01

Gallium-68 (68Ga) is a generator-produced radionuclide with a short half-life (t½ = 68 min) that is particularly well suited for molecular imaging by positron emission tomography (PET). Methods have been developed to synthesize 68Ga-labeled imaging agents possessing certain drawbacks, such as longer synthesis time because of a required final purification step, the use of organic solvents or concentrated hydrochloric acid (HCl). In our manuscript, we provide a detailed protocol for the use of an advantageous sodium chloride (NaCl)-based method for radiolabeling of chelator-modified peptides for molecular imaging. By working in a lead-shielded hot-cell system, 68Ga3+ of the generator eluate is trapped on a cation exchanger cartridge (100 mg, ∼8 mm long and 5 mm diameter) and then eluted with acidified 5 M NaCl solution directly into a sodium acetate-buffered solution containing a DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) or DOTA-like chelator-modified peptide. The main advantages of this procedure are the high efficiency and the absence of organic solvents. It can be applied to a variety of peptides, which are stable in 1 M NaCl solution at a pH value of 3–4 during reaction. After labeling, neutralization, sterile filtration and quality control (instant thin-layer chromatography (iTLC), HPLC and pH), the radiopharmaceutical can be directly administered to patients, without determination of organic solvents, which reduces the overall synthesis-to-release time. This procedure has been adapted easily to automated synthesis modules, which leads to a rapid preparation of 68Ga radiopharmaceuticals (12–16 min). PMID:27172166

Radiolabeling of DOTA-like conjugated peptides with generator-produced (68)Ga and using NaCl-based cationic elution method.

PubMed

Mueller, Dirk; Breeman, Wouter A P; Klette, Ingo; Gottschaldt, Michael; Odparlik, Andreas; Baehre, Manfred; Tworowska, Izabela; Schultz, Michael K

2016-06-01

Gallium-68 ((68)Ga) is a generator-produced radionuclide with a short half-life (t½ = 68 min) that is particularly well suited for molecular imaging by positron emission tomography (PET). Methods have been developed to synthesize (68)Ga-labeled imaging agents possessing certain drawbacks, such as longer synthesis time because of a required final purification step, the use of organic solvents or concentrated hydrochloric acid (HCl). In our manuscript, we provide a detailed protocol for the use of an advantageous sodium chloride (NaCl)-based method for radiolabeling of chelator-modified peptides for molecular imaging. By working in a lead-shielded hot-cell system,(68)Ga(3+) of the generator eluate is trapped on a cation exchanger cartridge (100 mg, ∼8 mm long and 5 mm diameter) and then eluted with acidified 5 M NaCl solution directly into a sodium acetate-buffered solution containing a DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) or DOTA-like chelator-modified peptide. The main advantages of this procedure are the high efficiency and the absence of organic solvents. It can be applied to a variety of peptides, which are stable in 1 M NaCl solution at a pH value of 3-4 during reaction. After labeling, neutralization, sterile filtration and quality control (instant thin-layer chromatography (iTLC), HPLC and pH), the radiopharmaceutical can be directly administered to patients, without determination of organic solvents, which reduces the overall synthesis-to-release time. This procedure has been adapted easily to automated synthesis modules, which leads to a rapid preparation of (68)Ga radiopharmaceuticals (12-16 min).

Compact heat and mass exchangers of the plate fin type in thermal sorption systems: Application in an absorption heat pump with the working pair CH3OH-LiBr/ZnBr2

NASA Astrophysics Data System (ADS)

Becker, Harry

The possible application of Compact Heat and Mass Exchangers (CHME) in a gas fired Absorption Heat Pump (AHP) for domestic heating is studied. The above mentioned heat and mass exchangers are of the plate type. The space between the parallel and plain plates is filled up with corrugated plates of a certain height. The plain and finned plates are stacked and welded together. This gives a heat and mass exchanger which is very compact, expressed by a high area density (m2/m3). This leads to heat and mass transfer processes with small temperature and concentration differences. For testing purposes a pilot plant was built using the above type of components in order to test their heat and/or mass transfer performance. Only the generator is of the Shell And Tube (SAT) type. As the working pair, CH3OH - LiBr/ ZnBr2 was chosen, with the alcohol as the solvent and the salt mixture as the absorbent. This leads to sub atmospheric working pressures with only solvent in the vapor phase. Three series of experiments have been carried out, during which the input parameters were varied over a certain range. It is concluded that the plate fin CHMES are very suitable for application in an AHP for domestic heating purposes.

Coexisting stable conformations of gaseous protein ions.

PubMed Central

Suckau, D; Shi, Y; Beu, S C; Senko, M W; Quinn, J P; Wampler, F M; McLafferty, F W

1993-01-01

For further insight into the role of solvent in protein conformer stabilization, the structural and dynamic properties of protein ions in vacuo have been probed by hydrogen-deuterium exchange in a Fourier-transform mass spectrometer. Multiply charged ions generated by electrospray ionization of five proteins show exchange reactions with 2H2O at 10(-7) torr (1 torr = 133.3 Pa) exhibiting pseudo-first-order kinetics. Gas-phase compactness of the S-S cross-linked RNase A relative to denatured S-derivatized RNase A is indicated by exchange of 35 and 135 hydrogen atoms, respectively. For pure cytochrome c ions, the existence of at least three distinct gaseous conformers is indicated by the substantially different values--52, 113, and 74--of reactive H atoms; the observation of these same values for ions of a number--2, 7, and 5, respectively--of different charge states indicates conformational insensitivity to coulombic forces. For each of these conformers, the compactness in vacuo indicated by these values corresponds directly to that of a known conformer structure in the solution from which the conformer ions are produced by electrospray. S-derivatized RNase A ions also exist as at least two gaseous conformers exchanging 50-140 H atoms. Gaseous conformer ions are isometrically stable for hours; removal of solvent greatly increases conformational rigidity. More specific ion-molecule reactions could provide further details of conformer structures. Images PMID:8381533

Solute-solvent complex switching dynamics of chloroform between acetone and dimethylsulfoxide-two-dimensional IR chemical exchange spectroscopy.

PubMed

Kwak, Kyungwon; Rosenfeld, Daniel E; Chung, Jean K; Fayer, Michael D

2008-11-06

Hydrogen bonds formed between C-H and various hydrogen bond acceptors play important roles in the structure of proteins and organic crystals, and the mechanisms of C-H bond cleavage reactions. Chloroform, a C-H hydrogen bond donor, can form weak hydrogen-bonded complexes with acetone and with dimethylsulfoxide (DMSO). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO, both types of hydrogen-bonded complexes exist. The two complexes, chloroform-acetone and chloroform-DMSO, are in equilibrium, and they rapidly interconvert by chloroform exchanging hydrogen bond acceptors. This fast hydrogen bond acceptor substitution reaction is probed using ultrafast two-dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy. Deuterated chloroform is used in the experiments, and the 2D-IR spectrum of the C-D stretching mode is measured. The chemical exchange of the chloroform hydrogen bonding partners is tracked by observing the time-dependent growth of off-diagonal peaks in the 2D-IR spectra. The measured substitution rate is 1/30 ps for an acetone molecule to replace a DMSO molecule in a chloroform-DMSO complex and 1/45 ps for a DMSO molecule to replace an acetone molecule in a chloroform-acetone complex. Free chloroform exists in the mixed solvent, and it acts as a reactive intermediate in the substitution reaction, analogous to a SN1 type reaction. From the measured rates and the equilibrium concentrations of acetone and DMSO, the dissociation rates for the chloroform-DMSO and chloroform-acetone complexes are found to be 1/24 ps and 1/5.5 ps, respectively. The difference between the measured rate for the complete substitution reaction and the rate for complex dissociation corresponds to the diffusion limited rate. The estimated diffusion limited rate agrees well with the result from a Smoluchowski treatment of diffusive reactions.

Active-Site Hydration and Water Diffusion in Cytochrome P450cam: A Highly Dynamic Process

PubMed Central

Miao, Yinglong; Baudry, Jerome

2011-01-01

Long-timescale molecular dynamics simulations (300 ns) are performed on both the apo- (i.e., camphor-free) and camphor-bound cytochrome P450cam (CYP101). Water diffusion into and out of the protein active site is observed without biased sampling methods. During the course of the molecular dynamics simulation, an average of 6.4 water molecules is observed in the camphor-binding site of the apo form, compared to zero water molecules in the binding site of the substrate-bound form, in agreement with the number of water molecules observed in crystal structures of the same species. However, as many as 12 water molecules can be present at a given time in the camphor-binding region of the active site in the case of apo-P450cam, revealing a highly dynamic process for hydration of the protein active site, with water molecules exchanging rapidly with the bulk solvent. Water molecules are also found to exchange locations frequently inside the active site, preferentially clustering in regions surrounding the water molecules observed in the crystal structure. Potential-of-mean-force calculations identify thermodynamically favored trans-protein pathways for the diffusion of water molecules between the protein active site and the bulk solvent. Binding of camphor in the active site modifies the free-energy landscape of P450cam channels toward favoring the diffusion of water molecules out of the protein active site. PMID:21943431

Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds.

PubMed

Obadia, Mona M; Mudraboyina, Bhanu P; Serghei, Anatoli; Montarnal, Damien; Drockenmuller, Eric

2015-05-13

Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

Enzymatic preparation of. cap alpha. - and. beta. -deuterated or tritiated amino acids with l-methionine. gamma. -lyase

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

Esaki, N.; Sawada, S.; Tanaka, H.

L-Methionine ..gamma..-lyase catalyzes the exchange of ..cap alpha..- and ..beta..-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium or tritium of solvents. The rate of ..cap alpha..-hydrogen exchange with deuterium was about 40 times faster than that of the elimination reactions. The deuterium and tritium were exchanged also with the ..cap alpha..- and ..beta..-hydrogens of the straight-chain amino acids which do not undergo the elimination: L-alanine, L-..cap alpha..-aminobutyrate, L-norvaline, and L-norleucine. No exchange occurs for the D-isomers, acidic L-amino acids, basic L-amino acids, and branched-chain L-amino acids, although ..cap alpha..-hydrogen of glycine, L-trypotophan, and L-phenylalanine is exchanged slowly. These enzymatic hydrogen-exchange reactionsmore » facilitate specific labeling of the L-amino acids with deuterium and tritium.« less

Multiscale investigation of chemical interference in proteins

NASA Astrophysics Data System (ADS)

Samiotakis, Antonios; Homouz, Dirar; Cheung, Margaret S.

2010-05-01

We developed a multiscale approach (MultiSCAAL) that integrates the potential of mean force obtained from all-atomistic molecular dynamics simulations with a knowledge-based energy function for coarse-grained molecular simulations in better exploring the energy landscape of a small protein under chemical interference such as chemical denaturation. An excessive amount of water molecules in all-atomistic molecular dynamics simulations often negatively impacts the sampling efficiency of some advanced sampling techniques such as the replica exchange method and it makes the investigation of chemical interferences on protein dynamics difficult. Thus, there is a need to develop an effective strategy that focuses on sampling structural changes in protein conformations rather than solvent molecule fluctuations. In this work, we address this issue by devising a multiscale simulation scheme (MultiSCAAL) that bridges the gap between all-atomistic molecular dynamics simulation and coarse-grained molecular simulation. The two key features of this scheme are the Boltzmann inversion and a protein atomistic reconstruction method we previously developed (SCAAL). Using MultiSCAAL, we were able to enhance the sampling efficiency of proteins solvated by explicit water molecules. Our method has been tested on the folding energy landscape of a small protein Trp-cage with explicit solvent under 8M urea using both the all-atomistic replica exchange molecular dynamics and MultiSCAAL. We compared computational analyses on ensemble conformations of Trp-cage with its available experimental NOE distances. The analysis demonstrated that conformations explored by MultiSCAAL better agree with the ones probed in the experiments because it can effectively capture the changes in side-chain orientations that can flip out of the hydrophobic pocket in the presence of urea and water molecules. In this regard, MultiSCAAL is a promising and effective sampling scheme for investigating chemical interference which presents a great challenge when modeling protein interactions in vivo.

Used Solvent Testing and Reclamation. Volume 2. Vapor Degreasing and Precision Cleaning Solvents

DTIC Science & Technology

1988-12-01

of 5 to 500 ppm in halogenated solvents using Karl - Fischer reagent. Arbitrary criteria to identify a spent solvent have evolved in various industries... methods of managing waste solvent. Some DOD installations are reclaiming used solvents rather than discarding them. Reclamation is feasible because the...most E E CT E reliable methods for testing solvent quality. Further testing isnecessary for chlorinated solvents to determine the inhibitor con- FEB 24

Single column comprehensive analysis of pharmaceutical preparations using dual-injection mixed-mode (ion-exchange and reversed-phase) and hydrophilic interaction liquid chromatography.

PubMed

Kazarian, Artaches A; Taylor, Mark R; Haddad, Paul R; Nesterenko, Pavel N; Paull, Brett

2013-12-01

The comprehensive separation and detection of hydrophobic and hydrophilic active pharmaceutical ingredients (APIs), their counter-ions (organic, inorganic) and excipients, using a single mixed-mode chromatographic column, and a dual injection approach is presented. Using a mixed-mode Thermo Fisher Acclaim Trinity P1 column, APIs, their counter-ions and possible degradants were first separated using a combination of anion-exchange, cation-exchange and hydrophobic interactions, using a mobile phase consisting of a dual organic modifier/salt concentration gradient. A complementary method was also developed using the same column for the separation of hydrophilic bulk excipients, using hydrophilic interaction liquid chromatography (HILIC) under high organic solvent mobile phase conditions. These two methods were then combined within a single gradient run using dual sample injection, with the first injection at the start of the applied gradient (mixed-mode retention of solutes), followed by a second sample injection at the end of the gradient (HILIC retention of solutes). Detection using both ultraviolet absorbance and refractive index enabled the sensitive detection of APIs and UV-absorbing counter-ions, together with quantitative determination of bulk excipients. The developed approach was applied successfully to the analysis of a dry powder inhalers (Flixotide(®), Spiriva(®)), enabling comprehensive quantification of all APIs and excipients in the sample. Copyright © 2013 Elsevier B.V. All rights reserved.

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

Umino, Satoru; Takahashi, Hideaki, E-mail: hideaki@m.tohoku.ac.jp; Morita, Akihiro

In a recent work, we developed a method [H. Takahashi et al., J. Chem. Phys. 143, 084104 (2015)] referred to as exchange-core function (ECF) approach, to compute exchange repulsion E{sub ex} between solute and solvent in the framework of the quantum mechanical (QM)/molecular mechanical (MM) method. The ECF, represented with a Slater function, plays an essential role in determining E{sub ex} on the basis of the overlap model. In the work of Takahashi et al. [J. Chem. Phys. 143, 084104 (2015)], it was demonstrated that our approach is successful in computing the hydrogen bond energies of minimal QM/MM systems includingmore » a cationic QM solute. We provide in this paper the extension of the ECF approach to the free energy calculation in condensed phase QM/MM systems by combining the ECF and the QM/MM-ER approach [H. Takahashi et al., J. Chem. Phys. 121, 3989 (2004)]. By virtue of the theory of solutions in energy representation, the free energy contribution δμ{sub ex} from the exchange repulsion was naturally formulated. We found that the ECF approach in combination with QM/MM-ER gives a substantial improvement on the calculation of the hydration free energy of a hydronium ion. This can be attributed to the fact that the ECF reasonably realizes the contraction of the electron density of the cation due to the deficit of an electron.« less

Solvent shift method for anti-precipitant screening of poorly soluble drugs using biorelevant medium and dimethyl sulfoxide.

PubMed

Yamashita, Taro; Ozaki, Shunsuke; Kushida, Ikuo

2011-10-31

96-well plate based anti-precipitant screening using bio-relevant medium FaSSIF (fasted-state simulated small intestinal fluid) is a useful technique for discovering anti-precipitants that maintain supersaturation of poorly soluble drugs. In a previous report, two disadvantages of the solvent evaporation method (solvent casting method) were mentioned: precipitation during the evaporation process and the use of volatile solvents to dissolve compounds. In this report, we propose a solvent shift method using DMSO (dimethyl sulfoxide). Initially, the drug substance was dissolved in DMSO at a high concentration and diluted with FaSSIF that contained anti-precipitants. To evaluate the validity of the method, itraconazole (ITZ) was used as the poorly soluble model drug. The solvent shift method resolved the disadvantages of the evaporation method, and AQOAT (HPMC-AS) was found as the most appropriate anti-precipitant for ITZ in a facile and expeditious manner when compared with the solvent evaporation method. In the large scale JP paddle method, AQOAT-based solid dispersion maintained a higher concentration than Tc-5Ew (HPMC)-based formulation; this result corresponded well with the small scale of the solvent shift method. Copyright © 2011 Elsevier B.V. All rights reserved.

A Flemion-based actuator with ionic liquid as solvent

NASA Astrophysics Data System (ADS)

Wang, Jin; Xu, Chunye; Taya, Minoru; Kuga, Yasuo

2007-04-01

A perfluorinated carboxylic acid membrane, i.e. Flemion, shows improved performance as actuator material compared with Nafion (perfluorinated sulfonic acid). Flemion has a higher ion exchange capacity and good mechanical strength. In particular, Flemion will deform with no back relaxation under applied electrical stimulus. However, with water as solvent, the operation of Flemion in air has serious problems, since water would evaporate quickly in air. Moreover, the electrochemical stability for use in water is around 1 V at room temperature. In previous work, investigations on Nafion with ionic liquid as solvents have been carried out by some researchers and good results have been obtained. In this work, we explore the use of highly stable ionic liquid instead of water as solvent in Flemion. Experimental results indicate that Flemion-based actuators with ionic liquid as solvent have improved stability as compared to the water samples. Although the forces exhibited by Flemion-based actuators with the use of ionic liquid decreased dramatically compared to water, these preliminary results suggest good potential for the use of Flemion with ionic liquid in future applications.

Flemion-based actuator with ionic liquid as solvent

NASA Astrophysics Data System (ADS)

Wang, Jin; Xu, Chunye; Taya, Minoru; Kuga, Yasuo

2006-03-01

A perfluorinated carboxylic acid membrane, i.e. Flemion, shows improved performance as actuator material compared with Nafion (perfluorinated sulfonic acide). Flemion has a higher ion exchange capacity and good mechanical strength. Especially, Flemion will deform with no back relaxation when applied electrical stimulus. However, with water as solvent, the operation of Flemion in air has serious problems. Since water would evaporate quickly in air. Moreover, the electrochemical stability for use in water is around 1V at room temperature. In previous work, investigations on Nafion with ionic liquid as solvents have been carried out and good results have been obtained. In this work, we explore the use of highly stable ionic liquid instead of water as solvent in Flemion. Experimental results indicate that Flemion based actuators with ionic liquid as solvent have improved stability as compared to the water samples. Although the forces exhibited by Flemion based actuators with the use of ionic liquid decreased dramatically as compared to water, these preliminary results suggest a good potential for use of Flemion with ionic liquid in some applications.

Organic solvent and temperature-enhanced ion chromatography-high resolution mass spectrometry for the determination of low molecular weight organic and inorganic anions.

PubMed

Gilchrist, Elizabeth S; Nesterenko, Pavel N; Smith, Norman W; Barron, Leon P

2015-03-20

There has recently been increased interest in coupling ion chromatography (IC) to high resolution mass spectrometry (HRMS) to enable highly sensitive and selective analysis. Herein, the first comprehensive study focusing on the direct coupling of suppressed IC to HRMS without the need for post-suppressor organic solvent modification is presented. Chromatographic selectivity and added HRMS sensitivity offered by organic solvent-modified IC eluents on a modern hyper-crosslinked polymeric anion-exchange resin (IonPac AS18) are shown using isocratic eluents containing 5-50 mM hydroxide with 0-80% methanol or acetonitrile for a range of low molecular weight anions (<165 Da). Comprehensive experiments on IC thermodynamics over a temperature range between 20-45 °C with the eluent containing up to 60% of acetonitrile or methanol revealed markedly different retention behaviour and selectivity for the selected analytes on the same polymer based ion-exchange resin. Optimised sensitivity with HRMS was achieved with as low as 30-40% organic eluent content. Analytical performance characteristics are presented and compared with other IC-MS based works. This study also presents the first application of IC-HRMS to forensic detection of trace low-order anionic explosive residues in latent human fingermarks. Copyright © 2015 Elsevier B.V. All rights reserved.

Methods for recovering a solvent from a fluid volume and methods of removing at least one compound from a nonpolar solvent

DOEpatents

Ginosar, Daniel M.; Wendt, Daniel S.; Petkovic, Lucia M.

2014-06-10

A method of removing a nonpolar solvent from a fluid volume that includes at least one nonpolar compound, such as a fat, an oil or a triglyceride, is provided. The method comprises contacting a fluid volume with an expanding gas to expand the nonpolar solvent and form a gas-expanded solvent. The gas-expanded solvent may have a substantially reduced density in comparison to the at least one nonpolar compound and/or a substantially reduced capacity to solubilize the nonpolar compound, causing the nonpolar compounds to separate from the gas-expanded nonpolar solvent into a separate liquid phase. The liquid phase including the at least one nonpolar compound may be separated from the gas-expanded solvent using conventional techniques. After separation of the liquid phase, at least one of the temperature and pressure may be reduced to separate the nonpolar solvent from the expanding gas such that the nonpolar solvent may be recovered and reused.

Polymers in separation processes

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina; Staszak, Katarzyna

2017-05-01

Application of polymer materials as membranes and ion-exchange resins was presented with a focus on their use for the recovery of metal ions from aqueous solutions. Several membrane techniques were described including reverse osmosis, nanofiltration, ultrafiltration, diffusion and Donnan dialysis, electrodialysis and membrane extraction system (polymer inclusion and supported membranes). Moreover, the examples of using ion-exchange resins in metal recovery were presented. The possibility of modification of the resin was discussed, including hybrid system with metal cation or metal oxide immobilized on polymer matrices or solvent impregnated resin.

Investigation of Proton Conductivity of Cation-Exchanged, Sulfonated Poly(b-Styrene-b-Isobutylene-b-Styrene) Membranes

DTIC Science & Technology

2009-09-01

solvents. Similar behavior was observed for Nafion -117 (also a polymer with ionic SO3H clusters) by other researchers (14). Results shown in this...pattern was only valid for ionic S-SIBS membranes exchanged with cations; neither acid form of SIBS-97-H nor Nafion -117 fell on this line. In order...10  vi INTENTIONALLY LEFT BLANK. 1 1. Introduction Research in ionic polymers has been gaining popularity in the scientific community

Improved durability of proton exchange membrane fuel cells by introducing Sn (IV) oxide into electrodes using an ion exchange method

NASA Astrophysics Data System (ADS)

Poulsen, M. G.; Larsen, M. J.; Andersen, S. M.

2017-03-01

Electrodes of Proton Exchange Membrane Fuel Cells (PEMFCs), consisting of catalyst-coated gas diffusion layers, were subjected to an optimized ion exchange procedure, in which tin (IV) oxide (SnO2) nanoparticles were introduced into them. Both methanol and sulfuric acid were tested as ion exchange solvents. SnO2 has previously been shown to exhibit radical scavenging abilities towards radicals inside the electrocatalyst layers. Its presence inside the electrodes was confirmed using X-ray photoelectron spectroscopy and X-ray fluorescence. After exposure to an accelerated stress test in a three-electrode setup, the electrodes containing SnO2 were found to have retained approximately 73.0% of their original Pt, while only 53.2% was retained in electrodes treated identically, but without Sn. Similarly, the SnO2-treated electrodes also experienced a smaller loss in electrochemical surface area in comparison to before the accelerated stress test. A membrane electrode assembly (MEA) constructed with a SnO2-containing anode was evaluated over 500 h. The results showed remarkably reduced OCV decay rate and end of test hydrogen crossover compared to the control MEA, indicating that SnO2 aids in impeding membrane thinning and pinhole formation. The results point toward a positive effect of SnO2 on fuel cell durability, by reducing the degradation of the membrane as well as of the ionomer in the electrocatalyst layer.

Apparatus and method for removing solvent from carbon dioxide in resin recycling system

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2009-01-06

A two-step resin recycling system and method solvent that produces essentially contaminant-free synthetic resin material. The system and method includes one or more solvent wash vessels to expose resin particles to a solvent, the solvent contacting the resin particles in the one or more solvent wash vessels to substantially remove contaminants on the resin particles. A separator is provided to separate the solvent from the resin particles after removal from the one or more solvent wash vessels. The resin particles are next exposed to carbon dioxide in a closed loop carbon dioxide system. The closed loop system includes a carbon dioxide vessel where the carbon dioxide is exposed to the resin, substantially removing any residual solvent remaining on the resin particles after separation. A separation vessel is also provided to separate the solvent from the solvent laden carbon dioxide. Both the carbon dioxide and the solvent are reused after separation in the separation vessel.

Nanosheets of oxides and hydroxides: Ultimate 2D charge-bearing functional crystallites.

PubMed

Ma, Renzhi; Sasaki, Takayoshi

2010-12-01

A wide variety of cation-exchangeable layered transition metal oxides and their relatively rare counterparts, anion-exchangeable layered hydroxides, have been exfoliated into individual host layers, i.e., nanosheets. Exfoliation is generally achieved via a high degree of swelling, typically driven either by intercalation of bulky organic ions (quaternary ammonium cations, propylammonium cations, etc.) for the layered oxides or by solvation with organic solvents (formamide, butanol, etc.) for the hydroxides. Ultimate two-dimensional (2D) anisotropy for the nanosheets, with thickness of around one nanometer versus lateral size ranging from submicrometer to several tens of micrometers, allows them to serve either as an ideal quantum system for fundamental study or as a basic building block for functional assembly. The charge-bearing inorganic macromolecule-like nanosheets can be assembled or organized through various solution-based processing techniques (e.g., flocculation, electrostatic sequential deposition, or the Langmuir-Blodgett method) to produce a range of nanocomposites, multilayer nanofilms, and core-shell nanoarchitectures, which have great potential for electronic, magnetic, optical, photochemical, and catalytic applications.

The free energy landscape for beta hairpin folding in explicit water.

PubMed

Zhou, R; Berne, B J; Germain, R

2001-12-18

The folding free energy landscape of the C-terminal beta hairpin of protein G has been explored in this study with explicit solvent under periodic boundary condition and OPLSAA force field. A highly parallel replica exchange method that combines molecular dynamics trajectories with a temperature exchange Monte Carlo process is used for sampling with the help of a new efficient algorithm P3ME/RESPA. The simulation results show that the hydrophobic core and the beta strand hydrogen bond form at roughly the same time. The free energy landscape with respect to various reaction coordinates is found to be rugged at low temperatures and becomes a smooth funnel-like landscape at about 360 K. In contrast to some very recent studies, no significant helical content has been found in our simulation at all temperatures studied. The beta hairpin population and hydrogen-bond probability are in reasonable agreement with the experiment at biological temperature, but both decay more slowly than the experiment with temperature.

The free energy landscape for hairpin folding in explicit water

NASA Astrophysics Data System (ADS)

Zhou, Ruhong; Berne, Bruce J.; Germain, Robert

2001-12-01

The folding free energy landscape of the C-terminal hairpin of protein G has been explored in this study with explicit solvent under periodic boundary condition and OPLSAA force field. A highly parallel replica exchange method that combines molecular dynamics trajectories with a temperature exchange Monte Carlo process is used for sampling with the help of a new efficient algorithm P3ME/RESPA. The simulation results show that the hydrophobic core and the strand hydrogen bond form at roughly the same time. The free energy landscape with respect to various reaction coordinates is found to be rugged at low temperatures and becomes a smooth funnel-like landscape at about 360 K. In contrast to some very recent studies, no significant helical content has been found in our simulation at all temperatures studied. The β hairpin population and hydrogen-bond probability are in reasonable agreement with the experiment at biological temperature, but both decay more slowly than the experiment with temperature.

The free energy landscape for β hairpin folding in explicit water

PubMed Central

Zhou, Ruhong; Berne, Bruce J.; Germain, Robert

2001-01-01

The folding free energy landscape of the C-terminal β hairpin of protein G has been explored in this study with explicit solvent under periodic boundary condition and oplsaa force field. A highly parallel replica exchange method that combines molecular dynamics trajectories with a temperature exchange Monte Carlo process is used for sampling with the help of a new efficient algorithm P3ME/RESPA. The simulation results show that the hydrophobic core and the β strand hydrogen bond form at roughly the same time. The free energy landscape with respect to various reaction coordinates is found to be rugged at low temperatures and becomes a smooth funnel-like landscape at about 360 K. In contrast to some very recent studies, no significant helical content has been found in our simulation at all temperatures studied. The β hairpin population and hydrogen-bond probability are in reasonable agreement with the experiment at biological temperature, but both decay more slowly than the experiment with temperature. PMID:11752441

Li+ solvation and kinetics of Li+-BF4-/PF6- ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

NASA Astrophysics Data System (ADS)

Chang, Tsun-Mei; Dang, Liem X.

2017-10-01

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li+ ions varied from 60 to 450 ps, depending on the correction method used. We found that the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.

Potential uranium supply from phosphoric acid: A U.S. analysis comparing solvent extraction and Ion exchange recovery

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

Kim, Haeyeon; G. Eggert, Roderick; W. Carlsen, Brett

Phosphate rock contains significant amounts of uranium, although in low concentrations. Recovery of uranium as a by-product from phosphoric acid, an intermediate product produced during the recovery of phosphorus from phosphate rock, is not unprecedented. Phosphoric acid plants ceased to produce uranium as a by-product in the early 1990s with the fall of uranium prices. In the last decade, this topic has regained attention due to higher uranium prices and expected increase in demand for uranium. Our study revisits the topic and estimates how much uranium might be recoverable from current phosphoric acid production in the United States and whatmore » the associated costs might be considering two different recovery processes: solvent extraction and ion exchange. Based on U.S. phosphoric acid production in 2014, 5.5 million pounds of U 3O 8 could have been recovered, more than domestic U.S. mine production of uranium in the same year. Annualized costs for a hypothetical uranium recovery plant are US$48-66 per pound U 3O 8 for solvent extraction, the process used historically in the United States to recover uranium from phosphoric acid. For ion exchange, not yet proven at a commercial scale for uranium recovery, the estimated costs are US$33-54 per pound U 3O 8. Our results suggest that it is technically possible for the United States to recover significant quantities of uranium from current phosphoric acid production. And for this type of uranium production to be economically attractive on a large scale, either recovery costs must fall or uranium prices rise.« less

Potential uranium supply from phosphoric acid: A U.S. analysis comparing solvent extraction and Ion exchange recovery

DOE PAGES

Kim, Haeyeon; G. Eggert, Roderick; W. Carlsen, Brett; ...

2016-06-16

Phosphate rock contains significant amounts of uranium, although in low concentrations. Recovery of uranium as a by-product from phosphoric acid, an intermediate product produced during the recovery of phosphorus from phosphate rock, is not unprecedented. Phosphoric acid plants ceased to produce uranium as a by-product in the early 1990s with the fall of uranium prices. In the last decade, this topic has regained attention due to higher uranium prices and expected increase in demand for uranium. Our study revisits the topic and estimates how much uranium might be recoverable from current phosphoric acid production in the United States and whatmore » the associated costs might be considering two different recovery processes: solvent extraction and ion exchange. Based on U.S. phosphoric acid production in 2014, 5.5 million pounds of U 3O 8 could have been recovered, more than domestic U.S. mine production of uranium in the same year. Annualized costs for a hypothetical uranium recovery plant are US$48-66 per pound U 3O 8 for solvent extraction, the process used historically in the United States to recover uranium from phosphoric acid. For ion exchange, not yet proven at a commercial scale for uranium recovery, the estimated costs are US$33-54 per pound U 3O 8. Our results suggest that it is technically possible for the United States to recover significant quantities of uranium from current phosphoric acid production. And for this type of uranium production to be economically attractive on a large scale, either recovery costs must fall or uranium prices rise.« less

Unfolding of a model protein on ion exchange and mixed mode chromatography surfaces.

PubMed

Gospodarek, Adrian M; Hiser, Diana E; O'Connell, John P; Fernandez, Erik J

2014-08-15

Recent studies with proteins indicate that conformational changes and aggregation can occur during ion exchange chromatography (IEC). Such behavior is not usually expected, but could lead to decreased yield and product degradation from both IEC and multi mode chromatography (MMC) that has ligands of both hydrophobic and charged functionalities. In this study, we used hydrogen exchange mass spectrometry to investigate unfolding of the model protein BSA on IEC and MMC surfaces under different solution conditions at 25°C. Increased solvent exposure, indicating greater unfolding relative to that in solution, was found for protein adsorbed on cationic IEC and MMC surfaces in the pH range of 3.0 to 4.5, where BSA has decreased stability in solution. There was no effect of anionic surfaces at pH values in the range from 6.0 to 9.0. Differences of solvent exposure of whole molecules when adsorbed and in solution suggest that adsorbed BSA unfolds at lower pH values and may show aggregation, depending upon pH and the surface type. Measurements on digested peptides showed that classifications of stability can be made for various regions; these are generally retained as pH is changed. When salt was added to MMC systems, where electrostatic interactions would be minimized, less solvent exposure was seen, implying that it is the cationic moieties, rather than the hydrophobic ligands, which cause greater surface unfolding at low salt concentrations. These results suggest that proteins of lower stability may exhibit unfolding and aggregation during IEC and MMC separations, as they can with hydrophobic interaction chromatography. Copyright © 2014 Elsevier B.V. All rights reserved.

Computing pKa Values in Different Solvents by Electrostatic Transformation.

PubMed

Rossini, Emanuele; Netz, Roland R; Knapp, Ernst-Walter

2016-07-12

We introduce a method that requires only moderate computational effort to compute pKa values of small molecules in different solvents with an average accuracy of better than 0.7 pH units. With a known pKa value in one solvent, the electrostatic transform method computes the pKa value in any other solvent if the proton solvation energy is known in both considered solvents. To apply the electrostatic transform method to a molecule, the electrostatic solvation energies of the protonated and deprotonated molecular species are computed in the two considered solvents using a dielectric continuum to describe the solvent. This is demonstrated for 30 molecules belonging to 10 different molecular families by considering 77 measured pKa values in 4 different solvents: water, acetonitrile, dimethyl sulfoxide, and methanol. The electrostatic transform method can be applied to any other solvent if the proton solvation energy is known. It is exclusively based on physicochemical principles, not using any empirical fetch factors or explicit solvent molecules, to obtain agreement with measured pKa values and is therefore ready to be generalized to other solute molecules and solvents. From the computed pKa values, we obtained relative proton solvation energies, which agree very well with the proton solvation energies computed recently by ab initio methods, and used these energies in the present study.

Synthesis and Characterization of Functionalized Metal-organic Frameworks

PubMed Central

Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A.; Hupp, Joseph T.; Farha, Omar K.

2014-01-01

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy. PMID:25225784

Development and validation of a fast static headspace GC method for determination of residual solvents in permethrin.

PubMed

Tian, Jingzhi; Rustum, Abu

2016-09-05

A fast static headspace gas chromatography (HS-GC) method was developed to separate all residual solvents present in commercial active pharmaceutical ingredient (API) batches of permethrin. A total of six residual solvents namely 2-methylpentane, 3-methylpentane, methylcyclopentane, n-hexane, cyclohexane and toluene were found in typical commercial batches of permethrin; and three of them are not in the list of ICH solvents. All six residual solvents were baseline separated in five minutes by the new method presented in this paper. The method was successfully validated as per International Conference on Harmonisation (ICH) guidelines. Evaluation of this method was conducted to separate 26 commonly used solvents in the manufacturing of various APIs, key intermediates of APIs and pharmaceutical excipients. The results of the evaluation demonstrated that this method can also be used as a general method to determine residual solvents in various APIs, intermediates and excipients that are used in pharmaceutical products. Copyright © 2016 Elsevier B.V. All rights reserved.

Methods for recovering a polar solvent from a fluid stream contaminated with at least one polar impurity

DOEpatents

Ginosar, Daniel M.; Wendt, Daniel S.

2012-11-13

A method of removing a polar solvent from a fluid volume contaminated with at least one polar impurity, such as a free fatty acid, is provided. The method comprises providing a fluid volume that includes at least one polar impurity dissolved in at least one solvent. The fluid volume is contacted with an expanding gas to remove the at least one solvent. The expanding gas may be dissolved into the at least one solvent in the fluid volume to form a gas-expanded solvent. The immiscibility of the polar impurities in the gas-expanded solvent enables separation of the polar impurities from the gas-expanded solvent. After separation of the polar impurities, at least one of the temperature and pressure may be reduced to separate the solvent from the expanding gas such that the clean solvent may be reused.

Numerical Treatment of Stokes Solvent Flow and Solute-Solvent Interfacial Dynamics for Nonpolar Molecules.

PubMed

Sun, Hui; Zhou, Shenggao; Moore, David K; Cheng, Li-Tien; Li, Bo

2016-05-01

We design and implement numerical methods for the incompressible Stokes solvent flow and solute-solvent interface motion for nonpolar molecules in aqueous solvent. The balance of viscous force, surface tension, and van der Waals type dispersive force leads to a traction boundary condition on the solute-solvent interface. To allow the change of solute volume, we design special numerical boundary conditions on the boundary of a computational domain through a consistency condition. We use a finite difference ghost fluid scheme to discretize the Stokes equation with such boundary conditions. The method is tested to have a second-order accuracy. We combine this ghost fluid method with the level-set method to simulate the motion of the solute-solvent interface that is governed by the solvent fluid velocity. Numerical examples show that our method can predict accurately the blow up time for a test example of curvature flow and reproduce the polymodal (e.g., dry and wet) states of hydration of some simple model molecular systems.

Numerical Treatment of Stokes Solvent Flow and Solute-Solvent Interfacial Dynamics for Nonpolar Molecules

PubMed Central

Sun, Hui; Zhou, Shenggao; Moore, David K.; Cheng, Li-Tien; Li, Bo

2015-01-01

We design and implement numerical methods for the incompressible Stokes solvent flow and solute-solvent interface motion for nonpolar molecules in aqueous solvent. The balance of viscous force, surface tension, and van der Waals type dispersive force leads to a traction boundary condition on the solute-solvent interface. To allow the change of solute volume, we design special numerical boundary conditions on the boundary of a computational domain through a consistency condition. We use a finite difference ghost fluid scheme to discretize the Stokes equation with such boundary conditions. The method is tested to have a second-order accuracy. We combine this ghost fluid method with the level-set method to simulate the motion of the solute-solvent interface that is governed by the solvent fluid velocity. Numerical examples show that our method can predict accurately the blow up time for a test example of curvature flow and reproduce the polymodal (e.g., dry and wet) states of hydration of some simple model molecular systems. PMID:27365866

Purification of dirucotide, a synthetic 17-aminoacid peptide, by ion exchange centrifugal partition chromatography.

PubMed

Boudesocque, Leslie; Forni, Luciano; Martinez, Agathe; Nuzillard, Jean-Marc; Giraud, Matthieu; Renault, Jean-Hugues

2017-09-01

Dirucotide is a synthetic drug candidate for the treatment of multiple sclerosis. This 17-aminoacid peptide was successfully purified by ion exchange centrifugal partition chromatography. The optimized conditions involved the biphasic methyl tert-butyl ether/acetonitrile/n-butanol/water (2:1:2:5, v/v) solvent system in the descending mode, the di(2-ethylhexyl)phosphoric acid cation-exchanger with an exchanger (di(2-ethylhexyl)phosphoric acid)/dirucotide mole ratio of 100 and Ca 2+ ions in aqueous solution as displacer. Critical impurities were efficiently eliminated and dirucotide was recovered in high yield and purity (69% and 98%, respectively) and with a productivity of 2.29g per liter of stationary phase per hour. Copyright © 2017 Elsevier B.V. All rights reserved.

Modulation of phase transition of thermosensitive liposomes with leucine zipper-structured lipopeptides.

PubMed

Xu, Xiejun; Xiao, Xingqing; Wang, Yiming; Xu, Shouhong; Liu, Honglai

2018-06-13

Targeted therapy for cancer requires thermosensitive components in drug carriers for controlled drug release against viral cells. The conformational transition characteristic of leucine zipper-structured lipopeptides is utilized in our lab to modulate the phase transition temperature of liposomes, thus achieving temperature-responsive control. In this study, we computationally examined the conformational transition behaviors of leucine zipper-structured lipopeptides that were modified at the N-terminus by distinct functional groups. The conformational transition temperatures of these lipopeptides were determined by structural analysis of the implicit-solvent replica exchange molecular dynamics simulation trajectories using the dihedral angle principal component analysis and the dictionary of protein secondary structure method. Our calculations revealed that the computed transition temperatures of the lipopeptides are in good agreement with the experimental measurements. The effect of hydrogen bonds on the conformational stability of the lipopeptide dimers was examined in conventional explicit-solvent molecular dynamics simulations. A quantitative correlation of the degree of structural dissociation of the dimers and their binding strength is well described by an exponential fit of the binding free energies to the conformation transition temperatures of the lipopeptides.

The influence of anharmonic and solvent effects on the theoretical vibrational spectra of the guanine-cytosine base pairs in Watson-Crick and Hoogsteen configurations.

PubMed

Bende, Attila; Muntean, Cristina M

2014-03-01

The theoretical IR and Raman spectra of the guanine-cytosine DNA base pairs in Watson-Crick and Hoogsteen configurations were computed using DFT method with M06-2X meta-hybrid GGA exchange-correlation functional, including the anharmonic corrections and solvent effects. The results for harmonic frequencies and their anharmonic corrections were compared with our previously calculated values obtained with the B3PW91 hybrid GGA functional. Significant differences were obtained for the anharmonic corrections calculated with the two different DFT functionals, especially for the stretching modes, while the corresponding harmonic frequencies did not differ considerable. For the Hoogtseen case the H⁺ vibration between the G-C base pair can be characterized as an asymmetric Duffing oscillator and therefore unrealistic anharmonic corrections for normal modes where this proton vibration is involved have been obtained. The spectral modification due to the anharmonic corrections, solvent effects and the influence of sugar-phosphate group for the Watson-Crick and Hoogsteen base pair configurations, respectively, were also discussed. For the Watson-Crick case also the influence of the stacking interaction on the theoretical IR and Raman spectra was analyzed. Including the anharmonic correction in our normal mode analysis is essential if one wants to obtain correct assignments of the theoretical frequency values as compared with the experimental spectra.

DNA Recombinase Proteins, their Function and Structure in the Active Form, a Computational Study

NASA Technical Reports Server (NTRS)

Carra, Claudio; Cucinotta, Francis A.

2007-01-01

Homologous recombination is a crucial sequence of reactions in all cells for the repair of double strand DNA (dsDNA) breaks. While it was traditionally considered as a means for generating genetic diversity, it is now known to be essential for restart of collapsed replication forks that have met a lesion on the DNA template (Cox et al., 2000). The central stage of this process requires the presence of the DNA recombinase protein, RecA in bacteria, RadA in archaea, or Rad51 in eukaryotes, which leads to an ATP-mediated DNA strand-exchange process. Despite many years of intense study, some aspects of the biochemical mechanism, and structure of the active form of recombinase proteins are not well understood. Our theoretical study is an attempt to shed light on the main structural and mechanistic issues encountered on the RecA of the e-coli, the RecA of the extremely radio resistant Deinococcus Radiodurans (promoting an inverse DNA strand-exchange repair), and the homolog human Rad51. The conformational changes are analyzed for the naked enzymes, and when they are linked to ATP and ADP. The average structures are determined over 2ns time scale of Langevian dynamics using a collision frequency of 1.0 ps(sup -1). The systems are inserted in an octahedron periodic box with a 10 Angstrom buffer of water molecules explicitly described by the TIP3P model. The corresponding binding free energies are calculated in an implicit solvent using the Poisson-Boltzmann solvent accessible surface area, MM-PBSA model. The role of the ATP is not only in stabilizing the interaction RecA-DNA, but its hydrolysis is required to allow the DNA strand-exchange to proceed. Furthermore, we extended our study, using the hybrid QM/MM method, on the mechanism of this chemical process. All the calculations were performed using the commercial code Amber 9.

Formation Kinetics of Aqueous Suspensions of Fullerenes:Meeting in New Orleans.

EPA Science Inventory

Stable colloidal suspension of C60 is commonly achieved through various solvent exchange techniques. Nevertheless, the additives such as tetrahydrofuran may be retained in the C60 aggregates, which may influence the surface properties of the suspension. In this study, colloidal...

Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents?

PubMed

Sánchez-Lozano, Marta; Otero, Nicolás; Hermida-Ramón, Jose M; Estévez, Carlos M; Mandado, Marcos

2011-03-17

The impact of the solvent environment on the stabilization of the complexes formed by fluorine (T-F) and cyanide (T-CN) substituted tweezers with halide anions has been investigated theoretically. The study was carried out using computational methodologies based on density functional theory (DFT) and symmetry adapted perturbation theory (SAPT). Interaction energies were obtained at the M05-2X/6-31+G* level. The obtained results show a large stability of the complexes in solvents with large dielectric constant and prove the suitability of these molecular tweezers as potential hosts for anion recognition in solution. A detailed analysis of the effects of the solvent on the electron withdrawing ability of the substituents and its influence on the complex stability has been performed. In particular, the interaction energy in solution was split up into intermonomer and solvent-complex terms. In turn, the intermonomer interaction energy was partitioned into electrostatic, exchange, and polarization terms. Polar resonance structures in T-CN complexes are favored by polar solvents, giving rise to a stabilization of the intermonomer interaction, the opposite is found for T-F complexes. The solvent-complex energy increases with the polarity of the solvent in T-CN complexes, nonetheless the energy reaches a maximum and then decreases slowly in T-F complexes. An electron density analysis was also performed before and after complexation, providing an explanation to the trends followed by the interaction energies and their different components in solution.

Dynamics of liquids, molecules, and proteins measured with ultrafast 2D IR vibrational echo chemical exchange spectroscopy.

PubMed

Fayer, M D

2009-01-01

A wide variety of molecular systems undergo fast structural changes under thermal equilibrium conditions. Such transformations are involved in a vast array of chemical problems. Experimentally measuring equilibrium dynamics is a challenging problem that is at the forefront of chemical research. This review describes ultrafast 2D IR vibrational echo chemical exchange experiments and applies them to several types of molecular systems. The formation and dissociation of organic solute-solvent complexes are directly observed. The dissociation times of 13 complexes, ranging from 4 ps to 140 ps, are shown to obey a relationship that depends on the complex's formation enthalpy. The rate of rotational gauche-trans isomerization around a carbon-carbon single bond is determined for a substituted ethane at room temperature in a low viscosity solvent. The results are used to obtain an approximate isomerization rate for ethane. Finally, the time dependence of a well-defined single structural transformation of a protein is measured.

Artificial muscles driven by the cooperative actuation of electrochemical molecular machines. Persistent discrepancies and challenges

NASA Astrophysics Data System (ADS)

Otero

2017-10-01

Here we review the persisting conceptual discrepancies between different research groups working on artificial muscles based on conducting polymers and other electroactive material. The basic question is if they can be treated as traditional electro-mechanical (physical) actuators driven by electric fields and described by some adaptation of their physical models or if, replicating natural muscles, they are electro-chemo-mechanical actuators driven by electrochemical reaction of the constitutive molecular machines: the polymeric chains. In that case the charge consumed by the reaction will control the volume variation of the muscular material and the motor displacement, following the basic and single Faraday's laws: the charge consumed by the reaction determines the number of exchanged ions and solvent, the film volume variation to lodge/expel them and the amplitude of the movement. Deviations from the linear relationships are due to the osmotic exchange of solvent and to the presence of parallel reactions from the electrolyte, which originate creeping effects. Challenges and limitations are underlined.

Hydrogen Exchange During Cell-Free Incorporation of Deuterated Amino Acids and an Approach to its Inhibition

PubMed Central

Tonelli, M.; Singarapu, K. K.; Markley, J. L.; Makino, S.; Sahu, S .C.; Matsubara, Y.; Endo, Y.; Kainosho, M.

2012-01-01

Perdeuteration, selective deuteration, and stereo array isotope labeling (SAIL) are valuable strategies for NMR studies of larger proteins and membrane proteins. To minimize scrambling of the label, it is best to use cell-free methods to prepare selectively labeled proteins. However, when proteins are prepared from deuterated amino acids by cell-free translation in H2O, exchange reactions can lead to contamination of 2H sites by 1H from the solvent. Examination of a sample of SAIL-chlorella ubiquitin prepared by Escherichia coli cell-free synthesis revealed that exchange had occurred at several residues (mainly at Gly, Ala, Asp, Asn, Glu, and Gln). We present results from a study aimed at identifying the exchanging sites and level of exchange and at testing a strategy for minimizing 1H contamination during wheat germ cell-free translation of proteins produced from deuterated amino acids by adding known inhibitors of transaminases (1 mM aminooxyacetic acid) and glutamate synthetase (0.1 mM L-methionine sulfoximine). By using a wheat germ cell-free expression system, we produced [U-2H,15N]-chlorella ubiquitin without and with added inhibitors, and [U-15N]-chlorella ubiquitin as a reference to determine the extent of deuterium incorporation. We also prepared a sample of [U-13C,15N]-chlorella ubiquitin, for use in assigning the sites of exchange. The added inhibitors did not reduce the protein yield and were successful in blocking hydrogen exchange at Cα sites with the exception of Gly. We discovered, in addition, that partial exchange occurred with or without the inhibitors at certain side-chain methyl and methylene groups: Ala-Hβ, Asn-Hβ, Asp-Hβ, Gln-Hγ, Glu-Hγ, and Lys-Hε. The side-chain labeling pattern, in particular the mixed chiral labeling resulting from partial exchange at certain sites, should be of interest in studies of large proteins, protein complexes, and membrane proteins. PMID:21984356

Rapid Estimation of Tocopherol Content in Linseed and Sunflower Oils-Reactivity and Assay.

PubMed

Prevc, Tjaša; Levart, Alenka; Cigić, Irena Kralj; Salobir, Janez; Ulrih, Nataša Poklar; Cigić, Blaž

2015-08-13

The reactivity of tocopherols with 2,2-diphenyl-1-picrylhydrazyl (DPPH) was studied in model systems in order to establish a method for quantifying vitamin E in plant oils. The method was optimized with respect to solvent composition of the assay medium, which has a large influence on the course of reaction of tocopherols with DPPH. The rate of reaction of α-tocopherol with DPPH is higher than that of γ-tocopherol in both protic and aprotic solvents. In ethyl acetate, routinely applied for the analysis of antioxidant potential (AOP) of plant oils, reactions of tocopherols with DPPH are slower and concentration of tocopherols in the assay has a large influence on their molar reactivity. In 2-propanol, however, two electrons are exchanged for both α- and γ-tocopherols, independent of their concentration. 2-propanol is not toxic and is fully compatible with polypropylene labware. The chromatographically determined content of tocopherols and their molar reactivity in the DPPH assay reveal that only tocopherols contribute to the AOP of sunflower oil, whereas the contribution of tocopherols to the AOP of linseed oil is 75%. The DPPH assay in 2-propanol can be applied for rapid and cheap estimation of vitamin E content in plant oils where tocopherols are major antioxidants.

A quantum mechanical-Poisson-Boltzmann equation approach for studying charge flow between ions and a dielectric continuum

NASA Astrophysics Data System (ADS)

Gogonea, Valentin; Merz, Kenneth M.

2000-02-01

This paper presents a theoretical model for the investigation of charge transfer between ions and a solvent treated as a dielectric continuum media. The method is a combination of a semiempirical effective Hamiltonian with a modified Poisson-Boltzmann equation which includes charge transfer in the form of a surface charge density positioned at the dielectric interface. The new Poisson-Boltzmann equation together with new boundary conditions results in a new set of equations for the electrostatic potential (or polarization charge densities). Charge transfer adds a new free energy component to the solvation free energy term, which accounts for all interactions between the transferred charge at the dielectric interface, the solute wave function and the solvent polarization charges. Practical calculations on a set of 19 anions and 17 cations demonstrate that charge exchange with a dielectric is present and it is in the range of 0.06-0.4 eu. Furthermore, the pattern of the magnitudes of charge transfer can be related to the acid-base properties of the ions in many cases, but exceptions are also found. Finally, we show that the method leads to an energy decomposition scheme of the total electrostatic energy, which can be used in mechanistic studies on protein and DNA interaction with water.

System and method for treatment of a flue gas

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

Spiry, Irina Pavlovna; Wood, Benjamin Rue; Singh, Surinder Prabhjot

A method for treatment of a flue gas involves feeding the flue gas and a lean solvent to an absorber. The method further involves reacting the flue gas with the lean solvent within the absorber to generate a clean flue gas and a rich solvent. The method also involves feeding the clean flue gas from the absorber and water from a source, to a wash tower to separate a stripped portion of the lean solvent from the clean flue gas to generate a washed clean flue gas and a mixture of the water and the stripped portion of the leanmore » solvent. The method further involves treating at least a portion of the mixture of the water and the stripped portion of the lean solvent via a separation system to separate the water from the stripped portion of the lean solvent.« less

Structural and theoretical basis for ligand exchange on thiolate monolayer protected gold nanoclusters.

PubMed

Heinecke, Christine L; Ni, Thomas W; Malola, Sami; Mäkinen, Ville; Wong, O Andrea; Häkkinen, Hannu; Ackerson, Christopher J

2012-08-15

Ligand exchange reactions are widely used for imparting new functionality on or integrating nanoparticles into devices. Thiolate-for-thiolate ligand exchange in monolayer protected gold nanoclusters has been used for over a decade; however, a firm structural basis of this reaction has been lacking. Herein, we present the first single-crystal X-ray structure of a partially exchanged Au(102)(p-MBA)(40)(p-BBT)(4) (p-MBA = para-mercaptobenzoic acid, p-BBT = para-bromobenzene thiol) with p-BBT as the incoming ligand. The crystal structure shows that 2 of the 22 symmetry-unique p-MBA ligand sites are partially exchanged to p-BBT under the initial fast kinetics in a 5 min timescale exchange reaction. Each of these ligand-binding sites is bonded to a different solvent-exposed Au atom, suggesting an associative mechanism for the initial ligand exchange. Density functional theory calculations modeling both thiol and thiolate incoming ligands postulate a mechanistic pathway for thiol-based ligand exchange. The discrete modification of a small set of ligand binding sites suggests Au(102)(p-MBA)(44) as a powerful platform for surface chemical engineering.

Ultrafast hydrogen exchange reveals specific structural events during the initial stages of folding of cytochrome c.

PubMed

Fazelinia, Hossein; Xu, Ming; Cheng, Hong; Roder, Heinrich

2014-01-15

Many proteins undergo a sharp decrease in chain dimensions during early stages of folding, prior to the rate-limiting step in folding. However, it remains unclear whether compact states are the result of specific folding events or a general hydrophobic collapse of the poly peptide chain driven by the change in solvent conditions. To address this fundamental question, we extended the temporal resolution of NMR-detected H/D exchange labeling experiments into the microsecond regime by adopting a microfluidics approach. By observing the competition between H/D exchange and folding as a function of labeling pH, coupled with direct measurement of exchange rates in the unfolded state, we were able to monitor hydrogen-bond formation for over 50 individual backbone NH groups within the initial 140 microseconds of folding of horse cytochrome c. Clusters of solvent-shielded amide protons were observed in two α-helical segments in the C-terminal half of the protein, while the N-terminal helix remained largely unstructured, suggesting that proximity in the primary structure is a major factor in promoting helix formation and association at early stages of folding, while the entropically more costly long-range contacts between the N- and C-terminal helices are established only during later stages. Our findings clearly indicate that the initial chain condensation in cytochrome c is driven by specific interactions among a subset of α-helical segments rather than a general hydrophobic collapse.

CO2-Binding Organic Liquids Gas Capture with Polarity-Swing-Assisted Regeneration Full Technology Feasibility Study B1 - Solvent-based Systems

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

Heldebrant, David J

PNNL, Fluor Corporation and Queens University (Kingston, ON) successfully completed a three year comprehensive study of the CO2BOL water-lean solvent platform with Polarity Swing Assisted Regeneration (PSAR). This study encompassed solvent synthesis, characterization, environmental toxicology, physical, thermodynamic and kinetic property measurements, Aspen Plus™ modeling and bench-scale testing of a candidate CO2BOL solvent molecule. Key Program Findings The key program findings are summarized as follows: • PSAR favorably reduced stripper duties and reboiler temperatures with little/no impact to absorption column • >90% CO2 capture was achievable at reasonable liquid-gas ratios in the absorber • High rich solvent viscosities (up to 600more » cP) were successfully demonstrated in the bench-scale system. However, the projected impacts of high viscosity to capital cost and operational limits compromised the other levelized cost of electricity benefits. • Low thermal conductivity of organics significantly increased the required cross exchanger surface area, and potentially other heat exchange surfaces. • CO2BOL had low evaporative losses during bench-scale testing • There was no evidence of foaming during bench scale testing • Current CO2BOL formulation costs project to be $35/kg • Ecotoxicity (Water Daphnia) was comparable between CO2BOL and MEA (169.47 versus 103.63 mg/L) • Full dehydration of the flue gas was determined to not be economically feasible. However, modest refrigeration (13 MW for the 550 MW reference system) was determined to be potentially economically feasible, and still produce a water-lean condition for the CO2BOLs (5 wt% steady-state water loading). • CO2BOLs testing with 5 wt% water loading did not compromise anhydrous performance behavior, and showed actual enhancement of CO2 capture performance. • Mass transfer of CO2BOLs was not greatly impeded by viscosity • Facile separation of antisolvent from lean CO2BOL was demonstrated on the bench cart • No measurable solvent degradation was observed over 4 months of testing – even with 5 wt% water present« less

Preparative isolation and purification of capsaicin and dihydrocapsaicin from Capsici Fructus using supercritical fluid extraction combined with high speed countercurrent chromatography.

PubMed

Yan, Rongwei; Zhao, Leilei; Tao, Junfei; Zou, Yong; Xu, Xinjun

2018-05-01

Supercritical fluid extraction with CO 2 (SFE-CO 2 ) was utilized for extraction of capsaicin (CA) and dihydrocapsaicin (DHCA) from Capsici Fructus, and then a two-step enrichment method for separating capsaicinoids from SFE-CO 2 extracts was developed. The process involved extraction with aqueous methanol and crystallization by alkali extraction and acid precipitation. Finally, a consecutive high-speed countercurrent chromatography (HSCCC) separation method was successfully applied in the purification of CA and DHCA from capsaicinoid crystal. The extraction pressure, extraction temperature and volume of co-solvent were optimized at 33 MPa, 41 °C and 75 mL, respectively, using response surface methodology; the extraction rates of CA and DHCA were about 93.18% and 93.49%, respectively. 407.43 mg capsaicinoid crystal was isolated from the SFE-CO 2 extracts obtained from 100 g capsicum powder by the two-step enrichment method. About 506 mg and 184 mg CA and DHCA with purities up to 98.31% and 96.68%, respectively, were obtained from 1 g capsaicinoid crystal in one HSCCC of three consecutive sample loadings without exchanging any solvent system. This method comprising SFE-CO 2 , a two-step enrichment and HSCCC was efficient, powerful and practical for the large-scale preparation of CA and DHCA from Capsici Fructus with high purity and high yield. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Inkjet printing of 2D layered materials.

PubMed

Li, Jiantong; Lemme, Max C; Östling, Mikael

2014-11-10

Inkjet printing of 2D layered materials, such as graphene and MoS2, has attracted great interests for emerging electronics. However, incompatible rheology, low concentration, severe aggregation and toxicity of solvents constitute critical challenges which hamper the manufacturing efficiency and product quality. Here, we introduce a simple and general technology concept (distillation-assisted solvent exchange) to efficiently overcome these challenges. By implementing the concept, we have demonstrated excellent jetting performance, ideal printing patterns and a variety of promising applications for inkjet printing of 2D layered materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Allantoin as a solid phase adsorbent for removing endotoxins.

PubMed

Vagenende, Vincent; Ching, Tim-Jang; Chua, Rui-Jing; Gagnon, Pete

2013-10-04

In this study we present a simple and robust method for removing endotoxins from protein solutions by using crystals of the small-molecule compound 2,5-dioxo-4-imidazolidinyl urea (allantoin) as a solid phase adsorbent. Allantoin crystalline powder is added to a protein solution at supersaturated concentrations, endotoxins bind and undissolved allantoin crystals with bound endotoxins are removed by filtration or centrifugation. This method removes an average of 99.98% endotoxin for 20 test proteins. The average protein recovery is ∼80%. Endotoxin binding is largely independent of pH, conductivity, reducing agent and various organic solvents. This is consistent with a hydrogen-bond based binding mechanism. Allantoin does not affect protein activity and stability, and the use of allantoin as a solid phase adsorbent provides better endotoxin removal than anion exchange, polymixin affinity and biological affinity methods for endotoxin clearance. Copyright © 2013 Elsevier B.V. All rights reserved.

Pilot-Scale Silicone Process for Low-Cost Carbon Dioxide Capture Preliminary Techno-Economic Analysis

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

Singh, Surinder; Spiry, Irina; Wood, Benjamin

This report presents system and economic analysis for a carbon-capture unit which uses an aminosilicone-based solvent for CO{sub 2} capture in a pulverized coal (PC) boiler. The aminosilicone solvent is a 60/40 wt/wt mixture of 3-aminopropyl end-capped polydimethylsiloxane (GAP-1m) with tri-ethylene glycol (TEG) as a co-solvent. For comparison purposes, the report also shows results for a carbon-capture unit based on a conventional approach using mono-ethanol amine (MEA). The first year removal cost of CO{sub 2} for the aminosilicone-based carbon-capture process ismore » $46.04/ton of CO2 as compared to $$60.25/ton of CO{sub 2} when MEA is used. The aminosilicone-based process has <77% of the CAPEX of a system using MEA solvent. The lower CAPEX is due to several factors, including the higher working capacity of the aminosilicone solvent compared the MEA, which reduces the solvent flow rate required, reducing equipment sizes. If it is determined that carbon steel can be used in the rich-lean heat exchanger in the carbon capture unit, the first year removal cost of CO{sub 2} decreases to $$44.12/ton. The aminosilicone-based solvent has a higher thermal stability than MEA, allowing desorption to be conducted at higher temperatures and pressures, decreasing the number of compressor stages needed. The aminosilicone-based solvent also has a lower vapor pressure, allowing the desorption to be conducted in a continuous-stirred tank reactor versus a more expensive packed column. The aminosilicone-based solvent has a lower heat capacity, which decreases the heat load on the desorber. In summary, the amino-silicone solvent has significant advantages over conventional systems using MEA.« less

Pilot-Scale Silicone Process for Low-Cost Carbon Dioxide Capture

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

Singh, Surinder; Spiry, Irina; Wood, Benjamin

This report presents system and economicanalysis for a carbon-capture unit which uses an aminosilicone-based solvent for CO₂ capture in a pulverized coal (PC) boiler. The aminosilicone solvent is a 60/40 wt/wt mixture of 3-aminopropyl end-capped polydimethylsiloxane (GAP-1m) with tri-ethylene glycol (TEG) as a co-solvent. Forcomparison purposes, the report also shows results for a carbon-capture unit based on a conventional approach using mono-ethanol amine (MEA). The first year removal cost of CO₂ for the aminosilicone-based carbon-capture process is $46.04/ton of CO₂ as compared to $60.25/ton of CO₂ when MEA is used. The aminosilicone- based process has <77% of the CAPEX ofmore » a system using MEA solvent. The lower CAPEX is due to several factors, including the higher working capacity of the aminosilicone solvent compared the MEA, which reduces the solvent flow rate required, reducing equipment sizes. If it is determined that carbon steel can be used in the rich-lean heat exchanger in the carbon capture unit, the first year removal cost of CO₂ decreases to $44.12/ton. The aminosilicone-based solvent has a higherthermal stability than MEA, allowing desorption to be conducted at higher temperatures and pressures, decreasing the number of compressor stages needed. The aminosilicone-based solvent also has a lowervapor pressure, allowing the desorption to be conducted in a continuous-stirred tank reactor versus a more expensive packed column. The aminosilicone-based solvent has a lowerheat capacity, which decreases the heat load on the desorber. In summary, the amino-silicone solvent has significant advantages overconventional systems using MEA.« less

Dissolution of covalent adaptable network polymers in organic solvent

NASA Astrophysics Data System (ADS)

Yu, Kai; Yang, Hua; Dao, Binh H.; Shi, Qian; Yakacki, Christopher M.

2017-12-01

It was recently reported that thermosetting polymers can be fully dissolved in a proper organic solvent utilizing a bond-exchange reaction (BER), where small molecules diffuse into the polymer, break the long polymer chains into short segments, and eventually dissolve the network when sufficient solvent is provided. The solvent-assisted dissolution approach was applied to fully recycle thermosets and their fiber composites. This paper presents the first multi-scale modeling framework to predict the dissolution kinetics and mechanics of thermosets in organic solvent. The model connects the micro-scale network dynamics with macro-scale material properties: in the micro-scale, a model is developed based on the kinetics of BERs to describe the cleavage rate of polymer chains and evolution of chain segment length during the dissolution. The micro-scale model is then fed into a continuum-level model with considerations of the transportation of solvent molecules and chain segments in the system. The model shows good prediction on conversion rate of functional groups, degradation of network mechanical properties, and dissolution rate of thermosets during the dissolution. It identifies the underlying kinetic factors governing the dissolution process, and reveals the influence of different material and processing variables on the dissolution process, such as time, temperature, catalyst concentration, and chain length between cross-links.

Simplified NaCl based (68)Ga concentration and labeling procedure for rapid synthesis of (68)Ga radiopharmaceuticals in high radiochemical purity.

PubMed

Mueller, Dirk; Klette, Ingo; Baum, Richard P; Gottschaldt, M; Schultz, Michael K; Breeman, Wouter A P

2012-08-15

A simple sodium chloride (NaCl) based (68)Ga eluate concentration and labeling method that enables rapid, high-efficiency labeling of DOTA conjugated peptides in high radiochemical purity is described. The method utilizes relatively few reagents and comprises minimal procedural steps. It is particularly well-suited for routine automated synthesis of clinical radiopharmaceuticals. For the (68)Ga generator eluate concentration step, commercially available cation-exchange cartridges and (68)Ga generators were used. The (68)Ga generator eluate was collected by use of a strong cation exchange cartridge. 98% of the total activity of (68)Ga was then eluted from the cation exchange cartridge with 0.5 mL of 5 M NaCl solution containing a small amount of 5.5 M HCl. After buffering with ammonium acetate, the eluate was used directly for radiolabeling of DOTATOC and DOTATATE. The (68)Ga-labeled peptides were obtained in higher radiochemical purity compared to other commonly used procedures, with radiochemical yields greater than 80%. The presence of (68)Ge could not be detected in the final product. The new method obviates the need for organic solvents, which eliminates the required quality control of the final product by gas chromatography, thereby reducing postsynthesis analytical effort significantly. The (68)Ga-labeled products were used directly, with no subsequent purification steps, such as solid-phase extraction. The NaCl method was further evaluated using an automated fluid handling system and it routinely facilitates radiochemical yields in excess of 65% in less than 15 min, with radiochemical purity consistently greater than 99% for the preparation of (68)Ga-DOTATOC.

Supercritical CO2 Cleaning System for Planetary Protection and Contamination Control Applications

NASA Technical Reports Server (NTRS)

Lin, Ying; Zhong, Fang; Aveline, David C.; Anderson, Mark S.

2012-01-01

Current spacecraft-compatible cleaning protocols involve a vapor degreaser, liquid sonication, and alcohol wiping. These methods are not very effective in removing live and dead microbes from spacecraft piece parts of slightly complicated geometry, such as tubing and loosely fitted nuts and bolts. Contamination control practices are traditionally focused on cleaning and monitoring of particulate and oily residual. Vapor degreaser and outgassing bakeout have not been proven to be effective in removing some less volatile, hydrophilic biomolecules of significant relevance to life detection. A precision cleaning technology was developed using supercritical CO2 (SCC). SCC is used as both solvent and carrier for removing organic and particulate contaminants. Supercritical fluid, like SCC, is characterized by physical and thermal properties that are between those of the pure liquid and gas phases. The fluid density is a function of the temperature and pressure. Its solvating power can be adjusted by changing the pressure or temperature, or adding a secondary solvent such as alcohol or water. Unlike a regular organic solvent, SCC has higher diffusivities, lower viscosity, and lower surface tension. It readily penetrates porous and fibrous solids and can reach hard-to-reach surfaces of the parts with complex geometry. Importantly, the CO2 solvent does not leave any residue. The results using this new cleaning device demonstrated that both supercritical CO2 with 5% water as a co-solvent can achieve cleanliness levels of 0.01 mg/cm2 or less for contaminants of a wide range of hydrophobicities. Experiments under the same conditions using compressed Martian air mix, which consists of 95% CO2, produced similar cleaning effectiveness on the hydrophobic compounds. The main components of the SCC cleaning system are a high-pressure cleaning vessel, a boil-off vessel located downstream from the cleaning vessel, a syringe-type high-pressure pump, a heat exchanger, and a back pressure regulator (BPR). After soaking the parts to be cleaned in the clean vessel for a period, the CO2 with contaminants is flushed out of the cleaning vessel using fresh CO2 in a first-in-first-out (FIFO) method. The contaminants are either precipitating out in the boil-off container or being trapped in a filter subsystem. The parts to be cleaned are secured in a basket inside and can be rotated up to 1,400 rpm by a magnetic drive. The fluid flows within the vessel generate tangential forces on the parts surfaces, enhancing the cleaning effectiveness and shortening the soaking time. During the FIFO flushing, the pump subsystem pushes fresh CO2 into the cleaning vessel at a constant flow rate between 0.01 and 200 mL/min, while the BPR regulates the pressure in the cleaning vessel to within 0.1 bar by controlling the needle position in an outlet valve. The fresh CO2 gas flows through the heat exchanger at a given temperature before entering the cleaning vessel. A platinum resistance thermometer (PRT) reads the cleaning vessel interior temperature that can be controlled to within 0.1 K. As a result, cleaning vessel temperature remains constant during the FIFO flushing. There is no change in solvent power during FIFO flushing since both temperature and pressure inside the cleaning vessel remain unchanged, thus minimizing contaminants left behind. During decompression, both temperature and pressure are strictly controlled to prevent bubbles from generating in the cleaning vessel that could stir up the contaminants that sank to the bottom by gravity.

Challenges in preparing, preserving and detecting para-water in bulk: overcoming proton exchange and other hurdles.

PubMed

Mammoli, Daniele; Salvi, Nicola; Milani, Jonas; Buratto, Roberto; Bornet, Aurélien; Sehgal, Akansha Ashvani; Canet, Estel; Pelupessy, Philippe; Carnevale, Diego; Jannin, Sami; Bodenhausen, Geoffrey

2015-10-28

Para-water is an analogue of para-hydrogen, where the two proton spins are in a quantum state that is antisymmetric under permutation, also known as singlet state. The populations of the nuclear spin states in para-water are believed to have long lifetimes just like other Long-Lived States (LLSs). This hypothesis can be verified by measuring the relaxation of an excess or a deficiency of para-water, also known as a "Triplet-Singlet Imbalance" (TSI), i.e., a difference between the average population of the three triplet states T (that are symmetric under permutation) and the population of the singlet state S. In analogy with our recent findings on ethanol and fumarate, we propose to adapt the procedure for Dissolution Dynamic Nuclear Polarization (D-DNP) to prepare such a TSI in frozen water at very low temperatures in the vicinity of 1.2 K. After rapid heating and dissolution using an aprotic solvent, the TSI should be largely preserved. To assess this hypothesis, we studied the lifetime of water as a molecular entity when diluted in various solvents. In neat liquid H2O, proton exchange rates have been characterized by spin-echo experiments on oxygen-17 in natural abundance, with and without proton decoupling. One-dimensional exchange spectroscopy (EXSY) has been used to study proton exchange rates in H2O, HDO and D2O mixtures diluted in various aprotic solvents. In the case of 50 mM H2O in dioxane-d8, the proton exchange lifetime is about 20 s. After dissolving, one can observe this TSI by monitoring intensities in oxygen-17 spectra of H2O (if necessary using isotopically enriched samples) where the AX2 system comprising a "spy" oxygen A and two protons X2 gives rise to binomial multiplets only if the TSI vanishes. Alternatively, fast chemical addition to a suitable substrate (such as an activated aldehyde or ketone) can provide AX2 systems where a carbon-13 acts as a spy nucleus. Proton signals that relax to equilibrium with two distinct time constants can be considered as a hallmark of a TSI. We optimized several experimental procedures designed to preserve and reveal dilute para-water in bulk.

Individual Basepair Stability of DNA and RNA Studied by NMR-Detected Solvent Exchange

PubMed Central

Steinert, Hannah S.; Rinnenthal, Jörg; Schwalbe, Harald

2012-01-01

In this study, we have optimized NMR methodology to determine the thermodynamic parameters of basepair opening in DNA and RNA duplexes by characterizing the temperature dependence of imino proton exchange rates of individual basepairs. Contributions of the nuclear Overhauser effect to exchange rates measured with inversion recovery experiments are quantified, and the influence of intrinsic and external catalysis exchange mechanisms on the imino proton exchange rates is analyzed. Basepairs in DNA and RNA have an approximately equal stability, and the enthalpy and entropy values of their basepair dissociation are correlated linearly. Furthermore, the compensation temperature, Tc, which is derived from the slope of the correlation, coincides with the melting temperature, and duplex unfolding occurs at that temperature where all basepairs are equally thermodynamically stable. The impact of protium-deuterium exchange of the imino hydrogen on the free energy of RNA basepair opening is investigated, and it is found that two A·U basepairs show distinct fractionation factors. PMID:22713572

Determination of chlorophenols in honey samples using in-situ ionic liquid-dispersive liquid-liquid microextraction as a pretreatment method followed by high-performance liquid chromatography.

PubMed

Fan, Chen; Li, Nai; Cao, Xueli

2015-05-01

In-situ ionic liquid-dispersive liquid-liquid microextraction (IL-DLLME) method was developed as a pretreatment method for the detection of six chlorophenols (CPs) in honey samples. The hydrophobic ionic liquid [C4MIM][NTf2], formed in-situ by the hydrophilic ionic liquid [C4MIM][BF4] and the ion exchange reagent LiNTf2 was used as the microextractant solvent of CPs from honey sample. Then the enriched analytes were back-extracted into 40 μL of 0.14 M NaOH solution and finally subjected to analysis by high-performance liquid chromatography. The method showed low limit of detection of CPs, 0.8-3.2 μg/L and high enrichment factor, 34-65 with the recoveries range from 91.60% to 114.33%. The method is simple, rapid, environmentally friendly and with high extraction efficiency. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

Computational scheme for pH-dependent binding free energy calculation with explicit solvent.

PubMed

Lee, Juyong; Miller, Benjamin T; Brooks, Bernard R

2016-01-01

We present a computational scheme to compute the pH-dependence of binding free energy with explicit solvent. Despite the importance of pH, the effect of pH has been generally neglected in binding free energy calculations because of a lack of accurate methods to model it. To address this limitation, we use a constant-pH methodology to obtain a true ensemble of multiple protonation states of a titratable system at a given pH and analyze the ensemble using the Bennett acceptance ratio (BAR) method. The constant pH method is based on the combination of enveloping distribution sampling (EDS) with the Hamiltonian replica exchange method (HREM), which yields an accurate semi-grand canonical ensemble of a titratable system. By considering the free energy change of constraining multiple protonation states to a single state or releasing a single protonation state to multiple states, the pH dependent binding free energy profile can be obtained. We perform benchmark simulations of a host-guest system: cucurbit[7]uril (CB[7]) and benzimidazole (BZ). BZ experiences a large pKa shift upon complex formation. The pH-dependent binding free energy profiles of the benchmark system are obtained with three different long-range interaction calculation schemes: a cutoff, the particle mesh Ewald (PME), and the isotropic periodic sum (IPS) method. Our scheme captures the pH-dependent behavior of binding free energy successfully. Absolute binding free energy values obtained with the PME and IPS methods are consistent, while cutoff method results are off by 2 kcal mol(-1) . We also discuss the characteristics of three long-range interaction calculation methods for constant-pH simulations. © 2015 The Protein Society.

On the dynamics of water molecules at the protein solute interfaces.

PubMed

Bernini, A; Spiga, O; Ciutti, A; Chiellini, S; Menciassi, N; Venditti, V; Niccolai, N

2004-10-01

Proteins, with the large variety of chemical groups they present at their molecular surface, are a class of molecules which can be very informative on most of the possible solute-solvent interactions. Hen egg white lysozyme has been used as a probe to investigate the complex solvent dynamics occurring at the protein surface, by analysing the results obtained from Nuclear Magnetic Resonance, X-ray diffractometry and Molecular Dynamics simulations. A consistent overall picture for the dynamics of water molecules close to the protein is obtained, suggesting that a rapid exchange occurs, in a picosecond timescale, among all the possible hydration surface sites both in solution and the solid state, excluding the possibility that solvent molecules can form liquid-crystal-like supramolecular adducts, which have been proposed as a molecular basis of 'memory of water'.

Aminosilicone solvent recovery methods and systems

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

Spiry, Irina Pavlovna; Perry, Robert James; Wood, Benjamin Rue

The present invention is directed to aminosilicone solvent recovery methods and systems. The methods and systems disclosed herein may be used to recover aminosilicone solvent from a carbon dioxide containing vapor stream, for example, a vapor stream that leaves an aminosilicone solvent desorber apparatus. The methods and systems of the invention utilize a first condensation process at a temperature from about 80.degree. C. to about 150.degree. C. and a second condensation process at a temperature from about 5.degree. C. to about 75.degree. C. The first condensation process yields recovered aminosilicone solvent. The second condensation process yields water.

X-Ray Fluorescence Solvent Detection at the Substrate-Adhesive Interface

NASA Technical Reports Server (NTRS)

Wurth, Laura; Evans, Kurt; Weber, Bart; Headrick, Sarah

2005-01-01

With environmental regulations limiting the use of volatile organic compounds, low-vapor pressure solvents have replaced traditional degreasing solvents for bond substrate preparation. When used to clean and prepare porous bond substrates such as phenolic composites, low vapor pressure solvents can penetrate deep into substrate pore networks and remain there for extended periods. Trapped solvents can interact with applied adhesives either prior to or during cure, potentially compromising bond properties. Currently, methods for characterizing solvent time-depth profiles in bond substrates are limited to bulk gravimetric or sectioning techniques. While sectioning techniques such as microtome allow construction of solvent depth profiles, their depth resolution and reliability are limited by substrate type. Sectioning techniques are particularly limited near the adhesive-substrate interface where depth resolution is further limited by adhesive-substrate hardness and, in the case of a partially cured adhesive, mechanical properties differences. Additionally, sectioning techniques cannot provide information about lateral solvent diffusion. Cross-section component mapping is an alternative method for measuring solvent migration in porous substrates that eliminates the issues associated with sectioning techniques. With cross-section mapping, the solvent-wiped substrate is sectioned perpendicular rather than parallel to the wiped surface, and the sectioned surface is analyzed for the solvent or solvent components of interest using a two-dimensional mapping or imaging technique. Solvent mapping can be performed using either direct or indirect methods. With a direct method, one or more solvent components are mapped using red or Raman spectroscopy together with a moveable sample stage and/or focal plane array detector. With an indirect method, an elemental "tag" not present in the substrate is added to the solvent before the substrate is wiped. Following cross sectioning, the tag element can then be mapped by its characteristic x-ray emission using either x-ray fluorescence, or electron-beam energy-and wavelength-dispersive x-ray spectrometry. The direct mapping techniques avoid issues of different diffusion or migration rates of solvents and elemental tags, while the indirect techniques avoid spectral resolution issues in cases where solvents and substrates have adjacent or overlapping peaks. In this study, cross-section component indirect mapping is being evaluated as a method for measuring migration of d-limonene based solvents in glass-cloth phenolic composite (GCP) prior to and during subsequent bonding and epoxy adhesive cure.

A Novel Method of Measuring the Phase Behavior and Rheology of Polyethylene Solutions Using a Multi-Pass Rheometer

NASA Astrophysics Data System (ADS)

Lee, Karen; Lacombe, Y.; Cheluget, E.

2008-07-01

The Advanced SCLAIRTECH™ Technology process is used to manufacture Linear Low Density Polyethylene using solution polymerization. In this process ethylene is polymerized in an inert solvent, which is subsequently evaporated and recycled. The reactor effluent in the process is a polymer solution containing the polyethylene product, which is separated from the solvent and unconverted ethylene/co-monomer before being extruded and pelletized. The design of unit operations in this process requires a detailed understanding of the thermophysical properties, phase behaviour and rheology of polymer containing streams at high temperature and pressure, and over a wide range of composition. This paper describes a device used to thermo-rheologically characterize polymer solutions under conditions prevailing in polymerization reactors, downstream heat exchangers and attendant phase separation vessels. The downstream processing of the Advanced SCLAIRTECH™ Technology reactor effluent occurs at temperatures and pressures near the critical point of the solvent and co-monomer mixture. In addition, the process trajectory encompasses regions of liquid-liquid and liquid-liquid-vapour co-existence, which are demarcated by a `cloud point' curve. Knowing the location of this phase boundary is essential for the design of downstream devolatilization processes and for optimizing operating conditions in existing plants. In addition, accurate solution rheology data are required for reliable equipment sizing and design. At NOVA Chemicals, a robust high-temperature and high-pressure-capable version of the Multi-Pass Rheometer (MPR) is used to provide data on solution rheology and phase boundary location. This sophisticated piece of equipment is used to quantify the effects of solvent types, comonomer, and free ethylene concentration on the properties of the reactor effluent. An example of the experimental methodology to characterize a polyethylene solution with hexane solvent, and the ethylene dosing technique developed for the MPR will be described. ™Advanced SCLAIRTECH is a trademark of NOVA Chemicals.

Acceleration of Lateral Equilibration in Mixed Lipid Bilayers Using Replica Exchange with Solute Tempering

PubMed Central

2015-01-01

The lateral heterogeneity of cellular membranes plays an important role in many biological functions such as signaling and regulating membrane proteins. This heterogeneity can result from preferential interactions between membrane components or interactions with membrane proteins. One major difficulty in molecular dynamics simulations aimed at studying the membrane heterogeneity is that lipids diffuse slowly and collectively in bilayers, and therefore, it is difficult to reach equilibrium in lateral organization in bilayer mixtures. Here, we propose the use of the replica exchange with solute tempering (REST) approach to accelerate lateral relaxation in heterogeneous bilayers. REST is based on the replica exchange method but tempers only the solute, leaving the temperature of the solvent fixed. Since the number of replicas in REST scales approximately only with the degrees of freedom in the solute, REST enables us to enhance the configuration sampling of lipid bilayers with fewer replicas, in comparison with the temperature replica exchange molecular dynamics simulation (T-REMD) where the number of replicas scales with the degrees of freedom of the entire system. We apply the REST method to a cholesterol and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) bilayer mixture and find that the lateral distribution functions of all molecular pair types converge much faster than in the standard MD simulation. The relative diffusion rate between molecules in REST is, on average, an order of magnitude faster than in the standard MD simulation. Although REST was initially proposed to study protein folding and its efficiency in protein folding is still under debate, we find a unique application of REST to accelerate lateral equilibration in mixed lipid membranes and suggest a promising way to probe membrane lateral heterogeneity through molecular dynamics simulation. PMID:25328493

Acceleration of Lateral Equilibration in Mixed Lipid Bilayers Using Replica Exchange with Solute Tempering.

PubMed

Huang, Kun; García, Angel E

2014-10-14

The lateral heterogeneity of cellular membranes plays an important role in many biological functions such as signaling and regulating membrane proteins. This heterogeneity can result from preferential interactions between membrane components or interactions with membrane proteins. One major difficulty in molecular dynamics simulations aimed at studying the membrane heterogeneity is that lipids diffuse slowly and collectively in bilayers, and therefore, it is difficult to reach equilibrium in lateral organization in bilayer mixtures. Here, we propose the use of the replica exchange with solute tempering (REST) approach to accelerate lateral relaxation in heterogeneous bilayers. REST is based on the replica exchange method but tempers only the solute, leaving the temperature of the solvent fixed. Since the number of replicas in REST scales approximately only with the degrees of freedom in the solute, REST enables us to enhance the configuration sampling of lipid bilayers with fewer replicas, in comparison with the temperature replica exchange molecular dynamics simulation (T-REMD) where the number of replicas scales with the degrees of freedom of the entire system. We apply the REST method to a cholesterol and 1,2-dipalmitoyl- sn -glycero-3-phosphocholine (DPPC) bilayer mixture and find that the lateral distribution functions of all molecular pair types converge much faster than in the standard MD simulation. The relative diffusion rate between molecules in REST is, on average, an order of magnitude faster than in the standard MD simulation. Although REST was initially proposed to study protein folding and its efficiency in protein folding is still under debate, we find a unique application of REST to accelerate lateral equilibration in mixed lipid membranes and suggest a promising way to probe membrane lateral heterogeneity through molecular dynamics simulation.

Replica-exchange molecular dynamics simulations of cellulose solvated in water and in the ionic liquid 1-butyl-3-methylimidazolium chloride

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

Mostofian, Barmak; Cheng, Xiaolin; Smith, Jeremy C.

2014-09-02

Ionic liquids have become a popular solvent for cellulose pretreatment in biorefineries due to their efficiency in dissolution and their reusability. Understanding the interactions between cations, anions, and cellulose is key to the development of better solvents and the improvement of pretreatment conditions. While previous studies described the interactions between ionic liquids and cellulose fibers, shedding light on the initial stages of the cellulose dissolution process, we study the end state of that process by exploring the structure and dynamics of a single cellulose decamer solvated in 1-butyl-3-methyl-imidazolium chloride (BmimCl) and in water using replica-exchange molecular dynamics. In both solvents,more » global structural features of the cellulose chain are similar. However, analyses of local structural properties show that cellulose explores greater conformational variability in the ionic liquid than in water. For instance, in BmimCl the cellulose intramolecular hydrogen bond O3H'••• O5 is disrupted more often resulting in greater flexibility of the solute. Our results indicate that the cellulose chain is more dynamic in BmimCl than in water, which may play a role in the favorable dissolution of cellulose in the ionic liquid. Here, the calculation of the configurational entropy of the cellulose decamer confirms its higher conformational flexibility in BmimCl than in water at elevated temperatures.« less

Supersonically Spray-Coated Colloidal Quantum Dot Ink Solar Cells

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

Choi, Hyekyoung; Lee, Jong-Gun; Mai, Xuan Dung

Controlling the thickness of quantum dot (QD) films is difficult using existing film formation techniques, which employ pre-ligand-exchanged PbS QD inks, because of several issues: 1) poor colloidal stability, 2) use of high-boiling-point solvents for QD dispersion, and 3) limitations associated with one-step deposition. Here in this paper, we suggest a new protocol for QD film deposition using electrical double-layered PbS QD inks, prepared by solution-phase ligand exchange using methyl ammonium lead iodide (MAPbI 3). The films are deposited by the supersonic spraying technique, which facilitates the rapid evaporation of the solvent and the subsequent deposition of the PbS QDmore » ink without requiring a post-deposition annealing treatment for solvent removal. The film thickness could be readily controlled by varying the number of spraying sweeps made across the substrate. This spray deposition process yields high-quality n-type QD films quickly (within 1 min) while minimizing the amount of the PbS QD ink used to less than 5 mg for one device (300-nm-thick absorbing layer, 2.5 x 2.5 cm 2). Further, the formation of an additional p-layer by treatment with mercaptopropionic acid allows for facile hole extraction from the QD films, resulting in a power conversion efficiency of 3.7% under 1.5 AM illumination.« less

Theoretical investigation on the dimerization of the deprotonated aquo ion of Al(III) in water.

PubMed

Qian, Zhaosheng; Feng, Hui; Zhang, Zhenjiang; Yang, Wenjing; Jin, Jing; Miao, Qiang; He, Lina; Bi, Shuping

2009-01-21

Reaction pathways, solvent effects and energy barriers have been investigated for the dimerization of the deprotonated aquo ion of Al(III) in aqueous solution by performing supramolecule density functional theory calculations. Two competing reaction pathways were investigated, sharing a common first step and third step, i.e. the formation of the aggregate II of two aluminium monomers and the doubly bridged dimer. One pathway involves a nucleophilic attack to undercoordinated metal center in the first step and then the loss of a coordinated water molecule. Another pathway involves a water exchange reaction in the first step and then the formation of the hydroxo bridge. The calculated results indicate that both pathways I and II are possible in aqueous solution. The direct participation of the solvent water molecule facilitates the dimerization, but the extremely large solvent shifts of the energy barriers for each reaction are attributed mainly to the bulk effect. The computed activation energies for the water exchange reactions are in good agreement with the available experimental values, namely, the calculated value 37.5 kJ mol(-1) compared to the experimental value 36.4 (+/-5) kJ mol(-1). In agreement with experimental observations in aqueous solution, the calculated results favor the transformation of singly-bridged to doubly-bridged aluminium ion, which is helpful to understand the complicated hydrolytic polymerizaiton of Al(III).

Supersonically Spray-Coated Colloidal Quantum Dot Ink Solar Cells

DOE PAGES

Choi, Hyekyoung; Lee, Jong-Gun; Mai, Xuan Dung; ...

2017-04-04

Controlling the thickness of quantum dot (QD) films is difficult using existing film formation techniques, which employ pre-ligand-exchanged PbS QD inks, because of several issues: 1) poor colloidal stability, 2) use of high-boiling-point solvents for QD dispersion, and 3) limitations associated with one-step deposition. Here in this paper, we suggest a new protocol for QD film deposition using electrical double-layered PbS QD inks, prepared by solution-phase ligand exchange using methyl ammonium lead iodide (MAPbI 3). The films are deposited by the supersonic spraying technique, which facilitates the rapid evaporation of the solvent and the subsequent deposition of the PbS QDmore » ink without requiring a post-deposition annealing treatment for solvent removal. The film thickness could be readily controlled by varying the number of spraying sweeps made across the substrate. This spray deposition process yields high-quality n-type QD films quickly (within 1 min) while minimizing the amount of the PbS QD ink used to less than 5 mg for one device (300-nm-thick absorbing layer, 2.5 x 2.5 cm 2). Further, the formation of an additional p-layer by treatment with mercaptopropionic acid allows for facile hole extraction from the QD films, resulting in a power conversion efficiency of 3.7% under 1.5 AM illumination.« less

Functionalized alkoxy arene diazonium salts from paracetamol.

PubMed

Schmidt, Bernd; Berger, René; Hölter, Frank

2010-03-21

Arene diazonium tetrafluoroborates can be synthesized from aromatic acetamides via a sequence of deacetylation, diazotation and precipitation, induced by anion exchange. The reaction is conducted as a convenient one-flask transformation with consecutive addition of the appropriate reagents. Exchange of solvents or removal of byproducts prior to isolation of the product is not required. The arene diazonium salts are isolated from the reaction mixture by simple filtration. Two complementary protocols are presented, and the utility of the reaction is exemplified for a synthesis of the diarylheptanoid natural product de-O-methyl centrolobine.

H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase

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

Esaki, N.; Nakayama, T.; Sawada, S.

Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the straight-chain L-amino acids which are not susceptible to elimination. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. Formore » L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically.« less

Analysis of trimethoprim, lincomycin, sulfadoxin and tylosin in swine manure using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry.

PubMed

Solliec, Morgan; Massé, Daniel; Sauvé, Sébastien

2014-10-01

A new extraction method coupled to a high throughput sample analysis technique was developed for the determination of four veterinary antibiotics. The analytes belong to different groups of antibiotics such as chemotherapeutics, sulfonamides, lincosamides and macrolides. Trimethoprim (TMP), sulfadoxin (SFX), lincomycin (LCM) and tylosin (TYL) were extracted from lyophilized manure using a sonication extraction. McIlvaine buffer and methanol (MeOH) were used as extraction buffers, followed by cation-exchange solid phase extraction (SPE) for clean-up. Analysis was performed by laser diode thermal desorption-atmospheric pressure chemical-ionization (LDTD-APCI) tandem mass spectrometry (MS/MS) with selected reaction monitoring (SRM) detection. The LDTD is a high throughput sample introduction method that reduces total analysis time to less than 15s per sample, compared to minutes when using traditional liquid chromatography (LC). Various SPE parameters were optimized after sample extraction: the stationary phase, the extraction solvent composition, the quantity of sample extracted and sample pH. LDTD parameters were also optimized: solvent deposition, carrier gas, laser power and corona discharge. The method limit of detection (MLD) ranged from 2.5 to 8.3 µg kg(-1) while the method limit of quantification (MLQ) ranged from 8.3 to 28µgkg(-1). Calibration curves in the manure matrix showed good linearity (R(2)≥ 0.996) for all analytes and the interday and intraday coefficients of variation were below 14%. Recoveries of analytes from manure ranged from 53% to 69%. The method was successfully applied to real manure samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Dendronization-induced phase-transfer, stabilization and self-assembly of large colloidal Au nanoparticles

NASA Astrophysics Data System (ADS)

Malassis, Ludivine; Jishkariani, Davit; Murray, Christopher B.; Donnio, Bertrand

2016-07-01

The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates.The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates. Electronic supplementary information (ESI) available: TEM microscope images. See DOI: 10.1039/c6nr03404g

Insights into the Hydrogen-Atom Transfer of the Blue Aroxyl.

PubMed

Bächle, Josua; Marković, Marijana; Kelterer, Anne-Marie; Grampp, Günter

2017-10-19

An experimental and theoretical study on hydrogen-atom transfer dynamics in the hydrogen-bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6-tri-tert-butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature-dependent alternating line-width effect in the continuous-wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy-atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post-Hartree-Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen-atom transfer along a parabolic reaction path caused by heavy-atom motion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H [Idaho Falls, ID; Todd, Terry A [Aberdeen, ID; Tranter, Troy J [Idaho Falls, ID; Horwitz, E Philip [Naperville, IL

2009-10-06

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Tranter, Troy J.; Horwitz, E. Philip

2007-01-02

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Optimization of technological conditions for one-pot synthesis of (S)-alpha-cyano-3-phenoxybenzyl acetate in organic media.

PubMed

Zhang, Ting-Zhou; Yang, Li-Rong; Zhu, Zi-Qiang

2005-03-01

Optically active form of alpha-cyano-3-phenoxybenzyl (CPB) alcohol, building block of pyrethroid insecticides, was synthesized as its acetate by the combination of anion-exchange resin (D301)-catalyzed transcyanation between m-phenoxybenzaldehyde (m-PBA) and acetone cyanohydrin (AC), and lipase (from Alcaligenes sp.)-catalyzed enantioselective transesterification of the resulting cyanohydrin with vinyl acetate. Through optimizing technological conditions, the catalyzing efficiency was improved considerably compared to methods previously reported. Concentrations of CPB acetate were determined by gas chromatograph. The enantio excess (e.e.) values of CPB acetate were measured by NMR (nuclear magnetic resonance) method. Effects of solvents and temperatures on this reaction were studied. Cyclohexane was shown to be the best solvent among the three tested solvents. 55 degrees C was the optimal temperature for higher degree of conversion. External diffusion limitation was excluded by raising the rotational speed to 220 r/min. However, internal diffusion could not be ignored, since the catalyst (lipase) was an immobilized enzyme and its particle dimension was not made small enough. The reaction rate was substantially accelerated when the reactant (m-PBA) concentration was as high as 249 mmol/L, but decreased when the initial concentration of m-PBA reached to 277 mmol/L. It was also found that the catalyzing capability of recovered lipase was high enough to use several batches. Study of the mole ratio of AC to m-PBA showed that 2:1 was the best choice. The strategy of adding base catalyst D301 was found to be an important factor in improving the degree of conversion of the reaction from 20% to 80%. The highest degree of conversion of the reaction has reached up to 80%.

Extracting organic matter on Mars: A comparison of methods involving subcritical water, surfactant solutions and organic solvents

NASA Astrophysics Data System (ADS)

Luong, Duy; Court, Richard W.; Sims, Mark R.; Cullen, David C.; Sephton, Mark A.

2014-09-01

The first step in many life detection protocols on Mars involves attempts to extract or isolate organic matter from its mineral matrix. A number of extraction options are available and include heat and solvent assisted methods. Recent operations on Mars indicate that heating samples can cause the loss or obfuscation of organic signals from target materials, raising the importance of solvent-based systems for future missions. Several solvent types are available (e.g. organic solvents, surfactant based solvents and subcritical water extraction) but a comparison of their efficiencies in Mars relevant materials is missing. We have spiked the well characterised Mars analogue material JSC Mars-1 with a number of representative organic standards. Extraction of the spiked JSC Mars-1 with the three solvent methods provides insights into the relative efficiency of these methods and indicates how they may be used on future Mars missions.

INITIAL OBSERVATIONS ON THE EFFECT OF HYPOBARIC AND HYPERBARIC PRESSURE ON CELL PERMEABILITY.

DTIC Science & Technology

erythrocytes in hypotonic saline at hypobaric and hyperbaric pressures showed an increase and decrease, respectively, in the extent of hemolysis when...resulted in an apparent alteration in the mechanics of solvent exchange or cell permeability, or both. Comparison of the relative hemolysis of human

Chapter 3. Determination of semivolatile organic compounds and polycyclic aromatic hydrocarbons in solids by gas chromatography/mass spectrometry

USGS Publications Warehouse

Zaugg, Steven D.; Burkhardt, Mark R.; Burbank, Teresa L.; Olson, Mary C.; Iverson, Jana L.; Schroeder, Michael P.

2006-01-01

A method for the determination of 38 polycyclic aromatic hydrocarbons (PAHs) and semivolatile organic compounds in solid samples is described. Samples are extracted using a pressurized solvent extraction system. The compounds of interest are extracted from the solid sample twice at 13,800 kilopascals; first at 120 degrees Celsius using a water/isopropyl alcohol mixture (50:50, volume-to-volume ratio), and then the sample is extracted at 200 degrees Celsius using a water/isopropyl alcohol mixture (80:20, volume-to-volume ratio). The compounds are isolated using disposable solid-phase extraction (SPE) cartridges containing divinylbenzene-vinylpyrrolidone copolymer resin. The cartridges are dried with nitrogen gas, and then sorbed compounds are eluted from the SPE material using a dichloromethane/diethyl ether mixture (80:20, volume-to-volume ratio) and passed through a sodium sulfate/Florisil SPE cartridge to remove residual water and to further clean up the extract. The concentrated extract is solvent exchanged into ethyl acetate and the solvent volume reduced to 0.5 milliliter. Internal standard compounds are added prior to analysis by capillary-column gas chromatography/mass spectrometry. Comparisons of PAH data for 28 sediment samples extracted by Soxhlet and the accelerated solvent extraction (ASE) method described in this report produced similar results. Extraction of PAH compounds from standard reference material using this method also compared favorably with Soxhlet extraction. The recoveries of PAHs less than molecular weight 202 (pyrene or fluoranthene) are higher by up to 20 percent using this ASE method, whereas the recoveries of PAHs greater than or equal to molecular weight 202 are equivalent. This ASE method of sample extraction of solids has advantages over conventional Soxhlet extraction by increasing automation of the extraction process, reducing extraction time, and using less solvent. Extract cleanup also is greatly simplified because SPE replaces commonly used gel permeation chromatography. The performance of the method (as expressed by mean recoveries and mean precision) was determined using Ottawa sand, a commercially available topsoil, and an environmental stream sediment, fortified at 1.5 and 15 micrograms per compound. Recoveries of PAH and semivolatile compounds in Ottawa sand samples fortified at 1.5 micrograms averaged 88 percent ? 9.4 percent relative standard deviation, and calculated initial method detection limits per compound averaged 14 micrograms per kilogram, assuming a 25-gram sample size. The recovery for 1,2,4-trichlorobenzene is less than 60 percent; thus, the concentration of this compound will always be reported as estimated with the E remark code. The analysis of 25 alkylated PAH homolog groups also can be determined with this method with extra data analysis and review, but because of the lack of authentic reference standard compounds, these results are considered to be semiquantitative. The PAH homolog groups are quantitated using the response factor of a parent PAH method compound, if available. Precision data for the alkylated PAH homologs detected in a marine sediment standard reference material (SRM 1944) also are presented to document and demonstrate method capability.

Higher Americium Oxidation State Research Roadmap

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

Mincher, Bruce J.; Law, Jack D.; Goff, George S.

2015-12-18

The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained undermore » the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non-solvent-extraction separations are also under investigation. The first would separate Am(VI) by co-crystallization with uranium and the other oxidizable actinides as their nitrate salts. This novel idea has been successful in lab scale testing, and merits further investigation. Similarly, success has been achieved in separations using inorganic or hybrid ion exchange materials to sorb the lanthanides and actinides, while allowing pentavalent americium to elute. This is the only technique currently investigating Am(V), despite the advantages of this oxidation state with regard to its higher stability. The ultimate destination for this roadmap is to develop an americium separation that can be applied under process conditions, preferably affording a co-separation of the actinyl (VI) ions. Toward that end, emphasis is given here to selection of a solvent extraction flowsheet for testing in the INL centrifugal contactor hot test bed during FY16. A solvent extraction process will be tested mainly because solvent extraction separations of Am(VI) are relatively mature and the test bed currently exists in a configuration to support them. Thus, a major goal of FY16 is to select the oxidant/ligand combination to run such a test using the contactors. The only ligands under consideration are DAAP and DEHBA. This is not to say that ion exchange and co-crystallization techniques are unimportant. They merit continued investigation, but are not mature enough for hot test bed testing at this time.« less

The extraction of essential oil from patchouli leaves (Pogostemon cablin Benth) using microwave hydrodistillation and solvent-free microwave extraction methods

NASA Astrophysics Data System (ADS)

Putri, D. K. Y.; Kusuma, H. S.; Syahputra, M. E.; Parasandi, D.; Mahfud, M.

2017-12-01

Patchouli plant (Pogostemon cablin Benth) is one of the important essential oil-producing plant, contributes more than 50% of total exports of Indonesia’s essential oil. However, the extraction of patchouli oil that has been done in Indonesia is generally still used conventional methods that require enormous amount of energy, high solvent usage, and long time of extraction. Therefore, in this study, patchouli oil extraction was carried out by using microwave hydrodistillation and solvent-free microwave extraction methods. Based on this research, it is known that the extraction of patchouli oil using microwave hydrodistillation method with longer extraction time (240 min) only produced patchouli oil’s yield 1.2 times greater than solvent-free microwave extraction method which require faster extraction time (120 min). Otherwise the analysis of electric consumption and the environmental impact, the solvent-free microwave extraction method showed a smaller amount when compared with microwave hydrodistillation method. It is conclude that the use of solvent-free microwave extraction method for patchouli oil extraction is suitably method as a new green technique.

Rates and mechanism of fluoride and water exchange in UO(2)F(5)(3-) and [UO(2)F(4)(H(2)O)](2-) studied by NMR spectroscopy and wave function based methods.

PubMed

Vallet, Valérie; Wahlgren, Ulf; Szabó, Zoltán; Grenthe, Ingmar

2002-10-21

The reaction mechanism for the exchange of fluoride in UO(2)F(5)(3-) and UO(2)F(4)(H(2)O)(2-) has been investigated experimentally using (19)F NMR spectroscopy at -5 degrees C, by studying the line broadening of the free fluoride, UO(2)F(4)(2-)(aq) and UO(2)F(5)(3-), and theoretically using quantum chemical methods to calculate the activation energy for different pathways. The new experimental data allowed us to make a more detailed study of chemical equilibria and exchange mechanisms than in previous studies. From the integrals of the different individual peaks in the new NMR spectra, we obtained the stepwise stability constant K(5) = 0.60 +/- 0.05 M(-1) for UO(2)F(5)(3-). The theoretical results indicate that the fluoride exchange pathway of lowest activation energy, 71 kJ/mol, in UO(2)F(5)(3-) is water assisted. The pure dissociative pathway has an activation energy of 75 kJ/mol, while the associative mechanism can be excluded as there is no stable UO(2)F(6)(4-) intermediate. The quantum chemical calculations have been made at the SCF/MP2 levels, using a conductor-like polarizable continuum model (CPCM) to describe the solvent. The effects of different model assumptions on the activation energy have been studied. The activation energy is not strongly dependent on the cavity size or on interactions between the complex and Na(+) counterions. However, the solvation of the complex and the leaving fluoride results in substantial changes in the activation energy. The mechanism for water exchange in UO(2)F(4)(H(2)O)(2-) has also been studied. We could eliminate the associative mechanism, the dissociative mechanism had the lowest activation energy, 39 kJ/mol, while the interchange mechanism has an activation energy that is approximately 50 kJ/mol higher.

The rapid and direct determination of ATP-ase activity by ion exchange chromatography and the application to the activity of heat shock protein-90

PubMed Central

Bartolini, Manuela; Wainer, Irving W.; Bertucci, Carlo; Andrisano, Vincenza

2012-01-01

Adenosine nucleotides are involved as substrates or co-factors in several biochemical reactions, catalyzed by enzymes, which modulate energy production, signal transduction and cell proliferation. We here report the development and optimization of an ion exchange liquid chromatography (LC) method for the determination of ATP, ADP and AMP. This method is specifically aimed at the determination of the ATP-ase activity of human heat shock protein 90 (Hsp90), a molecular chaperone that has emerged as target enzyme in cancer therapy. Separation of the three nucleotides was achieved in a 15-min run by using a disk shaped monolithic ethylene diamine stationary phase of small dimensions (2×6 mm i.d.), under a three-solvent gradient elution mode and UV detection at 256 nm. The described direct LC method resulted highly specific as a consequence of the baseline separation of the three adenosine nucleotides and could be applied to the determination of the enzymatic activity of ADP/ATP generating or consuming enzymes (such as kinases). Furthermore, comparison of the LOD and LOQ values of the LC method with those obtained with the malachite green assay, which is one of the most used indirect screening methodologies for ATP-ase activity, showed that the LC method has a similar range of application without presenting the drawbacks related to contamination by inorganic phosphate ions and glycerol, which are present in Hsp90 commercial samples. PMID:22497853

Optimization of the solvent-based dissolution method to sample volatile organic compound vapors for compound-specific isotope analysis.

PubMed

Bouchard, Daniel; Wanner, Philipp; Luo, Hong; McLoughlin, Patrick W; Henderson, James K; Pirkle, Robert J; Hunkeler, Daniel

2017-10-20

The methodology of the solvent-based dissolution method used to sample gas phase volatile organic compounds (VOC) for compound-specific isotope analysis (CSIA) was optimized to lower the method detection limits for TCE and benzene. The sampling methodology previously evaluated by [1] consists in pulling the air through a solvent to dissolve and accumulate the gaseous VOC. After the sampling process, the solvent can then be treated similarly as groundwater samples to perform routine CSIA by diluting an aliquot of the solvent into water to reach the required concentration of the targeted contaminant. Among solvents tested, tetraethylene glycol dimethyl ether (TGDE) showed the best aptitude for the method. TGDE has a great affinity with TCE and benzene, hence efficiently dissolving the compounds during their transition through the solvent. The method detection limit for TCE (5±1μg/m 3 ) and benzene (1.7±0.5μg/m 3 ) is lower when using TGDE compared to methanol, which was previously used (385μg/m 3 for TCE and 130μg/m 3 for benzene) [2]. The method detection limit refers to the minimal gas phase concentration in ambient air required to load sufficient VOC mass into TGDE to perform δ 13 C analysis. Due to a different analytical procedure, the method detection limit associated with δ 37 Cl analysis was found to be 156±6μg/m 3 for TCE. Furthermore, the experimental results validated the relationship between the gas phase TCE and the progressive accumulation of dissolved TCE in the solvent during the sampling process. Accordingly, based on the air-solvent partitioning coefficient, the sampling methodology (e.g. sampling rate, sampling duration, amount of solvent) and the final TCE concentration in the solvent, the concentration of TCE in the gas phase prevailing during the sampling event can be determined. Moreover, the possibility to analyse for TCE concentration in the solvent after sampling (or other targeted VOCs) allows the field deployment of the sampling method without the need to determine the initial gas phase TCE concentration. The simplified field deployment approach of the solvent-based dissolution method combined with the conventional analytical procedure used for groundwater samples substantially facilitates the application of CSIA to gas phase studies. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Chen, Wen-Hua; Yan, Hao-Jie; Chen, Hui

Dipyridyl sulphide ligands 4-(pyridin-4-ylmethylthio)pyridine (abbreviated as L1) and 3-(pyridin-4-ylmethylthio)pyridine (abbreviated as L2) have been designed and used as μ-{sub N},{sub N}-bridging linkages to construct coordination polymers with free –S–CH{sub 2}– groups as secondary donor sites. By use solvent control method, coordination polymers ([Ag{sub 3}SO{sub 4}(L1){sub 3}](Cl)·4.5H{sub 2}O){sub ∞}(1), ([Ag{sub 2}SO{sub 4}(L1){sub 2}]·6H{sub 2}O·2CH{sub 3}OH){sub ∞}(2), ([Ag{sub 2}SO{sub 4}(L2){sub 2}]·H{sub 2}O){sub ∞}(3) and ([Ag{sub 4}(SO{sub 4}){sub 2}(L2){sub 4}]·5H{sub 2}O){sub ∞}(4) with different architectures were obtained. Complexes 1, 3 and 4 feature 1D channel with different sizes and structures. Complex 1 exhibits guest exchange by THF and 1,4-dioxane, and Hg{sup 2+} sorptionmore » ability from solution due to its relative larger channel and available bonding sites of –S– exposed to the channel region. All complexes have been characterized through single-crystal and powder X-ray diffraction (PXRD), FT-IR spectra, X-ray photoelectron spectroscopy (XPS), elemental and thermogravimetric analyses. The guest exchange and Hg{sup 2+} sorption were monitored and identified, and the structure-property relationship of coordination polymers 1–4 are discussed. - Graphical abstract: Coordination polymers of silver(I) sulfate with secondary donor sites are shown guest exchange property and Hg{sup 2+} absorb ability from solution. This work provides a new method to construct functional materials with potential application. - Highlights: • New example of constructing functional coordination polymer with secondary donor methylthio group. • Guest exchange and interesting Hg(II) absorb ability from solution are investigated. • New method to construct functional materials with potential application.« less

METHOD FOR SOLVENT-ISOSTATIC PRESSING

DOEpatents

Archibald, P.B.

1962-09-18

This invention provides a method for producing densely compacted bodies having relatively large dimensions. The method comprises the addition of a small quantity of a suitable solvent to a powder which is to be compacted. The solvent- moistened powder is placed inside a flexible bag, and the bag is suspended in an isostatic press. The solvent is squeezed out of the powder by the isostatic pressure, and the resulting compacted body is recovered. The presence of the solvent markedly decreases the proportion of void space in the powder, thereby resulting in a denser, more homogeneous compact. Another effect of the solvent is that it allows the isostatic pressing operation to be conducted at substantially lower pressures than are conventionally employed. (AEC)

Performance of some DFT functionals with dispersion on modeling of the translational isomers of a solvent-switchable [2]rotaxane

NASA Astrophysics Data System (ADS)

Ivanov, Petko

2016-03-01

The balances of interactions were studied by computational methods in the translational isomers of a solvent switchable fullerene-stoppered [2]rotaxane (1) manifesting unexpected behavior, namely that due to favorable dispersion interactions the fullerene stopper becomes the second station upon change of the solvent. For comparison, another system, a pH switchable molecular shuttle (2), was also examined as an example of prevailing electrostatic interactions. Tested for 1 were five global hybrid Generalized Gradient Approximation functionals (B3LYP, B3LYP-D3, B3LYP-D3BJ, PBEh1PBE and APFD), one long-range corrected, range-separated functional with D2 empirical dispersion correction, ωB97XD, the Zhao-Truhlar's hybrid meta-GGA functional M06 with double the amount of nonlocal exchange (2X), and a pure functional, B97, with the Grimme's D3BJ dispersion (B97D3). The molecular mechanics method qualitatively correctly reproduced the behavior of the [2]rotaxanes, whereas the DFT models, except for M06-2X to some extent, failed in the case of significant dispersion interactions with participation of the fulleropyrrolidine stopper (rotaxane 1). Unexpectedly, the benzylic amide macrocycle tends to adopt preferentially 'boat'-like conformation in most of the cases. Four hydrogen bonds interconnect the axle with the wheel for the translational isomer with the macroring at the succinamide station (station II), whereas the number of hydrogen bonds vary for the isomer with the macroring at the fulleropyrrolidine stopper (station I) depending of the computational model used. The B3LYP and the PBEh1PBE results show strong preference of station II in the gas phase and in the model solvent DMSO. After including empirical dispersion correction, the translational isomer with the macroring at station I has the lower energy with B3LYP, both in the gas phase and in DMSO. The same result, but with higher preference of station I, was estimated with APFD, ωB97XD and B97D3. Only M06-2X presented qualitatively correct behavior for the relative stability of the two translational isomers, namely, slight preference of station II for the isolated molecule and higher relative energy of the same isomer with the model solvent DMSO. The electrostatic interactions in 2 have the decisive contribution both when the macroring is positioned at the dipeptide residue for the neutral form, and at the N-benzylalanine fragment after protonation, and the observed behavior of the [2]rotaxane is correctly reproduced by the methods used.

Rapid process for producing transparent, monolithic porous glass

DOEpatents

Coronado, Paul R [Livermore, CA

2006-02-14

A process for making transparent porous glass monoliths from gels. The glass is produced much faster and in much larger sizes than present technology for making porous glass. The process reduces the cost of making large porous glass monoliths because: 1) the process does not require solvent exchange nor additives to the gel to increase the drying rates, 2) only moderate temperatures and pressures are used so relatively inexpensive equipment is needed, an 3) net-shape glass monoliths are possible using this process. The process depends on the use of temperature to control the partial pressure of the gel solvent in a closed vessel, resulting in controlled shrinking during drying.

Anion exchange of organic carboxylate by soils responsible for positive Km-fc relationship from methanol mixture.

PubMed

Kim, Minhee; Han, Junho; Hyun, Seunghun

2013-09-01

The cosolvency model was not applicable for predicting the sorption of organic carboxylic acids. The reason of inapplicability was investigated by analyzing the solubility (Sm) and sorption (Km) of benzoic acid, 2,4-dichlorophenoxyacetic acid (2,4-D), and 2,4,6-trichlorophenol (2,4,6-TCP). The Sm and Km by two iron-rich soils was measured as a function of methanol volume fraction (fc), electrolyte compositions, and pH(app). For 2,4,6-TCP, the Km of both neutral and anion species was well-explainable by the cosolvency model, exemplifying the knowledge of cosolvency power (σ) being sufficient to describe its sorption. However, for benzoic acid and 2,4-D, the Km of organic anions increased with fc, illustrating the organic carboxylate to be responsible for the deviation. The Sm of organic anions was not affected by the ionic valence (Ca(2+) vs. K(+)) of liquid phase. Among hydrophilic quantities of the 2,4-D sorption, the fraction of anion exchange increased with fc while the fraction of Ca-bridge decreased in the same range. Adding solvent in soil-water system is likely to render soil surface charge more positive, fortifying the anion exchange, but opposing the formation of Ca-bridging. Therefore, it can be concluded that the positive Km-fc relationship is due to the anion exchange of organic carboxylate with positively charged soil surface, whose contribution is >50% of overall sorption at solvent-free system and becomes greater with fc up to 82%. Copyright © 2013. Published by Elsevier Ltd.

Investigations regarding the wet decontamination of fluorescent lamp waste using iodine in potassium iodide solutions

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

Tunsu, Cristian, E-mail: tunsu@chalmers.se; Ekberg, Christian; Foreman, Mark

Highlights: • A wet-based decontamination process for fluorescent lamp waste is proposed. • Mercury can be leached using iodine in potassium iodide solution. • The efficiency of the process increases with an increase in leachant concentration. • Selective leaching of mercury from rare earth elements is achieved. • Mercury is furthered recovered using ion exchange, reduction or solvent extraction. - Abstract: With the rising popularity of fluorescent lighting, simple and efficient methods for the decontamination of discarded lamps are needed. Due to their mercury content end-of-life fluorescent lamps are classified as hazardous waste, requiring special treatment for disposal. A simplemore » wet-based decontamination process is required, especially for streams where thermal desorption, a commonly used but energy demanding method, cannot be applied. In this study the potential of a wet-based process using iodine in potassium iodide solution was studied for the recovery of mercury from fluorescent lamp waste. The influence of the leaching agent’s concentration and solid/liquid ratio on the decontamination efficiency was investigated. The leaching behaviour of mercury was studied over time, as well as its recovery from the obtained leachates by means of anion exchange, reduction, and solvent extraction. Dissolution of more than 90% of the contained mercury was achieved using 0.025/0.05 M I{sub 2}/KI solution at 21 °C for two hours. The efficiency of the process increased with an increase in leachant concentration. 97.3 ± 0.6% of the mercury contained was dissolved at 21 °C, in two hours, using a 0.25/0.5 M I{sub 2}/KI solution and a solid to liquid ratio of 10% w/v. Iodine and mercury can be efficiently removed from the leachates using Dowex 1X8 anion exchange resin or reducing agents such as sodium hydrosulphite, allowing the disposal of the obtained solution as non-hazardous industrial wastewater. The extractant CyMe{sub 4}BTBP showed good removal of mercury, with an extraction efficiency of 97.5 ± 0.7% being achieved in a single stage. Better removal of mercury was achieved in a single stage using the extractants Cyanex 302 and Cyanex 923 in kerosene, respectively.« less

Sampling of Protein Folding Transitions: Multicanonical Versus Replica Exchange Molecular Dynamics.

PubMed

Jiang, Ping; Yaşar, Fatih; Hansmann, Ulrich H E

2013-08-13

We compare the efficiency of multicanonical and replica exchange molecular dynamics for the sampling of folding/unfolding events in simulations of proteins with end-to-end β -sheet. In Go-model simulations of the 75-residue MNK6, we observe improvement factors of 30 in the number of folding/unfolding events of multicanonical molecular dynamics over replica exchange molecular dynamics. As an application, we use this enhanced sampling to study the folding landscape of the 36-residue DS119 with an all-atom physical force field and implicit solvent. Here, we find that the rate-limiting step is the formation of the central helix that then provides a scaffold for the parallel β -sheet formed by the two chain ends.

Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

USGS Publications Warehouse

Mills, M.S.; Thurman, E.M.; Pedersen, M.J.

1993-01-01

Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).

Solvent-coordinate free-energy landscape view of water-mediated ion-pair dissociation

NASA Astrophysics Data System (ADS)

Yonetani, Yoshiteru

2017-12-01

Water-mediated ion-pair dissociation is studied by molecular dynamics simulations of NaCl in water. Multidimensional free-energy analysis clarifies the relation between two essential solvent coordinates: the water coordination number and water-bridge formation. These two are related in a complex way. Both are necessary to describe ion-pair dissociation. The mechanism constructed with both solvent variables clearly shows the individual roles. The water coordination number is critical for starting ion-pair dissociation. Water-bridge formation is also important because it increases the likelihood of ion-pair dissociation by reducing the dissociation free-energy barrier. Additional Ca-Cl and NH4-Cl calculations show that these conclusions are unaffected by changes in the ion charge and shape. The present results will contribute to future explorations of many other molecular events such as surface water exchange and protein-ligand dissociation because the same mechanism is involved in such events.

Dynamics of water in sulfonated poly(phenylene) membranes

NASA Astrophysics Data System (ADS)

Osti, Naresh; Etampawala, Thusitha; Shrestha, Umesh; Perahia, Dvora; Cornelius, Christopher

2011-03-01

The dynamics of water in networks formed by highly rigid ionic polymers, sulfonated poly(phenylene) as observed by quasi elastic neutron scattering (QENS) is presented. These rigid ionic polymers have potential as effective ion exchange membranes with impact on a large number of applications from water purification to clean energy, where its rigidity distinguishes it from other ionic polymers. Its transport characteristics are affected by its rigidness as well as by direct interactions with the solvent. Our QENS studies as a function of sulfonation levels, temperature and solvent content have shown that on the time scale of the measurement, the polymers are rigid. While macroscopically all samples swell, and transport water, the water molecules appear locally rather confined. Water however remind non-frozen to subzero temperatures. The results will be discussed in view of theoretical models including continues diffusion and hopping of solvent molecules.

Mechanism of α-ketol-type rearrangement of benzoin derivatives under basic conditions.

PubMed

Karino, Masahiro; Kubouchi, Daiki; Hamaoka, Kazuki; Umeyama, Shintaro; Yamataka, Hiroshi

2013-07-19

The mechanism of base-catalyzed rearrangement of ring-substituted benzoins in aqueous methanol was examined by kinetic and product analyses. Substituent effects on the rate and equilibrium constants revealed that the kinetic process has a different electron demand compared to the equilibrium process. Reactions in deuterated solvents showed that the rate of H/D exchange of the α-hydrogen is similar to the overall rate toward the equilibrium state. A proton-inventory experiment using partially deuterated solvents showed a linear dependence of the rate on the deuterium fraction of the solvent, indicating that only one deuterium isotope effect contributes to the overall rate process. All these results point to a mechanism in which the rearrangement is initiated by the rate-determining α-hydrogen abstraction rather than a mechanism with initial hydroxyl hydrogen abstraction as in the general α-ketol rearrangement.

Matrix solid-phase dispersion followed by gas chromatography tandem mass spectrometry for the determination of benzotriazole UV absorbers in sediments.

PubMed

Carpinteiro, I; Abuín, B; Ramil, M; Rodríguez, I; Cela, R

2012-01-01

A cost-effective and low solvent consumption method, based on the matrix solid-phase dispersion (MSPD) technique, for the determination of six benzotriazole UV absorbers in sediments is presented. Sieved samples (0.5 g) were first mixed in a mortar with a solid sorbent and then transferred to a polypropylene syringe containing a layer of clean-up co-sorbent. Analytes were eluted with a suitable solvent and further determined by gas chromatography with tandem mass spectrometry (GC-MS/MS). Under final conditions, diatomaceous earth and silica, deactivated to 10%, were used as inert dispersant and clean-up co-sorbent, respectively. Analytes were recovered using just 5 mL of dichloromethane, and this extract was concentrated and exchanged to 1 mL of isooctane. Further removal of co-extracted sulphur was achieved adding activated copper powder to final extracts, which were stored overnight, before injection in the GC-MS/MS system. The accuracy of the method was assessed with river and marine sediment samples showing different carbon contents and spiked at different concentrations in the range from 40 to 500 ng g(-1). Recoveries varied between 78% and 110% with associated standard deviations below 14%. The limits of quantification of the method stayed between 3 and 15 ng g(-1). Levels of target compounds in sediment samples ranged from not detected up to a maximum of 56 ng g(-1) for Tinuvin 328.

Molecular modelling of protein-protein/protein-solvent interactions

NASA Astrophysics Data System (ADS)

Luchko, Tyler

The inner workings of individual cells are based on intricate networks of protein-protein interactions. However, each of these individual protein interactions requires a complex physical interaction between proteins and their aqueous environment at the atomic scale. In this thesis, molecular dynamics simulations are used in three theoretical studies to gain insight at the atomic scale about protein hydration, protein structure and tubulin-tubulin (protein-protein) interactions, as found in microtubules. Also presented, in a fourth project, is a molecular model of solvation coupled with the Amber molecular modelling package, to facilitate further studies without the need of explicitly modelled water. Basic properties of a minimally solvated protein were calculated through an extended study of myoglobin hydration with explicit solvent, directly investigating water and protein polarization. Results indicate a close correlation between polarization of both water and protein and the onset of protein function. The methodology of explicit solvent molecular dynamics was further used to study tubulin and microtubules. Extensive conformational sampling of the carboxy-terminal tails of 8-tubulin was performed via replica exchange molecular dynamics, allowing the characterisation of the flexibility, secondary structure and binding domains of the C-terminal tails through statistical analysis methods. Mechanical properties of tubulin and microtubules were calculated with adaptive biasing force molecular dynamics. The function of the M-loop in microtubule stability was demonstrated in these simulations. The flexibility of this loop allowed constant contacts between the protofilaments to be maintained during simulations while the smooth deformation provided a spring-like restoring force. Additionally, calculating the free energy profile between the straight and bent tubulin configurations was used to test the proposed conformational change in tubulin, thought to cause microtubule destabilization. No conformational change was observed but a nucleotide dependent 'softening' of the interaction was found instead, suggesting that an entropic force in a microtubule configuration could be the mechanism of microtubule collapse. Finally, to overcome much of the computational costs associated with explicit soIvent calculations, a new combination of molecular dynamics with the 3D-reference interaction site model (3D-RISM) of solvation was integrated into the Amber molecular dynamics package. Our implementation of 3D-RISM shows excellent agreement with explicit solvent free energy calculations. Several optimisation techniques, including a new multiple time step method, provide a nearly 100 fold performance increase, giving similar computational performance to explicit solvent.

Micro-chemical synthesis of molecular probes on an electronic microfluidic device

PubMed Central

Keng, Pei Yuin; Chen, Supin; Ding, Huijiang; Sadeghi, Saman; Shah, Gaurav J.; Dooraghi, Alex; Phelps, Michael E.; Satyamurthy, Nagichettiar; Chatziioannou, Arion F.; Kim, Chang-Jin “CJ”; van Dam, R. Michael

2012-01-01

We have developed an all-electronic digital microfluidic device for microscale chemical synthesis in organic solvents, operated by electrowetting-on-dielectric (EWOD). As an example of the principles, we demonstrate the multistep synthesis of [18F]FDG, the most common radiotracer for positron emission tomography (PET), with high and reliable radio-fluorination efficiency of [18F]FTAG (88 ± 7%, n = 11) and quantitative hydrolysis to [18F]FDG (> 95%, n = 11). We furthermore show that batches of purified [18F]FDG can successfully be used for PET imaging in mice and that they pass typical quality control requirements for human use (including radiochemical purity, residual solvents, Kryptofix, chemical purity, and pH). We report statistical repeatability of the radiosynthesis rather than best-case results, demonstrating the robustness of the EWOD microfluidic platform. Exhibiting high compatibility with organic solvents and the ability to carry out sophisticated actuation and sensing of reaction droplets, EWOD is a unique platform for performing diverse microscale chemical syntheses in small volumes, including multistep processes with intermediate solvent-exchange steps. PMID:22210110

Comprehensive two-dimensional normal-phase liquid chromatography × reversed-phase liquid chromatography for analysis of toad skin.

PubMed

Li, Jia-Fu; Yan, Xia; Wu, Yun-Long; Fang, Mei-Juan; Wu, Zhen; Qiu, Ying-Kun

2017-04-15

An analytical two-dimensional normal-phase liquid chromatography × reversed-phase liquid chromatography (2D NPLC × RPLC) system was constructed with a newly developed thermal evaporation assisted adsorption (TEAA) interface. This novel TEAA interface with heating temperature above solvent boiling point allowed fast removal of organic NPLC solvent and successfully solved the solvent incompatibility problem between NPLC and RPLC. The system achieved rapid on-line solvent exchange between the two dimensions within a short modulation time of 190 s and was applied in the analysis of an extract from the skin of Bufo bufo gargarizans. This is the first time to realize the on-line comprehensive analysis of a moderate polar natural product by coupling NPLC with reversed phase ultra-high performance liquid chromatography (UHPLC). To be highlighted, with the TEAA interface, the 2D NPLC × RPLC system provided excellent resolution and orthogonality (75.2%), when compared with that of 2D RPLC × RPLC. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of Carbon Nanotube-Polyamide Nanocomposite-based Stir Bar Sorptive Extraction Coupled to HPLC-UV Applying Response Surface Methodology for the Analysis of Bisphenol A in Aqueous Samples.

PubMed

Ayazi, Z; Matin, A A

2016-11-01

A novel nanocomposite based on reinforcing of multiwalled carbon nanotubes in polyamide (PA) was prepared by solvent exchange method as stir bar coating. The morphology and surface characteristic of PA and CNT/PA coated stir bars were investigated using scanning electron microscopy. The stir bar coated by CNT/PA nanocomposite was used as an extraction device for stir bar sorptive extraction of bisphenol A from aqueous samples followed by high performance liquid chromatography-UV detection. The effect of CNTs doping level and oxidation of CNTs on the extraction capability of the coating was investigated. Response surface methodology applying central composite design was used for modeling and optimization of important factors influencing the extraction and desorption processes including extraction time, salt and methanol content, desorption solvent, its volume and desorption time. Limit of detection and linear dynamic range of the method were 0.3 ng mL -1 and 1-10 ng mL -1 , respectively. The method precision (RSD%) with four replicate determinations was 4.9% for distilled water at the concentration level of 10 ng mL -1 The obtained RSD% for reproducibility of stir bars was 7.4%. The developed method was successfully applied to the bottled mineral water samples, while the relative recoveries (RR%) were obtained to be in the range of 92.0-101.9%. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Multiscale implementation of infinite-swap replica exchange molecular dynamics.

PubMed

Yu, Tang-Qing; Lu, Jianfeng; Abrams, Cameron F; Vanden-Eijnden, Eric

2016-10-18

Replica exchange molecular dynamics (REMD) is a popular method to accelerate conformational sampling of complex molecular systems. The idea is to run several replicas of the system in parallel at different temperatures that are swapped periodically. These swaps are typically attempted every few MD steps and accepted or rejected according to a Metropolis-Hastings criterion. This guarantees that the joint distribution of the composite system of replicas is the normalized sum of the symmetrized product of the canonical distributions of these replicas at the different temperatures. Here we propose a different implementation of REMD in which (i) the swaps obey a continuous-time Markov jump process implemented via Gillespie's stochastic simulation algorithm (SSA), which also samples exactly the aforementioned joint distribution and has the advantage of being rejection free, and (ii) this REMD-SSA is combined with the heterogeneous multiscale method to accelerate the rate of the swaps and reach the so-called infinite-swap limit that is known to optimize sampling efficiency. The method is easy to implement and can be trivially parallelized. Here we illustrate its accuracy and efficiency on the examples of alanine dipeptide in vacuum and C-terminal β-hairpin of protein G in explicit solvent. In this latter example, our results indicate that the landscape of the protein is a triple funnel with two folded structures and one misfolded structure that are stabilized by H-bonds.

An Analogy Using Pennies and Dimes to Explain Chemical Kinetics Concepts

ERIC Educational Resources Information Center

Cortes-Figueroa, Jose E.; Perez, Wanda I.; Lopez, Jose R.; Moore-Russo, Deborah A.

2011-01-01

In this article, the authors present an analogy that uses coins and graphical analysis to teach kinetics concepts and resolve pseudo-first-order rate constants related to transition-metal complexes ligand-solvent exchange reactions. They describe an activity that is directed to upper-division undergraduate and graduate students. The activity…

A pillar[5]arene based gel from a low-molecular-weight gelator for sustained dye release in water.

PubMed

Yao, Yong; Sun, Yan; Yu, Huaxu; Chen, Wenrui; Dai, Hong; Shi, Yujun

2017-12-12

A soft gel based on pillar[5]arene was successfully prepared using a carbazone reaction. Furthermore, dyes such as TPP or TPPE can be incorporated into this gel and were observed to be released in a sustained way in water due to solvent exchange.

The Search for Nanobubbles by Using Specular and Off-Specular Neutron Reflectometry.

PubMed

Gutfreund, Philipp; Maccarini, Marco; Dennison, Andrew J C; Wolff, Max

2016-09-06

We apply specular and off-specular neutron reflection at the hydrophobic silicon/water interface to check for evidence of nanoscopic air bubbles whose presence is claimed after an ad hoc procedure of solvent exchange. Nanobubbles and/or a depletion layer at the hydrophobic/water interface have long been discussed and generated a plethora of controversial scientific results. By combining neutron reflectometry (NR), off-specular reflectometry (OSS), and grazing incidence small angle neutron scattering (GISANS), we studied the interface between hydrophobized silicon and heavy water before and after saturation with nitrogen gas. Our specular reflectometry results can be interpreted by assuming a submolecular sized depletion layer and the off-specular measurements show no change with nitrogen super saturated water. This picture is consistent with the assumption that, following the solvent exchange, no additional nanobubbles are introduced at significant concentrations (if present at all). Furthermore, we discuss the results in terms of the maximum surface coverage of nanobubbles that could be present on the hydrophobic surface compatibly with the sensitivity limit of these techniques.

Probing Conformational Dynamics of Tau Protein by Hydrogen/Deuterium Exchange Mass Spectrometry

NASA Astrophysics Data System (ADS)

Huang, Richard Y.-C.; Iacob, Roxana E.; Sankaranarayanan, Sethu; Yang, Ling; Ahlijanian, Michael; Tao, Li; Tymiak, Adrienne A.; Chen, Guodong

2018-01-01

Fibrillization of the microtubule-associated protein tau has been recognized as one of the signature pathologies of the nervous system in Alzheimer's disease, progressive supranuclear palsy, and other tauopathies. The conformational transition of tau in the fibrillization process, tau monomer to soluble aggregates to fibrils in particular, remains unclear. Here we report on the use of hydrogen/deuterium exchange mass spectrometry (HDX-MS) in combination with other biochemical approaches, including Thioflavin S fluorescence measurements, enzyme-linked immunosorbent assay (ELISA), and Western blotting to understand the heparin-induced tau's fibrillization. HDX-MS studies including anti-tau antibody epitope mapping experiments provided molecular level details of the full-length tau's conformational dynamics and its regional solvent accessibility upon soluble aggregates formation. The results demonstrate that R3 region in the full-length tau's microtubule binding repeat region (MTBR) is stabilized in the aggregation process, leaving both N and C terminal regions to be solvent exposed in the soluble aggregates and fibrils. The findings also illustrate the practical utility of orthogonal analytical methodologies for the characterization of protein higher order structure. [Figure not available: see fulltext.

Low molecular weight oligomers of amyloid peptides display β-barrel conformations: A replica exchange molecular dynamics study in explicit solvent

NASA Astrophysics Data System (ADS)

De Simone, Alfonso; Derreumaux, Philippe

2010-04-01

The self-assembly of proteins and peptides into amyloid fibrils is connected to over 40 pathological conditions including neurodegenerative diseases and systemic amyloidosis. Diffusible, low molecular weight protein and peptide oligomers that form in the early steps of aggregation appear to be the harmful cytotoxic species in the molecular etiology of these diseases. So far, the structural characterization of these oligomers has remained elusive owing to their transient and dynamic features. We here address, by means of full atomistic replica exchange molecular dynamics simulations, the energy landscape of heptamers of the amyloidogenic peptide NHVTLSQ from the beta-2 microglobulin protein. The simulations totaling 5 μs show that low molecular weight oligomers in explicit solvent consist of β-barrels in equilibrium with amorphous states and fibril-like assemblies. The results, also accounting for the influence of the pH on the conformational properties, provide a strong evidence of the formation of transient β-barrel assemblies in the early aggregation steps of amyloid-forming systems. Our findings are discussed in terms of oligomers cytotoxicity.

Accessing the Vibrational Signatures of Amino Acid Ions Embedded in Water Clusters

DOE PAGES

Voss, Jonathan M.; Fischer, Kaitlyn C.; Garand, Etienne

2018-04-16

We present an infrared predissociation (IRPD) study of microsolvated GlyH +(H 2O) n and GlyH +(D 2O) n clusters, formed inside of a cryogenic ion trap via condensation of H 2O or D 2O onto the protonated glycine ions. The resulting IRPD spectra, showing characteristic O–H and O–D stretches, indicate that H/D exchange reactions are quenched when the ion trap is held at 80 K, minimizing the presence of isotopomers. Comparisons of GlyH +(H 2O) n and GlyH +(D 2O) n spectra clearly highlight and distinguish the vibrational signatures of the water solvent molecules from those of the core GlyHmore » + ion, allowing for quick assessment of solvation structures. Without the aid of calculations, we can already infer solvation motifs and the presence of multiple conformations. Furthermore, the use of a cryogenic ion trap to cluster solvent molecules around ions of interest and control H/D exchange reactions is broadly applicable and should be extendable to studies of more complex peptidic ions in large solvated clusters.« less

Accessing the Vibrational Signatures of Amino Acid Ions Embedded in Water Clusters

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

Voss, Jonathan M.; Fischer, Kaitlyn C.; Garand, Etienne

We present an infrared predissociation (IRPD) study of microsolvated GlyH +(H 2O) n and GlyH +(D 2O) n clusters, formed inside of a cryogenic ion trap via condensation of H 2O or D 2O onto the protonated glycine ions. The resulting IRPD spectra, showing characteristic O–H and O–D stretches, indicate that H/D exchange reactions are quenched when the ion trap is held at 80 K, minimizing the presence of isotopomers. Comparisons of GlyH +(H 2O) n and GlyH +(D 2O) n spectra clearly highlight and distinguish the vibrational signatures of the water solvent molecules from those of the core GlyHmore » + ion, allowing for quick assessment of solvation structures. Without the aid of calculations, we can already infer solvation motifs and the presence of multiple conformations. Furthermore, the use of a cryogenic ion trap to cluster solvent molecules around ions of interest and control H/D exchange reactions is broadly applicable and should be extendable to studies of more complex peptidic ions in large solvated clusters.« less

Clusters of isoleucine, leucine, and valine side chains define cores of stability in high-energy states of globular proteins: Sequence determinants of structure and stability.

PubMed

Kathuria, Sagar V; Chan, Yvonne H; Nobrega, R Paul; Özen, Ayşegül; Matthews, C Robert

2016-03-01

Measurements of protection against exchange of main chain amide hydrogens (NH) with solvent hydrogens in globular proteins have provided remarkable insights into the structures of rare high-energy states that populate their folding free-energy surfaces. Lacking, however, has been a unifying theory that rationalizes these high-energy states in terms of the structures and sequences of their resident proteins. The Branched Aliphatic Side Chain (BASiC) hypothesis has been developed to explain the observed patterns of protection in a pair of TIM barrel proteins. This hypothesis supposes that the side chains of isoleucine, leucine, and valine (ILV) residues often form large hydrophobic clusters that very effectively impede the penetration of water to their underlying hydrogen bond networks and, thereby, enhance the protection against solvent exchange. The linkage between the secondary and tertiary structures enables these ILV clusters to serve as cores of stability in high-energy partially folded states. Statistically significant correlations between the locations of large ILV clusters in native conformations and strong protection against exchange for a variety of motifs reported in the literature support the generality of the BASiC hypothesis. The results also illustrate the necessity to elaborate this simple hypothesis to account for the roles of adjacent hydrocarbon moieties in defining stability cores of partially folded states along folding reaction coordinates. © 2015 The Protein Society.

Estimation of Hydrogen-Exchange Protection Factors from MD Simulation Based on Amide Hydrogen Bonding Analysis.

PubMed

Park, In-Hee; Venable, John D; Steckler, Caitlin; Cellitti, Susan E; Lesley, Scott A; Spraggon, Glen; Brock, Ansgar

2015-09-28

Hydrogen exchange (HX) studies have provided critical insight into our understanding of protein folding, structure, and dynamics. More recently, hydrogen exchange mass spectrometry (HX-MS) has become a widely applicable tool for HX studies. The interpretation of the wealth of data generated by HX-MS experiments as well as other HX methods would greatly benefit from the availability of exchange predictions derived from structures or models for comparison with experiment. Most reported computational HX modeling studies have employed solvent-accessible-surface-area based metrics in attempts to interpret HX data on the basis of structures or models. In this study, a computational HX-MS prediction method based on classification of the amide hydrogen bonding modes mimicking the local unfolding model is demonstrated. Analysis of the NH bonding configurations from molecular dynamics (MD) simulation snapshots is used to determine partitioning over bonded and nonbonded NH states and is directly mapped into a protection factor (PF) using a logistics growth function. Predicted PFs are then used for calculating deuteration values of peptides and compared with experimental data. Hydrogen exchange MS data for fatty acid synthase thioesterase (FAS-TE) collected for a range of pHs and temperatures was used for detailed evaluation of the approach. High correlation between prediction and experiment for observable fragment peptides is observed in the FAS-TE and additional benchmarking systems that included various apo/holo proteins for which literature data were available. In addition, it is shown that HX modeling can improve experimental resolution through decomposition of in-exchange curves into rate classes, which correlate with prediction from MD. Successful rate class decompositions provide further evidence that the presented approach captures the underlying physical processes correctly at the single residue level. This assessment is further strengthened in a comparison of residue resolved protection factor predictions for staphylococcal nuclease with NMR data, which was also used to compare prediction performance with other algorithms described in the literature. The demonstrated transferable and scalable MD based HX prediction approach adds significantly to the available tools for HX-MS data interpretation based on available structures and models.

Estimation of Hydrogen-Exchange Protection Factors from MD Simulation Based on Amide Hydrogen Bonding Analysis

PubMed Central

Park, In-Hee; Venable, John D.; Steckler, Caitlin; Cellitti, Susan E.; Lesley, Scott A.; Spraggon, Glen; Brock, Ansgar

2015-01-01

Hydrogen exchange (HX) studies have provided critical insight into our understanding of protein folding, structure and dynamics. More recently, Hydrogen Exchange Mass Spectrometry (HX-MS) has become a widely applicable tool for HX studies. The interpretation of the wealth of data generated by HX-MS experiments as well as other HX methods would greatly benefit from the availability of exchange predictions derived from structures or models for comparison with experiment. Most reported computational HX modeling studies have employed solvent-accessible-surface-area based metrics in attempts to interpret HX data on the basis of structures or models. In this study, a computational HX-MS prediction method based on classification of the amide hydrogen bonding modes mimicking the local unfolding model is demonstrated. Analysis of the NH bonding configurations from Molecular Dynamics (MD) simulation snapshots is used to determine partitioning over bonded and non-bonded NH states and is directly mapped into a protection factor (PF) using a logistics growth function. Predicted PFs are then used for calculating deuteration values of peptides and compared with experimental data. Hydrogen exchange MS data for Fatty acid synthase thioesterase (FAS-TE) collected for a range of pHs and temperatures was used for detailed evaluation of the approach. High correlation between prediction and experiment for observable fragment peptides is observed in the FAS-TE and additional benchmarking systems that included various apo/holo proteins for which literature data were available. In addition, it is shown that HX modeling can improve experimental resolution through decomposition of in-exchange curves into rate classes, which correlate with prediction from MD. Successful rate class decompositions provide further evidence that the presented approach captures the underlying physical processes correctly at the single residue level. This assessment is further strengthened in a comparison of residue resolved protection factor predictions for staphylococcal nuclease with NMR data, which was also used to compare prediction performance with other algorithms described in the literature. The demonstrated transferable and scalable MD based HX prediction approach adds significantly to the available tools for HX-MS data interpretation based on available structures and models. PMID:26241692

Dispersion and separation of nanostructured carbon in organic solvents

NASA Technical Reports Server (NTRS)

Evans, Christopher M. (Inventor); Ruf, Herbert J. (Inventor); Landi, Brian J. (Inventor); Raffaelle, Ryne P. (Inventor)

2011-01-01

The present invention relates to dispersions of nanostructured carbon in organic solvents containing alkyl amide compounds and/or diamide compounds. The invention also relates to methods of dispersing nanostructured carbon in organic solvents and methods of mobilizing nanostructured carbon. Also disclosed are methods of determining the purity of nanostructured carbon.

Solvent-based and solvent-free characterization of low solubility and low molecular weight polyamides by mass spectrometry: a complementary approach.

PubMed

Barrère, Caroline; Hubert-Roux, Marie; Lange, Catherine M; Rejaibi, Majed; Kebir, Nasreddine; Désilles, Nicolas; Lecamp, Laurence; Burel, Fabrice; Loutelier-Bourhis, Corinne

2012-06-15

Polyamides (PA) belong to the most used classes of polymers because of their attractive chemical and mechanical properties. In order to monitor original PA design, it is essential to develop analytical methods for the characterization of these compounds that are mostly insoluble in usual solvents. A low molecular weight polyamide (PA11), synthesized with a chain limiter, has been used as a model compound and characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the solvent-based approach, specific solvents for PA, i.e. trifluoroacetic acid (TFA) and hexafluoroisopropanol (HFIP), were tested. Solvent-based sample preparation methods, dried-droplet and thin layer, were optimized through the choice of matrix and salt. Solvent-based (thin layer) and solvent-free methods were then compared for this low solubility polymer. Ultra-high-performance liquid chromatography/electrospray ionization (UHPLC/ESI)-TOF-MS analyses were then used to confirm elemental compositions through accurate mass measurement. Sodium iodide (NaI) and 2,5-dihydroxybenzoic acid (2,5-DHB) are, respectively, the best cationizing agent and matrix. The dried-droplet sample preparation method led to inhomogeneous deposits, but the thin-layer method could overcome this problem. Moreover, the solvent-free approach was the easiest and safest sample preparation method giving equivalent results to solvent-based methods. Linear as well as cyclic oligomers were observed. Although the PA molecular weights obtained by MALDI-TOF-MS were lower than those obtained by (1)H NMR and acido-basic titration, this technique allowed us to determine the presence of cyclic and linear species, not differentiated by the other techniques. TFA was shown to induce modification of linear oligomers that permitted cyclic and linear oligomers to be clearly highlighted in spectra. Optimal sample preparation conditions were determined for the MALDI-TOF-MS analysis of PA11, a model of polyamide analogues. The advantages of the solvent-free and solvent-based approaches were shown. Molecular weight determination using MALDI was discussed. Copyright © 2012 John Wiley & Sons, Ltd.

Harnessing Thin-Film Continuous-Flow Assembly Lines.

PubMed

Britton, Joshua; Castle, Jared W; Weiss, Gregory A; Raston, Colin L

2016-07-25

Inspired by nature's ability to construct complex molecules through sequential synthetic transformations, an assembly line synthesis of α-aminophosphonates has been developed. In this approach, simple starting materials are continuously fed through a thin-film reactor where the intermediates accrue molecular complexity as they progress through the flow system. Flow chemistry allows rapid multistep transformations to occur via reaction compartmentalization, an approach not amenable to using conventional flasks. Thin film processing can also access facile in situ solvent exchange to drive reaction efficiency, and through this method, α-aminophosphonate synthesis requires only 443 s residence time to produce 3.22 g h(-1) . Assembly-line synthesis allows unprecedented reaction flexibility and processing efficiency. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mulliken Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

NASA Astrophysics Data System (ADS)

Rosokha, S. V.; Newton, M. D.; Head-Gordon, M.; Kochi, J. K.

2006-05-01

The paramagnetic [1:1] encounter complex (TCNE)2-rad is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor ( TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE)2-rad by its intervalence absorption band at the solvent-dependent wavelength of λIV ˜ 1500 nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of HDA = 1000 cm -1. The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of HDA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy ( λ) and the electronic coupling element ( HDA) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes.

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

Dang, Liem X.; Vo, Quynh N.; Nilsson, Mikael

We report one of the first simulations using a classical rate theory approach to predict the mechanism of the exchange process between water and aqueous uranyl ions. Using our water and ion-water polarizable force fields and molecular dynamics techniques, we computed the potentials of mean force for the uranyl ion-water pair as the function of pressures at ambient temperature. Subsequently, these simulated potentials of mean force were used to calculate rate constants using the transition rate theory; the time dependent transmission coefficients were also examined using the reactive flux method and Grote-Hynes treatments of the dynamic response of the solvent.more » The computed activation volumes using transition rate theory and the corrected rate constants are positive, thus the mechanism of this particular water-exchange is a dissociative process. We discuss our rate theory results and compare them with previously studies in which non-polarizable force fields were used. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less

Li + solvation and kinetics of Li +–BF 4 -/PF 6 - ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

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

Chang, Tsun-Mei; Dang, Liem X.

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine in this paper the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li + and the dissociation kinetics of ion pairs Li +–[BF 4] and Li +–[PF 6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li + ions varied from 60 to 450 ps, depending on themore » correction method used. We found that the relaxation times changed significantly from Li +–[BF 4] to Li +–[PF 6] ion pairs in EC. Finally, our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.« less

Oriented MOF-polymer Composite Nanofiber Membranes for High Proton Conductivity at High Temperature and Anhydrous Condition

PubMed Central

Wu, Bin; Pan, Jiefeng; Ge, Liang; Wu, Liang; Wang, Huanting; Xu, Tongwen

2014-01-01

The novel oriented electrospun nanofiber membrane composed of MOFs and SPPESK has been synthesized for proton exchange membrane fuel cell operating at high temperature and anhydrous conditions. It is clear that the oriented nanofiber membrane displays the higher proton conductivity than that of the disordered nanofiber membrane or the membrane prepared by conventional solvent-casting method (without nanofibers). Nanofibers within the membranes are significantly oriented. The proton conductivity of the oriented nanofiber membrane can reach up to (8.2 ± 0.16) × 10−2 S cm−1 at 160°C under anhydrous condition for the highly orientation of nanofibers. Moreover, the oxidative stability and resistance of methanol permeability of the nanofibers membrane are obviously improved with an increase in orientation of nanofibers. The observed methanol permeability of 0.707 × 10−7 cm2 s−1 is about 6% of Nafion-115. Consequently, orientated nanofibers membrane is proved to be a promising material as the proton exchange membrane for potential application in direct methanol fuel cells. PMID:25082522

Li + solvation and kinetics of Li +–BF 4 -/PF 6 - ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories

DOE PAGES

Chang, Tsun-Mei; Dang, Liem X.

2017-07-19

Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine in this paper the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li + and the dissociation kinetics of ion pairs Li +–[BF 4] and Li +–[PF 6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li + ions varied from 60 to 450 ps, depending on themore » correction method used. We found that the relaxation times changed significantly from Li +–[BF 4] to Li +–[PF 6] ion pairs in EC. Finally, our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.« less

Arsenic speciation and fucoxanthin analysis from seaweed dietary supplements using LC-MS.

PubMed

Avula, Bharathi; Wang, Yan-Hong; Khan, Ikhlas A

2015-01-01

The study involves the analysis of total arsenic (As) in metallic form, and organic and inorganic As species from seaweeds and dietary supplements. The analysis provides data for dietary exposure estimates of inorganic species that are considered more toxic to humans than organic and total As. Total As was determined by acid digestion followed by inductively coupled plasma (ICP)-MS. To characterize the As species, solvent extraction with sonication and microwave extraction using various aqueous and aqueous/organic solvent mixtures were initially evaluated. The optimum As speciation method was determined to be water extraction followed by anion exchange HPLC coupled with ICP-MS. Optimization of chromatographic conditions led to baseline separation for six As species, including As acid, arsenous acid, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, in approximately 8 min using gradient elution. Detection limits for all six compounds were in the range of 10-15 ng/mL. The data presented here will be valuable for the QA of analytical method development and surveys of total As and As species in dietary supplements. The most abundant As species found were arsenite [As(III)] and arsenate [As(V)]. The sum of inorganic As species present in the dietary supplements ranged from 1.2 to 31 μg/day. In addition, the dietary supplements purported to contain fucoxanthin, a carotenoid having pharmacological activities, were analyzed using ultra-performance LC-UV/MS.

Flash nano-precipitation of polymer blends: a role for fluid flow?

NASA Astrophysics Data System (ADS)

Grundy, Lorena; Mason, Lachlan; Chergui, Jalel; Juric, Damir; Craster, Richard V.; Lee, Victoria; Prudhomme, Robert; Priestley, Rodney; Matar, Omar K.

2017-11-01

Porous structures can be formed by the controlled precipitation of polymer blends; ranging from porous matrices, with applications in membrane filtration, to porous nano-particles, with applications in catalysis, targeted drug delivery and emulsion stabilisation. Under a diffusive exchange of solvent for non-solvent, prevailing conditions favour the decomposition of polymer blends into multiple phases. Interestingly, dynamic structures can be `trapped' via vitrification prior to thermodynamic equilibrium. A promising mechanism for large-scale polymer processing is flash nano-precipitation (FNP). FNP particle formation has recently been modelled using spinodal decomposition theory, however the influence of fluid flow on structure formation is yet to be clarified. In this study, we couple a Navier-Stokes equation to a Cahn-Hilliard model of spinodal decomposition. The framework is implemented using Code BLUE, a massively scalable fluid dynamics solver, and applied to flows within confined impinging jet mixers. The present method is valid for a wide range of mixing timescales spanning FNP and conventional immersion precipitation processes. Results aid in the fabrication of nano-scale polymer particles with tuneable internal porosities. EPSRC, UK, MEMPHIS program Grant (EP/K003976/1), RAEng Research Chair (OKM), PETRONAS.

Utilization of the dilute acidic sulfate effluent as resources by coupling solvent extraction-oxidation-hydrolysis.

PubMed

Ren, Xiulian; Wei, Qifeng; Chen, Yongxing; Guo, Jingjing; Wei, Sijie; Wang, Xiaofei

2015-12-15

The pollution risk of dilute acidic sulfate effluent (DASE),which is discharged from titanium dioxide factories heavily every year, has sparked the recycling of sulfuric acid, iron and water. In this study, a new green recovery process for the DASE is proposed based on coupling solventextraction-oxidation-hydrolysis. Compared to the conventional ways, this innovative method allows the effective extraction of sulfuric acid and the precipitation of FexOy·nH2O in onestep without adding inorganic neutralizer or precipitant. Trioctylamine (TOA) in kerosene (20-50%) was used as an organic phase for solvent extraction. The hydrolytic productions and the raffinate purified by a cation exchange were evaluated using XRD and ICP-OES, respectively. The initial pH of 0.63 and Fe(II) concentration of 0.1 mol/L in the DASE, the volume ratio of organic toaqueous phase (O/A) of 3/1, and reaction temperature of 25 °C were determined as the optimal conditions. Under this conditions, Fe(II) was transformed as yellow precipitation which was characterized as α-FeOOH, and pH of raffinate was in the range of 3.6-3.8. Copyright © 2015 Elsevier B.V. All rights reserved.

Fabrication of a novel hydrophobic/ion-exchange mixed-mode adsorbent for the dispersive solid-phase extraction of chlorophenols from environmental water samples.

PubMed

Gao, Li; Wei, Yinmao

2016-08-01

A novel mixed-mode adsorbent was prepared by functionalizing silica with tris(2-aminoethyl)amine and 3-phenoxybenzaldehyde as the main mixed-mode scaffold due to the presence of the plentiful amino groups and benzene rings in their molecules. The adsorption mechanism was probed with acidic, natural and basic compounds, and the mixed hydrophobic and ion-exchange interactions were found to be responsible for the adsorption of analytes. The suitability of dispersive solid-phase extraction was demonstrated in the determination of chlorophenols in environmental water. Several parameters, including sample pH, desorption solvent, ionic strength, adsorbent dose, and extraction time were optimized. Under the optimal extraction conditions, the proposed dispersive solid-phase extraction coupled with high-performance liquid chromatography showed good linearity range and acceptable limits of detection (0.22∽0.54 ng/mL) for five chlorophenols. Notably, the higher extraction recoveries (88.7∽109.7%) for five chlorophenols were obtained with smaller adsorbent dose (10 mg) and shorter extraction time (15 min) compared with the reported methods. The proposed method might be potentially applied in the determination of trace chlorophenols in real water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Features of the adsorption of naproxen enantiomers on weak chiral anion-exchangers in nonlinear chromatography

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

Asnin, Leonid; Kaczmarski, Krzysztof; Guiochon, Georges A

The retention mechanism of the enantiomers of naproxen on a Pirkle-type chiral stationary phase (CSP) was studied. This CSP is made of a porous silica grafted with quinidine carbamate. It can interact with the weak organic electrolyte naproxen either by adsorbing it or by ion-exchange. Using frontal chromatography, we explored the adsorption equilibrium under such experimental conditions that naproxen dissociates or cannot dissociate. Under conditions preventing ionic dissociation, the adsorption isotherms were measured, the adsorption energy distributions determined, and the chromatographic profiles calculated. Three different types of the adsorption sites were found for both enantiomers. The density and the bindingmore » energy of these sites depend on the nature of the organic modifier. Different solute species, anions, neutral molecules, solvent-ion associates, and solute dimers can coexist in solution, giving rise to different forms of adsorption. This study showed the unexpected occurrence of secondary steps in the breakthrough profiles of S-naproxen in the adsorption mode at high concentrations. Being enantioselective, this phenomenon was assumed to result from the association of solute molecules involving a chiral selector moiety. A multisite Langmuir adsorption model was used to calculate band profiles. Although this model accounts excellently for the experimental adsorption isotherms, it does not explain all the features of the breakthrough profiles. A comparison between the calculated and experimental profiles allowed useful conclusions concerning the effects of the adsorbate-adsorbate and adsorbate-solvent interactions on the adsorption mechanism.« less

Two tools for applying chromatographic retention data to the mass-based identification of peptides during hydrogen/deuterium exchange experiments by nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Gershon, P D

2010-12-15

Two tools are described for integrating LC elution position with mass-based data in hydrogen-deuterium exchange (HDX) experiments by nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry (nanoLC/MALDI-MS, a novel approach to HDX-MS). The first of these, 'TOF2H-Z Comparator', highlights peptides in HDX experiments that are potentially misidentified on the basis of mass alone. The program first calculates normalized values for the organic solvent concentration responsible for the elution of ions in nanoLC/MALDI HDX experiments. It then allows the solvent gradients for the multiple experiments contributing to an MS/MS-confirmed peptic peptide library to be brought into mutual alignment by iteratively re-modeling variables among LC parameters such as gradient shape, solvent species, fraction duration and LC dead time. Finally, using the program, high-probability chromatographic outliers can be flagged within HDX experimental data. The role of the second tool, 'TOF2H-XIC Comparator', is to normalize the LC chromatograms corresponding to all deuteration timepoints of all HDX experiments of a project, to a common reference. Accurate normalization facilitates the verification of chromatographic consistency between all ions whose spectral segments contribute to particular deuterium uptake plots. Gradient normalization in this manner revealed chromatographic inconsistencies between ions whose masses were either indistinguishable or separated by precise isotopic increments. Copyright © 2010 John Wiley & Sons, Ltd.

Creating nanoscale emulsions using condensation.

PubMed

Guha, Ingrid F; Anand, Sushant; Varanasi, Kripa K

2017-11-08

Nanoscale emulsions are essential components in numerous products, ranging from processed foods to novel drug delivery systems. Existing emulsification methods rely either on the breakup of larger droplets or solvent exchange/inversion. Here we report a simple, scalable method of creating nanoscale water-in-oil emulsions by condensing water vapor onto a subcooled oil-surfactant solution. Our technique enables a bottom-up approach to forming small-scale emulsions. Nanoscale water droplets nucleate at the oil/air interface and spontaneously disperse within the oil, due to the spreading dynamics of oil on water. Oil-soluble surfactants stabilize the resulting emulsions. We find that the oil-surfactant concentration controls the spreading behavior of oil on water, as well as the peak size, polydispersity, and stability of the resulting emulsions. Using condensation, we form emulsions with peak radii around 100 nm and polydispersities around 10%. This emulsion formation technique may open different routes to creating emulsions, colloidal systems, and emulsion-based materials.

One-pot synthesis of monodisperse CoFe2O4@Ag core-shell nanoparticles and their characterization.

PubMed

Hara, Shuta; Aisu, Jumpei; Kato, Masahiro; Aono, Takashige; Sugawa, Kosuke; Takase, Kouichi; Otsuki, Joe; Shimizu, Shigeru; Ikake, Hiroki

2018-06-08

In recent years, monodispersed magnetic nanoparticles with a core/shell structure are expected for their wide applications including magnetic fluid, recoverable catalysts, and biological analysis. However, their synthesis method needs numerous processes such as solvent substitution, exchange of protective agents, and centrifugation. A simple and rapid method for the synthesis of monodispersed core-shell nanoparticles makes it possible to accelerate their further applications. This paper describes a simple and rapid one-pot synthesis of core (CoFe 2 O 4 )-shell (Ag) nanoparticles with high monodispersity. The synthesized nanoparticles showed plasmonic light absorption owing to the Ag shell. Moreover, the magnetic property of the nanoparticles had a soft magnetic behavior at room temperature and a hard magnetic behavior at 5 K. In addition, the nanoparticles showed high monodispersity with a low polydispersity index (PDI) value of 0.083 in hexane.

Synthesis and characterization of nanoporous silica aerogel beads using cheap industrial grade sodium silacte precursor

NASA Astrophysics Data System (ADS)

Khan, Tasneem M. A.; Khan, Asiya; Sarawade, Pradip B.

2018-05-01

We report a method to synthesize low-density transparent mesoporous silica aerogel beads by ambient pressure drying (APD). The beads were prepared by acid-base sol-gel polymerization of sodium silicate in via the ball dropping method (BDM). To minimize shrinkage during drying, wet silica beads were initially prepared; their surfaces were then modified using trimethylchlorosilane (TMCS) via simultaneous solvent exchange and surface modification. The specific surface area and cumulative pore volume of the silica aerogel beads increased with an increase in the %V of TMCS. Silica aerogel beads with low packing bed density, high surface area, and large cumulative pore volume was obtained when TMCS was used. Properties of the final product were examined by BET, and TG-DT analyses. The hydrophobic silica aerogel beads were thermally stable up to 350°C. We discuss our results and compare our findings for modified versus unmodified silica beads.

One-pot synthesis of monodisperse CoFe2O4@Ag core-shell nanoparticles and their characterization

NASA Astrophysics Data System (ADS)

Hara, Shuta; Aisu, Jumpei; Kato, Masahiro; Aono, Takashige; Sugawa, Kosuke; Takase, Kouichi; Otsuki, Joe; Shimizu, Shigeru; Ikake, Hiroki

2018-06-01

In recent years, monodispersed magnetic nanoparticles with a core/shell structure are expected for their wide applications including magnetic fluid, recoverable catalysts, and biological analysis. However, their synthesis method needs numerous processes such as solvent substitution, exchange of protective agents, and centrifugation. A simple and rapid method for the synthesis of monodispersed core-shell nanoparticles makes it possible to accelerate their further applications. This paper describes a simple and rapid one-pot synthesis of core (CoFe2O4)-shell (Ag) nanoparticles with high monodispersity. The synthesized nanoparticles showed plasmonic light absorption owing to the Ag shell. Moreover, the magnetic property of the nanoparticles had a soft magnetic behavior at room temperature and a hard magnetic behavior at 5 K. In addition, the nanoparticles showed high monodispersity with a low polydispersity index (PDI) value of 0.083 in hexane.

Method for removing contaminants from plastic resin

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2008-12-09

A resin recycling method that produces essentially contaminant-free synthetic resin material in an environmentally safe and economical manner. The method includes receiving the resin in container form. The containers are then ground into resin particles. The particles are exposed to a solvent, the solvent contacting the resin particles and substantially removing contaminants on the resin particles. After separating the particles and the resin, a solvent removing agent is used to remove any residual solvent remaining on the resin particles after separation.

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

Deng, Xuchu; Hu, Mary Y.; Wei, Xiaoliang

Understanding the solvation structures of electrolytes should prove conducive for the development of nonaqueous redox flow batteries that hold considerable potential for future large scale energy storage systems. The utilization of an emerging ionic-derivatived ferrocene compound, ferrocenylmethyl dimethyl ethyl ammonium bis(trifluoromethanesulfonyl)imide (Fc1N112-TFSI), has recently overcome the issue of solubility in the supporting electrolyte. In this work, 13C, 1H and 17O NMR investigations were carried out using electrolyte solutions consisting of Fc1N112-TFSI as the solute and the mixed alkyl carbonate as the solvent. It was observed that the spectra of 13C experience changes of chemical shifts while those of 17O undergomore » linewidth broadening, indicating interactions between solute and solvent molecules. Quantum chemistry calculations of both molecular structures and chemical shifts (13C, 1H and 17O) are performed for interpreting experimental results and of understanding the detailed solvation structures and molecular dynamics. The results indicate that Fc1N112-TFSI is dissociated at varying degrees in mixed solvent depending on concentrations. Solvent molecules encircle Fc1N112 and TFSI respectively as solvation shells, rapidly exchanging with both bulk solvent and TFSI. Additionally, the solvent with high dielectric constant is more capable of dissociating Fc1N112-TFSI molecules compared with those with low dielectric constant. At saturated concentration, contact ion pairs are formed and the solvent molecules are interacting with the Fc rings rather than interacting with the ionic pendant arm of Fc1N112-TFSI. These studies will contribute to the development of nonaqueous electrolytes of storage systems.« less

Effect of Organic Solvents on Microalgae Growth, Metabolism and Industrial Bioproduct Extraction: A Review.

PubMed

Miazek, Krystian; Kratky, Lukas; Sulc, Radek; Jirout, Tomas; Aguedo, Mario; Richel, Aurore; Goffin, Dorothee

2017-07-04

In this review, the effect of organic solvents on microalgae cultures from molecular to industrial scale is presented. Traditional organic solvents and solvents of new generation-ionic liquids (ILs), are considered. Alterations in microalgal cell metabolism and synthesis of target products (pigments, proteins, lipids), as a result of exposure to organic solvents, are summarized. Applications of organic solvents as a carbon source for microalgal growth and production of target molecules are discussed. Possible implementation of various industrial effluents containing organic solvents into microalgal cultivation media, is evaluated. The effect of organic solvents on extraction of target compounds from microalgae is also considered. Techniques for lipid and carotenoid extraction from viable microalgal biomass (milking methods) and dead microalgal biomass (classical methods) are depicted. Moreover, the economic survey of lipid and carotenoid extraction from microalgae biomass, by means of different techniques and solvents, is conducted.

Effect of Organic Solvents on Microalgae Growth, Metabolism and Industrial Bioproduct Extraction: A Review

PubMed Central

Miazek, Krystian; Sulc, Radek; Jirout, Tomas; Aguedo, Mario; Goffin, Dorothee

2017-01-01

In this review, the effect of organic solvents on microalgae cultures from molecular to industrial scale is presented. Traditional organic solvents and solvents of new generation-ionic liquids (ILs), are considered. Alterations in microalgal cell metabolism and synthesis of target products (pigments, proteins, lipids), as a result of exposure to organic solvents, are summarized. Applications of organic solvents as a carbon source for microalgal growth and production of target molecules are discussed. Possible implementation of various industrial effluents containing organic solvents into microalgal cultivation media, is evaluated. The effect of organic solvents on extraction of target compounds from microalgae is also considered. Techniques for lipid and carotenoid extraction from viable microalgal biomass (milking methods) and dead microalgal biomass (classical methods) are depicted. Moreover, the economic survey of lipid and carotenoid extraction from microalgae biomass, by means of different techniques and solvents, is conducted. PMID:28677659

Double proton transfer in the complex of acetic acid with methanol: Theory versus experiment

NASA Astrophysics Data System (ADS)

Fernández-Ramos, Antonio; Smedarchina, Zorka; Rodríguez-Otero, Jesús

2001-01-01

To test the approximate instanton approach to intermolecular proton-transfer dynamics, we report multidimensional ab initio bimolecular rate constants of HH, HD, and DD exchange in the complex of acetic acid with methanol in tetrahydrofuran-d8, and compare them with the NMR (nuclear magnetic resonance) experiments of Gerritzen and Limbach. The bimolecular rate constants are evaluated as products of the exchange rates and the equilibrium rate constants of complex formation in solution. The two molecules form hydrogen-bond bridges and the exchange occurs via concerted transfer of two protons. The dynamics of this transfer is evaluated in the complete space of 36 vibrational degrees of freedom. The geometries of the two isolated molecules, the complex, and the transition states corresponding to double proton transfer are fully optimized at QCISD (quadratic configuration interaction including single and double substitutions) level of theory, and the normal-mode frequencies are calculated at MP2 (Møller-Plesset perturbation theory of second order) level with the 6-31G (d,p) basis set. The presence of the solvent is taken into account via single-point calculations over the gas phase geometries with the PCM (polarized continuum model). The proton exchange rate constants, calculated with the instanton method, show the effect of the structure and strength of the hydrogen bonds, reflected in the coupling between the tunneling motion and the other vibrations of the complex. Comparison with experiment, which shows substantial kinetic isotopic effects (KIE), indicates that tunneling prevails over classic exchange for the whole temperature range of observation. The unusual behavior of the experimental KIE upon single and double deuterium substitution is well reproduced and is related to the synchronicity of two-atom tunneling.

Methods of producing adsorption media including a metal oxide

DOEpatents

Mann, Nicholas R; Tranter, Troy J

2014-03-04

Methods of producing a metal oxide are disclosed. The method comprises dissolving a metal salt in a reaction solvent to form a metal salt/reaction solvent solution. The metal salt is converted to a metal oxide and a caustic solution is added to the metal oxide/reaction solvent solution to adjust the pH of the metal oxide/reaction solvent solution to less than approximately 7.0. The metal oxide is precipitated and recovered. A method of producing adsorption media including the metal oxide is also disclosed, as is a precursor of an active component including particles of a metal oxide.

Solvent signal suppression for high-resolution MAS-DNP

NASA Astrophysics Data System (ADS)

Lee, Daniel; Chaudhari, Sachin R.; De Paëpe, Gaël

2017-05-01

Dynamic nuclear polarization (DNP) has become a powerful tool to substantially increase the sensitivity of high-field magic angle spinning (MAS) solid-state NMR experiments. The addition of dissolved hyperpolarizing agents usually results in the presence of solvent signals that can overlap and obscure those of interest from the analyte. Here, two methods are proposed to suppress DNP solvent signals: a Forced Echo Dephasing experiment (FEDex) and TRAnsfer of Populations in DOuble Resonance Echo Dephasing (TRAPDORED) NMR. These methods reintroduce a heteronuclear dipolar interaction that is specific to the solvent, thereby forcing a dephasing of recoupled solvent spins and leaving acquired NMR spectra free of associated resonance overlap with the analyte. The potency of these methods is demonstrated on sample types common to MAS-DNP experiments, namely a frozen solution (of L-proline) and a powdered solid (progesterone), both containing deuterated glycerol as a DNP solvent. The proposed methods are efficient, simple to implement, compatible with other NMR experiments, and extendable past spectral editing for just DNP solvents. The sensitivity gains from MAS-DNP in conjunction with FEDex or TRAPDORED then permits rapid and uninterrupted sample analysis.

An extensible framework for capturing solvent effects in computer generated kinetic models.

PubMed

Jalan, Amrit; West, Richard H; Green, William H

2013-03-14

Detailed kinetic models provide useful mechanistic insight into a chemical system. Manual construction of such models is laborious and error-prone, which has led to the development of automated methods for exploring chemical pathways. These methods rely on fast, high-throughput estimation of species thermochemistry and kinetic parameters. In this paper, we present a methodology for extending automatic mechanism generation to solution phase systems which requires estimation of solvent effects on reaction rates and equilibria. The linear solvation energy relationship (LSER) method of Abraham and co-workers is combined with Mintz correlations to estimate ΔG(solv)°(T) in over 30 solvents using solute descriptors estimated from group additivity. Simple corrections are found to be adequate for the treatment of radical sites, as suggested by comparison with known experimental data. The performance of scaled particle theory expressions for enthalpic-entropic decomposition of ΔG(solv)°(T) is also presented along with the associated computational issues. Similar high-throughput methods for solvent effects on free-radical kinetics are only available for a handful of reactions due to lack of reliable experimental data, and continuum dielectric calculations offer an alternative method for their estimation. For illustration, we model liquid phase oxidation of tetralin in different solvents computing the solvent dependence for ROO• + ROO• and ROO• + solvent reactions using polarizable continuum quantum chemistry methods. The resulting kinetic models show an increase in oxidation rate with solvent polarity, consistent with experiment. Further work needed to make this approach more generally useful is outlined.

Chemical treatment of low-grade uranium ores. Extraction of uranium from tricalcium phosphate; TRAITEMENT CHIMIQUE DES MINERAIS PAUVRES D'URANIUM. EXTRACTION DE L'URANIUM DU PHOSPHATE TRICALCIQUE (in French)

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

Mechelynck, Ph.

1958-07-15

After an examination of the different processes for the treatment of uranium minerals, it is concluded that the extraction of uranium by ion exchange is not applicable to hydrochloric acid solutions of phosphates. A sulfuric or phosphoric solution can be used. For solvent extraction of uranium, sulfuric or phosphoric solutions are the best, but hydrochloric solutions can be used. The cost of the solvents used would determine the cost of the operation. It is necessary, in the case of liquid-liquid extraction, to filter or decant the solution before extraction. (tr-auth)

Method of analysis of polymerizable monomeric species in a complex mixture

DOEpatents

Hermes, Robert E

2014-03-18

Method of selective quantitation of a polymerizable monomeric species in a well spacer fluid, said method comprising the steps of adding at least one solvent having a refractive index of less than about 1.33 to a sample of the complex mixture to produce a solvent phase, and measuring the refractive index of the solvent phase.

Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2

DOEpatents

Matzger, Adam J.; Liu, Baojian; Wong-Foy, Antek G.

2016-07-19

Flowing supercritical CO.sub.2 is used to activate metal organic framework materials (MOF). MOFs are activated directly from N,N-dimethylformamide (DMF) thus avoiding exchange with a volatile solvent. Most MCPs display increased surface areas directly after treatment although those with coordinatively unsaturated metal centers benefit from additional heating.

Monitoring equilibrium reaction dynamics of a nearly barrierless molecular rotor using ultrafast vibrational echoes

NASA Astrophysics Data System (ADS)

Nilsen, Ian A.; Osborne, Derek G.; White, Aaron M.; Anna, Jessica M.; Kubarych, Kevin J.

2014-10-01

Using rapidly acquired spectral diffusion, a recently developed variation of heterodyne detected infrared photon echo spectroscopy, we observe ˜3 ps solvent independent spectral diffusion of benzene chromium tricarbonyl (C6H6Cr(CO)3, BCT) in a series of nonpolar linear alkane solvents. The spectral dynamics is attributed to low-barrier internal torsional motion. This tripod complex has two stable minima corresponding to staggered and eclipsed conformations, which differ in energy by roughly half of kBT. The solvent independence is due to the relative size of the rotor compared with the solvent molecules, which create a solvent cage in which torsional motion occurs largely free from solvent damping. Since the one-dimensional transition state is computed to be only 0.03 kBT above the higher energy eclipsed conformation, this model system offers an unusual, nearly barrierless reaction, which nevertheless is characterized by torsional coordinate dependent vibrational frequencies. Hence, by studying the spectral diffusion of the tripod carbonyls, it is possible to gain insight into the fundamental dynamics of internal rotational motion, and we find some evidence for the importance of non-diffusive ballistic motion even in the room-temperature liquid environment. Using several different approaches to describe equilibrium kinetics, as well as the influence of reactive dynamics on spectroscopic observables, we provide evidence that the low-barrier torsional motion of BCT provides an excellent test case for detailed studies of the links between chemical exchange and linear and nonlinear vibrational spectroscopy.

Multiresidue Screening Method for Detection of Benzimidazoles and their Metabolites in Liver and Muscle by High-Performance Liquid Chromatography: Method Development and Validation According to Commission Decision 2002/657/EC

PubMed Central

Prearo, Marino; Stella, Paola; Ostorero, Federica; Abete, Maria Cesarina

2014-01-01

The use of veterinary drugs may cause the presence of residues in food of animal origin if appropriate withdrawal periods are not respected. A high-performance liquid chromatography (HPLC) method has been developed for the simultaneous detection of 11 benzimidazole residues, including metabolites – albendazole, albendazole sulphoxide, albendazole sulphone, fenbendazole, fenbendazole sulphoxide (oxfendazole), fenbendazole sulphone, flubendazole, mebendazole, oxibendazole, thiabendazole, 5-hydroxythiabendazole – in bovine, ovine, equine, swine, rabbit and poultry liver and in bovine, swine and fish muscle. After extraction with a dicloromethane/acetonitrile solution (35/65 v/v) containing 5% ammonium hydroxide, the solvent was evaporated to dryness, the residue was dissolved in HCl 0.1 M, defatted with hexane, purified on a strong cation exchange solid-phase extraction cartridge and analysed in HPLC with diode array and fluorescence detectors. The method was validated as screening qualitative method evaluating, according to Commission Decision 2002/657/EC criteria, specificity, CCβ and β error at cut off level of 25 μg/kg and ruggedness. PMID:27800310

Hydrogen exchange mass spectrometry of bacteriorhodopsin reveals light-induced changes in the structural dynamics of a biomolecular machine.

PubMed

Pan, Yan; Brown, Leonid; Konermann, Lars

2011-12-21

Many proteins act as molecular machines that are fuelled by a nonthermal energy source. Examples include transmembrane pumps and stator-rotor complexes. These systems undergo cyclic motions (CMs) that are being driven along a well-defined conformational trajectory. Superimposed on these CMs are thermal fluctuations (TFs) that are coupled to stochastic motions of the solvent. Here we explore whether the TFs of a molecular machine are affected by the occurrence of CMs. Bacteriorhodopsin (BR) is a light-driven proton pump that serves as a model system in this study. The function of BR is based on a photocycle that involves trans/cis isomerization of a retinal chromophore, as well as motions of transmembrane helices. Hydrogen/deuterium exchange (HDX) mass spectrometry was used to monitor the TFs of BR, focusing on the monomeric form of the protein. Comparative HDX studies were conducted under illumination and in the dark. The HDX kinetics of BR are dramatically accelerated in the presence of light. The isotope exchange rates and the number of backbone amides involved in EX2 opening transitions increase roughly 2-fold upon illumination. In contrast, light/dark control experiments on retinal-free protein produced no discernible differences. It can be concluded that the extent of TFs in BR strongly depends on photon-driven CMs. The light-induced differences in HDX behavior are ascribed to protein destabilization. Specifically, the thermodynamic stability of the dark-adapted protein is estimated to be 5.5 kJ mol(-1) under the conditions of our work. This value represents the free energy difference between the folded state F and a significantly unfolded conformer U. Illumination reduces the stability of F by 2.2 kJ mol(-1). Mechanical agitation caused by isomerization of the chromophore is transferred to the surrounding protein scaffold, and subsequently, the energy dissipates into the solvent. Light-induced retinal motions therefore act analogously to an internal heat source that promotes the occurrence of TFs. Overall, our data highlight the potential of HDX methods for probing the structural dynamics of molecular machines under "engine on" and "engine off" conditions. © 2011 American Chemical Society

Extended Hansen solubility approach: naphthalene in individual solvents.

PubMed

Martin, A; Wu, P L; Adjei, A; Beerbower, A; Prausnitz, J M

1981-11-01

A multiple regression method using Hansen partial solubility parameters, delta D, delta p, and delta H, was used to reproduce the solubilities of naphthalene in pure polar and nonpolar solvents and to predict its solubility in untested solvents. The method, called the extended Hansen approach, was compared with the extended Hildebrand solubility approach and the universal-functional-group-activity-coefficient (UNIFAC) method. The Hildebrand regular solution theory was also used to calculate naphthalene solubility. Naphthalene, an aromatic molecule having no side chains or functional groups, is "well-behaved', i.e., its solubility in active solvents known to interact with drug molecules is fairly regular. Because of its simplicity, naphthalene is a suitable solute with which to initiate the difficult study of solubility phenomena. The three methods tested (Hildebrand regular solution theory was introduced only for comparison of solubilities in regular solution) yielded similar results, reproducing naphthalene solubilities within approximately 30% of literature values. In some cases, however, the error was considerably greater. The UNIFAC calculation is superior in that it requires only the solute's heat of fusion, the melting point, and a knowledge of chemical structures of solute and solvent. The extended Hansen and extended Hildebrand methods need experimental solubility data on which to carry out regression analysis. The extended Hansen approach was the method of second choice because of its adaptability to solutes and solvents from various classes. Sample calculations are included to illustrate methods of predicting solubilities in untested solvents at various temperatures. The UNIFAC method was successful in this regard.

The rapid and direct determination of ATPase activity by ion exchange chromatography and the application to the activity of heat shock protein-90.

PubMed

Bartolini, Manuela; Wainer, Irving W; Bertucci, Carlo; Andrisano, Vincenza

2013-01-25

Adenosine nucleotides are involved as substrates or co-factors in several biochemical reactions, catalyzed by enzymes, which modulate energy production, signal transduction and cell proliferation. We here report the development and optimization of an ion exchange liquid chromatography (LC) method for the determination of ATP, ADP and AMP. This method is specifically aimed at the determination of the ATP-ase activity of human heat shock protein 90 (Hsp90), a molecular chaperone that has emerged as target enzyme in cancer therapy. Separation of the three nucleotides was achieved in a 15-min run by using a disk shaped monolithic ethylene diamine stationary phase of small dimensions (2mm×6mm i.d.), under a three-solvent gradient elution mode and UV detection at 256nm. The described direct LC method resulted highly specific as a consequence of the baseline separation of the three adenosine nucleotides and could be applied to the determination of the enzymatic activity of ADP/ATP generating or consuming enzymes (such as kinases). Furthermore, comparison of the LOD and LOQ values of the LC method with those obtained with the malachite green assay, which is one of the most used indirect screening methodologies for ATP-ase activity, showed that the LC method has a similar range of application without presenting the drawbacks related to contamination by inorganic phosphate ions and glycerol, which are present in Hsp90 commercial samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Connecting Free Energy Surfaces in Implicit and Explicit Solvent: an Efficient Method to Compute Conformational and Solvation Free Energies

PubMed Central

Deng, Nanjie; Zhang, Bin W.; Levy, Ronald M.

2015-01-01

The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions and protein-ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ~3 kcal/mol at only ~8 % of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the explicit/implicit thermodynamic cycle. PMID:26236174

Connecting free energy surfaces in implicit and explicit solvent: an efficient method to compute conformational and solvation free energies.

PubMed

Deng, Nanjie; Zhang, Bin W; Levy, Ronald M

2015-06-09

The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions, and protein–ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ∼3 kcal/mol at only ∼8% of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the implicit/explicit thermodynamic cycle.

Method to produce biomass-derived compounds using a co-solvent system containing gamma-valerolactone

DOEpatents

Dumesic, James A.; Motagamwala, Ali Hussain

2017-06-27

A method to produce an aqueous solution of carbohydrates containing C5- and/or C6-sugar-containing oligomers and/or C5- and/or C6-sugar monomers in which biomass or a biomass-derived reactant is reacted with a solvent system having an organic solvent, and organic co-solvent, and water, in the presence of an acid. The method produces the desired product, while a substantial portion of any lignin present in the reactant appears as a precipitate in the product mixture.

Method of stripping metals from organic solvents

DOEpatents

Todd, Terry A [Aberdeen, ID; Law, Jack D [Pocatello, ID; Herbst, R Scott [Idaho Falls, ID; Romanovskiy, Valeriy N [St. Petersburg, RU; Smirnov, Igor V [St.-Petersburg, RU; Babain, Vasily A [St-Petersburg, RU; Esimantovski, Vyatcheslav M [St-Petersburg, RU

2009-02-24

A new method to strip metals from organic solvents in a manner that allows for the recycle of the stripping agent. The method utilizes carbonate solutions of organic amines with complexants, in low concentrations, to strip metals from organic solvents. The method allows for the distillation and reuse of organic amines. The concentrated metal/complexant fraction from distillation is more amenable to immobilization than solutions resulting from current practice.

Determination of water traces in various organic solvents using Karl Fischer method under FIA conditions.

PubMed

Dantan, N; Frenzel, W; Küppers, S

2000-05-31

Flow injection methods utilising the Karl Fischer (KF) reaction with spectrophotometric and potentiometric detection are described for the determination of the trace water content in various organic solvents. Optimisation of the methods resulted in an accessible (linear) working range of 0.01-0.2% water for many solvents studied with a typical precision of 1-2% R.S.D. Only 50 mul of organic solvent was injected and the sampling frequency was about 120 samples per h. Since the slopes of the calibration curves were different for different solvents appropriate calibration was required. Problems associated with spectrophotometric detection and caused by refractive index changes were pointed out and a nested-loop configuration was proposed to overcome this kind of interference. The potentiometric method with a novel flow-through detector cell was shown to surpass the performance of spectrophotometric detection in any respect. The characteristics of the procedures developed made them well applicable for on-line monitoring of technical solvent distillations in an industrial plant.

Assessing implicit models for nonpolar mean solvation forces: The importance of dispersion and volume terms

PubMed Central

Wagoner, Jason A.; Baker, Nathan A.

2006-01-01

Continuum solvation models provide appealing alternatives to explicit solvent methods because of their ability to reproduce solvation effects while alleviating the need for expensive sampling. Our previous work has demonstrated that Poisson-Boltzmann methods are capable of faithfully reproducing polar explicit solvent forces for dilute protein systems; however, the popular solvent-accessible surface area model was shown to be incapable of accurately describing nonpolar solvation forces at atomic-length scales. Therefore, alternate continuum methods are needed to reproduce nonpolar interactions at the atomic scale. In the present work, we address this issue by supplementing the solvent-accessible surface area model with additional volume and dispersion integral terms suggested by scaled particle models and Weeks–Chandler–Andersen theory, respectively. This more complete nonpolar implicit solvent model shows very good agreement with explicit solvent results and suggests that, although often overlooked, the inclusion of appropriate dispersion and volume terms are essential for an accurate implicit solvent description of atomic-scale nonpolar forces. PMID:16709675

Solvent cleaning system and method for removing contaminants from solvent used in resin recycling

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2009-01-06

A two step solvent and carbon dioxide based system that produces essentially contaminant-free synthetic resin material and which further includes a solvent cleaning system for periodically removing the contaminants from the solvent so that the solvent can be reused and the contaminants can be collected and safely discarded in an environmentally safe manner.

UV-Vis spectroscopic study and DFT calculation on the solvent effect of trimethoprim in neat solvents and aqueous mixtures.

PubMed

Almandoz, M C; Sancho, M I; Duchowicz, P R; Blanco, S E

2014-08-14

The solvatochromic behavior of trimethoprim (TMP) was analyzed using UV-Vis spectroscopy and DFT methods in neat and binary aqueous solvent mixtures. The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding interactions on the absorption maxima were evaluated by means of the linear solvation energy relationship concept of Kamlet and Taft. This analysis indicated that both interactions play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra of TMP and TMP:(solvent)n complexes in ACN and H2O using TD-DFT methods were in agreement with the experimental ones. Binary aqueous mixtures containing as co-solvents DMSO, ACN and EtOH were studied. Preferential solvation was detected as a nonideal behavior of the wavenumber curve respective to the analytical mole fraction of co-solvent in all binary systems. TMP molecules were preferentially solvated by the organic solvent over the whole composition range. Index of preferential solvation, as well as the influence of solvent parameters were calculated as a function of solvent composition. Copyright © 2014 Elsevier B.V. All rights reserved.

Moving protons with pendant amines: proton mobility in a nickel catalyst for oxidation of hydrogen.

PubMed

O'Hagan, Molly; Shaw, Wendy J; Raugei, Simone; Chen, Shentan; Yang, Jenny Y; Kilgore, Uriah J; DuBois, Daniel L; Bullock, R Morris

2011-09-14

Proton transport is ubiquitous in chemical and biological processes, including the reduction of dioxygen to water, the reduction of CO(2) to formate, and the production/oxidation of hydrogen. In this work we describe intramolecular proton transfer between Ni and positioned pendant amines for the hydrogen oxidation electrocatalyst [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+) (P(Cy)(2)N(Bn)(2) = 1,5-dibenzyl-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane). Rate constants are determined by variable-temperature one-dimensional NMR techniques and two-dimensional EXSY experiments. Computational studies provide insight into the details of the proton movement and energetics of these complexes. Intramolecular proton exchange processes are observed for two of the three experimentally observable isomers of the doubly protonated Ni(0) complex, [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+), which have N-H bonds but no Ni-H bonds. For these two isomers, with pendant amines positioned endo to the Ni, the rate constants for proton exchange range from 10(4) to 10(5) s(-1) at 25 °C, depending on isomer and solvent. No exchange is observed for protons on pendant amines positioned exo to the Ni. Analysis of the exchange as a function of temperature provides a barrier for proton exchange of ΔG(‡) = 11-12 kcal/mol for both isomers, with little dependence on solvent. Density functional theory calculations and molecular dynamics simulations support the experimental observations, suggesting metal-mediated intramolecular proton transfers between nitrogen atoms, with chair-to-boat isomerizations as the rate-limiting steps. Because of the fast rate of proton movement, this catalyst may be considered a metal center surrounded by a cloud of exchanging protons. The high intramolecular proton mobility provides information directly pertinent to the ability of pendant amines to accelerate proton transfers during catalysis of hydrogen oxidation. These results may also have broader implications for proton movement in homogeneous catalysts and enzymes in general, with specific implications for the proton channel in the Ni-Fe hydrogenase enzyme.

Development of Simulation Methods in the Gibbs Ensemble to Predict Polymer-Solvent Phase Equilibria

NASA Astrophysics Data System (ADS)

Gartner, Thomas; Epps, Thomas; Jayaraman, Arthi

Solvent vapor annealing (SVA) of polymer thin films is a promising method for post-deposition polymer film morphology control. The large number of important parameters relevant to SVA (polymer, solvent, and substrate chemistries, incoming film condition, annealing and solvent evaporation conditions) makes systematic experimental study of SVA a time-consuming endeavor, motivating the application of simulation and theory to the SVA system to provide both mechanistic insight and scans of this wide parameter space. However, to rigorously treat the phase equilibrium between polymer film and solvent vapor while still probing the dynamics of SVA, new simulation methods must be developed. In this presentation, we compare two methods to study polymer-solvent phase equilibrium-Gibbs Ensemble Molecular Dynamics (GEMD) and Hybrid Monte Carlo/Molecular Dynamics (Hybrid MC/MD). Liquid-vapor equilibrium results are presented for the Lennard Jones fluid and for coarse-grained polymer-solvent systems relevant to SVA. We found that the Hybrid MC/MD method is more stable and consistent than GEMD, but GEMD has significant advantages in computational efficiency. We propose that Hybrid MC/MD simulations be used for unfamiliar systems in certain choice conditions, followed by much faster GEMD simulations to map out the remainder of the phase window.

Extending the solvent-free MALDI sample preparation method.

PubMed

Hanton, Scott D; Parees, David M

2005-01-01

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is an important technique to characterize many different materials, including synthetic polymers. MALDI mass spectral data can be used to determine the polymer average molecular weights, repeat units, and end groups. One of the key issues in traditional MALDI sample preparation is making good solutions of the analyte and the matrix. Solvent-free sample preparation methods have been developed to address these issues. Previous results of solvent-free or dry prepared samples show some advantages over traditional wet sample preparation methods. Although the results of the published solvent-free sample preparation methods produced excellent mass spectra, we found the method to be very time-consuming, with significant tool cleaning, which presents a significant possibility of cross contamination. To address these issues, we developed an extension of the solvent-free method that replaces the mortar and pestle grinding with ball milling the sample in a glass vial with two small steel balls. This new method generates mass spectra with equal quality of the previous methods, but has significant advantages in productivity, eliminates cross contamination, and is applicable to liquid and soft or waxy analytes.

Metal retention in human transferrin: consequences of solvent composition in analytical sample preparation methods.

PubMed

Quarles, C Derrick; Randunu, K Manoj; Brumaghim, Julia L; Marcus, R Kenneth

2011-10-01

The analysis of metal-binding proteins requires careful sample manipulation to ensure that the metal-protein complex remains in its native state and the metal retention is preserved during sample preparation or analysis. Chemical analysis for the metal content in proteins typically involves some type of liquid chromatography/electrophoresis separation step coupled with an atomic (i.e., inductively coupled plasma-optical emission spectroscopy or -mass spectrometry) or molecular (i.e., electrospray ionization-mass spectrometry) analysis step that requires altered-solvent introduction techniques. UV-VIS absorbance is employed here to monitor the iron content in human holo-transferrin (Tf) under various solvent conditions, changing polarity, pH, ionic strength, and the ionic and hydrophobic environment of the protein. Iron loading percentages (i.e. 100% loading equates to 2 Fe(3+):1 Tf) were quantitatively determined to evaluate the effect of solvent composition on the retention of Fe(3+) in Tf. Maximum retention of Fe(3+) was found in buffered (20 mM Tris) solutions (96 ± 1%). Exposure to organic solvents and deionized H(2)O caused release of ~23-36% of the Fe(3+) from the binding pocket(s) at physiological pH (7.4). Salt concentrations similar to separation conditions used for ion exchange had little to no effect on Fe(3+) retention in holo-Tf. Unsurprisingly, changes in ionic strength caused by additions of guanidine HCl (0-10 M) to holo-Tf resulted in unfolding of the protein and loss of Fe(3+) from Tf; however, denaturing and metal loss was found not to be an instantaneous process for additions of 1-5 M guanidinium to Tf. In contrast, complete denaturing and loss of Fe(3+) was instantaneous with ≥6 M additions of guanidinium, and denaturing and loss of iron from Tf occurred in parallel proportions. Changes to the hydrophobicity of Tf (via addition of 0-14 M urea) had less effect on denaturing and release of Fe(3+) from the Tf binding pocket compared to changes in ionic strength. This journal is © The Royal Society of Chemistry 2011

Supercritical Fluid Technologies to Fabricate Proliposomes.

PubMed

Falconer, James R; Svirskis, Darren; Adil, Ali A; Wu, Zimei

2015-01-01

Proliposomes are stable drug carrier systems designed to form liposomes upon addition of an aqueous phase. In this review, current trends in the use of supercritical fluid (SCF) technologies to prepare proliposomes are discussed. SCF methods are used in pharmaceutical research and industry to address limitations associated with conventional methods of pro/liposome fabrication. The SCF solvent methods of proliposome preparation are eco-friendly (known as green technology) and, along with the SCF anti-solvent methods, could be advantageous over conventional methods; enabling better design of particle morphology (size and shape). The major hurdles of SCF methods include poor scalability to industrial manufacturing which may result in variable particle characteristics. In the case of SCF anti-solvent methods, another hurdle is the reliance on organic solvents. However, the amount of solvent required is typically less than that used by the conventional methods. Another hurdle is that most of the SCF methods used have complicated manufacturing processes, although once the setup has been completed, SCF technologies offer a single-step process in the preparation of proliposomes compared to the multiple steps required by many other methods. Furthermore, there is limited research into how proliposomes will be converted into liposomes for the end-user, and how such a product can be prepared reproducibly in terms of vesicle size and drug loading. These hurdles must be overcome and with more research, SCF methods, especially where the SCF acts as a solvent, have the potential to offer a strong alternative to the conventional methods to prepare proliposomes.

Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2007-03-27

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2004-06-22

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Method for removing impurities from an impurity-containing fluid stream

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.

2010-04-06

A method of removing at least one polar component from a fluid stream. The method comprises providing a fluid stream comprising at least one nonpolar component and at least one polar component. The fluid stream is contacted with a supercritical solvent to remove the at least one polar component. The at least one nonpolar component may be a fat or oil and the at least one polar component may be water, dirt, detergents, or mixtures thereof. The supercritical solvent may decrease solubility of the at least one polar component in the fluid stream. The supercritical solvent may function as a solvent or as a gas antisolvent. The supercritical solvent may dissolve the nonpolar components of the fluid stream, such as fats or oils, while the polar components may be substantially insoluble. Alternatively, the supercritical solvent may be used to increase the nonpolarity of the fluid stream.

Imino proton exchange rates imply an induced-fit binding mechanism for the VEGF165-targeting aptamer, Macugen

PubMed Central

Lee, Joon-Hwa; Jucker, Fiona; Pardi, Arthur

2008-01-01

The 2′-fluoro/2′-O-methyl modified RNA aptamer Macugen is a potent inhibitor of the angiogenic regulatory protein, VEGF165. Macugen binds with high affinity to the heparin-binding domain (HBD) of VEGF165. Hydrogen exchange rates of the imino protons were measured for free Macugen and Macugen bound to the HBD or full-length VEGF to better understand the mechanism for high affinity binding. The results here show that the internal loop and hairpin loop of Macugen are highly dynamic in the free state and are greatly stabilized and/or protected from solvent upon protein binding. PMID:18485899

Solvent Flux Method (SFM): A Case Study of Water Access to Candida antarctica Lipase B.

PubMed

Benson, Sven P; Pleiss, Jürgen

2014-11-11

The solvent flux method (SFM) was developed to comprehensively characterize the influx of solvent molecules from the solvent environment into the active site of a protein in the framework of molecular dynamics simulations. This was achieved by introducing a solvent concentration gradient as well as partially reorienting and rescaling the velocity vector of all solvent molecules contained within a spherical volume enclosing the protein, thus inducing an accelerated solvent influx toward the active site. In addition to the detection of solvent access pathway within the protein structure, it is hereby possible to identify potential amino acid positions relevant to solvent-related enzyme engineering with high statistical significance. The method is particularly aimed at improving the reverse hydrolysis reaction rates in nonaqueous media. Candida antarctica lipase B (CALB) binds to a triglyceride-water interface with its substrate entrance channel oriented toward the hydrophobic substrate interface. The lipase-triglyceride-water system served as a model system for SFM to evaluate the influx of water molecules to the active site. As a proof of principle for SFM, a previously known water access pathway in CALB was identified as the primary water channel. In addition, a secondary water channel and two pathways for water access which contribute to water leakage between the protein and the triglyceride-water interface were identified.

SAIDE: A Semi-Automated Interface for Hydrogen/Deuterium Exchange Mass Spectrometry.

PubMed

Villar, Maria T; Miller, Danny E; Fenton, Aron W; Artigues, Antonio

2010-01-01

Deuterium/hydrogen exchange in combination with mass spectrometry (DH MS) is a sensitive technique for detection of changes in protein conformation and dynamics. Since temperature, pH and timing control are the key elements for reliable and efficient measurement of hydrogen/deuterium content in proteins and peptides, we have developed a small, semiautomatic interface for deuterium exchange that interfaces the HPLC pumps with a mass spectrometer. This interface is relatively inexpensive to build, and provides efficient temperature and timing control in all stages of enzyme digestion, HPLC separation and mass analysis of the resulting peptides. We have tested this system with a series of standard tryptic peptides reconstituted in a solvent containing increasing concentration of deuterium. Our results demonstrate the use of this interface results in minimal loss of deuterium due to back exchange during HPLC desalting and separation. For peptides reconstituted in a buffer containing 100% deuterium, and assuming that all amide linkages have exchanged hydrogen with deuterium, the maximum loss of deuterium content is only 17% of the label, indicating the loss of only one deuterium molecule per peptide.

SAIDE: A Semi-Automated Interface for Hydrogen/Deuterium Exchange Mass Spectrometry

PubMed Central

Villar, Maria T.; Miller, Danny E.; Fenton, Aron W.; Artigues, Antonio

2011-01-01

Deuterium/hydrogen exchange in combination with mass spectrometry (DH MS) is a sensitive technique for detection of changes in protein conformation and dynamics. Since temperature, pH and timing control are the key elements for reliable and efficient measurement of hydrogen/deuterium content in proteins and peptides, we have developed a small, semiautomatic interface for deuterium exchange that interfaces the HPLC pumps with a mass spectrometer. This interface is relatively inexpensive to build, and provides efficient temperature and timing control in all stages of enzyme digestion, HPLC separation and mass analysis of the resulting peptides. We have tested this system with a series of standard tryptic peptides reconstituted in a solvent containing increasing concentration of deuterium. Our results demonstrate the use of this interface results in minimal loss of deuterium due to back exchange during HPLC desalting and separation. For peptides reconstituted in a buffer containing 100% deuterium, and assuming that all amide linkages have exchanged hydrogen with deuterium, the maximum loss of deuterium content is only 17% of the label, indicating the loss of only one deuterium molecule per peptide. PMID:25309638

A new procedure to produce lignocellulosic anion exchangers from agricultural waste materials.

PubMed

Orlando, U S; Baes, A U; Nishijima, W; Okada, M

2002-07-01

Two lignocellulosic agricultural waste materials (LCM), sugarcane bagasse (BG) and rice hull (RH), were converted into weak-base anion exchanger and evaluated for their exchanger capacity for nitrate. Pure cellulose (PC) and pure alkaline lignin (PL) were also used as reference materials to elucidate possible reactivity in LCM. Epoxy and amino groups were introduced into BG, RH, PC and PL substrates after the reaction with epichlorohydrin and dimethylamine in the presence of pyridine and an organic solvent N,N-dimethylformamide (DMF). Amino group incorporation into cellulose decreased with the presence of water in the reaction mixture and increased with the reaction time and presence of a catalyst (pyridine). The highest maximum nitrate exchange capacity (Qmax) and yields of the prepared exchangers was obtained from PL (1.8 mmol g(-1) and 412.5%), followed by BG (1.41 mmol g(-1) and 300%), PC (1.34 mmol g(-1) and 166%) and RH (1.32 mmol g(-1) and 180%). The proposed synthetic procedure was effective in modifying PL, PC and LCM chemically resulting in a higher yield and nitrate removal capacity.

Porous PVDF/PANI ion-exchange membrane (IEM) modified by polyvinylpyrrolidone (PVP) and lithium chloride in the application of membrane capacitive deionisation (MCDI).

PubMed

Zhang, Yiming; Zhang, Wei; Cházaro-Ruiz, Luis F

2018-05-01

In this work, polyvinylidene fluoride (PVDF)/polyaniline (PANI) heterogeneous anion-exchange membranes filled with pore-forming agents polyvinylpyrrolidone (PVP) and lithium chloride were prepared by the solution-casting technique using the solvent 1-methyl-2-pyrrolidone (NMP) and a two-step phase inversion procedure. Key properties of the as-prepared membranes, such as hydrophilicity, water content, ion exchange capacity, fixed ion concentration, conductivity and transport number were examined and compared between membranes in different conditions. The pore-forming hydrophilic additives PVP and lithium chloride to the casting solution appeared to improve the ion-exchange membranes (IEMs) by increasing the conductivity, transport number and hydrophilicity. The effects of increasing membrane drying time on the porosity of the as-prepared membranes were found to lower membrane porosity by reducing membrane water content. However, pore-forming agents were found to be able to stabilise membrane transport number with different drying times. As-prepared PVDF/PANI anion-exchange membrane with pore-forming agent is demonstrated to be a more efficient candidate for water purification (e.g. desalination) and other industrial applications.

Spatial organization of surface nanobubbles and its implications in their formation process.

PubMed

Lhuissier, Henri; Lohse, Detlef; Zhang, Xuehua

2014-02-21

We study the size and spatial distribution of surface nanobubbles formed by the solvent exchange method to gain insight into the mechanism of their formation. The analysis of Atomic Force Microscopy (AFM) images of nanobubbles formed on a hydrophobic surface reveals that the nanobubbles are not randomly located, which we attribute to the role of the history of nucleation during the formation. Moreover, the size of each nanobubble is found to be strongly correlated with the area of the bubble-depleted zone around it. The precise correlation suggests that the nanobubbles grow by diffusion of the gas from the bulk rather than by diffusion of the gas adsorbed on the surface. Lastly, the size distribution of the nanobubbles is found to be well described by a log-normal distribution.

Facile phase transfer of gold nanorods and nanospheres stabilized with block copolymers

PubMed Central

Derikov, Yaroslav I; Shandryuk, Georgiy A; Talroze, Raisa V; Ezhov, Alexander A

2018-01-01

A fast route to transfer Au nanoparticles from aqueous to organic media is proposed based on the use of a high molecular mass diblock copolymer of styrene and 2-vinylpyridine for ligand exchange at the nanoparticle surface. The method enables the preparation of stable sols of Au nanorods with sizes of up to tens of nanometers or Au nanospheres in various organic solvents. By comparing the optical absorbance spectra of Au hydro- and organosols with the data of numerical simulations of the surface plasmon resonance, we find that nanoparticles do not aggregate and confirm the transmission electron microscopy data regarding their shape and size. The proposed approach can be effective in preparing hybrid composites without the use of strong thiol and amine surfactants. PMID:29527437

Role of tautomerism in RNA biochemistry

PubMed Central

Singh, Vipender; Fedeles, Bogdan I.

2015-01-01

Heterocyclic nucleic acid bases and their analogs can adopt multiple tautomeric forms due to the presence of multiple solvent-exchangeable protons. In DNA, spontaneous formation of minor tautomers has been speculated to contribute to mutagenic mispairings during DNA replication, whereas in RNA, minor tautomeric forms have been proposed to enhance the structural and functional diversity of RNA enzymes and aptamers. This review summarizes the role of tautomerism in RNA biochemistry, specifically focusing on the role of tautomerism in catalysis of small self-cleaving ribozymes and recognition of ligand analogs by riboswitches. Considering that the presence of multiple tautomers of nucleic acid bases is a rare occurrence, and that tautomers typically interconvert on a fast time scale, methods for studying rapid tautomerism in the context of nucleic acids under biologically relevant aqueous conditions are also discussed. PMID:25516996

Nano interface potential influences in CdTe quantum dots and biolabeling

NASA Astrophysics Data System (ADS)

Kanagasubbulakshmi, S.; Kadirvelu, K.

2018-05-01

Nano interface influences in physiochemical properties of quantum dots (QDs) are the challenging approach to tailor its surface functionalities. In this study, a set of polar and non-polar solvents were selected to analyze the influences in solvent-based dynamic radius and surface potential of QDs. From the nano interface chemistry of polar and non-polar solvents, an appropriate mechanism of precipitation and hydrophobic ligand exchange strategy were elucidated by correlating Henry's equation. Further, the in vitro cytotoxic potential and antimicrobial activity of QDs were assessed to perform biolabeling. From the observations, an appropriate dosage of QDs was fixed to label the animal ((RAW 264.7 cell lines) and bacterial cells (Escherichia coli) for effective cell attachment. Biolabeling was achieved by tailoring nano interface chemistry of QDs without additional support of biomolecules. Bacterial cell wall-based interaction of QDs was evaluated using SEM and EDAX analysis. Thus, provided clear insights into the nano interface chemistry in the development of highly photostable QDs will be helpful in biomedical applications.

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

Thompson, G H; Thompson, M C

Solvent extraction of /sup 237/Np and /sup 238/Pu from irradiated neptunium is being investigated as a possible replacement for the currently used anion exchange process at the Savannah River Plant. Solvent extraction would reduce separations costs and waste volume and increase the production rate. The major difficulty in solvent extraction processing is maintaining neptunium and plutonium in the extractable IV or VI valence states during initial extraction. This study investigated the stability of these states. Results show that: The extractable M(IV) valence states of neptunium and plutonium are mutually unstable in plant dissolver solution (2 g/l /sup 237/Np, 0.4 g/lmore » /sup 238/Pu, 1.2M Al/sup 3 +/, 4.6M NO/sub 3//sup -/, and 1M H/sup +/). The reaction rates producing inextractable species from extractable M(IV) or M(VI) are fast enough that greater than or equal to 99.9 percent extractable species in /sup 237/Np--/sup 238/Pu mixtures cannot be maintained for a practicable processing period (24 hours).« less

Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

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

Qi, Long; Alamillo, Ricardo; Elliott, William A.

Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose ismore » depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.« less

Synthesis and spectral characterization of environmentally responsive fluorescent deoxycytidine analogs

PubMed Central

Elmehriki, Adam AH; Suchý, Mojmír; Chicas, Kirby J; Wojciechowski, Filip; Hudson, Robert HE

2014-01-01

Herein, we describe the synthesis and spectroscopic properties of five novel pyrrolodeoxycytidine analogs, and the related 5-(1-pyrenylethynyl)-2’-deoxycytidine analog; as well as fluorescence characterization of 5-(p-methoxyphenylethynyl)-2’-deoxyuridine. Within this series of compounds, rigidification of the structure from 6-phenylpyrrolodeoxycytidine to 5,6-benzopyrroldeoxycytidine made remarkable improvement of the fluorescence quantum yield (Φ ~1, EtOH) and substantially increased the Stokes shift. Exchange of the phenyl group of 6-phenylpyrrolodeoxycytidine for other heterocycles (benzofuryl or indolyl) produced an increase in the extinction coefficient at the excitation wavelength while preserving high quantum yields. The steady-state fluorescence response to the environment was determined by sensitivity of Stokes shift to solvent polarity. The effect of solvent polarity on fluorescence emission intensity was concurrently examined and showed that 5,6-benzopyrrolodeoxycytidine is highly sensitive to the presence of water. On the other hand, the previously synthesized 5-(p-methoxyphenylethynyl)-2’-deoxyuridine was found to be sensitive to solvent viscosity indicating molecular rotor behavior. PMID:25483932

Temperature-Dependent Implicit-Solvent Model of Polyethylene Glycol in Aqueous Solution.

PubMed

Chudoba, Richard; Heyda, Jan; Dzubiella, Joachim

2017-12-12

A temperature (T)-dependent coarse-grained (CG) Hamiltonian of polyethylene glycol/oxide (PEG/PEO) in aqueous solution is reported to be used in implicit-solvent material models in a wide temperature (i.e., solvent quality) range. The T-dependent nonbonded CG interactions are derived from a combined "bottom-up" and "top-down" approach. The pair potentials calculated from atomistic replica-exchange molecular dynamics simulations in combination with the iterative Boltzmann inversion are postrefined by benchmarking to experimental data of the radius of gyration. For better handling and a fully continuous transferability in T-space, the pair potentials are conveniently truncated and mapped to an analytic formula with three structural parameters expressed as explicit continuous functions of T. It is then demonstrated that this model without further adjustments successfully reproduces other experimentally known key thermodynamic properties of semidilute PEG solutions such as the full equation of state (i.e., T-dependent osmotic pressure) for various chain lengths as well as their cloud point (or collapse) temperature.

Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory : determination of organophosphate pesticides in whole water by continuous liquid-liquid extraction and capillary-column gas chromatography with flame photometric detection

USGS Publications Warehouse

Jha, Virendra K.; Wydoski, Duane S.

2003-01-01

A method for the isolation of 20 parent organophosphate pesticides and 5 organophosphate pesticide degradates from natural-water samples is described. Compounds are extracted from water samples with methylene chloride using a continuous liquid-liquid extractor for 6 hours. The solvent is evaporated using heat and a flow of nitrogen to a volume of 1 milliliter and solvent exchanged to ethyl acetate. Extracted compounds are determined by capillary-column gas chromatography with flame photometric detection. Single-operator derived method detection limits in three water-matrix samples ranged from 0.003 to 0.009 microgram per liter. Method performance was validated by spiking all compounds in three different matrices at three different concentrations. Eight replicates were analyzed at each concentration in each matrix. Mean recoveries of most method compounds spiked in surface-water samples ranged from 54 to 137 percent and those in ground-water samples ranged from 40 to 109 percent for all pesticides. Recoveries in reagent-water samples ranged from 42 to 104 percent for all pesticides. The only exception was O-ethyl-O-methyl-S-propylphosphorothioate, which had variable recovery in all three matrices ranging from 27 to 79 percent. As a result, the detected concentration of O-ethyl-O-methyl-S-propylphosphorothioate in samples is reported in this method with an estimated remark code. Based on the performance issue, two more compounds, disulfoton and ethion monoxon, also will be reported in this method with an estimated remark code. Estimated-value compounds, which are ?E-coded? in the data base, do not meet the performance criteria for unqualified quantification, but are retained in the method because the compounds are important owing to high use or potential environmental effects and because analytical performance has been consistent and reproducible.

A molecularly based theory for electron transfer reorganization energy.

PubMed

Zhuang, Bilin; Wang, Zhen-Gang

2015-12-14

Using field-theoretic techniques, we develop a molecularly based dipolar self-consistent-field theory (DSCFT) for charge solvation in pure solvents under equilibrium and nonequilibrium conditions and apply it to the reorganization energy of electron transfer reactions. The DSCFT uses a set of molecular parameters, such as the solvent molecule's permanent dipole moment and polarizability, thus avoiding approximations that are inherent in treating the solvent as a linear dielectric medium. A simple, analytical expression for the free energy is obtained in terms of the equilibrium and nonequilibrium electrostatic potential profiles and electric susceptibilities, which are obtained by solving a set of self-consistent equations. With no adjustable parameters, the DSCFT predicts activation energies and reorganization energies in good agreement with previous experiments and calculations for the electron transfer between metallic ions. Because the DSCFT is able to describe the properties of the solvent in the immediate vicinity of the charges, it is unnecessary to distinguish between the inner-sphere and outer-sphere solvent molecules in the calculation of the reorganization energy as in previous work. Furthermore, examining the nonequilibrium free energy surfaces of electron transfer, we find that the nonequilibrium free energy is well approximated by a double parabola for self-exchange reactions, but the curvature of the nonequilibrium free energy surface depends on the charges of the electron-transferring species, contrary to the prediction by the linear dielectric theory.

Analysis of biomolecular solvation sites by 3D-RISM theory.

PubMed

Sindhikara, Daniel J; Hirata, Fumio

2013-06-06

We derive, implement, and apply equilibrium solvation site analysis for biomolecules. Our method utilizes 3D-RISM calculations to quickly obtain equilibrium solvent distributions without either necessity of simulation or limits of solvent sampling. Our analysis of these distributions extracts highest likelihood poses of solvent as well as localized entropies, enthalpies, and solvation free energies. We demonstrate our method on a structure of HIV-1 protease where excellent structural and thermodynamic data are available for comparison. Our results, obtained within minutes, show systematic agreement with available experimental data. Further, our results are in good agreement with established simulation-based solvent analysis methods. This method can be used not only for visual analysis of active site solvation but also for virtual screening methods and experimental refinement.

Method for the simultaneous recovery of radionuclides from liquid radioactive wastes using a solvent

DOEpatents

Romanovskiy, Valeriy Nicholiavich; Smirnov, Igor V.; Babain, Vasiliy A.; Todd, Terry A.; Brewer, Ken N.

2001-01-01

The present invention relates to solvents, and methods, for selectively extracting and recovering radionuclides, especially cesium and strontium, rare earths and actinides from liquid radioactive wastes. More specifically, the invention relates to extracting agent solvent compositions comprising complex organoboron compounds, substituted polyethylene glycols, and neutral organophosphorus compounds in a diluent. The preferred solvent comprises a chlorinated cobalt dicarbollide, diphenyl-dibutylmethylenecarbamoylphosphine oxide, PEG-400, and a diluent of phenylpolyfluoroalkyl sulfone. The invention also provides a method of using the invention extracting agents to recover cesium, strontium, rare earths and actinides from liquid radioactive waste.

Designing Solvent Exchange-Induced In Situ Forming Gel from Aqueous Insoluble Polymers as Matrix Base for Periodontitis Treatment.

PubMed

Srichan, Tharatree; Phaechamud, Thawatchai

2017-01-01

An in situ forming gel is a dosage form which is promised for site-specific therapy such as periodontal pocket of periodontitis treatment. Ethylcellulose, bleached shellac, and Eudragit RS were applied in this study as a polymeric matrix for in situ forming gel employing N-methyl pyrrolidone (NMP) as solvent. Solutions comprising ethylcellulose, bleached shellac, and Eudragit RS in NMP were evaluated for viscosity, rheology, and rate of water penetration. Ease of administration by injection was determined as the force required to expel polymeric solutions through a needle using texture analyzer. In vitro gel formation and in vitro gel degradation were conducted after injection into phosphate buffer solution pH 6.8. Ethylcellulose, bleached shellac, and Eudragit RS could form the in situ gel, in vitro. Gel viscosity and pH value depended on percentage amount of the polymer, whereas the water diffusion at early period likely relied on types of polymer. Furthermore, the solutions containing higher polymer concentration exhibited the lower degree of degradation. All the preparations were acceptable as injectable dosage forms because the applied force was lower than 50 N. All of them inhibited Staphylococcus aureus, Escherichia coli, Candida albicans, Streptococcus mutans, and Porphyrommonas gingivalis growth owing to antimicrobial activity of NMP which exhibited a potential use for periodontitis treatment. Moreover, the developed systems presented as the solvent exchange induced in situ forming gel and showed capability to be incorporated with the suitable antimicrobial active compounds for periodontitis treatment which should be further studied.

Process chemistry of americium-241

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

Navratil, J.D.

1983-01-01

Americium-241, one of the most useful actinide isotopes, is produced as a by-product of plutonium scrap recovery operations. Rocky Flats has supplied high purity americium oxide to the US Department of Energy's Isotope Pool since 1962. Over the years, the evolving separation and purification processes have included such diverse operations as ion exchange, aqueous precipitation, and both molten-salt and organic-solvent extraction.

ANALYSIS OF PROTEIN DIGESTS BY nano- SCX/RP/MSMS WITH pH SALT GRADIENT SCX ELUTION

EPA Science Inventory

The objective of this study was to optimize chromatographic parameters for complex peptide mixture analyses using two dimensional nano-LC/MSMS system. It used a strong cation exchange (SCX) and reversed phase chromatography (RP). The SCX solvent system was designed to promote pep...

Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process.

PubMed

Reshetnikov, Roman V; Sponer, Jiri; Rassokhina, Olga I; Kopylov, Alexei M; Tsvetkov, Philipp O; Makarov, Alexander A; Golovin, Andrey V

2011-12-01

A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. © The Author(s) 2011. Published by Oxford University Press.

Oxidative stress-mediated hemolytic activity of solvent exchange-prepared fullerene (C60) nanoparticles

NASA Astrophysics Data System (ADS)

Trpkovic, Andreja; Todorovic-Markovic, Biljana; Kleut, Duska; Misirkic, Maja; Janjetovic, Kristina; Vucicevic, Ljubica; Pantovic, Aleksandar; Jovanovic, Svetlana; Dramicanin, Miroslav; Markovic, Zoran; Trajkovic, Vladimir

2010-09-01

The present study investigated the hemolytic properties of fullerene (C60) nanoparticles prepared by solvent exchange using tetrahydrofuran (nC60THF), or by mechanochemically assisted complexation with macrocyclic oligosaccharide gamma-cyclodextrin (nC60CDX) or the copolymer ethylene vinyl acetate-ethylene vinyl versatate (nC60EVA-EVV). The spectrophotometrical analysis of hemoglobin release revealed that only nC60THF, but not nC60CDX or nC60EVA-EVV, was able to cause lysis of human erythrocytes in a dose- and time-dependent manner. Atomic force microscopy revealed that nC60THF-mediated hemolysis was preceded by erythrocyte shrinkage and increase in cell surface roughness. A flow cytometric analysis confirmed a decrease in erythrocyte size and demonstrated a significant increase in reactive oxygen species production in red blood cells exposed to nC60THF. The nC60THF-triggered hemolytic activity was efficiently reduced by the antioxidants N-acetylcysteine and butylated hydroxyanisole, as well as by serum albumin, the most abundant protein in human blood plasma. These data indicate that nC60THF can cause serum albumin-preventable hemolysis through oxidative stress-mediated damage of the erythrocyte membrane.

Reactions driving conformational movements (molecular motors) in gels: conformational and structural chemical kinetics.

PubMed

Otero, Toribio F

2017-01-18

In this perspective the empirical kinetics of conducting polymers exchanging anions and solvent during electrochemical reactions to get dense reactive gels is reviewed. The reaction drives conformational movements of the chains (molecular motors), exchange of ions and solvent with the electrolyte and structural (relaxation, swelling, shrinking and compaction) gel changes. Reaction-driven structural changes are identified and quantified from electrochemical responses. The empirical reaction activation energy (E a ), the reaction coefficient (k) and the reaction orders (α and β) change as a function of the conformational energy variation during the reaction. This conformational energy becomes an empirical magnitude. E a , k, α and β include and provide quantitative conformational and structural information. The chemical kinetics becomes structural chemical kinetics (SCK) for reactions driving conformational movements of the reactants. The electrochemically stimulated conformational relaxation model describes empirical results and some results from the literature for biochemical reactions. In parallel the development of an emerging technological world of soft, wet, multifunctional and biomimetic tools and anthropomorphic robots driven by reactions of the constitutive material, as in biological organs, can be now envisaged being theoretically supported by the kinetic model.

Cation binding to 15-TBA quadruplex DNA is a multiple-pathway cation-dependent process

PubMed Central

Reshetnikov, Roman V.; Sponer, Jiri; Rassokhina, Olga I.; Kopylov, Alexei M.; Tsvetkov, Philipp O.; Makarov, Alexander A.; Golovin, Andrey V.

2011-01-01

A combination of explicit solvent molecular dynamics simulation (30 simulations reaching 4 µs in total), hybrid quantum mechanics/molecular mechanics approach and isothermal titration calorimetry was used to investigate the atomistic picture of ion binding to 15-mer thrombin-binding quadruplex DNA (G-DNA) aptamer. Binding of ions to G-DNA is complex multiple pathway process, which is strongly affected by the type of the cation. The individual ion-binding events are substantially modulated by the connecting loops of the aptamer, which play several roles. They stabilize the molecule during time periods when the bound ions are not present, they modulate the route of the ion into the stem and they also stabilize the internal ions by closing the gates through which the ions enter the quadruplex. Using our extensive simulations, we for the first time observed full spontaneous exchange of internal cation between quadruplex molecule and bulk solvent at atomistic resolution. The simulation suggests that expulsion of the internally bound ion is correlated with initial binding of the incoming ion. The incoming ion then readily replaces the bound ion while minimizing any destabilization of the solute molecule during the exchange. PMID:21893589

Effect of extraction method on the yield of furanocoumarins from fruits of Archangelica officinalis Hoffm.

PubMed

Waksmundzka-Hajnos, M; Petruczynik, A; Dragan, A; Wianowska, D; Dawidowicz, A L

2004-01-01

Optimal conditions for the extraction and analysis of furanocoumarins from fruits of Archangelica officinalis Hoffm. have been determined. The following extraction methods were used: exhaustive extraction in a Soxhlet apparatus, ultrasonication at 25 and 60 degrees C, microwave-assisted solvent extraction in open and closed systems, and accelerated solvent extraction (ASE). In most cases the yields of furanocoumarins were highest using the ASE method. The effects of extracting solvent, temperature and time of extraction using this method were investigated. The highest yield of furanocoumarins by ASE was obtained with methanol at 100-130 degrees C for 10 min. The extraction yields of furanocoumarins from plant material by ultrasonication at 60 degrees C and microwave-assisted solvent extraction in an open system were comparable to the extraction yields obtained in the time- and solvent-consuming exhaustive process involving the Soxhlet apparatus.

A novel organic solvent-based coupling method for the preparation of covalently immobilized proteins on gold.

PubMed Central

Parker, M. C.; Patel, N.; Davies, M. C.; Roberts, C. J.; Tendler, S. J.; Williams, P. M.

1996-01-01

A novel organic solvent-based coupling method has been developed for the covalent immobilization of biological material to gold surfaces. The method employs the polar organic solvent anhydrous 2,2,2-trifluoroethanol as the reaction medium and involves dissolution of the protein (catalase) in the solvent allowing protein coupling to proceed under basic conditions in a dry organic environment. The advantage of this method is that protein attachment is favored over hydrolysis of the coupling reagent. We have shown qualitatively and quantitatively that following attachment to the gold surface a significant proportion of the enzyme catalase remains catalytically active (at least 20-31%). PMID:8931151

Photolithography and Fluorescence Correlation Spectroscopy used to examine the rates of exchange in reverse micelle systems

NASA Astrophysics Data System (ADS)

Norris, Zach; Mawson, Cara; Johnson, Kyron; Kessler, Sarah; Rebecca, Anne; Wolf, Nathan; Lim, Michael; Nucci, Nathaniel

Reverse micelles are molecular complexes that encapsulate a nanoscale pool of water in a surfactant shell dissolved in non-polar solvent. These complexes have a wide range of applications, and in all cases, the degree to which reverse micelles (RM) exchange their contents is relevant for their use. Despite its importance, this aspect of RM behavior is poorly understood. Photolithography is employed here to create micro and nano scale fluidic systems in which mixing rates can be precisely measured using fluorescence correlation spectroscopy (FCS). Micro-channel patterns are etched using reactive ion etching process into a layer of silicon dioxide on crystalline silicon substrates. Solutions containing mixtures of reverse micelles, proteins, and fluorophores are placed into reservoirs in the patterns, while diffusion and exchange between RMs is monitored using a FCS system built from a modified confocal Raman spectrometer. Using this approach, the diffusion and exchange rates for RM systems are measured as a function of the components of the RM mixture. Funding provided by Rowan University.

Structural basis for profilin-mediated actin nucleotide exchange

PubMed Central

Porta, Jason C.; Borgstahl, Gloria E.O.

2015-01-01

Actin is a ubiquitous eukaryotic protein that is responsible for cellular scaffolding, motility and division. The ability of actin to form a helical filament is the driving force behind these cellular activities. Formation of a filament is dependent the successful exchange of actin’s ADP for ATP. Mammalian profilin is a small actin binding protein that catalyzes the exchange of nucleotide and facilitates the addition of an actin monomer to a growing filament. Here, crystal structures of profilin:actin have been determined showing an actively exchanging ATP. The structural analysis shows how the binding of profilin to the barbed end of actin causes a rotation of the small domain relative to the large domain. This conformational change is propagated to the ATP site and causes a shift in the nucleotide loops which in turn causes a repositioning of Ca2+ to its canonical position as the cleft closes around ATP. Reversing the solvent exposure of Trp-356 is also involved in cleft closure. In addition, secondary calcium binding sites were identified. PMID:22366544

Tuning a High Transmission Ion Guide to Prevent Gas-Phase Proton Exchange During H/D Exchange MS Analysis.

PubMed

Guttman, Miklos; Wales, Thomas E; Whittington, Dale; Engen, John R; Brown, Jeffery M; Lee, Kelly K

2016-04-01

Hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for protein structural analysis has been adopted for many purposes, including biopharmaceutical development. One of the benefits of examining amide proton exchange by mass spectrometry is that it can readily resolve different exchange regimes, as evidenced by either binomial or bimodal isotope patterns. By careful analysis of the isotope pattern during exchange, more insight can be obtained on protein behavior in solution. However, one must be sure that any observed bimodal isotope patterns are not artifacts of analysis and are reflective of the true behavior in solution. Sample carryover and certain stationary phases are known as potential sources of bimodal artifacts. Here, we describe an additional undocumented source of deuterium loss resulting in artificial bimodal patterns for certain highly charged peptides. We demonstrate that this phenomenon is predominantly due to gas-phase proton exchange between peptides and bulk solvent within the initial stages of high-transmission conjoined ion guides. Minor adjustments of the ion guide settings, as reported here, eliminate the phenomenon without sacrificing signal intensity. Such gas-phase deuterium loss should be appreciated for all HDX-MS studies using such ion optics, even for routine studies not focused on interpreting bimodal spectra. Graphical Abstract ᅟ.

Kinetics of exchange between zero-, one-, and two-hydrogen-bonded states of methyl and ethyl acetate in methanol.

PubMed

Chuntonov, Lev; Pazos, Ileana M; Ma, Jianqiang; Gai, Feng

2015-03-26

It has recently been shown that the ester carbonyl stretching vibration can be used as a sensitive probe of local electrostatic field in molecular systems. To further characterize this vibrational probe and extend its potential applications, we studied the kinetics of chemical exchange between differently hydrogen-bonded (H-bonded) ester carbonyl groups of methyl acetate (MA) and ethyl acetate (EA) in methanol. We found that, while both MA and EA can form zero, one, or two H-bonds with the solvent, the population of the 2hb state in MA is significantly smaller than that in EA. Using a combination of linear and nonlinear infrared measurements and numerical simulations, we further determined the rate constants for the exchange between these differently H-bonded states. We found that for MA the chemical exchange reaction between the two dominant states (i.e., 0hb and 1hb states) has a relaxation rate constant of 0.14 ps(-1), whereas for EA the three-state chemical exchange reaction occurs in a predominantly sequential manner with the following relaxation rate constants: 0.11 ps(-1) for exchange between 0hb and 1hb states and 0.12 ps(-1) for exchange between 1hb and 2hb states.

Effect of additives on the activity of tannase from Aspergillus awamori MTCC9299.

PubMed

Chhokar, Vinod; Sangwan, Meenakshi; Beniwal, Vikas; Nehra, Kiran; Nehra, Kaur S

2010-04-01

Tannase from Aspergillus awamori MTCC 9299 was purified using ammonium sulfate precipitation followed by ion-exchange chromatography. A purification fold of 19.5 with 13.5% yield was obtained. Temperature of 30 degrees C and pH of 5.5 were found optimum for tannase activity. The effects of metals and organic solvents on the activity of tannase were also studied. Metal ions Mg(+2), Mn(+2), Ca(+2), Na(+), and K(+) stimulated the tannase activity, while Cu(+2), Fe(+3), and Co(+2) acted as inhibitors of the enzyme. The addition of organic solvents like acetic acid, isoamylalcohol, chloroform, isopropyl alcohol, and ethanol completely inhibited the enzyme activity. However, butanol and benzene increased the enzyme activity.

Method of removing contaminants from plastic resins

DOEpatents

Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

2008-11-18

A method for removing contaminants from synthetic resin material containers using a first organic solvent system and a second carbon dioxide system. The organic solvent is utilized for removing the contaminants from the synthetic resin material and the carbon dioxide is used to separate any residual organic solvent from the synthetic resin material.

Method of removing contaminants from plastic resins

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; Delaurentiis, Gary M [Jamestown, CA

2007-08-07

A method for removing contaminants from synthetic resin material containers using a first organic solvent system and a second carbon dioxide system. The organic solvent is utilized for removing the contaminants from the synthetic resin material and the carbon dioxide is used to separate any residual organic solvent from the synthetic resin material.

Method for removing contaminants from plastic resin

DOEpatents

Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

2008-12-30

A method for removing contaminants from synthetic resin material containers using a first organic solvent system and a second carbon dioxide system. The organic solvent is utilized for removing the contaminants from the synthetic resin material and the carbon dioxide is used to separate any residual organic solvent from the synthetic resin material.

Cyclic Solvent Vapor Annealing for Rapid, Robust Vertical Orientation of Features in BCP Thin Films

NASA Astrophysics Data System (ADS)

Paradiso, Sean; Delaney, Kris; Fredrickson, Glenn

2015-03-01

Methods for reliably controlling block copolymer self assembly have seen much attention over the past decade as new applications for nanostructured thin films emerge in the fields of nanopatterning and lithography. While solvent assisted annealing techniques are established as flexible and simple methods for achieving long range order, solvent annealing alone exhibits a very weak thermodynamic driving force for vertically orienting domains with respect to the free surface. To address the desire for oriented features, we have investigated a cyclic solvent vapor annealing (CSVA) approach that combines the mobility benefits of solvent annealing with selective stress experienced by structures oriented parallel to the free surface as the film is repeatedly swollen with solvent and dried. Using dynamical self-consistent field theory (DSCFT) calculations, we establish the conditions under which the method significantly outperforms both static and cyclic thermal annealing and implicate the orientation selection as a consequence of the swelling/deswelling process. Our results suggest that CSVA may prove to be a potent method for the rapid formation of highly ordered, vertically oriented features in block copolymer thin films.

Solvent Extraction of Furfural From Biomass

NASA Technical Reports Server (NTRS)

Humphrey, M. F.

1984-01-01

Solvent-extraction method reduces energy required to remove furfural produced during acid hydrolysis of biomass. Acid hydrolysis performed in vessel containing both solvents and reacting ingredients. With intimate contact between solvents and aqueous hydrolyis liqour, furfural removed form liquor almost as fast as it forms.

Modeling of the phase equilibria of polystyrene in methylcyclohexane with semi-empirical quantum mechanical methods I.

PubMed

Wilczura-Wachnik, Hanna; Jónsdóttir, Svava Osk

2003-04-01

A method for calculating interaction parameters traditionally used in phase-equilibrium computations in low-molecular systems has been extended for the prediction of solvent activities of aromatic polymer solutions (polystyrene+methylcyclohexane). Using ethylbenzene as a model compound for the repeating unit of the polymer, the intermolecular interaction energies between the solvent molecule and the polymer were simulated. The semiempirical quantum chemical method AM1, and a method for sampling relevant internal orientations for a pair of molecules developed previously were used. Interaction energies are determined for three molecular pairs, the solvent and the model molecule, two solvent molecules and two model molecules, and used to calculated UNIQUAC interaction parameters, a(ij) and a(ji). Using these parameters, the solvent activities of the polystyrene 90,000 amu+methylcyclohexane system, and the total vapor pressures of the methylcyclohexane+ethylbenzene system were calculated. The latter system was compared to experimental data, giving qualitative agreement. Figure Solvent activities for the methylcylcohexane(1)+polystyrene(2) system at 316 K. Parameters aij (blue line) obtained with the AM1 method; parameters aij (pink line) from VLE data for the ethylbenzene+methylcyclohexane system. The abscissa is the polymer weight fraction defined as y2(x1)=(1mx1)M2/[x1M1+(1mx1)M2], where x1 is the solvent mole fraction and Mi are the molecular weights of the components.

Investigation of Cleanliness Verification Techniques for Rocket Engine Hardware

NASA Technical Reports Server (NTRS)

Fritzemeier, Marilyn L.; Skowronski, Raymund P.

1994-01-01

Oxidizer propellant systems for liquid-fueled rocket engines must meet stringent cleanliness requirements for particulate and nonvolatile residue. These requirements were established to limit residual contaminants which could block small orifices or ignite in the oxidizer system during engine operation. Limiting organic residues in high pressure oxygen systems, such as in the Space Shuttle Main Engine (SSME), is particularly important. The current method of cleanliness verification for the SSME uses an organic solvent flush of the critical hardware surfaces. The solvent is filtered and analyzed for particulate matter followed by gravimetric determination of the nonvolatile residue (NVR) content of the filtered solvent. The organic solvents currently specified for use (1, 1, 1-trichloroethane and CFC-113) are ozone-depleting chemicals slated for elimination by December 1995. A test program is in progress to evaluate alternative methods for cleanliness verification that do not require the use of ozone-depleting chemicals and that minimize or eliminate the use of solvents regulated as hazardous air pollutants or smog precursors. Initial results from the laboratory test program to evaluate aqueous-based methods and organic solvent flush methods for NVR verification are provided and compared with results obtained using the current method. Evaluation of the alternative methods was conducted using a range of contaminants encountered in the manufacture of rocket engine hardware.

Tetrahydrofuran-water extraction, in-line clean-up and selective liquid chromatography/tandem mass spectrometry for the quantitation of perfluorinated compounds in food at the low picogram per gram level.

PubMed

Ballesteros-Gómez, Ana; Rubio, Soledad; van Leeuwen, Stefan

2010-09-17

A new solvent extraction system was developed for extraction of PFCs from food. The extraction is carried out with 75:25 (v/v) tetrahydrofuran:water, a solvent mixture that provides an appropriate balance of hydrogen bonding, dispersion and dipole-dipole interactions to efficiently extract PFCs with chains containing 4-14 carbon atoms from foods. This mixture provided recoveries above 85% from foods including vegetables, fruits, fish, meat and bread; and above 75% from cheese. Clean-up with a weak anion exchange resin and Envi-carb SPE, which were coupled in line for simplicity, was found to minimize matrix effects (viz. enhancement or suppression of electrospray ionization). The target analytes (PFCs) were resolved on a perfluorooctyl phase column that proved effective in separating mass interferences for perfluorooctane sulfonate (PFOS) in fish and meat samples. The mass spectrometer was operated in the negative electrospray ionization mode and used to record two transitions per analyte and one per mass-labeled method internal standard. The target PFCs were quantified from solvent based calibration curves. The limits of detection (LODs) were as low as 1-5 pg analyte g(-1) food; by exception, those for C(4) and C(5) PFCs were somewhat higher (25-30 pg g(-1)) owing to their less favourable mass response. To the best of our knowledge these are among the best LODs for PFCs in foods reported to date. The analysis of a variety of foods revealed contamination with PFCs at levels from 4.5 to 75 pg g(-1) in 25% of samples (fish and packaged spinach). C(10)-C(14) PFCs were found in fish, which testifies to the need to control long-chain PFCs in this type of food. The proposed method is a useful tool for the development of a large-scale database for the presence of PFCs in foods. 2010 Elsevier B.V. All rights reserved.

Ion Exchange and Solvent Extraction: Supramolecular Aspects of Solvent Exchange Volume 21

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

Gloe, Karsten; Tasker, Peter A; Oshima, Tatsuya

Preface The theme of supramolecular chemistry (SC), entailing the organization of multiple species through noncovalent interactions, has permeated virtually all aspects of chemical endeavor over the past several decades. Given that the observed behavior of discrete molecular species depends upon their weak interactions with one another and with matrix components, one would have to conclude that SC must indeed form part of the fabric of chemistry itself. A vast literature now serves to categorize SC phenomena within a body of consistent terminology. The word supramolecular itself appears in the titles of dozens of books, several journals, and a dedicated encyclopedia.more » Not surprisingly, the theme of SC also permeates the field of solvent extraction (SX), inspiring the framework for this volume of Ion Exchange and Solvent Extraction. It is attempted in the six chapters of this volume to identify both how supramolecular behavior occurs and is studied in the context of SX and how SC is influencing the current direction of SX. Researchers and practitioners have long dealt with supramolecular interactions in SX. Indeed, the use of polar extractant molecules in nonpolar media virtually assures that aggregative interactions will dominate the solution behavior of SX. Analytical chemists working in the 1930s to the 1950s with simple mono- and bidentate chelating ligands as extractants noted that extraction of metal ions obeyed complicated mass-action equilibria involving complex stoichiometries. As chemists and engineers developed processes for nuclear and hydrometallurgical applications in the 1950s and 1960s, the preference for aliphatic diluents only enhanced the complexity and supramolecular nature of extraction chemistry. Use of physical techniques such as light scattering and vapor-pressure measurements together with various spectroscopic methods revealed organic-phase aggregates from well-defined dimers to small aggregates containing a few extractant molecules to large inverse micelles swollen with water molecules. Extraction systems involving long-chain cations such as alkylammonium species or long-chain anions such as sulfonates or carboxylates proved especially prone to extensive aggregate formation. The related phenomenon of third-phase formation in SX systems, long misunderstood, is now yielding to spectroscopic and scattering techniques showing extensive long-range organization. Over the last 50 years, tools for studying the structure and thermodynamics of aggregation have grown increasingly sophisticated, leading to a rich and detailed understanding of what we can now recognize as SC phenomena in SX. In the 1970s and 1980s, the rapid growth of SC elicited a paradigm shift in SX. The influence of SC principles had two major effects on the course of SX research. First, it provided a framework for understanding the supramolecular behavior that was already well appreciated in the field of SX, though earlier without the SC terminology. Second, it provided the conceptual tools to control supramolecular behavior in SX, direct it for intended functionality, and to simplify it. Extraction by designed reagents has been steadily progressing ever since, with commercial applications emerging to successfully validate this approach. With the discovery of crown ethers in the late 1960s, the advancement of extractant design has fruitfully employed the concept of inclusion. While considerable initial progress occurred with such molecules, especially because of their affinity and selectivity for alkali and alkaline earth metals, other molecular platforms such as calixarenes have proven more versatile. Multidentate receptors for partial to full inclusion of cations, anions, ion pairs, as well as neutral species, have now become commonplace for selective extraction. This volume of Ion Exchange and Solvent Extraction examines how the principles of SC are being employed both in advancing the design of new highly selective SX systems and in understanding aggregation phenomena in SX systems. Chapter 1 discusses the nature and definition of SC and how it is used generally in design of novel SX reagents. Major approaches using SC principles are outlined and illustrated. Chapter 2 expands upon the theme of ion-pair recognition and introduces outer-sphere recognition of metal complexes, a novel idea with the potential for structural control of solvation, casting a new light on solvent modifiers. Chapter 3 reviews the large literature of calixarenes as extraction reagents for metal ions, where the synthetic versatility of this family of compounds has produced vast possibilities for inclusion and selective separations. Chapter 4 extends such chemistry to extraction of biomolecules, where the potential for selective separations is only beginning to be explored through site recognition in macromolecules. In Chapter 5, a detailed examination of the liquid-liquid interface as an expression of supramolecular phenomena i...« less

MOF-5(Zn)-Fe2O4 nanocomposite based magnetic solid-phase microextraction followed by HPLC-UV for efficient enrichment of colchicine in root of colchicium extracts and plasma samples.

PubMed

Bahrani, Sonia; Ghaedi, Mehrorang; Dashtian, Kheibar; Ostovan, Abbas; Mansoorkhani, Mohammad Javad Khoshnood; Salehi, Amin

2017-11-01

In present work, facile method is developed for determination of colchicine in human plasma sample, autumn and spring root of colchicium extracts by ultrasound assisted dispersive magnetic solid phase microextraction followed by HPLC-UV method (UAD-MSPME-HPLC-UV). Magnetic (Fe 2 O 4 -nanoparticles) metal organic framework-5, (MOF-5(Zn)-Fe 2 O 4 NPs) was synthesized by dispersing MOF-5 and Fe(NO 3 ) 3 .9H 2 O in ethylene glycol (as capping agent) and NaOH (pH adjustment agent) by hydrothermal method. The prepared sorbent was characterized via XRD and SEM analysis and applied as magnetic solid phase in UAD-MSPME-HPLC-UV method. In this method, colchicine molecules were sorbed on MOF-5(Zn)-Fe 2 O 4 NPs sorbent by various mechanisms like ion exchange, hydrogen bonding and electrostatic, ᴨ-ᴨ, hard-hard and dipole-ion interaction followed by exposing sonication waves as incremental mass transfer agent and then the sorbent was separated from the sample matrix by an external magnetic fields. Subsequently, accumulated colchicine were eluted by small volume of desorption organic solvent. Influence of operational variables such as MOF-5(Zn)-Fe 2 O 4 NPs mass, volume of extracting solvent and sonication time on response property (recovery) were studied and optimized by central composite design (CCD) combined with desirability function (DF) approach. Under optimum condition, the method has wide linear calibration rang (0.5-1700ngmL -1 ) with reasonable detection limit (0.13ngmL -1 ) and R 2 =0.9971. Finally, the UAD-MSPME-HPLC-UV method was successfully applied for determination of colchicine autumn and spring root of colchicium extracts and plasma samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Solvent effects in time-dependent self-consistent field methods. I. Optical response calculations

DOE PAGES

Bjorgaard, J. A.; Kuzmenko, V.; Velizhanin, K. A.; ...

2015-01-22

In this study, we implement and examine three excited state solvent models in time-dependent self-consistent field methods using a consistent formalism which unambiguously shows their relationship. These are the linear response, state specific, and vertical excitation solvent models. Their effects on energies calculated with the equivalent of COSMO/CIS/AM1 are given for a set of test molecules with varying excited state charge transfer character. The resulting solvent effects are explained qualitatively using a dipole approximation. It is shown that the fundamental differences between these solvent models are reflected by the character of the calculated excitations.

Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2006-07-11

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2002-01-01

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Controlled drug delivery for glaucoma therapy using montmorillonite/Eudragit microspheres as an ion-exchange carrier

PubMed Central

Tian, Shuangyan; Li, Juan; Tao, Qi; Zhao, Yawen; Lv, Zhufen; Yang, Fan; Duan, Haoyun; Chen, Yanzhong; Zhou, Qingjun; Hou, Dongzhi

2018-01-01

Background Glaucoma is a serious eye disease that can lead to loss of vision. Unfortunately, effective treatments are limited by poor bioavailability of antiglaucoma medicine due to short residence time on the preocular surface. Materials and methods To solve this, we successfully prepared novel controlled-release ion-exchange microparticles to deliver betaxolol hydrochloride (BH). Montmorillonite/BH complex (Mt-BH) was prepared by acidification-intercalation, and this complex was encapsulated in microspheres (Mt-BH encapsulated microspheres [BMEMs]) by oil-in-oil emulsion–solvent evaporation method. The BH loaded into ion-exchange Mt was 47.45%±0.54%. After the encapsulation of Mt-BH into Eudragit microspheres, the encapsulation efficiency of BH into Eudragit microspheres was 94.35%±1.01% and BH loaded into Eudragit microspheres was 14.31%±0.47%. Results Both Fourier transform infrared spectra and X-ray diffraction patterns indicated that BH was successfully intercalated into acid-Mt to form Mt-BH and then Mt-BH was encapsulated into Eudragit microspheres to obtain BMEMs. Interestingly, in vitro release duration of the prepared BMEMs was extended to 12 hours, which is longer than both of the BH solution (2.5 hours) and the conventional BH microspheres (5 hours). Moreover, BMEM exhibited lower toxicity than that of BH solution as shown by the results of cytotoxicity tests, chorioallantoic membrane-trypan blue staining, and Draize rabbit eye test. In addition, both in vivo and in vitro preocular retention capacity study of BMEMs showed a prolonged retention time. The pharmacodynamics showed that BMEMs could extend the drug duration of action. Conclusion The developed BMEMs have the potential to be further applied as ocular drug delivery systems for the treatment of glaucoma. PMID:29391798

Application of enzyme-linked immunosorbent assay for measurement of polychlorinated biphenyls from hydrophobic solutions: Extracts of fish and dialysates of semipermeable membrane devices: Chapter 26

USGS Publications Warehouse

Zajicek, James L.; Tillitt, Donald E.; Huckins, James N.; Petty, Jimmie D.; Potts, Michael E.; Nardone, David A.

1996-01-01

Determination of PCBs in biological tissue extracts by enzyme-linked immunosorbent assays (ELISAs) can be problematic, since the hydrophobic solvents used for their extraction and isolation from interfering biochemicals have limited compatibility with the polar solvents (e.g. methanol/water) and the immunochemical reagents used in ELISA. Our studies of these solvent effects indicate that significant errors can occur when microliter volumes of PCB containing extracts, in hydrophobic solvents, are diluted directly into methanol/water diluents. Errors include low recovery and excess variability among sub-samples taken from the same sample dilution. These errors are associated with inhomogeneity of the dilution, which is readily visualized by the use of a hydrophobic dye, Solvent Blue 35. Solvent Blue 35 is also used to visualize the evaporative removal of hydrophobic solvent and the dissolution of the resulting PCB/dye residue by pure methanol and 50% (v/v) methanol/water, typical ELISA diluents. Evaporative removal of isooctane by an ambient temperature nitrogen purge with subsequent dissolution in 100% methanol gives near quantitative recovery of model PCB congeners. We also compare concentrations of total PCBs from ELISA (ePCB) to their corresponding concentrations determined from capillary gas chromatography (GC) in selected fish sample extracts and dialysates of semipermeable membrane device (SPMD) passive samplers using an optimized solvent exchange procedure. Based on Aroclor 1254 calibrations, ePCBs (ng/mL) determined in fish extracts are positively correlated with total PCB concentrations (ng/mL) determined by GC: ePCB = 1.16 * total-cPCB - 5.92. Measured ePCBs (ng/3 SPMDs) were also positively correlated (r2 = 0.999) with PCB totals (ng/3 SPMDs) measured by GC for dialysates of SPMDs: ePCB = 1.52 * total PCB - 212. Therefore, this ELISA system for PCBs can be a rapid alternative to traditional GC analyses for determination of PCBs in extracts of biota or in SPMD dialysates.

Method for destroying halocarbon compositions using a critical solvent

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Janikowski, Stuart K.

2006-01-10

A method for destroying halocarbons. Halocarbon materials are reacted in a dehalogenation process wherein they are combined with a solvent in the presence of a catalyst. A hydrogen-containing solvent is preferred which functions as both a solvating agent and hydrogen donor. To augment the hydrogen donation capacity of the solvent if needed (or when non-hydrogen-containing solvents are used), a supplemental hydrogen donor composition may be employed. In operation, at least one of the temperature and pressure of the solvent is maintained near, at, or above a critical level. For example, the solvent may be in (1) a supercritical state; (2) a state where one of the temperature or pressure thereof is at or above critical; or (3) a state where at least one of the temperature and pressure thereof is near-critical. This system provides numerous benefits including improved reaction rates, efficiency, and versatility.

Agglomeration of Celecoxib by Quasi Emulsion Solvent Diffusion Method: Effect of Stabilizer.

PubMed

Maghsoodi, Maryam; Nokhodchi, Ali

2016-12-01

Purpose: The quasi-emulsion solvent diffusion (QESD) has evolved into an effective technique to manufacture agglomerates of API crystals. Although, the proposed technique showed benefits, such as cost effectiveness, that is considerably sensitive to the choice of a stabilizer, which agonizes from a absence of systemic understanding in this field. In the present study, the combination of different solvents and stabilizers were compared to investigate any connections between the solvents and stabilizers. Methods: Agglomerates of celecoxib were prepared by QESD method using four different stabilizers (Tween 80, HPMC, PVP and SLS) and three different solvents (methyl acetate, ethyl acetate and isopropyl acetate). The solid state of obtained particles was investigated by differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) spectroscopy. The agglomerated were also evaluated in term of production yield, distribution of particles and dissolution behavior. Results: The results showed that the effectiveness of stabilizer in terms of particle size and particle size distribution is specific to each solvent candidate. A stabilizer with a lower HLB value is preferred which actually increased its effectiveness with the solvent candidates with higher lipophilicity. HPMC appeared to be the most versatile stabilizer because it showed a better stabilizing effect compared to other stabilizers in all solvents used. Conclusion: This study demonstrated that the efficiency of stabilizers in forming the celecoxib agglomerates by QESD was influenced by the HLB of the stabilizer and lipophilicity of the solvents.

Speciation and environmental risk assessment of heavy metal in bio-oil from liquefaction/pyrolysis of sewage sludge.

PubMed

Yuan, Xingzhong; Leng, Lijian; Huang, Huajun; Chen, Xiaohong; Wang, Hou; Xiao, Zhihua; Zhai, Yunbo; Chen, Hongmei; Zeng, Guangming

2015-02-01

Liquefaction bio-oil (LBO) produced with ethanol (or acetone) as the solvent and pyrolysis bio-oil (PBO) produced at 550°C (or 850°C) from sewage sludge (SS) were produced, and were characterized and evaluated in terms of their heavy metal (HM) composition. The total concentration, speciation and leaching characteristic of HMs (Cu, Cr, Pb, Zn, Cd, and Ni) in both LBO and PBO were investigated. The total concentration and exchangeable fraction of Zn and Ni in bio-oils were at surprisingly high levels. Quantitative risk assessment of HM in bio-oils was performed by the method of risk assessment code (RAC), potential ecological risk index (PERI) and geo-accumulation index (GAI). Ni in bio-oil produced by pyrolysis at 850°C (PBO850) and Zn in bio-oil by liquefaction at 360°C with ethanol as solvent (LBO-360E) were evaluated to possess very high risk to the environment according to RAC. Additionally, Cd in PBO850 and LBO-360E were evaluated by PERI to have very high risk and high risk, respectively, while Cd in all bio-oils was assessed moderately contaminated according to GAI. Copyright © 2014 Elsevier Ltd. All rights reserved.

(Un)Folding Mechanisms of the FBP28 WW Domain in Explicit Solvent Revealed by Multiple Rare Event Simulation Methods

PubMed Central

Juraszek, Jarek; Bolhuis, Peter G.

2010-01-01

Abstract We report a numerical study of the (un)folding routes of the truncated FBP28 WW domain at ambient conditions using a combination of four advanced rare event molecular simulation techniques. We explore the free energy landscape of the native state, the unfolded state, and possible intermediates, with replica exchange molecular dynamics. Subsequent application of bias-exchange metadynamics yields three tentative unfolding pathways at room temperature. Using these paths to initiate a transition path sampling simulation reveals the existence of two major folding routes, differing in the formation order of the two main hairpins, and in hydrophobic side-chain interactions. Having established that the hairpin strand separation distances can act as reasonable reaction coordinates, we employ metadynamics to compute the unfolding barriers and find that the barrier with the lowest free energy corresponds with the most likely pathway found by transition path sampling. The unfolding barrier at 300 K is ∼17 kBT ≈ 42 kJ/mol, in agreement with the experimental unfolding rate constant. This work shows that combining several powerful simulation techniques provides a more complete understanding of the kinetic mechanism of protein folding. PMID:20159161

Sigma Team for Advanced Actinide Recycle FY2015 Accomplishments and Directions

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

Moyer, Bruce A.

The Sigma Team for Minor Actinide Recycle (STAAR) has made notable progress in FY 2015 toward the overarching goal to develop more efficient separation methods for actinides in support of the United States Department of Energy (USDOE) objective of sustainable fuel cycles. Research in STAAR has been emphasizing the separation of americium and other minor actinides (MAs) to enable closed nuclear fuel recycle options, mainly within the paradigm of aqueous reprocessing of used oxide nuclear fuel dissolved in nitric acid. Its major scientific challenge concerns achieving selectivity for trivalent actinides vs lanthanides. Not only is this challenge yielding to researchmore » advances, but technology concepts such as ALSEP (Actinide Lanthanide Separation) are maturing toward demonstration readiness. Efforts are organized in five task areas: 1) combining bifunctional neutral extractants with an acidic extractant to form a single process solvent, developing a process flowsheet, and demonstrating it at bench scale; 2) oxidation of Am(III) to Am(VI) and subsequent separation with other multivalent actinides; 3) developing an effective soft-donor solvent system for An(III) selective extraction using mixed N,O-donor or all-N donor extractants such as triazinyl pyridine compounds; 4) testing of inorganic and hybrid-type ion exchange materials for MA separations; and 5) computer-aided molecular design to identify altogether new extractants and complexants and theory-based experimental data interpretation. Within these tasks, two strategies are employed, one involving oxidation of americium to its pentavalent or hexavalent state and one that seeks to selectively complex trivalent americium either in the aqueous phase or the solvent phase. Solvent extraction represents the primary separation method employed, though ion exchange and crystallization play an important role. Highlights of accomplishments include: Confirmation of the first-ever electrolytic oxidation of Am(III) in a noncomplexing aqueous solution and submission of this scientific breakthrough as a paper in Science; The first-ever co-crystallization of Am(VI) with UO 2(NO 3) 2 ∙ 6H 2O, opening the door to a new approach for separating hexavalent actinides as a group; Results showing that three potentially problematic metals will not present risk in ALSEP; Improvement in ALSEP contactor stripping kinetics to acceptable performance; A comparison of centrifugal contactors vs mixer-settlers showing the former performs better in ALSEP stripping; Synthesis of new mixed N,O-donor extractants with enhanced solubility and strength for selective trivalent actinide extraction; Development of computational methods showing promise in prediction of the selectivity of new extractants for trivalent actinides vs lanthanides; An order-of-magnitude improvement in aqueous Am/Eu complexation selectivity of an alternative macrocyclic stripping agent for ALSEP, potentially enabling an option for an Am product stream free from both Ln and Cm. An alternative aqueous combination of dipicolinate complexant and malonate buffer that may present options for ALSEP and TALSPEAK (Trivalent Actinide-Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) type separations. The ALSEP concept is advancing toward a benchtop flowsheet demonstration planned for FY 2016, and a bench-scale test bed at Idaho National Laboratory (INL) will be employed to demonstrate at least one tandem Am oxidation and separation concept. This report outlines the goals of the STAAR, significance of achieving these goals, STAAR organization around the above aims and questions, recent highlights, and future directions. The report also includes a listing of publications, reports, patents, and dissertations.« less

Method of making monodisperse nanoparticles

DOEpatents

Fan, Hongyon; Sun, Zaicheng

2012-10-16

A method of making particles of either spherical or cylindrical geometry with a characteristic diameter less than 50 nanometers by mixing at least one structure directing agent dissolved in a solvent with at least one amphiphilic block copolymer dissolved in a solvent to make a solution containing particles, where the particles can be subsequently separated and dispersed in a solvent of choice.

Semiconductor liquid crystal composition and methods for making the same

DOEpatents

Alivisatos, A. Paul; Li, Liang-shi

2005-04-26

Semiconductor liquid crystal compositions and methods for making such compositions are disclosed. One embodiment of the invention is directed to a liquid crystal composition including a solvent and semiconductor particles in the solvent. The solvent and the semiconductor particles are in an effective amount in the liquid crystal composition to form a liquid crystal phase.

Stability-limit "Ouzo region" boundaries for poly(lactide-co-glycolide) nanoparticles prepared by nanoprecipitation.

PubMed

Beck-Broichsitter, Moritz

2016-09-10

The introduction of "Ouzo diagrams" has enhanced the applicability of the basic nanoprecipitation process for drug delivery research. The current study investigated the interaction of two relevant polymer/solvent systems, which is thought to impact the location of the stability-limit "Ouzo boundary". Viscosity measurements (Kurata-Stockmayer-Fixman approach) and static light scattering (Debye method) underlined a distinct interplay of the employed polymer (poly(lactide-co-glycolide)) with the utilized organic solvents (acetone and tetrahydrofuran). Both methods indicated that tetrahydrofuran was the "better" solvent for poly(lactide-co-glycolide). Thus, nanoprecipitation of this polymer/solvent composition resulted in larger nanoparticles. This observation can be attributed to the chain configuration of poly(lactide-co-glycolide) in the organic solvent, which influenced the extent of the break-up of the injected solvent layer. Accordingly, the stability-limit curve of the "Ouzo region" was shifted to lower poly(lactide-co-glycolide) fractions for tetrahydrofuran. Overall, the location of the "Ouzo region", which is an essential tool for drug delivery research, is influenced by the employed organic solvent. The current study described two distinct methods suitable to identify relevant polymer-solvent interactions, which dictate the stability-limit "Ouzo boundary" for relevant poly(lactide-co-glycolide). Copyright © 2016 Elsevier B.V. All rights reserved.

Replacement solvents for use in chemical synthesis

DOEpatents

Molnar, Linda K.; Hatton, T. Alan; Buchwald, Stephen L.

2001-05-15

Replacement solvents for use in chemical synthesis include polymer-immobilized solvents having a flexible polymer backbone and a plurality of pendant groups attached onto the polymer backbone, the pendant groups comprising a flexible linking unit bound to the polymer backbone and to a terminal solvating moiety. The polymer-immobilized solvent may be dissolved in a benign medium. Replacement solvents for chemical reactions for which tetrahydrofuran or diethyl may be a solvent include substituted tetrahydrofurfuryl ethers and substituted tetrahydro-3-furan ethers. The replacement solvents may be readily recovered from the reaction train using conventional methods.

NMR analysis of t-butyl-catalyzed deuterium exchange at unactivated arene localities.

PubMed

Stack, Douglas E; Eastman, Rachel

2016-10-01

Regioselective labelling of arene rings via electrophilic exchange is often dictated by the electronic environment caused by substituents present on the aromatic system. Previously, we observed the presence of a t-butyl group, either covalently bond or added as an external reagent, could impart deuterium exchange to the unactivated, C1-position of estrone. Here, we provide nuclear magnetic resonance analysis of this exchange in a solvent system composed of 50:50 trifluoroacetic acid and D 2 O with either 2-t-butylestrone or estrone in the presence of t-butyl alcohol has shed insights into the mechanism of this t-butyl-catalyzed exchange. Fast exchange of the t-butyl group concurrent with the gradual reduction of the H1 proton signal in both systems suggest a mechanism involving ipso attack of the t-butyl position by deuterium. The reversible addition/elimination of the t-butyl group activates the H1 proton towards exchange by a mechanism of t-butyl incorporation, H1 activation and exchange, followed by eventual t-butyl elimination. Density functional calculations are consistent with the observation of fast t-butyl exchange concurrent with slower H1 exchange. The σ-complex resulting from ipso attack of deuterium at the t-butyl carbon was 6.6 kcal/mol lower in energy than that of the σ-complex resulting from deuterium attack at C1. A better understanding of the t-butyl-catalyzed exchange could help in the design of labelling recipes for other phenolic metabolites. Copyright © 2016 The Authors. Journal of Labelled Compounds and Radiopharmaceuticals published by John Wiley & Sons, Ltd.

Ion-exchange solid-phase extraction combined with liquid chromatography-tandem mass spectrometry for the determination of veterinary drugs in organic fertilizers.

PubMed

Zhao, Zhiyong; Zhang, Yanmei; Xuan, Yanfang; Song, Wei; Si, Wenshuai; Zhao, Zhihui; Rao, Qinxiong

2016-06-01

The analysis of veterinary drugs in organic fertilizers is crucial for an assessment of potential risks to soil microbial communities and human health. We develop a robust and sensitive method to quantitatively determine 19 veterinary drugs (amantadine, sulfonamides and fluoroquinolones) in organic fertilizers. The method involved a simple solid-liquid extraction step using the combination of acetonitrile and McIlvaine buffer as extraction solvent, followed by cleanup with a solid-phase extraction cartridge containing polymeric mixed-mode anion-exchange sorbents. Ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was used to separate and detect target analytes. We particularly focused on the optimization of sample clean-up step: different diluents and dilution factors were tested. The developed method was validated in terms of linearity, recovery, precision, sensitivity and specificity. The recoveries of all the drugs ranged from 70.9% to 112.7% at three concentration levels, with the intra-day and inter-day relative standard deviation lower than 15.7%. The limits of quantification were between 1.0 and 10.0μg/kg for all the drugs. Matrix effect was minimized by matrix-matched calibration curves. The analytical method was successfully applied for the survey of veterinary drugs contamination in 20 compost samples. The results indicated that fluoroquinolones had higher incidence rate and mean concentration levels ranging from 31.9 to 308.7μg/kg compared with other drugs. We expect the method will provide the basis for risk assessment of veterinary drugs in organic fertilizers. Copyright © 2016 Elsevier B.V. All rights reserved.

One-pot synthesis of water soluble iron nanoparticles using rationally-designed peptides and ligand release.

PubMed

Papst, Stefanie; Cheong, Soshan; Banholzer, Moritz J; Brimble, Margaret A; Williams, David E; Tilley, Richard D

2013-05-18

Herein we report the rational design of new phosphopeptides for control of nucleation, growth and aggregation of water-soluble, superparamagnetic iron-iron oxide core-shell nanoparticles. The use of the designed peptides enables a one-pot synthesis that avoids utilizing unstable or toxic iron precursors, organic solvents, and the need for exchange of capping agent after synthesis of the NPs.

Supramolecular organization of calix[4]pyrrole with a methyl-trialkylammonium anion exchanger leads to remarkable reversal of selectivity for sulfate extraction vs. nitrate

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

Borman, Christopher J.; Custelcean, Radu; Hay, Ben P.

Here, meso-Octamethylcalix[4]pyrrole (C4P) enhances sulfate selectivity in solvent extraction by Aliquat 336N, an effect ascribed to the supramolecular preorganization and thermodynamic stability imparted by insertion of the methyl group of the Aliquat cation into the cup of C4P in its cone conformation.

Process for thin film deposition of cadmium sulfide

DOEpatents

Muruska, H. Paul; Sansregret, Joseph L.; Young, Archie R.

1982-01-01

The present invention teaches a process for depositing layers of cadmium sulfide. The process includes depositing a layer of cadmium oxide by spray pyrolysis of a cadmium salt in an aqueous or organic solvent. The oxide film is then converted into cadmium sulfide by thermal ion exchange of the O.sup.-2 for S.sup.-2 by annealing the oxide layer in gaseous sulfur at elevated temperatures.

Comparison of MM/GBSA calculations based on explicit and implicit solvent simulations.

PubMed

Godschalk, Frithjof; Genheden, Samuel; Söderhjelm, Pär; Ryde, Ulf

2013-05-28

Molecular mechanics with generalised Born and surface area solvation (MM/GBSA) is a popular method to calculate the free energy of the binding of ligands to proteins. It involves molecular dynamics (MD) simulations with an explicit solvent of the protein-ligand complex to give a set of snapshots for which energies are calculated with an implicit solvent. This change in the solvation method (explicit → implicit) would strictly require that the energies are reweighted with the implicit-solvent energies, which is normally not done. In this paper we calculate MM/GBSA energies with two generalised Born models for snapshots generated by the same methods or by explicit-solvent simulations for five synthetic N-acetyllactosamine derivatives binding to galectin-3. We show that the resulting energies are very different both in absolute and relative terms, showing that the change in the solvent model is far from innocent and that standard MM/GBSA is not a consistent method. The ensembles generated with the various solvent models are quite different with root-mean-square deviations of 1.2-1.4 Å. The ensembles can be converted to each other by performing short MD simulations with the new method, but the convergence is slow, showing mean absolute differences in the calculated energies of 6-7 kJ mol(-1) after 2 ps simulations. Minimisations show even slower convergence and there are strong indications that the energies obtained from minimised structures are different from those obtained by MD.

Identification of histidine residues that act as zinc ligands in beta-lactamase II by differential tritium exchange.

PubMed Central

Baldwin, G S; Waley, S G; Abraham, E P

1979-01-01

1. Four histidine-containing peptides have been isolated from a tryptic digest of the Zn2+-requiring beta-lactamase II from Bacillus cereus. One of these peptides probably contains two histidine residues. 2. The presence of one equivalent of Zn2+ substantially decreases the rate of exchange of the C-2 proton in at least two and probably three of the histidine residues of these peptides for solvent 3H. 3. It is concluded that peptides containing at least two of the three histidine residues acting as Zn2+ ligands at the tighter Zn2+-binding site of beta-lactamase II have been identified. PMID:314287

Immobilized enzymes in blood plasma exchangers via radiation grafting

NASA Astrophysics Data System (ADS)

Gombotz, Wayne; Hoffman, Allan; Schmer, Gottfried; Uenoyama, Satoshi

The enzyme asparaginase was immobilized onto a porous hollow polypropylene (PP) fiber blood plasma exchange device for the treatment of acute lymphocytic leukemia. The devices were first radiation grafted with polymethacrylic acid (poly(MAAc)). This introduces carboxyl groups onto the surface of the fibers. Several variables were studied in the grafting reaction including the effects of solvent type and monomer concentration. The carboxyl groups were activated with N-hydroxy succinimide (NHS) using carbodiimide chemistry. Asparaginase was then covalently immobilized on the activated surfaces. Quantitative relationships were found relating the percent graft to the amount of immobilized enzyme which was active. The enzyme reactor was tested both in vitro and in vivo using a sheep as an animal model.

Solvent exchange in a metal–organic framework single crystal monitored by dynamic in situ X-ray diffraction

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

Cox, Jordan M.; Walton, Ian M.; Bateman, Gage

2017-07-25

Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamicin situX-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal–organic framework [Co(AIP)(bpy) 0.5(H 2O)]·2H 2O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.

Regulation of Phenylalanine Hydroxylase: Conformational Changes Upon Phenylalanine Binding Detected by H/D Exchange and Mass Spectrometry†

PubMed Central

Li, Jun; Dangott, Lawrence J.; Fitzpatrick, Paul F.

2010-01-01

Phenylalanine acts as an allosteric activator of the tetrahydropterin-dependent enzyme phenylalanine hydroxylase. Hydrogen/deuterium exchange monitored by mass spectrometry has been used to gain insight into local conformational changes accompanying activation of rat phenylalanine hydroxylase by phenylalanine. Peptides in the regulatory and catalytic domains that lie in the interface between these two domains show large increases in the extent of deuterium incorporation from solvent in the presence of phenylalanine. In contrast, the effects of phenylalanine on the exchange kinetics of a mutant enzyme lacking the regulatory domain are limited to peptides surrounding the binding site for the amino acid substrate. These results support a model in which the N-terminus of the protein acts as an inhibitory peptide, with phenylalanine binding causing a conformational change in the regulatory domain that alters the interaction between the catalytic and regulatory domains. PMID:20307070

Crosslinked anion exchange membranes prepared from poly(phenylene oxide) (PPO) for non-aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Li, Yun; Sniekers, Jeroen; Malaquias, João C.; Van Goethem, Cedric; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F. J.

2018-02-01

A stable and eco-friendly anion-exchange membrane (AEM) was prepared and applied in a non-aqueous all-copper redox flow battery (RFB). The AEM was prepared via a simple procedure, leading to a cross-linked structure containing quaternary ammonium groups without involvement of harmful trimethylamine. A network was thus constructed which ensured both ion transport and solvent resistance. The ion exchange capacity (IEC) of the membrane was tuned from 0.49 to 1.03 meq g-1 by varying the content of the 4, 4‧-bipyridine crosslinking agent. The membrane showed a good anion conductivity and retention of copper ions. As a proof of principle, a RFB single cell with this crosslinked membrane yielded a coulombic efficiency of 89%, a voltage efficiency of 61% and an energy efficiency of 54% at 7.5 mA cm-2.

Green extraction of grape skin phenolics by using deep eutectic solvents.

PubMed

Cvjetko Bubalo, Marina; Ćurko, Natka; Tomašević, Marina; Kovačević Ganić, Karin; Radojčić Redovniković, Ivana

2016-06-01

Conventional extraction techniques for plant phenolics are usually associated with high organic solvent consumption and long extraction times. In order to establish an environmentally friendly extraction method for grape skin phenolics, deep eutectic solvents (DES) as a green alternative to conventional solvents coupled with highly efficient microwave-assisted and ultrasound-assisted extraction methods (MAE and UAE, respectively) have been considered. Initially, screening of five different DES for proposed extraction was performed and choline chloride-based DES containing oxalic acid as a hydrogen bond donor with 25% of water was selected as the most promising one, resulting in more effective extraction of grape skin phenolic compounds compared to conventional solvents. Additionally, in our study, UAE proved to be the best extraction method with extraction efficiency superior to both MAE and conventional extraction method. The knowledge acquired in this study will contribute to further DES implementation in extraction of biologically active compounds from various plant sources. Copyright © 2016 Elsevier Ltd. All rights reserved.

Exploring a multi-scale method for molecular simulation in continuum solvent model: Explicit simulation of continuum solvent as an incompressible fluid.

PubMed

Xiao, Li; Luo, Ray

2017-12-07

We explored a multi-scale algorithm for the Poisson-Boltzmann continuum solvent model for more robust simulations of biomolecules. In this method, the continuum solvent/solute interface is explicitly simulated with a numerical fluid dynamics procedure, which is tightly coupled to the solute molecular dynamics simulation. There are multiple benefits to adopt such a strategy as presented below. At this stage of the development, only nonelectrostatic interactions, i.e., van der Waals and hydrophobic interactions, are included in the algorithm to assess the quality of the solvent-solute interface generated by the new method. Nevertheless, numerical challenges exist in accurately interpolating the highly nonlinear van der Waals term when solving the finite-difference fluid dynamics equations. We were able to bypass the challenge rigorously by merging the van der Waals potential and pressure together when solving the fluid dynamics equations and by considering its contribution in the free-boundary condition analytically. The multi-scale simulation method was first validated by reproducing the solute-solvent interface of a single atom with analytical solution. Next, we performed the relaxation simulation of a restrained symmetrical monomer and observed a symmetrical solvent interface at equilibrium with detailed surface features resembling those found on the solvent excluded surface. Four typical small molecular complexes were then tested, both volume and force balancing analyses showing that these simple complexes can reach equilibrium within the simulation time window. Finally, we studied the quality of the multi-scale solute-solvent interfaces for the four tested dimer complexes and found that they agree well with the boundaries as sampled in the explicit water simulations.

Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03217a Click here for additional data file.

PubMed Central

Crawford, Deborah; Casaban, José; Haydon, Robert; Giri, Nicola; McNally, Tony

2015-01-01

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)2(PPh3)2 as well as the commercially important metal organic frameworks (MOFs) Cu3(BTC)2 (HKUST-1), Zn(2-methylimidazolate)2 (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h–1 rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3–4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h–1. The space time yields (STYs) for these methods of up to 144 × 103 kg per m3 per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally. PMID:29308131

Method for forming energetic nanopowders

DOEpatents

Lee, Kien-Yin; Asay, Blaine W.; Kennedy, James E.

2013-10-15

A method for the preparation of neat energetic powders, having nanometer dimensions, is described herein. For these neat powder, a solution of a chosen energetic material is prepared in an aprotic solvent and later combined with liquid hexane that is miscible with such solvent. The energetic material chosen is less soluble in the liquid hexane than in the aprotic solvent and the liquid hexane is cooled to a temperature that is below that of the solvent solution. In order to form a precipitate of said neat powders, the solvent solution is rapidly combined with the liquid hexane. When the resulting precipitate is collected, it may be dried and filtered to yield an energetic nanopowder material.

Enhanced bulk heterojunction devices prepared by thermal and solvent vapor annealing processes

DOEpatents

Forrest, Stephen R.; Thompson, Mark E.; Wei, Guodan; Wang, Siyi

2017-09-19

A method of preparing a bulk heterojunction organic photovoltaic cell through combinations of thermal and solvent vapor annealing are described. Bulk heterojunction films may prepared by known methods such as spin coating, and then exposed to one or more vaporized solvents and thermally annealed in an effort to enhance the crystalline nature of the photoactive materials.

[Simultaneous determination of seven residual solvents in bovis calculus artifactus by headspace gas chromatography].

PubMed

Chi, Shuyao; Wu, Dike; Sun, Jinhong; Ye, Ruhan; Wang, Xiaoyan

2014-05-01

A headspace gas chromatography (HS-GC) method was developed for the simultaneous determination of seven residual solvents (petroleum ether (60-90 degrees C), acetone, ethyl acetate, methanol, methylene chloride, ethanol and butyl acetate) in bovis calculus artifactus. The DB-WAX capillary column and flame ionization detector (FID) were used for the separation and detection of the residual solvents, and the internal standard method was used for the quantification. The chromatographic conditions, such as equilibrium temperature and equilibrium time, were optimized. Under the optimized conditions, all of the seven residual solvents showed good linear relationships with good correlation coefficients (not less than 0.999 3) in the prescribed concentration range. At three spiked levels, the recoveries for the seven residual solvents were 94.7%-105.2% with the relative standard deviations (RSDs) less than 3.5%. The limits of detection (LODs) of the method were 0.43-5.23 mg/L, and the limits of quantification (LOQs) were 1.25-16.67 mg/L. The method is simple, rapid, sensitive and accurate, and is suitable for the simultaneous determination of the seven residual solvents in bovis calculus artifactus.

Solvent electronic polarization effects on a charge transfer excitation studied by the mean-field QM/MM method

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

Nakano, Hiroshi; Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Kyoto 615-8245

2015-12-31

Electronic polarization effects of a medium can have a significant impact on a chemical reaction in condensed phases. We discuss the effects on the charge transfer excitation of a chromophore, N,N-dimethyl-4-nitroaniline, in various solvents using the mean-field QM/MM method with a polarizable force field. The results show that the explicit consideration of the solvent electronic polarization effects is important especially for a solvent with a low dielectric constant when we study the solvatochromism of the chromophore.

Liquid paraffin as new dilution medium for the analysis of high boiling point residual solvents with static headspace-gas chromatography.

PubMed

D'Autry, Ward; Zheng, Chao; Bugalama, John; Wolfs, Kris; Hoogmartens, Jos; Adams, Erwin; Wang, Bochu; Van Schepdael, Ann

2011-07-15

Residual solvents are volatile organic compounds which can be present in pharmaceutical substances. A generic static headspace-gas chromatography analysis method for the identification and control of residual solvents is described in the European Pharmacopoeia. Although this method is proved to be suitable for the majority of samples and residual solvents, the method may lack sensitivity for high boiling point residual solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and benzyl alcohol. In this study, liquid paraffin was investigated as new dilution medium for the analysis of these residual solvents. The headspace-gas chromatography method was developed and optimized taking the official Pharmacopoeia method as a starting point. The optimized method was validated according to ICH criteria. It was found that the detection limits were below 1μg/vial for each compound, indicating a drastically increased sensitivity compared to the Pharmacopoeia method, which failed to detect the compounds at their respective limit concentrations. Linearity was evaluated based on the R(2) values, which were above 0.997 for all compounds, and inspection of residual plots. Instrument and method precision were examined by calculating the relative standard deviations (RSD) of repeated analyses within the linearity and accuracy experiments, respectively. It was found that all RSD values were below 10%. Accuracy was checked by a recovery experiment at three different levels. Mean recovery values were all in the range 95-105%. Finally, the optimized method was applied to residual DMSO analysis in four different Kollicoat(®) sample batches. Copyright © 2011 Elsevier B.V. All rights reserved.

A Simple RP-HPLC Method for Quantitation of Itopride HCl in Tablet Dosage Form.

PubMed

Thiruvengada, Rajan Vs; Mohamed, Saleem Ts; Ramkanth, S; Alagusundaram, M; Ganaprakash, K; Madhusudhana, Chetty C

2010-10-01

An isocratic reversed phase high-performance liquid chromatographic method with ultraviolet detection at 220 nm has been developed for the quantification of itopride hydrochloride in tablet dosage form. The quantification was carried out using C(8) column (250 mm × 4.6 mm), 5-μm particle size SS column. The mobile phase comprised of two solvents (Solvent A: buffer 1.4 mL ortho-phosphoric acid adjusted to pH 3.0 with triethyl amine and Solvent B: acetonitrile). The ratio of Solvent A: Solvent B was 75:25 v/v. The flow rate was 1.0 mL (-1)with UV detection at 220 nm. The method has been validated and proved to be robust. The calibration curve was linear in the concentration range of 80-120% with coefficient of correlation 0.9995. The percentage recovery for itopride HCl was 100.01%. The proposed method was validated for its selectivity, linearity, accuracy, and precision. The method was found to be suitable for the quality control of itopride HCl in tablet dosage formulation.

A Simple RP-HPLC Method for Quantitation of Itopride HCl in Tablet Dosage Form

PubMed Central

Thiruvengada, Rajan VS; Mohamed, Saleem TS; Ramkanth, S; Alagusundaram, M; Ganaprakash, K; Madhusudhana, Chetty C

2010-01-01

An isocratic reversed phase high-performance liquid chromatographic method with ultraviolet detection at 220 nm has been developed for the quantification of itopride hydrochloride in tablet dosage form. The quantification was carried out using C8 column (250 mm × 4.6 mm), 5-μm particle size SS column. The mobile phase comprised of two solvents (Solvent A: buffer 1.4 mL ortho-phosphoric acid adjusted to pH 3.0 with triethyl amine and Solvent B: acetonitrile). The ratio of Solvent A: Solvent B was 75:25 v/v. The flow rate was 1.0 mL -1with UV detection at 220 nm. The method has been validated and proved to be robust. The calibration curve was linear in the concentration range of 80-120% with coefficient of correlation 0.9995. The percentage recovery for itopride HCl was 100.01%. The proposed method was validated for its selectivity, linearity, accuracy, and precision. The method was found to be suitable for the quality control of itopride HCl in tablet dosage formulation. PMID:21264104

Morphology Control for Fully Printable Organic-Inorganic Bulk-heterojunction Solar Cells Based on a Ti-alkoxide and Semiconducting Polymer.

PubMed

Kato, Takehito; Oinuma, Chihiro; Otsuka, Munechika; Hagiwara, Naoki

2017-01-10

The photoactive layer of a typical organic thin-film bulk-heterojunction (BHJ) solar cell commonly uses fullerene derivatives as the electron-accepting material. However, fullerene derivatives are air-sensitive; therefore, air-stable material is needed as an alternative. In the present study, we propose and describe the properties of Ti-alkoxide as an alternative electron-accepting material to fullerene derivatives to create highly air-stable BHJ solar cells. It is well-known that controlling the morphology in the photoactive layer, which is constructed with fullerene derivatives as the electron acceptor, is important for obtaining a high overall efficiency through the solvent method. The conventional solvent method is useful for high-solubility materials, such as fullerene derivatives. However, for Ti-alkoxides, the conventional solvent method is insufficient, because they only dissolve in specific solvents. Here, we demonstrate a new approach to morphology control that uses the molecular bulkiness of Ti-alkoxides without the conventional solvent method. That is, this method is one approach to obtain highly efficient, air-stable, organic-inorganic bulk-heterojunction solar cells.

Extraction of basil leaves (ocimum canum) oleoresin with ethyl acetate solvent by using soxhletation method

NASA Astrophysics Data System (ADS)

Tambun, R.; Purba, R. R. H.; Ginting, H. K.

2017-09-01

The goal of this research is to produce oleoresin from basil leaves (Ocimum canum) by using soxhletation method and ethyl acetate as solvent. Basil commonly used in culinary as fresh vegetables. Basil contains essential oils and oleoresin that are used as flavouring agent in food, in cosmetic and ingredient in traditional medicine. The extraction method commonly used to obtain oleoresin is maceration. The problem of this method is many solvents necessary and need time to extract the raw material. To resolve the problem and to produce more oleoresin, we use soxhletation method with a combination of extraction time and ratio from the material with a solvent. The analysis consists of yield, density, refractive index, and essential oil content. The best treatment of basil leaves oleoresin extraction is at ratio of material and solvent 1:6 (w / v) for 6 hours extraction time. In this condition, the yield of basil oleoresin is 20.152%, 0.9688 g/cm3 of density, 1.502 of refractive index, 15.77% of essential oil content, and the colour of oleoresin product is dark-green.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

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

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.