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Sample records for water proton relaxation

  1. Nuclear magnetic relaxation studies of water in frozen biological tissues. Cross-relaxation effects between protein and bound water protons

    Science.gov (United States)

    Escanyé, J. M.; Canet, D.; Robert, J.

    Water proton longitudinal relaxation has been investigated in frozen mouse tissues including tumors. The nonfreezable water which gives rise to a relatively sharp NMR signal at this temperature (263 K) is identified as water bound to macromolecules. Measurements have been carried out by the nonselective inversion-recovery method at 90 and 6 MHz. Partially selective inversion has been achieved at 90 MHz by the DANTE sequence. The experimental data are analyzed by means of Solomon-type equations. This analysis provides the cross-relaxation term from which the dipolar contribution to water relaxation rate, arising from interactions with macromolecular protons, is calculated. This contribution seems to be dominant. The number of water protons interacting with a given macromolecular proton is found to be of the order of 10. The data at both frequencies can be consistently interpreted in terms of water diffusion, with a characteristic time of about 10 -9 sec. These conclusions are valid for all the tissues investigated here, their relaxation parameters exhibiting only slight differences.

  2. [Spin-lattice relaxation of water protons in plant and animal cells].

    Science.gov (United States)

    Samuilov, F D; Nikiforov, E A; Nikiforova, V I

    2012-01-01

    NMR-spin echo method has been used to study spin-lattice relaxation time of protons T1 in plant and animal cells - muscle tissue of fish, the cells of which unlike plant cells have no developed system of vacuoles, plastids and a solid cell wall. According to the values of T1 time a new NMR parameter K, a coefficient of relaxation effectiveness of a cell structure, has been calculated. This parameter can be used for quantitative characterization of the influence of different cell structures, the tissue water interact with, for a time of spin-lattice relaxation of water protons. It has been ascertained that the values of K coefficient in animal tissue and in storing tissues of some plants differ little; it may be stipulated by permanent transmembrane water exchange which occurs at high rate in the living cell. It has been concluded that there exists a certain similarity between water state in protoplast of plant and animal cells.

  3. Magnetic Resonance Water Proton Relaxation in Protein Solutions and Tissue: T1ρ Dispersion Characterization

    Science.gov (United States)

    Chen, Enn-Ling; Kim, Raymond J.

    2010-01-01

    Background Image contrast in clinical MRI is often determined by differences in tissue water proton relaxation behavior. However, many aspects of water proton relaxation in complex biological media, such as protein solutions and tissue are not well understood, perhaps due to the limited empirical data. Principal Findings Water proton T1, T2, and T1ρ of protein solutions and tissue were measured systematically under multiple conditions. Crosslinking or aggregation of protein decreased T2 and T1ρ, but did not change high-field T1. T1ρ dispersion profiles were similar for crosslinked protein solutions, myocardial tissue, and cartilage, and exhibited power law behavior with T1ρ(0) values that closely approximated T2. The T1ρ dispersion of mobile protein solutions was flat above 5 kHz, but showed a steep curve below 5 kHz that was sensitive to changes in pH. The T1ρ dispersion of crosslinked BSA and cartilage in DMSO solvent closely resembled that of water solvent above 5 kHz but showed decreased dispersion below 5 kHz. Conclusions Proton exchange is a minor pathway for tissue T1 and T1ρ relaxation above 5 kHz. Potential models for relaxation are discussed, however the same molecular mechanism appears to be responsible across 5 decades of frequencies from T1ρ to T1. PMID:20052404

  4. Magnetic properties, water proton relaxivities, and in-vivo MR images of paramagnetic nanoparticles

    Science.gov (United States)

    Lee, Gang Ho; Chang, Yongmin

    2015-07-01

    In this mini review, magnetic resonance imaging (MRI) contrast agents based on lanthanideoxide (Ln2O3) nanoparticles are described. Ln2O3 (Ln = Gd, Dy, Ho, and Er) nanoparticles are paramagnetic, but show appreciable magnetic moments at room temperature and even at ultrasmall particle diameters. Among Ln2O3 nanoparticles, Gd2O3 nanoparticles show larger longitudinal water proton relaxivity (r1) values than Gd-chelates because of the large amount of Gd in the nanoparticle, and the other Ln2O3 nanoparticles (Ln = Dy, Ho, and Er) show appreciable transverse water proton relaxivity (r2) values. Therefore, Gd2O3 nanoparticles are potential T1 MRI contrast agents while the other Ln2O3 nanoparticles are potential T2 MRI contrast agents at high MR fields.

  5. Proton magnetic relaxation study of the thermodynamic characteristics of water adsorbed by cellulose fibers

    Science.gov (United States)

    Grunin, Yu. B.; Grunin, L. Yu.; Masas, D. S.; Talantsev, V. I.; Sheveleva, N. N.

    2016-11-01

    The possibility of determining the thermodynamic parameters that characterize the sorption properties of cellulose and the state of water associated with its fibers is demonstrated using modern concepts of the structure of this vegetable polymer and methods based on theories of adsorption and NMR relaxation in heterogeneous systems.

  6. A proton NMR relaxation study of water dynamics in bovine serum albumin nanoparticles.

    Science.gov (United States)

    Belotti, Monica; Martinelli, Andrea; Gianferri, Raffaella; Brosio, Elvino

    2010-01-14

    Water dynamics and compartmentation in glutaraldehyde cross-linked bovine serum albumin nanoparticles have been investigated by an integrated nuclear magnetic resonance (NMR) protocol based on water relaxation times and self-diffusion coefficients measurements. Multi-exponentially of water relaxation curves has been accounted for according to a diffusive and chemical exchange model (see B. P. Hills, S. F. Takacs and P. S. Belton, Mol. Phys., 1989, 67(4), 903, and Mol. Phys., 1989, 67(4), 913; E. Brosio, M. Belotti and R. Gianferri, in Food Science and Technology: New Research, ed. L. V. Greco and M. N. Bruno, Nova Science Publishers, Hauppauge (NY), 2008) that made it possible to single out water molecules in the molecular spaces in the interior of albumin nanoparticles, in the meso-cavities formed by packed nanoparticles and in the meniscus on top of the nanoparticles suspension. A quantitative rationalization of T(2) values of water different components allowed morphological information to be acquired as for the size of water filled compartments, while self-diffusion coefficient measurements of water excess or fluxed packed nanoparticles suspensions are describers of transport properties of soft biomaterials. The paper reports an NMR approach that can be seen as a general and relevant method to characterize excess-water-swollen soft biomaterials.

  7. Various ligand-coated ultrasmall gadolinium-oxide nanoparticles: Water proton relaxivity and in-vivo T1 MR image

    Science.gov (United States)

    Park, Ja Young; Kim, Sung June; Lee, Gang Ho; Jin, Seonguk; Chang, Yongmin; Bae, Ji Eun; Chae, Kwon Seok

    2015-04-01

    Surface coating of nanoparticles with ligands is essential in magnetic resonance imaging (MRI) because of solubility in water and biocompatibility. In this study, five organic molecules were used for surface coating of ultrasmall gadolinium-oxide (Gd2O3) nanoparticles (d avg = 2.0 nm). All of the samples showed large longitudinal (r1) and transverse (r2) water proton relaxivities with r2/r1 ratios that were close to one, corresponding to ideal conditions for T1 MRI contrast agents. Finally, in-vivo T1 MR images were acquired to prove the effectiveness of the surface-coated ultrasmall Gd2O3 nanoparticles as a T1 MRI contrast agent.

  8. Proton magnetic relaxation dispersion in aqueous biopolymer systems

    Science.gov (United States)

    Conti, S.

    Investigation of the magnetic field dependence of proton spin-lattice relaxation in solutions of bovine fibrinogen has been performed for Larmor frequencies between 50 Hz and 60 MHz, and complemented with measurements of spin-spin relaxation rates at 2 kHz and 25 MHz. A thorough analysis of experimental data, including the effects of protein concentration, temperature, pH and isotopic dilution, leads to an overall relaxation scheme consistent with T1 and T2 values at both low and high magnetic fields. The scheme involves water molecules slightly anisotropically bound on proteins as well as slow exchanging protein protons magnetically coupled to solute nuclei. A coherent picture, reminiscent of the traditional hydration layer, can be obtained for bound water. A major conclusion is that transfer of single protons may contribute substantially to the chemical exchange between free and bound water.

  9. Transverse relaxation of scalar-coupled protons.

    Science.gov (United States)

    Segawa, Takuya F; Baishya, Bikash; Bodenhausen, Geoffrey

    2010-10-25

    In a preliminary communication (B. Baishya, T. F. Segawa, G. Bodenhausen, J. Am. Chem. Soc. 2009, 131, 17538-17539), we recently demonstrated that it is possible to obtain clean echo decays of protons in biomolecules despite the presence of homonuclear scalar couplings. These unmodulated decays allow one to determine apparent transverse relaxation rates R(2) (app) of individual protons. Herein, we report the observation of R(2) (app) for three methyl protons, four amide H(N) protons, and all 11 backbone H(α) protons in cyclosporin A. If the proton resonances overlap, their R(2) (app) rates can be measured by transferring their magnetization to neighboring (13)C nuclei, which are less prone to overlap. The R(2) (app) rates of protons attached to (13)C are faster than those attached to (12)C because of (13)C-(1)H dipolar interactions. The differences of these rates allow the determination of local correlation functions. Backbone H(N) and H(α) protons that have fast decay rates R(2) (app) also feature fast longitudinal relaxation rates R(1) and intense NOESY cross peaks that are typical of crowded environments. Variations of R(2) (app) rates of backbone H(α) protons in similar amino acids reflect differences in local environments.

  10. High Relaxivity Gd(III)–DNA Gold Nanostars: Investigation of Shape Effects on Proton Relaxation

    Science.gov (United States)

    Rotz, Matthew W.; Culver, Kayla S. B.; Parigi, Giacomo; MacRenaris, Keith W.; Luchinat, Claudio; Odom, Teri W.; Meade, Thomas J.

    2015-01-01

    Gadolinium(III) nanoconjugate contrast agents (CAs) have distinct advantages over their small-molecule counterparts in magnetic resonance imaging. In addition to increased Gd(III) payload, a significant improvement in proton relaxation efficiency, or relaxivity (r1), is often observed. In this work, we describe the synthesis and characterization of a nanoconjugate CA created by covalent attachment of Gd(III) to thiolated DNA (Gd(III)–DNA), followed by surface conjugation onto gold nanostars (DNA–Gd@stars). These conjugates exhibit remarkable r1 with values up to 98 mM−1 s−1. Additionally, DNA–Gd@stars show efficient Gd(III) delivery and biocompatibility in vitro and generate significant contrast enhancement when imaged at 7 T. Using nuclear magnetic relaxation dispersion analysis, we attribute the high performance of the DNA–Gd@stars to an increased contribution of second-sphere relaxivity compared to that of spherical CA equivalents (DNA–Gd@spheres). Importantly, the surface of the gold nanostar contains Gd(III)–DNA in regions of positive, negative, and neutral curvature. We hypothesize that the proton relaxation enhancement observed results from the presence of a unique hydrophilic environment produced by Gd(III)–DNA in these regions, which allows second-sphere water molecules to remain adjacent to Gd(III) ions for up to 10 times longer than diffusion. These results establish that particle shape and second-sphere relaxivity are important considerations in the design of Gd(III) nanoconjugate CAs. PMID:25723190

  11. Vibrational and structural relaxation of hydrated protons in Nafion membranes

    Science.gov (United States)

    Liu, Liyuan; Lotze, Stephan; Bakker, Huib J.

    2017-02-01

    We study the vibrational dynamics of the bending mode at 1730 cm-1 of proton hydration structures in Nafion membranes with polarization-resolved infrared (IR) pump-probe spectroscopy. The bending mode relaxes to an intermediate state with a time constant T1 of 170 ± 30 fs. Subsequently, the dissipated energy equilibrates with Teq of 1.5 ± 0.2 ps. The transient absorption signals show a long-living anisotropy, which indicates that for part of the excited proton hydration clusters the vibrational energy dissipation results in a local structural change, e.g. the breaking of a local hydrogen bond. This structural relaxation relaxes with a time constant of 38 ± 4 ps.

  12. Vibrational Relaxation of the Aqueous Proton in Acetonitrile: Ultrafast Cluster Cooling and Vibrational Predissociation.

    Science.gov (United States)

    Ottosson, N; Liu, L; Bakker, H J

    2016-07-28

    We study the ultrafast O-H stretch vibrational relaxation dynamics of protonated water clusters embedded in a matrix of deuterated acetonitrile, using polarization-resolved mid-IR femtosecond spectroscopy. The clusters are produced by mixing triflic (trifluoromethanesulfonic) acid and H2O in molar ratios of 1:1, 1:2, and 1:3, thus varying the degree of hydration of the proton. At all hydration levels the excited O-H stretch vibration of the hydrated proton shows an ultrafast vibrational relaxation with a time constant T1 cooling of the clusters reveals a long-living, underlying transient absorption change with high anisotropy. We argue that this feature stems from the vibrational predissociation of a small fraction of the proton hydration structures, directly following the ultrafast infrared excitation.

  13. Protein-bound water molecule counting by resolution of (1)H spin-lattice relaxation mechanisms.

    OpenAIRE

    Kiihne, S; Bryant, R G

    2000-01-01

    Water proton spin-lattice relaxation is studied in dilute solutions of bovine serum albumin as a function of magnetic field strength, oxygen concentration, and solvent deuteration. In contrast to previous studies conducted at high protein concentrations, the observed relaxation dispersion is accurately Lorentzian with an effective correlation time of 41 +/- 3 ns when measured at low proton and low protein concentrations to minimize protein aggregation. Elimination of oxygen flattens the relax...

  14. Longitudinal proton relaxation rates in rabbit tissues after intravenous injection of free and chelated Mn2+

    Energy Technology Data Exchange (ETDEWEB)

    Spiller, M.; Brown, R.D. III; Koenig, S.H.; Wolf, G.L.

    1988-11-01

    The factors that determine the field-dependent increase in 1/T1 of tissue water protons were investigated for MnCl2 and Mn2+ (PDTA) (1,3-propylenediamine-N,N',N'',N'''-tetraacetic acid) introduced intravenously into rabbits. Mn2+ was used in preference to other paramagnetic ions in part because of the distinct NMRD profiles (magnetic field dependence of 1/T1) of free Mn2+ ions, their small chelate complexes, and their macromolecular conjugates, and in part because the relatively low toxicity of Mn2+ is favorable for animal studies. Tissue content of Mn2+ was determined in all samples by inductively coupled plasma analyses the state of Mn2+ in excised tissues was determined from the form of the 1/T1 NMRD profile of water protons; and distribution of contrast agent within tissue and access of water on a T1 time scale were determined by double-exponential analyses of proton relaxation behavior in intact doped tissue, as well as by the change of single-exponential relaxation rates and proton signal intensity upon gentle disruption of the tissue. MnCl2 is found in all tissues, except fat and skeletal muscle, but liver is most avid at low dose, and Mn2+ accumulates in spleen after high doses. Chelation targets Mn2+ to liver and kidney, saturating the liver chemically at relatively low dose. We suggest that pronounced increase in tissue relaxivity results from irrotationally bound Mn2+, ostensibly associated with the polar head groups of cell membranes. Compartmentalization of contrast agent and restricted diffusion of tissue water influences the maximum relaxation rates attainable, so that there is an optimal dose of these contrast agents which is rather low.

  15. Longitudinal proton relaxation rates in rabbit tissues after intravenous injection of free and chelated Mn2+.

    Science.gov (United States)

    Spiller, M; Brown, R D; Koenig, S H; Wolf, G L

    1988-11-01

    The factors that determine the field-dependent increase in 1/T1 of tissue water protons were investigated for MnCl2 and Mn2+ (PDTA) (1,3-propylenediamine-N,N',N'',N'''-tetraacetic acid) introduced intravenously into rabbits. Mn2+ was used in preference to other paramagnetic ions in part because of the distinct NMRD profiles (magnetic field dependence of 1/T1) of free Mn2+ ions, their small chelate complexes, and their macromolecular conjugates, and in part because the relatively low toxicity of Mn2+ is favorable for animal studies. Tissue content of Mn2+ was determined in all samples by inductively coupled plasma analyses the state of Mn2+ in excised tissues was determined from the form of the 1/T1 NMRD profile of water protons; and distribution of contrast agent within tissue and access of water on a T1 time scale were determined by double-exponential analyses of proton relaxation behavior in intact doped tissue, as well as by the change of single-exponential relaxation rates and proton signal intensity upon gentle disruption of the tissue. MnCl2 is found in all tissues, except fat and skeletal muscle, but liver is most avid at low dose, and Mn2+ accumulates in spleen after high doses. Chelation targets Mn2+ to liver and kidney, saturating the liver chemically at relatively low dose. We suggest that pronounced increase in tissue relaxivity results from irrotationally bound Mn2+, ostensibly associated with the polar head groups of cell membranes. Compartmentalization of contrast agent and restricted diffusion of tissue water influences the maximum relaxation rates attainable, so that there is an optimal dose of these contrast agents which is rather low.

  16. The effect of polymer coatings on proton transverse relaxivities of aqueous suspensions of magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Carroll, Matthew R J; House, Michael J; Woodward, Robert C; St Pierre, Timothy G [School of Physics, University of Western Australia, 35 Stirling Hwy, Crawley, WA 6009 (Australia); Huffstetler, Phillip P; Miles, William C; Goff, Jonathon D; Davis, Richey M; Riffle, Judy S, E-mail: stpierre@physics.uwa.edu.au [Macromolecules and Interfaces Institute, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061 (United States)

    2011-08-12

    Iron oxide magnetic nanoparticles are good candidates for magnetic resonance imaging (MRI) contrast agents due to their high magnetic susceptibilities. Here we investigate 19 polyether-coated magnetite nanoparticle systems comprising three series. All systems were synthesized from the same batch of magnetite nanoparticles. A different polyether was used for each series. Each series comprised systems with systematically varied polyether loadings per particle. A highly significant (p < 0.0001) linear correlation (r = 0.956) was found between the proton relaxivity and the intensity-weighted average diameter measured by dynamic light scattering in the 19 particle systems studied. The intensity-weighted average diameter measured by dynamic light scattering is sensitive to small number fractions of larger particles/aggregates. We conclude that the primary effect leading to differences in proton relaxivity between systems arises from the small degree of aggregation within the samples, which appears to be determined by the nature of the polymer and, for one system, the degree of polymer loading of the particles. For the polyether coatings used in this study, any changes in relaxivity from differences in water exclusion or diffusion rates caused by the polymer are minor in comparison with the changes in relaxivity resulting from variations in the degree of aggregation.

  17. Molecular dynamics simulations of proton transverse relaxation times in suspensions of magnetic nanoparticles.

    Science.gov (United States)

    Panczyk, Tomasz; Konczak, Lukasz; Zapotoczny, Szczepan; Szabelski, Pawel; Nowakowska, Maria

    2015-01-01

    In this work we have analyzed the influence of various factors on the transverse relaxation times T2 of water protons in suspension of magnetic nanoparticles. For that purpose we developed a full molecular dynamics force field which includes the effects of dispersion interactions between magnetic nanoparticles and water molecules, electrostatic interactions between charged nanoparticles and magnetic dipole-dipole and dipole-external field interactions. We also accounted for the magnetization reversal within the nanoparticles body frames due to finite magnetic anisotropy barriers. The force field together with the Langevin dynamics imposed on water molecules and the nanoparticles allowed us to monitor the dephasing of water protons in real time. Thus, we were able to determine the T2 relaxation times including the effects of the adsorption of water on the nanoparticles' surfaces, thermal fluctuations of the orientation of nanoparticles' magnetizations as well as the effects of the core-shell architecture of nanoparticles and their agglomeration into clusters. We found that there exists an optimal cluster size for which T2 is minimized and that the retardation of water molecules motion, due to adsorption on the nanoparticles surfaces, has some effect in the measured T2 times. The typical strengths of the external magnetic fields in MRI are enough to keep the magnetizations fixed along the field direction, however, in the case of low magnetic fields, we observed significant enhancement of T2 due to thermal fluctuations of the orientations of magnetizations. Copyright © 2014 Elsevier Inc. All rights reserved.

  18. Proton Electrodynamics in Liquid Water

    OpenAIRE

    Volkov, A. A.; Artemov, V. G.; A. V. Pronin

    2013-01-01

    The dielectric spectrum of liquid water, $10^{4} - 10^{11}$ Hz, is interpreted in terms of diffusion of charges, formed as a result of self-ionization of H$_{2}$O molecules. This approach explains the Debye relaxation and the dc conductivity as two manifestations of this diffusion. The Debye relaxation is due to the charge diffusion with a fast recombination rate, $1/\\tau_{2}$, while the dc conductivity is a manifestation of the diffusion with a much slower recombination rate, $1/\\tau_{1}$. A...

  19. Temperature dependence of proton NMR relaxation times at earth's magnetic field

    Science.gov (United States)

    Niedbalski, Peter; Kiswandhi, Andhika; Parish, Christopher; Ferguson, Sarah; Cervantes, Eduardo; Oomen, Anisha; Krishnan, Anagha; Goyal, Aayush; Lumata, Lloyd

    The theoretical description of relaxation processes for protons, well established and experimentally verified at conventional nuclear magnetic resonance (NMR) fields, has remained untested at low fields despite significant advances in low field NMR technology. In this study, proton spin-lattice relaxation (T1) times in pure water and water doped with varying concentrations of the paramagnetic agent copper chloride have been measured from 6 to 92oC at earth's magnetic field (1700 Hz). Results show a linear increase of T1 with temperature for each of the samples studied. Increasing the concentration of the copper chloride greatly reduced T1 and reduced dependence on temperature. The consistency of the results with theory is an important confirmation of past results, while the ability of an ultra-low field NMR system to do contrast-enhanced magnetic resonance imaging (MRI) is promising for future applicability to low-cost medical imaging and chemical identification. This work is supported by US Dept of Defense Award No. W81XWH-14-1-0048 and the Robert A. Welch Foundation Grant No. AT-1877.

  20. Vibrational relaxation of pure liquid water

    NARCIS (Netherlands)

    Lindner, J; Vohringer, P; Pshenichnikov, MS; Cringus, D; Wiersma, DA; Mostovoy, M; Vöhringer, Peter; Pshenichnikov, Maxim S.

    2006-01-01

    Multicolor infrared ultrafast spectroscopy is applied to investigate the vibrational relaxation dynamics in liquid water at room temperature. In a sequence of experiments, both the stretching and the bending mode are photoexcited and probed. A unified model, capable of the reproduction of as much as

  1. Analysis of microporosity and setting of reactive powder concrete by proton nuclear relaxation.

    Science.gov (United States)

    Philippot, S; Korb, J P; Petit, D; Zanni, H

    1998-01-01

    The proton spin-lattice relaxation measured at several frequencies leads to a resolved distribution of four Tli for reactive powder concrete (RPC). The typical Tli frequency dependences are quantitatively interpreted by a biphasic fast exchange model and a proton nuclear relaxation of hydrated paramagnetic ions at the surface of the pores. This leads to an estimation of the pore sizes. We present the first application of this nuclear relaxation method to follow in situ the kinetics of the hydration and setting of such material.

  2. Experimental validation of proton transverse relaxivity models for superparamagnetic nanoparticle MRI contrast agents

    Energy Technology Data Exchange (ETDEWEB)

    Carroll, Matthew R J; Woodward, Robert C; House, Michael J; St Pierre, Timothy G [Centre for Strategic Nanofabrication, School of Physics, University of Western Australia, 35 Stirling Highway, Crawley, WA 6009 (Australia); Teoh, Wey Yang; Amal, Rose [ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering and Industrial Chemistry, University of New South Wales, Sydney, NSW 2052 (Australia); Hanley, Tracey L, E-mail: stpierre@physics.uwa.edu.au [Bragg Institute, Australian Nuclear Science and Technology Organization, New Illawarra Road, Lucas Heights, NSW 2234 (Australia)

    2010-01-22

    Analytical models of proton transverse relaxation rate enhancement by magnetic nanoparticles were tested by making measurements on model experimental systems in a field of 1.4 T. Proton relaxivities were measured for five aqueous suspensions of iron oxide (maghemite) nanoparticles with nominal mean particle sizes of 6, 8, 10, 11, and 13 nm. Proton relaxivity increased with mean particle size ranging from 13 s{sup -1} mM Fe{sup -1} for the 6 nm sample, up to 254 s{sup -1} mM Fe{sup -1} for the 13 nm sample. A strong correlation between the measured and predicted values of the relaxivity was observed, with the predicted values being consistently higher than the measured values. The results indicate that the models give a reasonable agreement with experimental results and hence can be used as the basis for the design of new magnetic resonance imaging contrast and labelling agents.

  3. Nuclear magnetic resonance and proton relaxation times in experimental heterotopic heart transplantation

    Energy Technology Data Exchange (ETDEWEB)

    Eugene, M.; Lechat, P.; Hadjiisky, P.; Teillac, A.; Grosgogeat, Y.; Cabrol, C.

    1986-01-01

    It should be possible to detect heart transplant rejection by nuclear magnetic resonance (NMR) imaging if it induces myocardial T1 and T2 proton relaxation time alterations or both. We studied 20 Lewis rats after a heterotopic heart transplantation. In vitro measurement of T1 and T2 was performed on a Minispec PC20 (Bruker) 3 to 9 days after transplantation. Histologic analysis allowed the quantification of rejection process based on cellular infiltration and myocardiolysis. Water content, a major determinant of relaxation time, was also studied. T1 and T2 were significantly prolonged in heterotopic vs orthotopic hearts (638 +/- 41 msec vs 606 +/- 22 msec for T1, p less than 0.01 and 58.2 +/- 8.4 msec vs 47.4 +/- 1.9 msec for T2, p less than 0.001). Water content was also increased in heterotopic hearts (76.4 +/- 2.3 vs 73.8 +/- 1.0, p less than 0.01). Most importantly, we found close correlations between T1 and especially T2 vs water content, cellular infiltration, and myocardiolysis. We conclude that rejection reaction should be noninvasively detected by NMR imaging, particularly with pulse sequences emphasizing T2.

  4. Proton Electrodynamics in Liquid Water

    CERN Document Server

    Volkov, A A; Pronin, A V

    2013-01-01

    The dielectric spectrum of liquid water, $10^{4} - 10^{11}$ Hz, is interpreted in terms of diffusion of charges, formed as a result of self-ionization of H$_{2}$O molecules. This approach explains the Debye relaxation and the dc conductivity as two manifestations of this diffusion. The Debye relaxation is due to the charge diffusion with a fast recombination rate, $1/\\tau_{2}$, while the dc conductivity is a manifestation of the diffusion with a much slower recombination rate, $1/\\tau_{1}$. Applying a simple model based on Brownian-like diffusion, we find $\\tau_{2} \\simeq 10^{-11}$ s and $\\tau_{1} \\simeq 10^{-6}$ s, and the concentrations of the charge carriers, involved in each of the two processes, $N_{2} \\simeq 5 \\times 10^{26}$ m$^{-3}$ and $N_{1} \\simeq 10^{14}$ m$^{-3}$. Further, we relate $N_{2}$ and $N_{1}$ to the total concentration of H$_{3}$O$^{+}$--OH$^{-}$ pairs and to the pH index, respectively, and find the lifetime of a single water molecule, $\\tau_{0} \\simeq 10^{-9}$ s. Finally, we show that ...

  5. The State of Water in Proton Conducting Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Allcock, Harry R.; Benesi, Alan; Macdonald, Digby D.

    2010-08-27

    The research carried out under grant No. DE-FG02-07ER46371, "The State of Water in Proton Conducting Membranes", during the period June 1, 2008 - May 31, 2010 was comprised of three related parts. These are: 1. An examination of the state of water in classical proton conduction membranes with the use of deuterium T1 NMR spectroscopy (Allcock and Benesi groups). 2. A dielectric relaxation examination of the behavior of water in classical ionomer membranes (Macdonald program). 3. Attempts to synthesize new proton-conduction polymers and membranes derived from the polyphosphazene system. (Allcock program) All three are closely related, crucial aspects of the design and development of new and improved polymer electrolyte fuel cell membranes on which the future of fuel cell technology for portable applications depends.

  6. Vibrational energy relaxation pathways of water

    Science.gov (United States)

    Pakoulev, Andrei; Wang, Zhaohui; Pang, Yoonsoo; Dlott, Dana D.

    2003-10-01

    Vibrational energy relaxation (VR) of the OH stretch νOH and bend δH 2O in water is studied by the mid-IR pump with anti-Stokes Raman probe technique. The broad νOH band in water consists of two inhomogeneously broadened subbands. VR in the larger red-shifted subband νOHR, with T1=0.55 ps, is shown to occur by the mechanism νOH→ δH 2O (1/3) and νOH → ground state (2/3). VR in the smaller longer-lived blue-shifted subband νOHB, with T1=0.75 ps, occurs by the mechanism νOH → ground state. The bending fundamental δH 2O decays directly to the ground state with T1=1.4 ps.

  7. Modelling proton transfer in water molecule chains

    CERN Document Server

    Korzhimanov, Artem; Shutova, Tatiana; Samuelsson, Goran

    2011-01-01

    The process of protons transport in molecular water chains is of fundamental interest for many biological systems. Although many features of such systems can be analyzed using large-scale computational modeling, other features are better understood in terms of simplified model problems. Here we have tested, analytically and numerically, a model describing the classical proton hopping process in molecular water chains. In order to capture the main features of the proton hopping process in such molecular chains, we use a simplified model for our analysis. In particular, our discrete model describes a 1D chain of water molecules situated in an external protein channel structure, and each water molecule is allowed to oscillate around its equilibrium point in this system, while the protons are allowed to move along the line of neighboring oxygen atoms. The occurrence and properties of nonlinear solitary transport structures, allowing for much faster proton transport, are discussed, and the possible implications of...

  8. Kinetics of proton transport in water

    DEFF Research Database (Denmark)

    Kornyshev, A.A.; Kuznetsov, A.M.; Spohr, E.

    2003-01-01

    The excess proton mobility in water has attracted scientific attention for more than a century. Detailed theoretical concepts and models are also presently in strong focus in efforts toward understanding this ubiquitous phenomenon. In the present report, we discuss a theoretical framework...... for rationalizing the excess proton mobility, based on computer simulations, theory of proton transfer (PT) in condensed media, and analysis of classical proton conductivity experiments over broad temperature ranges. The mechanistic options involved are (i) classical hydrodynamic motion of the hydronium ion (H3O......+), (ii) proton transfer from hydronium to a neighboring water molecule, and (iii) structural diffusion of the Zundel complex (H5O2+), the processes all controlled by orientational fluctuations or hydrogen bond breaking in neighboring hydration shells. Spontaneous conversion of excess proton states...

  9. Proton Migration in Clusters Consisting of Protonated Pyridine Solvated by Water Molecules.

    Science.gov (United States)

    Berthias, Francis; Feketeová, Linda; Chermette, Henry; Forquet, Valérian; Morell, Christophe; Abdoul-Carime, Hassan; Farizon, Bernadette; Farizon, Michel; Märk, Tilmann D

    2015-10-26

    Proton transfer (PT) from protonated pyridine to water molecules is observed after excitation of microhydrated protonated pyridine (Py) clusters PyH(+) (H2 O)n (n=0-5) is induced by a single collision with an Ar atom at high incident velocity (95×10(3)  m s(-1) ). Besides the fragmentation channel associated with the evaporation of water molecules, the charged-fragment mass spectrum shows competition between the production of the PyH(+) ion (or its corresponding charged fragments) and the production of H(+) (H2 O) or H(+) (H2 O)2 ions. The increase in the production of protonated water fragments as a function of the number of H2 O molecules in the parent cluster ion as well sd the observation of a stable H(+) (H2 O)2 fragment, even in the case of the dissociation of PyH(+) (H2 O)2 , are evidence of the crucial role of PT in the relaxation process, even for a small number of solvating water molecules.

  10. Analysis of microporosity of reactive powder concrete by proton nuclear relaxation

    Science.gov (United States)

    Philippot, S.; Korb, J.-P.; Petit, D.; Counio, G.; Zanni, H.

    1998-02-01

    The proton spin-lattice relaxation leads to a resolved distribution of four Tl,i, frequency dependences are interpreted by a biphasic fast exchange model of proton and paramagnetic hydrated ions at the surface of the pores. This leads to an estimation of the pore sizes. La relaxation longitudinale des protons du béton de poudres réactives donne une distribution de quatre Tl,i. Leurs dépendances en fréquence sont interprétées par un modèle d'échange biphasique rapide et la présence d'ions paramagnétiques hydratés à la surface des pores. On estime ainsi la taille moyenne des pores.

  11. Local mechanical stress relaxation of Gunn diodes irradiated by protons

    Science.gov (United States)

    Gradoboev, A. V.; Tesleva, E. P.

    2017-05-01

    The aim of the work is studying the impact of Gunn diodes thermocompression bonding conditions upon their resistance to being radiated with protons of various energies. It was established that the tough conditions of Gunn diodes thermocompression bonding results in local mechanic stresses introduced into the active layer of the device, reduction of electron mobility because of the faults introduction and, subsequently, to reduction of operating current, power of UHF generation, percentage of qualitative units production and general reduction of production efficiency of the devices with required characteristics. Irradiation of Gunn diodes produced under the tough conditions of thermocompression bonding with protons which energy is (40-60) MeV with an absorbed dose of (1-6)·102 Gy does not practically reduce the radiation resistance of Gunn diodes produced with application of the given technique. This technique can be recommended for all semiconductor devices on the base of GaAs, which parameters depend significantly upon the mobility of the electrons, to increase the efficiency of production.

  12. Continuous monitoring of the zinc-phosphate acid-base cement setting reaction by proton nuclear magnetic relaxation

    Science.gov (United States)

    Apih, T.; Lebar, A.; Pawlig, O.; Trettin, R.

    2001-06-01

    Proton nuclear magnetic relaxation is a well-established technique for continuous and non destructive monitoring of hydration of conventional Portland building cements. Here, we demonstrate the feasibility of nuclear magnetic resonance (NMR) monitoring of the setting reaction of zinc-phosphate acid-base dental cements, which harden in minutes as compared to days, as in the case of Portland cements. We compare the setting of cement powder (mainly, zinc oxide) prepared with clinically used aluminum-modified orthophosphoric acid solution with the setting of a model system where cement powder is mixed with pure orthophosphoric acid solution. In contrast to previously published NMR studies of setting Portland cements, where a decrease of spin-lattice relaxation time is attributed to enhanced relaxation at the growing internal surface, spin-lattice relaxation time T1 increases during the set of clinically used zinc-phosphate cement. Comparison of these results with a detailed study of diffusion, viscosity, and magnetic-field dispersion of T1 in pure and aluminum-modified orthophosphoric acid demonstrates that the increase of T1 in the setting cement is connected with the increase of molecular mobility in the residual phosphoric acid solution. Although not taken into account so far, such effects may also significantly influence the relaxation times in setting Portland cements, particularly when admixtures with an effect on water viscosity are used.

  13. Structure and Dynamics of a Trinuclear Gadolinium(III) Complex: The Effect of Intramolecular Electron Spin Relaxation on Its Proton Relaxivity(1).

    Science.gov (United States)

    Tóth É, Éva; Helm, Lothar; Merbach, André E.; Hedinger, Roman; Hegetschweiler, Kaspar; Jánossy, András

    1998-08-10

    The trinuclear [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) complex has been characterized in aqueous solution as a model compound from the point of view of MRI: the parameters that affect proton relaxivity have been determined in a combined variable temperature, pressure, and multiple-field (17)O NMR, EPR, and NMRD study. The solution structure of the complex was found to be the same as in solid state: the total coordination number of the lanthanide(III) ion is 8 with two inner-sphere water molecules. EPR measurements proved a strong intramolecular dipole-dipole interaction between Gd(III) electron spins. This mechanism dominates electron spin relaxation at high magnetic fields (B > 5 T). Its proportion to the overall relaxation decreases with decreasing magnetic field and becomes a minor term at fields used in MRI. Consequently, it cannot increase the electronic relaxation rates to such an extent that they limit proton relaxivity. [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) undergoes a relatively slow water exchange (k(ex)(298) = (1.1 +/- 0.2) x 10(7) s(-1)) compared to the Gd(III) aqua ion, while the mechanism is much more associatively activated as shown by the activation volume (DeltaV () = (-12.7 +/- 1.5) cm(3) mol(-)(1)). The lower exchange rate, as compared to [Gd(H(2)O)(8)](3+) and [Gd(PDTA)(H(2)O)(2)](-), can be explained with the higher rigidity of the [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) which considerably slows down the transition from the eight-coordinate reactant to the nine-coordinate transition state. The unexpectedly low rotational correlation time of the complex is interpreted in terms of a spherical structure with a large hydrophobic surface avoiding the formation of a substantial hydration sphere around [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+).

  14. Kinetics of proton transport in water

    DEFF Research Database (Denmark)

    Kornyshev, A.A.; Kuznetsov, A.M.; Spohr, E.

    2003-01-01

    for rationalizing the excess proton mobility, based on computer simulations, theory of proton transfer (PT) in condensed media, and analysis of classical proton conductivity experiments over broad temperature ranges. The mechanistic options involved are (i) classical hydrodynamic motion of the hydronium ion (H3O......+), (ii) proton transfer from hydronium to a neighboring water molecule, and (iii) structural diffusion of the Zundel complex (H5O2+), the processes all controlled by orientational fluctuations or hydrogen bond breaking in neighboring hydration shells. Spontaneous conversion of excess proton states...... between Zundel and hydrated hydronium states and between hydrated and bare hydronium states are the crucial parts of the scheme. A comparison between experimental data and molecular dynamics (MD) simulations shows that prototropic structural diffusion is determined by comparable contributions...

  15. High resolution NMR study of T{sub 1} magnetic relaxation dispersion. IV. Proton relaxation in amino acids and Met-enkephalin pentapeptide

    Energy Technology Data Exchange (ETDEWEB)

    Pravdivtsev, Andrey N.; Yurkovskaya, Alexandra V.; Ivanov, Konstantin L., E-mail: ivanov@tomo.nsc.ru [International Tomography Center, Institutskaya 3a, Novosibirsk 630090 (Russian Federation); Department of Physics, Novosibirsk State University, Pirogova 2, Novosibirsk 630090 (Russian Federation); Vieth, Hans-Martin [Institut für Experimentalphysik, Freie Universität Berlin Arnimallee 14, 14195 Berlin (Germany)

    2014-10-21

    Nuclear Magnetic Relaxation Dispersion (NMRD) of protons was studied in the pentapeptide Met-enkephalin and the amino acids, which constitute it. Experiments were run by using high-resolution Nuclear Magnetic Resonance (NMR) in combination with fast field-cycling, thus enabling measuring NMRD curves for all individual protons. As in earlier works, Papers I–III, pronounced effects of intramolecular scalar spin-spin interactions, J-couplings, on spin relaxation were found. Notably, at low fields J-couplings tend to equalize the apparent relaxation rates within networks of coupled protons. In Met-enkephalin, in contrast to the free amino acids, there is a sharp increase in the proton T{sub 1}-relaxation times at high fields due to the changes in the regime of molecular motion. The experimental data are in good agreement with theory. From modelling the relaxation experiments we were able to determine motional correlation times of different residues in Met-enkephalin with atomic resolution. This allows us to draw conclusions about preferential conformation of the pentapeptide in solution, which is also in agreement with data from two-dimensional NMR experiments (rotating frame Overhauser effect spectroscopy). Altogether, our study demonstrates that high-resolution NMR studies of magnetic field-dependent relaxation allow one to probe molecular mobility in biomolecules with atomic resolution.

  16. Ultrafast vibrational energy relaxation of the water bridge.

    Science.gov (United States)

    Piatkowski, Lukasz; Wexler, Adam D; Fuchs, Elmar C; Schoenmaker, Hinco; Bakker, Huib J

    2012-05-14

    We report the energy relaxation of the OH stretch vibration of HDO molecules contained in an HDO:D(2)O water bridge using femtosecond mid-infrared pump-probe spectroscopy. We found that the vibrational lifetime is shorter (~630 ± 50 fs) than for HDO molecules in bulk HDO:D(2)O (~740 ± 40 fs). In contrast, the thermalization dynamics following the vibrational relaxation are much slower (~1.5 ± 0.4 ps) than in bulk HDO:D(2)O (~250 ± 90 fs). These differences in energy relaxation dynamics strongly indicate that the water bridge and bulk water differ on a molecular scale.

  17. TU-EF-BRA-02: Longitudinal Proton Spin Relaxation and T1-Imaging

    Energy Technology Data Exchange (ETDEWEB)

    Lemen, L. [Univ Cincinnati (United States)

    2015-06-15

    NMR, and Proton Density MRI of the 1D Patient - Anthony Wolbarst Net Voxel Magnetization, m(x,t). T1-MRI; The MRI Device - Lisa Lemen ‘Classical’ NMR; FID Imaging in 1D via k-Space - Nathan Yanasak Spin-Echo; S-E/Spin Warp in a 2D Slice - Ronald Price Magnetic resonance imaging not only reveals the structural, anatomic details of the body, as does CT, but also it can provide information on the physiological status and pathologies of its tissues, like nuclear medicine. It can display high-quality slice and 3D images of organs and vessels viewed from any perspective, with resolution better than 1 mm. MRI is perhaps most extraordinary and notable for the plethora of ways in which it can create unique forms of image contrast, reflective of fundamentally different biophysical phenomena. As with ultrasound, there is no risk from ionizing radiation to the patient or staff, since no X-rays or radioactive nuclei are involved. Instead, MRI harnesses magnetic fields and radio waves to probe the stable nuclei of the ordinary hydrogen atoms (isolated protons) occurring in water and lipid molecules within and around cells. MRI consists, in essence, of creating spatial maps of the electromagnetic environments around these hydrogen nuclei. Spatial variations in the proton milieus can be related to clinical differences in the biochemical and physiological properties and conditions of the associated tissues. Imaging of proton density (PD), and of the tissue proton spin relaxation times known as T1 and T2, all can reveal important clinical information, but they do so with approaches so dissimilar from one another that each is chosen for only certain clinical situations. T1 and T2 in a voxel are determined by different aspects of the rotations and other motions of the water and lipid molecules involved, as constrained by the local biophysical surroundings within and between its cells – and they, in turn, depend on the type of tissue and its state of health. Three other common

  18. Histidine side-chain dynamics and protonation monitored by {sup 13}C CPMG NMR relaxation dispersion

    Energy Technology Data Exchange (ETDEWEB)

    Hass, Mathias A. S. [Leiden University, Institute of Chemistry (Netherlands); Yilmaz, Ali [University of Copenhagen, Department of Medicinal Chemistry, Faculty of Pharmaceutical Sciences (Denmark); Christensen, Hans E. M. [Technical University of Denmark, Department of Chemistry (Denmark); Led, Jens J. [University of Copenhagen, Department of Chemistry (Denmark)], E-mail: led@kiku.dk

    2009-08-15

    The use of {sup 13}C NMR relaxation dispersion experiments to monitor micro-millisecond fluctuations in the protonation states of histidine residues in proteins is investigated. To illustrate the approach, measurements on three specifically {sup 13}C labeled histidine residues in plastocyanin (PCu) from Anabaena variabilis (A.v.) are presented. Significant Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion is observed for {sup 13}C{sup {epsilon}}{sup 1} nuclei in the histidine imidazole rings of A.v. PCu. The chemical shift changes obtained from the CPMG dispersion data are in good agreement with those obtained from the chemical shift titration experiments, and the CPMG derived exchange rates agree with those obtained previously from {sup 15}N backbone relaxation measurements. Compared to measurements of backbone nuclei, {sup 13}C{sup {epsilon}}{sup 1} dispersion provides a more direct method to monitor interchanging protonation states or other kinds of conformational changes of histidine side chains or their environment. Advantages and shortcomings of using the {sup 13}C{sup {epsilon}}{sup 1} dispersion experiments in combination with chemical shift titration experiments to obtain information on exchange dynamics of the histidine side chains are discussed.

  19. MR-visible water content in human brain: a proton MRS study

    DEFF Research Database (Denmark)

    Christiansen, P; Toft, P B; Gideon, P

    1994-01-01

    In vivo measurement of metabolite concentrations in the human brain by means of proton-MRS contributes significantly to the clinical evaluation of patients with diseases of the brain. The fully relaxed water signal has been proposed as an internal standard for calibration of the MRS measurements...

  20. Histidine side-chain dynamics and protonation monitored by C-13 CPMG NMR relaxation dispersion

    DEFF Research Database (Denmark)

    Hass, M. A. S.; Yilmaz, A.; Christensen, Hans Erik Mølager;

    2009-01-01

    The use of C-13 NMR relaxation dispersion experiments to monitor micro-millisecond fluctuations in the protonation states of histidine residues in proteins is investigated. To illustrate the approach, measurements on three specifically C-13 labeled histidine residues in plastocyanin (PCu) from...... Anabaena variabilis (A.v.) are presented. Significant Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion is observed for C-13(epsilon 1) nuclei in the histidine imidazole rings of A.v. PCu. The chemical shift changes obtained from the CPMG dispersion data are in good agreement with those obtained from...... or other kinds of conformational changes of histidine side chains or their environment. Advantages and shortcomings of using the C-13(epsilon 1) dispersion experiments in combination with chemical shift titration experiments to obtain information on exchange dynamics of the histidine side chains...

  1. Dielectric Relaxation in Dimethyl Sulfoxide/Water Mixtures Studied by Microwave Dielectric Relaxation Spectroscopy

    Science.gov (United States)

    Lu, Zijie; Manias, Evangelos; MacDonald, Digby D.; Lanagan, Michael

    2009-10-01

    Dielectric spectra of dimethyl sulfoxide (DMSO)/water mixtures, over the entire concentration range, have been measured using the transmission line method at frequencies from 45 MHz to 26 GHz and at temperatures of 298-318 K. The relaxation times of the mixtures show a maximum at an intermediate molar fraction of DMSO. The specific structure of mixtures in different concentration regions was determined by the dielectric relaxation dynamics, obtained from the effect of temperature on the relaxation time. A water structure "breaking effect" is observed in dilute aqueous solutions. The average number of hydrogen bonds per water molecule in these mixtures is found to be reduced compared to pure water. The increase in the dielectric relaxation time in DMSO/water mixtures is attributed to the spatial (steric) constraints of DMSO molecules on the hydrogen-bond network, rather than being due to hydrophobic hydration of the methyl groups. The interaction between water and DMSO by hydrogen bonding reaches a maximum at a DMSO molar fraction of 0.33, reflected by the maximum activation enthalpy for dielectric relaxation in this concentration, suggesting the formation of a stoichiometric compound, H2O-DMSO-H2O. In highly concentrated solutions, negative activation entropies are observed, indicating the presence of aggregates of DMSO molecules. A distinct antiparallel arrangement of dipoles is obtained for neat DMSO in the liquid state according to the Kirkwood correlation factor (gK = 0.5), calculated from the static permittivity. The similarity of the dielectric behavior of pure DMSO and DMSO-rich mixtures suggests that dipole-dipole interactions contribute significantly to the rotational relaxation process in these solutions.

  2. NMR relaxation and water self-diffusion studies in whey protein solutions and gels.

    Science.gov (United States)

    Colsenet, Roxane; Mariette, François; Cambert, Mireille

    2005-08-24

    The changes in water proton transverse relaxation behavior induced by aggregation of whey proteins are explained in terms of the simple molecular processes of diffusion and chemical exchange. The water self-diffusion coefficient was measured in whey protein solutions and gels by the pulsed field gradient NMR method. As expected, water self-diffusion was reduced with increased protein concentrations. Whatever the concentration, the water molecules were free to diffuse over distances varying from 15 to 47 mum. Water diffusion was constant over these distances, demonstrating that no restrictions were found to explain the water hindrance. The modification in protein structure by gelation induced a decrease in water diffusion. The effects of protein concentration on water diffusion are discussed and modeled. Two approaches were compared, the obstruction effect induced by a spherical particle and the cell model, which considered two water compartments with specific self-diffusion coefficients.

  3. The effect of polymer coatings on proton transverse relaxivities of aqueous suspensions of magnetic nanoparticles.

    Science.gov (United States)

    Carroll, Matthew R J; Huffstetler, Phillip P; Miles, William C; Goff, Jonathon D; Davis, Richey M; Riffle, Judy S; House, Michael J; Woodward, Robert C; St Pierre, Timothy G

    2011-08-12

    Iron oxide magnetic nanoparticles are good candidates for magnetic resonance imaging (MRI) contrast agents due to their high magnetic susceptibilities. Here we investigate 19 polyether-coated magnetite nanoparticle systems comprising three series. All systems were synthesized from the same batch of magnetite nanoparticles. A different polyether was used for each series. Each series comprised systems with systematically varied polyether loadings per particle. A highly significant (p coatings used in this study, any changes in relaxivity from differences in water exclusion or diffusion rates caused by the polymer are minor in comparison with the changes in relaxivity resulting from variations in the degree of aggregation.

  4. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, Benjamin Joel [Univ. of California, Berkeley, CA (United States)

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in ~240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH2I2 and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a ~350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  5. Softening temperature of lyophilized bovine serum albumin and gamma-globulin as measured by spin-spin relaxation time of protein protons.

    Science.gov (United States)

    Yoshioka, S; Aso, Y; Kojima, S

    1997-04-01

    We investigated the usefulness of the spin-spin relaxation time (T2) of protein protons as a probe for evaluating the molecular flexibility of freeze-dried protein formulations. It is proposed that the microscopic softening temperature determined from changes in the T2 of protein protons (Ts(T2)) is an important characteristic of freeze-dried protein formulations, the glass transition temperature (Tg) of which is generally difficult to determine by differential scanning calorimetry. We determined the molecular flexibility of lyophilized bovine serum albumin (BSA) and bovine gamma-globulin (BGG) by measuring the T2 of protein and water protons as well as the spin-lattice relaxation time (T1) of the latter as a function of temperature. The flexibility of freeze-dried BSA and BGG cakes markedly varied at temperatures above and below the Ts(T2), affecting the stability of the proteins. The denaturation and subsequent aggregation of lyophilized BSA and BGG cakes with a relatively high water content was enhanced in the softened state at temperatures above the Ts(T2). Lyophilized cakes with an extremely low water content were significantly denatured, even in the unsoftened state at temperatures below the Ts(T2), probably due to the thermodynamically unstable structures of protein molecules generated by a loss of structural water.

  6. Femtosecond Dynamics of Fundamental Reaction Processes in Liquids: Proton Transfer, Geminate Recombination, Isomerization and Vibrational Relaxation.

    Science.gov (United States)

    Schwartz, Benjamin Joel

    Femtosecond and picosecond transient absorption spectroscopy are used to probe several fundamental aspects of chemical reactivity in the condensed phase including proton transfer, germinate recombination, isomerization and vibrational relaxation. The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured for the first time, and the effects of external hydrogen-bonding interactions on the proton transfer are studied in detail. The proton transfer takes place in ~240 fsec in non-polar environments, but becomes faster than the instrumental resolution of 110 fsec in methanol solutions. A simple model is proposed to explain these results. The dynamics following photodissociation of CH _2I_2 and other small molecules provide the first direct observations of germinate recombination. The recombination of many different photodissociating species occurs on a ~350 fsec time scale. Results also show that recombination yields but not rates depend on the molecular details of the solvent environment and suggest that recombination kinetics are dominated by a single collision with the surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. The data show no simple correlation between the hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes. This strongly implies that the isomerization of these systems does not provide a suitable testing ground for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in the photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial

  7. SU-E-I-64: Transverse Relaxation Time in Methylene Protons of Non-Alcoholic Fatty Liver Disease Rats

    Energy Technology Data Exchange (ETDEWEB)

    Song, K-H; Lee, D-W; Choe, B-Y [Department of Biomedical Engineering, Research Institute of Biomedical Engineering, College of Medicine, The Catholic University of Korea, Seoul, Seoul (Korea, Republic of)

    2015-06-15

    Purpose: The aim of this study was to evaluate transverse relaxation time of methylene resonance compared to other lipid resonances. Methods: The examinations were performed using a 3.0 T scanner with a point — resolved spectroscopy (PRESS) sequence. Lipid relaxation time in a lipid phantom filled with canola oil was estimated considering repetition time (TR) as 6000 msec and echo time (TE) as 40 — 550 msec. For in vivo proton magnetic resonance spectroscopy ({sup 1}H — MRS), eight male Sprague — Dawley rats were given free access to a normal - chow (NC) and eight other male Sprague-Dawley rats were given free access to a high — fat (HF) diet. Both groups drank water ad libitum. T{sub 2} measurements in the rats’ livers were conducted at a fixed TR of 6000 msec and TE of 40 – 220 msec. Exponential curve fitting quality was calculated through the coefficients of determination (R{sup 2}). Results: A chemical analysis of phantom and liver was not performed but a T{sub 2} decay curve was acquired. The T{sub 2} relaxation time of methylene resonance was estimated as follows: NC rats, 37.07 ± 4.32 msec; HF rats, 31.43 ± 1.81 msec (p < 0.05). The extrapolated M0 values were higher in HF rats than in NC rats (p < 0.005). Conclusion: This study of {sup 1}H-MRS led to sufficient spectral resolution and signal — to — noise ratio differences to characterize all observable resonances for yielding T{sub 2} relaxation times of methylene resonance. {sup 1}H — MRS relaxation times may be useful for quantitative characterization of various liver diseases, including fatty liver disease. This study was supported by grant (2012-007883 and 2014R1A2A1A10050270) from the Mid-career Researcher Program through the NRF funded by Ministry of Science. In addition, this study was supported by the Industrial R&D of MOTIE/KEIT (10048997, Development of the core technology for integrated therapy devices based on real-time MRI-guided tumor tracking)

  8. Collective relaxation of protein protons at very low magnetic field: a new window on protein dynamics and aggregation.

    Science.gov (United States)

    Luchinat, Claudio; Parigi, Giacomo

    2007-02-07

    Since the recent availability of high sensitivity field-cycling relaxometers, it has become possible to measure the protein proton relaxation in millimolar protein solutions as a function of magnetic field. In principle, this provides direct access to the so-called spectral density function of protein protons and, hence, to a full set of dynamic parameters. Understanding the dynamic behavior of biological molecules is increasingly appreciated as crucial to understanding their function. However, theoretical tools to analyze the collective relaxation behavior of protons in solute macromolecules over a wide range of magnetic fields are lacking. A complete relaxation matrix analysis of such behavior is described here. This analysis provides excellent predictions of the experimental proton magnetization decays/recoveries-measured to an unprecedented level of accuracy by a last-generation fast field-cycling relaxometer-of two different globular proteins, hen egg white lysozyme and human serum albumin. The new experimentally validated theoretical model is then used to extract dynamic information on these systems. A "collective" order parameter SC2, different from, but complementary to, that commonly extracted from heteronuclear relaxation measurements at high field, is defined and measured. An accurate estimate of the rotational correlation time is obtained: in the case of lysozyme it agrees very well with theoretical predictions; in the case of serum albumin it provides evidence for aggregation at millimolar concentration.

  9. Identification of Structural Relaxation in the Dielectric Response of Water

    Science.gov (United States)

    Hansen, Jesper S.; Kisliuk, Alexander; Sokolov, Alexei P.; Gainaru, Catalin

    2016-06-01

    One century ago pioneering dielectric results obtained for water and n -alcohols triggered the advent of molecular rotation diffusion theory considered by Debye to describe the primary dielectric absorption in these liquids. Comparing dielectric, viscoelastic, and light scattering results, we unambiguously demonstrate that the structural relaxation appears only as a high-frequency shoulder in the dielectric spectra of water. In contrast, the main dielectric peak is related to a supramolecular structure, analogous to the Debye-like peak observed in monoalcohols.

  10. Relaxation of axially confined 400 GeV/c protons to planar channeling in a bent crystal

    CERN Document Server

    Bandiera, L; Bagli, E; Germogli, G; Guidi, V; Sytov, A; Kirillin, I V; Shul'ga, N F; Berra, A; Lietti, D; Prest, M; De Salvador, D; Vallazza, E

    2016-01-01

    An investigation on the mechanism of relaxation of axially confined 400 GeV/c protons to planar channeling in a bent crystal was carried out at the extracted line H8 from CERN Super Proton Synchrotron. The experimental results were critically compared to computer simulations, showing a good agreement. We firmly individuated a necessary condition for the exploitation of axial confinement or its relaxation for particle beam manipulation in high-energy accelerators. We demonstrated that with a short bent crystal, aligned with one of its main axis to the beam direction, it is possible to realize either a total beam steerer or a beam splitter with adjustable intensity. In particular, in the latter case, a complete relaxation from axial confinement to planar channeling takes place, resulting in beam splitting into the two strongest skew planar channels.

  11. Relaxation of axially confined 400 GeV/c protons to planar channeling in a bent crystal

    Energy Technology Data Exchange (ETDEWEB)

    Bandiera, L.; Mazzolari, A.; Bagli, E.; Germogli, G.; Guidi, V. [Universita di Ferrara, Dipartimento di Fisica, Ferrara (Italy); INFN, Ferrara (Italy); Sytov, A. [Universita di Ferrara, Dipartimento di Fisica, Ferrara (Italy); Belarusian State University, Research Institute for Nuclear Problems, Minsk (Belarus); INFN, Ferrara (Italy); Kirillin, I.V. [National Science Center ' ' Kharkov Institute of Physics and Technology' ' , Akhiezer Institute for Theoretical Physics, Kharkov (Ukraine); Shul' ga, N.F. [National Science Center ' ' Kharkov Institute of Physics and Technology' ' , Akhiezer Institute for Theoretical Physics, Kharkov (Ukraine); V.N. Karazin Kharkov National University, Kharkov (Ukraine); Berra, A.; Lietti, D.; Prest, M. [Universita dell' Insubria, Como (Italy); INFN Sezione di Milano Bicocca, Milan (Italy); De Salvador, D. [INFN Laboratori Nazionali di Legnaro, Legnaro (Italy); Universita di Padova, Dipartimento di Fisica, Padua (Italy); Vallazza, E. [INFN Sezione di Trieste, Trieste (Italy)

    2016-02-15

    An investigation on the mechanism of relaxation of axially confined 400 GeV/c protons to planar channeling in a bent crystal was carried out at the extracted line H8 from CERN Super Proton Synchrotron. The experimental results were critically compared to computer simulations, showing a good agreement. We identified a necessary condition for the exploitation of axial confinement or its relaxation for particle beam manipulation in high-energy accelerators. We introduce the idea of using a short bent crystal, aligned with one of its main axis to the beam direction, as a beam steerer or a beam splitter with adjustable intensity in the field of particle accelerators. In particular, in the latter case, a complete relaxation from axial confinement to planar channeling takes place, resulting in beam splitting into the two strongest skew planar channels. (orig.)

  12. Spin-lattice relaxation study of the methyl proton dynamics in solid 9,10-dimethyltriptycene (DMT).

    Science.gov (United States)

    Piślewski, N; Tritt-Goc, J; Bielejewski, M; Rachocki, A; Ratajczyk, T; Szymański, S

    2009-06-01

    Proton spin-lattice relaxation studies are performed for powder samples of 9,10-dimethyltriptycene (DMT) and its isotopomer DMT-d(12) in which all the non-methyl protons in the molecule are replaced by deuterons. The relaxation data are interpreted in terms of the conventional relaxation theory based on the random jump model in which the Pauli correlations between the relevant spin and torsional states are discarded. The Arrhenius activation energies, obtained from the relaxation data, 25.3 and 24.8 kJ mol(-1) for DMT and DMT-d(12), respectively, are very high as for the methyl groups. The validity of the jump model in the present case is considered from the perspective of Haupt theory in which the Pauli principle is explicitly invoked. To this purpose, the dynamic quantities entering the Haupt model are reinterpreted in the spirit of the damped quantum rotation (DQR) approach introduced recently for the purpose of NMR lineshape studies of hindered molecular rotators. Theoretical modelling of the relevant methyl group dynamics, based on the DQR theory, was performed. From these calculations it is inferred that direct assessments of the torsional barrier heights, based on the Arrhenius activation energies extracted from relaxation data, should be treated with caution.

  13. Electrical Mobility of Protons and Proton-Holes in Pure Water Characterized by Physics-Based Water Model

    Science.gov (United States)

    Jie, Binbin; Sah, Chihtang

    Pure water has been characterized empirically for nearly a century, as dissociation into hydronium (H3O)1+ and hydroxide (HO)1- ions. Last March, we reported that the ~40 year experimental industrial standard of chemical equilibrium reaction constant, the ion product, can be accounted for by a statistical-physics-based concentration product of two electrical charge carriers, the positively charged protons, p+, and the negatively charged proton holes or prohols, p-, with a thermal activation energy or proton trapping well depth of Ep + / p - = 576 meV, in the 0-100OC pure liquid water. We now report that the empirically fitted industrial standard experimental data (1985, 1987, 2005) of the two dc ion mobilities in liquid water, can also be accounted for by trapping-limited drift of protons and prohols through proton channels of lower proton electrical potential valleys, Ep+/0 Pauling statistical model using the 1933 Bernal-Fowler water rule.

  14. Probing the hydration of composite cement pastes containing fly ash and silica fume by proton NMR spin-lattice relaxation

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Proton NMR spin-lattice relaxation (T1) was used as a prober for observing the hydration process of composite cement pastes blending fly ash and silica fume during the early age.The distribution at initial time,evolution curves and signals intensity of T1 were shown in this paper.Results demonstrate that the T1 distribution curves at initial time exhibit two peaks,which are regarded as two different water phases in the pastes.The evolution curves of T1 are in good agreement with the hydration process of composite pastes and could be roughly divided into four stages:initial period,dormant period,acceleration period and steady period.The hydration mechanism for each stage was discussed.The hydration of the composite cement pastes was retarded by the addition of fly ash and silica fume when compared to that of pure cement.However,the hydration degree of the cement in the blends was promoted.

  15. Proton Transfer in Nucleobases is Mediated by Water

    Energy Technology Data Exchange (ETDEWEB)

    Khistyaev, Kirill; Golan, Amir; Bravaya, Ksenia B.; Orms, Natalie; Krylov, Anna I.; Ahmed, Musahid

    2013-08-08

    Water plays a central role in chemistry and biology by mediating the interactions between molecules, altering energy levels of solvated species, modifying potential energy proles along reaction coordinates, and facilitating ecient proton transport through ion channels and interfaces. This study investigates proton transfer in a model system comprising dry and microhydrated clusters of nucleobases. With mass spectrometry and tunable vacuum ultraviolet synchrotron radiation, we show that water shuts down ionization-induced proton transfer between nucleobases, which is very ecient in dry clusters. Instead, a new pathway opens up in which protonated nucleo bases are generated by proton transfer from the ionized water molecule and elimination of a hydroxyl radical. Electronic structure calculations reveal that the shape of the potential energy prole along the proton transfer coordinate depends strongly on the character of the molecular orbital from which the electron is removed, i.e., the proton transfer from water to nucleobases is barrierless when an ionized state localized on water is accessed. The computed energetics of proton transfer is in excellent agreement with the experimental appearance energies. Possible adiabatic passage on the ground electronic state of the ionized system, while energetically accessible at lower energies, is not ecient. Thus, proton transfer is controlled electronically, by the character of the ionized state, rather than statistically, by simple energy considerations.

  16. Interactions of acetylcholinesterase with salvianolic acid B and rosmarinic acid from Salvia miltiorhiza water extract investigated by NMR relaxation rate

    Institute of Scientific and Technical Information of China (English)

    Guo Wei Yin; Yi Ming Li; Wei Wei; Shan Hao Jiang; Da Yuan Zhu; Wei Hong Du

    2008-01-01

    In order to understand whether the ameliorating effect on old ages memory disorder by the root of Salvia miltiorhiza is related to the acetylcholinesterase (AChE) inhibition, two main ingredients, salvianolic acid B (1) and rosmarinic acid (2), which were isolated from S. Miltiorhiza water extract, were investigated in vitro by NMR relaxation rate in this work. The results showed that the proton selective relaxation rates and the molecular rotational correlation time of proton pairs for compounds 1 and 2 increased significantly by adding of AChE in mixing solution. The study reveals that the two compounds might bind to the enzyme and have AChE inhibitory effect, which could contribute to the ameliorating effect at some extent on old ages memory disorder.

  17. Ultrafast Librational Relaxation of H2O in Liquid Water

    DEFF Research Database (Denmark)

    Petersen, Jakob; Møller, Klaus Braagaard; Rey, Rossend

    2013-01-01

    The ultrafast librational (hindered rotational) relaxation of a rotationally excited H2O molecule in pure liquid water is investigated by means of classical nonequilibrium molecular dynamics simulations and a power and work analysis. This analysis allows the mechanism of the energy transfer from...... the excited H2O to its water neighbors, which occurs on a sub-100 fs time scale, to be followed in molecular detail, i.e., to determine which water molecules receive the energy and in which degrees of freedom. It is found that the dominant energy flow is to the four hydrogen-bonded water partners in the first...... hydration shell, dominated by those partners’ rotational motion, in a fairly symmetric fashion over the hydration shell. The minority component of the energy transfer, to these neighboring waters’ translational motion, exhibits an asymmetry in energy reception between hydrogen-bond-donating and -accepting...

  18. Contribution of proton NMR relaxation to the investigation of molecular dynamics in columnar mesophases of discotic and polycatenar molecules

    Indian Academy of Sciences (India)

    A C Ribeiro; P J Sebastiao; C Cruz

    2003-08-01

    We present in this work a review concerning wide frequency range 1 proton NMR relaxation studies performed in compounds exhibiting columnar mesophases, namely the Colho mesophase in the case of a liquid crystal of discotic molecules and the h mesophase in the case of a liquid crystal of biforked molecules. These NMR relaxation studies were performed combining conventional and fast field cycling NMR techniques in a frequency range between 100 Hz and 300 MHz. The possibility of probing such a large frequency range has provided a way to effectively distinguish the influence, on the 1 relaxation profiles, of the different molecular movements observed in this type of mesophases. In addition, we present a comparison between the molecular dynamics in columnar (h) and lamellar (SmC) mesophases exhibited by the same biforked compound.

  19. Correlation between Morphology, Water Uptake, and Proton Conductivity in Radiation-Grafted Proton-Exchange Membranes

    DEFF Research Database (Denmark)

    Balog, Sandor; Gasser, Urs; Mortensen, Kell;

    2010-01-01

    An SANS investigation of hydrated proton exchange membranes is presented. Our membranes were synthesized by radiation-induced grafting of ETFE with styrene in the presence of a crosslinker, followed by sulfonation of the styrene. The contrast variation method was used to understand the relationship...... between morphology, water uptake, and proton conductivity. The membranes are separated into two phases. The amorphous phase hosts the water and swells upon hydration, swelling being inversely proportional to the degree of crosslinking. Hydration and proton conductivity exhibit linear dependence...

  20. Vanadium proton exchange membrane water electrolyser

    Science.gov (United States)

    Noack, Jens; Roznyatovskaya, Nataliya; Pinkwart, Karsten; Tübke, Jens

    2017-05-01

    In order to reverse the reactions of vanadium oxygen fuel cells and to regenerate vanadium redox flow battery electrolytes that have been oxidised by atmospheric oxygen, a vanadium proton exchange membrane water electrolyser was set up and investigated. Using an existing cell with a commercial and iridium-based catalyst coated membrane, it was possible to fully reduce V3.5+ and V3+ solutions to V2+ with the formation of oxygen and with coulomb efficiencies of over 96%. The cell achieved a maximum current density of 75 mA/cm2 during this process and was limited by the proximity of the V(III) reduction to the hydrogen evolution reaction. Due to the specific reaction mechanisms of V(IV) and V(III) ions, V(III) solutions were reduced with an energy efficiency of 61%, making this process nearly twice as energy efficient as the reduction of V(IV) to V(III). Polarisation curves and electrochemical impedance spectroscopy were used to further investigate the losses of half-cell reactions and to find ways of further increasing efficiency and performance levels.

  1. The Frequency-Dependence of the NMR Longitudinal Relaxation Rate, T(1)(-1), of Water in Cysts of the Brine Shrimp

    Science.gov (United States)

    Egan, Thomas F.

    The NMR spin-lattice relaxation rate, T(,1)(' -1), of water is independent of the Larmor frequency, (omega)/2(pi), in the normal rf range. However, T(,1)('-1) of intracellular water in biological systems, which accounts for as much as 80% of the cell mass, is frequency-dependent. This indicates that the NMR properties of water in the cellular environment are influenced by long-correlation time processes due to the interaction of water with proteins and other macromolecular constituents of the cell. In this research, the relaxation rate T(,1)(' -1) of water in the Artemia (brine shrimp) cyst is examined as a function of: (1) the proton NMR Larmor frequency for .01 Artemia cysts between 10 and 500 MHz. At lower Larmor frequencies, below 1 MHz, the relaxation rates of water in brine shrimp cysts are influenced by additional relexation mechanisms; translational diffusion of hydration water is one possibility.

  2. Water sorption-induced crystallization, structural relaxations and strength analysis of relaxation times in amorphous lactose/whey protein systems

    OpenAIRE

    Fan, Fanghui; Mou, Tian; Nurhadi, Bambang; Roos, Yrjö H.

    2016-01-01

    Water sorption-induced crystallization, α-relaxations and relaxation times of freeze-dried lactose/whey protein isolate (WPI) systems were studied using dynamic dewpoint isotherms (DDI) method and dielectric analysis (DEA), respectively. The fractional water sorption behavior of lactose/WPI mixtures shown at aw ≤ 0.44 and the critical aw for water sorption-related crystallization (aw(cr)) of lactose were strongly affected by protein content based on DDI data. DEA results showed that the α-rel...

  3. Protonated Melamine Sponge for Effective Oil/Water Separation

    Science.gov (United States)

    Wang, Chih-Feng; Huang, Hsiang-Ching; Chen, Liang-Ting

    2015-09-01

    In this study, we fabricated a superhydrophilic and underwater superoleophobic protonated melamine sponge for effective separation of water-rich immiscible oil/water mixtures with extremely high separation efficiency. This protonated melamine sponge exhibited excellent antifouling properties and could be used to separate oil/water mixtures continuously for up to 12 h without any increase in the oil content in filtrate. Moreover, our compressed protonated melamine sponge could separate both surfactant-free and -stabilized oil-in-water emulsions with high separation efficiencies. The high performance of this protonated melamine sponge and its efficient, energy- and cost-effective preparation suggest that it has great potential for use in practical applications.

  4. Potentiometric Studies on the Protonation Constants and Protonation Energies of Some Diamines in Methanol + Water Mixtures

    Directory of Open Access Journals (Sweden)

    Sangita Sharma

    2007-01-01

    Full Text Available The protonation constants of diamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, o-phenylenediamine, m-phenylene-diamine, p-phenylenediamine were determined on the basis of Bjerrum and Calvin method in methanol-water mixtures. A pH metric method was used for calculation of protonation constants. The effects of solvents on protonation constant have been determined at ionic strength 0.2 M dm-3 (NaClO4 and temperature 30±0.1oC under nitrogen atmosphere. FORTRAN (IV programs were used for calculation of protonation constants and distribution of species like H2L, HL, L in equilibrium state. The logarithm of the protonation constants decrease in aliphatic diamines and increase in aromatic diamines with increase in methanol content in mixed equilibria. The verification of constants are explained on the basis of solute-solvent interaction, solvation, proton transfer processes and dielectric constant of equilibria. Protonation energies have been calculated theoretically using computational methods and these protonation energies for aromatic diamines are higher than aliphatic diamines.

  5. Proton production, neutralisation and reduction in a floating water bridge

    Science.gov (United States)

    Sammer, Martina; Wexler, Adam D.; Kuntke, Philipp; Wiltsche, Helmar; Stanulewicz, Natalia; Lankmayr, Ernst; Woisetschläger, Jakob; Fuchs, Elmar C.

    2015-10-01

    This work reports on proton production, transport, reduction and neutralization in floating aqueous bridges under the application of a high dc voltage (‘floating water bridge’). Recently possible mechanisms for proton transfer through the bridge were suggested. In this work we visualize and describe the production of protons in the anolyte and their neutralization in the catholyte. Apart from that, protons are reduced to hydrogen due to electrolysis. Microbubbles are detached instantly, due to the electrohydrodynamic flow at the electrode surface. No larger, visible bubbles are formed and the system degasses through the bridge due to its higher local temperature. A detailed analysis of trace elements originating from beaker material, anode or the atmosphere is presented, showing that their influence on the overall conduction compared to the contribution of protons is negligible. Finally, an electrochemical rationale of high voltage electrolysis of low ionic strength solutions is presented.

  6. Excess protons in mesoscopic water-acetone nanoclusters

    OpenAIRE

    Semino, Rocío; Martí Rabassa, Jordi; Guàrdia Manuel, Elvira; Laria, Daniel

    2012-01-01

    We carried out molecular dynamics simulation experiments to examine equilibrium and dynamical characteristics of the solvation of excess protons in mesoscopic, [m:n] binary polar clusters comprising m = 50 water molecules and n = 6, 25, and 100 acetone molecules. Contrasting from what is found in conventional macroscopic phases, the characteristics of the proton solvation are dictated, to a large extent, by the nature of the concentration fluctuations prevailing within the clusters. At low ac...

  7. The elliptical oscillations of the protons of water molecules

    Directory of Open Access Journals (Sweden)

    Николай Тимофеевич Малафаев

    2017-01-01

    Full Text Available The analysis of elliptical oscillations of the protons of water molecules by means of a dual-frequency pendulum model is carried out. The vibrational mode is determined, for which the average angles of pendulum deviation are consistent with the corners of bends of hydrogen bonds in water. The possibility of occurrence of elliptical and ellipse-like rotation of protons in the liquid water around the axis of molecules bonds in a non-uniform in the angle field of intermolecular forces is proved

  8. On the feasibility of water calorimetry with scanned proton radiation.

    Science.gov (United States)

    Sassowsky, M; Pedroni, E

    2005-11-21

    Water calorimetry is considered to be the most direct primary method to realize the physical quantity gray for absorbed dose to water. The Swiss Federal Office of Metrology and Accreditation (METAS) has routinely operated a water calorimeter as primary standard for photon radiation since 2001. Nowadays, cancer therapy with proton radiation has become increasingly important and is a well established method. In the framework of the ProScan project conducted by the Paul Scherrer Institute (PSI), the spot-scanning technique is prepared for the subsequent application in hospitals, and adjusted to the recent findings of clinical research. In the absence of primary standards for proton radiation, the metrological traceability is assured by calibrating secondary standards in 60Co radiation and correcting with calculated beam quality correction factors. It is internationally recognized that the development of primary standards for proton radiation is highly desirable. In a common project of PSI and METAS, it is investigated whether a modified version of the water calorimeter in operation at METAS is suitable as primary standard for scanned proton radiation. A feasibility study has been conducted to investigate the linear energy transfer (LET) dependence of the heat defect and the influence of the time and space structure of the scanned beam on the homogeneity and stability of the temperature field in the water calorimeter. Simulations are validated against experimental data of the existing calorimeter used with photon radiation and extended to scanned proton radiation.

  9. Synergetic effect of size and morphology of cobalt ferrite nanoparticles on proton relaxivity.

    Science.gov (United States)

    N, Venkatesha; Srivastava, Chandan; Hegde, Veena

    2014-12-01

    Cobalt ferrite nanoparticles with average sizes of 14, 9 and 6 nm were synthesised by the chemical co-precipitation technique. Average particle sizes were varied by changing the chitosan surfactant to precursor molar ratio in the reaction mixture. Transmission electron microscopy images revealed a faceted and irregular morphology for the as-synthesised nanoparticles. Magnetic measurements revealed a ferromagnetic nature for the 14 and 9 nm particles and a superparamagnetic nature for the 6 nm particles. An increase in saturation magnetisation with increasing particle size was noted. Relaxivity measurements were carried out to determine T2 value as a function of particle size using nuclear magnetic resonance measurements. The relaxivity coefficient increased with decrease in particle size and decrease in the saturation magnetisation value. The observed trend in the change of relaxivity value with particle size was attributed to the faceted nature of as-synthesised nanoparticles. Faceted morphology results in the creation of high gradient of magnetic field in the regions adjacent to the facet edges increasing the relaxivity value. The effect of edges in increasing the relaxivity value increases with decrease in the particle size because of an increase in the total number of edges per particle dispersion.

  10. Alternating electron and proton transfer steps in photosynthetic water oxidation.

    Science.gov (United States)

    Klauss, André; Haumann, Michael; Dau, Holger

    2012-10-02

    Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S(2) → S(3) transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (Y Z OX). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein-water interface is characterized by a high activation energy (E(a) = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S(0) → S(1) transition are similar (τ, approximately 100 µs; E(a) = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established.

  11. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation. [Spiropyrans

    Energy Technology Data Exchange (ETDEWEB)

    Schwartz, B.J.

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in [approximately]240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH[sub 2]I[sub 2] and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a [approximately]350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  12. Observation of three behaviors in confined liquid water within a nanopool hosting proton-transfer reactions.

    Science.gov (United States)

    Douhal, Abderrazzak; Angulo, Gonzalo; Gil, Michal; Organero, Juan Angel; Sanz, Mikel; Tormo, Laura

    2007-05-17

    In this contribution, we report on studies of rotational and diffusional dynamics of 7-hydroxyquinoline (7HQ) within a reverse micelle (RM) containing different amounts of water. Analyzed in terms of the wobbling-in-a-cone model, the data reveal structural and dynamical properties of the nanopool. We clearly observed three regions in the behavior of confined water molecules within the RM hosting a double proton-transfer reaction between the probe and water. This observation remarkably reproduces the change of calculated water density within this life-mimicking medium. The number of water molecules per AOT head in the transition regions changes from 2 to 5, the latter being very near to the full solvation number (6) of the RM heads. Moreover, the H-bonds breaking and making within the RM to give new structures of the probe strongly affect the environment fluidization in different extents, reflected in different relaxation times of these structures; however, they are of similar sizes. We discuss the role of RM confinement and the proton-transfer dynamics on the behavior of water and their relationships to the packing of water molecules in the studied range of concentrations.

  13. Relaxation time: a proton NMR-based approach as a metric to measure reactivity of engineered nanomaterials

    Science.gov (United States)

    Paruthi, Archini; Misra, Superb K.

    2017-08-01

    The toxicological impact of engineered nanoparticles in environmental or biological milieu is very difficult to predict and control because of the complexity of interactions of nanoparticles with the varied constituents in the suspended media. Nanoparticles are different from their bulk counterparts due to their high surface area-to-volume ratio per unit mass, which plays a vital role in bioavailability of these nanoparticles to its surroundings. This study explores how changes in the spin-spin nuclear relaxation time can be used to gauge the availability of surface area and suspension stability of selected nanoparticles (CuO, ZnO, and SiO2), in a range of simulated media. Spin-spin nuclear relaxation time can be mathematically correlated to wetted surface area, which is well backed up by the data of hydrodynamic size measurements and suspension stability. We monitored the change in spin-spin relaxation time for all the nanoparticles, over a range of concentrations (2.5 -100 ppm) in deionized water and artificial seawater. Selective concentrations of nanoparticle suspensions were subjected for temporal studies over a period of 48 hrs to understand the concept of spin-spin nuclear relaxation time-based reactivity of nanoparticle suspension. The nanoparticles showed high degree of agglomeration, when suspended in artificial seawater. This was captured by a decrease in spin-spin nuclear relaxation time and also an increment in the hydrodynamic size of the nanoparticles.

  14. Studies of Water V. Five Phonons in Protonic Semiconductor Lattice Model of Pure Liquid Water

    Science.gov (United States)

    Jie, Binbin; Sah, Chihtang

    2017-07-01

    We report physics based confirmation (~1% RMS deviation), by existing experimental data, of proton-prohol (proton-hole) ion product (pH) and mobilities in pure liquid water (0-100{}{{o}}C, 1-atm pressure) anticipated from our melted-ice Hexagonal-Close-Packed (H{}2O){}4 Lattice Model. Five phonons are identified. (1) A propagating protonic phonon (520.9 meV from lone-pair-blue-shifted stretching mode of isolated water molecule) absorbed to generate a proton-prohol pair or detrap a tightly-bound proton. (2) Two (173.4 and 196.6 meV) bending-breathing protonic-proholic or protonic phonons absorbed during de-trapping-limited proton or proton-prohol mobilities. (3) Two propagating oxygenic-wateric Debye-Dispersive phonons (30.3 and 27.5 meV) absorbed during scattering-limited proton or proton-prohol mobilities. Summer School in Theoretical Physics funded by the National Natural Science Foundation of China, on Soft Materials Physics, hosted by the Physics Department of Xiamen University, China, during August 1 to 14, 2016. This was also just presented at the 2017 March Meeting (March 14 to 16) of the American Physical Society in New Orleans, USA.

  15. Femtosecond and temperature-dependent picosecond dynamics of ultrafast excited-state proton transfer in water-dioxane mixtures.

    Science.gov (United States)

    Freitas, Adilson A; Quina, Frank H; Maçanita, António A L

    2014-11-13

    Synthetic flavylium salts like the 7-hydroxy-4-methylflavylium (HMF) cation have been used as prototypes to study the chemistry and photochemistry of anthocyanins, the major group of water-soluble pigments in the plant kingdom. In this work, a combination of fluorescence upconversion with femtosecond time resolution and time-correlated single photon counting (TCSPC) with picosecond time resolution have been employed to investigate in details the excited-state proton transfer (ESPT) of HMF in water and in binary water/1,4-dioxane mixtures. TCSPC measurements as a function of temperature provide activation parameters for all of the individual rate constants involved in the proton transfer, including those for dissociation and recombination of the geminate excited base-proton pair (A*···H(+)) that can be detected in the water/dioxane mixtures (but not in water). Unlike the other rate constants, the deprotonation rate constant kd shows a non-Arrhenius dependence on temperature in both water and water/dioxane mixtures. At low temperatures kd is close to the dielectric relaxation rate of the solvent with a barrier of ca. 8 kJ mol(-1), suggesting that the solvent reorganization is the rate-limiting step. At higher temperatures (>30 °C) the proton transfer process is nearly barrierless and solvent-dependent. Fluorescence upconversion results in H2O, D2O, and water/dioxane mixtures confirm the two-step model for the ESPT of HMF and provide additional details of the early events prior to the onset of proton transfer, attributed to conformational relaxation and solvent reaccommodation around the initially formed excited state. The results are consistent with DFT calculations that indicate that charge redistribution occurs after rather than prior to the onset of the ESPT process.

  16. Proton-decoupled CPMG: a better experiment for measuring (15)N R2 relaxation in disordered proteins.

    Science.gov (United States)

    Yuwen, Tairan; Skrynnikov, Nikolai R

    2014-04-01

    (15)N R2 relaxation is one of the most informative experiments for characterization of intrinsically disordered proteins (IDPs). Small changes in nitrogen R2 rates are often used to determine how IDPs respond to various biologically relevant perturbations such as point mutations, posttranslational modifications and weak ligand interactions. However collecting high-quality (15)N relaxation data can be difficult. Of necessity, the samples of IDPs are often prepared with low protein concentration and the measurement time can be limited because of rapid sample degradation. Furthermore, due to hardware limitations standard experiments such as (15)N spin-lock and CPMG can sample the relaxation decay only to ca. 150ms. This is much shorter than (15)N T2 times in disordered proteins at or near physiological temperature. As a result, the sampling of relaxation decay profiles in these experiments is suboptimal, which further lowers the precision of the measurements. Here we report a new implementation of the proton-decoupled (PD) CPMG experiment which allows one to sample (15)N R2 relaxation decay up to ca. 0.5-1s. The new experiment has been validated through comparison with the well-established spin-lock measurement. Using dilute samples of denatured ubiquitin, we have demonstrated that PD-CPMG produces up to 3-fold improvement in the precision of the data. It is expected that for intrinsically disordered proteins the gains may be even more substantial. We have also shown that this sequence has a number of favorable properties: (i) the spectra are recorded with narrow linewidth in nitrogen dimension; (ii) (15)N offset correction is small and easy to calculate; (iii) the experiment is immune to various spurious effects arising from solvent exchange; (iv) the results are stable with respect to pulse miscalibration and rf field inhomogeneity; (v) with minimal change, the pulse sequence can also be used to measure R2 relaxation of (15)N(ε) spins in arginine side chains. We

  17. Quantum mechanical alternative to Arrhenius equation in the interpretation of proton spin-lattice relaxation data for the methyl groups in solids

    KAUST Repository

    Bernatowicz, Piotr

    2015-10-01

    Theory of nuclear spin-lattice relaxation in methyl groups in solids has been a recurring problem in nuclear magnetic resonance (NMR) spectroscopy. The current view is that, except for extreme cases of low torsional barriers where special quantum effects are at stake, the relaxation behaviour of the nuclear spins in methyl groups is controlled by thermally activated classical jumps of the methyl group between its three orientations. The temperature effects on the relaxation rates can be modelled by Arrhenius behaviour of the correlation time of the jump process. The entire variety of relaxation effects in protonated methyl groups has recently been given a consistently quantum mechanical explanation not invoking the jump model regardless of the temperature range. It exploits the damped quantum rotation (DQR) theory originally developed to describe NMR line shape effects for hindered methyl groups. In the DQR model, the incoherent dynamics of the methyl group include two quantum rate, i.e., coherence-damping processes. For proton relaxation only one of these processes is relevant. In this paper, temperature-dependent proton spin-lattice relaxation data for the methyl groups in polycrystalline methyltriphenyl silane and methyltriphenyl germanium, both deuterated in aromatic positions, are reported and interpreted in terms of the DQR model. A comparison with the conventional approach exploiting the phenomenological Arrhenius equation is made. The present observations provide further indications that incoherent motions of molecular moieties in condensed phase can retain quantum character over much broad temperature range than is commonly thought.

  18. A quantum mechanical alternative to the Arrhenius equation in the interpretation of proton spin-lattice relaxation data for the methyl groups in solids.

    Science.gov (United States)

    Bernatowicz, Piotr; Shkurenko, Aleksander; Osior, Agnieszka; Kamieński, Bohdan; Szymański, Sławomir

    2015-11-21

    The theory of nuclear spin-lattice relaxation in methyl groups in solids has been a recurring problem in nuclear magnetic resonance (NMR) spectroscopy. The current view is that, except for extreme cases of low torsional barriers where special quantum effects are at stake, the relaxation behaviour of the nuclear spins in methyl groups is controlled by thermally activated classical jumps of the methyl group between its three orientations. The temperature effects on the relaxation rates can be modelled by Arrhenius behaviour of the correlation time of the jump process. The entire variety of relaxation effects in protonated methyl groups have recently been given a consistent quantum mechanical explanation not invoking the jump model regardless of the temperature range. It exploits the damped quantum rotation (DQR) theory originally developed to describe NMR line shape effects for hindered methyl groups. In the DQR model, the incoherent dynamics of the methyl group include two quantum rate (i.e., coherence-damping) processes. For proton relaxation only one of these processes is relevant. In this paper, temperature-dependent proton spin-lattice relaxation data for the methyl groups in polycrystalline methyltriphenyl silane and methyltriphenyl germanium, both deuterated in aromatic positions, are reported and interpreted in terms of the DQR model. A comparison with the conventional approach exploiting the phenomenological Arrhenius equation is made. The present observations provide further indications that incoherent motions of molecular moieties in the condensed phase can retain quantum character over much broader temperature range than is commonly thought.

  19. Proton transfer in liquid water confined inside graphene slabs.

    Science.gov (United States)

    Tahat, Amani; Martí, Jordi

    2015-09-01

    The microscopic structure and dynamics of an excess proton in water constrained in narrow graphene slabs between 0.7 and 3.1 nm wide has been studied by means of a series of molecular dynamics simulations. Interaction of water and carbon with the proton species was modeled using a multistate empirical valence bond Hamiltonian model. The analysis of the effects of confinement on proton solvation structure and on its dynamical properties has been considered for varying densities. The system is organized in one interfacial and a bulk-like region, both of variable size. In the widest interplate separations, the lone proton shows a marked tendency to place itself in the bulk phase of the system, due to the repulsive interaction with the carbon atoms. However, as the system is compressed and the proton is forced to move to the vicinity of graphene walls it moves closer to the interface, producing a neat enhancement of the local structure. We found a marked slowdown of proton transfer when the separation of the two graphene plates is reduced. In the case of lowest distances between graphene plates (0.7 and 0.9 nm), only one or two water layers persist and the two-dimensional character of water structure becomes evident. By means of spectroscopical analysis, we observed the persistence of Zundel and Eigen structures in all cases, although at low interplate separations a signature frequency band around 2500 cm^{-1} suffers a blue shift and moves to characteristic values of asymmetric hydronium ion vibrations, indicating some unstability of the typical Zundel-Eigen moieties and their eventual conversion to a single hydronium species solvated by water.

  20. Correlated proton-electron hole dynamics in protonated water clusters upon extreme ultraviolet photoionization

    Directory of Open Access Journals (Sweden)

    Zheng Li

    2016-07-01

    Full Text Available The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2On after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. For situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20 to 40 fs driven by strong non-adiabatic effects.

  1. Glass transition and relaxation dynamics of propylene glycol-water solutions confined in clay

    Science.gov (United States)

    Elamin, Khalid; Björklund, Jimmy; Nyhlén, Fredrik; Yttergren, Madeleine; Mârtensson, Lena; Swenson, Jan

    2014-07-01

    The molecular dynamics of aqueous solutions of propylene glycol (PG) and propylene glycol methylether (PGME) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy and differential scanning calorimetry. As typical for liquids in confined geometries the intensity of the cooperative α-relaxation becomes considerably more suppressed than the more local β-like relaxation processes. In fact, at high water contents the calorimetric glass transition and related structural α-relaxation cannot even be observed, due to the confinement. Thus, the intensity of the viscosity related α-relaxation is dramatically reduced, but its time scale as well as the related glass transition temperature Tg are for both systems only weakly influenced by the confinement. In the case of the PGME-water solutions it is an important finding since in the corresponding bulk system a pronounced non-monotonic concentration dependence of the glass transition related dynamics has been observed due to the growth of hydrogen bonded relaxing entities of water bridging between PGME molecules [J. Sjöström, J. Mattsson, R. Bergman, and J. Swenson, Phys. Chem. B 115, 10013 (2011)]. The present results suggest that the same type of structural entities are formed in the quasi-two-dimensional space between the clay platelets. It is also observed that the main water relaxation cannot be distinguished from the β-relaxation of PG or PGME in the concentration range up to intermediate water contents. This suggests that these two processes are coupled and that the water molecules affect the time scale of the β-relaxation. However, this is most likely true also for the corresponding bulk solutions, which exhibit similar time scales of this combined relaxation process below Tg. Finally, it is found that at higher water contents the water relaxation does not merge with, or follow, the α-relaxation above Tg, but instead crosses the α-relaxation

  2. Water or realistic compositions in proton radiotherapy? An analytical study.

    Science.gov (United States)

    Rasouli, Fatemeh S; Masoudi, S Farhad

    2017-03-01

    Pre-clinical tests and simulation studies for radiotherapy are generally carried out using water or simplified materials. Investigating the effects of defining compositionally realistic media in proton transport studies was the objective of this work. Accurate modeling of the Bragg curve is a fundamental requirement for such a study. An equation previously validated by experiments provides an appropriate analytical method for proton dose calculation in depth of the target. Owing to the dependency on protons ranges and the probability of undergoing non-elastic nuclear interactions (NNI), this formula comprises three parameters with values specified for initial proton energy and for the target material. As a result, knowledge of the depth-dose distribution using this analytical model is limited to the materials for which the data has been provided in nuclear data tables. In this study, we used our general formulas for calculating the protons ranges and the probability of undergoing NNI in desired compounds and mixtures with an arbitrary number of constituent elements. Furthermore, the protons dose distribution in the depth of these targets was leading off with determining the parameters appeared in the employed model using our mathematically easy to handle relations. For a number of tissues which may be of interest in proton radiotherapy studies but are missing in reference data tables, the mentioned parameters were calculated. Moreover, the resultant values for the protons ranges and the probability of undergoing NNIs were compared with those in water. The results showed that the differences between the position of Bragg peaks in water and realistic media considered in this study were energy dependent, and ranged between a few millimeters. For proton beams of arbitrary chosen initial energies, the maximum dose delivered to the realistic media varied between about -0.02-4.42% in comparison with that to water. The effects observed (both in penetration and in the

  3. Water-assisted proton transfer in ferredoxin I.

    Science.gov (United States)

    Lutz, Stephan; Tubert-Brohman, Ivan; Yang, Yonggang; Meuwly, Markus

    2011-07-08

    The role of water molecules in assisting proton transfer (PT) is investigated for the proton-pumping protein ferredoxin I (FdI) from Azotobacter vinelandii. It was shown previously that individual water molecules can stabilize between Asp(15) and the buried [3Fe-4S](0) cluster and thus can potentially act as a proton relay in transferring H(+) from the protein to the μ(2) sulfur atom. Here, we generalize molecular mechanics with proton transfer to studying proton transfer reactions in the condensed phase. Both umbrella sampling simulations and electronic structure calculations suggest that the PT Asp(15)-COOH + H(2)O + [3Fe-4S](0) → Asp(15)-COO(-) + H(2)O + [3Fe-4S](0) H(+) is concerted, and no stable intermediate hydronium ion (H(3)O(+)) is expected. The free energy difference of 11.7 kcal/mol for the forward reaction is in good agreement with the experimental value (13.3 kcal/mol). For the reverse reaction (Asp(15)-COO(-) + H(2)O + [3Fe-4S](0)H(+) → Asp(15)-COOH + H(2)O + [3Fe-4S](0)), a larger barrier than for the forward reaction is correctly predicted, but it is quantitatively overestimated (23.1 kcal/mol from simulations versus 14.1 from experiment). Possible reasons for this discrepancy are discussed. Compared with the water-assisted process (ΔE ≈ 10 kcal/mol), water-unassisted proton transfer yields a considerably higher barrier of ΔE ≈ 35 kcal/mol.

  4. Proton cycling, buffering, and reaction stoichiometry in natural waters

    NARCIS (Netherlands)

    Hofmann, A.F.; Middelburg, J.J.; Soetaert, K.; Wolf-Gladrow, D.A.; Meysman, F.J.R.

    2010-01-01

    Ongoing acidification of the global ocean necessitates a solid understanding of how biogeochemical processes are driving proton cycling and observed pH changes in natural waters. The standard way of calculating the pH evolution of an aquatic system is to specify first how biogeochemical processes af

  5. Dynamics of water and hydrated protons in confinement

    NARCIS (Netherlands)

    Liu, L.

    2015-01-01

    In this thesis the dynamics of water and hydrated protons in confinement has been studied using nonlinear spectroscopy methods, including IR pump-probe spectroscopy and vibrational sum frequency generation spectroscopy (VSFG spectroscopy). Using the IR pump-probe spectroscopy, we first investigated

  6. Superconductivity and Fast Proton Transport in Nanoconfined Water

    CERN Document Server

    Johnson, K H

    2016-01-01

    A real-space molecular-orbital description of Cooper pairing in conjunction with the dynamic Jahn-Teller mechanism for high-Tc superconductivity predicts that electron-doped water confined to the nanoscale environment of a carbon nanotube or biological macromolecule should superconduct below and exhibit fast proton transport above the transition temperature, Tc = 230 degK (-43 degC).

  7. Water exchange in plant tissue studied by proton NMR in the presence of paramagnetic centers.

    Science.gov (United States)

    Bacić, G; Ratković, S

    1984-04-01

    The proton NMR relaxation of water in maize roots in the presence of paramagnetic centers, Mn2+, Mn- EDTA2 -, and dextran-magnetite was measured. It was shown that the NMR method of Conlon and Outhred (1972, Biochem. Biophys. Acta. 288:354-361) can be applied to a heterogenous multicellular system, and the water exchange time between cortical cells and the extracellular space can be calculated. The water exchange is presumably controlled by the intracellular unstirred layers. The Mn- EDTA2 - complex is a suitable paramagnetic compound for complex tissue, while the application of dextran-magnetite is probably restricted to studies of water exchange in cell suspensions. The water free space of the root and viscosity of the cells cytoplasm was estimated with the use of Mn- EDTA2 -. The convenience of proton NMR for studying the multiphase uptake of paramagnetic ions by plant root as well as their transport to leaves is demonstrated. A simple and rapid NMR technique (spin-echo recovery) for continuous measurement of the uptake process is presented.

  8. Electron and proton elastic scattering in water vapour

    Energy Technology Data Exchange (ETDEWEB)

    Champion, C., E-mail: champion@univ-metz.fr [Universite Paul Verlaine-Metz, Laboratoire de Physique Moleculaire et des Collisions, 1 Boulevard Arago, Technopole 2000, 57078 Metz (France); Universite Bordeaux 1, CNRS/IN2P3, Centre d' Etudes Nucleaires de Bordeaux Gradignan, CENBG, Chemin du Solarium, BP120, 33175 Gradignan (France); Incerti, S.; Tran, H.N. [Universite Bordeaux 1, CNRS/IN2P3, Centre d' Etudes Nucleaires de Bordeaux Gradignan, CENBG, Chemin du Solarium, BP120, 33175 Gradignan (France); El Bitar, Z. [Institut Pluridisciplinaire Hubert Curien, 23 rue du Loess, BP28, 67037 Strasbourg, Cedex 2 (France)

    2012-02-15

    In the present work, we report theoretical differential and integrated cross sections of the elastic scattering process for sub-thermalization electrons (E{sub inc} {approx_equal} 10 meV-10 keV) and 1 keV-1 MeV protons in water vapour. The calculations are performed within the quantum mechanical framework for electrons whereas classical calculations are provided for protons. The results obtained in this free-parameter theoretical treatment are compared to available data and quantitative differences are reported.

  9. Microscopic models for proton transfer in water and strongly hydrogen-bonded complexes with a single-well proton potential

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. "Structural diffusion" of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation...... of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a "gated" shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor...... and acceptor. The short-range and long-range proton transfer as "structural diffusion" of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen...

  10. Probing Brownian relaxation in water-glycerol mixtures using magnetic hyperthermia

    Science.gov (United States)

    Nemala, Humeshkar; Milgie, Michael; Wadehra, Anshu; Thakur, Jagdish; Naik, Vaman; Naik, Ratna

    2013-03-01

    Generation of heat by magnetic nanoparticles in the presence of an external oscillating magnetic field is known as magnetic hyperthermia (MHT). This heat is generated by two mechanisms: the Neel relaxation and Brownian relaxation. While the internal spin relaxation of the nanoparticles known as Neel relaxation is largely dependent on the magnetic properties of the nanoparticles, the physical motion of the particle or the Brownian relaxation is largely dependent on the viscous properties of the carrier liquid. The MHT properties of dextran coated iron oxide nanoparticles have been investigated at a frequency of 400KHz. To understand the influence of Brownian relaxation on heating, we probe the MHT properties of these ferrofluids in water-glycerol mixtures of varying viscosities. The heat generation is quantified using the specific absorption rate (SAR) and its maximum at a particular temperature is discussed with reference to the viscosity.

  11. Water hydrogen bonding in proton exchange and neutral polymer membranes

    Science.gov (United States)

    Smedley, Sarah Black

    Understanding the dynamics of water sorbed into polymer films is critical to reveal structure-property relationships in membranes for energy and water treatment applications, where membranes must interact with water to facilitate or inhibit the transport of ions. The chemical structure of the polymer has drastic effects on the transport properties of the membrane due to the morphological structure of the polymer and how water is interacting with the functional groups on the polymer backbone. Therefore studying the dynamics of water adsorbed into a membrane will give insight into how water-polymer interactions influence transport properties of the film. With a better understanding of how to design materials to have specific properties, we can accelerate development of smarter materials for both energy and water treatment applications to increase efficiency and create high-flux materials and processes. The goal of this dissertation is to investigate the water-polymer interactions in proton exchange and uncharged membranes and make correlations to their charge densities and transport properties. A linear Fourier Transform Infrared (FTIR) spectroscopic method for measuring the hydrogen bonding distribution of water sorbed in proton exchange membranes is described in this thesis. The information on the distribution of the microenvironments of water in an ionic polymer is critical to understanding the effects of different acidic groups on the proton conductivity of proton exchange membranes at low relative humidity. The OD stretch of dilute HOD in H2O is a single, well-defined vibrational band. When HOD in dilute H2O is sorbed into a proton exchange membrane, the OD stretch peak shifts based on the microenvironment that water encounters within the nanophase separated structure of the material. This peak shift is a signature of different hydrogen bonding populations within the membrane, which can be deconvoluted rigorously for dilute HOD in H 2O compared to only

  12. Analysis of Water Management in Proton Exchange Membrane Fuel Cells

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A two-dimensional, steady-state, isothermal water-management model for a complete proton exchange membrane fuel cell (PEMFC) was developed. The model includes the transport in the diffusion layer and the proton exchange membrane (PEM) with a pseudo-homogeneous model for the cathode catalyst layer. The predicted fuel cell performance with variable cathode porosities compares well with experimental results. The model is then used to investigate the effects of some structural parameters, such as the rib size, the interdigitated flow field, and various operating conditions including the gas flow rate, the cell temperature and pressure, humidification, and the relative humidity at the inlet. Water management is best achieved by tuning the anode operating conditions.

  13. Effects of water,Na+ and Ca2+ on stress-relaxation properties of surimi gel

    Institute of Scientific and Technical Information of China (English)

    刘友明; 栗瑞娟; 赵思明; 熊善柏

    2008-01-01

    Surimi gel was made from silver carp(hypophthalmichthys molitrix).Texture analyzer was adopted to measure stress-relaxation curve to study the effects of water,Na+ and Ca2+ on relaxation properties of surimi gel,so as to provide the basic data for development of surimi gel products.Micromodel of gel based on continuous phase of protein network with water embed and dispersed phase of myofibril was established.Stress-relaxation properties of the gel were imitated by use of five-element relaxation mathematical model,with high fitted precision.The results show that addition of water can reduce hardness of gel;Na+ and Ca2+ can improve the viscoelasticity of gel.

  14. Flexible and rigid structures in HIV-1 p17 matrix protein monitored by relaxation and amide proton exchange with NMR.

    Science.gov (United States)

    Ohori, Yuka; Okazaki, Honoka; Watanabe, Satoru; Tochio, Naoya; Arai, Munehito; Kigawa, Takanori; Nishimura, Chiaki

    2014-03-01

    The HIV-1 p17 matrix protein is a multifunctional protein that interacts with other molecules including proteins and membranes. The dynamic structure between its folded and partially unfolded states can be critical for the recognition of interacting molecules. One of the most important roles of the p17 matrix protein is its localization to the plasma membrane with the Gag polyprotein. The myristyl group attached to the N-terminus on the p17 matrix protein functions as an anchor for binding to the plasma membrane. Biochemical studies revealed that two regions are important for its function: D14-L31 and V84-V88. Here, the dynamic structures of the p17 matrix protein were studied using NMR for relaxation and amide proton exchange experiments at the physiological pH of 7.0. The results revealed that the α12-loop, which includes the 14-31 region, was relatively flexible, and that helix 4, including the 84-88 region, was the most protected helix in this protein. However, the residues in the α34-loop near helix 4 had a low order parameter and high exchange rate of amide protons, indicating high flexibility. This region is probably flexible because this loop functions as a hinge for optimizing the interactions between helices 3 and 4. The C-terminal long region of K113-Y132 adopted a disordered structure. Furthermore, the C-terminal helix 5 appeared to be slightly destabilized due to the flexible C-terminal tail based on the order parameters. Thus, the dynamic structure of the p17 matrix protein may be related to its multiple functions.

  15. Cooking effects on water distribution in potatoes using nuclear magnetic resonance relaxation.

    Science.gov (United States)

    Mortensen, Margit; Thybo, Anette K; Bertram, Hanne C; Andersen, Henrik J; Engelsen, Søren B

    2005-07-27

    Continuous low-field (LF) (1)H NMR relaxometry was used to monitor the structural changes during cooking of potatoes with two different dry matter (DM) contents. A principal component analysis of the relaxation decay curves revealed major events related to water mobility during cooking, which occur at 53 and 60 degrees C for potatoes with medium and low DM contents, respectively. Exponential analysis of the relaxation decays reveals two major water populations in the potato: a slow-relaxing (assigned to water in cytoplasm and extracellular cavities) water component, T(22) ( approximately 350-550 ms), and a fast-relaxing component (primarily assigned to water associated with starch and cell walls), T(21) ( approximately 45-65 ms). Significant DM dependent shifts in both the T(21) and T(22) relaxation time constants were observed during cooking, indicating that starch gelatinizes between 53 and 70 degrees C with water exchanging with the hydroxyls of starch (transition in T(21)) and cells start to disrupt with an increase in diffusion volumes at approximately 60 degrees C (transition in T(22)). The study reveals that continuous LF NMR measurement is an excellent and highly sensitive method to study changes in water mobility and water populations during the cooking of potatoes.

  16. Dielectric relaxation time and structure of bound water in biological materials

    Energy Technology Data Exchange (ETDEWEB)

    Mashimo, S.; Kuwabara, S.; Yagihara, S.; Higasi, K.

    1987-12-03

    The dielectric behavior of living tissues and a number of biological materials was examined by new equipment of the time domain reflectometry method in a wide frequency range of 10/sup 7/-10/sup 10/ Hz. The authors found two peaks of Debye absorption around 100 MHz and 20 GHz for all the materials. The low-frequency absorption is probably due to bound water while the high-frequency absorption to free water. From the observed relaxation times of bound water a hypothesis is ventured on the structure of bound water and its relaxation mechanism.

  17. Molecular Dynamics Simulation on Charge Transfer Relaxation between Myoglobin and Water

    Institute of Scientific and Technical Information of China (English)

    CHENG Wei; ZHANG Feng-Shou; ZHANG Bo-Yang; ZHOU Hong-Yu

    2007-01-01

    Dynamical processes of myoglobin after photon-excited charge transfer between Fe ion and surrounding water anion ale simulated by a molecular dynamics model.The roles of Coulomb interaction effect and water effect in the relaxation process are discussed.It is found that the relaxations before and after charge transfer are similar.Strong Coulomb interactions and less water mobility decrease Coulomb energy fluctuations.An extra transferred charge of Fe ion has impact on water packing with a distance up to 0.86nm.

  18. State of water in starch-water systems in the gelatinization temperature range as investigated using dielectric relaxation spectroscopy

    Science.gov (United States)

    Motwani, Tanuj

    Starch-water interactions occurring during gelatinization are critical for developing a mechanistic understanding of the gelatinization process. The overall goal of this project was to investigate the state of water in starch-water systems in the gelatinization temperature range using dielectric relaxation spectroscopy. In the first part of the project, the dielectric response of native wheat starch-water slurries was measured at seven different starch concentrations between 5--60% starch (w/w) in the frequency range of 200 MHz--20 GHz at 25°C. The deconvolution of the dielectric spectra using the Debye model revealed presence of up to three relaxation processes. The relaxation time range of what were considered to be the high, intermediate and low frequency relaxations were 4--9 ps, 20--25 ps and 230--620 ps, respectively. The high frequency relaxation was observed at all starch concentrations, while the intermediate and low frequency relaxation were only observed at starch concentrations of 10% and above, and 30% and above, respectively. The high frequency relaxation was attributed to bulk water, while the intermediate and low frequency relaxations were attributed to rotationally restrained water molecules present in the starch-water system. To investigate the state of water in the gelatinization temperature range, the dielectric response, gelatinization enthalpy and water absorption by 10%, 30% or 50% starch slurries were measured after heating the slurries to different end temperatures between 40--90°C for 30 min. The high frequency relaxation time for 10% starch slurry dropped significantly (P0.159) by heating up to 80°C. The intermediate and low frequency relaxation times were not significantly influenced (P>0.712) by heating for all starch concentrations. Also, the amount of water associated with the three relaxations was not significantly influenced by heating (P >0.187). The water absorption results indicated that highest water uptake was achieved in

  19. Quantum Monte Carlo study of the protonated water dimer

    CERN Document Server

    Dagrada, Mario; Saitta, Antonino M; Sorella, Sandro; Mauri, Francesco

    2013-01-01

    We report an extensive theoretical study of the protonated water dimer (Zundel ion) by means of the highly correlated variational Monte Carlo and lattice regularized Monte Carlo approaches. This system represents the simplest model for proton transfer (PT) and a correct description of its properties is essential in order to understand the PT mechanism in more complex acqueous systems. Our Jastrow correlated AGP wave function ensures an accurate treatment of electron correlations. Exploiting the advantages of contracting the primitive basis set over atomic hybrid orbitals, we are able to limit dramatically the number of variational parameters with a systematic control on the numerical precision, crucial in order to simulate larger systems. We investigate energetics and geometrical properties of the Zundel ion as a function of the oxygen-oxygen distance, taken as reaction coordinate. In both cases, our QMC results are found in excellent agreement with coupled cluster CCSD(T) technique, the quantum chemistry "go...

  20. Proton Transfers at the Air-Water Interface

    Science.gov (United States)

    Mishra, Himanshu

    Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes. Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O +(g), can protonate most (non-alkane) organic species, whereas H 3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the 'function' of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the

  1. Origins of Protons in C-H Bond Insertion Products of Phenols: Proton-Self-Sufficient Function via Water Molecules.

    Science.gov (United States)

    Luo, Zhoujie; Gao, Ya; Zhu, Tong; Zhang, John Zenghui; Xia, Fei

    2017-08-31

    Water molecules can serve as proton shuttles for proton transfer in the C-H bond insertion reactions catalyzed by transition metal complexes. Recently, the control experiments performed for C-H bond insertion of phenol and anisol by gold carbenes show that large discrepancy exists in the yields of hydrogenated and deuterated products. Thus, we conducted a detailed theoretical analysis on the function of water molecules in the C-H bond insertion reactions. The comparison of calculated results and control experiments indicates that the solution water molecules play a crucial role of proton shuttle in C-H bond insertion. In particular, it was found that the hydroxyl groups in phenols were capable of donating protons via water shuttles for the production of C-H products, which had a substantial influence on the yields of inserted products. The hydroxyl groups instead of C-H bonds in phenols function like "proton reservoirs" in the C-H bond insertion, which we call the "proton self-sufficient" (PSS) function of phenol. The PSS function of phenol indicates that the substrates with and without proton reservoirs will lead to different C-H bond insertion products.

  2. Water equivalence of some plastic-water phantom materials for clinical proton beam dosimetry

    Energy Technology Data Exchange (ETDEWEB)

    Al-Sulaiti, L., E-mail: l.al-sulaiti@surrey.ac.uk [Physics Department, University of Surrey, Guildford (United Kingdom); Radiation Dosimetry Team, National Physical Laboratory, Teddington (United Kingdom); Shipley, D.; Thomas, R. [Radiation Dosimetry Team, National Physical Laboratory, Teddington (United Kingdom); Owen, P. [Physics Department, University of Surrey, Guildford (United Kingdom); Radiation Dosimetry Team, National Physical Laboratory, Teddington (United Kingdom); Kacperek, A. [Douglas Cyclotron, Clatterbridge Centre for Oncology, Wirral (United Kingdom); Regan, P.H. [Physics Department, University of Surrey, Guildford (United Kingdom); Palmans, H. [Radiation Dosimetry Team, National Physical Laboratory, Teddington (United Kingdom)

    2012-07-15

    Plastic-water phantom materials are not exactly water equivalent since they have a different elemental composition and different interaction cross sections for protons than water. Several studies of the water equivalence of plastic-water phantom materials have been reported for photon and electron beams, but none for clinical proton beams. In proton beams, the difference between non-elastic nuclear interactions in plastic-water phantom materials compared to those in water should be considered. In this work, the water equivalence of Plastic Water{sup Registered-Sign} (PW){sup 1}, Plastic Water{sup Registered-Sign} Diagnostic Therapy (PWDT){sup 1} and solid water (WT1){sup 2} phantoms was studied for clinical proton energies of 60 MeV and 200 MeV. This was done by evaluating the fluence correction factor at equivalent depths; first with respect to water and then with respect to graphite by experiment and Monte Carlo (MC) simulations using FLUKA. MC simulations showed that the fluence correction with respect to water was less than 0.5% up to the entire penetration depth of the protons at 60 MeV and less than 1% at 200 MeV up to 20 cm depth for PWDT, PW and WT1. With respect to graphite the fluence correction was about 0.5% for 60 MeV and about 4% for 200 MeV. The experimental results for modulated and un-modulated 60 MeV proton beams showed good agreement with the MC simulated fluence correction factors with respect to graphite deviating less than 1% from unity for the three plastic-water phantoms. - Highlights: Black-Right-Pointing-Pointer We study plastic-water in clinical proton beams by experiment and Monte Carlo. Black-Right-Pointing-Pointer We obtain fluence correction factors for water and graphite. Black-Right-Pointing-Pointer The correction factor for water was close to 1 at 60 MeV and <0.990 at 200 MeV. Black-Right-Pointing-Pointer The correction factor for graphite was {approx}0.5% at 60 MeV and up to 4% at 200 MeV.

  3. Structural relaxation of acridine orange dimer in bulk water and inside a single live lung cell

    Science.gov (United States)

    Chowdhury, Rajdeep; Nandi, Somen; Halder, Ritaban; Jana, Biman; Bhattacharyya, Kankan

    2016-02-01

    Structural relaxation of the acridine orange (AO) dimer in bulk water and inside a single live lung cell is studied using time resolved confocal microscopy and molecular dynamics (MD) simulations. The emission maxima ( λem max ˜ 630 nm) of AO in a lung cancer cell (A549) and a non-cancer lung fibroblast cell (WI38) suggest that AO exists as a dimer inside the cell. Time-dependent red shift in emission maximum indicates dynamic relaxation of the AO dimer (in the excited state) with a time constant of 500-600 ps, both in bulk water and inside the cell. We have calculated the equilibrium relaxation dynamics of the AO dimer in the ground state using MD simulations and found a slow component of time scale ˜350 ps. The intra- and inter-molecular components of the total relaxation dynamics of the AO dimer reveal the presence of a slow component of the order of a few hundred picoseconds. Upon restricting intra-molecular dye dynamics by harmonic constraint between AO monomers, the slow component vanishes. Combining the experimental observations and MD simulation results, we ascribe the slow component of the dynamic relaxation of the AO dimer to the structural relaxation, namely, fluctuations in the distance between the two monomers and associated fluctuation in the number of water molecules.

  4. Graphene oxide-Fe{sub 3}O{sub 4} nanoparticle composite with high transverse proton relaxivity value for magnetic resonance imaging

    Energy Technology Data Exchange (ETDEWEB)

    Venkatesha, N.; Srivastava, Chandan, E-mail: csrivastava@materials.iisc.ernet.in [Department of Materials Engineering, Indian Institute of Science, Bangalore 560012 (India); Poojar, Pavan; Geethanath, Sairam [Medical Imaging Research Centre, Dayananda Sagar Institutions, Bangalore 560078 (India); Qurishi, Yasrib [Department of Molecular Reproduction, Development and Genetics, Indian Institute of Science, Bangalore 560012 (India)

    2015-04-21

    The potential of graphene oxide–Fe{sub 3}O{sub 4} nanoparticle (GO-Fe{sub 3}O{sub 4}) composite as an image contrast enhancing material in magnetic resonance imaging has been investigated. Proton relaxivity values were obtained in three different homogeneous dispersions of GO-Fe{sub 3}O{sub 4} composites synthesized by precipitating Fe{sub 3}O{sub 4} nanoparticles in three different reaction mixtures containing 0.01 g, 0.1 g, and 0.2 g of graphene oxide. A noticeable difference in proton relaxivity values was observed between the three cases. A comprehensive structural and magnetic characterization revealed discrete differences in the extent of reduction of the graphene oxide and spacing between the graphene oxide sheets in the three composites. The GO-Fe{sub 3}O{sub 4} composite framework that contained graphene oxide with least extent of reduction of the carboxyl groups and largest spacing between the graphene oxide sheets provided the optimum structure for yielding a very high transverse proton relaxivity value. It was found that the GO-Fe{sub 3}O{sub 4} composites possessed good biocompatibility with normal cell lines, whereas they exhibited considerable toxicity towards breast cancer cells.

  5. Nanometer-scale water- and proton-diffusion heterogeneities across water channels in polymer electrolyte membranes.

    Science.gov (United States)

    Song, Jinsuk; Han, Oc Hee; Han, Songi

    2015-03-16

    Nafion, the most widely used polymer for electrolyte membranes (PEMs) in fuel cells, consists of a fluorocarbon backbone and acidic groups that, upon hydration, swell to form percolated channels through which water and ions diffuse. Although the effects of the channel structures and the acidic groups on water/ion transport have been studied before, the surface chemistry or the spatially heterogeneous diffusivity across water channels has never been shown to directly influence water/ion transport. By the use of molecular spin probes that are selectively partitioned into heterogeneous regions of the PEM and Overhauser dynamic nuclear polarization relaxometry, this study reveals that both water and proton diffusivity are significantly faster near the fluorocarbon and the acidic groups lining the water channels than within the water channels. The concept that surface chemistry at the (sub)nanometer scale dictates water and proton diffusivity invokes a new design principle for PEMs.

  6. Water Soluble Polymers as Proton Exchange Membranes for Fuel Cells

    Directory of Open Access Journals (Sweden)

    Bing-Joe Hwang

    2012-03-01

    Full Text Available The relentless increase in the demand for useable power from energy-hungry economies continues to drive energy-material related research. Fuel cells, as a future potential power source that provide clean-at-the-point-of-use power offer many advantages such as high efficiency, high energy density, quiet operation, and environmental friendliness. Critical to the operation of the fuel cell is the proton exchange membrane (polymer electrolyte membrane responsible for internal proton transport from the anode to the cathode. PEMs have the following requirements: high protonic conductivity, low electronic conductivity, impermeability to fuel gas or liquid, good mechanical toughness in both the dry and hydrated states, and high oxidative and hydrolytic stability in the actual fuel cell environment. Water soluble polymers represent an immensely diverse class of polymers. In this comprehensive review the initial focus is on those members of this group that have attracted publication interest, principally: chitosan, poly (ethylene glycol, poly (vinyl alcohol, poly (vinylpyrrolidone, poly (2-acrylamido-2-methyl-1-propanesulfonic acid and poly (styrene sulfonic acid. The paper then considers in detail the relationship of structure to functionality in the context of polymer blends and polymer based networks together with the effects of membrane crosslinking on IPN and semi IPN architectures. This is followed by a review of pore-filling and other impregnation approaches. Throughout the paper detailed numerical results are given for comparison to today’s state-of-the-art Nafion® based materials.

  7. Proton transfer pathways in an aspartate-water cluster sampled by a network of discrete states

    Science.gov (United States)

    Reidelbach, Marco; Betz, Fridtjof; Mäusle, Raquel Maya; Imhof, Petra

    2016-08-01

    Proton transfer reactions are complex transitions due to the size and flexibility of the hydrogen-bonded networks along which the protons may ;hop;. The combination of molecular dynamics based sampling of water positions and orientations with direct sampling of proton positions is an efficient way to capture the interplay of these degrees of freedom in a transition network. The energetically most favourable pathway in the proton transfer network computed for an aspartate-water cluster shows the pre-orientation of water molecules and aspartate side chains to be a pre-requisite for the subsequent concerted proton transfer to the product state.

  8. Sorption induced relaxations during water diffusion in S-PEEK

    NARCIS (Netherlands)

    Potreck, Jens; Uyar, Fuat; Sijbesma, Hylke; Nijmeijer, Kitty; Stamatialis, Dimitris; Wessling, Matthias

    2009-01-01

    This paper presents an analysis of the sorption kinetics of water vapor and liquid water in the glassy polymer sulfonated poly(ether ether ketone) (S-PEEK). Sorption isotherms are determined experimentally using a gravimetric sorption balance, and the relative contributions of Fickian diffusion and

  9. A computational component analysis of dielectric relaxation and THz spectra of water/AOT reverse micelles with different water loading

    Science.gov (United States)

    Schmollngruber, Michael; Braun, Daniel; Steinhauser, Othmar

    2016-12-01

    In this computational study, we present molecular dynamics simulations of water/aerosol-OT/isooctane reverse micelles with different water loading. We compare these systems in terms of a detailed analysis of dielectric relaxation spectra and water librations in the THz region. The spectra are decomposed into contributions by molecular species and contributions from individual water solvation shells. Additionally, micellar tumbling motion is shown to have a profound influence on the observed dielectric relaxation spectra, if relaxation by internal reorganization and micellar tumbling occurs within similar time scales. A formalism to directly quantify the effect of micellar tumbling motion on a recorded dielectric spectrum is developed. Since micellar rotational diffusion obeys the laws of hydrodynamics, this method is applicable in an experimental context as well, only knowing the viscosity of the outside medium and the average volume of the reverse micelle.

  10. Site-specific protonation kinetics of acidic side chains in proteins determined by pH-dependent carboxyl (13)C NMR relaxation.

    Science.gov (United States)

    Wallerstein, Johan; Weininger, Ulrich; Khan, M Ashhar I; Linse, Sara; Akke, Mikael

    2015-03-04

    Proton-transfer dynamics plays a critical role in many biochemical processes, such as proton pumping across membranes and enzyme catalysis. The large majority of enzymes utilize acid-base catalysis and proton-transfer mechanisms, where the rates of proton transfer can be rate limiting for the overall reaction. However, measurement of proton-exchange kinetics for individual side-chain carboxyl groups in proteins has been achieved in only a handful of cases, which typically have involved comparative analysis of mutant proteins in the context of reaction network modeling. Here we describe an approach to determine site-specific protonation and deprotonation rate constants (kon and koff, respectively) of carboxyl side chains, based on (13)C NMR relaxation measurements as a function of pH. We validated the method using an extensively studied model system, the B1 domain of protein G, for which we measured rate constants koff in the range (0.1-3) × 10(6) s(-1) and kon in the range (0.6-300) × 10(9) M(-1) s(-1), which correspond to acid-base equilibrium dissociation constants (Ka) in excellent agreement with previous results determined by chemical shift titrations. Our results further reveal a linear free-energy relationship between log kon and pKa, which provides information on the free-energy landscape of the protonation reaction, showing that the variability among residues in these parameters arises primarily from the extent of charge stabilization of the deprotonated state by the protein environment. We find that side-chain carboxyls with extreme values of koff or kon are involved in hydrogen bonding, thus providing a mechanistic explanation for the observed stabilization of the protonated or deprotonated state.

  11. Another challenge to paramagnetic relaxation theory: a study of paramagnetic proton NMR relaxation in closely related series of pyridine-derivatised dysprosium complexes.

    Science.gov (United States)

    Rogers, Nicola J; Finney, Katie-Louise N A; Senanayake, P Kanthi; Parker, David

    2016-02-14

    Measurements of the relaxation rate behaviour of two series of dysprosium complexes have been performed in solution, over the field range 1.0 to 16.5 Tesla. The field dependence has been modelled using Bloch-Redfield-Wangsness theory, allowing estimates of the electronic relaxation time, T1e, and the size of the magnetic susceptibility, μeff, to be made. Changes in relaxation rate of the order of 50% at higher fields were measured, following variation of the para-substituent in the single pyridine donor. The magnetic susceptibilities deviated unexpectedly from the free-ion values for certain derivatives in each series examined, in a manner that was independent of the electron-releasing/withdrawing ability of the pyridine substituent, suggesting that the polarisability of just one pyridine donor in octadenate ligands can play a significant role in defining the magnetic susceptibility anisotropy.

  12. Molecular dynamics simulations of NMR relaxation and diffusion of bulk hydrocarbons and water

    Science.gov (United States)

    Singer, Philip M.; Asthagiri, Dilip; Chapman, Walter G.; Hirasaki, George J.

    2017-04-01

    Molecular dynamics (MD) simulations are used to investigate 1H nuclear magnetic resonance (NMR) relaxation and diffusion of bulk n-C5H12 to n-C17H36 hydrocarbons and bulk water. The MD simulations of the 1H NMR relaxation times T1,2 in the fast motion regime where T1 =T2 agree with measured (de-oxygenated) T2 data at ambient conditions, without any adjustable parameters in the interpretation of the simulation data. Likewise, the translational diffusion DT coefficients calculated using simulation configurations agree with measured diffusion data at ambient conditions. The agreement between the predicted and experimentally measured NMR relaxation times and diffusion coefficient also validate the forcefields used in the simulation. The molecular simulations naturally separate intramolecular from intermolecular dipole-dipole interactions helping bring new insight into the two NMR relaxation mechanisms as a function of molecular chain-length (i.e. carbon number). Comparison of the MD simulation results of the two relaxation mechanisms with traditional hard-sphere models used in interpreting NMR data reveals important limitations in the latter. With increasing chain length, there is substantial deviation in the molecular size inferred on the basis of the radius of gyration from simulation and the fitted hard-sphere radii required to rationalize the relaxation times. This deviation is characteristic of the local nature of the NMR measurement, one that is well-captured by molecular simulations.

  13. Water diffusion-exchange effect on the paramagnetic relaxation enhancement in off-resonance rotating frame

    Science.gov (United States)

    Zhang, Huiming; Xie, Yang; Ji, Tongyu

    2007-06-01

    The off-resonance rotating frame technique based on the spin relaxation properties of off-resonance T1 ρ can significantly increase the sensitivity of detecting paramagnetic labeling at high magnetic fields by MRI. However, the in vivo detectable dimension for labeled cell clusters/tissues in T1 ρ-weighted images is limited by the water diffusion-exchange between mesoscopic scale compartments. An experimental investigation of the effect of water diffusion-exchange between compartments on the paramagnetic relaxation enhancement of paramagnetic agent compartment is presented for in vitro/ in vivo models. In these models, the size of paramagnetic agent compartment is comparable to the mean diffusion displacement of water molecules during the long RF pulses that are used to generate the off-resonance rotating frame. The three main objectives of this study were: (1) to qualitatively correlate the effect of water diffusion-exchange with the RF parameters of the long pulse and the rates of water diffusion, (2) to explore the effect of water diffusion-exchange on the paramagnetic relaxation enhancement in vitro, and (3) to demonstrate the paramagnetic relaxation enhancement in vivo. The in vitro models include the water permeable dialysis tubes or water permeable hollow fibers embedded in cross-linked proteins gels. The MWCO of the dialysis tubes was chosen from 0.1 to 15 kDa to control the water diffusion rate. Thin hollow fibers were chosen to provide sub-millimeter scale compartments for the paramagnetic agents. The in vivo model utilized the rat cerebral vasculatures as a paramagnetic agent compartment, and intravascular agents (Gd-DTPA) 30-BSA were administrated into the compartment via bolus injections. Both in vitro and in vivo results demonstrate that the paramagnetic relaxation enhancement is predominant in the T1 ρ-weighted image in the presence of water diffusion-exchange. The T1 ρ contrast has substantially higher sensitivity than the conventional T1

  14. Effects of water concentration in the coating solution on the wall relaxation rate of octadecyltrichlorosilane coated rubidium vapor cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Guiying; Wei, Lihua; Wang, Meiling; Zhao, Kaifeng, E-mail: zhaokf@fudan.edu.cn [Institute of Modern Physics, Department of Nuclear Science and Technology, Fudan University, Shanghai 200433, China and Applied Ion Beam Physics Laboratory, Key Laboratory of the Ministry of Education, Fudan University, Shanghai 200433 (China)

    2015-01-28

    High quality anti-relaxation surface coatings for atomic vapor cells are essential for the preservation of atomic spin coherence and the enhancement of measurement sensitivity. In this paper, we studied the effects of water concentration in octadecyltrichlorosilane (OTS) coating solution on the relaxation rate and its reproducibility of OTS coated Rubidium vapor cells. We found that appropriate water concentration can improve the anti-relaxation performance of OTS coated cells.

  15. Time Resolved Broadband Terahertz Relaxation Dynamics of Electron in Water

    DEFF Research Database (Denmark)

    Wang, Tianwu; Iwaszczuk, Krzysztof; Cooke, David G.;

    We investigated the transient response of the solvated electron in water ejected by photodetachment from potassium ferrocyanide using time resolved terahertz spectroscopy (TSTS). Ultrabroadband THz transients are generated and detected by a two-color femtosecond-induced air plasma and air biased...... coherent detection, respectively. We find that the measured frequency dependent conductivity can be well described by a Drude-Smith model, supplemented by a Lorentz model oscillating near 5 THz....

  16. Investigations on high performance proton exchange membrane water electrolyzer

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Lirong [School of Materials and Metallurgy, Northeastern University, Shenyang 110004 (China)]|[Institute of Fuel Cell, Shanghai Jiao Tong University, Shanghai 200240 (China); Sui, Sheng [Institute of Fuel Cell, Shanghai Jiao Tong University, Shanghai 200240 (China); Zhai, Yuchun [School of Materials and Metallurgy, Northeastern University, Shenyang 110004 (China)

    2009-01-15

    In order to improve proton exchange membrane water electrolyzer (PEMWE) performance, some factors related to the processes of preparing the Membrane Electrode Assemblies (MEAs), such as iridium (Ir) electrocatalyst loading and Nafion {sup registered} content at the anode, thicknesses of proton exchange membrane and gas diffusion layers (GDLs), were examined. In addition, a home-made supported Ir/titanium carbide (Ir/TiC, 20% Ir by weight) was developed for the anode. With best commercial Ir catalyst loading of 1.5 mg cm{sup -2} Ir at the anode, the cell's current densities of 1346 mA cm{sup -2}, 1820 mA cm{sup -2} and 2250 mA cm{sup -2} were achieved at the cell potentials of 1.80 V, 1.90 V and 2.00 V, respectively. A PEMWE with 0.3 mg cm{sup -2} Ir loading of Ir/TiC anode catalyst was comparatively stable and gave current densities of 840 mA cm{sup -2}, 1130 mA cm{sup -2} and 1463 mA cm{sup -2} at the cell potentials of 1.80 V, 1.90 V and 2.00 V, respectively. Based on catalysis efficiency of Amperes per milligram of Ir, the Ir/TiC catalyst is found to be more active than unsupported Ir catalyst. (author)

  17. Gold nanoparticles functionalised with fast water exchanging Gd3+ chelates: linker effects on the relaxivity.

    Science.gov (United States)

    Ferreira, Miguel F; Gonçalves, Janaina; Mousavi, Bibimaryam; Prata, Maria I M; Rodrigues, Sérgio P J; Calle, Daniel; López-Larrubia, Pilar; Cerdan, Sebastian; Rodrigues, Tiago B; Ferreira, Paula M; Helm, Lothar; Martins, José A; Geraldes, Carlos F G C

    2015-03-07

    The relaxivity displayed by Gd(3+) chelates immobilized onto gold nanoparticles is the result of the complex interplay between the nanoparticle size, the water exchange rate and the chelate structure. In this work we study the effect of the length of ω-thioalkyl linkers, anchoring fast water exchanging Gd(3+) chelates onto gold nanoparticles, on the relaxivity of the immobilized chelates. Gold nanoparticles functionalized with Gd(3+) chelates of mercaptoundecanoyl and lipoyl amide conjugates of the DO3A-N-(α-amino)propionate chelator were prepared and studied as potential CA for MRI. High relaxivities per chelate, of the order of magnitude 28-38 mM(-1) s(-1) (30 MHz, 25 °C), were attained thanks to simultaneous optimization of the rotational correlation time and of the water exchange rate. Fast local rotational motions of the immobilized chelates around connecting linkers (internal flexibility) still limit the attainable relaxivity. The degree of internal flexibility of the immobilized chelates seems not to be correlated with the length of the connecting linkers. Biodistribution and MRI studies in mice suggest that the in vivo behavior of the gold nanoparticles was determined mainly by size. Small nanoparticles (HD = 3.9 nm) undergo fast renal clearance and avoidance of the RES organs while larger nanoparticles (HD = 4.8 nm) undergo predominantly hepatobiliary excretion. High relaxivities, allied to chelate and nanoparticle stability and fast renal clearance in vivo suggest that functionalized gold nanoparticles hold great potential for further investigation as MRI contrast agents. This study contributes to a better understanding of the effect of linker length on the relaxivity of gold nanoparticles functionalized with Gd(3+) complexes. It is a relevant contribution towards "design rules" for nanostructures functionalized with Gd(3+) chelates as Contrast Agents for MRI and multimodal imaging.

  18. Experimental investigation of picosecond dynamics following interactions between laser accelerated protons and water

    Science.gov (United States)

    Senje, L.; Coughlan, M.; Jung, D.; Taylor, M.; Nersisyan, G.; Riley, D.; Lewis, C. L. S.; Lundh, O.; Wahlström, C.-G.; Zepf, M.; Dromey, B.

    2017-03-01

    We report direct experimental measurements with picosecond time resolution of how high energy protons interact with water at extreme dose levels (kGy), delivered in a single pulse with the duration of less than 80 ps. The unique synchronisation possibilities of laser accelerated protons with an optical probe pulse were utilized to investigate the energy deposition of fast protons in water on a time scale down to only a few picoseconds. This was measured using absorbance changes in the water, induced by a population of solvated electrons created in the tracks of the high energy protons. Our results indicate that for sufficiently high doses delivered in short pulses, intertrack effects will affect the yield of solvated electrons. The experimental scheme allows for investigation of the ultrafast mechanisms occurring in proton water radiolysis, an area of physics especially important due to its relevance in biology and for proton therapy.

  19. Umbrella sampling of proton transfer in a creatine-water system

    Science.gov (United States)

    Ivchenko, Olga; Bachert, Peter; Imhof, Petra

    2014-04-01

    Proton transfer reactions are among the most common processes in chemistry and biology. Proton transfer between creatine and surrounding solvent water is underlying the chemical exchange saturation transfer used as a contrast in magnetic resonance imaging. The free energy barrier, determined by first-principles umbrella sampling simulations (EaDFT 3 kcal/mol) is in the same order of magnitude as the experimentally obtained activation energy. The underlying mechanism is a first proton transfer from the guanidinium group to the water pool, followed by a second transition where a proton is "transferred back" from the nearest water molecule to the deprotonated nitrogen atom of creatine.

  20. Proton transfer from the bulk to the bound ubiquinone QB of the reaction center in chromatophores of Rhodobacter sphaeroides: Retarded conveyance by neutral water

    Science.gov (United States)

    Gopta, Oksana A.; Cherepanov, Dmitry A.; Junge, Wolfgang; Mulkidjanian, Armen Y.

    1999-01-01

    The mechanism of proton transfer from the bulk into the membrane protein interior was studied. The light-induced reduction of a bound ubiquinone molecule QB by the photosynthetic reaction center is accompanied by proton trapping. We used kinetic spectroscopy to measure (i) the electron transfer to QB (at 450 nm), (ii) the electrogenic proton delivery from the surface to the QB site (by electrochromic carotenoid response at 524 nm), and (iii) the disappearance of protons from the bulk solution (by pH indicators). The electron transfer to QB− and the proton-related electrogenesis proceeded with the same time constant of ≈100 μs (at pH 6.2), whereas the alkalinization in the bulk was distinctly delayed (τ ≈ 400 μs). We investigated the latter reaction as a function of the pH indicator concentration, the added pH buffers, and the temperature. The results led us to the following conclusions: (i) proton transfer from the surface-located acidic groups into the QB site followed the reduction of QB without measurable delay; (ii) the reprotonation of these surface groups by pH indicators and hydronium ions was impeded, supposedly, because of their slow diffusion in the surface water layer; and (iii) as a result, the protons were slowly donated by neutral water to refill the proton vacancies at the surface. It is conceivable that the same mechanism accounts for the delayed relaxation of the surface pH changes into the bulk observed previously with bacteriorhodopsin membranes and thylakoids. Concerning the coupling between proton pumps in bioenergetic membranes, our results imply a tendency for the transient confinement of protons at the membrane surface. PMID:10557290

  1. Magnetization Transfer Induced Biexponential Longitudinal Relaxation

    Science.gov (United States)

    Prantner, Andrew M.; Bretthorst, G. Larry; Neil, Jeffrey J.; Garbow, Joel R.; Ackerman, Joseph J.H.

    2009-01-01

    Longitudinal relaxation of brain water 1H magnetization in mammalian brain in vivo is typically analyzed on a per voxel basis using a monoexponential model, thereby assigning a single relaxation time constant to all 1H magnetization within a given voxel. This approach was tested by obtaining inversion recovery data from grey matter of rats at 64 exponentially-spaced recovery times. Using Bayesian probability for model selection, brain water data were best represented by a biexponential function characterized by fast and slow relaxation components. At 4.7 T, the amplitude fraction of the rapidly relaxing component is 3.4 ± 0.7 % with a rate constant of 44 ± 12 s-1 (mean ± SD; 174 voxels from 4 rats). The rate constant of the slow relaxing component is 0.66 ± 0.04 s-1. At 11.7 T, the corresponding values are 6.9 ± 0.9 %, 19 ± 5 s-1, and 0.48 ± 0.02 s-1 (151 voxels from 4 rats). Several putative mechanisms for biexponential relaxation behavior were evaluated, and magnetization transfer between bulk water protons and non-aqueous protons was determined to be the source of biexponential longitudinal relaxation. MR methods requiring accurate quantification of longitudinal relaxation may need to take this effect explicitly into account. PMID:18759367

  2. SOLVENT EFFECT ON PROTONATION OF TPPS IN WATER-DMF ...

    African Journals Online (AJOL)

    Also, relationship with reciprocal of dielectric constant was ... The free base TPPS (H2tpps4-), Figure 1, can be protonated by one or two protons on ... clear that protonation brings about the redistribution of electron density in porphyrin core, ...

  3. Application of Schrödinger equation to study the tunnelling dynamics of proton transfer in the hydrogen bond of 2,5-dinitrobenzoic acid: proton T1 T1rho, and deuteron T1 relaxation methods.

    Science.gov (United States)

    Latanowicz, L; Medycki, W

    2007-02-22

    Temperature measurements of proton T1 (24.7 MHz), deuteron (deuterated hydroxyl group) T1 (55.2 MHz), and proton T1(rho) (B1 = 9 G) spin-lattice relaxation times of 2,5-dinitrobenzoic acid have been performed. An analysis of present experimental data together with previously published proton T1 (55.2 MHz) data has revealed the following molecular motions: proton/deuteron transfer in the hydrogen bond and two-site hopping of the whole dimer. It is shown that the proton-transfer dynamics are characterized by two correlation times tau(ov) and tau(tu), describing two fundamentally different motional processes, namely, thermally activated jumps over the barrier and tunneling through the barrier. The temperature dependence of 1/tau(tu) is the solution of Schrödinger's equation, which also yields the temperature T(tun), where begins the tunnel pathway for proton transfer. A new equation for the spectral density function of complex motion consisting of the three motions is derived. The third motion (two-site hopping of the whole dimer characterized by tau(lib) correlation time) is responsible for a proton T1(rho) minimum in high temperatures, just below the melting point. Such a minimum is not reached by T1 temperature dependencies. The minimum of T1(rho) assigned to the classical hopping of a hydrogen-bonded proton occurs in the same low-temperature regime in which the flattening of the temperature dependencies of T1 points to the dominance of incoherent tunneling. This experimental fact denies the known theories predicting the intermediate temperature regime where a smooth transition between classical and quantum tunneling dynamics is expected. The fit of the derived theoretical equations to the experimental data T1(rho) and T1 is satisfactory. The correlation times obtained for deuterons indicate deuteron-transfer dynamics much slower than proton-transfer dynamics. It is concluded that the classical proton transfer takes place over the whole temperature regime, while

  4. Hydrogen-1 NMR relaxation time studies in membrane: anesthetic systems; Variacao dos tempos de relaxacao longitudinal de protons em sistemas membranares contendo anestesicos locais

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, L.M.A.; Fraceto, L.; Paula, E. de [Universidade Estadual de Campinas, SP (Brazil). Dept. de Bioquimica; Franzoni, L.; Spisni, A. [Universita degli Studi di Parma, Parma (Italy). Ist. di Chimica Biologica

    1997-12-31

    The study of local anesthetics`(LA) interaction with model phospholipid membranes is justified by the direct correlation between anesthetic`s hydrophobicity and its potency/toxicity. By the same reason, uncharged LA species seems to play a crucial role in anesthesia. Most clinically used LA are small amphiphilics with a protonated amine group (pKa around 8). Although both charged (protonated) and uncharged forms can coexist at physiological pH, it has been shown (Lee, Biochim. Biophys. Acta 514:95, 1978; Screier et al. Biochim. Biophys. Acta 769:231, 1984) that the real anesthetic pka can be down-shifted, due to differential partition into membranes, increasing the ratio of uncharged species at pH 7.4. We have measured {sup 1}H-NMR longitudinal relaxation times (T{sub 1}) for phospholipid and three local anesthetics (tetracaine, lidocaine, benzocaine), in sonicated vesicles at a 3:1 molar ratio. All the LA protons have shown smaller T{sub 1} in this system than in isotropic phases, reflecting LA immobilization caused by insertion in the membrane. T{sub 1} values for the lipid protons in the presence of LA were analyzed, in an attempt to identify specific LA:lipid contact regions. (author) 13 refs., 3 figs., 1 tabs.

  5. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

    Science.gov (United States)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V.

    2016-01-01

    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

  6. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V., E-mail: aneimark@rutgers.edu [Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854-8058 (United States)

    2016-01-07

    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

  7. Texture analysis using proton density and T2 relaxation in patients with histological usual interstitial pneumonia (UIP) or nonspecific interstitial pneumonia (NSIP).

    Science.gov (United States)

    Buzan, Maria T A; Wetscherek, Andreas; Heussel, Claus Peter; Kreuter, Michael; Herth, Felix J; Warth, Arne; Kauczor, Hans-Ulrich; Pop, Carmen Monica; Dinkel, Julien

    2017-01-01

    The purpose of our study was to assess proton density (PD) and T2 relaxation time of usual interstitial pneumonia (UIP) and nonspecific interstitial pneumonia (NSIP) and to evaluate their utility in differentiating the two patterns. Furthermore, we aim to investigate whether these two parameters could help differentiate active-inflammatory and stable-fibrotic lesions in NSIP. 32 patients (mean age: 69 years; M:F, 1:1) with pathologically proven disease (UIP:NSIP, 1:1), underwent thoracic thin-section multislice CT scan and 1.5T MRI. A total of 437 regions-of-interest (ROIs) were classified at CT as advanced, moderate or mild alterations. Based on multi-echo single-shot TSE sequence acquired at five echo times, with breath-holding at end-expiration and ECG-triggering, entire lung T2 and PD maps were generated from each subject. The T2 relaxation time and the respective signal intensity were quantified by performing a ROI measurement on the T2 and PD maps in the corresponding CT selected areas of the lung. UIP and NSIP regional patterns could not be differentiated by T2 relaxation times or PD values alone. Overall, a strong positive correlation was found between T2 relaxation and PD in NSIP, r = 0.64, prelaxation showed significant statistical difference between active-inflammatory and stable-fibrotic NSIP regions at all levels, p0.05. T2 relaxation times and PD values may provide helpful quantitative information for differentiating NSIP from UIP pattern. These parameters have the potential to differentiate active-inflammatory and stable-fibrotic lesions in NSIP.

  8. Stress relaxation study of water atomized Cu-Cr-Zr powder alloys consolidated by inverse warm extrusion

    Energy Technology Data Exchange (ETDEWEB)

    Poblano-Salas, C.A., E-mail: carlos.poblano@ciateq.m [CIATEQ A.C., Centro de Tecnologia Avanzada, Av. Manantiales 23 A, Parque Industrial Bernardo Quintana, El Marques, Queretaro, C.P. 76246 (Mexico); Barceinas-Sanchez, J.D.O., E-mail: obarceinas@ipn.m [CICATA-IPN, Centro de Investigacion en Ciencia Aplicada y Tecnologia Avanzada, Cerro Blanco 141, Colinas del Cimatario, Santiago de Queretaro, Queretaro, C.P. 76090 (Mexico)

    2009-10-19

    Stress relaxation testing in compression at high temperature was performed on Cu-Cr-Zr alloys produced by consolidation of water atomized powders. Precipitation and recrystallization were monitored during stress relaxation experiments carried out at an ageing temperature of 723 K. Pre-straining imposed to the Cu-Cr-Zr samples prior to stress relaxation testing resulted in reduced hardness compared to that reported for conventionally-aged alloys; it also resulted in shorter times for achieving maximum strengthening on ageing.

  9. The excess proton at the air-water interface: The role of instantaneous liquid interfaces

    Science.gov (United States)

    Giberti, Federico; Hassanali, Ali A.

    2017-06-01

    The magnitude of the pH of the surface of water continues to be a contentious topic in the physical chemistry of aqueous interfaces. Recent theoretical studies have shown little or no preference for the proton to be at the surface compared to the bulk. Using ab initio molecular dynamics simulations, we revisit the propensity of the excess proton for the air-water interface with a particular focus on the role of instantaneous liquid interfaces. We find a more pronounced presence for the proton to be at the air-water interface. The enhanced water structuring around the proton results in the presence of proton wires that run parallel to the surface as well as a hydrophobic environment made up of under-coordinated topological defect water molecules, both of which create favorable conditions for proton confinement at the surface. The Grotthuss mechanism within the structured water layer involves a mixture of both concerted and closely spaced stepwise proton hops. The proton makes excursions within the first solvation layer either in proximity to or along the instantaneous interface.

  10. A subzero 1H NMR relaxation investigation of water dynamics in tomato pericarp.

    Science.gov (United States)

    Foucat, Loïc; Lahaye, Marc

    2014-09-01

    (1)H NMR relaxation times (T1 and T2) were measured at low field (0.47 T) in pericarp tissues of three tomato genotypes (Ferum, LA0147 and Levovil) at subzero temperature (-20 °C) and two ripening stages (mature green and red). The unfrozen water dynamics was characterised by two T1 and three T2 components. The relaxation time values and their associated relative populations allowed differentiating the ripening stage of only LA0147 and Levovil lines. But the three genotypes were unequivocally discriminated at the red ripe stage. The unfrozen water distribution was discussed in terms of specific interactions, especially with sugars, in relation with their osmoprotectant effects.

  11. Origin of proton affinity to membrane/water interfaces.

    Science.gov (United States)

    Weichselbaum, Ewald; Österbauer, Maria; Knyazev, Denis G; Batishchev, Oleg V; Akimov, Sergey A; Hai Nguyen, Trung; Zhang, Chao; Knör, Günther; Agmon, Noam; Carloni, Paolo; Pohl, Peter

    2017-07-03

    Proton diffusion along biological membranes is vitally important for cellular energetics. Here we extended previous time-resolved fluorescence measurements to study the time and temperature dependence of surface proton transport. We determined the Gibbs activation energy barrier ΔG (‡)r that opposes proton surface-to-bulk release from Arrhenius plots of (i) protons' surface diffusion constant and (ii) the rate coefficient for proton surface-to-bulk release. The large size of ΔG (‡)r disproves that quasi-equilibrium exists in our experiments between protons in the near-membrane layers and in the aqueous bulk. Instead, non-equilibrium kinetics describes the proton travel between the site of its photo-release and its arrival at a distant membrane patch at different temperatures. ΔG (‡)r contains only a minor enthalpic contribution that roughly corresponds to the breakage of a single hydrogen bond. Thus, our experiments reveal an entropic trap that ensures channeling of highly mobile protons along the membrane interface in the absence of potent acceptors.

  12. Effect of Water Content on Enthalpic Relaxations in Porcine Septal Cartilage.

    Science.gov (United States)

    Chae, Y; Protsenko, D; Lavernia, E J; Wong, B J F

    2009-03-01

    Cartilage thermoforming is an emerging surgical technology which uses heat to accelerate stress relaxation in mechanically deformed tissue specimens. Heat induced shape change in cartilage is associated with complex thermo mechanical behavior of which the mechanisms are still a subject of debate. Differential scanning calorimetry (DSC) was used to characterize the threshold temperatures and enthalpies in cartilage as a function of water content. The DSC identified two enthalpic events in porcine nasal septal cartilage, which depend on the water content. The change in the water content of cartilage impacts the interactions between matrix macromolecules and water molecules, which may be associated with a bound-free water transformation (reversible process) and a denaturation of cartilage (irreversible process).

  13. Cooperative dynamics of didodecyldimethylammonium bromide / water / n-dodecane microemulsions: a dielectric relaxation study

    OpenAIRE

    Wachter, Wolfgang

    2008-01-01

    A systematic study of the dielectric relaxation spectra of W/O (water-in-oil) microemulsions composed of didodecyldimethylammonium bromide (DDAB), water (W) and n-dodecane (D) has been made over the whole stability region in the phase diagram and over a wide range of frequencies (0.005 < nu/GHz < 89) at 25 °C. The spectra were best described by a superposition of six or five Debye processes, respectively, depending on the position of the sample in the phase diagram. Process 1 at 40 ns can be ...

  14. Role of water states on water uptake and proton transport in Nafion using molecular simulations and bimodal network

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Gi Suk [Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Mechanical Engineering; Kaviany, Massoud [Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Mechanical Engineering; Gostick, Jeffrey T. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division; Kientiz, Brian [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division; Weber, Adam Z. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division; Kim, Moo Hwan [Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of). Dept. of Mechanical Engineering

    2011-04-07

    In this paper, using molecular simulations and a bimodal-domain network, the role of water state on Nafion water uptake and water and proton transport is investigated. Although the smaller domains provide moderate transport pathways, their effectiveness remains low due to strong, resistive water molecules/domain surface interactions. Finally, the water occupancy of the larger domains yields bulk-like water, and causes the observed transition in the water uptake and significant increases in transport properties.

  15. Monte carlo computation of the energy deposited by protons in water, bone and adipose

    Science.gov (United States)

    Küçer, Rahmi; Küçer, Nermin; Türemen, Görkem

    2013-02-01

    Protons are most suitable for treating deeply-seated tumors due to their unique depth dose distribution. The maximum dose of protons is a pronounced peak, called the Bragg peak, with zero dose behind the peak. The objective of radiation therapy with protons is to deliver the dose to the target volume by using this type of distribution. This is achieved with a finite number of Bragg peaks at the depth of the target volume. The location of the peak in terms of depth depends on the energy of the protons. Simulations are used to determine the depth dose distribution of proton beams passing through tissue, so it is important that experimental data agree with the simulation data. In this study, we used the FLUKA computer code to determine the correct position of the Bragg peak for proton beams passing through water, bone and adipose, and the results were compared with experimental data.

  16. Simplified quantification of labile proton concentration-weighted chemical exchange rate (kws) with RF saturation time dependent ratiometric analysis (QUESTRA) - Normalization of relaxation and RF irradiation spillover effects for improved quantitative chemical exchange saturation transfer (CEST) MRI

    Science.gov (United States)

    Sun, Phillip Zhe

    2012-01-01

    Chemical exchange saturation transfer (CEST) MRI is an emerging imaging technique capable of detecting dilute proteins/peptides and microenvironmental properties, with promising in vivo applications. However, CEST MRI contrast is complex, varying not only with the labile proton concentration and exchange rate, but also with experimental conditions such as field strength and RF irradiation scheme. Furthermore, the optimal RF irradiation power depends on the exchange rate, which must be estimated in order to optimize the CEST MRI experiments. Although methods including numerical fitting with modified Bloch-McConnell equations, quantification of exchange rate with RF saturation time and power (QUEST and QUESP), have been proposed to address this relationship, they require multiple-parameter non-linear fitting and accurate relaxation measurement. Our work here extended the QUEST algorithm with ratiometric analysis (QUESTRA) that normalizes the magnetization transfer ratio (MTR) at labile and reference frequencies, which effectively eliminates the confounding relaxation and RF spillover effects. Specifically, the QUESTRA contrast approaches its steady state mono-exponentially at a rate determined by the reverse exchange rate (kws), with little dependence on bulk water T1, T2, RF power and chemical shift. The proposed algorithm was confirmed numerically, and validated experimentally using a tissue-like phantom of serially titrated pH compartments. PMID:21842497

  17. Simplified quantification of labile proton concentration-weighted chemical exchange rate (k(ws) ) with RF saturation time dependent ratiometric analysis (QUESTRA): normalization of relaxation and RF irradiation spillover effects for improved quantitative chemical exchange saturation transfer (CEST) MRI.

    Science.gov (United States)

    Sun, Phillip Zhe

    2012-04-01

    Chemical exchange saturation transfer MRI is an emerging imaging technique capable of detecting dilute proteins/peptides and microenvironmental properties, with promising in vivo applications. However, chemical exchange saturation transfer MRI contrast is complex, varying not only with the labile proton concentration and exchange rate, but also with experimental conditions such as field strength and radiofrequency (RF) irradiation scheme. Furthermore, the optimal RF irradiation power depends on the exchange rate, which must be estimated in order to optimize the chemical exchange saturation transfer MRI experiments. Although methods including numerical fitting with modified Bloch-McConnell equations, quantification of exchange rate with RF saturation time and power (QUEST and QUESP), have been proposed to address this relationship, they require multiple-parameter non-linear fitting and accurate relaxation measurement. Our work extended the QUEST algorithm with ratiometric analysis (QUESTRA) that normalizes the magnetization transfer ratio at labile and reference frequencies, which effectively eliminates the confounding relaxation and RF spillover effects. Specifically, the QUESTRA contrast approaches its steady state mono-exponentially at a rate determined by the reverse exchange rate (k(ws) ), with little dependence on bulk water T(1) , T(2) , RF power and chemical shift. The proposed algorithm was confirmed numerically, and validated experimentally using a tissue-like phantom of serially titrated pH compartments.

  18. Poly(alkylene biguanides) as proton conductors for high-temperature PEMFCs

    Energy Technology Data Exchange (ETDEWEB)

    Britz, Jochen; Meyer, Wolfgang H.; Wegner, Gerhard [Max Planck Institute for Polymer Research, Mainz (Germany)

    2010-02-23

    Poly(alkylene biguanides) are novel high-temperature proton conductors. This long-known class of polymers is presented as surprisingly stable high-temperature proton-conducting materials in the form of water-free HCl conjugates. Proton conductivity is dominated by free volume relaxation. Application in the context of fuel-cell membranes is discussed. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  19. Additivity of water sorption, alpha-relaxations and crystallization inhibition in lactose-maltodextrin systems.

    Science.gov (United States)

    Potes, Naritchaya; Kerry, Joseph P; Roos, Yrjö H

    2012-08-01

    Water sorption of lactose-maltodextrin (MD) systems, structural relaxations and lactose crystallization were studied. Accurate water sorption data for non-crystalline lactose previously not available over a wide range of water activity, aw (maltodextrin (MD) systems were strongly affected by water and MD. At high MD contents, inhibition of crystallization was significant. Inhibition with a high dextrose equivalent (DE) MD was more pronounced possibly because of molecular number and size effects. At 0.55-0.76aw, inhibition increased with increasing MD content. At aw>0.66, the rate of lactose crystallization decreased at increasing MD contents. Different MDs with similar Tg in lactose-MD systems showed different crystallization inhibition effects. The results of the present study showed that the DE in selection of MD for applications has important effects on component crystallization characteristics.

  20. MP4 study of the multimode coupling in protonated water dimer

    Science.gov (United States)

    Pitsevich, G.; Malevich, A.; Kozlovskaya, E.; Shalamberidze, E.; Doroshenko, I.; Pogorelov, V.; Mahnach, E.; Sapeshko, V.; Balevicius, V.

    2017-07-01

    The structure and frequencies of the protonated water dimer normal vibrations were calculated at the MP4/Aug-cc-pVTZ level of theory. Shared proton stretching vibrations were analyzed by constructing 4D potential energy surface using normal coordinates Q6 ,Q7 ,Q8 ,Q9 , which describe intermolecular vibration of water monomers, stretching and bending vibrations of the shared proton, respectively. 1-4 dimensional vibrational Schrödinger equations were solved using the discrete variable representation method. Values of some anharmonic constants, responsible for the triple and quadruple modes coupling with the shared proton stretching vibrations were obtained. The efficiency of the hybrid method in the determination of the frequency of shared proton stretching vibrations was demonstrated during the solution of the vibrational problem with nD reduced dimension for all used values of n (n = 1-4).

  1. Wide-ranging molecular mobilities of water in active pharmaceutical ingredient (API) hydrates as determined by NMR relaxation times.

    Science.gov (United States)

    Yoshioka, Sumie; Aso, Yukio; Osako, Tsutomu; Kawanishi, Toru

    2008-10-01

    In order to examine the possibility of determining the molecular mobility of hydration water in active pharmaceutical ingredient (API) hydrates by NMR relaxation measurement, spin-spin relaxation and spin-lattice relaxation were measured for the 11 API hydrates listed in the Japanese Pharmacopeia using pulsed (1)H-NMR. For hydration water that has relatively high mobility and shows Lorentzian decay, molecular mobility as determined by spin-spin relaxation time (T(2)) was correlated with ease of evaporation under both nonisothermal and isothermal conditions, as determined by DSC and water vapor sorption isotherm analysis, respectively. Thus, T(2) may be considered a useful parameter which indicates the molecular mobility of hydration water. In contrast, for hydration water that has low mobility and shows Gaussian decay, T(2) was found not to correlate with ease of evaporation under nonisothermal conditions, which suggests that in this case, the molecular mobility of hydration water was too low to be determined by T(2). A wide range of water mobilities was found among API hydrates, from low mobility that could not be evaluated by NMR relaxation time, such as that of the water molecules in pipemidic acid hydrate, to high mobility that could be evaluated by this method, such as that of the water molecules in ceftazidime hydrate. (c) 2008 Wiley-Liss, Inc. and the American Pharmacists Association

  2. In vivo field dependence of proton relaxation times in human brain, liver and skeletal muscle: a multicenter study

    DEFF Research Database (Denmark)

    Henriksen, O; de Certaines, J D; Spisni, A;

    1993-01-01

    T1 and T2 relaxation times are fundamental parameters for signal contrast behaviour in MRI. A number of ex vivo relaxometry studies have dealt with the magnetic field dispersion of T1. By means of multicenter study within the frame of the COMAC BME Concerted Action on Tissue Characterization by MRI...... and MRS, the in vivo field dispersion of T1 and T2 has been measured in order to evaluate whether ex vivo data are representative for the in vivo situation. Brain, skeletal muscle, and liver of healthy human volunteers were studied. Fifteen MR units with a field strength ranging from 0.08 T to 1.5 T took...... part in the trial, which comprised 218 volunteers. All the MR systems were tested for measurement accuracy using the Eurospin TO5 test object. The measured relaxation data were subsequently corrected according to the obtained calibration curves. The results showed a clear field dispersion of T1...

  3. Protic Salt Polymer Membranes: High-Temperature Water-Free Proton-Conducting Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Gervasio, Dominic Francis [Univ. of Arizona, Tucson, AZ (United States)

    2010-09-30

    This research on proton-containing (protic) salts directly addresses proton conduction at high and low temperatures. This research is unique, because no water is used for proton ionization nor conduction, so the properties of water do not limit proton fuel cells. A protic salt is all that is needed to give rise to ionized proton and to support proton mobility. A protic salt forms when proton transfers from an acid to a base. Protic salts were found to have proton conductivities that are as high as or higher than the best aqueous electrolytes at ambient pressures and comparable temperatures without or with water present. Proton conductivity of the protic salts occurs providing two conditions exist: i) the energy difference is about 0.8 eV between the protic-salt state versus the state in which the acid and base are separated and 2) the chemical constituents rotate freely. The physical state of these proton-conducting salts can be liquid, plastic crystal as well as solid organic and inorganic polymer membranes and their mixtures. Many acids and bases can be used to make a protic salt which allows tailoring of proton conductivity, as well as other properties that affect their use as electrolytes in fuel cells, such as, stability, adsorption on catalysts, environmental impact, etc. During this project, highly proton conducting (~ 0.1S/cm) protic salts were made that are stable under fuel-cell operating conditions and that gave highly efficient fuel cells. The high efficiency is attributed to an improved oxygen electroreduction process on Pt which was found to be virtually reversible in a number of liquid protic salts with low water activity (< 1% water). Solid flexible non-porous composite membranes, made from inorganic polymer (e.g., 10%indium 90%tin pyrophosphate, ITP) and organic polymer (e.g., polyvinyl pyridinium phosphate, PVPP), were found that give conductivity and fuel cell performances similar to phosphoric acid electrolyte with no need for hydration at

  4. Hysteresis effect of ammonium and water protons by 1H MAS NMR in (NH4)2CuBr4·2H2O

    Science.gov (United States)

    Lim, Ae Ran; Cho, Jiung

    2017-10-01

    The chemical shifts, linewidths, and spin-lattice relaxation times for ammonium and water protons in (NH4)2CuBr4·2H2O were investigated by 1H magic angle spinning nuclear magnetic resonance (MAS NMR) with a focus on the roles of NH4+ and H2O at high temperatures. The changes in the temperature dependence of the data near Td (=360 K) were related to variations of the H environments; the mechanism above Td was related to hydrogen-bond transfer involving breakage of the weak part of the hydrogen bond. The hysteresis effects for the ammonium and water protons in (NH4)2CuBr4·2H2O by MAS NMR were described with respect to heating and cooling.

  5. Multiple breath-hold proton spectroscopy of human liver at 3T: Relaxation times and concentrations of glycogen, choline, and lipids.

    Science.gov (United States)

    Weis, Jan; Kullberg, Joel; Ahlström, Håkan

    2017-04-17

    To evaluate the feasibility of an expiration multiple breath-hold (1) H-MRS technique to measure glycogen (Glycg), choline-containing compounds (CCC), and lipid relaxation times T1 , T2 , and their concentrations in normal human liver. Thirty healthy volunteers were recruited. Experiments were performed at 3T. Multiple expiration breath-hold single-voxel point-resolved spectroscopy (PRESS) technique was used for localization. Water-suppressed spectra were used for the estimation of Glycg, CCC, lipid methylene (CH2 )n relaxation times and concentrations. Residual water lines were removed by the Hankel Lanczos singular value decomposition filter. After phase correction and frequency alignment, spectra were averaged and processed by LCModel. Summed signals of Glycg resonances H2H4', H3, and H5 between 3.6 and 4 ppm were used to estimate their apparent relaxation times and concentration. Glycg, CCC, and lipid content were estimated from relaxation corrected spectral intensity ratios to unsuppressed water line. Relaxation times were measured for liver Glycg (T1 , 892 ± 126 msec; T2 , 13 ± 4 msec), CCC (T1 , 842 ± 75 msec; T2 , 50 ± 5 msec), lipid (CH2 )n (T1 , 402 ± 19 msec; T2 , 52 ± 3 msec), and water (T1 , 990 ± 89 msec; T2 , 30 ± 2 msec). Mean CCC and lipid concentrations of healthy liver were 7.8 ± 1.3 mM and 15.8 ± 23.6 mM, respectively. Glycg content was found lower in the morning (48 ± 21 mM) compared to the afternoon (145 ± 50 mM). Multiple breath-hold (1) H-MRS together with dedicated postprocessing is a feasible technique for the quantification of liver Glycg, CCC, and lipid relaxation times and concentrations. 1 J. Magn. Reson. Imaging 2017. © 2017 International Society for Magnetic Resonance in Medicine.

  6. Solvent-Induced Proton Hopping at a Water-Oxide Interface.

    Science.gov (United States)

    Tocci, Gabriele; Michaelides, Angelos

    2014-02-01

    Despite widespread interest, a detailed understanding of the dynamics of proton transfer at interfaces is lacking. Here, we use ab initio molecular dynamics to unravel the connection between interfacial water structure and proton transfer for the widely studied and experimentally well-characterized water-ZnO(101̅0) interface. We find that upon going from a single layer of adsorbed water to a liquid multilayer, changes in the structure are accompanied by a dramatic increase in the proton-transfer rate at the surface. We show how hydrogen bonding and rather specific hydrogen-bond fluctuations at the interface are responsible for the change in the structure and proton-transfer dynamics. The implications of this for the chemical reactivity and for the modeling of complex wet oxide interfaces in general are also discussed.

  7. Structural relaxation in the hydrogen-bonding liquids N-methylacetamide and water studied by optical Kerr-effect spectroscopy

    CERN Document Server

    Turton, David A; 10.1063/1.2897432

    2009-01-01

    Structural relaxation in the peptide model N-methylacetamide (NMA) is studied experimentally by ultrafast optical Kerr-effect spectroscopy over the normal-liquid temperature range and compared to the relaxation measured in water at room temperature. It is seen that in both hydrogen-bonding liquids, beta relaxation is present and in each case it is found that this can be described by the Cole-Cole function. For NMA in this temperature range, the alpha and beta relaxations are each found to have an Arrhenius temperature dependence with indistinguishable activation energies. It is known that the variations on the Debye function, including the Cole-Cole function, are unphysical, and we introduce two general modifications: one allows for the initial rise of the function, determined by the librational frequencies, and the second allows the function to be terminated in the alpha relaxation.

  8. Structural relaxation in the hydrogen-bonding liquids N-methylacetamide and water studied by optical Kerr effect spectroscopy.

    Science.gov (United States)

    Turton, David A; Wynne, Klaas

    2008-04-21

    Structural relaxation in the peptide model N-methylacetamide (NMA) is studied experimentally by ultrafast optical Kerr effect spectroscopy over the normal-liquid temperature range and compared to the relaxation measured in water at room temperature. It is seen that in both hydrogen-bonding liquids, beta relaxation is present, and in each case, it is found that this can be described by the Cole-Cole function. For NMA in this temperature range, the alpha and beta relaxations are each found to have an Arrhenius temperature dependence with indistinguishable activation energies. It is known that the variations on the Debye function, including the Cole-Cole function, are unphysical, and we introduce two general modifications: One allows for the initial rise of the function, determined by the librational frequencies, and the second allows the function to be terminated in the alpha relaxation.

  9. THE TISSUE HYDRATION STATE IN UW-PRESERVED HUMAN DONOR LIVERS - A CLINICAL-STUDY OF THE RELATION BETWEEN PROTON MAGNETIC-RESONANCE RELAXATION-TIMES, DONOR CONDITION, PRESERVATION PROCEDURE, AND EARLY GRAFT FUNCTION

    NARCIS (Netherlands)

    WOLF, RFE; DENBUTTER, G; KAMMAN, RL; DEKETH, HP; SLUTTER, WJ; SLOOFF, MJH

    1994-01-01

    To determine the relation between tissue hydration state-as indicated by tissue proton magnetic resonance relaxation times-in UW-preserved human donor livers and viability parameters of the donor and early graft function, ''ex vivo'' magnetic resonance relaxometry was performed with a clinical MR im

  10. THE TISSUE HYDRATION STATE IN UW-PRESERVED HUMAN DONOR LIVERS - A CLINICAL-STUDY OF THE RELATION BETWEEN PROTON MAGNETIC-RESONANCE RELAXATION-TIMES, DONOR CONDITION, PRESERVATION PROCEDURE, AND EARLY GRAFT FUNCTION

    NARCIS (Netherlands)

    WOLF, RFE; DENBUTTER, G; KAMMAN, RL; DEKETH, HP; SLUTTER, WJ; SLOOFF, MJH

    1994-01-01

    To determine the relation between tissue hydration state-as indicated by tissue proton magnetic resonance relaxation times-in UW-preserved human donor livers and viability parameters of the donor and early graft function, ''ex vivo'' magnetic resonance relaxometry was performed with a clinical MR

  11. Dual reorientation relaxation routes of water molecules in oxyanion’s hydration shell: A molecular geometry perspective

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin, E-mail: gaoyq@pku.edu.cn [Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering and Biodynamic Optical Imaging Center, Peking University, Beijing 100871 (China)

    2015-12-14

    In this study, we examine how complex ions such as oxyanions influence the dynamic properties of water and whether differences exist between simple halide anions and oxyanions. Nitrate anion is taken as an example to investigate the hydration properties of oxyanions. Reorientation relaxation of its hydration water can occur through two different routes: water can either break its hydrogen bond with the nitrate to form one with another water or switch between two oxygen atoms of the same nitrate. The latter molecular mechanism increases the residence time of oxyanion’s hydration water and thus nitrate anion slows down the translational motion of neighbouring water. But it is also a “structure breaker” in that it accelerates the reorientation relaxation of hydration water. Such a result illustrates that differences do exist between the hydration of oxyanions and simple halide anions as a result of different molecular geometries. Furthermore, the rotation of the nitrate solute is coupled with the hydrogen bond rearrangement of its hydration water. The nitrate anion can either tilt along the axis perpendicularly to the plane or rotate in the plane. We find that the two reorientation relaxation routes of the hydration water lead to different relaxation dynamics in each of the two above movements of the nitrate solute. The current study suggests that molecular geometry could play an important role in solute hydration and dynamics.

  12. Correlation between vestibular sensitization and leg muscle relaxation under weightlessness simulated by water immersion.

    Science.gov (United States)

    Mitarai, G; Mano, T; Yamazaki, Y

    1981-01-01

    The experiments were designed to determine the contribution of the leg muscle relaxation to the sensitization of the vestibular function under weightlessness, The neuromuscular unit (NMU) discharges were continuously recorded with microelectrodes from the anti-gravitational soleus muscle and its antagonist, the tibialis anterior, of a man standing first upright on the level floor of a dry water tank, and then gradually being immersed in water till it reached his neck; while he was buoyed with an airtube placed under his armpit. In each of the successive states, the caloric nystagmus was evoked, analyzed and compared with the NMU discharge as well as with subjective symptoms associated with the nystagmus. The results indicate that the nystagmogenic activity had a significant correlation with the appearance of the active NMU in the soleus, and they also suggest that the reduction of ascending signals from the antigravity muscles might be one of the causes of atypical vestibular responses occuring in weightlessness.

  13. Proton momentum distributions in water: A path integral molecular dynamics study

    Science.gov (United States)

    Srinivasan, Varadharajan; Morrone, Joseph A.; Sebastiani, Daniel; Car, Roberto

    2007-03-01

    Recent neutron Compton scattering experiments have detected the proton momentum distributions of water. This density in momentum space is a quantum mechanical property of the proton, due to the confining anharmonic potential from covalent and hydrogen bonds. The theoretical calculation of this property can be carried out via ``open'' path integral expressions. In this work, we present an extension of the staging path integral molecular dynamics method, which is then employed to calculate the proton momentum distributions of water in the solid, liquid, and supercritical phases. We utilize the SPC/F2 empirical force field to model the system's interactions. The calculated momentum distributions depict both agreement and discrepancies with experiment. The differences may be explained by the deviation of the force field from the true interactions. These distributions provide an abundance of information about the environment and interactions surrounding the proton.

  14. Classical and quantum theories of proton disorder in hexagonal water ice

    OpenAIRE

    Benton, Owen; Sikora, Olga; Shannon, Nic

    2015-01-01

    It has been known since the pioneering work of Bernal, Fowler and Pauling that common, hexagonal (Ih) water ice is the archetype of a frustrated material : a proton-bonded network in which protons satisfy strong local constraints - the "ice rules" - but do not order. While this proton disorder is well established, there is now a growing body of evidence that quantum effects may also have a role to play in the physics of ice at low temperatures. In this Article we use a combination of numerica...

  15. Proton energy determinations in water and in tissue-like material

    Energy Technology Data Exchange (ETDEWEB)

    Laitano, R.F. [Ist. Nazionale di Metrologia delle Radiazioni Ionizzanti, ENEA, Roma (Italy); Rosetti, M. [Div. di Fisica Applicata, ENEA, Bologna (Italy)

    1997-09-01

    The mean energy of proton beams in water and in a tissue substitute, respectively, were determined as a function of SOBP width, beam size and initial energy spread. Then an analytical expression to obtain the proton mean energy as a function of phantom depth and initial energy was established. This expression differs from the analogous ones reported in some current dosimetry protocols in that it accounts for the nuclear interaction effects in determining the mean energy. The preliminary results of the calculations referred to above are reported together with some comments on the specification of the proton beam quality for clinical dosimetry. (orig.)

  16. Fast mapping of the T2 relaxation time of cerebral metabolites using proton echo-planar spectroscopic imaging (PEPSI).

    Science.gov (United States)

    Tsai, Shang-Yueh; Posse, Stefan; Lin, Yi-Ru; Ko, Cheng-Wen; Otazo, Ricardo; Chung, Hsiao-Wen; Lin, Fa-Hsuan

    2007-05-01

    Metabolite T2 is necessary for accurate quantification of the absolute concentration of metabolites using long-echo-time (TE) acquisition schemes. However, lengthy data acquisition times pose a major challenge to mapping metabolite T2. In this study we used proton echo-planar spectroscopic imaging (PEPSI) at 3T to obtain fast T2 maps of three major cerebral metabolites: N-acetyl-aspartate (NAA), creatine (Cre), and choline (Cho). We showed that PEPSI spectra matched T2 values obtained using single-voxel spectroscopy (SVS). Data acquisition for 2D metabolite maps with a voxel volume of 0.95 ml (32 x 32 image matrix) can be completed in 25 min using five TEs and eight averages. A sufficient spectral signal-to-noise ratio (SNR) for T2 estimation was validated by high Pearson's correlation coefficients between logarithmic MR signals and TEs (R2 = 0.98, 0.97, and 0.95 for NAA, Cre, and Cho, respectively). In agreement with previous studies, we found that the T2 values of NAA, but not Cre and Cho, were significantly different between gray matter (GM) and white matter (WM; P PEPSI and SVS scans was less than 9%. Consistent spatial distributions of T2 were found in six healthy subjects, and disagreement among subjects was less than 10%. In summary, the PEPSI technique is a robust method to obtain fast mapping of metabolite T2.

  17. Changes in Porcine Muscle Water Characteristics during Growth—An in Vitro Low-Field NMR Relaxation Study

    Science.gov (United States)

    Bertram, Hanne Christine; Rasmussen, Marianne; Busk, Hans; Oksbjerg, Niels; Karlsson, Anders Hans; Andersen, Henrik Jørgen

    2002-08-01

    This study investigates the effects of developmental stage and muscle type on the mobility and distribution of water within skeletal muscles, using low-field 1H-NMR transverse relaxation measurements in vitro on four different porcine muscles ( M. longissimus dorsi, M. semitendinosus, M. biceps femoris, M. vastus intermedius) from a total of 48 pigs slaughtered at various weight classes between 25 kg and 150 kg. Principal component analysis (PCA) revealed effects of both slaughter weight and muscle type on the transverse relaxation decay. Independent of developmental stage and muscle type, distributed exponential analysis of the NMR T 2 relaxation data imparted the existence of three distinct water populations, T 2b, T 21, and T 22, with relaxation times of approximately 1-10, 45-120, and 200-500 ms, respectively. The most profound change during muscle growth was a shift toward faster relaxation in the intermediate time constant, T 21. It decreased by approx. 24% in all four muscle types during the period from 25 to 150 kg live weight. Determination of dry matter, fat, and protein content in the muscles showed that the changes in relaxation time of the intermediate time constant, T 21, during growth should be ascribed mainly to a change in protein content, as the protein content explained 77% of the variation in the T 21 time constant. Partial least squares (PLS) regression revealed validated correlations in the region of 0.58 to 0.77 between NMR transverse relaxation data and muscle development for all the four muscle types, which indicates that NMR relaxation measurements may be used in the prediction of muscle developmental stage.

  18. Water proton configurations in structures I, II, and H clathrate hydrate unit cells.

    Science.gov (United States)

    Takeuchi, Fumihito; Hiratsuka, Masaki; Ohmura, Ryo; Alavi, Saman; Sum, Amadeu K; Yasuoka, Kenji

    2013-03-28

    Position and orientation of water protons need to be specified when the molecular simulation studies are performed for clathrate hydrates. Positions of oxygen atoms in water are experimentally determined by X-ray diffraction analysis of clathrate hydrate structures, but positions of water hydrogen atoms in the lattice are disordered. This study reports a determination of the water proton coordinates in unit cell of structure I (sI), II (sII), and H (sH) clathrate hydrates that satisfy the ice rules, have the lowest potential energy configuration for the protons, and give a net zero dipole moment. Possible proton coordinates in the unit cell were chosen by analyzing the symmetry of protons on the hexagonal or pentagonal faces in the hydrate cages and generating all possible proton distributions which satisfy the ice rules. We found that in the sI and sII unit cells, proton distributions with small net dipole moments have fairly narrow potential energy spreads of about 1 kJ∕mol. The total Coulomb potential on a test unit charge placed in the cage center for the minimum energy∕minimum dipole unit cell configurations was calculated. In the sI small cages, the Coulomb potential energy spread in each class of cage is less than 0.1 kJ∕mol, while the potential energy spread increases to values up to 6 kJ∕mol in sH and 15 kJ∕mol in the sII cages. The guest environments inside the cages can therefore be substantially different in the sII case. Cartesian coordinates for oxygen and hydrogen atoms in the sI, sII, and sH unit cells are reported for reference.

  19. A Monte Carlo calculation of subexcitation and vibrationally-relaxing electron spectra in irradiated liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Cobut, V.; Frongillo, Y.; Jay-Gerin, J.-P. (Sherbrooke Univ., PQ (Canada). Faculte de Medecine); Patau, J.-P. (Toulouse-3 Univ., 31 (France))

    1992-12-01

    An energy spectrum of ''subexcitation electrons'' produced in liquid water by electrons with initial energies of a few keV is obtained by using a Monte Carlo transport simulation calculation. It is found that the introduction of vibrational-excitation cross sections leads to the appearance of a sharp peak in the probability density function near the electronic-excitation threshold. Electrons contributing to this peak are shown to be more naturally described if a novel energy spectrum, that we propose to name ''vibrationally-relaxing electron'' spectrum, is introduced. The corresponding distribution function is presented, and an empirical expression of it is given. (author).

  20. Electronic stopping power calculation for water under the Lindhard formalism for application in proton computed tomography

    Science.gov (United States)

    Guerrero, A. F.; Mesa, J.

    2016-07-01

    Because of the behavior that charged particles have when they interact with biological material, proton therapy is shaping the future of radiation therapy in cancer treatment. The planning of radiation therapy is made up of several stages. The first one is the diagnostic image, in which you have an idea of the density, size and type of tumor being treated; to understand this it is important to know how the particles beam interacts with the tissue. In this work, by using de Lindhard formalism and the Y.R. Waghmare model for the charge distribution of the proton, the electronic stopping power (SP) for a proton beam interacting with a liquid water target in the range of proton energies 101 eV - 1010 eV taking into account all the charge states is calculated.

  1. Correlated dynamics of the motion of proton-hole wave packets in a photoionized water cluster.

    Science.gov (United States)

    Li, Zheng; Madjet, Mohamed El-Amine; Vendrell, Oriol; Santra, Robin

    2013-01-18

    We explore the correlated dynamics of an electron hole and a proton after ionization of a protonated water cluster by extreme ultraviolet light. An ultrafast decay mechanism is found in which the proton-hole dynamics after the ionization are driven by electrostatic repulsion and involve a strong coupling between the nuclear and electronic degrees of freedom. We describe the system by a quantum-dynamical approach and show that nonadiabatic effects are a key element of the mechanism by which electron and proton repel each other and become localized at opposite sides of the cluster. Based on the generality of the decay mechanism, similar effects may be expected for other ionized systems featuring hydrogen bonds.

  2. Hydration and translocation of an excess proton in water clusters: An ab initio molecular dynamics study

    Indian Academy of Sciences (India)

    Arindam Bankura; Amalendu Chandra

    2005-10-01

    The hydration structure and translocation of an excess proton in hydrogen bonded water clusters of two different sizes are investigated by means of finite temperature quantum simulations. The simulations are performed by employing the method of Car–Parrinello molecular dynamics where the forces on the nuclei are obtained directly from `on the fly' quantum electronic structure calculations. Since no predefined interaction potentials are used in this scheme, it is ideally suited to study proton translocation processes which proceed through breaking and formation of chemical bonds. The coordination number of the hydrated proton and the index of oxygen to which the excess proton is attached are calculated along the simulation trajectories for both the clusters.

  3. Dynamics of Proton Transfer to Internal Water during the Photosynthetic Oxygen-Evolving Cycle.

    Science.gov (United States)

    Brahmachari, Udita; Barry, Bridgette A

    2016-11-10

    In photosynthesis, the light-driven oxidation of water is a sustainable process, which converts solar to chemical energy and produces protons and oxygen. To enable biomimetic strategies, the mechanism of photosynthetic oxygen evolution must be elucidated. Here, we provide information concerning a critical step in the oxygen-evolving, or S-state, cycle. During this S3-to-S0 transition, oxygen is produced, and substrate water binds to the manganese-calcium catalytic site. Our spectroscopic and H2(18)O labeling experiments show that this S3-to-S0 step is associated with the protonation of an internal water cluster in a hydrogen-bonding network, which contains calcium. When compared to the protonated water cluster, formed during a preceding step, the S1-to-S2 transition, the S3-to-S0 hydronium ion is likely to be coordinated by additional water molecules. This evidence shows that internal water and the hydrogen bonding network act as a transient proton acceptor at multiple points in the oxygen-evolving cycle.

  4. Simultaneous measurement of total water content and myelin water fraction in brain at 3T using a T2 relaxation based method.

    Science.gov (United States)

    Meyers, Sandra M; Kolind, Shannon H; MacKay, Alex L

    2017-04-01

    This work demonstrates the in vivo application of a T2 relaxation based total water content (TWC) measurement technique at 3T in healthy human brain, and evaluates accuracy using simulations that model brain tissue. The benefit of using T2 relaxation is that it provides simultaneous measurements of myelin water fraction, which correlates to myelin content. T2 relaxation data was collected from 10 healthy human subjects with a gradient and spin echo (GRASE) sequence, along with inversion recovery for T1 mapping. Voxel-wise T2 distributions were calculated by fitting the T2 relaxation data with a non-negative least squares algorithm incorporating B1(+) inhomogeneity corrections. TWC was the sum of the signals in the T2 distribution, corrected for T1 relaxation and receiver coil inhomogeneity, relative to either an external water standard or cerebrospinal fluid (CSF). Simulations were performed to determine theoretical errors in TWC. TWC values measured in healthy human brain relative to both external and CSF standards agreed with literature values. Simulations demonstrated that TWC could be measured to within 3-4% accuracy. In vivo TWC measurement using T2 relaxation at 3T works well and provides a valuable tool for studying neurological diseases with both myelin and water changes. Copyright © 2016 Elsevier Inc. All rights reserved.

  5. First-Principles Investigation of Electronic Excitation Dynamics in Water under Proton Irradiation

    Science.gov (United States)

    Reeves, Kyle; Kanai, Yosuke

    2015-03-01

    A predictive and quantitative understanding of electronic excitation dynamics in water under proton irradiation is of great importance in many technological areas ranging from utilizing proton beam therapy to preventing nuclear reactor damages. Despite its importance, an atomistic description of the excitation mechanism has yet to be fully understood. Identifying how a high-energy proton dissipates its kinetic energy into the electronic excitation is crucial for predicting atomistic damages, later resulting in the formation of different chemical species. In this work, we use our new, large-scale first-principles Ehrenfest dynamics method based on real-time time-dependent density functional theory to simulate the electronic response of bulk water to a fast-moving proton. In particular, we will discuss the topological nature of the electronic excitation as a function of the proton velocity. We will employ maximally-localized functions to bridge our quantitative findings from first-principles simulations to a conceptual understanding in the field of water radiolysis.

  6. Proton momentum distribution in water: an open path integral molecular dynamics study

    Science.gov (United States)

    Morrone, Joseph A.; Srinivasan, Varadharajan; Sebastiani, Daniel; Car, Roberto

    2007-06-01

    Recent neutron Compton scattering experiments have detected the proton momentum distribution in water. The theoretical calculation of this property can be carried out via "open" path integral expressions. In this work, present an extension of the staging path integral molecular dynamics method, which is then employed to calculate the proton momentum distributions of water in the solid, liquid, and supercritical phases. We utilize a flexible, single point charge empirical force field to model the system's interactions. The calculated momentum distributions depict both agreement and discrepancies with experiment. The differences may be explained by the deviation of the force field from the true interactions. These distributions provide an abundance of information about the environment and interactions surrounding the proton.

  7. Water adsorption and proton conduction in metal-organic frameworks: Insights from molecular simulations

    Science.gov (United States)

    Paesani, Francesco

    2014-03-01

    Metal-organic frameworks (MOFs) are a relatively new class of porous materials that hold great potential for a wide range of applications in chemistry, materials science, and nanoengineering. Compared to other porous materials such as zeolites, MOF properties are highly tunable. In particular, it has been shown that both size and shape of the MOF pores can be rationally designed for specific applications. For example, the ability to modify the framework properties with respect to hydrophilicity/hydrophobicity and acidity/basicity can enable the direct control of proton conduction through carrier molecules adsorbed inside the pores. Here, I report on our current efforts aimed at providing a molecular-level characterization of water-mediated proton conduction through the MOF pores. Particular emphasis will be put on correlation between proton conduction and both structural and chemical properties of the frameworks as well as on the dynamical behavior of water confined in the MOF pores. NSF award number: DMR-130510

  8. Toward a predictive understanding of water and charge transport in proton exchange membranes.

    Science.gov (United States)

    Selvan, Myvizhi Esai; Calvo-Muñoz, Elisa; Keffer, David J

    2011-03-31

    An analytical model for water and charge transport in highly acidic and highly confined systems such as proton exchange membranes of fuel cells is developed and compared to available experimental data. The model is based on observations from both experiment and multiscale simulation. The model accounts for three factors in the system including acidity, confinement, and connectivity. This model has its basis in the molecular-level mechanisms of water transport but has been coarse-grained to the extent that it can be expressed in an analytical form. The model uses the concentration of H(3)O(+) ion to characterize acidity, interfacial surface area per water molecule to characterize confinement, and percolation theory to describe connectivity. Several important results are presented. First, an integrated multiscale simulation approach including both molecular dynamics simulation and confined random walk theory is capable of quantitatively reproducing experimentally measured self-diffusivities of water in the perfluorinated sulfonic acid proton exchange membrane material, Nafion. The simulations, across a range of hydration conditions from minimally hydrated to fully saturated, have an average error for the self-diffusivity of water of 16% relative to experiment. Second, accounting for three factors-acidity, confinement, and connectivity-is necessary and sufficient to understand the self-diffusivity of water in proton exchange membranes. Third, an analytical model based on percolation theory is capable of quantitatively reproducing experimentally measured self-diffusivities of both water and charge in Nafion across a full range of hydration.

  9. The Mg2+-containing Water Cluster of Mammalian Cytochrome c Oxidase Collects Four Pumping Proton Equivalents in Each Catalytic Cycle.

    Science.gov (United States)

    Yano, Naomine; Muramoto, Kazumasa; Shimada, Atsuhiro; Takemura, Shuhei; Baba, Junpei; Fujisawa, Hidenori; Mochizuki, Masao; Shinzawa-Itoh, Kyoko; Yamashita, Eiki; Tsukihara, Tomitake; Yoshikawa, Shinya

    2016-11-11

    Bovine heart cytochrome c oxidase (CcO) pumps four proton equivalents per catalytic cycle through the H-pathway, a proton-conducting pathway, which includes a hydrogen bond network and a water channel operating in tandem. Protons are transferred by H3O(+) through the water channel from the N-side into the hydrogen bond network, where they are pumped to the P-side by electrostatic repulsion between protons and net positive charges created at heme a as a result of electron donation to O2 bound to heme a3 To block backward proton movement, the water channel remains closed after O2 binding until the sequential four-proton pumping process is complete. Thus, the hydrogen bond network must collect four proton equivalents before O2 binding. However, a region with the capacity to accept four proton equivalents was not discernable in the x-ray structures of the hydrogen bond network. The present x-ray structures of oxidized/reduced bovine CcO are improved from 1.8/1.9 to 1.5/1.6 Å resolution, increasing the structural information by 1.7/1.6 times and revealing that a large water cluster, which includes a Mg(2+) ion, is linked to the H-pathway. The cluster contains enough proton acceptor groups to retain four proton equivalents. The redox-coupled x-ray structural changes in Glu(198), which bridges the Mg(2+) and CuA (the initial electron acceptor from cytochrome c) sites, suggest that the CuA-Glu(198)-Mg(2+) system drives redox-coupled transfer of protons pooled in the water cluster to the H-pathway. Thus, these x-ray structures indicate that the Mg(2+)-containing water cluster is the crucial structural element providing the effective proton pumping in bovine CcO.

  10. Water exit pathways and proton pumping mechanism in B-type cytochrome c oxidase from molecular dynamics simulations.

    Science.gov (United States)

    Yang, Longhua; Skjevik, Åge A; Han Du, Wen-Ge; Noodleman, Louis; Walker, Ross C; Götz, Andreas W

    2016-09-01

    Cytochrome c oxidase (CcO) is a vital enzyme that catalyzes the reduction of molecular oxygen to water and pumps protons across mitochondrial and bacterial membranes. While proton uptake channels as well as water exit channels have been identified for A-type CcOs, the means by which water and protons exit B-type CcOs remain unclear. In this work, we investigate potential mechanisms for proton transport above the dinuclear center (DNC) in ba3-type CcO of Thermus thermophilus. Using long-time scale, all-atom molecular dynamics (MD) simulations for several relevant protonation states, we identify a potential mechanism for proton transport that involves propionate A of the active site heme a3 and residues Asp372, His376 and Glu126(II), with residue His376 acting as the proton-loading site. The proposed proton transport process involves a rotation of residue His376 and is in line with experimental findings. We also demonstrate how the strength of the salt bridge between residues Arg225 and Asp287 depends on the protonation state and that this salt bridge is unlikely to act as a simple electrostatic gate that prevents proton backflow. We identify two water exit pathways that connect the water pool above the DNC to the outer P-side of the membrane, which can potentially also act as proton exit transport pathways. Importantly, these water exit pathways can be blocked by narrowing the entrance channel between residues Gln151(II) and Arg449/Arg450 or by obstructing the entrance through a conformational change of residue Tyr136, respectively, both of which seem to be affected by protonation of residue His376.

  11. Water uptake by growing cells: an assessment of the controlling roles of wall relaxation, solute uptake, and hydraulic conductance

    Science.gov (United States)

    Cosgrove, D. J.

    1993-01-01

    Growing plant cells increase in volume principally by water uptake into the vacuole. There are only three general mechanisms by which a cell can modulate the process of water uptake: (a) by relaxing wall stress to reduce cell turgor pressure (thereby reducing cell water potential), (b) by modifying the solute content of the cell or its surroundings (likewise affecting water potential), and (c) by changing the hydraulic conductance of the water uptake pathway (this works only for cells remote from water potential equilibrium). Recent studies supporting each of these potential mechanisms are reviewed and critically assessed. The importance of solute uptake and hydraulic conductance is advocated by some recent studies, but the evidence is indirect and conclusions remain controversial. For most growing plant cells with substantial turgor pressure, it appears that reduction in cell turgor pressure, as a consequence of wall relaxation, serves as the major initiator and control point for plant cell enlargement. Two views of wall relaxation as a viscoelastic or a chemorheological process are compared and distinguished.

  12. NMR Water Self-Diffusion and Relaxation Studies on Sodium Polyacrylate Solutions and Gels in Physiologic Ionic Solutions.

    Science.gov (United States)

    Bai, Ruiliang; Basser, Peter J; Briber, Robert M; Horkay, Ferenc

    2014-03-15

    Water self-diffusion coefficients and longitudinal relaxation rates in sodium polyacrylate solutions and gels were measured by NMR, as a function of polymer content and structure in a physiological concentration range of monovalent and divalent cations, Ca(2+) and Na(+). Several physical models describing the self-diffusion of the solvent were applied and compared. A free-volume model was found to be in good agreement with the experimental results over a wide range of polymer concentrations. The longitudinal relaxation rate exhibited linear dependence on polymer concentration below a critical concentration and showed non-linear behavior at higher concentrations. Both the water self-diffusion and relaxation were less influenced by the polymer in the gel state than in the uncrosslinked polymer solutions. The effect of Na(+) on the mobility of water molecules was practically undetectable. By contrast, addition of Ca(2+) strongly increased the longitudinal relaxation rate while its effect on the self-diffusion coefficient was much less pronounced.

  13. Fast Removal of Residual Water in Proton Spectra.

    Science.gov (United States)

    Vanhamme; Fierro; Van Huffel S; de Beer R

    1998-06-01

    Quantification of metabolites in 1H spectra is difficult because of the presence of an unwanted water signal. Preprocessing, or removing the water contribution of a 1H spectrum, in the time domain is usually done using the state-space approach HSVD. HSVD removes the residual water and its side lobes, thereby reducing the baseline for the metabolites of interest and allowing subsequent data analysis using more sophisticated nonlinear least squares algorithms. However, the HSVD algorithm is computationally expensive because it estimates the signal subspace using the singular value decomposition (SVD). We show here that replacing the SVD by a low-rank revealing decomposition speeds up the computations without affecting the accuracy of the wanted parameter estimates. Copyright 1998 Academic Press.

  14. Comparison of the secondary electrons produced by proton and electron beams in water

    Energy Technology Data Exchange (ETDEWEB)

    Kia, Mohammad Reza, E-mail: m-r-kia@aut.ac.ir; Noshad, Houshyar [Department of Energy Engineering and Physics, Amirkabir University of Technology (Tehran Polytechnic), P.O. Box 15875-4413, Hafez Avenue, Tehran (Iran, Islamic Republic of)

    2016-05-15

    The secondary electrons produced in water by electron and proton beams are compared with each other. The total ionization cross section (TICS) for an electron impact in water is obtained by using the binary-encounter-Bethe model. Hence, an empirical equation based on two adjustable fitting parameters is presented to determine the TICS for proton impact in media. In order to calculate the projectile trajectory, a set of stochastic differential equations based on the inelastic collision, elastic scattering, and bremsstrahlung emission are used. In accordance with the projectile trajectory, the depth dose deposition, electron energy loss distribution in a certain depth, and secondary electrons produced in water are calculated. The obtained results for the depth dose deposition and energy loss distribution in certain depth for electron and proton beams with various incident energies in media are in excellent agreement with the reported experimental data. The difference between the profiles for the depth dose deposition and production of secondary electrons for a proton beam can be ignored approximately. But, these profiles for an electron beam are completely different due to the effect of elastic scattering on electron trajectory.

  15. Comparison of the secondary electrons produced by proton and electron beams in water

    Science.gov (United States)

    Kia, Mohammad Reza; Noshad, Houshyar

    2016-05-01

    The secondary electrons produced in water by electron and proton beams are compared with each other. The total ionization cross section (TICS) for an electron impact in water is obtained by using the binary-encounter-Bethe model. Hence, an empirical equation based on two adjustable fitting parameters is presented to determine the TICS for proton impact in media. In order to calculate the projectile trajectory, a set of stochastic differential equations based on the inelastic collision, elastic scattering, and bremsstrahlung emission are used. In accordance with the projectile trajectory, the depth dose deposition, electron energy loss distribution in a certain depth, and secondary electrons produced in water are calculated. The obtained results for the depth dose deposition and energy loss distribution in certain depth for electron and proton beams with various incident energies in media are in excellent agreement with the reported experimental data. The difference between the profiles for the depth dose deposition and production of secondary electrons for a proton beam can be ignored approximately. But, these profiles for an electron beam are completely different due to the effect of elastic scattering on electron trajectory.

  16. Hybrid approaches to magnetic resonance thermometry using the proton resonance frequency shift and the spin-lattice relaxation time T1

    Science.gov (United States)

    Diakite, Mahamadou

    Minimally invasive thermal therapy under Magnetic Resonance Imaging (MRI) guidance is becoming popular with several applications in the process of getting FDA approval. The ability to determine in near real-time the temperature map of a tumor and its surrounding tissue makes MR thermometry very attractive and well suited for thermal treatment. The proton resonance frequency shift (PRF) is currently the gold standard method for temperature monitoring using MRI. However, its incapacity to measure temperature in fatty tissue limits the scope of its applicability. The spin lattice relaxation time T1, on the other hand, has shown good temperature sensitivity and works well in all types of tissues. In this dissertation, we have addressed a number of challenges currently affecting MRI thermometry. A non-CPMG Turbo Spin Echo (TSE) sequence has been implemented to monitor the temperature rise due to the high RF power deposition inherent to this sequence at high field (3T and higher). This new implementation allows TSE sequences to be used safely without altering their high contrast properties which make them appealing in clinical settings. Tissue damage assessment during thermal therapy is critical for the safety of the patient. We have developed a new hybrid PRF-T1 sequence that has the capability to provide simultaneously in near real-time the temperature map and T1 information, which is a good indication of the state of the tissue. The simplicity and the real-time capability of the newly developed sequence make it an ideal tool for tissue damage assessment. Temperature monitoring during thermal therapy in organs with large fat content have been hindered by the lack of an MRI thermometry method that can provide simultaneous temperature in fat and aqueous tissue. A new sequence and acquisition scheme have been developed to address this issue. In sum, this dissertation proposed several pulse sequence implementation techniques and an acquisition scheme to overcome some of

  17. Submillimeter ionoacoustic range determination for protons in water at a clinical synchrocyclotron

    Science.gov (United States)

    Lehrack, Sebastian; Assmann, Walter; Bertrand, Damien; Henrotin, Sebastien; Herault, Joel; Heymans, Vincent; Vander Stappen, Francois; Thirolf, Peter G.; Vidal, Marie; Van de Walle, Jarno; Parodi, Katia

    2017-09-01

    Proton ranges in water between 145 MeV to 227 MeV initial energy have been measured at a clinical superconducting synchrocyclotron using the acoustic signal induced by the ion dose deposition (ionoacoustic effect). Detection of ultrasound waves was performed by a very sensitive hydrophone and signals were stored in a digital oscilloscope triggered by secondary prompt gammas. The ionoacoustic range measurements were compared to existing range data from a calibrated range detector setup on-site and agreement of better than 1 mm was found at a Bragg peak dose of about 10 Gy for 220 MeV initial proton energy, compatible with the experimental errors. Ionoacoustics has thus the potential to measure the Bragg peak position with submillimeter accuracy during proton therapy, possibly correlated with ultrasound tissue imaging.

  18. Interfacial air/water proton conduction from long distances by sulfolobus solfataricus archaeal bolaform lipids.

    Science.gov (United States)

    Vilalta, I; Gliozzi, A; Prats, M

    1996-08-15

    The stability, structural organization, and the ability to transfer protons long distances have been investigated in monolayers formed from archael bolaform lipids at the air/water interface. The lipids employed were the fractions GroR2Gro (R represents an acyl group with variable chain length typically consisting of 0-4 cyclopentane rings and 40 isoprenoid residues) and GroR2GroNon-Ol (Non-ol represents nonitol) extracted from Sulfolobus solfataricus by hydrolysis of the cytoplasmic membrane. GroR2-GroNon-ol films exhibit a very peculiar behaviour: the monolayer surface pressure increases with time, regardless of its low or high initial value. This finding is related to the possibility of GroR2GroNon-ol molecules to assume an upright (a metastable) or a U-shaped (stable) configuration. In the gaseous state and in the collapsed state of the film, no lateral proton conduction was observed. However, in the pressure range 0 < pi < 25 mN/m for GroR2Gro and 0 < pi < 30 mN/m for GroR2GroNon-ol monolayers, a lateral proton conduction at the air/water interface was observed. The structural organization of these bipolar lipids at the air/water interface can be related to the lateral proton conduction; it is possible to conclude that whatever configuration these lipids may adopt, they are able to structure the air/water interface in a hydrogen bond network that supports lateral proton conduction. This process may be ascribed to a percolation phenomenon occurring when the polar lipid head groups form a structured lattice of hydrogen bonds.

  19. Bond breaking, electron pushing, and proton pulling: active and passive roles in the interaction between aqueous ions and water as manifested in the O 1s Auger decay.

    Science.gov (United States)

    Pokapanich, W; Ottosson, N; Svensson, S; Ohrwall, G; Winter, B; Björneholm, O

    2012-01-12

    A core-ionized H(2)O molecule in liquid water primarily relaxes through normal Auger decay, leading to a two-hole final state in which both valence holes are localized on the same water molecule. Electronic coupling to the environment, however, allows for alternative decays resembling Intermolecular Coulombic Decay (ICD), producing final states with one of the holes delocalized on a neighboring water molecule. Here we present an experimental study of such minority processes, which adds to our understanding of dynamic interactions of electronically excited H(2)O molecules with their local surrounding in liquid water and aqueous solution. We show that the solvation of metal-halide salts considerably influences these minority decay channels from the water O 1s(-1) state. By breaking water-water bonds, both the metal cations and halide anions are found to reduce the decay into water-water delocalized states, thus having a ″passive″ effect on the Auger spectrum. The halide anions also play an ″active″ role by opening a new ICD-like decay pathway into water-halide delocalized states. The importance of this contribution increases from F(-) to I(-), which we suggest to be caused by a directional polarization of the halide anion toward the core-ionized H(2)O(+) cation in the intermediate state of the Auger process. This increases the electronic overlap between the two centers and makes delocalized decays more probable. We furthermore show that F(-), the smallest and most strongly hydrated of the halides, plays an additional role as proton puller during the core-hole lifetime, resulting in proton dynamics on the low femtosecond time scale. Our results represent a step forward toward a better understanding of how aqueous solutions, when exposed to soft X-rays, channel excess energy. This has implications for several aspects of physical and radiation chemistry, as well as biology.

  20. Correlation of T1 and T2 relaxation rates in normal bone-marrow water with serum ferritin concentration

    Energy Technology Data Exchange (ETDEWEB)

    Ishizaka, H. [Tano General Hospital, Gunma (Japan). Dept. of Radiology]|[Gunma Univ. Hospital (Japan). Dept. of Diagnostic Radiology; Ishijima, H. [Gunma Univ. Hospital (Japan). Dept. of Diagnostic Radiology

    1997-11-01

    Purpose: This study was made to clarify the paramagnetic effect of iron stored in the hematopoietic tissue of bone marrow. Material and methods: The T1 and T2 relaxation times of bone-marrow water in the L1-3 vertebrae of 20 healthy individuals were measured by MR imaging with a 1.5 T magnet. The chemical shift misregistration effect was used to isolate the bone-marrow water. The results were compared with the serum ferritin concentration. Results and Conclusion: Although no correlation between the T1 relaxation rate of the water fraction and the serum ferritin concentration was evident, the T2 relaxation rate of the water fraction showed strong linear correlation with the serum ferritin concentration (r=0.87, p<0.001). Thus, T2 of bone-marrow water accurately reflects the amount of iron in normal bone marrow. This finding may be useful in the evaluation of the characteristics of hematopoietic tissue in bone marrow. (orig.).

  1. Spectroscopic characterization of changes of DOM deprotonation-protonation properties in water treatment processes.

    Science.gov (United States)

    Yan, Mingquan; Dryer, Deborah; Korshin, Gregory V

    2016-04-01

    The deprotonation-protonation properties of dissolved organic matter (DOM) in drinking water produced at critical treatment points were quantified using absorbance spectra in combination with DOM fractionation data. Analysis of differential spectra of DOM present in inlet, settled and filtered waters from two large treatment plants and their fractions were obtained. The data demonstrated the presence of six Gaussian bands largely associated with carboxylic and phenolic DOM functionalities. Properties of the protonation-active groups of DOM in raw and treated waters were further examined based on data of potentiometric titrations at pH from 2.5 to 10. Interpretation of the differential log-transformed absorbance at wavelength 350 nm (DlnA350) based on the NICA-Donnan model showed that the normalized concentrations of low- and high-affinity protonation-active groups in residual DOMs increases as a result of water treatment. This was consistent with the results of DOM fractionation. This study demonstrates that changes of the composition and reactivity of DOM found in drinking water treatment sequences can be quantified based on the examination of their optical properties.

  2. An optimized method for (15)N R(1) relaxation rate measurements in non-deuterated proteins.

    Science.gov (United States)

    Gairí, Margarida; Dyachenko, Andrey; González, M Teresa; Feliz, Miguel; Pons, Miquel; Giralt, Ernest

    2015-06-01

    (15)N longitudinal relaxation rates are extensively used for the characterization of protein dynamics; however, their accurate measurement is hindered by systematic errors. (15)N CSA/(1)H-(15)N dipolar cross-correlated relaxation (CC) and amide proton exchange saturation transfer from water protons are the two main sources of systematic errors in the determination of (15)N R1 rates through (1)H-(15)N HSQC-based experiments. CC is usually suppressed through a train of 180° proton pulses applied during the variable (15)N relaxation period (T), which can perturb water magnetization. Thus CC cancellation is required in such a way as to minimize water saturation effects. Here we examined the level of water saturation during the T period caused by various types of inversion proton pulses to suppress CC: (I) amide-selective IBURP-2; (II) cosine-modulated IBURP-2; (III) Watergate-like blocks; and (IV) non-selective hard. We additionally demonstrate the effect of uncontrolled saturation of aliphatic protons on (15)N R1 rates. In this paper we present an optimized pulse sequence that takes into account the crucial effect of controlling also the saturation of the aliphatic protons during (15)N R1 measurements in non-deuterated proteins. We show that using cosine-modulated IBURP-2 pulses spaced 40 ms to cancel CC in this optimized pulse program is the method of choice to minimize systematic errors coming from water and aliphatic protons saturation effects.

  3. A dose calculation algorithm with correction for proton-nucleus interactions in non-water materials for proton radiotherapy treatment planning

    Science.gov (United States)

    Inaniwa, T.; Kanematsu, N.; Sato, S.; Kohno, R.

    2016-01-01

    In treatment planning for proton radiotherapy, the dose measured in water is applied to the patient dose calculation with density scaling by stopping power ratio {ρ\\text{S}} . Since the body tissues are chemically different from water, this approximation may cause dose calculation errors, especially due to differences in nuclear interactions. We proposed and validated an algorithm for correcting these errors. The dose in water is decomposed into three constituents according to the physical interactions of protons in water: the dose from primary protons continuously slowing down by electromagnetic interactions, the dose from protons scattered by elastic and/or inelastic interactions, and the dose resulting from nonelastic interactions. The proportions of the three dose constituents differ between body tissues and water. We determine correction factors for the proportion of dose constituents with Monte Carlo simulations in various standard body tissues, and formulated them as functions of their {ρ\\text{S}} for patient dose calculation. The influence of nuclear interactions on dose was assessed by comparing the Monte Carlo simulated dose and the uncorrected dose in common phantom materials. The influence around the Bragg peak amounted to  -6% for polytetrafluoroethylene and 0.3% for polyethylene. The validity of the correction method was confirmed by comparing the simulated and corrected doses in the materials. The deviation was below 0.8% for all materials. The accuracy of the correction factors derived with Monte Carlo simulations was separately verified through irradiation experiments with a 235 MeV proton beam using common phantom materials. The corrected doses agreed with the measurements within 0.4% for all materials except graphite. The influence on tumor dose was assessed in a prostate case. The dose reduction in the tumor was below 0.5%. Our results verify that this algorithm is practical and accurate for proton radiotherapy treatment planning, and

  4. Encapsulation and characterization of proton-bound amine homodimers in a water-soluble, self-assembled supramolecular host

    OpenAIRE

    Pluth, Michael D.; Fiedler, Dorothea; Mugridge, Jeffrey S.; Bergman, Robert G.; Raymond, Kenneth N.

    2009-01-01

    Cyclic amines can be encapsulated in a water-soluble self-assembled supramolecular host upon protonation. The hydrogen-bonding ability of the cyclic amines, as well as the reduced degrees of rotational freedom, allows for the formation of proton-bound homodimers inside of the assembly that are otherwise not observable in aqueous solution. The generality of homodimer formation was explored with small N-alkyl aziridines, azetidines, pyrrolidines, and piperidines. Proton-bound homodimer formatio...

  5. Water management in proton exchange membrane fuel cells using integrated electroosmotic pumping

    Science.gov (United States)

    Buie, Cullen R.; Posner, Jonathan D.; Fabian, Tibor; Cha, Suk-Won; Kim, Daejoong; Prinz, Fritz B.; Eaton, John K.; Santiago, Juan G.

    Recent experimental and numerical investigations on proton exchange membrane fuel cells (PEMFCs) emphasize water management as a critical factor in the design of robust, high efficiency systems. Although various water management strategies have been proposed, water is still typically removed by pumping air into cathode channels at flow rates significantly higher than required by fuel cell stoichiometry. Such methods are thermodynamically unfavorable and constrain cathode flow channel design. We have developed proton exchange membrane fuel cells (PEMFCs) with integrated planar electroosmotic (EO) pumping structures that actively remove liquid water from cathode flow channels. EO pumps can relieve cathode design barriers and facilitate efficient water management in fuel cells. EO pumps have no moving parts, scale appropriately with fuel cells, operate across a wide range of conditions, and consume a small fraction of fuel cell power. We demonstrate and quantify the efficacy of EO water pumping using controlled experiments in a single channel cathode flow structure. Our results show that, under certain operating conditions, removing water from the cathode using integrated EO pumping structures improves fuel cell performance and stability. The application of EO pumps for liquid water removal from PEMFC cathodes extends their operational range and reduces air flow rates.

  6. Water management in proton exchange membrane fuel cells using integrated electroosmotic pumping

    Energy Technology Data Exchange (ETDEWEB)

    Buie, Cullen R.; Posner, Jonathan D.; Fabian, Tibor; Cha, Suk-Won; Kim, Daejoong; Prinz, Fritz B.; Eaton, John K.; Santiago, Juan G. [Department of Mechanical Engineering, Stanford University, Stanford, CA 94305 (United States)

    2006-10-20

    Recent experimental and numerical investigations on proton exchange membrane fuel cells (PEMFCs) emphasize water management as a critical factor in the design of robust, high efficiency systems. Although various water management strategies have been proposed, water is still typically removed by pumping air into cathode channels at flow rates significantly higher than required by fuel cell stoichiometry. Such methods are thermodynamically unfavorable and constrain cathode flow channel design. We have developed proton exchange membrane fuel cells (PEMFCs) with integrated planar electroosmotic (EO) pumping structures that actively remove liquid water from cathode flow channels. EO pumps can relieve cathode design barriers and facilitate efficient water management in fuel cells. EO pumps have no moving parts, scale appropriately with fuel cells, operate across a wide range of conditions, and consume a small fraction of fuel cell power. We demonstrate and quantify the efficacy of EO water pumping using controlled experiments in a single channel cathode flow structure. Our results show that, under certain operating conditions, removing water from the cathode using integrated EO pumping structures improves fuel cell performance and stability. The application of EO pumps for liquid water removal from PEMFC cathodes extends their operational range and reduces air flow rates. (author)

  7. Peroxyl Radical Reactions in Water Solution: A Gym for Proton-Coupled Electron-Transfer Theories.

    Science.gov (United States)

    Amorati, Riccardo; Baschieri, Andrea; Morroni, Gloria; Gambino, Rossana; Valgimigli, Luca

    2016-06-01

    The reactions of alkylperoxyl radicals with phenols have remained difficult to investigate in water. We describe herein a simple and reliable method based on the inhibited autoxidation of water/THF mixtures, which we calibrated against pulse radiolysis. With this method we measured the rate constants kinh for the reactions of 2-tetrahydrofuranylperoxyl radicals with reference compounds: urate, ascorbate, ferrocenes, 2,2,5,7,8-pentamethyl-6-chromanol, Trolox, 6-hydroxy-2,5,7,8-tetramethylchroman-2-acetic acid, 2,6-di-tert-butyl-4-methoxyphenol, 4-methoxyphenol, catechol and 3,5-di-tert-butylcatechol. The role of pH was investigated: the value of kinh for Trolox and 4-methoxyphenol increased 11- and 50-fold from pH 2.1 to 12, respectively, which indicate the occurrence of a SPLET-like mechanism. H(D) kinetic isotope effects combined with pH and solvent effects suggest that different types of proton-coupled electron transfer (PCET) mechanisms are involved in water: less electron-rich phenols react at low pH by concerted electron-proton transfer (EPT) to the peroxyl radical, whereas more electron-rich phenols and phenoxide anions react by multi-site EPT in which water acts as proton relay.

  8. Proton transfer pathways, energy landscape, and kinetics in creatine-water systems.

    Science.gov (United States)

    Ivchenko, Olga; Whittleston, Chris S; Carr, Joanne M; Imhof, Petra; Goerke, Steffen; Bachert, Peter; Wales, David J

    2014-02-27

    We study the exchange processes of the metabolite creatine, which is present in both tumorous and normal tissues and has NH2 and NH groups that can transfer protons to water. Creatine produces chemical exchange saturation transfer (CEST) contrast in magnetic resonance imaging (MRI). The proton transfer pathway from zwitterionic creatine to water is examined using a kinetic transition network constructed from the discrete path sampling approach and an approximate quantum-chemical energy function, employing the self-consistent-charge density-functional tight-binding (SCC-DFTB) method. The resulting potential energy surface is visualized by constructing disconnectivity graphs. The energy landscape consists of two distinct regions corresponding to the zwitterionic creatine structures and deprotonated creatine. The activation energy that characterizes the proton transfer from the creatine NH2 group to water was determined from an Arrhenius fit of rate constants as a function of temperature, obtained from harmonic transition state theory. The result is in reasonable agreement with values obtained in water exchange spectroscopy (WEX) experiments.

  9. Employing Hot Wire Anemometry to Directly Measure the Water Balance of a Proton Exchange Membrane Fuel Cell

    DEFF Research Database (Denmark)

    Shakhshir, Saher Al; Berning, Torsten

    Proton exchange membrane fuel cells (PEMFC’s) are currently being commercialized for various applications ranging from automotive to stationary such as powering telecom back-up units. In PEMFC’s, oxygen from air is internally combined with hydrogen to form water and produce electricity and waste...... heat. One critical technical problem of these fuel cells is still the water management: the proton exchange membrane in the center of these fuel cells has to be hydrated in order to stay proton-conductive while excessive liquid water can lead to cell flooding and increased degradation rates. Clearly...

  10. (1)H relaxivity of water in aqueous suspensions of Gd(3+)-loaded NaY nanozeolites and AlTUD-1 mesoporous material: the influence of Si/Al ratio and pore size.

    Science.gov (United States)

    Norek, Małgorzata; Neves, Isabel C; Peters, Joop A

    2007-07-23

    The results of a (1)H nuclear magnetic relaxation dispersion (NMRD) and EPR study on aqueous suspensions of Gd(3+)-loaded NaY nanozeolites and AlTUD-1 mesoporous material are described. Upon increase of the Si/Al ratio from 1.7 to 4.0 in the Gd(3+)-loaded zeolites, the relaxation rate per mM Gd(3+) (r1) at 40 MHz and 25 degrees C increases from 14 to 27 s(-)1 mM(-1). The NMRD and EPR data were fitted with a previously developed two-step model that considers the system as a concentrated aqueous solution of Gd(3+) in the interior of the zeolite that is in exchange with the bulk water outside the zeolite. The results show that the observed increase in relaxivity can mainly be attributed to the residence lifetime of the water protons in the interior of the material, which decreased from 0.3 to 0.2 micros, upon the increase of the Si/Al ratio. This can be explained by the decreased interaction of water with the zeolite walls as a result of the increased hydrophobicity. The importance of the exchange rate of water between the inside and the outside of the material was further demonstrated by the relatively high relaxivity (33 s(-1) mM(-1) at 40 MHz, 25 degrees C) observed for a suspension of the Gd(3+)-loaded mesoporous material AlTUD-1. Unfortunately, Gd(3+) leaches rather easily from that material, but not from the Gd(3+)-loaded NaY zeolites, which may have potential as contrast agents for magnetic resonance imaging.

  11. submitter A model for the accurate computation of the lateral scattering of protons in water

    CERN Document Server

    Bellinzona, EV; Embriaco, A; Ferrari, A; Fontana, A; Mairani, A; Parodi, K; Rotondi, A; Sala, P; Tessonnier, T

    2016-01-01

    A pencil beam model for the calculation of the lateral scattering in water of protons for any therapeutic energy and depth is presented. It is based on the full Molière theory, taking into account the energy loss and the effects of mixtures and compounds. Concerning the electromagnetic part, the model has no free parameters and is in very good agreement with the FLUKA Monte Carlo (MC) code. The effects of the nuclear interactions are parametrized with a two-parameter tail function, adjusted on MC data calculated with FLUKA. The model, after the convolution with the beam and the detector response, is in agreement with recent proton data in water from HIT. The model gives results with the same accuracy of the MC codes based on Molière theory, with a much shorter computing time.

  12. Protonation of water clusters in the cavities of acidic zeolites: (H2O)n.H-chabazite, n = 1-4.

    Science.gov (United States)

    Vener, Mikhail V; Rozanska, Xavier; Sauer, Joachim

    2009-03-21

    Proton forms of zeolite chabazite (H-SSZ-13) loaded with 1 to 4 water molecules per acid site are examined by density functional theory with periodic boundary conditions. Equilibrium structures are determined by localizing minima on the potential energy surface and harmonic vibrational frequencies are calculated. Average structures, proton dynamics and anharmonic spectra at finite temperature (350 K) are determined by molecular dynamics (MD). The protonation state is found to depend on the number of water molecules per acid site (loading) following the trend of increasing proton affinity with increasing cluster size. Single water molecules are not protonated, the protonated water dimer is the most stable equilibrium structure with the PBE functional, but not with BLYP. MD shows that even with PBE, the protonated water dimer is not stable at finite temperature. The protonated water trimer may be formed as a short-lived species, but the protonated water tetramer is the smallest stable protonated cluster. For the same global loading (2 : 1), a heterogeneous distribution of adsorbed water molecules over the cells is more stable than a homogeneous one (1 : 1/3 : 1 vs. 2 : 1/2 : 1 for a double cell), i.e. non-protonated and protonated water clusters may exist simultaneously in polyhydrated H-SSZ13. Adsorption energies (0 K) per water molecule decrease from 71 to 51 kJ mol(-1) for n = 1 to n = 4.

  13. Protein and water dynamics in bovine serum albumin-water mixtures over wide ranges of composition.

    Science.gov (United States)

    Panagopoulou, A; Kyritsis, A; Shinyashiki, N; Pissis, P

    2012-04-19

    Dielectric dynamic behavior of bovine serum albumin (BSA)-water mixtures over wide ranges of water fractions, from dry protein until 40 wt % in water, was studied through dielectric relaxation spectroscopy (DRS). The α relaxation associated with the glass transition of the hydrated system was identified. The evolution of the low temperature dielectric relaxation of small polar groups of the protein surface with hydration level results in the enhancement of dielectric response and the decrease of relaxation times, until a critical water fraction, which corresponds to the percolation threshold for protonic conductivity. For water fractions higher than the critical one, the position of the secondary ν relaxation of water saturates in the Arrhenius diagram, while contributions originating from water molecules in excess (uncrystallized water or ice) follow separate relaxation modes slower than the ν relaxation.

  14. Ab Initio Studies on the Preferred Site of Protonation in Cytisine in the Gas Phase and Water

    Directory of Open Access Journals (Sweden)

    Małgorzata Darowska

    2005-01-01

    Full Text Available Abstract: Ab initio calculations (HF, MP2, DFT for isolated and PCM for solvated molecules were performed for cytisine (1 and its model compounds: N-methyl-2-pyridone (2 and piperidine (3. Among three heteroatomic functions (carbonyl oxygen, pyridone and piperidine nitrogens considered as the possible sites of protonation in 1, surprisingly the carbonyl oxygen takes preferentially the proton in the gas phase whereas in water the piperidine nitrogen is firstly protonated. For model compounds, the piperidine nitrogen in 3 is more basic than the carbonyl oxygen in 2 in both, the gas phase and water.

  15. Theoretical study of intermolecular proton transfer reaction in isolated 5-hydroxyisoxazole-water complexes

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Ping G. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China); Liang, Yong H. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China)], E-mail: yonghliang@hotmail.com; Tang, Zhen Q. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (China)

    2006-03-20

    A systematic investigation in isolated 5-hydroxyisoxazole-water complexes (5-HIO . (H{sub 2}O) {sub n} n = 1-3) is performed at the DFT level, employing B3LYP/6-31G(d, p) basis set. Single-point energy calculations are also performed at the MP2 level using B3LYP/6-31G(d, p) optimized geometries and the 6-311++G(d, p) basis set. The computational results show that the keto tautomer K{sub 2} is the most stable isomer in the gas phase, and the tautomer K{sub 1} to be the next most stable tautomer. Hydrogen bonding between HIO and the water molecule(s) will dramatically lower the barrier by a concerted multiple proton transfer mechanism. The proton transfer process of 3WE {sub cis} {r_reversible} 3WK{sub 1} and 2WE {sub trans} {r_reversible} 2WK{sub 2} is found to be more efficient in two tautomerization, and the barrier heights are 7.03 and 14.15 kcal/mol at B3LYP/6-31G(d, p) level, respectively. However, the proton transfer reaction between E {sub cis} and K{sub 1} cannot happen without solvent-assisted.

  16. Modeling proton and alpha elastic scattering in liquid water in Geant4-DNA

    Energy Technology Data Exchange (ETDEWEB)

    Tran, H.N., E-mail: tranngochoang@tdt.edu.vn [Division of Nuclear Physics, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Faculty of Applied Sciences, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); El Bitar, Z. [Institut Pluridisciplinaire Hubert Curien/IN2P3/CNRS, Strasbourg (France); Champion, C. [Univ. Bordeaux, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Karamitros, M. [Univ. Bordeaux, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, INCIA, UMR 5287, F-33400 Talence (France); Bernal, M.A. [Instituto de FísicaGleb Wataghin, Universida de Estadual de Campinas, SP (Brazil); Francis, Z. [Université Saint Joseph, Faculty of Science, Department of Physics, Beirut (Lebanon); The Open University, Faculty of Science, Department of Physical Sciences, Walton Hall, MK7 6AA Milton Keynes (United Kingdom); Ivantchenko, V. [Ecoanalytica, 119899 Moscow (Russian Federation); Lee, S.B.; Shin, J.I. [Proton Therapy Center, National Cancer Center, 323 Ilsan-ro, Ilsandong-gu, Goyang-si, Gyeonggi-do 410-769 (Korea, Republic of); Incerti, S. [Univ. Bordeaux, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France)

    2015-01-15

    Elastic scattering of protons and alpha (α) particles by water molecules cannot be neglected at low incident energies. However, this physical process is currently not available in the “Geant4-DNA” extension of the Geant4 Monte Carlo simulation toolkit. In this work, we report on theoretical differential and integral cross sections of the elastic scattering process for 100 eV–1 MeV incident protons and for 100 eV–10 MeV incident α particles in liquid water. The calculations are performed within the classical framework described by Everhart et al., Ziegler et al. and by the ICRU 49 Report. Then, we propose an implementation of the corresponding classes into the Geant4-DNA toolkit for modeling the elastic scattering of protons and α particles. Stopping powers as well as ranges are also reported. Then, it clearly appears that the account of the elastic scattering process in the slowing-down of the charged particle improves the agreement with the existing data in particular with the ICRU recommendations.

  17. Influence of compression on water sorption, glass transition, and enthalpy relaxation behavior of freeze-dried amorphous sugar matrices.

    Science.gov (United States)

    Imamura, Koreyoshi; Kagotani, Ryo; Nomura, Mayo; Tanaka, Kazuhiro; Kinugawa, Kohshi; Nakanishi, Kazuhiro

    2011-04-15

    An amorphous matrix comprised of sugar molecules are frequently used in the pharmaceutical industry. The compression of the amorphous sugar matrix improves the handling. Herein, the influence of compression on the water sorption of an amorphous sugar matrix was investigated. Amorphous sugar samples were prepared by freeze-drying, using several types of sugars, and compressed at 0-443 MPa. The compressed amorphous sugar samples as well as uncompressed samples were rehumidified at given RHs, and the equilibrium water content and glass transition temperature (T(g)) were then measured. Compression resulted in a decrease in the equilibrium water content of the matrix, the magnitude of which was more significant for smaller sized sugars. Diffusivity of water vapor in the sample was also decreased to one-hundredth by the compression. The T(g) value for a given RH remained unchanged, irrespective of the compression. Accordingly, the decrease in T(g) with increasing water content increased as the result of compression. The structural relaxation of the amorphous sugar matrices were also examined and found to be accelerated to the level of a non-porous amorphous sugar matrix as the result of the compression. The findings indicate that pores contained in freeze-dried sugar samples interfere with the propagation of structural relaxation.

  18. Silicon hydride nanocrystals as catalysts for proton production in water-organic liquid mixtures

    KAUST Repository

    Chaieb, Sahraoui

    2014-08-05

    Embodiments of the present methods may be used to produce energy in the form of an electrical current from water without the use of fossil fuel. Silicon hydride is very easy to make. This procedure in conjunction with an enzyme to produce hydrogen gas for fuel cells and other small devices. In fuel cells the production of protons may be bypassed, and an oxidant such as permanganate or oxygen from air may be used to drive the fuel cells. In such an embodiment, an intermediate reaction may not be needed to produce protons. In one embodiment, membrane-less laminar flow fuel cells with an external grid for oxygen supply from the air may be used.

  19. Dynamic characteristic of amitriptyline in water by ultrasonic relaxation method and molecular orbital calculation.

    Science.gov (United States)

    Nishikawa, Sadakatsu; Kamimura, Eri

    2011-02-03

    Ultrasonic absorption coefficients in the frequency range of 0.8-220 MHz have been measured in aqueous solution of amitriptyline (3-(10,11-dihydro-5H-dibenzo[a,d]cycloheptene-5-ylidene)-N,N-dimethyl-1-propanamine) in the concentration range from 0.20 to 0.60 mol dm(-3) at 25 °C. A single relaxational phenomenon has been observed, and the relaxation frequency is independent of the concentration. It has been also observed that the amplitude of the relaxational absorption increases linearly with the analytical concentration. From these ultrasonic relaxation data, it has been concluded that the relaxation is associated with a unimolecular reaction due to a conformational change of the solute molecule, such as a structural change due to a rotational motion of a group in the solute molecule. Molecular orbital semiempirical methods using AM1 (Austin model 1) and PM3 (modified neglect of diatomic overlap parametric method 3) have been applied to obtain the standard enthalpy of formation for amitriptyline molecule at various dihedral angles around one of the bonds in alkylamine side chain. The results have shown the two clear minimum standard enthalpies of formation for amitriptyline. From the difference of the two values, the standard enthalpy change between the two stable conformers has been calculated be 2.9 kJ mol(-1). On a rough assumption that the standard enthalpy change reflects the standard free energy change, the equilibrium constant for the rotational isomers has been estimated to be 0.31. Combining this value with the experimental ultrasonic relaxation frequency, the backward and forward rate constants have been evaluated. The standard enthalpy change of the reaction has been also estimated from the concentration dependence of the maximum absorption per wavelength, and it has been close to that calculated by the semiempirical methods. The ultrasonic absorption measurements have been also carried out in amitriptyline solution in the presence of

  20. IR spectroscopy of protonation in benzene-water nanoclusters: hydronium, zundel, and eigen at a hydrophobic interface.

    Science.gov (United States)

    Cheng, Timothy C; Bandyopadhyay, Biswajit; Mosley, Jonathan D; Duncan, Michael A

    2012-08-08

    The structure of ions in water at a hydrophobic interface influences important processes throughout chemistry and biology. However, experiments to measure these structures are limited by the distribution of configurations present and the inability to selectively probe the interfacial region. Here, protonated nanoclusters containing benzene and water are produced in the gas phase, size-selected, and investigated with infrared laser spectroscopy. Proton stretch, free OH, and hydrogen-bonding vibrations uniquely define protonation sites and hydrogen-bonding networks. The structures consist of protonated water clusters binding to the hydrophobic interface of neutral benzene via one or more π-hydrogen bonds. Comparison to the spectra of isolated hydronium, zundel, or eigen ions reveals the inductive effects and local ordering induced by the interface. The structures and interactions revealed here represent key features expected for aqueous hydrophobic interfaces.

  1. Excited-state proton transfer of photoexcited pyranine in water observed by femtosecond stimulated Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Han, Fangyuan; Liu, Weimin; Fang, Chong, E-mail: Chong.Fang@oregonstate.edu

    2013-08-30

    Highlights: • A number of low – frequency modes are sequentially observed in photoexcited HPTS. • Evidence of coherent quantum beat in several low – frequency modes with anharmonic coupling. • The most transient low – frequency mode is the symmetric ring breathing of HPTS. • Excited – state proton transfer occurs nonadiabatically on the 5–200 ps timescale. • Kinetic isotope effect is 3–4 for the two-stage ESPT components in water. - Abstract: We use femtosecond stimulated Raman spectroscopy (FSRS) to illuminate the choreography of intermolecular excited-state proton transfer (ESPT) of photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) in water. The multidimensional reaction coordinate responsible for photoacidity is revealed to involve sequential activation of characteristic skeletal motions during the ca. 1 ps preparation stage preceding ESPT. The initial ring-coplanarity breaking follows in-plane ring breathing (191 cm{sup −1}), and is facilitated by HPTS ring wagging (108 cm{sup −1}) and ring-H out-of-plane motions (321, 362, 952 cm{sup −1}), which largely decay within ∼1 ps. ESPT then occurs with intrinsic inhomogeneity via various number of intervening water molecules over relatively larger distances than those in acetate–water system. The intricate relationship between the time-resolved excited-state vibrational modes of HPTS reveals the essential role of coherent low-frequency skeletal motions gating ESPT, and the multi-staged proton-transfer process having the kinetic isotope effect (KIE) value of 3–4 in aqueous solution on the 5–200 ps timescale.

  2. Mass spectrometric and quantum chemical determination of proton water clustering equilibria

    Science.gov (United States)

    Likholyot, Alexander; Lemke, Kono H.; Hovey, Jamey K.; Seward, Terry M.

    2007-05-01

    We report on the thermochemistry of proton hydration by water in the gas phase both experimentally using high-pressure mass spectrometry (HPMS) and theoretically using multilevel G3, G3B3, CBS-Q, CBS-QB3, CBS/QCI-APNO as well as density functional theory (DFT) calculations. Gas phase hydration enthalpies and entropies for protonated water cluster equilibria with up to 7 waters (i.e., n ⩽ 7H 3O +·(H 2O) n) were observed and exhibited non-monotonic behavior for successive hydration steps as well as enthalpy and entropy anomalies at higher cluster rank numbers. In particular, there is a significant jump in the stepwise enthalpies and entropies of cluster formation for n varying from 6 to 8. This behavior can be successfully interpreted using cluster geometries obtained from quantum chemical calculations by considering the number of additional hydrogen bonds formed at each hydration step and simultaneous weakening of ion-solvent interaction with increasing cluster size. The measured total hydration energy for the attachment of the first six water molecules around the hydronium ion was found to account for more than 60% of total bulk hydration free energy.

  3. ATR-FTIR study of water in Nafion membrane combined with proton conductivity measurements during hydration/dehydration cycle.

    Science.gov (United States)

    Kunimatsu, Keiji; Bae, Byungchan; Miyatake, Kenji; Uchida, Hiroyuki; Watanabe, Masahiro

    2011-04-21

    We have conducted combined time-resolved attenuated total reflection Fourier transform infrared (ATR-FTIR) and proton conductivity measurements of Nafion NRE211 membrane during hydration/dehydration cycles at room temperature. Conductivity change was interpreted in terms of different states of water in the membrane based on its δ(HOH) vibrational spectra. It was found that hydration of a dry membrane leads first to complete dissociation of the sulfonic acid groups to liberate hydrated protons, which are isolated from each other and have δ(HOH) vibrational frequency around 1740 cm(-1). The initial hydration is not accompanied by a significant increase of the proton conductivity. Further hydration gives rise to a rapid increase of the conductivity in proportion to intensity of a new δ(HOH) band around 1630 cm(-1). This was interpreted in terms of formation of channels of weakly hydrogen-bonded water to combine the isolated hydrophilic domains containing hydrated protons and hydrated sulfonate ions produced during the initial stage of hydration. Upon dehydration, proton conductivity drops first very rapidly due to loss of the weakly hydrogen bonded water from the channels to leave hydrophilic domains isolated in the membrane. Dehydration of the protons proceeds very slowly after significant loss of the proton conductivity.

  4. Spin-locking versus chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons.

    Science.gov (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

    2011-05-01

    Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of nonequivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolite phantoms with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: (i) on-resonance SL is most sensitive to chemical exchanges in the intermediate-exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. (ii) Offset frequency-dependent SL and CEST spectra are very similar and can be explained well with an SL model recently developed by Trott and Palmer (J Magn Reson 2002;154:157-160). (iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. (iv) The asymmetry of the magnetization transfer ratio (MTR(asym)) is highly dependent on the choice of saturation pulse power. In the intermediate-exchange regime, MTR(asym) becomes complicated and should be interpreted with care.

  5. Water equivalent thickness values of materials used in beams of protons, helium, carbon and iron ions

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Rui; Newhauser, Wayne D [Graduate School of Biomedical Sciences, University of Texas at Houston, 6767 Bertner, Houston, TX 77030 (United States); Taddei, Phillip J [Department of Radiation Physics, Unit 1202, University of Texas MD Anderson Cancer Center, 1515 Holcombe Boulevard, Houston, TX 77030 (United States); Fitzek, Markus M [Midwest Proton Radiotherapy Institute, 2425 Milo B Sampson Lane, Bloomington, IN 47408 (United States)], E-mail: wnewhaus@mdanderson.org

    2010-05-07

    Heavy charged particle beam radiotherapy for cancer is of increasing interest because it delivers a highly conformal radiation dose to the target volume. Accurate knowledge of the range of a heavy charged particle beam after it penetrates a patient's body or other materials in the beam line is very important and is usually stated in terms of the water equivalent thickness (WET). However, methods of calculating WET for heavy charged particle beams are lacking. Our objective was to test several simple analytical formulas previously developed for proton beams for their ability to calculate WET values for materials exposed to beams of protons, helium, carbon and iron ions. Experimentally measured heavy charged particle beam ranges and WET values from an iterative numerical method were compared with the WET values calculated by the analytical formulas. In most cases, the deviations were within 1 mm. We conclude that the analytical formulas originally developed for proton beams can also be used to calculate WET values for helium, carbon and iron ion beams with good accuracy.

  6. Water equivalent thickness analysis of immobilization devices for clinical implementation in proton therapy.

    Science.gov (United States)

    Wroe, A J; Ghebremedhin, A; Gordon, I R; Schulte, R W; Slater, J D

    2014-10-01

    Immobilization devices can impact not only the inter- and intra-fraction motion of the patient, but also the range uncertainty of the treatment beam in proton therapy. In order to limit additional range uncertainty, the water equivalent thickness (WET) of the immobilization device needs to be well known and accurately reflected in the calculations by the treatment planning system (TPS). The method presented here focusses on the use of a nozzle-mounted variable range shifter and precision-machined polystyrene blocks of known WET to evaluate commercial immobilization devices prior to clinical implementation. CT studies were also completed to evaluate the internal uniformity of the immobilization devices under study. Mul- tiple inserts of the kVue platform (Qfix Systems, Avondale, PA) were evaluated as part of this study. The results indicate that the inserts are largely interchangeable across a given design type and that the measured WET values agree with those generated by the TPS with a maxi- mum difference less than 1 mm. The WET of the devices, as determined by the TPS, was not impacted by CT beam hardening normally experienced during clinical use. The reproduc- ibility of the WET method was also determined to be better than ±0.02 mm. In conclusion, the testing of immobilization prior to implementation in proton therapy is essential in order to ascertain their impact on the proton treatment and the methodology described here can also be applied to other immobilization systems.

  7. Inelastic-collision cross sections of liquid water for interactions of energetic protons

    CERN Document Server

    Dingfelder, M; Paretzke, H G

    2000-01-01

    Cross-section data for inelastic interactions of energetic protons with liquid water, for use, e.g. as input in track structure analysis, are derived for an energy range from 0.1 keV to 10 GeV. At proton kinetic energies above about 500 keV, the first Born approximation and the dielectric-response function determined earlier are used. At proton energies above several hundred MeV in particular, the Fermi-density effect is also incorporated. At energies below about 500 keV, which corresponds to a residual range of about 8.9x10 sup - sup 6 m, cross-section values are derived semi-empirically by an extensive and critical analysis of experimental and theoretical information concerning not only cross sections for individual processes such as ionisation, excitation, and charge transfer but also stopping power and other relevant quantities. Spectra of secondary electrons resulting from ionising collisions are also presented. The analysis also includes considerations of phase effects on cross sections.

  8. Water equivalent thickness values of materials used in beams of protons, helium, carbon and iron ions.

    Science.gov (United States)

    Zhang, Rui; Taddei, Phillip J; Fitzek, Markus M; Newhauser, Wayne D

    2010-05-07

    Heavy charged particle beam radiotherapy for cancer is of increasing interest because it delivers a highly conformal radiation dose to the target volume. Accurate knowledge of the range of a heavy charged particle beam after it penetrates a patient's body or other materials in the beam line is very important and is usually stated in terms of the water equivalent thickness (WET). However, methods of calculating WET for heavy charged particle beams are lacking. Our objective was to test several simple analytical formulas previously developed for proton beams for their ability to calculate WET values for materials exposed to beams of protons, helium, carbon and iron ions. Experimentally measured heavy charged particle beam ranges and WET values from an iterative numerical method were compared with the WET values calculated by the analytical formulas. In most cases, the deviations were within 1 mm. We conclude that the analytical formulas originally developed for proton beams can also be used to calculate WET values for helium, carbon and iron ion beams with good accuracy.

  9. Development of a proton-exchange membrane electrochemical reclaimed water post-treatment system

    Science.gov (United States)

    Kaba, Lamine; Verostko, Charles E.; Hitchens, G. D.; Murphy, Oliver J.

    1991-01-01

    A single-cell electrochemical reactor that utilizes a proton exchange membrane (PEM) as a solid electrolyte is being investigated for posttreatment of reclaimed waste waters with low or negligible electrolyte content. Posttreatment is a final 'polishing' of reclaimed waste waters prior to reuse, and involves removing organic impurities at levels as high as 100 ppm to below 500 ppb total organic carbon (TOC) content to provide disinfection. The system does not utilize or produce either expendable hardware components or chemicals and has no moving parts. Test data and kinetic analysis are presented. The feasibility and application for water reclamation processes in controlled ecological environments (e.g., lunar/Mars habitats) are also presented. Test results show that the electrochemical single cell reactor provides effective posttreatment.

  10. Theoretical Structures of Triflic Acid-Water Clusters and the Molecular Mechanism of Proton Dissociation

    Energy Technology Data Exchange (ETDEWEB)

    Paddison, S.J.; Pratt, L.R.; Zawodzinski, T.A.

    1998-11-01

    Structural and energetic information required for recently proposed quasi-chemical theories of solution chemistry have been obtained for clusters of water with triflic acid, CF{sub 3}SO{sub 3}H(H{sub 2}O){sub n} for n=1-6. Quantum mechanical calculations on the clusters indicate that the acid proton does not dissociate with n=1 or 2 hydrating water molecules, but does dissociate for n>=3 water molecule partners. The computed minimum energy structures indicate that both ''Eigen'' (H{sub 9}O{sub 4}{sup +}) (n=3,4,6) and ''Zundel'' (H{sub 5}O{sub 2}{sup +}) (n=5) structures are likely to play a role in the molecular mechanism of acid dissociation in Nafion{reg_sign}.

  11. A review of water flooding issues in the proton exchange membrane fuel cell

    Science.gov (United States)

    Li, Hui; Tang, Yanghua; Wang, Zhenwei; Shi, Zheng; Wu, Shaohong; Song, Datong; Zhang, Jianlu; Fatih, Khalid; Zhang, Jiujun; Wang, Haijiang; Liu, Zhongsheng; Abouatallah, Rami; Mazza, Antonio

    We have reviewed more than 100 references that are related to water management in proton exchange membrane (PEM) fuel cells, with a particular focus on the issue of water flooding, its diagnosis and mitigation. It was found that extensive work has been carried out on the issues of flooding during the last two decades, including prediction through numerical modeling, detection by experimental measurements, and mitigation through the design of cell components and manipulating the operating conditions. Two classes of strategies to mitigate flooding have been developed. The first is based on system design and engineering, which is often accompanied by significant parasitic power loss. The second class is based on membrane electrode assembly (MEA) design and engineering, and involves modifying the material and structural properties of the gas diffusion layer (GDL), cathode catalyst layer (CCL) and membrane to function in the presence of liquid water. In this review, several insightful directions are also suggested for future investigation.

  12. Testing Thermo-acoustic Sound Generation in Water with Proton and Laser Beams

    CERN Document Server

    Graf, K; Hoessl, J; Kappes, A; Karg, T; Katz, U; Lahmann, R; Naumann, C; Salomon, K; Stegmann, C

    2005-01-01

    Experiments were performed at a proton accelerator and an infrared laser acility to investigate the sound generation caused by the energy deposition of pulsed particle and laser beams in water. The beams with an energy range of 1 PeV to 400 PeV per proton beam spill and up to 10 EeV for the laser pulse were dumped into a water volume and the resulting acoustic signals were recorded with pressure sensitive sensors. Measurements were performed at varying pulse energies, sensor positions, beam diameters and temperatures. The data is well described by simulations based on the thermo-acoustic model. This implies that the primary mechanism for sound generation by the energy deposition of particles propagating in water is the local heating of the media giving rise to an expansion or contraction of the medium resulting in a pressure pulse with bipolar shape. A possible application of this effect would be the acoustical detection of neutrinos with energies greater than 1 EeV.

  13. Proton transfer in hydrogen-bonded network of phenol molecules: intracluster formation of water.

    Science.gov (United States)

    Lengyel, Jozef; Gorejová, Radka; Herman, Zdeněk; Fárník, Michal

    2013-11-07

    Electron ionization and time-of-flight mass spectrometry was used to investigate the phenol clusters (PhOH)n of different size from single molecule to large clusters: in coexpansion with He, the dimers n = 2 are mostly generated; in Ar, large species of n ≥ 10 also occur. Besides [(PhOH)n](+•) cluster ion series, hydrated phenol cluster ions [(PhOH)n·xH2O](+•) with up to x = 3 water molecules and dehydrated phenol clusters [(PhOH)n-H2O](+•) were observed. The hydrated phenol series exhibits minima and maxima that are interpreted as evidence for proton transfer between the hydrogen bonded cluster ions of cyclic structures. The proton transfer leads to a water generation within the clusters, and subsequent elimination of the diphenyl ether molecule(s) from the cluster yields the hydrated phenol cluster ions. Alternatively, a water molecule release yields a series of dehydrated phenols, among which the diphenyl ether ion [PhOPh](+•) (n = 2) constitutes the maximum.

  14. Excited-state proton transfer of photoexcited pyranine in water observed by femtosecond stimulated Raman spectroscopy

    Science.gov (United States)

    Han, Fangyuan; Liu, Weimin; Fang, Chong

    2013-08-01

    We use femtosecond stimulated Raman spectroscopy (FSRS) to illuminate the choreography of intermolecular excited-state proton transfer (ESPT) of photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) in water. The multidimensional reaction coordinate responsible for photoacidity is revealed to involve sequential activation of characteristic skeletal motions during the ca. 1 ps preparation stage preceding ESPT. The initial ring-coplanarity breaking follows in-plane ring breathing (191 cm-1), and is facilitated by HPTS ring wagging (108 cm-1) and ring-H out-of-plane motions (321, 362, 952 cm-1), which largely decay within ∼1 ps. ESPT then occurs with intrinsic inhomogeneity via various number of intervening water molecules over relatively larger distances than those in acetate-water system. The intricate relationship between the time-resolved excited-state vibrational modes of HPTS reveals the essential role of coherent low-frequency skeletal motions gating ESPT, and the multi-staged proton-transfer process having the kinetic isotope effect (KIE) value of 3-4 in aqueous solution on the 5-200 ps timescale.

  15. Perturbation of water-equivalent thickness as a surrogate for respiratory motion in proton therapy.

    Science.gov (United States)

    Matney, Jason E; Park, Peter C; Li, Heng; Court, Laurence E; Zhu, X Ron; Dong, Lei; Liu, Wei; Mohan, Radhe

    2016-03-08

    Respiratory motion is traditionally assessed using tumor motion magnitude. In proton therapy, respiratory motion causes density variations along the beam path that result in uncertainties of proton range. This work has investigated the use of water-equivalent thickness (WET) to quantitatively assess the effects of respiratory motion on calculated dose in passively scattered proton therapy (PSPT). A cohort of 29 locally advanced non-small cell lung cancer patients treated with 87 PSPT treatment fields were selected for analysis. The variation in WET (ΔWET) along each field was calculated between exhale and inhale phases of the simulation four-dimensional computed tomography. The change in calculated dose (ΔDose) between full-inhale and full-exhale phase was quantified for each field using dose differences, 3D gamma analysis, and differential area under the curve (ΔAUC) analysis. Pearson correlation coefficients were calculated between ΔDose and ΔWET. Three PSPT plans were redesigned using field angles to minimize variations in ΔWET and compared to the original plans. The median ΔWET over 87 treatment fields ranged from 1-9 mm, while the ΔWET 95th percentile value ranged up to 42 mm. The ΔWET was significantly correlated (p respiratory motion, as ΔAUC values were reduced by more than 60% in all three cases. The tumor motion magnitude alone does not capture the potential dosimetric error due to respiratory motion because the proton range is sensitive to the motion of all patient anatomy. The use of ΔWET has been demonstrated to identify situations where respiratory motion can impact the calculated dose. Angular analysis of ΔWET may be capable of designing radiotherapy plans that are more robust to the effects of respiratory motion.

  16. Protonation of a hydroxide anion bridging two divalent magnesium cations in water probed by first-principles metadynamics simulation.

    Science.gov (United States)

    Park, Jung Mee; Boero, Mauro

    2010-09-01

    The protonation of a hydroxide anion (OH(-)) located between two magnesium cations (Mg(2+)) in aqueous solution has been investigated by first-principles metadynamics simulation. We observe that the complex Mg(2+)-OH(-)-Mg(2+) is stabilized by the coparticipation of the hydroxide anion to the first hydration shells of both the Mg(2+) cations. Contrary to the cases of OH(-) in pure water, the transfer of protons in the presence of the divalent metal ions turns out to be a slow chemical event. This can be ascribed to the decreased proton affinity of the bridging OH(-). Metadynamics simulation, used to overcome the difficulty of the long time scale required by the protonation of the bridging OH(-), has shown that the system possesses a great stability on the reactant state, characterized by a bioctahedral (6,6) solvation structure around the two Mg(2+) cations. The exploration of the free energy landscape shows that this stable bioctahedral configuration converts into a lower coordinated (5,6) structure, leading to a proton transfer from a water molecule belonging to the first solvation shell of the Mg(2+) ion having the lower coordination to the bridging OH(-); the free energy barrier for the protonation reaction is 11 kcal/mol, meaning that the bridging hydroxide is a weak base. During the proton transfer, the bridging OH(-) reverts to an H(2)O molecule, and this breaks the electrostatic coupling of the two Mg(2+) ions, which depart independently with their own hydration shells, one of which is entirely formed by water molecules. The second one carries the newly created OH(-). Our results show that the flexibility in the metal coordination plays a crucial role in both the protonation process of the bridging OH(-) and the separation of the metal cations, providing useful insight into the nature of proton transfer in binuclear divalent metal ions, with several biological implications, such as, for instance, transesterification of catalytic RNA.

  17. Geant4 Simulation Study of Dose Distribution and Energy Straggling for Proton and Carbon Ion Beams in Water

    Directory of Open Access Journals (Sweden)

    Zhao Qiang

    2016-01-01

    Full Text Available Dose distribution and energy straggling for proton and carbon ion beams in water are investigated by using a hadrontherapy model based on the Geant4 toolkit. By gridding water phantom in N×N×N voxels along X, Y and Z axes, irradiation dose distribution in all the voxels is calculated. Results indicate that carbon ion beams have more advantages than proton beams. Proton beams have bigger width of the Bragg peak and broader lateral dose distribution than carbon ion beams for the same position of Bragg peaks. Carbon ion has a higher local ionization density and produces more secondary electrons than proton, so carbon ion beams can achieve a higher value of relative biological effectiveness.

  18. Molecular dynamics simulations of proton-ordered water confined in low-diameter carbon nanotubes.

    Science.gov (United States)

    Li, Shujuan; Schmidt, Burkhard

    2015-03-21

    The present work deals with molecular dynamics simulations of water confined in single-walled carbon nanotubes (CNTs), with emphasis on the proton-ordering of water and its polarization. First, the water occupancy of open-ended armchair and zigzag CNTs immersed in water under ambient NPT conditions is calculated for various water models, and for varying Lennard-Jones parameters of the water-carbon interaction. As a function of the CNT diameter, the water density displays several oscillations before converging to the bulk value. Based on these results, the water structures encapsulated in 10 nm long armchair CNTs (n,n) with 5 ≤ n ≤ 10, are investigated under NVT conditions. Inside the smallest nanotubes (n = 5, 6) highly ferroelectric (FE), quasi-one-dimensional water chains are found while inside the other CNTs water molecules assemble into single-walled ice nanotubes (INTs). There are several, near-degenerate minimum energy INT structures: single helical structures were found for 7 ≤ n ≤ 10, in all cases in FE arrangement. In addition, a double helical INT structure was found for n = 8 with an even higher polarization. Prism-like structures were found only for 8 ≤ n ≤ 10 with various FE, ferrielectric (FI), and antiferroelectric (AF, n = 9, 10) proton ordering. The coexistence of the nearly iso-energetic FE, FI, and AF INT structures separated by high barriers renders the molecular dynamics highly metastable, typically with nanosecond timescales at room temperature. Hence, the replica exchange simulation method is used to obtain populations of different INT states at finite temperatures. Many of the FE INT structures confined in low-diameter CNTs are still prevalent at room temperature. Both helix-helix and helix-prism structural transitions are detected which can be either continuous (around 470 K for n = 8) or discontinuous (at 218 K for n = 9). Also melting-like transitions are found in which the INT structures are disrupted leading to a loss of FE

  19. Water sandwiched by a pair of aromatic rings in a proton-conducting metal-organic framework.

    Science.gov (United States)

    Dong, Xi-Yan; Li, Xue; Li, Bo; Zhu, Yan-Yan; Zang, Shuang-Quan; Tang, Ming-Sheng

    2016-11-15

    The interactions between water molecules and aromatic rings are known to be common and important in physics, chemistry and life sciences. Benzene-water complexes are the main prototype systems for O-Hπ and lone-pair (lp)π interactions in theoretical research, however solid state examples are very rare. Here, the solid state example of water sandwiched by a pair of aromatic rings is observed in a silver-mellitate framework, where lpπ and O-Hπ interactions coexist. The coexistence of these two interactions has been further verified by theoretical calculations. In addition, ammonium ions and water molecules as proton sources, and strongly H-bonded nets as the pathway of proton transport, make the reported MOFs (metal-organic frameworks) exhibit distinct proton conduction.

  20. Non-monotonic, distance-dependent relaxation of water in reverse micelles: propagation of surface induced frustration along hydrogen bond networks.

    Science.gov (United States)

    Biswas, Rajib; Chakraborti, Tamaghna; Bagchi, Biman; Ayappa, K G

    2012-07-07

    Layer-wise, distance-dependent orientational relaxation of water confined in reverse micelles (RM) is studied using theoretical and computational tools. We use both a newly constructed "spins on a ring" (SOR) Ising-type model (with Shore-Zwanzig rotational dynamics) and atomistic simulations with explicit water. Our study explores the effect of reverse micelle size and role of intermolecular correlations, compromised by the presence of a highly polar surface, on the distance (from the interface) dependence of water relaxation. The "spins on a ring" model can capture some aspects of distance dependence of relaxation, such as acceleration of orientational relaxation at intermediate layers. In atomistic simulations, layer-wise decomposition of hydrogen bond formation pattern clearly reveals that hydrogen bond arrangement of water at a certain distance away from the surface can remain frustrated due to the interaction with the polar surface head groups. This layer-wise analysis also reveals the presence of a non-monotonic slow relaxation component which can be attributed to this frustration effect and which is accentuated in small to intermediate size RMs. For large size RMs, the long time component decreases monotonically from the interface to the interior of the RMs with slowest relaxation observed at the interface.

  1. The local order of supercooled water in solution with LiCl studied by NMR proton chemical shift

    Science.gov (United States)

    Corsaro, C.; Mallamace, D.; Vasi, S.; Cicero, N.; Dugo, G.; Mallamace, F.

    2016-05-01

    We study by means of Nuclear Magnetic Resonance (NMR) spectroscopy the local order of water molecules in solution with lithium chloride at eutectic concentration. In particular, by measuring the proton chemical shift as a function of the temperature in the interval 203{ K}Widom line for water supporting the liquid-liquid transition hypothesis.

  2. Vibrational and rotational relaxation in mixtures of water vapor and oxygen

    Science.gov (United States)

    Bass, H. E.; Keeton, R. G.; Williams, D.

    1976-01-01

    Experimental measurements of sound absorption in air, measurements of ultrasonic absorption in H2O/O2 mixtures at 500 K, and experimental measurements in mixtures of H2O with other impurities have been analyzed to determine the energy transfer rates in mixtures of O2 and H2O as a function of temperature. A set of energy transfer rate coefficients was found that give results consistent with all the experimental data examined and with vibrational energy transfer theory. The rotational relaxation time for H2O/O2 mixtures was determined from the 500 K ultrasonic measurements.

  3. Nuclear halo of a 177\\,MeV proton beam in water

    CERN Document Server

    Gottschalk, Bernard; Daartz, Juliane; Wagner, Miles S

    2014-01-01

    The dose distribution of a pencil beam in a water tank consists of a core, a halo and an aura. The core consists of primary protons which suffer multiple Coulomb scattering (MCS) and slow down by multiple collisions with atomic electrons (Bethe-Bloch theory). The halo consists of charged secondaries, many of them protons, from elastic interactions with H, elastic and inelastic interactions with O, and nonelastic interactions with O. We show that the halo radius is roughly one third of the beam range. The aura consists of neutral secondaries (neutrons and gamma rays) and the charged particles they set in motion. We have measured the core/halo at 177 MeV using a test beam offset in a water tank. The beam monitor was a plane parallel ionization chamber (IC) and the field IC a dose calibrated Exradin T1. Our dose measurements are absolute. We took depth-dose scans at ten displacements from the beam axis ranging from 0 to 10 cm. The dose spans five orders of magnitude, and the transition from halo to aura is obvio...

  4. Ballistic Protons and Microwave-induced Water Solitons in Bioenergetic Transformations

    Directory of Open Access Journals (Sweden)

    Reuven Tirosh

    2006-09-01

    Full Text Available Active streaming (AS of liquid water is considered to generate and overcomepressure gradients, so as to drive cell motility and muscle contraction by hydrauliccompression. This idea had led to reconstitution of cytoplasm streaming and musclecontraction by utilizing the actin-myosin ATPase system in conditions that exclude acontinuous protein network. These reconstitution experiments had disproved a contractileprotein mechanism and inspired a theoretical investigation of the AS hypothesis, aspresented in this article. Here, a molecular quantitative model is constructed for a chemicalreaction that might generate the elementary component of such AS within the pure waterphase. Being guided by the laws of energy and momentum conservation and by the physicalchemistry of water, a vectorial electro-mechano-chemical conversion is considered, asfollows: A ballistic H+ may be released from H2O-H+ at a velocity of 10km/sec, carrying akinetic energy of 0.5 proton*volt. By coherent exchange of microwave photons during 10-10sec, the ballistic proton can induce cooperative precession of about 13300 electrically-polarized water molecule dimers, extending along 0.5 μm. The dynamic dimers rearrangealong the proton path into a pile of non-radiating rings that compose a persistent rowing-likewater soliton. During a life-time of 20 msec, this soliton can generate and overcome amaximal pressure head of 1 kgwt/cm2 at a streaming velocity of 25 μm/sec and intrinsicpower density of 5 Watt/cm3. In this view, the actin-myosin ATPase is proposed to catalyzestereo-specific cleavage of H2O-H+ , so as to generate unidirectional fluxes of ballisticprotons and water solitons along each actin filament. Critical requirements and evidentialpredictions precipitate consistent implications to the physical chemistry of water, enzymatichydrolysis and synthesis of ATP, trans-membrane signaling, intracellular transport, cellmotility, intercellular interaction, and associated

  5. Vibrational Förster transfer to hydrated protons.

    Science.gov (United States)

    Timmer, R L A; Tielrooij, K J; Bakker, H J

    2010-05-21

    We have studied the influence of excess protons on the vibrational energy relaxation of the O-H and O-D stretching modes in water using femtosecond pump-probe spectroscopy. Without excess protons, we observe exponential decays with time constants of 1.7 and 4.3 ps for the bulk and anion bound O-D stretch vibrations. The addition of protons introduces a new energy relaxation pathway, which leads to an increasingly nonexponential decay of the O-D stretch vibration. This new pathway is attributed to a distance-dependent long range dipole-dipole (Forster) interaction between the O-D stretching vibration and modes associated with dissolved protons. The high efficiency of hydrated protons as receptors of vibrational energy follows from the very large absorption cross section and broad bandwidth of protons in water. For a proton concentration of 1M we find that Forster energy transfer occurs over an average distance of 4.5 A, which corresponds to a separation of about two water molecules.

  6. A review of proton exchange membrane water electrolysis on degradation mechanisms and mitigation strategies

    Science.gov (United States)

    Feng, Qi; Yuan, Xiao-Zi; Liu, Gaoyang; Wei, Bing; Zhang, Zhen; Li, Hui; Wang, Haijiang

    2017-10-01

    Proton exchange membrane water electrolysis (PEMWE) is an advanced and effective solution to the primary energy storage technologies. A better understanding of performance and durability of PEMWE is critical for the engineers and researchers to further advance this technology for its market penetration, and for the manufacturers of PEM water electrolyzers to implement quality control procedures for the production line or on-site process monitoring/diagnosis. This paper reviews the published works on performance degradations and mitigation strategies for PEMWE. Sources of degradation for individual components are introduced. With degradation causes discussed and degradation mechanisms examined, the review emphasizes on feasible strategies to mitigate the components degradation. To avoid lengthy real lifetime degradation tests and their high costs, the importance of accelerated stress tests and protocols is highlighted for various components. In the end, R&D directions are proposed to move the PEMWE technology forward to become a key element in future energy scenarios.

  7. Self-overcoming of the boiling condition by pressure increment in a water target irradiated by proton beam

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Bong Hwan, E-mail: burnn@kirams.re.kr [Korea Institute of Radiological and Medical Sciences (KIRMAS), 75 Nowon-Gil, Nowon-Gu, Seoul 139-706 (Korea, Republic of); Kang, Joonsun; Jung, In Su; Ram, Han Ga; Park, Yeun Soo [Korea Institute of Radiological and Medical Sciences (KIRMAS), 75 Nowon-Gil, Nowon-Gu, Seoul 139-706 (Korea, Republic of); Cho, Hyung Hee [Department of Mechanical Engineering, Yonsei University, 134 Sinchon-Dong, Seodaemun-Gu, Seoul 120-749 (Korea, Republic of)

    2013-11-11

    An experiment was conducted to examine and visualize the boiling phenomena inside a water target by irradiating it with a proton beam from MC-50 cyclotron. The boiling phenomena were recorded with a CMOS camera. While an increase of the fraction of the water vapor volume is generally considered to be normal when water is boiled by a proton beam, our experiment showed the opposite result. The volume expansion of the liquid water exceeded the compressibility of the initial air volume. A grid structure in front of the entrance window foil held the target volume constant. Therefore, the phenomena inside the target underwent an isochoric process, and the pressure inside the target was increased rapidly beyond the pressure at the boiling point. Consequently, there was no more bulk boiling in the Bragg-peak region in the target water. Our results show that the boiling of the water can be controlled by controlling the equilibrium pressure of the water target.

  8. In vivo relaxation of N-acetyl-aspartate, creatine plus phosphocreatine, and choline containing compounds during the course of brain infarction: a proton MRS study

    DEFF Research Database (Denmark)

    Gideon, P; Henriksen, O

    1992-01-01

    the course of infarction can be explained by changes in T1 and T2 relaxation times, eight patients with acute stroke were studied. STEAM sequences with varying echo delay times and repetition times were used to measure T1 and T2 of N-acetyl-aspartate (NAA), creatine plus phosphocreatine (Cr+PCr) and choline...

  9. Encapsulation and Characterization of Proton-Bound Amine Homodimers in a Water Soluble, Self-Assembled Supramolecular Host

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael; Fiedler, Dorothea; Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth

    2008-10-01

    Cyclic amines can be encapsulated in a water-soluble self-assembled supramolecular host upon protonation. The hydrogen bonding ability of the cyclic amines, as well as the reduced degrees of rotational freedom, allows for the formation of proton-bound homodimers inside of the assembly which are otherwise not observable in aqueous solution. The generality of homodimer formation was explored with small N-alkyl aziridines, azetidines, pyrrolidines and piperidines. Proton-bound homodimer formation is observed for N-alkylaziridines (R = methyl, isopropyl, tert-butyl), N-alkylazetidines (R = isopropyl, tertbutyl), and N-methylpyrrolidine. At high concentration, formation of a proton-bound homotrimer is observed in the case of N-methylaziridine. The homodimers stay intact inside the assembly over a large concentration range, thereby suggesting cooperative encapsulation. Both G3(MP2)B3 and G3B3 calculations of the proton-bound homodimers were used to investigate the enthalpy of the hydrogen bond in the proton-bound homodimers and suggest that the enthalpic gain upon formation of the proton-bound homodimers may drive guest encapsulation.

  10. Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture.

    Science.gov (United States)

    Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki

    2015-05-28

    The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol(-1). On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol(-1). The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

  11. Experimental study of the atmospheric neutrino backgrounds for proton decay to positron and neutral pion searches in water Cherenkov detectors

    CERN Document Server

    Mine, S; Andringa, S; Aoki, S; Argyriades, J; Asakura, K; Ashie, R; Berghaus, F; Berns, H; Bhang, H; Blondel, A; Borghi, S; Bouchez, J; Burguet-Castell, J; Casper, D; Catala, J; Cavata, C; Cervera-Villanueva, Anselmo; Chen, S M; Cho, K O; Choi, J H; Dore, U; Espinal, X; Fechner, M; Fernández, E; Fujii, Y; Fukuda, Y; Gomez-Cadenas, J; Gran, R; Hara, T; Hasegawa, M; Hasegawa, T; Hayato, Y; Helmer, R L; Hiraide, K; Hosaka, J; Ichikawa, A K; Iinuma, M; Ikeda, A; Ishida, T; Ishihara, K; Ishii, T; Ishitsuka, M; Itow, Y; Iwashita, T; Jang, H I; Jeon, E J; Jeong, I S; Joo, K K; Jover, G; Jung, C K; Kajita, T; Kameda, J; Kaneyuki, K; Kato, I; Kearns, E; Kim, C O; Khabibullin, M; Khotjantsev, A; Kielczewska, D; Kim, J Y; Kim, S B; Kitching, P; Kobayashi, K; Kobayashi, T; Konaka, A; Koshio, Y; Kropp, W; Kudenko, Yu; Kuno, Y; Kurimoto, Y; Kutter, T; Learned, J; Likhoded, S; Lim, I T; Loverre, P F; Ludovici, L; Maesaka, H; Mallet, J; Mariani, C; Matsuno, S; Matveev, V; McConnel, K; McGrew, C; Mikheyev, S; Minamino, A; Mineev, O; Mitsuda, C; Miura, M; Moriguchi, Y; Moriyama, S; Nakadaira, T; Nakahata, M; Nakamura, K; Nakano, I; Nakaya, T; Nakayama, S; Namba, T; Nambu, R; Nawang, S; Nishikawa, K; Nitta, K; Nova, F; Novella, P; Obayashi, Y; Okada, A; Okumura, K; Oser, S M; Oyama, Y; Pac, M Y; Pierre, F; Rodríguez, A; Saji, C; Sakuda, M; Sánchez, F; Scholberg, K; Schroeter, R; Sekiguchi, M; Shiozawa, M; Shiraishi, K; Sitjes, G; Smy, M; Sobel, H; Sorel, M; Stone, J; Sulak, L; Suzuki, A; Suzuki, Y; Tada, M; Takahashi, T; Takenaga, Y; Takeuchi, Y; Taki, K; Takubo, Y; Tamura, N; Tanaka, M; Terri, R; T'Jampens, S; Tornero-Lopez, A; Totsuka, Y; Vagins, M; Whitehead, L; Walter, C W; Wang, W; Wilkes, R J; Yamada, S; Yamada, Y; Yamamoto, S; Yanagisawa, C; Yershov, N; Yokoyama, H; Yokoyama, M; Yoo, J; Yoshida, M; Zalipska, J

    2008-01-01

    The atmospheric neutrino background for proton decay to positron and neutral pion in ring imaging water Cherenkov detectors is studied with an artificial accelerator neutrino beam for the first time. In total, about 314,000 neutrino events corresponding to about 10 megaton-years of atmospheric neutrino interactions were collected by a 1,000 ton water Cherenkov detector (KT). The KT charged-current single neutral pion production data are well reproduced by simulation programs of neutrino and secondary hadronic interactions used in the Super-Kamiokande (SK) proton decay search. The obtained proton to positron and neutral pion background rate by the KT data for SK from the atmospheric neutrinos whose energies are below 3 GeV is about two per megaton-year. This result is also relevant to possible future, megaton-scale water Cherenkov detectors.

  12. Correlated dynamics of the motion of proton-hole wave-packets in a photoionized water cluster

    CERN Document Server

    Li, Zheng; Vendrell, Oriol; Santra, Robin

    2012-01-01

    We explore the correlated dynamics of an electron-hole and a proton after ionization of a protonated water cluster by extreme ultra-violet (XUV) light. An ultrafast decay mechanism is found in which the proton--hole dynamics after the ionization are driven by electrostatic repulsion and involve a strong coupling between the nuclear and electronic degrees of freedom. We describe the system by a quantum-dynamical approach and show that non-adiabatic effects are a key element of the mechanism by which electron and proton repel each other and become localized at opposite sides of the cluster. Based on the generality of the decay mechanism, similar effects may be expected for other ionized systems featuring hydrogen bonds.

  13. The temperature effect on the combined Brownian and Néel relaxation processes in a water-based magnetic fluid

    Energy Technology Data Exchange (ETDEWEB)

    Obeada, Cecilia N.; Malaescu, I., E-mail: malaescu@physics.uvt.ro

    2013-09-01

    In the present paper the temperature effect on the interplay of Brownian and Néel relaxation processes, in a water-based magnetic fluid with mixed magnetite and tetragonal maghemite particles was analyzed. In consequence, the frequency (f=ω/2π) and temperature (T) dependencies of the complex magnetic permeability, μ(f,T)=μ′(f,T)−iμ''(f,T), over the frequency range 3 kHz–2 MHz and at various values of temperatures within the range (25–90) °C were measured. The imaginary component of the complex magnetic permeability μ''(f,T) shows two maxima: the first maximum is a large one, in the frequency range (10–40) kHz, being present only at temperatures below 60 °C and the second maximum, around the frequency of 1 MHz, is present at all temperatures at which measurements were made. The first maximum is assigned to the Brownian relaxation process of particle agglomerations within the sample, which have the hydrodynamic diameter in order of (30–33) nm. The second maximum of μ''(f,T) component is assigned to the Néel relaxation process of tetragonal maghemite particles. The results are intended to clarify some fundamental issues concerning the magnetic properties of magnetic fluids in low-frequency field and can be used to study particle agglomeration processes in magnetic fluids, but also for biomedical applications such as cancer treatment by magnetic hyperthermia of tissues.

  14. Proton transfer from water to ketyl radical anion: Assessment of critical size of hydrated cluster and free energy barrier in solution from first principles simulations

    Science.gov (United States)

    Biswas, Sohag; Dasgupta, Teesta; Mallik, Bhabani S.

    2016-09-01

    We present the reactivity of an organic intermediate by studying the proton transfer process from water to ketyl radical anion using gas phase electronic structure calculations and the metadynamics method based first principles molecular dynamics (FPMD) simulations. Our results indicate that during the micro solvation of anion by water molecules systematically, the presence of minimum three water molecules in the gas phase cluster is sufficient to observe the proton transfer event. The analysis of trajectories obtained from initial FPMD simulation of an aqueous solution of the anion does not show any evident of complete transfer of the proton from water. The cooperativity of water molecules and the relatively weak anion-water interaction in liquid state prohibit the full release of the proton. Using biasing potential through first principles metadynamics simulations, we report the observation of proton transfer reaction from water to ketyl radical anion with a barrier height of 16.0 kJ/mol.

  15. The proton momentum distribution in strongly H-bonded phases of water; a critical test of electrostatic models

    CERN Document Server

    Burnham, C J; Hayashi, T; Mukamel, S; Napoleon, R L; Keyes, T

    2011-01-01

    Water is often viewed as a collection of monomers interacting electrostatically with each other. We compare the water proton momentum distributions from recent neutron scattering data with those calculated from two electronic structure based models. We find that below 500 K the electrostatic models are not able to even qualitatively account for the sizable vibrational zero-point contribution to the enthalpy of vaporization. This discrepancy is evidence that the change in the proton well upon solvation cannot be entirely explained by electrostatic effects alone.

  16. Employing Hot Wire Anemometry to Directly Measure the Water Balance in a Proton Exchange membrane Fuel Cell

    DEFF Research Database (Denmark)

    Shakhshir, Saher Al; Hussain, Nabeel; Berning, Torsten

    2015-01-01

    Water management in proton exchange membrane fuel cells (PEMFC’s) remains a critical problem for their durability, cost, and performance. Because the anode side of this fuel cell has the tendency to become dehydrated, measuring the water balance can be an important diagnosis tool during fuel cell...... can be directly converted into the fuel cell water balance. In this work, experimental ex-situ results are presented and the elegance and usefulness of this method is demonstrated....

  17. Interaction of ionic liquid with water with variation of water content in 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF6])/TX-100/water ternary microemulsions monitored by solvent and rotational relaxation of coumarin 153 and coumarin 490.

    Science.gov (United States)

    Seth, Debabrata; Chakraborty, Anjan; Setua, Palash; Sarkar, Nilmoni

    2007-06-14

    The interaction of water with room temperature ionic liquid (RTIL) [bmim][PF6] has been studied in [bmim][PF6]/TX-100/water ternary microemulsions by solvent and rotational relaxation of coumarin 153 (C-153) and coumarin 490 (C-490). The rotational relaxation and average solvation time of C-153 and C-490 gradually decrease with increase in water content of the microemulsions. The gradual increase in the size of the microemulsion with increase in w0 (w0=[water]/[surfactant]) is evident from dynamic light scattering measurements. Consequently the mobility of the water molecules also increases. In comparison to pure water the retardation of solvation time in the RTIL containing ternary microemulsions is very less. The authors have also reported the solvation time of C-490 in neat [bmim][PF6]. The solvation time of C-490 in neat [bmim][PF6] is bimodal with time constants of 400 ps and 1.10 ns.

  18. Void-Assisted Ion-Paired Proton Transfer at Water-Ionic Liquid Interfaces.

    Science.gov (United States)

    de Eulate, Eva Alvarez; Silvester, Debbie S; Arrigan, Damien W M

    2015-12-01

    At the water-trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H(+)) and deuterium ions (D(+)) was identified. Alkali metal cations (such as Li(+), Na(+), K(+)) did not undergo this transfer. H(+)/D(+) transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP](-), resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton-coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

  19. The calculation of proton and secondary electron stopping powers in liquid water.

    Science.gov (United States)

    Marouane, Abdelhak; Inchaouh, Jamal; Ouaskit, Said; Fathi, Ahmed

    2012-07-01

    The stopping power of energetic protons in liquid water has been calculated using a new model based on different theoretical and semi-empirical approaches. In this model, we consider the relativistic corrections along with the electronic and nuclear stopping power. The present work accounts for the different interactions made with electrons and nuclei inside the target. Interactions of the incident particle with the target's electrons dominate in the high energy regime; in the low energy regime, the interactions of the projectile with the target nuclei contribute importantly and are included in the calculation. We also compute the stopping cross sections and the stopping power of secondary electrons ejected from proton and hydrogen ionization impact, and generated by hydrogen electron loss processes. The consideration of secondary electrons' stopping power can contribute to the study of nano-dosimetry. Our results are in good agreement with existing experimental data. This calculation model can be useful for different applications in medical physics and space radiation health, such as hadron therapy for cancer treatment or radiation protection for astronauts.

  20. Low resolution 1H NMR assignment of proton populations in pound cake and its polymeric ingredients.

    Science.gov (United States)

    Luyts, A; Wilderjans, E; Waterschoot, J; Van Haesendonck, I; Brijs, K; Courtin, C M; Hills, B; Delcour, J A

    2013-08-15

    Based on a model system approach, five different proton populations were distinguished in pound cake crumb using one dimensional low resolution (1)H NMR spectroscopy. In free induction decay (FID) measurements, proton populations were assigned to (i) non-exchanging CH protons of crystalline starch, proteins and crystalline fat and (ii) non-exchanging CH protons of amorphous starch and gluten, which are in little contact with water. In Carr-Purcell-Meiboom-Gill (CPMG) measurements, three proton populations were distinguished. The CPMG population with the lowest mobility and the FID population with the highest mobility represent the same proton population. The two CPMG proton populations with the highest mobility were assigned to exchanging protons (i.e., protons of water, starch, gluten, egg proteins and sugar) and protons of lipids (i.e., protons of egg yolk lipids and amorphous lipid fraction of margarine) respectively. Based on their spin-lattice relaxation times (T1), two dimensional (1)H NMR spectroscopy further resolved the two proton populations with the highest mobility into three and two proton populations, respectively.

  1. Are there Helium-like Protonic States of Individual Water Molecules in Liquid H2O?

    CERN Document Server

    Mueller-Herold, Ulrich

    2015-01-01

    Are there indications that individual H2O molecules in liquid water can loose their bent structure, i.e. that the protons give up their rigid angular correlation and behave largely uncorrelated, similar to electrons in the ground-state of helium? In agreement with the two-state picture of liquid water this would allow for the thermal coexistence of tetraedrically coordinated and spherical water molecules in the liquid. In the Hooke-Calogero model of a confined triatomic of XY2-type it is shown that energetically low-lying zero orbital-momentum states, which are bent if unconfined can change to helium-like shape under increasing confinement strength f. For the respective states this occurs at different values for f. It turns out that at f = 2.79 a bent and a helium-like state can thermally coexist. In order to characterize more precisely 'helium-like' angular correlation a maximum entropy estimate for the marginal correlation of electrons in the helium ground state is given. KEY WORDS: Liquid water, molecular ...

  2. Decoupling hydrogen and oxygen evolution during electrolytic water splitting using an electron-coupled-proton buffer.

    Science.gov (United States)

    Symes, Mark D; Cronin, Leroy

    2013-05-01

    Hydrogen is essential to several key industrial processes and could play a major role as an energy carrier in a future 'hydrogen economy'. Although the majority of the world's hydrogen supply currently comes from the reformation of fossil fuels, its generation from water using renewables-generated power could provide a hydrogen source without increasing atmospheric CO₂ levels. Conventional water electrolysis produces H₂ and O₂ simultaneously, such that these gases must be generated in separate spaces to prevent their mixing. Herein, using the polyoxometalate H₃PMo₁₂O₄₀, we introduce the concept of the electron-coupled-proton buffer (ECPB), whereby O₂ and H₂ can be produced at separate times during water electrolysis. This could have advantages in preventing gas mixing in the headspaces of high-pressure electrolysis cells, with implications for safety and electrolyser degradation. Furthermore, we demonstrate that temporally separated O₂ and H₂ production allows greater flexibility regarding the membranes and electrodes that can be used in water-splitting cells.

  3. Hydrogen bonding and vibrational energy relaxation of interfacial water: A full DFT molecular dynamics simulation.

    Science.gov (United States)

    Jeon, Jonggu; Hsieh, Cho-Shuen; Nagata, Yuki; Bonn, Mischa; Cho, Minhaeng

    2017-07-28

    The air-water interface has been a subject of extensive theoretical and experimental studies due to its ubiquity in nature and its importance as a model system for aqueous hydrophobic interfaces. We report on the structure and vibrational energy transfer dynamics of this interfacial water system studied with equilibrium and non-equilibrium molecular dynamics simulations employing a density functional theory -based description of the system and the kinetic energy spectral density analysis. The interfacial water molecules are found to make fewer and weaker hydrogen (H)-bonds on average compared to those in the bulk. We also find that (i) the H-bonded OH groups conjugate to the free OH exhibit rather low vibrational frequencies (3000-3500 cm(-1)); (ii) the presence of a significant fraction (>10%) of free and randomly oriented water molecules at the interface ("labile water"), neither of whose OH groups are strong H-bond donors; (iii) the inertial rotation of free OH groups, especially from the labile water, contribute to the population decay of excited free OH groups with comparable rate and magnitude as intramolecular energy transfer between the OH groups. These results suggest that the labile water, which might not be easily detectable by the conventional vibrational sum frequency generation method, plays an important role in the surface water dynamics.

  4. Hydrogen bonding and vibrational energy relaxation of interfacial water: A full DFT molecular dynamics simulation

    Science.gov (United States)

    Jeon, Jonggu; Hsieh, Cho-Shuen; Nagata, Yuki; Bonn, Mischa; Cho, Minhaeng

    2017-07-01

    The air-water interface has been a subject of extensive theoretical and experimental studies due to its ubiquity in nature and its importance as a model system for aqueous hydrophobic interfaces. We report on the structure and vibrational energy transfer dynamics of this interfacial water system studied with equilibrium and non-equilibrium molecular dynamics simulations employing a density functional theory -based description of the system and the kinetic energy spectral density analysis. The interfacial water molecules are found to make fewer and weaker hydrogen (H)-bonds on average compared to those in the bulk. We also find that (i) the H-bonded OH groups conjugate to the free OH exhibit rather low vibrational frequencies (3000-3500 cm-1); (ii) the presence of a significant fraction (>10%) of free and randomly oriented water molecules at the interface ("labile water"), neither of whose OH groups are strong H-bond donors; (iii) the inertial rotation of free OH groups, especially from the labile water, contribute to the population decay of excited free OH groups with comparable rate and magnitude as intramolecular energy transfer between the OH groups. These results suggest that the labile water, which might not be easily detectable by the conventional vibrational sum frequency generation method, plays an important role in the surface water dynamics.

  5. Relaxivities of hydrogen protons in aqueous solutions of PEG-coated rod-shaped manganese-nickel-ferrite (Mn{sub 0.4}Ni{sub 0.6}Fe{sub 2}O{sub 4}) nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Iqbal, Yousaf; Bae, Hongsub; Rhee, Ilsu [Kyungpook National University, Daegu (Korea, Republic of); Hong, Sungwook; Hong, Sungwook [Daegu University, Gyeongsan (Korea, Republic of)

    2014-11-15

    Spinel-structured manganese (Mn)-nickel (Ni)-ferrite nanoparticles were synthesized using a chemical co-precipitation method. Coating with PEG (polyethylene glycol) was simultaneously conducted along with the synthesis of Mn-Ni-ferrites. The X-ray diffraction (XRD) and the Fourier-transform infrared (FTIR) analyses revealed a cubic spinel ferrite structure of the synthesized nanoparticles. Transmission electron microscopy (TEM) images showed that the synthesized nanoparticles were rod-shaped with a uniform size distribution and that the average length and width were 15.13 ± 1.32 nm and 3.78 ± 0.71 nm, respectively. The bonding status of PEG on the nanoparticle surface was checked by using FTIR. The relaxivities of the hydrogen protons in the aqueous solutions of the coated particles were determined by using nuclear magnetic resonance (NMR) spectrometry. The T{sub 1} and the T{sub 2} relaxivities were 0.34 ± 0.11 mM{sup -1}s{sup -1} and 29.91 ± 0.98 mM{sup -1}s{sup -1}, respectively. This indicates that the synthesized PEG-coated Mn-Ni-ferrite nanoparticles are suitable for use as T{sub 2} contrast agents.

  6. Total water, phosphorus relaxation and inter-atomic organic to inorganic interface are new determinants of trabecular bone integrity.

    Science.gov (United States)

    Rai, Ratan Kumar; Barbhuyan, Tarun; Singh, Chandan; Mittal, Monika; Khan, Mohd Parvez; Sinha, Neeraj; Chattopadhyay, Naibedya

    2013-01-01

    Bone is the living composite biomaterial having unique structural property. Presently, there is a considerable gap in our understanding of bone structure and composition in the native state, particularly with respect to the trabecular bone, which is metabolically more active than cortical bones, and is readily lost in post-menopausal osteoporosis. We used solid-state nuclear magnetic resonance (NMR) to compare trabecular bone structure and composition in the native state between normal, bone loss and bone restoration conditions in rat. Trabecular osteopenia was induced by lactation as well as prolonged estrogen deficiency (bilateral ovariectomy, Ovx). Ovx rats with established osteopenia were administered with PTH (parathyroid hormone, trabecular restoration group), and restoration was allowed to become comparable to sham Ovx (control) group using bone mineral density (BMD) and µCT determinants. We used a technique combining (1)H NMR spectroscopy with (31)P and (13)C to measure various NMR parameters described below. Our results revealed that trabecular bones had diminished total water content, inorganic phosphorus NMR relaxation time (T1) and space between the collagen and inorganic phosphorus in the osteopenic groups compared to control, and these changes were significantly reversed in the bone restoration group. Remarkably, bound water was decreased in both osteopenic and bone restoration groups compared to control. Total water and T1 correlated strongly with trabecular bone density, volume, thickness, connectivity, spacing and resistance to compression. Bound water did not correlate with any of the microarchitectural and compression parameters. We conclude that total water, T1 and atomic space between the crystal and organic surface are altered in the trabecular bones of osteopenic rats, and PTH reverses these parameters. Furthermore, from these data, it appears that total water and T1 could serve as trabecular surrogates of micro-architecture and compression

  7. Total water, phosphorus relaxation and inter-atomic organic to inorganic interface are new determinants of trabecular bone integrity.

    Directory of Open Access Journals (Sweden)

    Ratan Kumar Rai

    Full Text Available Bone is the living composite biomaterial having unique structural property. Presently, there is a considerable gap in our understanding of bone structure and composition in the native state, particularly with respect to the trabecular bone, which is metabolically more active than cortical bones, and is readily lost in post-menopausal osteoporosis. We used solid-state nuclear magnetic resonance (NMR to compare trabecular bone structure and composition in the native state between normal, bone loss and bone restoration conditions in rat. Trabecular osteopenia was induced by lactation as well as prolonged estrogen deficiency (bilateral ovariectomy, Ovx. Ovx rats with established osteopenia were administered with PTH (parathyroid hormone, trabecular restoration group, and restoration was allowed to become comparable to sham Ovx (control group using bone mineral density (BMD and µCT determinants. We used a technique combining (1H NMR spectroscopy with (31P and (13C to measure various NMR parameters described below. Our results revealed that trabecular bones had diminished total water content, inorganic phosphorus NMR relaxation time (T1 and space between the collagen and inorganic phosphorus in the osteopenic groups compared to control, and these changes were significantly reversed in the bone restoration group. Remarkably, bound water was decreased in both osteopenic and bone restoration groups compared to control. Total water and T1 correlated strongly with trabecular bone density, volume, thickness, connectivity, spacing and resistance to compression. Bound water did not correlate with any of the microarchitectural and compression parameters. We conclude that total water, T1 and atomic space between the crystal and organic surface are altered in the trabecular bones of osteopenic rats, and PTH reverses these parameters. Furthermore, from these data, it appears that total water and T1 could serve as trabecular surrogates of micro-architecture and

  8. Picosecond Fluorescence Dynamics of Tryptophan and 5-Fluorotryptophan in Monellin : Slow Water-Protein Relaxation Unmasked

    NARCIS (Netherlands)

    Xu, Jianhua; Chen, Binbin; Callis, Patrik Robert; Muiño, Pedro L; Rozeboom, Henriette J; Broos, Jaap; Toptygin, Dmitri; Brand, Ludwig; Knutson, Jay R

    2015-01-01

    Time Dependent Fluorescence Stokes (emission wavelength) Shifts (TDFSS) from tryptophan (Trp) following sub-picosecond excitation are increasingly used to investigate protein dynamics, most recently enabling active research interest into water dynamics near the surface of proteins. Unlike many fluor

  9. Picosecond Fluorescence Dynamics of Tryptophan and 5-Fluorotryptophan in Monellin : Slow Water-Protein Relaxation Unmasked

    NARCIS (Netherlands)

    Xu, Jianhua; Chen, Binbin; Callis, Patrik Robert; Muiño, Pedro L; Rozeboom, Henriette J; Broos, Jaap; Toptygin, Dmitri; Brand, Ludwig; Knutson, Jay R

    2015-01-01

    Time Dependent Fluorescence Stokes (emission wavelength) Shifts (TDFSS) from tryptophan (Trp) following sub-picosecond excitation are increasingly used to investigate protein dynamics, most recently enabling active research interest into water dynamics near the surface of proteins. Unlike many

  10. DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

    NARCIS (Netherlands)

    García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard

    2016-01-01

    DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a

  11. Employing Hot Wire Anemometry to Directly Measure the Water Balance of a Commercial Proton Exchange Membrane Fuel Cell Stack

    DEFF Research Database (Denmark)

    Shakhshir, Saher Al; Berning, Torsten

    2016-01-01

    Proton exchange membrane fuel cells (PEMFC’s) are currently being commercialized for various applications ranging from automotive (e.g. the Toyota Mirai) to stationary such as powering telecom backup units. In PEMFC’s, oxygen from air is internally combined with hydrogen to form water and produce...

  12. Quantitative Measurement of Longitudinal and Transverse Cross-Relaxation Rates: An Application to the Analysis of the Internal Dynamics of Ranalexin in Water and Trifluoroethanol

    Science.gov (United States)

    Malliavin, T. E.; Desvaux, H.; Aumelas, A.; Chavanieu, A.; Delsuc, M. A.

    1999-09-01

    We describe a quantitative processing method which gives access to the longitudinal and transverse cross-relaxation rates from off-resonance ROESY intensities. This method takes advantage of the dependence of the off-resonance ROESY experiments at any mixing time and any spin-lock angle θ on two relaxation matrices, the longitudinal and the transverse ones. This allows one to take into account multistep magnetization transfers even if the measurements are performed only at one or two mixing times. The ratio of the longitudinal to transverse cross-relaxation rates can then be used as a local indicator of the internal dynamics, without assuming a structure or a model of motion. After validation of this processing method by numerical simulations, it is applied to the analysis of the dynamics of the peptide ranalexin dissolved in pure water and in water/TFE.

  13. Water, proton, and oxygen transport in high IEC, short side chain PFSA ionomer membranes: consequences of a frustrated network.

    Science.gov (United States)

    Luo, Xiaoyan; Holdcroft, Steven; Mani, Ana; Zhang, Yongming; Shi, Zhiqing

    2011-10-28

    The effect of ion exchange capacity (IEC) on the water sorption properties of high IEC, short side chain (SSC) PFSA ionomer membranes, and the relationships between water content, proton conductivity, proton mobility, water permeation, oxygen diffusion, and oxygen permeation are investigated. SSC PFSA ionomer membranes possessing 1.3, 1.4, and 1.5 mmol g(-1) IEC are compared to a series of long side chain (LSC) PFSA ionomer membranes ranging in IEC from 0.9 to 1.13 mmol g(-1). At 25 °C, fully-hydrated SSC ionomer membranes are characterized as possessing higher water contents (56-75 vol%), moderate λ values (15-18), high analytical acid concentrations (2-2.8 M), and moderate conductivity (88-115 mS/cm); but lower than anticipated effective proton mobility. Complementary measurements of water permeability, oxygen diffusion, and oxygen permeability also yield lower than expected values given their much higher water contents. Potential benefits afforded by reducing the side chain length of PFSA ionomer membranes, such as increased crystallinity, higher IEC, and high hydrated acid concentration are offset by a less-developed, frustrated hydrophilic percolation network, which provides a motivation for future improvements of transport properties for this class of material. This journal is © the Owner Societies 2011

  14. Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer. II. Infrared spectrum and vibrational dynamics

    DEFF Research Database (Denmark)

    Vendrell, Oriol; Gatti, Fabien; Meyer, Hans-Dieter

    2007-01-01

    the fundamentals and several overtones of the vibrational motion are computed. The spectrum of H5O2+ is shaped to a large extent by couplings of the proton-transfer motion to large amplitude fluxional motions of the water molecules, water bending and water-water stretch motions. These couplings are identified...... and discussed, and the corresponding spectral lines are assigned. The large couplings featured by H5O2+ do not hinder, however, to describe the coupled vibrational motion by well defined simple types of vibration (stretching, bending; etc.) based on well defined modes of vibration, in terms of which...

  15. Impact of heat and water management on proton exchange membrane fuel cells degradation in automotive application

    Science.gov (United States)

    Nandjou, F.; Poirot-Crouvezier, J.-P.; Chandesris, M.; Blachot, J.-F.; Bonnaud, C.; Bultel, Y.

    2016-09-01

    In Proton Exchange Membrane Fuel Cells, local temperature is a driving force for many degradation mechanisms such as hygrothermal deformation and creep of the membrane, platinum dissolution and bipolar plates corrosion. In order to investigate and quantify those effects in automotive application, durability testing is conducted in this work. During the ageing tests, the local performance and temperature are investigated using in situ measurements of a printed circuit board. At the end of life, post-mortem analyses of the aged components are conducted. The experimental results are compared with the simulated temperature and humidity in the cell obtained from a pseudo-3D multiphysics model in order to correlate the observed degradations to the local conditions inside the stack. The primary cause of failure in automotive cycling is pinhole/crack formation in the membrane, induced by high variations of its water content over time. It is also observed that water condensation largely increases the probability of the bipolar plates corrosion while evaporation phenomena induce local deposits in the cell.

  16. Electronic stopping power of liquid water for protons down to the Bragg peak.

    Science.gov (United States)

    Emfietzoglou, D; Pathak, A; Nikjoo, H

    2007-01-01

    An improved dielectric response model that accurately represents the recent experimental data for liquid water over the whole Bethe surface is used to calculate the electronic stopping power of protons (of fixed-charge) in liquid water from several MeV down to the Bragg peak region. The results are by approximately 20% lower than the ICRU values and earlier studies. A shell-correction term with a contribution of 15-20% to Bethe's high-energy stopping number is obtained. The present work offers a first-principle approach for stopping power calculations that overcomes the well-known limitations of Bethe's stopping theory, namely, the need for separate determination of the mean excitation energy (the I-value) and the shell-corrections. In particular, all type of inner-shell effects are built into the model through the kinematically restricted integrals over the Bethe surface. The net contribution of higher-order corrections is found to be minimal over most of the present range. Thus, within the uncertainty of the dielectric model (few %) the present calculations are 'exact' down to approximately 100 keV.

  17. Nuclear magnetic relaxation by the dipolar EMOR mechanism: Multi-spin systems

    Science.gov (United States)

    Chang, Zhiwei; Halle, Bertil

    2017-08-01

    In aqueous systems with immobilized macromolecules, including biological tissues, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. Starting from the stochastic Liouville equation, we have previously developed a rigorous EMOR relaxation theory for dipole-coupled two-spin and three-spin systems. Here, we extend the stochastic Liouville theory to four-spin systems and use these exact results as a guide for constructing an approximate multi-spin theory, valid for spin systems of arbitrary size. This so-called generalized stochastic Redfield equation (GSRE) theory includes the effects of longitudinal-transverse cross-mode relaxation, which gives rise to an inverted step in the relaxation dispersion profile, and coherent spin mode transfer among solid-like spins, which may be regarded as generalized spin diffusion. The GSRE theory is compared to an existing theory, based on the extended Solomon equations, which does not incorporate these phenomena. Relaxation dispersion profiles are computed from the GSRE theory for systems of up to 16 protons, taken from protein crystal structures. These profiles span the range from the motional narrowing limit, where the coherent mode transfer plays a major role, to the ultra-slow motion limit, where the zero-field rate is closely related to the strong-collision limit of the dipolar relaxation rate. Although a quantitative analysis of experimental data is beyond the scope of this work, it is clear from the magnitude of the predicted relaxation rate and the shape of the relaxation dispersion profile that the dipolar EMOR mechanism is the principal cause of water-1H low-field longitudinal relaxation in aqueous systems of immobilized macromolecules, including soft biological tissues. The relaxation theory developed here therefore provides a basis for molecular-level interpretation of endogenous soft

  18. Spin Echo Studies on Cellular Water

    CERN Document Server

    Chang, D C; Nichols, B L; Rorschach, H E

    2014-01-01

    Previous studies indicated that the physical state of cellular water could be significantly different from pure liquid water. To experimentally investigate this possibility, we conducted a series of spin-echo NMR measurements on water protons in rat skeletal muscle. Our result indicated that the spin-lattice relaxation time and the spin-spin relaxation time of cellular water protons are both significantly shorter than that of pure water (by 4.3-fold and 34-fold, respectively). Furthermore, the spin diffusion coefficient of water proton is almost 1/2 of that of pure water. These data suggest that cellular water is in a more ordered state in comparison to pure water.

  19. Proton-transfer reactions of acridine in water-containing ionic-liquid-rich mixtures.

    Science.gov (United States)

    Kumar, Vinod; Pandey, Ashish; Pandey, Siddharth

    2013-12-02

    To assess the potential of ionic liquids (ILs) as a solubilizing media that facilitates proton-transfer reactions, acridine prototropism is investigated using UV/Vis molecular absorbance as well as steady-state and time-resolved fluorescence with different ILs in the presence of a small amount of dilute acid or base. It is found that protonation and deprotonation of acridine, when dissolved in different ILs, can be triggered by the addition of a small amount of dilute aqueous HCl and NaOH, respectively, in both the ground and excited states, irrespective of the identity of the IL. However, the amount of dilute acid/base needed to protonate/deprotonate acridine dissolved in different ILs is found to vary from one IL to another. Steady-state fluorescence measurements also imply the presence of interactions between the acidic proton(s) of IL cation and excited acridine. The interconversion of neutral and protonated acridine, as well as the presence of a weakly fluorescent complex between excited acridine and the acidic proton(s) of the IL cation, is further corroborated by the parameters recovered from the fitting of the excited-state intensity-decay data. It is established that ILs as solubilizing media readily support facile proton transfer in both ground and excited states.

  20. Consideration of fractal and ion-water cooperative interactions in aqueous Na2SO4 and K2SO4 solutions by dielectric relaxation spectroscopy

    Science.gov (United States)

    Liu, Shuang; Jia, Guo-zhu; Zhang, Shu

    2016-01-01

    This paper presents the analysis of the fractal and the ion-water cooperative interactions in aqueous Na2SO4 and K2SO4 solutions underlying the Cole-Cole symmetrical broadening and depicts the Cole-Cole relaxation process. Fractal analysis with α(ln(τ)) diagram from dielectric relaxation spectroscopy (DRS) draws a consistent microscopic picture of ion-water cooperative interactions in aqueous Na2SO4 and K2SO4 solutions. The density of the water molecules perturbed by ions in the hydration shell almost linearly increases with salt concentrations. The water molecules network perturbed by ions contributing to dielectric constant beyond the first hydration shell is obtained.

  1. Spencer-Attix water/medium stopping-power ratios for the dosimetry of proton pencil beams.

    Science.gov (United States)

    Gomà, C; Andreo, P; Sempau, J

    2013-04-21

    This paper uses Monte Carlo simulations to calculate the Spencer-Attix water/medium stopping-power ratios (sw, med) for the dosimetry of scanned proton pencil beams. It includes proton energies from 30 to 350 MeV and typical detection materials such as air (ionization chambers), radiochromic film, gadolinium oxysulfide (scintillating screens), silicon and lithium fluoride. Track-ends and particles heavier than protons were found to have a negligible effect on the water/air stopping-power ratios (sw, air), whereas the mean excitation energy values were found to carry the largest source of uncertainty. The initial energy spread of the beam was found to have a minor influence on the sw, air values in depth. The water/medium stopping-power ratios as a function of depth in water were found to be quite constant for air and radiochromic film-within 2.5%. Also, the sw, med values were found to have no clinically relevant dependence on the radial distance-except for the case of gadolinium oxysulfide and proton radiography beams. In conclusion, the most suitable detection materials for depth-dose measurements in water were found to be air and radiochromic film active layer, although a small correction is still needed to compensate for the different sw, med values between the plateau and the Bragg peak region. Also, all the detection materials studied in this work-except for gadolinium oxysulfide-were found to be suitable for lateral dose profiles and field-specific dose distribution measurements in water.

  2. Electrochemical studies of water insertion and proton -ceramic interaction in substituted perovskite SrZr 0.9 Ln 0.1 O 2.95

    OpenAIRE

    Lacroix, Olivier; Rahmouni, Kamal; Sirat, Abdelkader; Takenouti, Hisasi; Deslouis, Claude; Keddam, Michel; Sala, Béatrice

    2014-01-01

    International audience; Because of their high ionic conduction even at relatively low temperatures, proton conducting ceramics are one of the most promising electrolytes for fuel cell. In contrast to oxide-ion conductors, proton-conducting systems, especially in an electrolyser plant, could operate below 600°C, critical temperature for mechanical and hot corrosion resistance of common stainless steels. Proton conduction in perovskite type ceramic was analyzed under the water molecules inserti...

  3. Calculation of the protons stopping power in water using dielectric formalism in the MELF-GOS approach; Calculo do poder de freamento de protons em agua utilizando o formalismo dieletrico na aproximacao MELF-GOS

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Franciane; Mazer, Amanda Cristina; Hormaza, Joel Mesa [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Botucatu, SP (Brazil)

    2016-07-01

    In order to calculate the stopping power of protons, there are many very successful models at high energies, which are extrapolated to low-energy regions. From the point of view of application of proton beam in cancer treatment is just this low energy region the most relevant due to the dose deposition profile in depth for protons. In this work, we present a calculation of the stopping power of protons in a water target using the dielectric formalism in MELF-GOS approach. The results when compared to other models show good agreement for energies above 100 keV and lower values below this energy. This result should impact the range of values of protons and the Bragg peak position. (author)

  4. Fourier transform infrared difference and time-resolved infrared detection of the electron and proton transfer dynamics in photosynthetic water oxidation.

    Science.gov (United States)

    Noguchi, Takumi

    2015-01-01

    Photosynthetic water oxidation, which provides the electrons necessary for CO₂ reduction and releases O₂ and protons, is performed at the Mn₄CaO₅ cluster in photosystem II (PSII). In this review, studies that assessed the mechanism of water oxidation using infrared spectroscopy are summarized focusing on electron and proton transfer dynamics. Structural changes in proteins and water molecules between intermediates known as Si states (i=0-3) were detected using flash-induced Fourier transform infrared (FTIR) difference spectroscopy. Electron flow in PSII and proton release from substrate water were monitored using the infrared changes in ferricyanide as an exogenous electron acceptor and Mes buffer as a proton acceptor. Time-resolved infrared (TRIR) spectroscopy provided information on the dynamics of proton-coupled electron transfer during the S-state transitions. In particular, a drastic proton movement during the lag phase (~200μs) before electron transfer in the S3→S0 transition was detected directly by monitoring the infrared absorption of a polarizable proton in a hydrogen bond network. Furthermore, the proton release pathways in the PSII proteins were analyzed by FTIR difference measurements in combination with site-directed mutagenesis, isotopic substitutions, and quantum chemical calculations. Therefore, infrared spectroscopy is a powerful tool for understanding the molecular mechanism of photosynthetic water oxidation. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems.

  5. Calculation of the transport and relaxation properties of dilute water vapor

    Science.gov (United States)

    Hellmann, Robert; Bich, Eckard; Vogel, Eckhard; Dickinson, Alan S.; Vesovic, Velisa

    2009-07-01

    Transport properties of dilute water vapor have been calculated in the rigid-rotor approximation using four different potential energy hypersurfaces and the classical-trajectory method. Results are reported for shear viscosity, self-diffusion, thermal conductivity, and volume viscosity in the dilute-gas limit for the temperature range of 250-2500 K. Of these four surfaces the CC-pol surface of Bukowski et al. [J. Chem. Phys. 128, 094314 (2008)] is in best accord with the available measurements. Very good agreement is found with the most accurate results for viscosity in the whole temperature range of the experiments. For thermal conductivity the deviations of the calculated values from the experimental data increase systematically with increasing temperature to around 5% at 1100 K. For both self-diffusion and volume viscosity, the much more limited number of available measurements are generally consistent with the calculated values, apart from the lower temperature isotopically labeled diffusion measurements.

  6. Complex dielectric permittivity and dielectric relaxation of heavy water along its curve of existence

    Energy Technology Data Exchange (ETDEWEB)

    Nabokov, O.A.; Lyubimov, Yu.A.

    1985-10-01

    The authors previously studied the complex dielectric permittivity of ordinary water at 70-200/sup 0/C. Similar measurements were performed in this work for D/sub 2/O by incomplete filling of a microwave resonator at a frequency of about 9.3 GHz. Distilled 99.8% D/sub 2/O was used. For D/sub 2/O, the value of tau/sub D/T/eta (where eta is the viscosity) increases with increasing temperature, so that at 140/sup 0/C its change goes beyond the limits of error of the measurement of tau/sub D/ and eta. The gradual increase in tau/sub D/T/eta and tau/sub D/D with temperature indicates weakening of the interaction between orientation and translation movements of the liquid D/sub 2/O molecules with increasing temperature. 11 references, 1 figure.

  7. Stochastic relaxation of the contact line of a water drop on a solid substrate subjected to white noise vibration: roles of hysteresis.

    Science.gov (United States)

    Mettu, Srinivas; Chaudhury, Manoj K

    2010-06-01

    Relaxation of the three phase contact line of a sessile drop of water on a low energy surface is studied by subjecting it to a white noise vibration. While a spring force acts on the contact line whenever the contact angle deviates from its equilibrium value, it is opposed by hysteresis. The drop, therefore, remains pinned at a metastable state. With an appropriate amount of vibration, the drop can reach a global equilibrium state irrespective of its initial state, be it advanced or retreated. While the end state is free of hysteresis, the current study sheds light on the dynamics of relaxation that is analyzed in conjunction with a modified Langevin equation. Instead of exhibiting a smooth relaxation as predicted by the Langevin equation with a smooth background potential, stepwise relaxation is observed in most cases. These stepwise relaxations can be explained if the background potential is made slightly corrugated that signifies the existence of metastable states of a drop on a surface. The fluctuation of the displacement of the contact line is highly non-Gaussian. It is shown that an exponential distribution of the displacement fluctuation arises due to the nonlinear hysteresis term in the Langevin equation. The observations of stick-slip motion, the large time of relaxation, and the anomalous displacement fluctuation suggest that hysteresis is present during the relaxation process of the drop even though the final state reached by the drop is free of hysteresis. Finally, we compare the displacement fluctuations of the contact line on two different surfaces: a silicone rubber and a fluorocarbon monolayer. Although the displacement fluctuation is exponential in both cases, the later surface exhibits a greater variance of the distribution than the former plausibly due to differences in hysteresis. This result indicates that the fluctuation of displacement may be used as a tool to study the surface property of a low energy substrate.

  8. Multinuclear solid state nuclear magnetic resonance investigation of water penetration in proton exchange membrane Nafion-117 by mechanical spinning.

    Science.gov (United States)

    Sabarinathan, Venkatachalam; Wu, Zhen; Cheng, Ren-Hao; Ding, Shangwu

    2013-05-30

    (1)H, (17)O, and (19)F solid state NMR spectroscopies have been used to investigate water penetration in Nafion-117 under mechanical spinning. It is found that both (1)H and (17)O spectra depend on the orientation of the membrane with respect to the magnetic field. The intensities of the side chain (19)F spectra depend slightly on the orientation of membrane with respect to the magnetic field, but the backbone (19)F spectra do not exhibit orientation dependence. By analyzing the orientation dependent (1)H and (17)O spectra and time-resolved (1)H spectra, we show that the water loaded in Nafion-117, under high spinning speed, may penetrate into regions that are normally inaccessible by water. Water penetration is enhanced as the spinning speed is increased or the spinning time is increased. In the meantime, mechanical spinning accelerates water exchange. It is also found that water penetration by mechanical spinning is persistent; i.e., after spinning, water remains in those newly found regions. While water penetration changes the pores and channels in Nafion, (19)F spectra indicate that the chemical environments of the polymer backbone do not show change. These results provide new insights about the structure and dynamics of Nafion-117 and related materials. They are relevant to proton exchange membrane aging and offer enlightening points of view on antiaging and modification of this material for better proton conductivity. It is also interesting to view this phenomenon in the perspective of forced nanofiltration.

  9. Thermal and water management of low temperature Proton Exchange Membrane Fuel Cell in fork-lift truck power system

    DEFF Research Database (Denmark)

    Hosseinzadeh, Elham; Rokni, Masoud; Rabbani, Raja Abid

    2013-01-01

    A general zero-dimensional Proton Exchange Membrane Fuel Cell (PEMFC) model has been developed for forklift truck application. The balance of plant (BOP) comprises of a compressor, an air humidifier, a set of heat exchangers and a recirculation pump. Water and thermal management of the fuel cell...... voltage when membrane is fully hydrated otherwise it causes a drastic voltage drop in the stack. Furthermore, by substituting liquid water with water-ethylene glycol mixture of 50%, the mass flow of coolant increases by about 32-33% in the inner loop and 60-65% in the outer loop for all ranges of current...

  10. The investigation of excited state proton transfer mechanism in water-bridged 7-azaindole

    Science.gov (United States)

    Zhang, Yong-Jia; Zhao, Jin-Feng; Li, Yong-Qing

    2016-01-01

    Based on the time-dependent density functional theory (TDDFT), the excited-state intermolecular proton transfer (ESIPT) mechanism of water-bridged 7-azaindole has been investigated theoretically. The calculations of primary bond lengths and the IR vibrational spectra between the S0 state and the S1 state that verified the intramolecular hydrogen bond were strengthened. The fact that reproduced experimental absorbance and fluorescence emission spectra well theoretically demonstrate that the TDDFT theory we adopted is reasonable and effective. In addition, intramolecular charge transfer based on the frontier molecular orbitals demonstrated the indication of the ESIPT reaction. The constructed potential energy curves of ground state and the first excited state based on keeping the H2···O3 and H6···N7 distances fixed at a series of values have been used to illustrate the ESIPT process. A relative lower barrier of 5.94 kcal/mol in the S1 state potential energy curve for type II (lower than that of 9.82 kcal/mol in the S1 state for type I) demonstrates that type II ESIPT process occurs firstly in 7Al-2H2O complex.

  11. Quantification of Water-Soluble Metabolites in Medicinal Mushrooms Using Proton NMR Spectroscopy.

    Science.gov (United States)

    Lo, Yu-Chang; Chien, Shih-Chang; Mishchuk, Darya O; Slupsky, Carolyn M; Mau, Jeng-Leun

    2016-01-01

    The water-soluble metabolites in 5 mushrooms were identified and quantified using proton nuclear magnetic resonance (NMR) spectroscopy and software for targeted metabolite detection and quantification. In total, 35 compounds were found in Agaricus brasiliensis, 25 in Taiwanofungus camphoratus, 23 in Ganoderma lucidum (Taiwan) and Lentinus edodes, and 16 in G. lucidum (China). Total amounts of all identified metabolites in A. brasiliensis, T. camphoratus, G. lucidum, G. lucidum (China), and L. edodes were 149,950.51, 12,834.18, 9,549.09, 2,788.41, and 111,726.51 mg/kg dry weight, respectively. These metabolites were categorized into 4 groups: free amino acids and derivatives, carbohydrates, carboxylic acids, and nucleosides. Carbohydrates were the most abundant metabolites among all 4 groups, with mannitol having the highest concentration among all analyzed metabolites (848-94,104 mg/kg dry weight). Principal components analysis (PCA) showed obvious distinction among the metabolites of the 5 different kinds of mushrooms analyzed in this study. Thus PCA could provide an optional analytical way of identifying and recognizing the compositions of flavor products. Furthermore, the results of this study demonstrate that NMRbased metabolomics is a powerful tool for differentiating between various medicinal mushrooms.

  12. Energy related germination and survival rates of water-imbibed Arabidopsis seeds irradiated with protons

    Energy Technology Data Exchange (ETDEWEB)

    Qin, H.L. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Xue, J.M. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Lai, J.N. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Wang, J.Y. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Zhang, W.M. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Miao, Q. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Yan, S. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Zhao, W.J. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); He, F. [School of Life Science, Peking University, Beijing 100871 (China); Gu, H.Y. [School of Life Science, Peking University, Beijing 100871 (China); Wang, Y.G. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China)]. E-mail: ygwang@pku.edu.cn

    2006-04-15

    In order to investigate the influence of ion energy on the germination and survival rates, water-imbibed Arabidopsis seeds were irradiated with protons in atmosphere. The ion fluence used in this experiment was in the range of 4 x 10{sup 9}-1 x 10{sup 14} ions/cm{sup 2}. The ion energy is from 1.1 MeV to 6.5 MeV. According to the structure of the seed and TRIM simulation, the ions with the energy of 6.5 MeV can irradiate the shoot apical meristem directly whereas the ions with the energy of 1.1 MeV cannot. The results showed that both the germination and survival rates decrease while increasing the ion fluence, and the fluence-respond curve for each energy has different character. Besides the shoot apical meristem (SAM), which is generally considered as the main radiobiological target, the existence of a secondary target around SAM is proposed in this paper.

  13. Evaluation of the water-equivalence of plastic materials in low- and high-energy clinical proton beams.

    Science.gov (United States)

    Lourenço, A; Shipley, D; Wellock, N; Thomas, R; Bouchard, H; Kacperek, A; Fracchiolla, F; Lorentini, S; Schwarz, M; MacDougall, N; Royle, G; Palmans, H

    2017-05-21

    The aim of this work was to evaluate the water-equivalence of new trial plastics designed specifically for light-ion beam dosimetry as well as commercially available plastics in clinical proton beams. The water-equivalence of materials was tested by computing a plastic-to-water conversion factor, [Formula: see text]. Trial materials were characterized experimentally in 60 MeV and 226 MeV un-modulated proton beams and the results were compared with Monte Carlo simulations using the FLUKA code. For the high-energy beam, a comparison between the trial plastics and various commercial plastics was also performed using FLUKA and Geant4 Monte Carlo codes. Experimental information was obtained from laterally integrated depth-dose ionization chamber measurements in water, with and without plastic slabs with variable thicknesses in front of the water phantom. Fluence correction factors, [Formula: see text], between water and various materials were also derived using the Monte Carlo method. For the 60 MeV proton beam, [Formula: see text] and [Formula: see text] factors were within 1% from unity for all trial plastics. For the 226 MeV proton beam, experimental [Formula: see text] values deviated from unity by a maximum of about 1% for the three trial plastics and experimental results showed no advantage regarding which of the plastics was the most equivalent to water. Different magnitudes of corrections were found between Geant4 and FLUKA for the various materials due mainly to the use of different nonelastic nuclear data. Nevertheless, for the 226 MeV proton beam, [Formula: see text] correction factors were within 2% from unity for all the materials. Considering the results from the two Monte Carlo codes, PMMA and trial plastic #3 had the smallest [Formula: see text] values, where maximum deviations from unity were 1%, however, PMMA range differed by 16% from that of water. Overall, [Formula: see text] factors were deviating more from unity than [Formula: see text] factors

  14. Enhancement of 4-electron O2 reduction by a Cu(ii)-pyridylamine complex via protonation of a pendant pyridine in the second coordination sphere in water.

    Science.gov (United States)

    Kotani, Hiroaki; Yagi, Tomomi; Ishizuka, Tomoya; Kojima, Takahiko

    2015-09-07

    We have synthesised a novel copper(ii) complex with a pyridine pendant as a proton relay port for electrocatalytic 4e(-) reduction of O2 in water. The enhancement of the electrocatalytic O2 reduction via protonation of the pyridine pendant is demonstrated in comparison with a copper(ii) complex without the pyridine pendant.

  15. Water mobility and microstructure evolution in the germinating Medicago truncatula seed studied by NMR relaxometry. A revisited interpretation of multicomponent relaxation.

    Science.gov (United States)

    Lahaye, Marc; Falourd, Xavier; Limami, Anis M; Foucat, Loïc

    2015-02-18

    The water status of Medicago truncatula Gaertn. seed was followed by low-field NMR relaxometry during germination with and without oryzalin or fusicoccin used as growth modulators. T1 and T2 relaxation times and proportions P1 and P2 were determined on fresh, frozen, and freeze-thawed samples to characterize changes in water dynamics and compartmentation and in the nonfreezing water fraction. The results demonstrate that low-field NMR relaxometry allowed differentiating germination phases and events occurring during them as well as perturbations related to the presence of growth modulators. The results provide clear evidence that the classical multicomponent relaxation interpretation cannot directly relate T2 components and morphological compartments in biological tissue.

  16. Factors for converting dose measured in polystyrene phantoms to dose reported in water phantoms for incident proton beams

    Energy Technology Data Exchange (ETDEWEB)

    Moyers, M. F.; Vatnitsky, A. S.; Vatnitsky, S. M. [Loma Linda University Medical Center, Loma Linda, California 92354 (United States); Guthrie Clinic/Robert Packard Hospital, Sayre, Pennsylvania 18840 (United States); EBG MedAustron, Wiener Neustadt, Austria A2700 (Austria)

    2011-10-15

    Purpose: Previous dosimetry protocols allowed calibrations of proton beamline dose monitors to be performed in plastic phantoms. Nevertheless, dose determinations were referenced to absorbed dose-to-muscle or absorbed dose-to-water. The IAEA Code of Practice TRS 398 recommended that dose calibrations be performed with ionization chambers only in water phantoms because plastic-to-water dose conversion factors were not available with sufficient accuracy at the time of its writing. These factors are necessary, however, to evaluate the difference in doses delivered to patients if switching from calibration in plastic to a protocol that only allows calibration in water. Methods: This work measured polystyrene-to-water dose conversion factors for this purpose. Uncertainties in the results due to temperature, geometry, and chamber effects were minimized by using special experimental set-up procedures. The measurements were validated by Monte Carlo simulations. Results: At the peak of non-range-modulated beams, measured polystyrene-to-water factors ranged from 1.015 to 1.024 for beams with ranges from 36 to 315 mm. For beams with the same ranges and medium sized modulations, the factors ranged from 1.005 to 1.019. The measured results were used to generate tables of polystyrene-to-water dose conversion factors. Conclusions: The dose conversion factors can be used at clinical proton facilities to support beamline and patient specific dose per monitor unit calibrations performed in polystyrene phantoms.

  17. Synthesis and Water Uptake of Sulfonated Poly (phthalazinone ether sulfone ketone)/Polyacrylic Acid Proton Exchange Membranes

    Institute of Scientific and Technical Information of China (English)

    Xue Mei WU; Gao Hong HE; Lin GAO; Shuang GU; Zheng Wen HU; Ping Jing YAO

    2006-01-01

    Novel SPPESK/PAA composite proton exchange membranes with semi-interpenetrating polymer network (sIPN) structure have been synthesized through the in-situ polymerization of acrylic acid (AA) in the presence of sulfonated poly (phthalazinone ether sulfone ketone) (SPPESK). The composite membranes were identified by FT-IR analysis. Water uptake of the composite membranes was as high as 89.7% at 90℃, nearly one time higher than that of the corresponding SPPESK membrane.

  18. Low-energy proton stopping power of N2, O2 and water vapor and deviations from Bragg's rule

    Science.gov (United States)

    Xu, Y. J.; Khandelwal, G. S.; Wilson, J. W.

    1984-01-01

    A modified local plasma model, based on the works of Lindhard and Winther; and Bethe, Brown, and Walske, is established. The Gordon-Kim model for molecular electron density is used to calculate stopping power of N2, O2, and water vapor for protons of energy ranging from 40 keV to 2.5 MeV, resulting in good agreement with experimental data. Deviations from Bragg's rule are evaluated and are discussed under the present theoretical model.

  19. Sulphonated imidized graphene oxide (SIGO) based polymer electrolyte membrane for improved water retention, stability and proton conductivity

    Science.gov (United States)

    Pandey, Ravi P.; Shahi, Vinod K.

    2015-12-01

    Sulphonated imidized graphene oxide (SIGO) (graphene oxide (GO) tethered sulphonated polyimide) has been successfully synthesized by polycondensation reaction using dianhydride and sulphonated diamine. Polymer electrolyte membranes (PEMs) are prepared by using SIGO (different wt%) and sulphonated poly(imide) (SPI). Resultant SPI/SIGO composite PEMs exhibit improved stabilities (thermal, mechanical and oxidative) and good water-retention properties (high bound water content responsible for proton conduction at high temperature by internal self-humidification). Incorporation of covalent bonded SIGO into SPI matrix results hydrophobic-hydrophilic phase separation and facile architecture of proton conducting path. Well optimized sulphonated poly(imide)/sulphonated imidized graphene oxide (15 wt%) (SPI/SIGO-15) composite membrane shows 2.24 meq g-1 ion-exchange capacity (IEC); 11.38 × 10-2 S cm-1 proton conductivity; 5.12% bound water content; and 10.52 × 10-7 cm2 s-1 methanol permeability. Maximum power density for pristine SPI membrane (57.12 mW cm-2) improves to 78.53 mW cm-2 for SPI/SIGO-15 membrane, in single-cell direct methanol fuel cell (DMFC) test at 70 °C using 2 M methanol fuel. Under similar experimental conditions, Nafion 117 membrane exhibits 62.40 mW cm-2 maximum power density. Reported strategy for the preparation of PEMs, offers a useful protocol for grafting of functionalized inorganic materials with in organic polymer chain by imidization.

  20. Embedding of Hollow Polymer Microspheres with Hydrophilic Shell in Nafion Matrix as Proton and Water Micro-Reservoir

    Directory of Open Access Journals (Sweden)

    Zhaolin Liu

    2012-08-01

    Full Text Available Assimilating hydrophilic hollow polymer spheres (HPS into Nafion matrix by a loading of 0.5 wt % led to a restructured hydrophilic channel, composed of the pendant sulfonic acid groups (–SO3H and the imbedded hydrophilic hollow spheres. The tiny hydrophilic hollow chamber was critical to retaining moisture and facilitating proton transfer in the composite membranes. To obtain such a tiny cavity structure, the synthesis included selective generation of a hydrophilic polymer shell on silica microsphere template and the subsequent removal of the template by etching. The hydrophilic HPS (100–200 nm possessed two different spherical shells, the styrenic network with pendant sulfonic acid groups and with methacrylic acid groups, respectively. By behaving as microreservoirs of water, the hydrophilic HPS promoted the Grotthus mechanism and, hence, enhanced proton transport efficiency through the inter-sphere path. In addition, the HPS with the –SO3H borne shell played a more effective role than those with the –CO2H borne shell in augmenting proton transport, in particular under low humidity or at medium temperatures. Single H2-PEMFC test at 70 °C using dry H2/O2 further verified the impactful role of hydrophilic HPS in sustaining higher proton flux as compared to pristine Nafion membrane.

  1. Absolute quantitative proton NMR spectroscopy based on the amplitude of the local water suppression pulse. Quantification of brain water and metabolites

    DEFF Research Database (Denmark)

    Danielsen, E R; Henriksen, O

    1994-01-01

    Quantification in localized proton NMR spectroscopy has been achieved by various methods in recent years. A new method for absolute quantification is described in this paper. The method simultaneously rules out problems with B1 field inhomogeneity and coil loading, utilizing a relation between...... the locally optimized amplitude of a chemical shift selective water suppression pulse and the acquired signal. Validity and feasibility of quantification using the method of the water suppression pulse is demonstrated. Brain water and cerebral metabolites have been quantified in a study of 12 healthy...

  2. The study of neutron spectra in water bath from Pb target irradiated by 250MeV/u protons

    CERN Document Server

    Li, Yanyan; Ju, Yongqin; Ma, Fei; Zhang, Hongbin; Chen, Liang; Ge, Honglin; Luo, Peng; Zhou, Bin; Zhang, Yanbin; Li, Jianyang; Xu, Junkui; Wang, Songlin; Yang, Yongwei; Yang, Lei

    2014-01-01

    The spallation neutrons were produced by the irradiation of Pb with 250 MeV protons. The Pb target was surrounded by water which was used to slow down the emitted neutrons. The moderated neutrons in the water bath were measured by using the resonance detectors of Au, Mn and In with Cd cover. According to the measured activities of the foils, the neutron flux at different resonance energy were deduced and the epithermal neutron spectra were proposed. Corresponding results calculated with the Monte Carlo code MCNPX were compared with the experimental data to check the validity of the code.

  3. The Effect of Inhomogeneous Compression on Water Transport in the Cathode of a Proton Exchange Membrane Fuel Cell

    DEFF Research Database (Denmark)

    Olesen, Anders Christian; Berning, Torsten; Kær, Søren Knudsen

    2012-01-01

    A three-dimensional, multicomponent, two-fluid model developed in the commercial CFD package CFX 13 (ANSYS Inc.) is used to investigate the effect of porous media compression on water transport in a proton exchange membrane fuel cell (PEMFC). The PEMFC model only consist of the cathode channel, gas...... diffusion layer, microporous layer, and catalyst layer, excluding the membrane and anode. In the porous media liquid water transport is described by the capillary pressure gradient, momentum loss via the Darcy-Forchheimer equation, and mass transfer between phases by a nonequilibrium phase change model...

  4. Antimony doped tin oxides and their composites with tin pyrophosphates as catalyst supports for oxygen evolution reaction in proton exchange membrane water electrolysis

    DEFF Research Database (Denmark)

    Xu, Junyuan; Li, Qingfeng; Hansen, Martin Kalmar

    2012-01-01

    Proton exchange membrane water electrolysers operating at typically 80 °C or at further elevated temperatures suffer from insufficient catalyst activity and durability. In this work, antimony doped tin oxide nanoparticles were synthesized and further doped with an inorganic proton conducting phase...... based on tin pyrophosphates as the catalyst support. The materials showed an overall conductivity of 0.57 S cm−1 at 130 °C under the water vapor atmosphere with a contribution of the proton conduction. Using this composite support, iridium oxide nanoparticle catalysts were prepared and characterized...

  5. Modulation of proton transfer in the water wire of dioxolane-linked gramicidin channels by lipid membranes.

    Science.gov (United States)

    de Godoy, C M; Cukierman, S

    2001-09-01

    Proton conductance (g(H)) in single SS stereoisomers of dioxolane-linked gramicidin A (gA) channels were measured in different phospholipid bilayers at different HCl concentrations. In particular, measurements were obtained in bilayers made of 1,2-diphytanoyl 3-phosphocholine (DiPhPC) or its ethylated derivative 1,2-diphytanoyl 3-ethyl-phosphocholine (et-DiPhPC,). The difference between these phospholipids is that in et-DiPhPC one of the phosphate oxygens is covalently linked to an ethyl group and cannot be protonated. In relatively dilute acid solutions, g(H) in DiPhPC is significantly higher than in et-DiPhPC. At high acid concentrations, g(H) is the same in both diphytanoyl bilayers. Such differences in g(H) can be accounted for by surface charge effects at the membrane/solution interfaces. In the linear portion of the log g(H)-log [H] relationship, g(H) values in diphytanoyl bilayers were significantly larger (approximately 10-fold) than in neutral glyceryl monooleate (GMO) membranes. The slopes of the linear log-log relationships between g(H) and [H] in diphytanoyl and GMO bilayers are essentially the same (approximately 0.76). This slope is significantly lower than the slope of the log-log plot of proton conductivity versus proton concentration in aqueous solutions (approximately 1.00). Because the chemical composition of the membrane-channel/solution interface is strikingly different in GMO and diphytanoyl bilayers, the reduced slope in g(H)-[HCl] relationships may be a characteristic of proton transfer in the water wire inside the SS channel. Values of g(H) in diphytanoyl bilayers were also significantly larger than in membranes made of the more common biological phospholipids 1-palmitoyl 2-oleoyl phosphocholine (POPC) or 1-palmitoyl 2-oleoyl phosphoethanolamine (POPE). These differences, however, cannot be accounted for by different surface charge effects or by different internal dipole potentials. On the other hand, maximum g(H) measured in the SS channel

  6. An optimized method for {sup 15}N R{sub 1} relaxation rate measurements in non-deuterated proteins

    Energy Technology Data Exchange (ETDEWEB)

    Gairí, Margarida, E-mail: mgairi@rmn.ub.edu [University of Barcelona (CCiTUB), NMR Facility, Scientific and Technological Centers (Spain); Dyachenko, Andrey [Institute for Research in Biomedicine (IRB) (Spain); González, M. Teresa; Feliz, Miguel [University of Barcelona (CCiTUB), NMR Facility, Scientific and Technological Centers (Spain); Pons, Miquel [University of Barcelona, Biomolecular NMR Laboratory and Organic Chemistry Department (Spain); Giralt, Ernest, E-mail: ernest.giralt@irbbarcelona.org [Institute for Research in Biomedicine (IRB) (Spain)

    2015-06-15

    {sup 15}N longitudinal relaxation rates are extensively used for the characterization of protein dynamics; however, their accurate measurement is hindered by systematic errors. {sup 15}N CSA/{sup 1}H–{sup 15}N dipolar cross-correlated relaxation (CC) and amide proton exchange saturation transfer from water protons are the two main sources of systematic errors in the determination of {sup 15}N R{sub 1} rates through {sup 1}H–{sup 15}N HSQC-based experiments. CC is usually suppressed through a train of 180° proton pulses applied during the variable {sup 15}N relaxation period (T), which can perturb water magnetization. Thus CC cancellation is required in such a way as to minimize water saturation effects. Here we examined the level of water saturation during the T period caused by various types of inversion proton pulses to suppress CC: (I) amide-selective IBURP-2; (II) cosine-modulated IBURP-2; (III) Watergate-like blocks; and (IV) non-selective hard. We additionally demonstrate the effect of uncontrolled saturation of aliphatic protons on {sup 15}N R{sub 1} rates. In this paper we present an optimized pulse sequence that takes into account the crucial effect of controlling also the saturation of the aliphatic protons during {sup 15}N R{sub 1} measurements in non-deuterated proteins. We show that using cosine-modulated IBURP-2 pulses spaced 40 ms to cancel CC in this optimized pulse program is the method of choice to minimize systematic errors coming from water and aliphatic protons saturation effects.

  7. Formaldehyde mediated proton-transport catalysis in the ketene-water radical cation CH2C(O)OH2+

    Science.gov (United States)

    Lee, Richard; Ruttink, Paul J. A.; Burgers, Peter C.; Terlouw, Johan K.

    2006-09-01

    Previous studies have shown that the solitary ketene-water ion CH2C(O)OH2+ (1) does not isomerize into CH2C(OH)2+ (2), its more stable hydrogen shift isomer. Tandem mass spectrometry based collision experiments reveal that this isomerization does take place in the CH2O loss from low-energy 1,3-dihydroxyacetone ions (HOCH2)2CO+. A mechanistic analysis using the CBS-QB3 model chemistry shows that such molecular ions rearrange into hydrogen-bridged radical cations [CH2C(O)O(H)-H...OCH2]+ in which the CH2O molecule catalyzes the transformation 1 --> 2 prior to dissociation. The barrier for the unassisted reaction, 29 kcal mol-1, is reduced to a mere 0.6 kcal mol-1 for the catalysed transformation. Formaldehyde is an efficient catalyst because its proton affinity meets the criterion for facile proton-transport catalysis.

  8. Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions.

    Science.gov (United States)

    Kim, Sung Yeon; Kim, Suhan; Park, Moon Jeong

    2010-10-05

    Proton exchange fuel cells (PEFCs) have the potential to provide power for a variety of applications ranging from electronic devices to transportation vehicles. A major challenge towards economically viable PEFCs is finding an electrolyte that is both durable and easily passes protons. In this article, we study novel anhydrous proton-conducting membranes, formed by incorporating ionic liquids into synthetic block co-polymer electrolytes, poly(styrenesulphonate-b-methylbutylene) (S(n)MB(m)), as high-temperature PEFCs. The resulting membranes are transparent, flexible and thermally stable up to 180 °C. The increases in the sulphonation level of S(n)MB(m) co-polymers (proton supplier) and the concentration of the ionic liquid (proton mediator) produce an overall increase in conductivity. Morphology effects were studied by X-ray scattering and electron microscopy. Compared with membranes having discrete ionic domains (including Nafion 117), the nanostructured membranes revealed over an order of magnitude increase in conductivity with the highest conductivity of 0.045 S cm(-1) obtained at 165 °C.

  9. Membrane inlet proton transfer reaction mass spectrometry (MI-PTRMS) for direct measurements of VOCs in water

    Science.gov (United States)

    Boscaini, Elena; Alexander, Michael L.; Prazeller, Peter; Märk, Tilmann D.

    2004-12-01

    The use of a membrane inlet proton transfer reaction mass spectrometry (MI-PTRMS) system was investigated for the quantitative analysis of VOCs directly from water. Compounds playing an important role in environmental, biological and health issues such as methanol, acetonitrile, acetone, dimethylsulfide (DMS), isoprene, benzene, and toluene have been analyzed both in fresh and salty water. The system shows very good sensitivity, reproducibility, and a linear response of up to five orders of magnitude. The detection limit for DMS is about 100 ppt and for methanol is about 10 ppb both in fresh and salty water. The response time of the various compounds across the membrane is on the order of a few minutes. This fast response and the fact that the PTRMS can perform absolute measurements without the necessity of calibration make the system suitable for on-line and -site measurements of VOCs directly from water.

  10. Helical water chain mediated proton conductivity in homochiral metal-organic frameworks with unprecedented zeolitic unh-topology.

    Science.gov (United States)

    Sahoo, Subash Chandra; Kundu, Tanay; Banerjee, Rahul

    2011-11-09

    Four new homochiral metal-organic framework (MOF) isomers, [Zn(l-L(Cl))(Cl)](H(2)O)(2) (1), [Zn(l-L(Br))(Br)](H(2)O)(2) (2), [Zn(d-L(Cl))(Cl)](H(2)O)(2) (3), and [Zn(d-L(Br))(Br)](H(2)O)(2) (4) [L = 3-methyl-2-(pyridin-4-ylmethylamino)butanoic acid], have been synthesized by using a derivative of L-/D-valine and Zn(CH(3)COO)(2)·2H(2)O. A three-periodic lattice with a parallel 1D helical channel was formed along the crystallographic c-axis. Molecular rearrangement results in an unprecedented zeolitic unh-topology in 1-4. In each case, two lattice water molecules (one H-bonded to halogen atoms) form a secondary helical continuous water chain inside the molecular helix. MOFs 1 and 2 shows different water adsorption properties and hence different water affinity. The arrangement of water molecules inside the channel was monitored by variable-temperature single-crystal X-ray diffraction, which indicated that MOF 1 has a higher water holding capacity than MOF 2. In MOF 1, water escapes at 80 °C, while in 2 the same happens at a much lower temperature (∼40 °C). All the MOFs reported here shows reversible crystallization by readily reabsorbing moisture. In MOFs 1 and 2, the frameworks are stable after solvent removal, which is confirmed by a single-crystal to single-crystal transformation. MOFs 1 and 3 show high proton conductivity of 4.45 × 10(-5) and 4.42 × 10(-5) S cm(-1), respectively, while 2 and 4 shows zero proton conductivity. The above result is attributed to the fact that MOF 1 has a higher water holding capacity than MOF 2.

  11. Theoretical prediction of single-site enthalpies of surface protonation for oxides and silicates in water

    Energy Technology Data Exchange (ETDEWEB)

    Sverjensky, D.A.; Sahai, N. [Johns Hopkins Univ., Baltimore, MD (United States). Morton K. Blaustein Dept. of Earth and Planetary Sciences

    1998-12-01

    Surface protonation is the most fundamental adsorption process of geochemical interest. Yet remarkably little is known about protonation of mineral surfaces at temperatures greater than 25 C. Experimentally derived standard enthalpies of surface protonation, {Delta}H{degree}{sub r,1}, {Delta}H{degree}{sub r,2}, and {Delta}H{degree}{sub r,ZPC}, correspond to the reactions >SOH + H{sup +} = >SOH{sub 2}{sup +}; >SO{sup {minus}} + H{sup +} = >SOH; and >SO{sup {minus}} + 2H{sup +} = >SOH{sub 2}{sup +}, respectively, and provide a starting point for evaluating the role of surface protonation in geochemical processes at elevated temperatures. However, the experimental data for oxides do not have a theoretical explanation, and data are completely lacking for silicates other than SiO{sub 2}. In the present study, the combination of crystal chemical and Born solvation theory provides a theoretical basis for explaining the variation of the enthalpies of protonation of oxides. Experimental values of {Delta}H{degree}{sub r,1}, {Delta}H{degree}{sub r,2}, and {Delta}H{degree}{sub r,ZPC} consistent with the triple layer model can be expressed in terms of the inverse of the dielectric constant (1/{epsilon}) and the Pauling bond strength per angstrom (s/r{sub M-OH}) of each mineral. Predicted standard enthalpies of surface protonation for oxides and silicates extend over the ranges (in kcal/mole):{Delta}H{degree}{sub r,1} {approx} {minus}3 to {minus}15; {Delta}H{degree}{sub r,2} {approx} {minus}5 to {minus}18; {Delta}H{degree}{sub r,ZPC} {approx} {minus}4 to {minus}33.

  12. Voltage Gated Ion Channel Function: Gating, Conduction, and the Role of Water and Protons

    Energy Technology Data Exchange (ETDEWEB)

    Kariev, Alisher M.; Green, Michael E.

    2012-02-26

    Ion channels, which are found in every biological cell, regulate the concentration of electrolytes, and are responsible for multiple biological functions, including in particular the propagation of nerve impulses. The channels with the latter function are gated (opened) by a voltage signal, which allows Na+ into the cell and K+ out. These channels have several positively charged amino acids on a transmembrane domain of their voltage sensor, and it is generally considered, based primarily on two lines of experimental evidence, that these charges move with respect to the membrane to open the channel. At least three forms of motion, with greatly differing extents and mechanisms of motion, have been proposed. There is a “gating current”, a capacitative current preceding the channel opening, that corresponds to several charges (for one class of channel typically 12–13) crossing the membrane field, which may not require protein physically crossing a large fraction of the membrane. The coupling to the opening of the channel would in these models depend on the motion. The conduction itself is usually assumed to require the “gate” of the channel to be pulled apart to allow ions to enter as a section of the protein partially crosses the membrane, and a selectivity filter at the opposite end of the channel determines the ion which is allowed to pass through. We will here primarily consider K+ channels, although Na+ channels are similar. We propose that the mechanism of gating differs from that which is generally accepted, in that the positively charged residues need not move (there may be some motion, but not as gating current). Instead, protons may constitute the gating current, causing the gate to open; opening consists of only increasing the diameter at the gate from approximately 6 Å to approximately 12 Å. We propose in addition that the gate oscillates rather than simply opens, and the ion experiences a barrier to its motion across the channel that is tuned

  13. Voltage Gated Ion Channel Function: Gating, Conduction, and the Role of Water and Protons

    Directory of Open Access Journals (Sweden)

    Alisher M. Kariev

    2012-02-01

    Full Text Available Ion channels, which are found in every biological cell, regulate the concentration of electrolytes, and are responsible for multiple biological functions, including in particular the propagation of nerve impulses. The channels with the latter function are gated (opened by a voltage signal, which allows Na+ into the cell and K+ out. These channels have several positively charged amino acids on a transmembrane domain of their voltage sensor, and it is generally considered, based primarily on two lines of experimental evidence, that these charges move with respect to the membrane to open the channel. At least three forms of motion, with greatly differing extents and mechanisms of motion, have been proposed. There is a “gating current”, a capacitative current preceding the channel opening, that corresponds to several charges (for one class of channel typically 12–13 crossing the membrane field, which may not require protein physically crossing a large fraction of the membrane. The coupling to the opening of the channel would in these models depend on the motion. The conduction itself is usually assumed to require the “gate” of the channel to be pulled apart to allow ions to enter as a section of the protein partially crosses the membrane, and a selectivity filter at the opposite end of the channel determines the ion which is allowed to pass through. We will here primarily consider K+ channels, although Na+ channels are similar. We propose that the mechanism of gating differs from that which is generally accepted, in that the positively charged residues need not move (there may be some motion, but not as gating current. Instead, protons may constitute the gating current, causing the gate to open; opening consists of only increasing the diameter at the gate from approximately 6 Å to approximately 12 Å. We propose in addition that the gate oscillates rather than simply opens, and the ion experiences a barrier to its motion across the

  14. [Death in a relaxation tank].

    Science.gov (United States)

    Rupp, Wolf; Simon, Karl-Heinz; Bohnert, Michael

    2009-01-01

    Complete relaxation can be achieved by floating in a darkened, sound-proof relaxation tank filled with salinated water kept at body temperature. Under these conditions, meditation exercises up to self-hypnosis may lead to deep relaxation with physical and mental revitalization. A user manipulated his tank, presumably to completely cut off all optical and acoustic stimuli and accidentally also covered the ventilation hole. The man was found dead in his relaxation tank. The findings suggested lack of oxygen as the cause of death.

  15. An Investigation of Structure Transition in Sodium Dodecyl Trioxyethylene Sulfate/n-Butanol/n-Octane/Water System by Dielectric Relaxation Spectroscopy Method

    Institute of Scientific and Technical Information of China (English)

    MU Jian-hai; ZHAO Kong-shuang; WEI Su-xiang; LI Ying; LI Gan-zuo

    2004-01-01

    The phase diagram of the quaternary system of sodium dodecyl trioxyethylene sulfate(SDES)/n-butanol/n-octane/water was obtained at (30.0±0.1) ℃. There exists a clear, isotropic, and low-viscosity L phase, which can be divided into W/O, bi-continuous(B.C.) and O/W microemulsions by conductivity measurement results. Dielectric Relaxation Spectroscopy(DRS) measurements, including permittivity, conductivity, relaxation strength, characteristic relaxation time, dielectric parameters, phase parameters, etc., were applied to investigating the microstructures of the system mentioned above. For the samples with a fixed SDES/n-butanol mass ratio of 4/6 including 20%(mass fraction) of n-octane, DRS indicated a structure transition from a W/O to an O/W via a B.C. microemulsion with the increase of the water content. For the samples with a fixed (SDES/20%n-octane)/H2O mass ratio of 5/5, DRS presented that there only exists a onefold structure of a W/O microemulsion as the (n-butanol/20%n-octane) content increases. The results obtained from DRS are in good agreement with those from the phase diagram.

  16. Faster Proton dynamics of water on SnO2 compared to TiO2.

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Nitin [ORNL; Kent, Paul R [ORNL; Bandura, Andrei V. [St. Petersburg State University, St. Petersburg, Russia; Kubicki, James D. [Pennsylvania State University; Wesolowski, David J [ORNL; Cole, David R [ORNL; Sofo, Jorge O. [Pennsylvania State University

    2011-01-01

    Proton jump processes in the hydration layer on the iso-structural TiO2 rutile (110) and SnO2 cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates. 2011 American Institute of Physics. [doi:10.1063/1.3509386

  17. Validation of nuclear models in Geant4 using the halo of a proton pencil beam stopping in water

    CERN Document Server

    Hall, David C; Paganetti, Harald; Gottschalk, Bernard

    2015-01-01

    A proton pencil beam is associated with a surrounding low-dose envelope, originating from nuclear interactions. It is important for treatment planning systems to accurately model this envelope when performing dose calculations for pencil beam scanning treatments, and Monte Carlo (MC) codes are commonly used for this purpose. This work aims to validate the nuclear models employed by the Geant4 MC code, by comparing the simulated absolute dose distribution to a recent experiment of a 177 MeV proton pencil beam stopping in water. Impressive agreement is observed over five orders of magnitude, with both the shape and normalisation well modelled. The normalisations of two depth dose curves are lower than experiment, though this could be explained by an experimental positioning error. The Geant4 neutron production model is also verified in the distal region. The entrance dose is poorly modelled, suggesting an unaccounted upstream source of low-energy protons. Recommendations are given for a follow-up experiment whi...

  18. Proton Transfer Dynamics at the Membrane/Water Interface: Dependence on the Fixed and Mobile pH Buffers, on the Size and Form of Membrane Particles, and on the Interfacial Potential Barrier

    OpenAIRE

    Cherepanov, Dmitry A.; Junge, Wolfgang; Armen Y Mulkidjanian

    2004-01-01

    Crossing the membrane/water interface is an indispensable step in the transmembrane proton transfer. Elsewhere we have shown that the low dielectric permittivity of the surface water gives rise to a potential barrier for ions, so that the surface pH can deviate from that in the bulk water at steady operation of proton pumps. Here we addressed the retardation in the pulsed proton transfer across the interface as observed when light-triggered membrane proton pumps ejected or captured protons. B...

  19. Proton transfer through hydrogen bonds in two-dimensional water layers: A theoretical study based on ab initio and quantum-classical simulations

    Energy Technology Data Exchange (ETDEWEB)

    Bankura, Arindam; Chandra, Amalendu, E-mail: amalen@iitk.ac.in [Department of Chemistry, Indian Institute of Technology, Kanpur 208016 (India)

    2015-01-28

    The dynamics of proton transfer (PT) through hydrogen bonds in a two-dimensional water layer confined between two graphene sheets at room temperature are investigated through ab initio and quantum-classical simulations. The excess proton is found to be mostly solvated as an Eigen cation where the hydronium ion donates three hydrogen bonds to the neighboring water molecules. In the solvation shell of the hydronium ion, the three coordinated water molecules with two donor hydrogen bonds are found to be properly presolvated to accept a proton. Although no hydrogen bond needs to be broken for transfer of a proton to such presolvated water molecules from the hydronium ion, the PT rate is still found to be not as fast as it is for one-dimensional chains. Here, the PT is slowed down as the probability of finding a water with two donor hydrogen bonds in the solvation shell of the hydronium ion is found to be only 25%-30%. The hydroxide ion is found to be solvated mainly as a complex anion where it accepts four H-bonds through its oxygen atom and the hydrogen atom of the hydroxide ion remains free all the time. Here, the presolvation of the hydroxide ion to accept a proton requires that one of its hydrogen bonds is broken and the proton comes from a neighboring water molecule with two acceptor and one donor hydrogen bonds. The coordination number reduction by breaking of a hydrogen bond is a slow process, and also the population of water molecules with two acceptor and one donor hydrogen bonds is only 20%-25% of the total number of water molecules. All these factors together tend to slow down the hydroxide ion migration rate in two-dimensional water layers compared to that in three-dimensional bulk water.

  20. Proton transfer through hydrogen bonds in two-dimensional water layers: A theoretical study based on ab initio and quantum-classical simulations

    Science.gov (United States)

    Bankura, Arindam; Chandra, Amalendu

    2015-01-01

    The dynamics of proton transfer (PT) through hydrogen bonds in a two-dimensional water layer confined between two graphene sheets at room temperature are investigated through ab initio and quantum-classical simulations. The excess proton is found to be mostly solvated as an Eigen cation where the hydronium ion donates three hydrogen bonds to the neighboring water molecules. In the solvation shell of the hydronium ion, the three coordinated water molecules with two donor hydrogen bonds are found to be properly presolvated to accept a proton. Although no hydrogen bond needs to be broken for transfer of a proton to such presolvated water molecules from the hydronium ion, the PT rate is still found to be not as fast as it is for one-dimensional chains. Here, the PT is slowed down as the probability of finding a water with two donor hydrogen bonds in the solvation shell of the hydronium ion is found to be only 25%-30%. The hydroxide ion is found to be solvated mainly as a complex anion where it accepts four H-bonds through its oxygen atom and the hydrogen atom of the hydroxide ion remains free all the time. Here, the presolvation of the hydroxide ion to accept a proton requires that one of its hydrogen bonds is broken and the proton comes from a neighboring water molecule with two acceptor and one donor hydrogen bonds. The coordination number reduction by breaking of a hydrogen bond is a slow process, and also the population of water molecules with two acceptor and one donor hydrogen bonds is only 20%-25% of the total number of water molecules. All these factors together tend to slow down the hydroxide ion migration rate in two-dimensional water layers compared to that in three-dimensional bulk water.

  1. Density Functional Study on the Mechanism of Collision Reaction among Protons,N2 and Water Vapor

    Institute of Scientific and Technical Information of China (English)

    SUN,Hao(孙昊); PAN,Xiu-Mei(潘秀梅); ZHAO,Min(赵岷); LIU,Peng-Jun(刘朋军); SU,Zhong-Min(苏忠民); WANG,Rong-Shun(王荣顺)

    2004-01-01

    The mechanism of collision reaction among protons, N2 and water vapor was theoretically studied using Density Functional Theory. The geometries of reactants, transition states, intermediates and products were optimized at the B3LYP/6-311 + G** level by the BERNY gradient analysis method. Transition states and intermediates have been identified by vibrational frequency analysis. The relationship among reactants, intermediates, transition states and products was affirmed by IRC calculation. The variations of energy and geometry along the IRC-determined reaction paths were described. The possible reaction pathways were represented and the optimal one was decided from the viewpoint of energy.

  2. Changes in the zero-point energy of the protons as the source of the binding energy of water to A-phase DNA.

    Science.gov (United States)

    Reiter, G F; Senesi, R; Mayers, J

    2010-10-01

    The measured changes in the zero-point kinetic energy of the protons are entirely responsible for the binding energy of water molecules to A phase DNA at the concentration of 6  water molecules/base pair. The changes in kinetic energy can be expected to be a significant contribution to the energy balance in intracellular biological processes and the properties of nano-confined water. The shape of the momentum distribution in the dehydrated A phase is consistent with coherent delocalization of some of the protons in a double well potential, with a separation of the wells of 0.2 Å.

  3. Structural water cluster as a possible proton acceptor in the adduct decay reaction of oat phototropin 1 LOV2 domain.

    Science.gov (United States)

    Chan, Ruby H; Bogomolni, Roberto A

    2012-09-06

    LOV domains (Light, Oxygen, Voltage) are the light-sensory modules of phototropins, the blue-light photoreceptor kinases in plants, and of a wide variety of flavoproteins found in all three domains of life. These 12 kDa modules bind a flavin chromophore (FMN or FAD) noncovalently and undergo a photochemical activation in which the sulfur atom of a conserved cysteine forms an adduct to the C(4a) carbon of the flavin. The adduct breaks spontaneously in a base-catalyzed reaction involving a rate-limiting proton-transfer step, regenerating the dark state in seconds. This photocycle involves chromophore and protein structural changes that activate the C-terminal serine/threonine kinase. Previous studies (Biochemistry 2007, 46, 7016-7021) showed that decreased hydration obtained at high glycerol concentrations stabilizes the adduct state in a manner similar to that attained at low temperatures, resulting in much longer adduct decay times. This kinetic effect was attributed to an increased protein rigidity that hindered structural fluctuations necessary for the decay reaction. In this work, we studied the adduct decay kinetics of oat phototropin 1 (phot1) LOV2 at varying hydration using a specially designed chamber that allowed for measurement of UV-visible and FTIR spectra of the same samples. Therefore, we obtained LOV protein concentrations, adduct decay kinetics, and the different populations of bound water by deconvolution of the broad water absorption peak around 3500 cm(-1). A linear dependence of the adduct decay rate constant on the concentration of double and triple hydrogen-bonded waters strongly suggests that the adduct decay is a pseudo-first-order reaction in which both the adduct and the strongly bound waters are reactants. We suggest that a cluster of strongly bound water functions as the proton acceptor in the rate-limiting step of adduct decay.

  4. Proton Transfer Isomerization of Pyrazole in the Ground State:σν sπ Mechanism and Water Assisting Effect

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The proton transfer isomerization of pyrazole and the water assisting effect by looping 1 to 4 water molecules on the singlet state potential energy surface have been investigated by using hybrid density functional theory method (B3PW91) with a 6-311++G** basis set. Two mechanisms were proposed to explain the mono- and multi-water assisting effects, respectively. The reactants and products of all groups have been characterized on their potential energy surfaces. For the isomerization of monomolecule pyrazole, the isomerization energy barrier is 46.4 kcal·mol-1. For the monohydration assisting mechanism, the reactant complex is connected to the product complex via two saddle points. The corresponding isomerization barriers are 46.7and 23.0 kcal(mol-1, respectively. As to the multihydration assisting mechanism, the isomerization barriers are 12.0, 10.9 and 13.14 kcal(mol-1 accordingly, when the number of water molecules is 2, 3 and 4, respectively. The multihydration assisting isomerization can occur in water-dominated environments, for example, in the organism, and thereby is crucial to energy transference. The deproton and dehydrogen energies of monomolecule pyrazole and various hydrated pyrazoles were calculated and then found much bigger than the isomerization barriers of their relative complexes, suggesting the impossibility of deprotonation or dehydrogenation. The isomerization of pyrazole is a proton-coupling-electron-migration process, but two different mechanisms are noticed, viz.σ- and π-type mechanisms. The π-bond of pyrazole participates in isomerization in the π-type mechanism, whereas only σelectron takes part in isomerization in the σ-type mechanism.

  5. Nuclear magnetic resonance relaxation characterisation of water status of developing grains of maize (Zea mays L.) grown at different nitrogen levels.

    Science.gov (United States)

    Krishnan, Prameela; Chopra, Usha Kiran; Verma, Ajay Pal Singh; Joshi, Devendra Kumar; Chand, Ishwar

    2014-04-01

    Changes in water status of developing grains of maize (Zea mays L.) grown under different nitrogen levels were characterized by nuclear magnetic resonance (NMR) spectroscopy. There were distinct changes in water status of grains due to the application of different levels of nitrogen (0, 120 and 180 kg N ha(-1)). A comparison of the grain developmental characteristics, composition and physical properties indicated that, not only the developmental characteristics like grain weight, grain number/ear, and rate of grain filling increased, but also bound water characterized by the T2 component of NMR relaxation increased with nitrogen application (50-70%) and developmental stages leading to maturation (10-60%). The consistency in the patterns of responses to free water and intermediate water to increasing levels of nitrogen application and grain maturity suggested that nitrogen application resulted in more proportion of water to both bound- and intermediate states and less in free state. These changes are further corroborated by the concomitant increases in protein and starch contents in grains from higher nitrogen treatments as macromolecules like protein and starch retain more amount of water in the bound state. The results of the changes in T2 showed that water status during grain development was not only affected by developmental processes but also by nitrogen supply to plants. This study strongly indicated a clear nutrient and developmental stage dependence of grain tissue water status in maize.

  6. Distance-dependent proton transfer along water wires connecting acid-base pairs

    NARCIS (Netherlands)

    Cox, M.J.; Timmer, R.L.A.; Bakker, H.J.; Park, S.; Agmon, N.

    2009-01-01

    We report time-resolved mid-IR kinetics for the ultrafast acid−base reaction between photoexcited 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS), and acetate at three concentrations (0.5, 1.0, and 2.0 M) and three temperatures (5, 30, and 65 °C) in liquid D2O. The observed proton-trans

  7. NMR studies of the protonation states of pyridoxal-5‧-phosphate in water

    Science.gov (United States)

    Chan-Huot, Monique; Niether, Christiane; Sharif, Shasad; Tolstoy, Peter M.; Toney, Michael D.; Limbach, Hans-Heinrich

    2010-07-01

    We have measured the 13C NMR spectra of the cofactor pyridoxal-5'-phosphate (vitamin B 6, PLP) at 278 K in aqueous solution as a function of pH. By 13C enrichment of PLP in the C-4' and C-5' positions we were able to measure spectra down to pH 1. From the dependence of the 13C chemical shifts on pH, the p Ka values of PLP could be determined. In particular, the heretofore uncharacterized protonation state of PLP, in which the phosphate group as well as the pyridine ring and the phenolic groups are fully protonated, has been analyzed. The corresponding p Ka value of 2.4 indicates that the phosphate group is solely involved in the first deprotonation step. The 15N chemical shifts of the pyridine ring of PLP published previously are in good agreement with the new results. These shifts contain information about the tautomerism of the different protonation states of PLP. The implications of these findings for the biological function of PLP are discussed.

  8. Aggregation behavior and electrical properties of amphiphilic pyrrole-tailed ionic liquids in water, from the viewpoint of dielectric relaxation spectroscopy.

    Science.gov (United States)

    Fan, Xiaoqing; Zhao, Kongshuang

    2014-05-14

    The self-aggregation behavior of amphiphilic pyrrole-tailed imidazolium ionic liquids (Py(CH₂)₁₂mim⁺Br⁻: Py = pyrrole, mim = methylimidazolium) in water is investigated by dielectric spectroscopy from 40 Hz to 110 MHz. Dielectric determination shows that the critical micelle concentration (CMC) is 8.5 mM, which is lower than that for traditional ionic surfactants. The thermodynamic parameter of the micellization, the Gibbs free energy ΔG, was calculated for Py(CH₂)₁₂mim⁺Br⁻ and compared to those of the corresponding C(n)mim⁺Br⁻ (n = 12, 14). It was found that the main driven forces of the Py(CH₂)₁₂mim⁺Br⁻ aggregation were hydrophobic interaction and π-π interactions among the adjacent Py groups. Further, the structure of aggregation was speculated theoretically that Py groups partially insert into the alkyl chains and the staggered arrangement in micelles is formed. When the concentration of Py(CH₂)₁₂mim⁺Br⁻ is higher than CMC, two remarkable relaxations which originated from diffusion of counterions and interfacial polarization between the micelles and solution, were observed at about 1.3 MHz and 55 MHz. The relaxation parameters representing the real properties of the whole system were obtained by fitting the experimental data with Cole-Cole equation. A dielectric model characterizing the structure and electrical properties of spherical micelles was proposed by which the conductivity, permittivity and the volume fraction of micelles as well as electrical properties of solution were calculated from the relaxation parameters. An intriguingly high permittivity of about 150 for the micelle was found to be a direct consequence of the strong orientational order of water molecules inside the core of micelle, and essentially is attributed to the special structure of the micelle. Furthermore, the calculation of the interfacial electrokinetic parameters of the micelles, i.e., the surface conductivity, surface charge density

  9. Thermo-acoustic Sound Generation in the Interaction of Pulsed Proton and Laser Beams with a Water Target

    CERN Document Server

    Lahmann, R; Graf, K; Hößl, J; Kappes, A; Katz, U; Mecke, K; Schwemmer, S

    2015-01-01

    The generation of hydrodynamic radiation in interactions of pulsed proton and laser beams with matter is explored. The beams were directed into a water target and the resulting acoustic signals were recorded with pressure sensitive sensors. Measurements were performed with varying pulse energies, sensor positions, beam diameters and temperatures. The obtained data are matched by simulation results based on the thermo-acoustic model with uncertainties at a level of 10%. The results imply that the primary mechanism for sound generation by the energy deposition of particles propagating in water is the local heating of the medium. The heating results in a fast expansion or contraction and a pressure pulse of bipolar shape is emitted into the surrounding medium. An interesting, widely discussed application of this effect could be the detection of ultra-high energetic cosmic neutrinos in future large-scale acoustic neutrino detectors. For this application a validation of the sound generation mechanism to high accur...

  10. Applying hot wire anemometry to directly measure the water balance in a proton exchange membrane fuel cell - Part 1

    DEFF Research Database (Denmark)

    Berning, Torsten; Al Shakhshir, Saher

    2015-01-01

    In order to accurately determine the water balance of a proton exchange membrane fuel cell it has recently been suggested to employ constant temperature anemometry (CTA), a frequently used method to measure the velocity of a fluid stream. CTA relies on convective heat transfer around a heated wire...... at around 200 °C. The heat loss to the fluid stream is balanced by electrical power dissipation, and the required voltage E is the output signal which is highly sensitive to the heat transfer coefficient of the wire and therefore provides accurate readings. This work explains the theory and summarizes...... the equations required to calculate the heat transfer coefficient and the resulting voltage signal as function of the fuel cell water balance. The most critical and least understood part is the determination of the Nusselt number to calculate the heat transfer between the wire and the gas stream. Different...

  11. Nuclear magnetic relaxation by the dipolar EMOR mechanism: Three-spin systems

    Science.gov (United States)

    Chang, Zhiwei; Halle, Bertil

    2016-07-01

    In aqueous systems with immobilized macromolecules, including biological tissue, the longitudinal spin relaxation of water protons is primarily induced by exchange-mediated orientational randomization (EMOR) of intra- and intermolecular magnetic dipole-dipole couplings. Starting from the stochastic Liouville equation, we have developed a non-perturbative theory that can describe relaxation by the dipolar EMOR mechanism over the full range of exchange rates, dipole couplings, and Larmor frequencies. Here, we implement the general dipolar EMOR theory for a macromolecule-bound three-spin system, where one, two, or all three spins exchange with the bulk solution phase. In contrast to the previously studied two-spin system with a single dipole coupling, there are now three dipole couplings, so relaxation is affected by distinct correlations as well as by self-correlations. Moreover, relaxation can now couple the magnetizations with three-spin modes and, in the presence of a static dipole coupling, with two-spin modes. As a result of this complexity, three secondary dispersion steps with different physical origins can appear in the longitudinal relaxation dispersion profile, in addition to the primary dispersion step at the Larmor frequency matching the exchange rate. Furthermore, and in contrast to the two-spin system, longitudinal relaxation can be significantly affected by chemical shifts and by the odd-valued ("imaginary") part of the spectral density function. We anticipate that the detailed studies of two-spin and three-spin systems that have now been completed will provide the foundation for developing an approximate multi-spin dipolar EMOR theory sufficiently accurate and computationally efficient to allow quantitative molecular-level interpretation of frequency-dependent water-proton longitudinal relaxation data from biophysical model systems and soft biological tissue.

  12. Relaxation study of cement based grouting material using nuclear magnetic resonance

    Institute of Scientific and Technical Information of China (English)

    Li Xianzhong; Lin Baiquan; Zhai Cheng; Ni Guanhua; Li Ziwen

    2012-01-01

    Aiming at actual condition of poor effect of hole sealing for the reason of poor cement paste fluidity in the process of coal mine gas drainage,by adding a water reducing agent,cement paste for hole sealing was produced.The changes of initial distribution,weighted average values and total relaxation signal intensity of transverse relaxation time (T2) of water in pure cement paste and water reducing agent added cement paste were studied with low field proton nuclear magnetic resonance (NMR).The results show that there are four peaks in T2 distribution curves of cement paste:the first peak is related to the bound water in flocculation,the second and the third peaks are related to the water in flocculation,water reducing agent makes it extending towards the long relaxation time,increasing its liquidity,and the fourth peak is related to the free water.By using weighted average values of T2 and total relaxation signal intensity,hydration process of cement pastes could be roughly divided into four stages:the initial period,reaction period,accelerated period and steady period.By analyzing the periods,it makes sure that the grouting process should be completed in the reaction period in the site,and the drainage process should be started in the steady period.The results have great guiding significance to the hole sealing and methane drainage.

  13. Relaxation study of cement based grouting material using nuclear magnetic resonance

    Institute of Scientific and Technical Information of China (English)

    Li; Xianzhong; Lin; Baiquan; Zhai; Cheng; Ni; Guanhua; Li; Ziwen

    2012-01-01

    Aiming at actual condition of poor effect of hole sealing for the reason of poor cement paste fluidity in the process of coal mine gas drainage,by adding a water reducing agent,cement paste for hole sealing was produced.The changes of initial distribution,weighted average values and total relaxation signal intensity of transverse relaxation time(T 2) of water in pure cement paste and water reducing agent added cement paste were studied with low field proton nuclear magnetic resonance(NMR).The results show that there are four peaks in T2 distribution curves of cement paste:the first peak is related to the bound water in flocculation,the second and the third peaks are related to the water in flocculation,water reducing agent makes it extending towards the long relaxation time,increasing its liquidity,and the fourth peak is related to the free water.By using weighted average values of T2 and total relaxation signal intensity,hydration process of cement pastes could be roughly divided into four stages:the initial period,reaction period,accelerated period and steady period.By analyzing the periods,it makes sure that the grouting process should be completed in the reaction period in the site,and the drainage process should be started in the steady period.The results have great guiding significance to the hole sealing and methane drainage.

  14. Dynamical theory of spin relaxation

    Science.gov (United States)

    Field, Timothy R.; Bain, Alex D.

    2013-02-01

    The dynamics of a spin system is usually calculated using the density matrix. However, the usual formulation in terms of the density matrix predicts that the signal will decay to zero, and does not address the issue of individual spin dynamics. Using stochastic calculus, we develop a dynamical theory of spin relaxation, the origins of which lie in the component spin fluctuations. This entails consideration of random pure states for individual protons, and how these pure states are correctly combined when the density matrix is formulated. Both the lattice and the spins are treated quantum mechanically. Such treatment incorporates both the processes of spin-spin and (finite temperature) spin-lattice relaxation. Our results reveal the intimate connections between spin noise and conventional spin relaxation.

  15. High Relaxivity Gadolinium Hydroxypyridonate-Viral Capsid Conjugates: Nano-sized MRI Contrast Agents

    Energy Technology Data Exchange (ETDEWEB)

    Meux, Susan C.; Datta, Ankona; Hooker, Jacob M.; Botta, Mauro; Francis, Matthew B.; Aime, Silvio; Raymond, Kenneth N.

    2007-08-29

    High relaxivity macromolecular contrast agents based on the conjugation of gadolinium chelates to the interior and exterior surfaces of MS2 viral capsids are assessed. The proton nuclear magnetic relaxation dispersion (NMRD) profiles of the conjugates show up to a five-fold increase in relaxivity, leading to a peak relaxivity (per Gd{sup 3+} ion) of 41.6 mM{sup -1}s{sup -1} at 30 MHz for the internally modified capsids. Modification of the exterior was achieved through conjugation to flexible lysines, while internal modification was accomplished by conjugation to relatively rigid tyrosines. Higher relaxivities were obtained for the internally modified capsids, showing that (1) there is facile diffusion of water to the interior of capsids and (2) the rigidity of the linker attaching the complex to the macromolecule is important for obtaining high relaxivity enhancements. The viral capsid conjugated gadolinium hydroxypyridonate complexes appear to possess two inner-sphere water molecules (q = 2) and the NMRD fittings highlight the differences in the local motion for the internal ({tau}{sub RI} = 440 ps) and external ({tau}{sub RI} = 310 ps) conjugates. These results indicate that there are significant advantages of using the internal surface of the capsids for contrast agent attachment, leaving the exterior surface available for the installation of tissue targeting groups.

  16. Estimation of free copper ion concentrations in blood serum using T1 relaxation rates

    Science.gov (United States)

    Blicharska, Barbara; Witek, Magdalena; Fornal, Maria; MacKay, Alex L.

    2008-09-01

    The water proton relaxation rate constant R1 = 1/ T1 (at 60 MHz) of blood serum is substantially increased by the presence of free Cu 2+ ions at concentrations above normal physiological levels. Addition of chelating agents to serum containing paramagnetic Cu 2+ nulls this effect. This was demonstrated by looking at the effect of adding a chelating agent—D-penicillamine (D-PEN) to CuSO 4 and CuCl 2 aqueous solutions as well as to rabbit blood serum. We propose that the measurement of water proton spin-lattice relaxation rate constants before and after chelation may be used as an alternative approach for monitoring the presence of free copper ions in blood serum. This method may be used in the diagnosis of some diseases (leukaemia, liver diseases and particularly Wilson's disease) because, in contrast to conventional methods like spectrophotometry which records the total number of both bound and free ions, the proton relaxation technique is sensitive solely to free paramagnetic ions dissolved in blood serum. The change in R1 upon chelation was found to be less than 0.06 s -1 for serum from healthy subjects but greater than 0.06 s -1 for serum from untreated Wilson's patients.

  17. Mechanisms and kinetics of noncatalytic ether reaction in supercritical water. 2. Proton-transferred fragmentation of dimethyl ether to formaldehyde in competition with hydrolysis.

    Science.gov (United States)

    Nagai, Yasuharu; Matubayasi, Nobuyuki; Nakahara, Masaru

    2005-04-28

    Noncatalytic reaction pathways and rates of dimethyl ether (DME) in supercritical water are determined in a tube reactor made of quartz according to liquid- and gas-phase 1H and 13C NMR observations. The reaction is studied at two concentrations (0.1 and 0.5 M) in supercritical water at 400 degrees C and over a water-density range of 0.1-0.6 g/cm3. The supercritical water reaction is compared with the neat one (in the absence of solvent) at 0.1 M and 400 degrees C. DME is found to decompose through (i) the proton-transferred fragmentation to methane and formaldehyde and (ii) the hydrolysis to methanol. Formaldehyde from reaction (i) is consecutively subjected to four types of redox reactions. Two of them proceed even without solvent: (iii) the unimolecular proton-transferred decarbonylation forming hydrogen and carbon monoxide and (iv) the bimolecular self-disproportionation generating methanol and carbon monoxide. When the solvent water is present, two additional paths are open: (v) the bimolecular self-disproportionation of formaldehyde with reactant water, producing methanol and formic acid, and (vi) the bimolecular cross-disproportionation between formaldehyde and formic acid, yielding methanol and carbonic acid. Methanol is produced through the three types of disproportionations (iv)-(vi) as well as the hydrolysis (ii). The presence of solvent water decelerates the proton-transferred fragmentation of DME; the rate constant is reduced by 40% at 0.5 g/cm3. This is caused by the suppression of low-frequency concerted motion corresponding to the reaction coordinate for the simultaneous C-O bond scission and proton transfer from one methyl carbon to the other. In contrast to the proton-transferred fragmentation, the hydrolysis of DME is markedly accelerated by increasing the water density. The latter becomes more important than the former in supercritical water at densities greater than 0.5 g/cm3.

  18. Effect of the Bethe surface description on the electronic excitations induced by energetic proton beams in liquid water and DNA

    Energy Technology Data Exchange (ETDEWEB)

    Abril, Isabel, E-mail: ias@ua.e [Departament de Fisica Aplicada, Universitat d' Alacant, Apartat 99, E-03080 Alacant (Spain); Denton, Cristian D.; Vera, Pablo de [Departament de Fisica Aplicada, Universitat d' Alacant, Apartat 99, E-03080 Alacant (Spain); Kyriakou, Ioanna; Emfietzoglou, Dimitris [Medical Physics Laboratory, University of Ioannina Medical School, Ioannina 451 10 (Greece); Garcia-Molina, Rafael [Departamento de Fisica - CIOyN, Universidad de Murcia, Apartado 4021, E-30080 Murcia (Spain)

    2010-06-15

    The irradiation of biological systems by energetic ion beams has multiple applications in medical physics and space radiation health, such as hadrontherapy for cancer treatment or protection of astronauts against space radiation. Therefore, for a better control and understanding of the effects of radiation damage in living tissues, it is necessary to advance an accurate description of the energy loss from the ion beam to the target. In the present work we use the dielectric formalism to calculate the probability for an energetic proton to produce electronic excitations in two targets of high biological interest, namely, liquid water and DNA. Also, the mean energy of the electronic excitations in these targets is found as a function of the incident proton energy. The electronic response of the target, characterized by its energy-loss function (ELF), is described by several models that fit the available experimental optical data (at zero momentum transfer), but use different approaches to obtain the Bethe surface, that is, to extend the ELF to any energy and momentum transferred.

  19. Effect of the Bethe surface description on the electronic excitations induced by energetic proton beams in liquid water and DNA

    Science.gov (United States)

    Abril, Isabel; Denton, Cristian D.; de Vera, Pablo; Kyriakou, Ioanna; Emfietzoglou, Dimitris; Garcia-Molina, Rafael

    2010-06-01

    The irradiation of biological systems by energetic ion beams has multiple applications in medical physics and space radiation health, such as hadrontherapy for cancer treatment or protection of astronauts against space radiation. Therefore, for a better control and understanding of the effects of radiation damage in living tissues, it is necessary to advance an accurate description of the energy loss from the ion beam to the target. In the present work we use the dielectric formalism to calculate the probability for an energetic proton to produce electronic excitations in two targets of high biological interest, namely, liquid water and DNA. Also, the mean energy of the electronic excitations in these targets is found as a function of the incident proton energy. The electronic response of the target, characterized by its energy-loss function (ELF), is described by several models that fit the available experimental optical data (at zero momentum transfer), but use different approaches to obtain the Bethe surface, that is, to extend the ELF to any energy and momentum transferred.

  20. Application of differential scanning calorimetry to measure the differential binding of ions, water and protons in the unfolding of DNA molecules.

    Science.gov (United States)

    Olsen, Chris M; Shikiya, Ronald; Ganugula, Rajkumar; Reiling-Steffensmeier, Calliste; Khutsishvili, Irine; Johnson, Sarah E; Marky, Luis A

    2016-05-01

    The overall stability of DNA molecules globally depends on base-pair stacking, base-pairing, polyelectrolyte effect and hydration contributions. In order to understand how they carry out their biological roles, it is essential to have a complete physical description of how the folding of nucleic acids takes place, including their ion and water binding. To investigate the role of ions, water and protons in the stability and melting behavior of DNA structures, we report here an experimental approach i.e., mainly differential scanning calorimetry (DSC), to determine linking numbers: the differential binding of ions (Δnion), water (ΔnW) and protons (ΔnH(+)) in the helix-coil transition of DNA molecules. We use DSC and temperature-dependent UV spectroscopic techniques to measure the differential binding of ions, water, and protons for the unfolding of a variety of DNA molecules: salmon testes DNA (ST-DNA), one dodecamer, one undecamer and one decamer duplexes, nine hairpin loops, and two triplexes. These methods can be applied to any conformational transition of a biomolecule. We determined complete thermodynamic profiles, including all three linking numbers, for the unfolding of each molecule. The favorable folding of a DNA helix results from a favorable enthalpy-unfavorable entropy compensation. DSC thermograms and UV melts as a function of salt, osmolyte and proton concentrations yielded releases of ions and water. Therefore, the favorable folding of each DNA molecule results from the formation of base-pair stacks and uptake of both counterions and water molecules. In addition, the triplex with C(+)GC base triplets yielded an uptake of protons. Furthermore, the folding of a DNA duplex is accompanied by a lower uptake of ions and a similar uptake of four water molecules as the DNA helix gets shorter. In addition, the oligomer duplexes and hairpin thermodynamic data suggest ion and water binding depends on the DNA sequence rather than DNA composition. Copyright

  1. Commissioning dose computation models for spot scanning proton beams in water for a commercially available treatment planning system

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, X. R.; Poenisch, F.; Lii, M.; Sawakuchi, G. O.; Titt, U.; Bues, M.; Song, X.; Zhang, X.; Li, Y.; Ciangaru, G.; Li, H.; Taylor, M. B.; Suzuki, K.; Mohan, R.; Gillin, M. T.; Sahoo, N. [Department of Radiation Physics, University of Texas MD Anderson Cancer Center, Houston, Texas 77030 (United States)

    2013-04-15

    Purpose: To present our method and experience in commissioning dose models in water for spot scanning proton therapy in a commercial treatment planning system (TPS). Methods: The input data required by the TPS included in-air transverse profiles and integral depth doses (IDDs). All input data were obtained from Monte Carlo (MC) simulations that had been validated by measurements. MC-generated IDDs were converted to units of Gy mm{sup 2}/MU using the measured IDDs at a depth of 2 cm employing the largest commercially available parallel-plate ionization chamber. The sensitive area of the chamber was insufficient to fully encompass the entire lateral dose deposited at depth by a pencil beam (spot). To correct for the detector size, correction factors as a function of proton energy were defined and determined using MC. The fluence of individual spots was initially modeled as a single Gaussian (SG) function and later as a double Gaussian (DG) function. The DG fluence model was introduced to account for the spot fluence due to contributions of large angle scattering from the devices within the scanning nozzle, especially from the spot profile monitor. To validate the DG fluence model, we compared calculations and measurements, including doses at the center of spread out Bragg peaks (SOBPs) as a function of nominal field size, range, and SOBP width, lateral dose profiles, and depth doses for different widths of SOBP. Dose models were validated extensively with patient treatment field-specific measurements. Results: We demonstrated that the DG fluence model is necessary for predicting the field size dependence of dose distributions. With this model, the calculated doses at the center of SOBPs as a function of nominal field size, range, and SOBP width, lateral dose profiles and depth doses for rectangular target volumes agreed well with respective measured values. With the DG fluence model for our scanning proton beam line, we successfully treated more than 500 patients

  2. Molecular dynamics simulations of triflic acid and triflate ion/water mixtures: a proton conducting electrolytic component in fuel cells.

    Science.gov (United States)

    Sunda, Anurag Prakash; Venkatnathan, Arun

    2011-11-30

    Triflic acid is a functional group of perflourosulfonated polymer electrolyte membranes where the sulfonate group is responsible for proton conduction. However, even at extremely low hydration, triflic acid exists as a triflate ion. In this work, we have developed a force-field for triflic acid and triflate ion by deriving force-field parameters using ab initio calculations and incorporated these parameters with the Optimized Potentials for Liquid Simulations - All Atom (OPLS-AA) force-field. We have employed classical molecular dynamics (MD) simulations with the developed force field to characterize structural and dynamical properties of triflic acid (270-450 K) and triflate ion/water mixtures (300 K). The radial distribution functions (RDFs) show the hydrophobic nature of CF(3) group and presence of strong hydrogen bonding in triflic acid and temperature has an insignificant effect. Results from our MD simulations show that the diffusion of triflic acid increases with temperature. The RDFs from triflate ion/water mixtures shows that increasing hydration causes water molecules to orient around the SO(3)(-) group of triflate ions, solvate the hydronium ions, and other water molecules. The diffusion of triflate ions, hydronium ion, and water molecules shows an increase with hydration. At λ = 1, the diffusion of triflate ion is 30 times lower than the diffusion of triflic acid due to the formation of stable triflate ion-hydronium ion complex. With increasing hydration, water molecules break the stability of triflate ion-hydronium ion complex leading to enhanced diffusion. The RDFs and diffusion coefficients of triflate ions, hydronium ions and water molecules resemble qualitatively the previous findings using per-fluorosulfonated membranes.

  3. Coupled modeling of water transport and air-droplet interaction in the electrode of a proton exchange membrane fuel cell

    Science.gov (United States)

    Esposito, Angelo; Pianese, Cesare; Guezennec, Yann G.

    In this work, an accurate and computationally fast model for liquid water transport within a proton exchange membrane fuel cell (PEMFC) electrode is developed by lumping the space-dependence of the relevant variables. Capillarity is considered as the main transport mechanism within the gas diffusion layer (GDL). The novelty of the model lies in the coupled simulation of the water transport at the interface between gas diffusion layer and gas flow channel (GFC). This is achieved with a phenomenological description of the process that allows its simulation with relative simplicity. Moreover, a detailed two-dimensional visualization of such interface is achieved via geometric simulation of water droplets formation, growth, coalescence and detachment on the surface of the GDL. The model is useful for optimization analysis oriented to both PEMFC design and balance of plant. Furthermore, the accomplishment of reduced computational time and good accuracy makes the model suitable for control strategy implementation to ensure PEM fuel cells operation within optimal electrode water content.

  4. A dielectric response study of the electronic stopping power of liquid water for energetic protons and a new I-value for water.

    Science.gov (United States)

    Emfietzoglou, D; Garcia-Molina, R; Kyriakou, I; Abril, I; Nikjoo, H

    2009-06-07

    The electronic stopping power of liquid water for protons over the 50 keV to 10 MeV energy range is studied using an improved dielectric response model which is in good agreement with the best available experimental data. The mean excitation energy (I) of stopping power theory is calculated to be 77.8 eV. Shell corrections are accounted for in a self-consistent manner through analytic dispersion relations for the momentum dependence of the dielectric function. It is shown that widely used dispersion schemes based on the random-phase approximation (RPA) can result in sizeable errors due to the neglect of damping and local field effects that lead to a momentum broadening and shifting of the energy-loss function. Low-energy Born corrections for the Barkas, Bloch and charge-state effects practically cancel out down to 100 keV proton energies. Differences with ICRU Report 49 stopping power values and earlier calculations are found to be at the approximately 20% level in the region of the stopping maximum. The present work overcomes the limitations of the Bethe formula below 1 MeV and improves the accuracy of previous calculations through a more consistent account of the dielectric response properties of liquid water.

  5. Explanation of Effect of Added Water on Dye-Sensitized Nanocrystalline TiO2 Solar Cell: Correlation between Performance and Carrier Relaxation Kinetics

    Science.gov (United States)

    Zhao, Hui; Yin, Xiong; Li, Heng; Lin, Yuan; Weng, Yu-Xiang

    2007-11-01

    Time-resolved mid-IR transient absorption spectroscopy is employed to explore the mechanism of improving the performance of dye-sensitized TiO2 solar cell (DSSC) when a certain amount of H2O is added into the electrolyte. The relaxation kinetics of dye-sensitized TiO2 nanocrystalline film and the corresponding DSSC performance are investigated under different conditions. It is found that the interfacial charge recombination is retarded and electron injection efficiency is increased in the water vapour and in the electrolyte when D2O is added. The values of open-circuit photovoltage Voc and the short-circuit photocurrent Jsc of the cells are linearly correlated to the product of the two decay time constants. We also observed that Voc well correlates with electron injection efficiency. It provides a preliminary microscopic account for the function of the added water in improving the performance of DSSCs.

  6. Explanation of Effect of Added Water on Dye-Sensitized Nanocrystalline TiO2 Solar Cell: Correlation between Performance and Carrier Relaxation Kinetics

    Institute of Scientific and Technical Information of China (English)

    ZHAO Hui; YIN Xiong; LI Heng; LIN Yuan; WENG Yu-Xiang

    2007-01-01

    Time-resolved mid-IR transient absorption spectroscopy is employed to explore the mechanism of improving the performance of dye-sensitized TiOi solar cell (DSSC) when a certain amount of HiO is added into the electrolyte. The relaxation kinetics of dye-sensitized TiO2 nanocrystalline film and the corresponding DSSC performance are investigated under different conditions. It is found that the interfacial charge recombination is retarded and electron injection efficiency is increased in the water vapour and in the electrolyte when D2O is added. The values of open-circuit photovoltage Voc and the short-circuit photocurrent Jsc of the cells are linearly correlated to the product of the two decay time constants. We also observed that Voc well correlates with electron injection efficiency. It provides a preliminary microscopic account for the function of the added water in improving the performance of DSSCs.

  7. Single and multiple electron removal and fragmentation in collisions of protons with water molecules

    Science.gov (United States)

    Gulyás, L.; Egri, S.; Ghavaminia, H.; Igarashi, A.

    2016-03-01

    Single and multiple electron removal processes (capture and ionization) in proton-H2O collisions have been investigated applying the continuum distorted wave with eikonal initial-state model within the framework of independent electron approach. Probabilities and cross sections for electron capture are derived from the same quantities evaluated for ionization using the continuity of transition quantities across the ionization threshold. Dissociation and fragmentation cross sections for the H2Oq + (q =1 -3) ions have been evaluated by considering branching ratios that include the effect of multiple electron removal transitions. The results are compared with experimental and other theoretical data in the range of impact energies from 30 kev to 5 MeV. Generally, the evaluated cross sections and fragmentation yields show good agreement with experiments at impact energies above 100-150 keV.

  8. Natural relaxation

    Science.gov (United States)

    Marzola, Luca; Raidal, Martti

    2016-11-01

    Motivated by natural inflation, we propose a relaxation mechanism consistent with inflationary cosmology that explains the hierarchy between the electroweak scale and Planck scale. This scenario is based on a selection mechanism that identifies the low-scale dynamics as the one that is screened from UV physics. The scenario also predicts the near-criticality and metastability of the Standard Model (SM) vacuum state, explaining the Higgs boson mass observed at the Large Hadron Collider (LHC). Once Majorana right-handed neutrinos are introduced to provide a viable reheating channel, our framework yields a corresponding mass scale that allows for the seesaw mechanism as well as for standard thermal leptogenesis. We argue that considering singlet scalar dark matter extensions of the proposed scenario could solve the vacuum stability problem and discuss how the cosmological constant problem is possibly addressed.

  9. Non-noble metal based electro-catalyst compositions for proton exchange membrane based water electrolysis and methods of making

    Energy Technology Data Exchange (ETDEWEB)

    Kumta, Prashant N.; Kadakia, Karan Sandeep; Datta, Moni Kanchan; Velikokhatnyi, Oleg

    2017-02-07

    The invention provides electro-catalyst compositions for an anode electrode of a proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VII of the Periodic Table. The compositions can be prepared using a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.

  10. Relationship between water departure and capacity loss of α and β-PbO 2 using an all solid-state system: Estimation of proton diffusion coefficient

    Science.gov (United States)

    Zerroual, L.; Fitas, R.; Djellouli, B.; Chelali, N.

    The proton diffusion coefficient for both fresh and heat-treated (140 and 230 °C, respectively) α and β-PbO 2 electrodes was estimated at room temperature using Galvanostatic Intermittent Titration Technique (GITT). PbO 2 samples were prepared by electroformation of cured plates. HSbO 3· xH 2O with a conductivity of 3.29 × 10 -3 Ω -1 cm -1, was used as solid protonic conductor (SPC) electrolyte. It was found that when structural water is removed, the capacity of both α and β-PbO 2 electrodes decreases and the ohmic drop increases. The departure of structural water affects considerably the value of proton diffusion coefficient.

  11. Relationship between water departure and capacity loss of {alpha} and {beta}-PbO{sub 2} using an all solid-state system: Estimation of proton diffusion coefficient

    Energy Technology Data Exchange (ETDEWEB)

    Zerroual, L.; Fitas, R.; Djellouli, B.; Chelali, N. [Laboratoire d' Energetique et Electrochimie du Solide, Universite Ferhat ABBAS, Setif 19000 (Algeria)

    2006-08-25

    The proton diffusion coefficient for both fresh and heat-treated (140 and 230{sup o}C, respectively) {alpha} and {beta}-PbO{sub 2} electrodes was estimated at room temperature using Galvanostatic Intermittent Titration Technique (GITT). PbO{sub 2} samples were prepared by electroformation of cured plates. HSbO{sub 3}.xH{sub 2}O with a conductivity of 3.29x10{sup -3}{omega}{sup -1}cm{sup -1}, was used as solid protonic conductor (SPC) electrolyte. It was found that when structural water is removed, the capacity of both {alpha} and {beta}-PbO{sub 2} electrodes decreases and the ohmic drop increases. The departure of structural water affects considerably the value of proton diffusion coefficient. (author)

  12. Eigen-like hydrated protons traveling with a local distortion through the water nanotube in new molecular porous crystals {[M(III)(H2bim)3](TMA)·20H2O}n (M = Co, Rh, Ru).

    Science.gov (United States)

    Matsui, Hiroshi; Tadokoro, Makoto

    2012-10-14

    In molecular porous crystals {[M(III)(H(2)bim)(3)](TMA)·20H(2)O}(n) (M = Co, Rh, Ru), the structural property of confined water network and the dynamics of mobile hydrated protons have been examined by the measurement of infrared spectrum and microwave conductivity. The water network undergoes first order phase transition from the ice nanotube (INT) to the water nanotube (WNT) around 200 K, while the infrared spectral features for these states are almost equivalent. Consequently, the water molecules in WNT dynamically fluctuate in the vicinity of the regulated position in INT with maintaining the O-O distance. The additional band observed around 2200 cm(-1) reveals the emergence of an Eigen-like protonic hydrate, around which the O-O distance locally shrinks to ~2.56 Å. The microwave conductivity exhibiting activation-type behavior, isotope effect and anisotropy indicates that the water nanotube is a quasi one-dimensional high proton conductor. Together with the neutron experimental results, we have clarified that the proton and protonic hole are generated by the self-dissociation in some water molecules just hydrated to the carboxylate oxygen atom of trimesic acid. The Eigen-like hydrated proton and protonic hole contribute to the intrinsic proton conduction accompanying local distortions. The carrier density dominated by the intrinsic ionic equilibrium is not large, whereas the actual mobility, which is higher than 1 × 10(-2) (cm(2)/Vs), yields the present high proton conductivity.

  13. NMR studies of proton exchange kinetics in aqueous formaldehyde solutions

    Science.gov (United States)

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2014-05-01

    Aqueous solutions of formaldehyde, formalin, are commonly used for tissue fixation and preservation. Treatment with formalin is known to shorten the tissue transverse relaxation time T2. Part of this shortening is due to the effect of formalin on the water T2. In the present work we show that the shortening of water T2 is a result of proton exchange between water and the major constituent of aqueous solutions of formaldehyde, methylene glycol. We report the observation of the signal of the hydroxyl protons of methylene glycol at 2 ppm to high frequency of the water signal that can be seen at low temperatures and at pH range of 6.0 ± 1.5 and, at conditions where it cannot be observed by the single pulse experiment, it can be detected indirectly through the water signal by the chemical exchange saturation transfer (CEST) experiment. The above finding made it possible to obtain the exchange rate between the hydroxyl protons of the methylene glycol and water in aqueous formaldehyde solutions, either using the dispersion of the spin-lattice relaxation rate in the rotating frame (1/T1ρ) or, at the slow exchange regime, from the line width hydroxyl protons of methylene glycol. The exchange rate was ∼104 s-1 at pH 7.4 and 37 °C, the activation energy, 50.2 kJ/mol and its pH dependence at 1.1 °C was fitted to: k (s-1) = 520 + 6.5 × 107[H+] + 3.0 × 109[OH-].

  14. Simultaneous spectral and temporal analyses of kinetic energies in nonequilibrium systems: theory and application to vibrational relaxation of O-D stretch mode of HOD in water.

    Science.gov (United States)

    Jeon, Jonggu; Lim, Joon Hyung; Kim, Seongheun; Kim, Heejae; Cho, Minhaeng

    2015-05-28

    A time series of kinetic energies (KE) from classical molecular dynamics (MD) simulation contains fundamental information on system dynamics. It can also be analyzed in the frequency domain through Fourier transformation (FT) of velocity correlation functions, providing energy content of different spectral regions. By limiting the FT time span, we have previously shown that spectral resolution of KE evolution is possible in the nonequilibrium situations [Jeon and Cho, J. Chem. Phys. 2011, 135, 214504]. In this paper, we refine the method by employing the concept of instantaneous power spectra, extending it to reflect an instantaneous time-correlation of velocities with those in the future as well as with those in the past, and present a new method to obtain the instantaneous spectral density of KE (iKESD). This approach enables the simultaneous spectral and temporal resolution of KE with unlimited time precision. We discuss the formal and novel properties of the new iKESD approaches and how to optimize computational methods and determine parameters for practical applications. The method is specifically applied to the nonequilibrium MD simulation of vibrational relaxation of the OD stretch mode in a hydrated HOD molecule by employing a hybrid quantum mechanical/molecular mechanical (QM/MM) potential. We directly compare the computational results with the OD band population relaxation time profiles extracted from the IR pump-probe measurements for 5% HOD in water. The calculated iKESD yields the OD bond relaxation time scale ∼30% larger than the experimental value, and this decay is largely frequency-independent if the classical anharmonicity is accounted for. From the integrated iKESD over intra- and intermolecular bands, the major energy transfer pathways were found to involve the HOD bending mode in the subps range, then the internal modes of the solvent until 5 ps after excitation, and eventually the solvent intermolecular modes. Also, strong hydrogen

  15. Does urea alter the collective hydrogen-bond dynamics in water? A dielectric relaxation study in the terahertz-frequency region.

    Science.gov (United States)

    Samanta, Nirnay; Das Mahanta, Debasish; Kumar Mitra, Rajib

    2014-12-01

    We report the ultrafast collective hydrogen-bond dynamics of water in the extended hydration layer of urea by using terahertz time-domain spectroscopy in the frequency region of 0.3-2.0 THz. The complex dielectric function has been fitted using a Debye relaxation model, and the timescales obtained are in the order of approximately 9 ps and 200 fs for bulk water; this exhibits a considerable acceleration beyond the 4 M urea concentration and indicates a possible disruption in the collective hydrogen-bonded water-network structure, which, in turn, provides an indirect support for the water "structure-breaking" ability of urea. With 5 M urea in the presence of different concentrations of trimethylamine-N-oxide (TMAO), it was found that these parameters essentially follow the trend observed for TMAO itself, which signifies that any possible disruption of the water structure by urea is outdone by the strong hydrogen-bonding ability of TMAO, which explains its ability to revive urea-denatured proteins to their respective native states.

  16. Water free proton conducting membranes based on poly-4-vinylpyridinebisulfate for fuel cells

    Science.gov (United States)

    Narayanan, Sekharipuram R. (Inventor); Yen, Shiao-Pin S. (Inventor)

    2007-01-01

    Disclosed are methods for forming a water-free electrolyte membrane useful in fuel cells. Also provided is a water-free electrolyte membrane comprising a quaternized amine salt including poly-4-vinylpyridinebisulfate, a poly-4-vinylpyridinebisulfate silica composite, and a combination thereof and a fuel cell comprising the membrane.

  17. Polaronic exciton in self-organized assemblies of protonated meso-tetraphenylporphine dimers and water at room temperature

    Science.gov (United States)

    Udal'tsov, Alexander V.

    2016-12-01

    Assemblies consisting of protonated meso-tetraphenylporphine (TPP) dimers and water have been investigated by UV-vis and infrared (IR) spectroscopy and by atomic force microscopy (AFM) in thin layers. Features of electronic absorption spectra of the assemblies are interpreted in terms of hole polaron combined with exciton theory using quantum well with parameters obtained from the dimer structure. It appears to be hole polaron moving defines kinetic energy of polaronic exciton confined in a quantum well when the electron absorbs photon. Hole polaron characteristics such as polaron self-energy, energy of Frank-Condon transitions, and radius of hole polaron moving through water are found to be 1.38 eV, 0.2445 eV, and 0.246 Å, respectively. A doublet at 1944, 1960 cm-1 (0.2412, 0.2432 eV) observed in IR spectra matches the energy of Frank-Condon transitions. Excitation energies estimated using molecular parameters for polaronic excitons in pure water and in the TPP dimers are found in a good agreement with the experimental data.

  18. Local area water removal analysis of a proton exchange membrane fuel cell under gas purge conditions.

    Science.gov (United States)

    Lee, Chi-Yuan; Lee, Yu-Ming; Lee, Shuo-Jen

    2012-01-01

    In this study, local area water content distribution under various gas purging conditions are experimentally analyzed for the first time. The local high frequency resistance (HFR) is measured using novel micro sensors. The results reveal that the liquid water removal rate in a membrane electrode assembly (MEA) is non-uniform. In the under-the-channel area, the removal of liquid water is governed by both convective and diffusive flux of the through-plane drying. Thus, almost all of the liquid water is removed within 30 s of purging with gas. However, liquid water that is stored in the under-the-rib area is not easy to remove during 1 min of gas purging. Therefore, the re-hydration of the membrane by internal diffusive flux is faster than that in the under-the-channel area. Consequently, local fuel starvation and membrane degradation can degrade the performance of a fuel cell that is started from cold.

  19. Applying hot-wire anemometry to directly measure the water balance in a proton exchange membrane fuel cell for a pre-humidified hydrogen stream

    DEFF Research Database (Denmark)

    Berning, Torsten; Shakhshir, Saher Al

    2016-01-01

    In a recent publication it has been shown how the water balance in a proton exchange membrane fuel cell can be determined employing hot wire anemometry. The hot wire sensor has to be placed into the anode outlet pipe of the operating fuel cell, and the voltage signal E that is read from the senso...

  20. Near-Barrierless Ammonium Bisulfate Formation via a Loop-Structure Promoted Proton-Transfer Mechanism on the Surface of Water.

    Science.gov (United States)

    Li, Lei; Kumar, Manoj; Zhu, Chongqin; Zhong, Jie; Francisco, Joseph S; Zeng, Xiao Cheng

    2016-02-17

    In the atmosphere, a well-known and conventional pathway toward the formation of ammonium sulfate is through the neutralization of sulfuric acid with ammonia (NH3) in water droplets. Here, we present direct ab initio molecular dynamics simulation evidence of the formation of ammonium bisulfate (NH4HSO4) from the hydrated NH3 and SO3 molecules in a water trimer as well as on the surface of a water droplet. This reaction suggests a new mechanism for the formation of ammonium sulfate in the atmosphere, especially when the concentration of NH3 is high (e.g., ∼10 μg m(-3)) in the air. Contrary to the water monomer and dimer, the water trimer enables near-barrierless proton transfer via the formation of a unique loop structure around the reaction center. The formation of the loop structure promotes the splitting of a water molecule in the proton-transfer center, resulting in the generation a NH4(+)/HSO4(-) ion pair. The loop-structure promoted proton-transfer mechanism is expected to be ubiquitous on the surface of cloud droplets with adsorbed NH3 and SO3 molecules and, thus, may play an important role in the nucleation of aerosol particles (e.g., fine particles PM2.5) in water droplets.

  1. Behavioural Change according to the Si/Al Ratio of Successive Na-Mordenites Observed through Their Dielectric Relaxation during Water Vapour Adsorption Process

    Directory of Open Access Journals (Sweden)

    Sekou Diaby

    2016-01-01

    Full Text Available The experimental study of water vapour adsorption phenomenon on a zeolite, by dielectric relaxation measurement, makes it possible to determine the variations in the exchangeable cation hopping activation energy, on the surface of the solid, in relation to the number of adsorbed molecules. The present work shows that it is possible to explain the change observed in the energy, by means of simple assumptions based, on the one hand, on the models used in order to simulate the adsorption process and, on the other hand, on the distribution of the molecules adsorbed near the exchangeable cations. Thus, the phenomenological interpretation suggested here, about the change in the exchangeable cation hopping energy, obtained by dielectric relaxation measurement, makes us with a mind to conceive a simple method for explaining the results leading to new information on the organization of the first adsorbed molecules on the surface of the studied zeolite. Then, it can be verified that these conclusions confirm the assumptions already developed for interpreting the inferences from previous experiments carried out by means of other techniques.

  2. Measurement of LET (linear energy transfer) spectra using CR-39 at different depths of water irradiated by 171 MeV protons: A comparison with Monte Carlo simulation

    Energy Technology Data Exchange (ETDEWEB)

    Sahoo, G.S. [Health Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Tripathy, S.P., E-mail: sam.tripathy@gmail.com [Health Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Homi Bhabha National Institute, Mumbai 400094 (India); Molokanov, A.G.; Aleynikov, V.E. [Joint Institute for Nuclear Research, Dubna 141980 (Russian Federation); Sharma, S.D. [Homi Bhabha National Institute, Mumbai 400094 (India); Radiological Physics & Advisory Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Bandyopadhyay, T. [Health Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Homi Bhabha National Institute, Mumbai 400094 (India)

    2016-05-11

    In this work, we have used CR-39 detectors to estimate the LET (linear energy transfer) spectrum of secondary particles due to 171 MeV proton beam at different depths of water including the Bragg peak region. The measured LET spectra were compared with those obtained from FLUKA Monte Carlo simulation. The absorbed dose (D{sub LET}), dose equivalent (H{sub LET}) were estimated using the LET spectra. The values of D{sub LET} and H{sub LET} per incident proton fluence were found to increase with the increase in depth of water and were maximum at Bragg peak. - Highlights: • Measurement of LET spectrometry using CR-39 detectors at different depths of water. • Comparison of measured spectra with FLUKA Monte carlo simulation. • Absorbed dose and dose equivalent was found to increase with depth of water.

  3. Excited state proton transfer in 9-aminoacridine carboxamides in water and in DNA

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Charles A. [Iowa State Univ., Ames, IA (United States)

    1995-09-26

    The 9-aminoacridine molecule is important in several different fields of chemistry. The absorption and fluorescence spectra of this compound are pH sensitive and it is this property that allowed it to be used as a pH probe in different chemical environments. The compound exhibits proton transfer reactions which are among the most fundamental of chemical reactions. The planarity of 9-aminoacridine allows it to intercalate into DNA. Intercalation is a process in which the aromatic flat surface of the intercalator inserts between adjacent base pairs of DNA. The large surface area of 9-aminoacridine`s fused tricyclic ring system allows strong intercalative binding through van der Waals attractions. 9-aminoacridine and many of its derivatives have been tried as possible antitumor drugs. The cytotoxicity of an antitumor agent can be dramatically increased through the addition of one or two cationic side chains. This increase in cytotoxicity using the 9-aminoacridine compound as a parent molecule has been investigated through various derivatives with cationic side chains consisting of different number of carbon atoms between the proximal and distal N atoms. Similar derivatives varied the position of the carboxamide side chain on the aromatic ring system. The objective of this work is to first create a baseline study of the excited state kinetics of the 9-aminoacridine carboxamides in the absence of DNA. The baseline study will allow the excited state kinetics of these antitumor drugs when placed in DNA to be more fully understood.

  4. Single- and Multiple-Electron Removal Processes in Proton-Water Vapor Collisions

    Science.gov (United States)

    Murakami, Mitsuko; Kirchner, Tom; Horbatsch, Marko; Jürgen Lüdde, Hans

    2012-06-01

    Charge-state correlated cross sections for single- and multiple-electron removal processes due to capture and ionization in proton-H2O collisions are calculated by using the non-perturbative basis generator method adapted for ion-molecule collisions [1]. Orbital-specific cross sections for vacancy production are evaluated using this method to predict the yields of charged fragments (H2O^+, OH^+, H^+, O^+) according to branching ratios known to be valid at high impact energies. At intermediate and low energies, we obtain fragmentation results on the basis of predicted multi-electron removal cross sections, and explain most of the available experimental data [2]. The cross sections for charge transfer and for ionization are also compared with recent multi-center classical-trajectory Monte Carlo calculations [3] for impact energies from 20keV to several MeV. [4pt] [1] H.J. L"udde et al, Phys. Rev. A 80, 060702(R) (2009)[0pt] [2] M. Murakami et al, to be submitted to Phys. Rev. A (2012)[0pt] [3] C. Illescas et al, Phys. Rev. A 83, 052704 (2011)

  5. Pore network model of the cathode catalyst layer of proton exchange membrane fuel cells: Analysis of water management and electrical performance

    OpenAIRE

    El Hannach, Mohamed; Prat, Marc; Pauchet, Joël

    2012-01-01

    International audience; A pore network modeling approach is developed to study multiphase transport phenomena inside a porous structure representative of the Cathode Catalyst Layer (CCL) of Proton Exchange Membrane Fuel Cell. A full coupling between two-phase transport, charge transport and heat transport is considered. The liquid water evaporation is also taken into account. The current density profile and the liquid water distribution and production are investigated to understand the liquid...

  6. Surface Protonics Promotes Catalysis

    Science.gov (United States)

    Manabe, R.; Okada, S.; Inagaki, R.; Oshima, K.; Ogo, S.; Sekine, Y.

    2016-12-01

    Catalytic steam reforming of methane for hydrogen production proceeds even at 473 K over 1 wt% Pd/CeO2 catalyst in an electric field, thanks to the surface protonics. Kinetic analyses demonstrated the synergetic effect between catalytic reaction and electric field, revealing strengthened water pressure dependence of the reaction rate when applying an electric field, with one-third the apparent activation energy at the lower reaction temperature range. Operando-IR measurements revealed that proton conduction via adsorbed water on the catalyst surface occurred during electric field application. Methane was activated by proton collision at the Pd-CeO2 interface, based on the inverse kinetic isotope effect. Proton conduction on the catalyst surface plays an important role in methane activation at low temperature. This report is the first describing promotion of the catalytic reaction by surface protonics.

  7. Water Availability as a Measure of Cellulose Hydrolysis Efficiency

    DEFF Research Database (Denmark)

    Hsieh, Chia-Wen

    of sugars, salts, and surfactants impact the water relaxation time. Systems with high concentrations of sugars and salts tend to have low water availability, as these form strong interactions with water to keep their solubility, leaving less water available for hydrolysis. Thus, cellulase performance...... to measure properties of the liquid phase, where water protons are characterized based on their mobility in the system as measured by their relaxation time. Studies of cellulose hydrolysis at low dry matter show that the contents of the liquid phase influence the final hydrolysis yield, as the presence...

  8. Simple expressions of the nuclear relaxation rate enhancement due to quadrupole nuclei in slowly tumbling molecules

    Energy Technology Data Exchange (ETDEWEB)

    Fries, Pascal H., E-mail: pascal-h.fries@cea.fr [Université Grenoble Alpes, INAC-SCIB, RICC, F-38000 Grenoble (France); CEA, INAC-SCIB, RICC, F-38000 Grenoble (France); Belorizky, Elie [Université Grenoble Alpes, LIPHY, F-38000 Grenoble (France); CEA, Leti-Clinatec, F-38000 Grenoble (France)

    2015-07-28

    For slowly tumbling entities or quasi-rigid lattices, we derive very simple analytical expressions of the quadrupole relaxation enhancement (QRE) of the longitudinal relaxation rate R{sub 1} of nuclear spins I due to their intramolecular magnetic dipolar coupling with quadrupole nuclei of arbitrary spins S ≥ 1. These expressions are obtained by using the adiabatic approximation for evaluating the time evolution operator of the quantum states of the quadrupole nuclei S. They are valid when the gyromagnetic ratio of the spin S is much smaller than that of the spin I. The theory predicts quadrupole resonant peaks in the dispersion curve of R{sub 1} vs magnetic field. The number, positions, relative intensities, Lorentzian shapes, and widths of these peaks are explained in terms of the following properties: the magnitude of the quadrupole Hamiltonian and the asymmetry parameter of the electric field gradient (EFG) acting on the spin S, the S-I inter-spin orientation with respect to the EFG principal axes, the rotational correlation time of the entity carrying the S–I pair, and/or the proper relaxation time of the spin S. The theory is first applied to protein amide protons undergoing dipolar coupling with fast-relaxing quadrupole {sup 14}N nuclei and mediating the QRE to the observed bulk water protons. The theoretical QRE agrees well with its experimental counterpart for various systems such as bovine pancreatic trypsin inhibitor and cartilages. The anomalous behaviour of the relaxation rate of protons in synthetic aluminium silicate imogolite nano-tubes due to the QRE of {sup 27}Al (S = 5/2) nuclei is also explained.

  9. Electronic and vibrational spectra of protonated benzaldehyde-water clusters, [BZ-(H2O)n≤5]H+: evidence for ground-state proton transfer to solvent for n ≥ 3.

    Science.gov (United States)

    Dopfer, Otto; Patzer, Alexander; Chakraborty, Shamik; Alata, Ivan; Omidyan, Reza; Broquier, Michel; Dedonder, Claude; Jouvet, Christophe

    2014-03-28

    Vibrational and electronic photodissociation spectra of mass-selected protonated benzaldehyde-(water)n clusters, [BZ-(H2O)n]H(+) with n ≤ 5, are analyzed by quantum chemical calculations to determine the protonation site in the ground electronic state (S0) and ππ(*) excited state (S1) as a function of microhydration. IR spectra of [BZ-(H2O)n]H(+) with n ≤ 2 are consistent with BZH(+)-(H2O)n type structures, in which the excess proton is localized on benzaldehyde. IR spectra of clusters with n ≥ 3 are assigned to structures, in which the excess proton is located on the (H2O)n solvent moiety, BZ-(H2O)nH(+). Quantum chemical calculations at the B3LYP, MP2, and ri-CC2 levels support the conclusion of proton transfer from BZH(+) to the solvent moiety in the S0 state for hydration sizes larger than the critical value nc = 3. The vibronic spectrum of the S1 ← S0 transition (ππ(*)) of the n = 1 cluster is consistent with a cis-BZH(+)-H2O structure in both electronic states. The large blueshift of the S1 origin by 2106 cm(-1) upon hydration with a single H2O ligand indicates that the proton affinity of BZ is substantially increased upon S1 excitation, thus strongly destabilizing the hydrogen bond to the solvent. The adiabatic S1 excitation energy and vibronic structure calculated at the ri-CC2/aug-cc-pVDZ level agrees well with the measured spectrum, supporting the notion of a cis-BZH(+)-H2O geometry. The doubly hydrated species, cis-BZH(+)-(H2O)2, does not absorb in the spectral range of 23 000-27 400 cm(-1), because of the additional large blueshift of the ππ(*) transition upon attachment of the second H2O molecule. Calculations predict roughly linear and large incremental blueshifts for the ππ(*) transition in [BZ-(H2O)n]H(+) as a function of n. In the size range n ≥ 3, the calculations predict a proton transfer from the (H2O)nH(+) solvent back to the BZ solute upon electronic ππ(*) excitation.

  10. Electronic and vibrational spectra of protonated benzaldehyde-water clusters, [BZ-(H2O)n≤5]H+: Evidence for ground-state proton transfer to solvent for n ≥ 3

    Science.gov (United States)

    Dopfer, Otto; Patzer, Alexander; Chakraborty, Shamik; Alata, Ivan; Omidyan, Reza; Broquier, Michel; Dedonder, Claude; Jouvet, Christophe

    2014-03-01

    Vibrational and electronic photodissociation spectra of mass-selected protonated benzaldehyde-(water)n clusters, [BZ-(H2O)n]H+ with n ≤ 5, are analyzed by quantum chemical calculations to determine the protonation site in the ground electronic state (S0) and ππ* excited state (S1) as a function of microhydration. IR spectra of [BZ-(H2O)n]H+ with n ≤ 2 are consistent with BZH+-(H2O)n type structures, in which the excess proton is localized on benzaldehyde. IR spectra of clusters with n ≥ 3 are assigned to structures, in which the excess proton is located on the (H2O)n solvent moiety, BZ-(H2O)nH+. Quantum chemical calculations at the B3LYP, MP2, and ri-CC2 levels support the conclusion of proton transfer from BZH+ to the solvent moiety in the S0 state for hydration sizes larger than the critical value nc = 3. The vibronic spectrum of the S1 ← S0 transition (ππ*) of the n = 1 cluster is consistent with a cis-BZH+-H2O structure in both electronic states. The large blueshift of the S1 origin by 2106 cm-1 upon hydration with a single H2O ligand indicates that the proton affinity of BZ is substantially increased upon S1 excitation, thus strongly destabilizing the hydrogen bond to the solvent. The adiabatic S1 excitation energy and vibronic structure calculated at the ri-CC2/aug-cc-pVDZ level agrees well with the measured spectrum, supporting the notion of a cis-BZH+-H2O geometry. The doubly hydrated species, cis-BZH+-(H2O)2, does not absorb in the spectral range of 23 000-27 400 cm-1, because of the additional large blueshift of the ππ* transition upon attachment of the second H2O molecule. Calculations predict roughly linear and large incremental blueshifts for the ππ* transition in [BZ-(H2O)n]H+ as a function of n. In the size range n ≥ 3, the calculations predict a proton transfer from the (H2O)nH+ solvent back to the BZ solute upon electronic ππ* excitation.

  11. Changes in the zero point energy of the protons as the source of the binding energy of water to A phase DNA

    CERN Document Server

    Reiter, G F; Mayers, J

    2010-01-01

    The zero point kinetic energy of protons in water is large on the scale of chemical interaction energies(29 Kj/mol in bulk room temperature water). Its value depends upon the structure of the hydrogen bond network, and can change as the network is confined or as water interacts with surfaces. These changes have been observed to be large on a chemical scale for water confined in carbon nanotubes and in the pores of xerogel, and may play a fundamental, and neglected, role in biological processes involving confined water. We measure the average momentum distribution of the protons in salmon Na-DNA using Deep Inelastic Neutron Scattering, for a weakly hydrated (6w/bp) and a dehydrated fiber sample. This permits the determination of the change in total kinetic energy of the system per water molecule removed from the DNA and placed in the bulk liquid. This energy is equal, within errors, to the measured enthalpy for the same process, demonstrating that changes in the zero point motion of the protons, arising from c...

  12. Water types and their relaxation behavior in partially rehydrated CaFe-mixed binary oxide obtained from CaFe-layered double hydroxide in the 155-298 K temperature range.

    Science.gov (United States)

    Bugris, Valéria; Haspel, Henrik; Kukovecz, Ákos; Kónya, Zoltán; Sipiczki, Mónika; Sipos, Pál; Pálinkó, István

    2013-10-29

    Heat-treated CaFe-layered double hydroxide samples were equilibrated under conditions of various relative humidities (11%, 43% and 75%). Measurements by FT-IR and dielectric relaxation spectroscopies revealed that partial to full reconstruction of the layered structure took place. Water types taking part in the reconstruction process were identified via dielectric relaxation measurements either at 298 K or on the flash-cooled (to 155 K) samples. The dynamics of water molecules at the various positions was also studied by this method, allowing the flash-cooled samples to warm up to 298 K.

  13. Key role of water in proton transfer at the Q(o)-site of the cytochrome bc(1) complex predicted by atomistic molecular dynamics simulations

    DEFF Research Database (Denmark)

    Postila, P. A.; Kaszuba, K.; Sarewicz, M.

    2013-01-01

    on the simulations we are able to show the atom-level binding modes of two substrate forms: quinol (QH(2)) and quinone (Q). The QH(2) binding at the Q(o)-site involves a coordinated water arrangement that produces an exceptionally close and stable interaction between the cyt b and iron sulfur protein subunits....... In this arrangement water molecules are positioned suitably in relation to the hydroxyls of the QH(2) ring to act as the primary acceptors of protons detaching from the oxidized substrate. In contrast, water does not have a similar role in the Q binding at the Q(o)-site. Moreover, the coordinated water molecule...

  14. A bio-inspired, small molecule electron-coupled-proton buffer for decoupling the half-reactions of electrolytic water splitting.

    Science.gov (United States)

    Rausch, Benjamin; Symes, Mark D; Cronin, Leroy

    2013-09-18

    Electron-coupled-proton buffers (ECPBs) allow H2 and O2 evolution to be separated from each other in time during the electrolysis of water. Natural photosynthetic systems achieve an analogous feat during water splitting and employ a range of intermediate redox mediators such as quinone derivatives to aid this process. Drawing on this natural example, we show that a low molecular weight quinone derivative is capable of decoupling H2 evolution from O2 evolution at scale during electrochemical water splitting. This work could significantly lower the cost of ECPBs, paving the way for their more widespread adoption in water splitting.

  15. Study of neutron spectra in a water bath from a Pb target irradiated by 250 MeV protons

    Science.gov (United States)

    Li, Yan-Yan; Zhang, Xue-Ying; Ju, Yong-Qin; Ma, Fei; Zhang, Hong-Bin; Chen, Liang; Ge, Hong-Lin; Wan, Bo; Luo, Peng; Zhou, Bin; Zhang, Yan-Bin; Li, Jian-Yang; Xu, Jun-Kui; Wang, Song-Lin; Yang, Yong-Wei; Yang, Lei

    2015-04-01

    Spallation neutrons were produced by the irradiation of Pb with 250 MeV protons. The Pb target was surrounded by water which was used to slow down the emitted neutrons. The moderated neutrons in the water bath were measured by using the resonance detectors of Au, Mn and In with a cadmium (Cd) cover. According to the measured activities of the foils, the neutron flux at different resonance energies were deduced and the epithermal neutron spectra were proposed. Corresponding results calculated with the Monte Carlo code MCNPX were compared with the experimental data to check the validity of the code. The comparison showed that the simulation could give a good prediction for the neutron spectra above 50 eV, while the finite thickness of the foils greatly effected the experimental data in low energy. It was also found that the resonance detectors themselves had great impact on the simulated energy spectra. Supported by National Natural Science Foundation and Strategic Priority Research Program of the Chinese Academy of Sciences (11305229, 11105186, 91226107, 91026009, XDA03030300)

  16. Effects of thermal conduction and convection on temperature profile in a water calorimeter for proton beams

    Energy Technology Data Exchange (ETDEWEB)

    Gargioni, E.; Manfredotti, C. [Torino Univ. (Italy). Dipt. di Fisica; Laitano, R.F.; Guerra, A.S. [Ist. Nazionale di Metrologia delle Radiazioni Ionizzanti, ENEA, Roma (Italy)

    1997-09-01

    In water calorimetry, in addition to the temperature increase due to beam energy deposition in water, unwanted thermal effects occur during and after calorimeter irradiation. This should be accounted for by applying proper corrections to the experimental results. In order to determine such corrections heat flow calculations were performed using the `finite element` method. This method applies even to complex 3D geometries with not necessarily symmetric conditions. Some preliminary results of these calculations are presented together with a description of the analytical method for the evaluation of the correction factors that should be applied to the experimental results to account for the above thermal effects. (orig.)

  17. Optimal pressure sensor placement for leak localisation using a relaxed isolation index : application to the Barcelona water network

    OpenAIRE

    Cugueró Escofet, Miquel Àngel; Puig Cayuela, Vicenç; Quevedo Casín, Joseba Jokin; Blesa Izquierdo, Joaquim

    2015-01-01

    Water distribution networks are large complex systems that are affected by leaks, which often entail high costs and may severely jeopardize the overall water distribution performance. Successful leak localisation is paramount in order to minimize the impact of these leaks when occurring. Sensor placement is a key issue in the leak localisation process, since the overall performance and success of the leak isolation method highly depends on the choice of the sensors gathering data from the net...

  18. 1H relaxation dispersion in solutions of nitroxide radicals: Influence of electron spin relaxation

    Science.gov (United States)

    Kruk, D.; Korpała, A.; Kubica, A.; Kowalewski, J.; Rössler, E. A.; Moscicki, J.

    2013-03-01

    The work presents a theory of nuclear (1H) spin-lattice relaxation dispersion for solutions of 15N and 14N radicals, including electron spin relaxation effects. The theory is a generalization of the approach presented by Kruk et al. [J. Chem. Phys. 137, 044512 (2012)], 10.1063/1.4736854. The electron spin relaxation is attributed to the anisotropic part of the electron spin-nitrogen spin hyperfine interaction modulated by rotational dynamics of the paramagnetic molecule, and described by means of Redfield relaxation theory. The 1H relaxation is caused by electron spin-proton spin dipole-dipole interactions which are modulated by relative translational motion of the solvent and solute molecules. The spectral density characterizing the translational dynamics is described by the force-free-hard-sphere model. The electronic relaxation influences the 1H relaxation by contributing to the fluctuations of the inter-molecular dipolar interactions. The developed theory is tested against 1H spin-lattice relaxation dispersion data for glycerol solutions of 4-oxo-TEMPO-d16-15N and 4-oxo-TEMPO-d16-14N covering the frequency range of 10 kHz-20 MHz. The studies are carried out as a function of temperature starting at 328 K and going down to 290 K. The theory gives a consistent overall interpretation of the experimental data for both 14N and 15N systems and explains the features of 1H relaxation dispersion resulting from the electron spin relaxation.

  19. Experimental research on water management in proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Li-jun; Chen, Wen-can; Qin, Ming-jun [Institute of Thermal Energy Engineering, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Ren, Geng-po [Shanghai Energy Conservation Supervision Center, Shanghai 200011 (China)

    2009-04-15

    A simulated cathode flow channel experiment system was set up based on the gas flow rate and water flow rate in the PEM fuel cell. With the assistance of the visualization system, high-sensitivity double parallel conductance probes flow regime inspecting technique was adopted successfully in the experiment system to inspect the flow regime of the gas-liquid two-phase flow in the PEM fuel cell. The research results show that the double parallel conductance probes inspecting system and the flow regime image system for the gas-liquid two-phase flow in the PEM fuel cell simulated channel both can judge the slug flow and annular flow in it, and the double parallel conductance probes flow regime inspecting system can divide the annular flow into three subtypes. The main probes inspecting system and the assistant image system validate reciprocally, which enhances the experimental veracity. The typical flow regimes of the PEM fuel cell simulated channel include slug flow, annular flow with big water film wave, annular flow with small water film wave and annular flow without water film wave. With the increase of the liquid superficial velocity, the frequencies of liquid slug and wave of liquid film increase. The flow regime map in the flow channel of the PEM fuel cell was developed. The flow regime of the gas-liquid two-phase flow in a PEM fuel cell in different operating conditions can be forecasted with this map. With the PEM fuel cell operating condition in this study, the flow regimes of gas-liquid two-phase flow for different cases are all annular flow with small water film wave, and the liquid film waves more with bigger current density. With the location closer to the channel outlet, the liquid film waves are more for the same current density. (author)

  20. Experimental research on water management in proton exchange membrane fuel cells

    Science.gov (United States)

    Yu, Li-jun; Chen, Wen-can; Qin, Ming-jun; Ren, Geng-po

    A simulated cathode flow channel experiment system was set up based on the gas flow rate and water flow rate in the PEM fuel cell. With the assistance of the visualization system, high-sensitivity double parallel conductance probes flow regime inspecting technique was adopted successfully in the experiment system to inspect the flow regime of the gas-liquid two-phase flow in the PEM fuel cell. The research results show that the double parallel conductance probes inspecting system and the flow regime image system for the gas-liquid two-phase flow in the PEM fuel cell simulated channel both can judge the slug flow and annular flow in it, and the double parallel conductance probes flow regime inspecting system can divide the annular flow into three subtypes. The main probes inspecting system and the assistant image system validate reciprocally, which enhances the experimental veracity. The typical flow regimes of the PEM fuel cell simulated channel include slug flow, annular flow with big water film wave, annular flow with small water film wave and annular flow without water film wave. With the increase of the liquid superficial velocity, the frequencies of liquid slug and wave of liquid film increase. The flow regime map in the flow channel of the PEM fuel cell was developed. The flow regime of the gas-liquid two-phase flow in a PEM fuel cell in different operating conditions can be forecasted with this map. With the PEM fuel cell operating condition in this study, the flow regimes of gas-liquid two-phase flow for different cases are all annular flow with small water film wave, and the liquid film waves more with bigger current density. With the location closer to the channel outlet, the liquid film waves are more for the same current density.

  1. Water equivalent path length calculations using scatter-corrected head and neck CBCT images to evaluate patients for adaptive proton therapy

    Science.gov (United States)

    Kim, Jihun; Park, Yang-Kyun; Sharp, Gregory; Busse, Paul; Winey, Brian

    2017-01-01

    Proton therapy has dosimetric advantages due to the well-defined range of the proton beam over photon radiotherapy. When the proton beams, however, are delivered to the patient in fractionated radiation treatment, the treatment outcome is affected by delivery uncertainties such as anatomic change in the patient and daily patient setup error. This study aims at establishing a method to evaluate the dosimetric impact of the anatomic change and patient setup error during head and neck proton therapy. Range variations due to the delivery uncertainties were assessed by calculating water equivalent path length (WEPL) to the distal edge of tumor volume using planning CT and weekly treatment cone-beam CT (CBCT) images. Specifically, mean difference and root mean squared deviation (RMSD) of the distal WEPLs were calculated as the weekly range variations. To accurately calculate the distal WEPLs, an existing CBCT scatter correction algorithm was used. An automatic rigid registration was used to align the planning CT and treatment CBCT images, simulating a six degree-of-freedom couch correction at treatments. The authors conclude that the dosimetric impact of the anatomic change and patient setup error was reasonably captured in the differences of the distal WEPL variation with a range calculation uncertainty of 2%. The proposed method to calculate the distal WEPL using the scatter-corrected CBCT images can be an essential tool to decide the necessity of re-planning in adaptive proton therapy.

  2. LAVENDER AROMATERAPHY AS A RELAXANT

    Directory of Open Access Journals (Sweden)

    IGA Prima Dewi AP

    2013-02-01

    Full Text Available Aromatherapy is a kind of treatment that used aroma with aromatherapy essential oil. Extraction process from essential oil generally doing in three methods, there are distilling with water (boiled, distilling with water and steam, and distilling with steam. One of the most favorite aroma is lavender. The main content from lavender is linalyl acetate and linalool (C10H18O. Linalool is main active contents in lavender which can use for anti-anxiety (relaxation. Based on some research, the conclusion indicates that essential oil from lavender can give relaxation (carminative, sedative, reduce anxiety level and increasing mood.

  3. Development of T2-relaxation values in regional brain sites during adolescence.

    Science.gov (United States)

    Kumar, Rajesh; Delshad, Sean; Macey, Paul M; Woo, Mary A; Harper, Ronald M

    2011-02-01

    Brain tissue changes accompany multiple neurodegenerative and developmental conditions in adolescents. Complex processes that occur in the developing brain with disease can be evaluated accurately only against normal aging processes. Normal developmental changes in different brain areas alter tissue water content, which can be assessed by magnetic resonance (MR) T2 relaxometry. We acquired proton-density (PD) and T2-weighted images from 31 subjects (mean age±S.D., 17.4±4.9 years; 18 male), using a 3.0-T MR imaging scanner. Voxel-by-voxel T2-relaxation values were calculated, and whole-brain T2-relaxation maps constructed and normalized to a common space template. We created a set of regions of interest (ROIs) over cortical gray and white matter, basal ganglia, amygdala, thalamic, hypothalamic, pontine and cerebellar sites, with sizes of ROIs varying from 12 to 243 mm(3); regional T2-relaxation values were determined from these ROIs and normalized T2-relaxation maps. Correlations between R2 (1/T2) values in these sites and age were assessed with Pearson's correlation procedures, and gender differences in regional T2-relaxation values were evaluated with independent-samples t tests. Several brain regions, but not all, showed principally positive correlations between R2 values and age; negative correlations emerged in the cerebellar peduncles. No significant differences in T2-relaxation values emerged between males and females for those areas, except for the mid pons and left occipital white matter; males showed higher T2-relaxation values over females. The findings indicate that T2-relaxation values vary with development between brain structures, and emphasize the need to correct for such age-related effects during any determination of potential changes from control values.

  4. Modeling secondary particle tracks generated by intermediate- and low-energy protons in water with the Low-Energy Particle Track Simulation code

    Science.gov (United States)

    Verkhovtsev, Alexey; Traore, Ali; Muñoz, Antonio; Blanco, Francisco; García, Gustavo

    2017-01-01

    Using a recent extension of the Low-Energy Particle Track Simulation (LEPTS) Monte Carlo code, we model the slowing-down of heavy charged particles propagating in water, combined with an explicit molecular-level description of radiation effects due to the formation of secondary electrons, their propagation through the medium, and electron-induced molecular dissociations. As a case study, we consider the transport of protons with the initial energy of 1 MeV until their thermalization, so that we cover the energy range that contributes mainly to the energy deposition in the Bragg peak region. In order to include protons into the simulation procedure, a comprehensive dataset of integral and differential cross sections of elastic and inelastic scattering of intermediate- and low-energy protons from water molecules is created. Experimental and theoretical cross sections available in the literature are carefully examined, compared and verified. The ionization cross section by protons includes recent experimental measurements of the production of different charged fragments.

  5. Nuclear halo of a 177 MeV proton beam in water: theory, measurement and parameterization

    CERN Document Server

    Gottschalk, Bernard; Daartz, Juliane; Wagner, Miles S

    2014-01-01

    The dose distribution of a monoenergetic pencil beam in water consists of an electromagnetic "core", a "halo" from charged nuclear secondaries, and a much larger "aura" from neutral secondaries. These regions overlap, but each has distinct spatial characteristics. We have measured the core/halo using a 177MeV test beam offset in a water tank. The beam monitor was a fluence calibrated plane parallel ionization chamber (IC) and the field chamber, a dose calibrated Exradin T1, so the dose measurements are absolute (MeV/g/p). We performed depth-dose scans at ten displacements from the beam axis ranging from 0 to 10cm. The dose spans five orders of magnitude, and the transition from halo to aura is clearly visible. We have performed model-dependent (MD) and model-independent (MI) fits to the data. The MD fit separates the dose into core, elastic/inelastic nuclear, nonelastic nuclear and aura terms, and achieves a global rms measurement/fit ratio of 15%. The MI fit uses cubic splines and the same ratio is 9%. We re...

  6. Protons and how they are transported by proton pumps.

    Science.gov (United States)

    Buch-Pedersen, M J; Pedersen, B P; Veierskov, B; Nissen, P; Palmgren, M G

    2009-01-01

    The very high mobility of protons in aqueous solutions demands special features of membrane proton transporters to sustain efficient yet regulated proton transport across biological membranes. By the use of the chemical energy of ATP, plasma-membrane-embedded ATPases extrude protons from cells of plants and fungi to generate electrochemical proton gradients. The recently published crystal structure of a plasma membrane H(+)-ATPase contributes to our knowledge about the mechanism of these essential enzymes. Taking the biochemical and structural data together, we are now able to describe the basic molecular components that allow the plasma membrane proton H(+)-ATPase to carry out proton transport against large membrane potentials. When divergent proton pumps such as the plasma membrane H(+)-ATPase, bacteriorhodopsin, and F(O)F(1) ATP synthase are compared, unifying mechanistic premises for biological proton pumps emerge. Most notably, the minimal pumping apparatus of all pumps consists of a central proton acceptor/donor, a positively charged residue to control pK(a) changes of the proton acceptor/donor, and bound water molecules to facilitate rapid proton transport along proton wires.

  7. The Role of the Primitive Relaxation in the Dynamics of Aqueous Mixtures, Nano-confined Water and Hydrated Proteins

    Science.gov (United States)

    2010-01-01

    S. Ancherbaka, P. A. Rollaa, N. Shinyashikic aDipartimento di Fisica , Università di Pisa and CNR-IPCF, Largo Bruno Pontecorvo 3 ,I-56127, Pisa...Dipartimento di Fisica ,Universita di Pisa and CNR-IPCF,Largo Bruno Pontecorvo 3, I-56127,Pisa, Italy, , 8. PERFORMING ORGANIZATION REPORT NUMBER 9...reduce the water molecular clusters down to sizes smaller than the critical size necessary for homogenous nucleation. Another effect of the confinement

  8. Proton Therapy

    Science.gov (United States)

    ... IMRT) Brain Tumor Treatment Brain Tumors Prostate Cancer Lung Cancer Treatment Lung Cancer Head and Neck Cancer Images related to Proton Therapy Videos related to Proton Therapy Sponsored by Please ...

  9. Proton Decay

    OpenAIRE

    Hikosaka, Koki

    2002-01-01

    We discuss the status of supersymmetric grand unified theories [SUSY GUTs] with regards to the observation of proton decay. In this talk we focus on SUSY GUTs in 4 dimensions. We outline the major theoretical uncertainties present in the calculation of the proton lifetime and then present our best estimate of an absolute upper bound on the predicted proton lifetime. Towards the end, we consider some new results in higher dimensional GUTs and the ramifications for proton decay.

  10. Non-additive response of blends of rice and potato starch during heating at intermediate water contents: A differential scanning calorimetry and proton nuclear magnetic resonance study.

    Science.gov (United States)

    Bosmans, Geertrui M; Pareyt, Bram; Delcour, Jan A

    2016-02-01

    The impact of different hydration levels, on gelatinization of potato starch (PS), rice starch (RS) and a 1:1 blend thereof, was investigated by differential scanning calorimetry and related to nuclear magnetic resonance proton distributions of hydrated samples, before and after heating. At 20% or 30% hydration, the visual appearance of all samples was that of a wet powder, and limited, if any, gelatinization occurred upon heating. At 30% hydration, changes in proton distributions were observed and related to plasticization of amorphous regions in the granules. At 50% hydration, the PS-RS blend appeared more liquid-like than other hydrated samples and showed more pronounced gelatinization than expected based on additive behavior of pure starches. This was due to an additional mobile water fraction in the unheated PS-RS blend, originating from differences in water distribution due to altered stacking of granules and/or altered hydration of PS due to presence of cations in RS.

  11. Spectroscopic signatures of proton transfer dynamics in the water dimer cation

    Energy Technology Data Exchange (ETDEWEB)

    Kamarchik, Eugene; Kostko, Oleg; Bowman, Joel M.; Ahmed, Musahid; Krylov, Anna I.

    2009-12-21

    Using full dimensional EOM-IP-CCSD/aug-cc-pVTZ potential energy surfaces, the photoelectron spectrum, vibrational structure, and ionization dynamics of the water dimer radical cation, (H2O)+2, were computed. We also report an experimental photoelectron spectrum which is derived from photoionization efficiency measurements and compares favorably with the theoretical spectrum. The vibrational structure is also compared with the recent experimental work of Gardenier et al. [J. Phys. Chem. A 113, 4772 (2009)] and the recent theoretical calculations by Cheng et al. [J. Phys. Chem. A 113 13779 (2009)]. A reduced dimensionality nuclear Hamiltonian was used to compute the ionization dynamics for both the ground state and first excited state of the cation. The dynamics show markedly different behavior and spectroscopic signatures depending on which state of the cation is accessed by the ionization. Ionization to the ground-state cation surface induces a hydrogen transfer which is complete within 50 femtoseconds, whereas ionization to the first excited state results in a much slower process.

  12. Development of gas diffusion layer using water based carbon slurry for proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Lin, J.F.; Liu, X.; Adame, A.; Villacorta, R. [Fuel Cell Research Laboratory, Engineering Technology Department, Arizona State University, Mesa, AZ 85212 (United States); Wertz, J. [Hollingsworth and Vose Co., A.K. Nicholson Research Lab, 219 Townsend Road, West Groton, MA 01472 (United States); Ahmad, R.; Thommes, M. [Quantachrome Instruments, 1900 Corporate Drive, Boynton Beach, FL 33426 (United States); Kannan, A.M., E-mail: amk@asu.ed [Fuel Cell Research Laboratory, Engineering Technology Department, Arizona State University, Mesa, AZ 85212 (United States)

    2011-01-01

    The micro-porous layer of gas diffusion layers (GDLs) was fabricated with the carbon slurry dispersed in water containing sodium dodecyl sulfate (SDS), by wire rod coating process. The aqueous carbon slurry with micelle-encapsulation was highly consistent and stable without losing any homogeneity even after adding polytetrafluoroethylene (PTFE) binder for hundreds of hours. The surface morphology, contact angle and pore size distribution of the GDLs were examined using SEM, Goniometer and Hg Porosimeter, respectively. GDLs fabricated with various SDS concentrations were assembled into MEAs and evaluated in a single cell PEMFC under diverse operating relative humidity (RH) conditions using H{sub 2}/O{sub 2} and H{sub 2}/air as reactants. The peak power density of the single cell using the GDLs with optimum SDS concentration was 1400 and 500 mW cm{sup -2} with H{sub 2}/O{sub 2} and H{sub 2}/air at 90% RH, respectively. GDLs were also fabricated with isopropyl alcohol (IPA) based carbon slurry for fuel cell performance comparison. It was found that the composition of the carbon slurry, specifically SDS concentration played a critical role in controlling the pore diameter as well as the corresponding pore volumes of the GDLs.

  13. The Conformation and Assignment of the Proton NMR Spectrum in Water of DX600, a Bioactive Peptide with a Random Coil Conformation

    Directory of Open Access Journals (Sweden)

    Wayne E. Steinmetz

    2011-01-01

    Full Text Available DX600, a small peptide with 26 residues, is a potent, highly selective inhibitor of angiotensin converting enzyme 2 (ACE2. A range of NMR methods including TOCSY and ROESY yield an assignment of its proton spectrum in water and constraints on its conformation. Constrained molecular dynamics simulations of solvated DX600 show that the peptide's most abundant conformer adopts a predominantly random coil conformation. Constrained by the disulfide bond, its backbone defines an overhand knot with frayed ends.

  14. Synthesis and relaxivity of Gd(Ⅲ), Fe(Ⅲ) and Mn(Ⅱ)complexes with dihydropyridine derivative of diethylenetriaminepentaacetic acid

    Institute of Scientific and Technical Information of China (English)

    CHANG; Jianhua; ZHENG; Shuzhan; JIAN; Yajun; BAI; Yinjuan

    2005-01-01

    A novel ligand of DTPA-dihydropyridine derivative was synthesized by reaction of DTPA-dianhydride with 4-aniline-1,4-dihydropyridine. Its complexes of gadolinium, manganese and iron were prepared. Their spin-lattice relaxivities (T1) were investigated. The results show that the NMR T1 relaxivitives (R1) for complexes of Fe(Ⅲ), Mn(Ⅱ) are less than that of Gd(Ⅲ) complex,which has a high relaxivity (R1) on the surrounding water protons, indicating that the Gd(Ⅲ) complex possesses the precondition to be contrast agents for magnetic resonance imaging.

  15. Characterization of mu s-ms dynamics of proteins using a combined analysis of N-15 NMR relaxation and chemical shift: Conformational exchange in plastocyanin induced by histidine protonations

    DEFF Research Database (Denmark)

    Hass, M. A. S.; Thuesen, Marianne Hallberg; Christensen, Hans Erik Mølager

    2004-01-01

    An approach is presented that allows a detailed, quantitative characterization of conformational exchange processes in proteins on the mus-ms time scale. The approach relies on a combined analysis of NMR relaxation rates and chemical shift changes and requires that the chemical shift...... of the exchanging species can be determined independently of the relaxation rates. The applicability of the approach is demonstrated by a detailed analysis of the conformational exchange processes previously observed in the reduced form of the blue copper protein, plastocyanin from the cyanobacteria Anabaena...... quantitatively by the correlation between the R-ex terms and the corresponding chemical shift differences of the exchanging species. By this approach, the R-ex terms of N-15 nuclei belonging to contiguous regions in the protein could be assigned to the same exchange process. Furthermore, the analysis...

  16. Theoretical prediction of single-site surface-protonation equilibrium constants for oxides and silicates in water

    Energy Technology Data Exchange (ETDEWEB)

    Sverjensky, D.A.; Sahai, N. [Johns Hopkins Univ., Baltimore, MD (United States)

    1996-10-01

    The equilibrium constants for surface protonation of solid oxides and silicates can be estimated from theoretical considerations and known properties of the solids for use in the constant capacitance, diffuse double layer or triple layer models of surface complexation. The theoretical considerations take into account Born solvation theory for the adsorbing proton, electrostatic interactions of the adsorbing proton with a surface oxygen and an underlying metal, and an intrinsic binding of the proton to the surface. As a consequence, the equilibrium constants for the {nu}th ({nu} = 1 or 2) surface protonation reaction on the kth solid can be expressed in terms of the inverse of the dielectric constant of the solid (1/{epsilon}{sub k}) and an average Pauling bond strength per angstrom (s/r{sub M-OH}) for the solid according to log K{sub {nu}} = M{sub {nu}}(1/{epsilon}{sub k}) - B{sub {nu}}(s/r{sub M-OH}) + log K{sub ii,{nu}}{sup {double_prime}}, where the coefficients M{sub {nu}} B{sub {nu}} and K{sub ii{nu}}{sup {double_prime}} are constants characteristic of all oxides and silicates for each surface complexation model. Evaluation of these constants using experimental data for TiO{sub 2}, {gamma}-alumina, Al{sub 2}O{sub 3} FeOOH, Fe(OH){sub 3}, silica, quartz. and kaolinite permits widespread prediction of surface protonation equilibrium constants from the known bulk structure properties 1/{epsilon}{sub k} and s/r{sub M-OH}. Such predictions should replace attempts to estimate surface protonation equilibrium constants for solids from empirical correlations with aqueous equilibrium constants. Surface protonation constants should also not be estimated from correlations with only the Pauling bond strength because these neglect specific treatment of salvation. 92 refs., 14 figs., 4 tabs.

  17. Dielectric relaxation and solvation dynamics in a prototypical ionic liquid + dipolar protic liquid mixture: 1-butyl-3-methylimidazolium tetrafluoroborate + water.

    Science.gov (United States)

    Zhang, Xin-Xing; Liang, Min; Hunger, Johannes; Buchner, Richard; Maroncelli, Mark

    2013-12-12

    Dielectric and solvation data on mixtures of 1-butyl-3-methylimidazilium tetrafluoroborate ([Im41][BF4]) + water are reported and used to examine the utility of dielectric solvation models. Dielectric permittivity and loss spectra (25 °C) were recorded over the frequency range 200 MHz to 89 GHz at 17 compositions and fit to a 4-Debye form. Dynamic Stokes shift measurements on the solute coumarin 153 (C153), made by combining fluorescence upconversion (80 fs resolution) and time-correlated single photon counting data (20 ns range), were used to determine the solvation response at 7 compositions (20.5 °C). All properties measured here were found to depend upon mixture composition in a simple continuous manner, especially when viewed in terms of volume fraction. Solvation response functions predicted by a simple dielectric continuum model are similar to but ∼7-fold faster than the spectral response functions measured with C153. The solvation data are in better agreement with the recently published predictions of a semimolecular model of Biswas and co-workers [J. Phys. Chem. B 2011, 115, 4011], but these latter predictions are systematically slow by a factor of ∼3.

  18. Applying hot-wire anemometry to directly measure the water balance in a proton exchange membrane fuel cell - Part 2: Experimental

    DEFF Research Database (Denmark)

    Al Shakhshir, Saher; Andreasen, Søren Juhl; Berning, Torsten

    2016-01-01

    can be directly converted into the fuel cell water balance. In this work an ex-situ experimental investigation is performed to examine the effect of the wire diameter and the outlet pipe diameter on the voltage signal. For a laboratory fuel cell where the mass flow rate the anode outlet is small......In order to better understand and more accurately measure the water balance in a proton exchange membrane fuel cell, our group has recently proposed to apply hot wire anemometry in the fuel cell's anode outlet. It was theoretically shown that the electrical signal obtained from the hot wire sensor...

  19. Electronic and vibrational spectra of protonated benzaldehyde-water clusters, [BZ-(H{sub 2}O){sub n≤5}]H{sup +}: Evidence for ground-state proton transfer to solvent for n ≥ 3

    Energy Technology Data Exchange (ETDEWEB)

    Dopfer, Otto, E-mail: dopfer@physik.tu-berlin.de; Patzer, Alexander; Chakraborty, Shamik [Institut für Optik und Atomare Physik, Technische Universität Berlin, Hardenbergstrasse 36, 10623 Berlin (Germany); Alata, Ivan; Omidyan, Reza; Broquier, Michel [Institut des Sciences Moleculaires d’Orsay, UMR-CNRS 8214, and Centre Laser de l’Université Paris Sud/LUMAT FR 2764, Batiment 106, l’Université Paris Sud 11, 91405 Orsay Cedex (France); Dedonder, Claude; Jouvet, Christophe [Physique des Interactions Ioniques et Moléculaires, UMR-CNRS 7345 Aix Marseille Université, Avenue Escadrille Normandie-Niémen, 13397 Marseille Cedex 20 (France)

    2014-03-28

    Vibrational and electronic photodissociation spectra of mass-selected protonated benzaldehyde-(water){sub n} clusters, [BZ-(H{sub 2}O){sub n}]H{sup +} with n ≤ 5, are analyzed by quantum chemical calculations to determine the protonation site in the ground electronic state (S{sub 0}) and ππ{sup *} excited state (S{sub 1}) as a function of microhydration. IR spectra of [BZ-(H{sub 2}O){sub n}]H{sup +} with n ≤ 2 are consistent with BZH{sup +}-(H{sub 2}O){sub n} type structures, in which the excess proton is localized on benzaldehyde. IR spectra of clusters with n ≥ 3 are assigned to structures, in which the excess proton is located on the (H{sub 2}O){sub n} solvent moiety, BZ-(H{sub 2}O){sub n}H{sup +}. Quantum chemical calculations at the B3LYP, MP2, and ri-CC2 levels support the conclusion of proton transfer from BZH{sup +} to the solvent moiety in the S{sub 0} state for hydration sizes larger than the critical value n{sub c} = 3. The vibronic spectrum of the S{sub 1} ← S{sub 0} transition (ππ{sup *}) of the n = 1 cluster is consistent with a cis-BZH{sup +}-H{sub 2}O structure in both electronic states. The large blueshift of the S{sub 1} origin by 2106 cm{sup −1} upon hydration with a single H{sub 2}O ligand indicates that the proton affinity of BZ is substantially increased upon S{sub 1} excitation, thus strongly destabilizing the hydrogen bond to the solvent. The adiabatic S{sub 1} excitation energy and vibronic structure calculated at the ri-CC2/aug-cc-pVDZ level agrees well with the measured spectrum, supporting the notion of a cis-BZH{sup +}-H{sub 2}O geometry. The doubly hydrated species, cis-BZH{sup +}-(H{sub 2}O){sub 2}, does not absorb in the spectral range of 23 000–27 400 cm{sup −1}, because of the additional large blueshift of the ππ{sup *} transition upon attachment of the second H{sub 2}O molecule. Calculations predict roughly linear and large incremental blueshifts for the ππ{sup *} transition in [BZ-(H{sub 2}O){sub n

  20. Multi-scales nuclear spin relaxation of liquids in porous media

    Science.gov (United States)

    Korb, Jean-Pierre

    2010-03-01

    The magnetic field dependence of the nuclear spin-lattice relaxation rate 1/T(ω) is a rich source of dynamical information for characterizing the molecular dynamics of liquids in confined environments. Varying the magnetic field changes the Larmor frequency ω, and thus the fluctuations to which the nuclear spin relaxation is sensitive. Moreover, this method permits a more complete characterization of the dynamics than the usual measurements as a function of temperature at fixed magnetic field strength, because many common solvent liquids have phase transitions that may alter significantly the character of the dynamics over the temperature range usually studied. Further, the magnetic field dependence of the spin-lattice relaxation rate, 1/T(ω), provides a good test of the theories that relate the measurement to the microdynamical behavior of the liquid. This is especially true in spatially confined systems where the effects of reduced dimensionality may force more frequent reencounters of the studied proton spin-bearing molecules with paramagnetic impurities at the pore surfaces that may alter the correlation functions that enter the relaxation equations in a fundamental way. We show by low field NMR relaxation that changing the amount of surface paramagnetic impurities leads to striking different pore-size dependences of the relaxation times T and T of liquids in pores. Here, we focus mainly on high surface area porous materials including calibrated porous silica glasses, granular packings, heterogeneous catalytic materials, cement-based materials and natural porous materials such as clay minerals and rocks. Recent highlights NMR relaxation works are reviewed for these porous materials, like continuous characterization of the evolving microstructure of various cementitious materials and measurement of wettability in reservoir carbonate rocks. Although, the recent applications of 2-dimensional T-T and T-z-store-T correlation experiments for characterization of

  1. Design of Gd(III)-based magnetic resonance imaging contrast agents: static and transient zero-field splitting contributions to the electronic relaxation and their impact on relaxivity.

    Science.gov (United States)

    Benmelouka, Meriem; Borel, Alain; Moriggi, Loick; Helm, Lothar; Merbach, André E

    2007-02-01

    A multiple-frequency (9.4-325 GHz) and variable-temperature (276-320 K) electron paramagnetic resonance (EPR) study on low molecular weight gadolinium(III) complexes for potential use as magnetic resonance imaging (MRI) contrast agents has been performed. Peak-to-peak linewidths Delta Hpp and central magnetic fields have been analyzed within the Redfield approximation taking into account the static zero-field splitting (ZFS) up to the sixth order and the transient ZFS up to the second order. Longitudinal electronic relaxation is dominated by the static ZFS contribution at low magnetic fields (B 1.5 T). Whereas the static ZFS clearly depends on the nature of the chelating ligand, the transient ZFS does not. For the relatively fast rotating molecules studied water proton relaxivity is mainly limited by the fast rotation and electronic relaxation has only a marked influence at frequencies below 30 MHz. From our EPR results we can conclude that electronic relaxation will have no influence on the efficiency of Gd(III)-based MRI contrast agents designed for studies at very high magnetic fields (B > 3T).

  2. Excited-State Deactivation of Adenine by Electron-Driven Proton-Transfer Reactions in Adenine-Water Clusters: A Computational Study.

    Science.gov (United States)

    Wu, Xiuxiu; Karsili, Tolga N V; Domcke, Wolfgang

    2016-05-04

    The reactivity of photoexcited 9H-adenine with hydrogen-bonded water molecules in the 9H-adenine-(H2 O)5 cluster is investigated by using ab initio electronic structure methods, focusing on the photoreactivity of the three basic sites of 9H-adenine. The energy profiles of excited-state reaction paths for electron/proton transfer from water to adenine are computed. For two of the three sites, a barrierless or nearly barrierless reaction path towards a low-lying S1 -S0 conical intersection is found. This reaction mechanism, which is specific for adenine in an aqueous environment, can explain the substantially shortened excited-state lifetime of 9H-adenine in water. Depending on the branching ratio of the nonadiabatic dynamics at the S1 -S0 conical intersection, the electron/proton transfer process can enhance the photostability of 9H-adenine in water or can lead to the generation of adenine-H(⋅) and OH(⋅) free radicals. Although the branching ratio is yet unknown, these findings indicate that adenine might have served as a catalyst for energy harvesting by water splitting in the early stages of the evolution of life. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Mechanisms for proton release during water oxidation in the S2 to S3 and S3 to S4 transitions in photosystem II.

    Science.gov (United States)

    Siegbahn, Per E M

    2012-04-14

    The new high-resolution X-ray structure of photosystem II has allowed more detailed studies than before of water oxidation at the oxygen evolving complex (OEC). In the present study the two final S-transitions of water oxidation are studied. The electron coupled proton transfers are followed from the center of the OEC to Asp61, which is considered as the start of the transfer chain through the protein to the lumenal side. It is found that the proton transfers occur in multiple steps. Structures of intermediates and energy diagrams are derived and compared to experimental observations. Since the new experimental structure of the OEC is very similar to the one suggested earlier by density functional calculations, the O-O bond formation step remains essentially the same as the one suggested five years ago. An interesting new result is that the barrier for proton transfer within the OEC actually competes with the O-O bond formation step of being rate-limiting.

  4. Relaxation Techniques for Health

    Science.gov (United States)

    ... R S T U V W X Y Z Relaxation Techniques for Health Share: On This Page What’s the ... Bottom Line? How much do we know about relaxation techniques? A substantial amount of research has been done ...

  5. Comparison of longitudinal metabolite relaxation times in different regions of the human brain at 1.5 and 3 Tesla.

    Science.gov (United States)

    Ethofer, Thomas; Mader, Irina; Seeger, Uwe; Helms, Gunther; Erb, Michael; Grodd, Wolfgang; Ludolph, Albert; Klose, Uwe

    2003-12-01

    In vivo longitudinal relaxation times of N-acetyl compounds (NA), choline-containing substances (Cho), creatine (Cr), myo-inositol (mI), and tissue water were measured at 1.5 and 3 T using a point-resolved spectroscopy (PRESS) sequence with short echo time (TE). T(1) values were determined in six different brain regions: the occipital gray matter (GM), occipital white matter (WM), motor cortex, frontoparietal WM, thalamus, and cerebellum. The T(1) relaxation times of water protons were 26-38% longer at 3 T than at 1.5 T. Significantly longer metabolite T(1) values at 3 T (11-36%) were found for NA, Cho, and Cr in the motor cortex, frontoparietal WM, and thalamus. The amounts of GM, WM, and cerebrospinal fluid (CSF) within the voxel were determined by segmentation of a 3D image data set. No influence of tissue composition on metabolite T(1) values was found, while the longitudinal relaxation times of water protons were strongly correlated with the relative GM content. Copyright 2003 Wiley-Liss, Inc.

  6. Proton Therapy

    Science.gov (United States)

    Oelfke, Uwe

    Proton therapy is one of the most rapidly developing new treatment technologies in radiation oncology. This treatment approach has — after roughly 40 years of technical developments — reached a mature state that allows a widespread clinical application. We therefore review the basic physical and radio-biological properties of proton beams. The main physical aspect is the elemental dose distribution arising from an infinitely narrow proton pencil beam. This includes the physics of proton stopping powers and the concept of CSDA range. Furthermore, the process of multiple Coulomb scattering is discussed for the lateral dose distribution. Next, the basic terms for the description of radio-biological properties of proton beams like LET and RBE are briefly introduced. Finally, the main concepts of modern proton dose delivery concepts are introduced before the standard method of inverse treatment planning for hadron therapy is presented.

  7. Latent Period of Relaxation.

    Science.gov (United States)

    Kobayashi, M; Irisawa, H

    1961-10-27

    The latent period of relaxation of molluscan myocardium due to anodal current is much longer than that of contraction. Although the rate and the grade of relaxation are intimately related to both the stimulus condition and the muscle tension, the latent period of relaxation remains constant, except when the temperature of the bathing fluid is changed.

  8. Protonated/deprotonated properties of a room temperature ionic liquid-water system: N, N-Diethyl-N-methyl-N-2-methoxyethyl ammonium tetrafluoroborate

    Science.gov (United States)

    Aono, Masami; Abe, Hiroshi; Takekiyo, Takahiro; Yoshimura, Yukihiro

    2014-04-01

    The pH oscillations related to the protonation/deprotonation process in a room temperature ionic liquid (RTIL)-water system were observed at fixed temperatures. The RTIL was hydrophilic N, N-diethyl-N-methyl-N-2-methoxyethyl ammonium tetrafluoroborate ([DEME][BF4]). The rhythmic oscillations of pH were observed only at a water concentration of approximately 90 mol%, where the equilibrated pH value was approximately 3. In contrast, in the water-poor region from 6 to 10 mol% H2O, the pH was almost constant at approximately 8 within the investigated timeframe. The acid-base properties of the [DEME][BF4]-water mixture are related to particular aggregations in the liquid phase.

  9. Water vapour solubility and conductivity study of the proton conductor BaCe(0.9 − x)ZrxY0.1O(3 − δ)

    DEFF Research Database (Denmark)

    Ricote, Sandrine; Bonanos, Nikolaos; Caboche, G:

    2009-01-01

    The perovskite BaCe(0.9 − x)ZrxY0.1O(3 − δ) has been prepared by solid state reaction at 1400 °C and conventional sintering at 1700 °C. Water uptake experiments performed between 400 and 600 °C, at a water vapour pressure of 0.02 atm, provide data on the concentration of protons incorporated.......56 eV to 0.59 eV in the water exchanged state with values 0.03 to 0.04 eV higher in the heavy water exchanged state. Impedance spectra measured at 200 °C showed a reduction in grain boundary resistivity with increasing cerium content. The stability of the compounds to carbon dioxide has been studied...

  10. Advantages of chemical exchange-sensitive spin-lock (CESL) over chemical exchange saturation transfer (CEST) for hydroxyl- and amine-water proton exchange studies.

    Science.gov (United States)

    Jin, Tao; Kim, Seong-Gi

    2014-11-01

    The chemical exchange (CE) rate of endogenous hydroxyl and amine protons with water is often comparable to the difference in their chemical shifts. These intermediate exchange processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, the sensitivity is not optimal and, more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the properties of CEST signals are compared with those of a CE-sensitive spin-lock (CESL) technique irradiating at the labile proton frequency. First, using a higher power and shorter irradiation in CE-MRI, we obtain: (i) an increased selectivity to faster CE rates via a higher sensitivity to faster CEs and a lower sensitivity to slower CEs and magnetization transfer processes; and (ii) a decreased in vivo asymmetric magnetization transfer contrast measured at ±15 ppm. The sensitivity gain of CESL over CEST is higher for a higher power and shorter irradiation. Unlike CESL, CEST signals oscillate at a very high power and short irradiation. Second, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with an asymmetric population approximation, which can be used for quantitative CE-MRI and validated by simulations of Bloch-McConnell equations and phantom experiments. Finally, the in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 = 500 Hz is 18% higher in sensitivity for CESL than CEST at 9.4 T. Overall, CESL provides better exchange rate selectivity and sensitivity than CEST; therefore, CESL is more suitable for CE-MRI of intermediate exchange protons.

  11. Faster Proton Transfer Dynamics of Water on SnO2 Compared to TiO2

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Nitin [ORNL; Kent, Paul R [ORNL; Bandura, Andrei V. [St. Petersburg State University, St. Petersburg, Russia; Kubicki, James D. [Pennsylvania State University; Wesolowski, David J [ORNL; Cole, David R [ORNL; Sofo, Jorge O. [Pennsylvania State University

    2011-01-01

    Proton jump processes in the hydration layer on the isostructural TiO2 rutile (110) and SnO2 cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O-H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates.

  12. Faster proton transfer dynamics of water on SnO2 compared to TiO2.

    Science.gov (United States)

    Kumar, Nitin; Kent, Paul R C; Bandura, Andrei V; Kubicki, James D; Wesolowski, David J; Cole, David R; Sofo, Jorge O

    2011-01-28

    Proton jump processes in the hydration layer on the iso-structural TiO(2) rutile (110) and SnO(2) cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O-H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates.

  13. Dielectric dispersion and protonic conduction in hydrated purple membrane.

    Science.gov (United States)

    Kovács, I; Váró, G

    1988-01-01

    Dielectric dispersion effects were studied in purple membranes of different hydration levels. The capacitance and conductivity were measured over the frequency range of 10(2) Hz to 10(5) Hz. With increase in the hydration level, the conductivity increases sharply above the critical hydration of hc = 0.06 g H2O/g protein. This critical hydration is close to the extent of the first continuous strongly bound water layer and is interpreted as the threshold for percolative proton transfer. The capacitance increases continuously with increasing hydration and a larger increase above the water content of 0.1 g H2O/g protein can be seen only at low frequencies. Maxwell-Wagner relaxation also appears above this hydration, showing the presence of a bulk water phase.

  14. L X-Rays RYIED Oscillations and Proton-NMRD of Gd2O3 Nanoparticles

    Directory of Open Access Journals (Sweden)

    A. Taborda

    2011-01-01

    variations still present different patterns for Gd2O3 pellet and Gd2O3 nanoparticles. Proton NMRD T1(ω data for Gd2O3 nanoparticles and Gd-DOTA water solutions published by Bridot et al. and Toth et al., respectively, were reproduced using a model for paramagnetic substances in water solutions and identical electronic relaxation times. The analysis of both techniques results points collective electron behaviour as the explanation for the different observations on X-ray data of Gd2O3 nanoparticles and bulk material.

  15. Validation of pore network simulations of ex-situ water distributions in a gas diffusion layer of proton exchange membrane fuel cells with X-ray tomographic images

    Science.gov (United States)

    Agaesse, Tristan; Lamibrac, Adrien; Büchi, Felix N.; Pauchet, Joel; Prat, Marc

    2016-11-01

    Understanding and modeling two-phase flows in the gas diffusion layer (GDL) of proton exchange membrane fuel cells are important in order to improve fuel cells performance. They are scientifically challenging because of the peculiarities of GDLs microstructures. In the present work, simulations on a pore network model are compared to X-ray tomographic images of water distributions during an ex-situ water invasion experiment. A method based on watershed segmentation was developed to extract a pore network from the 3D segmented image of the dry GDL. Pore network modeling and a full morphology model were then used to perform two-phase simulations and compared to the experimental data. The results show good agreement between experimental and simulated microscopic water distributions. Pore network extraction parameters were also benchmarked using the experimental data and results from full morphology simulations.

  16. Influence of water content and drying on the physical structure of native hyaluronan

    NARCIS (Netherlands)

    Prusova, A.; Vergeldt, F.J.; Kucerik, J.

    2013-01-01

    Hydration properties of semi-diluted hyaluronan were studied by means of time domain nuclear magnetic resonance. Based on the transverse proton relaxation times T2, the plasticization of hyaluronan which was precipitated by isopropylalcohol and dried in the oven have been determined at water content

  17. Quasi-elastic neutron scattering studies on dynamics of water confined in nanoporous copper rubeanate hydrates.

    Science.gov (United States)

    Yamada, Takeshi; Yonamine, Ryo; Yamada, Teppei; Kitagawa, Hiroshi; Tyagi, Madhusudan; Nagao, Michihiro; Yamamuro, Osamu

    2011-11-24

    We have investigated the mechanism of the first order transition and proton conductivity in copper rubeanate hydrates from microscopic and dynamical points of view. Three different types of neutron spectrometer-time-of-flight, backscattering, and neutron spin echo-were used to cover a wide dynamic range (1 ps to 100 ns). We found that the water molecules adsorbed in the pore are divided into "free water" having diffusion coefficients similar to those of bulk water at room temperature and "condensed water" which is about 10 times slower than bulk water owing to the interaction with the pore wall. The hydrogen atoms in the pore wall exhibited no relaxation within the measured time scales. The free water has, in the framework of the jump-diffusion model, smaller activation energy, longer residence time, and longer jump distance than bulk water. The neutron spin echo measurement revealed that the first order transition is a kind of liquid-liquid transition at which the free water is condensed on the pore surface in the low temperature phase. On cooling the condensed water, the relaxation time starts to deviate from the VFT equation around 200 K as previously observed in the water confined in nanoporous silicates. The free water plays an important role as the proton carrier but the proton conductivity is mainly governed by the number of protons provided into the adsorbed water from the pore wall.

  18. Detailed mechanisms of (1)H spin-lattice relaxation in ammonium dihydrogen phosphate confirmed by magic angle spinning.

    Science.gov (United States)

    Hayashi, Shigenobu; Jimura, Keiko

    2017-07-08

    Mechanisms of the (1)H spin-lattice relaxation in NH4H2PO4 were studied in detail by use of the effect of magic angle spinning on the relaxation. The acid and the ammonium protons have different relaxation times at the spinning rates higher than 10 kHz due to suppression of spin diffusion between the two kinds of protons. The intrinsic relaxation times not affected by the spin diffusion and the spin-diffusion assisted relaxation times were evaluated separately, taking into consideration temperature dependence. Both mechanisms contribute to the (1)H relaxation of the acid protons comparatively. The spin-diffusion assisted relaxation mechanism was suppressed to the level lower than the experimental errors at the spinning rate of 30 kHz. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Seven steps of alternating electron and proton transfer in photosystem II water oxidation traced by time-resolved photothermal beam deflection at improved sensitivity.

    Science.gov (United States)

    Klauss, André; Haumann, Michael; Dau, Holger

    2015-02-12

    The intricate orchestration of electron transfer (ET) and proton transfer (PT) at the Mn4CaOn-cluster of photosystem II (PSII) is mechanistically pivotal but clearly insufficiently understood. Preparations of PSII membrane particles were investigated using a kinetically competent and sensitive method, photothermal beam deflection (PBD), to monitor apparent volume changes of the PSII protein. Driven by nanosecond laser flashes, the PSII was synchronously stepped through its water-oxidation cycle involving four (semi)stable states (S0, S1, S2, and S3) and minimally three additional transiently formed intermediates. The PBD approach was optimized as compared to our previous experiments, resulting in superior signal quality and resolution of more reaction steps. Now seven transitions were detected and attributed, according to the H/D-exchange, temperature, and pH effects on their time constants, to ET or PT events. The ET steps oxidizing the Mn4CaOn cluster in the S2 → S3 and S0 → S1 transitions, a biphasic PT prior to the O2-evolving reaction, as well as the reoxidation of the primary quinone acceptor (QA(-)) at the PSII acceptor side were detected for the first time by PBD. The associated volume changes involve (i) initial formation of charged groups resulting in contraction assignable to electrostriction, (ii) volume contraction explainable by reduced metal-ligand distances upon manganese oxidation, and (iii) charge-compensating proton removal resulting in volume expansion due to electrostriction reversal. These results support a reaction cycle of water oxidation exhibiting alternate ET and PT steps. An extended kinetic scheme for the O2-evolving S3 ⇒ S0 transition is proposed, which includes crucial structural and protonic events.

  20. Phosphoric acid-doped poly(1-vinyl-1,2,4-triazole) as water-free proton conducting polymer electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Celik, Sevim Ue.; Aslan, Ayse; Bozkurt, Ayhan [Department of Chemistry, Fatih University, 34500 Bueyuekcekmece-Istanbul (Turkey)

    2008-08-15

    The development of anhydrous proton conducting membrane is important for the operation of polymer electrolyte membrane fuel cell (PEMFC) at intermediate temperature (100-200 C). In the present work, poly(1-vinyl-1,2,4-triazole), PVTri was produced by free radical polymerization of 1-vinyl-1,2,4-triazole with a high yield. The molecular weight of the homopolymer was measured via gel permeation chromatography (GPC) and M{sub w} was found to be 104,216 g/mol. The structure of the homopolymer was proved by solid state {sup 13}C CP-MAS NMR spectroscopy. The polymer was doped with phosphoric acid at various molar ratios x = 1 and x = 2. The proton transfer from H{sub 3}PO{sub 4} to the triazole rings was proved with Fourier-transform infrared spectroscopy (FT-IR). Thermogravimetry (TG) analysis showed that the samples are thermally stable up to approximately 250 C. Differential scanning calorimetry (DSC) results illustrated the homogeneity of the materials as well as the plasticizing effect of the dopant. The electrochemical stability of the materials was studied by cyclic voltammetry (CV). The proton conductivity of these materials increased with dopant concentration and the temperature. In the anhydrous state, the proton conductivity of PVTri 1 H{sub 3}PO{sub 4} is 5 x 10{sup -} {sup 3} S/cm at 150 C and the conductivity of PVTri 2 H{sub 3}PO{sub 4} was 4 x 10{sup -} {sup 3} S/cm at 140 C. (author)

  1. Analyze of Impedance for Water Management in Proton Exchange Membrane Fuel Cells Using Factorial Design of (DoE) Methodology

    OpenAIRE

    Khaled Mammar; Abdelkader Chaker

    2014-01-01

    Electrochemical impedance spectroscopy (EIS) is a very powerful tool for exploitation as a rich source of Proton Exchange Membrane Fuel Cell (PEMFC) diagnostic information. A primary goal of this work is to develop a suitable PEMFC impedance model, which can be used to analyze flooding and drying of the fuel cell. For this one a novel optimization method based on Factorial Design methodology is used. It was applied to parametric analysis of electrochemical impedance Thus it is pos...

  2. Conceptual design of proton beam window

    Energy Technology Data Exchange (ETDEWEB)

    Teraoku, Takuji; Kaminaga, Masanori; Terada, Atsuhiko; Ishikura, Syuichi; Kinoshita, Hidetaka; Hino, Ryutaro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2001-03-01

    In a MW-scale neutron scattering facility coupled with a high-intensity proton accelerator, a proton beam window is installed as the boundary between a high vacuum region of the proton beam transport line and a helium environment around the target assembly working as a neutron source. The window is cooled by water so as to remove high volumetric heat generated by the proton beam. A concept of the flat-type proton beam window consisting of two plates of 3 mm thick was proposed, which was found to be feasible under the proton beam power of 5 MW through thermal-hydraulic and structural strength analyses. (authors)

  3. Hangman Catalysis for Photo–and Photoelectro–Chemical Activation of Water Proton-Coupled Electron Transfer Mechanisms of Small Molecule Activation

    Energy Technology Data Exchange (ETDEWEB)

    Nocera, Daniel G. [Harvard Univ., Cambridge, MA (United States)

    2013-03-15

    The weakest link for the large-scale deployment of solar energy and for that matter, any renewable energy source, is its storage. The energy needs of future society demands are so large that storage must be in the form of fuels owing to their high energy density. Indeed, society has intuitively understood this disparity in energy density as it has developed over the last century as all large-scale energy storage in our society is in the form of fuels. But these fuels are carbon-based. The imperative for the discipline of chemistry, and more generally science, is to develop fuel storage methods that are easily scalable, carbon-neutral and sustainable. These methods demand the creation of catalysts to manage the multi-electron, multi-proton transformations of the conversion of small molecules into fuels. The splitting of water using solar light is a fuel-forming reaction that meets the imperative of large scale energy storage. As light does not directly act on water to engender its splitting into its elemental components, we have designed “hangman” catalysts to effect the energy conversion processes needed for the fuel forming reactions. The hangman construct utilizes a pendant acid/base functionality within the secondary coordination sphere that is “hung” above the redox platform onto which substrate binds. In this way, we can precisely control the delivery of a proton to the substrate, thus ensuring efficient coupling between the proton and electron. An emphasis was on the coupling of electron and proton in the hydrogen evolution reaction (HER) on Ni, Co and Fe porphyrin platforms. Electrokinetic rate laws were developed to define the proton-coupled electron transfer (PCET) mechanism. The HER of Co and Fe porphyrins was metal-centered. Surprisingly, HER this was not the case for Ni porphyrins. In this system, the PCET occurred at the porphyrin platform to give rise to a phlorin. This is one of the first examples of an HER occurring via ligand non

  4. Heteronuclear transverse and longitudinal relaxation in AX4 spin systems: Application to 15N relaxations in 15NH4 +

    OpenAIRE

    Werbeck, Nicolas D; Hansen, D. Flemming

    2014-01-01

    The equations that describe the time-evolution of transverse and longitudinal 15N magnetisations in tetrahedral ammonium ions, 15NH4 +, are derived from the Bloch-Wangsness-Redfield density operator relaxation theory. It is assumed that the relaxation of the spin-states is dominated by (1) the intra-molecular 15N–1H and 1H–1H dipole–dipole interactions and (2) interactions of the ammonium protons with remote spins, which also include the contribution to the relaxations that arise from the exc...

  5. Using the water signal to detect invisible exchanging protons in the catalytic triad of a serine protease

    Energy Technology Data Exchange (ETDEWEB)

    Lauzon, Carolyn B.; Zijl, Peter van [Johns Hopkins University School of Medicine, Department of Radiology and Radiological Sciences (United States); Stivers, James T., E-mail: jstivers@jhmi.edu [Johns Hopkins University School of Medicine, Department of Pharmacology and Molecular Sciences (United States)

    2011-08-15

    Chemical Exchange Saturation Transfer (CEST) is an MRI approach that can indirectly detect exchange broadened protons that are invisible in traditional NMR spectra. We modified the CEST pulse sequence for use on high-resolution spectrometers and developed a quantitative approach for measuring exchange rates based upon CEST spectra. This new methodology was applied to the rapidly exchanging H{delta}1 and H{epsilon}2 protons of His57 in the catalytic triad of bovine chymotrypsinogen-A (bCT-A). CEST enabled observation of H{epsilon}2 at neutral pH values, and also allowed measurement of solvent exchange rates for His57-H{delta}1 and His57-H{epsilon}2 across a wide pH range (3-10). H{delta}1 exchange was only dependent upon the charge state of the His57 (k{sub ex,Im+} = 470 s{sup -1}, k{sub ex,Im} = 50 s{sup -1}), while H{epsilon}2 exchange was found to be catalyzed by hydroxide ion and phosphate base (k(OH){sup -} = 1.7 Multiplication-Sign 10{sup 10} M{sup -1} s{sup -1}, K(HPO){sub 4}{sup 2-} = 1.7 Multiplication-Sign 10{sup 6} M{sup -1} s{sup -1}), reflecting its greater exposure to solute catalysts. Concomitant with the disappearance of the H{epsilon}2 signal as the pH was increased above its pK{sub a}, was the appearance of a novel signal ({delta} = 12 ppm), which we assigned to H{gamma} of the nearby Ser195 nucleophile, that is hydrogen bonded to N{epsilon}2 of neutral His57. The chemical shift of H{gamma} is about 7 ppm downfield from a typical hydroxyl proton, suggesting a highly polarized O-H{gamma} bond. The significant alkoxide character of O{gamma} indicates that Ser195 is preactivated for nucleophilic attack before substrate binding. CEST should be generally useful for mechanistic investigations of many enzymes with labile protons involved in active site chemistry.

  6. Analyze of Impedance for Water Management in Proton Exchange Membrane Fuel Cells Using Factorial Design of (DoE Methodology

    Directory of Open Access Journals (Sweden)

    Khaled Mammar

    2014-12-01

    Full Text Available Electrochemical impedance spectroscopy (EIS is a very powerful tool for exploitation as a rich source of Proton Exchange Membrane Fuel Cell (PEMFC diagnostic information. A primary goal of this work is to develop a suitable PEMFC impedance model, which can be used to analyze flooding and drying of the fuel cell. For this one a novel optimization method based on Factorial Design methodology is used. It was applied to parametric analysis of electrochemical impedance Thus it is possible to evaluate the relative importance of each parameter to the simulation accuracy. Furthermore this work presents an analysis of the PEMFC impedance behavior in the case of flooding and drying.

  7. Dosimetric verification in water of a Monte Carlo treatment planning tool for proton, helium, carbon and oxygen ion beams at the Heidelberg Ion Beam Therapy Center.

    Science.gov (United States)

    Tessonnier, T; Böhlen, T T; Ceruti, F; Ferrari, A; Sala, P; Brons, S; Haberer, T; Debus, J; Parodi, K; Mairani, A

    2017-07-31

    The introduction of 'new' ion species in particle therapy needs to be supported by a thorough assessment of their dosimetric properties and by treatment planning comparisons with clinically used proton and carbon ion beams. In addition to the latter two ions, helium and oxygen ion beams are foreseen at the Heidelberg Ion Beam Therapy Center (HIT) as potential assets for improving clinical outcomes in the near future. We present in this study a dosimetric validation of a FLUKA-based Monte Carlo treatment planning tool (MCTP) for protons, helium, carbon and oxygen ions for spread-out Bragg peaks in water. The comparisons between the ions show the dosimetric advantages of helium and heavier ion beams in terms of their distal and lateral fall-offs with respect to protons, reducing the lateral size of the region receiving 50% of the planned dose up to 12 mm. However, carbon and oxygen ions showed significant doses beyond the target due to the higher fragmentation tail compared to lighter ions (p and He), up to 25%. The Monte Carlo predictions were found to be in excellent geometrical agreement with the measurements, with deviations below 1 mm for all parameters investigated such as target and lateral size as well as distal fall-offs. Measured and simulated absolute dose values agreed within about 2.5% on the overall dose distributions. The MCTP tool, which supports the usage of multiple state-of-the-art relative biological effectiveness models, will provide a solid engine for treatment planning comparisons at HIT.

  8. Dosimetric verification in water of a Monte Carlo treatment planning tool for proton, helium, carbon and oxygen ion beams at the Heidelberg Ion Beam Therapy Center

    Science.gov (United States)

    Tessonnier, T.; Böhlen, T. T.; Ceruti, F.; Ferrari, A.; Sala, P.; Brons, S.; Haberer, T.; Debus, J.; Parodi, K.; Mairani, A.

    2017-08-01

    The introduction of ‘new’ ion species in particle therapy needs to be supported by a thorough assessment of their dosimetric properties and by treatment planning comparisons with clinically used proton and carbon ion beams. In addition to the latter two ions, helium and oxygen ion beams are foreseen at the Heidelberg Ion Beam Therapy Center (HIT) as potential assets for improving clinical outcomes in the near future. We present in this study a dosimetric validation of a FLUKA-based Monte Carlo treatment planning tool (MCTP) for protons, helium, carbon and oxygen ions for spread-out Bragg peaks in water. The comparisons between the ions show the dosimetric advantages of helium and heavier ion beams in terms of their distal and lateral fall-offs with respect to protons, reducing the lateral size of the region receiving 50% of the planned dose up to 12 mm. However, carbon and oxygen ions showed significant doses beyond the target due to the higher fragmentation tail compared to lighter ions (p and He), up to 25%. The Monte Carlo predictions were found to be in excellent geometrical agreement with the measurements, with deviations below 1 mm for all parameters investigated such as target and lateral size as well as distal fall-offs. Measured and simulated absolute dose values agreed within about 2.5% on the overall dose distributions. The MCTP tool, which supports the usage of multiple state-of-the-art relative biological effectiveness models, will provide a solid engine for treatment planning comparisons at HIT.

  9. Combined quantification of fatty infiltration, T 1-relaxation times and T 2*-relaxation times in normal-appearing skeletal muscle of controls and dystrophic patients.

    Science.gov (United States)

    Leporq, Benjamin; Le Troter, Arnaud; Le Fur, Yann; Salort-Campana, Emmanuelle; Guye, Maxime; Beuf, Olivier; Attarian, Shahram; Bendahan, David

    2017-08-01

    To evaluate the combination of a fat-water separation method with an automated segmentation algorithm to quantify the intermuscular fatty-infiltrated fraction, the relaxation times, and the microscopic fatty infiltration in the normal-appearing muscle. MR acquisitions were performed at 1.5T in seven patients with facio-scapulo-humeral dystrophy and eight controls. Disease severity was assessed using commonly used scales for the upper and lower limbs. The fat-water separation method provided proton density fat fraction (PDFF) and relaxation times maps (T 2* and T 1). The segmentation algorithm distinguished adipose tissue and normal-appearing muscle from the T 2* map and combined active contours, a clustering analysis, and a morphological closing process to calculate the index of fatty infiltration (IFI) in the muscle compartment defined as the relative amount of pixels with the ratio between the number of pixels within IMAT and the total number of pixels (IMAT + normal appearing muscle). In patients, relaxation times were longer and a larger fatty infiltration has been quantified in the normal-appearing muscle. T 2* and PDFF distributions were broader. The relaxation times were correlated to the Vignos scale whereas the microscopic fatty infiltration was linked to the Medwin-Gardner-Walton scale. The IFI was linked to a composite clinical severity scale gathering the whole set of scales. The MRI indices quantified within the normal-appearing muscle could be considered as potential biomarkers of dystrophies and quantitatively illustrate tissue alterations such as inflammation and fatty infiltration.

  10. NMR spectroscopy study of local correlations in water

    Science.gov (United States)

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Stanley, H. Eugene

    2016-12-01

    Using nuclear magnetic resonance we study the dynamics of the hydrogen bond (HB) sub-domains in bulk and emulsified water across a wide temperature range that includes the supercooled regime. We measure the proton spin-lattice T1 and spin-spin T2 relaxation times to understand the hydrophilic interactions that determine the properties of water. We use (i) the Bloembergen, Purcell, and Pound approach that focuses on a single characteristic correlation time τc, and (ii) the Powles and Hubbard approach that measures the proton rotational time τθ. We find that when the temperature is low both relaxation times are strongly correlated when the HB lifetime is long, and that when the temperature is high a decrease in the HB lifetime destroys the water clusters and decouples the dynamic modes of the system.

  11. Synthesis and characterization of water-dispersible core/shell Mn-doped magnetite/Au nanoparticles for proton radiotherapy

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jeong Chan [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-05-15

    The surface modification of the nanomaterials is required for the biomedical use to give physiological stability, surface reactivity and targeting properties. Among many approaches for the surface modification with materials, such as polymers, organic ligands and metals, one of the most attractive ways is to employ metals. The fabrication of metal-based, monolayer coated magnetic nanoparticles has been intensively studied. However, the synthesis of metal-capped magnetic nanoparticles with monodispersities and controllable sizes is still challenged. Recently, gold-capped magnetic nanoparticles have been reported to increase stability and to provide biocompatibility. Gold-coated magnetic nanoparticles are an attractive system, which can be stabilized in biological conditions and readily functionalized through well-established surface modification chemistry. In addition, the Au coating offers plasmonic properties to magnetic nanoparticles. This makes the magnetic/Au core/shell combinations interesting for magnetic and optical applications. The monodisperse Mn:Fe3O4/Au nanoparticles have been prepared in organic solvent first and then transferred from an organic phase to an aqueous solution. The resulting core/shell-structured nanoparticles may be an attractive system for biomedical applications, which are needed both magnetic resonance imaging and optical imaging. In addition, the resulting nanoparticles may be useful for proton radiotherapy due to the enhanced therapeutic effects of secondary radiation stemmed from gold and proton beam bombardment.

  12. In vivo relaxation time measurements on a murine tumor model--prolongation of T1 after photodynamic therapy.

    Science.gov (United States)

    Liu, Y H; Hawk, R M; Ramaprasad, S

    1995-01-01

    RIF tumors implanted on mice feet were investigated for changes in relaxation times (T1 and T2) after photodynamic therapy (PDT). Photodynamic therapy was performed using Photofrin II as the photosensitizer and laser light at 630 nm. A home-built proton solenoid coil in the balanced configuration was used to accommodate the tumors, and the relaxation times were measured before, immediately after, and up to several hours after therapy. Several control experiments were performed untreated tumors, tumors treated with Photofrin II alone, or tumors treated with laser light alone. Significant increases in T1s of water protons were observed after PDT treatment. In all experiments, 31P spectra were recorded before and after the therapy to study the tumor status and to confirm the onset of PDT. These studies show significant prolongation of T1s after the PDT treatment. The spin-spin relaxation measurements, on the other hand, did not show such prolongation in T2 values after PDT treatment.

  13. 1H nuclear magnetic resonance study of low-temperature water dynamics in a water-soaked perfluorosulfonic acid ionomer Nafion film

    Science.gov (United States)

    Han, Jun Hee; Lee, Kyu Won; Lee, Cheol Eui

    2017-01-01

    We have employed proton nuclear magnetic resonance (NMR) spectroscopy in order to study the low-temperature water dynamics in a water-soaked perfluorosulfonic acid ionomer Nafion (NR-211) film. According to the recent models, Nafion may comprise water strongly bound to the sulfonic acid group, hydration water, and condensed water species. In this work, three separate NMR peaks from the water species revealing distinct behaviors were identified. A significant portion of the "bound" water remained unfrozen down to 200 K, whereas a slow-to-fast motional limit transition was observed at TM=220 K from the relaxation measurements.

  14. Evaluation of relaxation time measurements by magnetic resonance imaging. A phantom study

    DEFF Research Database (Denmark)

    Kjaer, L; Thomsen, C; Henriksen, O

    1987-01-01

    Several circumstances may explain the great variation in reported proton T1 and T2 relaxation times usually seen. This study was designed to evaluate the accuracy of relaxation time measurements by magnetic resonance imaging (MRI) operating at 1.5 tesla. Using a phantom of nine boxes with different...

  15. The influence of humidification and temperature differences between inlet gases on water transport through the membrane of a proton exchange membrane fuel cell

    Science.gov (United States)

    Huang, Kuan-Jen; Hwang, Sheng-Jye; Lai, Wei-Hsiang

    2015-06-01

    This paper discusses the effects of humidification and temperature differences of the anode and cathode on water transport in a proton exchange membrane fuel cell. Heaters are used to cause a difference in gas temperature between two electrodes before the gases enter the fuel cell. The results show that when the temperature of the cathode is higher than that of the anode, the electro-osmotic drag is suppressed. In contrast, when the temperature of the anode is higher than that of cathode, it is enhanced. These effects are more significant when the temperature difference between the anode and cathode is greater. The same trends are seen with back diffusion. Three cases are tested, and the results show that the suppression due to the temperature difference occurs even when the relative humidity is low at the hotter side. The water transport tendencies of electro-osmotic drag and back diffusion in different situations can be expressed as dominant percentages calculated by the water masses collected at the anode and cathode. The suppression effect due to the temperature difference is relatively insignificant with regard to back diffusion compared to electro-osmosis, so water tends to accumulate on the anode rather than the cathode side.

  16. Detection of Amide and Aromatic Proton Resonances of Human Brain Metabolites Using Localized Correlated Spectroscopy Combined with Two Different Water Suppression Schemes

    Directory of Open Access Journals (Sweden)

    Rajakumar Nagarajan

    2010-06-01

    Full Text Available The purpose of the study was to demonstrate the J-coupling connectivity network between the amide, aliphatic, and aromatic proton resonances of metabolites in human brain using two-dimensional (2D localized correlated spectroscopy (L-COSY. Two different global water suppression techniques were combined with L-COSY, one before and another after localizing the volume of interest (VOI. Phantom solutions containing several cerebral metabolites at physiological concentrations were evaluated initially for sequence optimization. Nine healthy volunteers were scanned using a 3T whole body MRI scanner. The VOI for 2D L-COSY was placed in the right occipital white/gray matter region. The 2D cross and diagonal peak volumes were measured for several metabolites such as N-acetyl aspartate (NAA, creatine (Cr, free choline (Ch, glutamate/glutamine (Glx, aspartate (Asp, myo-inositol (mI, GABA, glutathione (GSH, phosphocholine (PCh, phosphoethanolamine (PE, tyrosine (Tyr, lactate (Lac, macromolecules (MM and homocarnosine (Car. Using the pre-water suppression technique with L-COSY, the above mentioned metabolites were clearly identifiable and the relative ratios of metabolites were calculated. In addition to detecting multitude of aliphatic resonances in the high field region, we have demonstrated that the amide and aromatic resonances can also be detected using 2D L-COSY by pre water suppression more reliably than the post-water suppression.

  17. Indentation load relaxation test

    Energy Technology Data Exchange (ETDEWEB)

    Hannula, S.P.; Stone, D.; Li, C.Y. (Cornell Univ., Ithaca, NY (USA))

    Most of the models that are used to describe the nonelastic behavior of materials utilize stress-strain rate relations which can be obtained by a load relaxation test. The conventional load relaxation test, however, cannot be performed if the volume of the material to be tested is very small. For such applications the indentation type of test offers an attractive means of obtaining data necessary for materials characterization. In this work the feasibility of the indentation load relaxation test is studied. Experimental techniques are described together with results on Al, Cu and 316 SS. These results are compared to those of conventional uniaxial load relaxation tests, and the conversion of the load-indentation rate data into the stress-strain rate data is discussed.

  18. Relaxation techniques for stress

    Science.gov (United States)

    ... problems such as high blood pressure, stomachaches, headaches, anxiety, and depression. Using relaxation techniques can help you feel calm. These exercises can also help you manage stress and ease the effects of stress on your body.

  19. Proton geriatrics

    Science.gov (United States)

    Kephart, Thomas W.; Nakagawa, Norio

    1984-07-01

    An SO(10) model with particle spectrum and low energy gauge group identical to that of minimal SU (5) below MX but with a nonstandard charge assignment is shown to agree with the experimental best value of sin2θw(Mw) and the lower bound on the proton lifetime.

  20. Proton Radiobiology

    Directory of Open Access Journals (Sweden)

    Francesco Tommasino

    2015-02-01

    Full Text Available In addition to the physical advantages (Bragg peak, the use of charged particles in cancer therapy can be associated with distinct biological effects compared to X-rays. While heavy ions (densely ionizing radiation are known to have an energy- and charge-dependent increased Relative Biological Effectiveness (RBE, protons should not be very different from sparsely ionizing photons. A slightly increased biological effectiveness is taken into account in proton treatment planning by assuming a fixed RBE of 1.1 for the whole radiation field. However, data emerging from recent studies suggest that, for several end points of clinical relevance, the biological response is differentially modulated by protons compared to photons. In parallel, research in the field of medical physics highlighted how variations in RBE that are currently neglected might actually result in deposition of significant doses in healthy organs. This seems to be relevant in particular for normal tissues in the entrance region and for organs at risk close behind the tumor. All these aspects will be considered and discussed in this review, highlighting how a re-discussion of the role of a variable RBE in proton therapy might be well-timed.

  1. Unusually Flexible Indium(III) Metal-Organic Polyhedra Materials for Detecting Trace Amounts of Water in Organic Solvents and High Proton Conductivity.

    Science.gov (United States)

    Du, Xi; Fan, Ruiqing; Qiang, Liangsheng; Song, Yang; Xing, Kai; Chen, Wei; Wang, Ping; Yang, Yulin

    2017-03-20

    Humidity-induced single-crystal transformation was observed in the indium metal-organic polyhedra [In2(TCPB)2]·2H2O (In1), where H3TCPB is 1,3,5-tri(4-carboxyphenoxy)benzene. When the humidity is above 58% relative humidity (RH) at room temperature, the neutral compound In1 could be successfully converted into the positively charged compound In1-H along with the color change from yellow to deep red, which also undergoes a reversible transformation into In1 driven by thermal dehydration. Notably, the color of In1 takes only 5 min to change under 58% RH at room temperature, which is much quicker than common desiccant bluestone. As the water content is increased from 0.0% to 0.2% in acetonitrile solvent, compound In1 exhibits rapid detection of trace amounts of water through turn-off luminescence sensing mechanism with a low detection limit of 2.95 × 10(-4)%. Because of the formation of extensive hydrogen-bonding network between the metal-organic polyhedra (MOPs) and surrounding guest OH(-) ions, compound In1-H, along with isostructural Ga1-H, displays excellent proton conductivity up to 2.84 × 10(-4) and 2.26 × 10(-4) S cm(-1) at 298 K and 98% RH, respectively. Furthermore, the activation energies are found to be 0.28 eV for In1-H and 0.34 eV for Ga1-H. This method of incorporation of OH(-) ions to obtain high proton conductivity MOPs with low activation energy demonstrates the advantage of OH(-) ion conduction in the solid-state materials.

  2. Perturbations and quantum relaxation

    CERN Document Server

    Kandhadai, Adithya

    2016-01-01

    We investigate whether small perturbations can cause relaxation to quantum equilibrium over very long timescales. We consider in particular a two-dimensional harmonic oscillator, which can serve as a model of a field mode on expanding space. We assume an initial wave function with small perturbations to the ground state. We present evidence that the trajectories are highly confined so as to preclude relaxation to equilibrium even over very long timescales. Cosmological implications are briefly discussed.

  3. Diffusion-Oscillatory Dynamics in Liquid Water on Data of Dielectric Spectroscopy

    CERN Document Server

    Volkov, A A; Volkov, A A; Sysoev, N N

    2016-01-01

    When analyzing the broadband absorption spectrum of liquid water (10^10 - 10^13 Hz), we find its relaxation-resonance features to be an indication of Frenkel's translation-oscillation motion of particles, which is fundamentally inherent to liquids. We have developed a model of water structure, of which the dynamics is due to diffusion of particles, neutral H2O molecules and H3O+ and OH- ions - with their periodic localizations and mutual transformations. This model establishes for the first time a link between the dc conductivity, the Debye and the high frequency sub-Debye relaxations and the infrared absorption peak at 180 cm-1. The model reveals the characteristic times of the relaxations, 50 ps and 3 ps, as the lifetimes of water molecules and water ions, respectively. The model sheds light on the anomalous mobility of a proton and casts doubt on the long lifetime of a water molecule, 10 hours, commonly associated with autoionization.

  4. Variations of water uptake, lipid consumption, and dynamics during the germination of Sesamum indicum seed: a nuclear magnetic resonance spectroscopic investigation.

    Science.gov (United States)

    Sarkar, Bimal Kumar; Yang, Wei-Yuan; Wu, Zhen; Tang, Huiru; Ding, Shangwu

    2009-09-23

    Germination in sesame seeds (Sesamum indicum L.) in water and in indole-3-acetic acid (IAA) solution is investigated with magic-angle-spinning (MAS) solid state nuclear magnetic resonance (NMR) spectroscopy, supplemented by liquid state NMR spectroscopy. The spectra show good resolution and can be assigned with sufficient confidence. The characteristic spectral peaks and relaxation rates were monitored during the entire course of germination for better understanding of the biophysical and biochemical mechanisms involved in the triphasic water uptake of the seed. A highly positive correlation is found between water uptake and lipid consumption during germination. No significant variation is observed in the relaxation times for the lipid protons during the first two stages of triphasic water uptake, while evident differences are observed for water proton relaxation rates in all stages. Although the total amount of water uptake is largely not changed as a result of IAA, the addition of IAA in seed-germination medium has shown some prominent effects on the germination process, e.g, it suppresses lipid consumption and water mobility, and it reduces the longitudinal and transverse relaxation times of lipid protons and causes a more scattered range for these parameters.

  5. Restrained Proton Indicator in Combined Quantum-Mechanics/Molecular-Mechanics Dynamics Simulations of Proton Transfer through a Carbon Nanotube.

    Science.gov (United States)

    Duster, Adam W; Lin, Hai

    2017-09-14

    Recently, a collective variable "proton indicator" was purposed for tracking an excess proton solvated in bulk water in molecular dynamics simulations. In this work, we demonstrate the feasibility of utilizing the position of this proton indicator as a reaction coordinate to model an excess proton migrating through a hydrophobic carbon nanotube in combined quantum-mechanics/molecular-mechanics simulations. Our results indicate that applying a harmonic restraint to the proton indicator in the bulk solvent near the nanotube pore entrance leads to the recruitment of water molecules into the pore. This is consistent with an earlier study that employed a multistate empirical valence bond potential and a different representation (center of excess charge) of the proton. We attribute this water recruitment to the delocalized nature of the solvated proton, which prefers to be in high-dielectric bulk solvent. While water recruitment into the pore is considered an artifact in the present simulations (because of the artificially imposed restraint on the proton), if the proton were naturally restrained, it could assist in building water wires prior to proton transfer through the pore. The potential of mean force for a proton translocation through the water-filled pore was computed by umbrella sampling, where the bias potentials were applied to the proton indicator. The free energy curve and barrier heights agree reasonably with those in the literature. The results suggest that the proton indicator can be used as a reaction coordinate in simulations of proton transport in confined environments.

  6. The Effect of Nitrogen Cross-over on Proton Exchange Membrane Fuel Cell Water Balance Measurements Using Constant Temperature Anemometry

    DEFF Research Database (Denmark)

    Al Shakhshir, Saher; Berning, Torsten; Kær, Søren Knudsen

    2016-01-01

    A novel method to obtain an ad-hoc and real time electrical signal of the PEMFC water balance by employing a constant temperature hot wire anemometry has been developed by our fuel cell research group. In this work, the effect of nitrogen-cross over on this method is experimentally demonstrated....... This is due to the effect of 1% nitrogen on power law constant’s “m” which can be used in determining the water balance as explained in previous work was extremely low. Thus, the hot wire technique for measuring the PEMFC water balance is still accurate with the nitrogen cross-over...

  7. Absolute quantitative proton NMR spectroscopy based on the amplitude of the local water suppression pulse. Quantification of brain water and metabolites

    DEFF Research Database (Denmark)

    Danielsen, E R; Henriksen, O

    1994-01-01

    the locally optimized amplitude of a chemical shift selective water suppression pulse and the acquired signal. Validity and feasibility of quantification using the method of the water suppression pulse is demonstrated. Brain water and cerebral metabolites have been quantified in a study of 12 healthy...

  8. Effects of Low to Intermediate Water Concentrations on Proton-Coupled Electron Transfer (PCET) Reactions of Flavins in Aprotic Solvents and a Comparison with the PCET Reactions of Quinones.

    Science.gov (United States)

    Tan, Serena L J; Novianti, Maria L; Webster, Richard D

    2015-11-05

    The electrochemical reduction mechanisms of 2 synthesized flavins (Flox) were examined in detail in deoxygenated solutions of DMSO containing varying amounts of water, utilizing variable scan rate cyclic voltammetry (ν = 0.1-20 V s(-1)), controlled-potential bulk electrolysis, and UV-vis spectroscopy. Flavin 1, which contains a hydrogen atom at N(3), is capable of donating its proton to other reduced flavin species. After 1e(-) reduction, the initially formed Fl(•-) receives a proton from another Flox to form FlH(•) (and concomitantly produce the deprotonated flavin, Fl(-)), although the equilibrium constant for this process favors the back reaction. Any FlH(•) formed at the electrode surface immediately undergoes another 1e(-) reduction to form FlH(-), which reacts with Fl(-) to form 2 molecules of Fl(•-). Further 1e(-) reduction of Fl(•-) at more negative potentials produces the dianion, Fl(2-), which can also be protonated by another Flox to form FlH(-) and Fl(-). Flavin 2, which is methylated at N(3) (and therefore has no acidic proton), undergoes a simple chemically reversible 1e(-) reduction process in DMSO provided the water content is low (solvents results in protonation of the anion radical species, Fl(•-), for both flavins, causing an increase in the amount of FlH(-) in solution. This behavior contrasts with what is observed for quinones, which are also reduced in two 1e(-) steps in aprotic organic solvents to form the radical anions and dianions, but are able to exist in hydrogen-bonded forms (with trace or added water) without undergoing protonation.

  9. Vibrational and Rotational Energy Relaxation in Liquids

    DEFF Research Database (Denmark)

    Petersen, Jakob

    the intramolecular dynamics during photodissociation is investigated. The apparent agreement with quantum mechanical calculations is shown to be in contrast to the applicability of the individual approximations used in deriving the model from a quantum mechanical treatment. In the spirit of the Bersohn-Zewail model......, the vibrational energy relaxation of I2 subsequent to photodissociation and recombination in CCl4 is studied using classical Molecular Dynamics simulations. The vibrational relaxation times and the time-dependent I-I pair distribution function are compared to new experimental results, and a qualitative agreement...... is found in both cases. Furthermore, the rotational energy relaxation of H2O in liquid water is studied via simulations and a power-and-work analysis. The mechanism of the energy transfer from the rotationally excited H2O molecule to its water neighbors is elucidated, i.e. the energy-accepting degrees...

  10. Proton radiography to improve proton therapy treatment

    NARCIS (Netherlands)

    Takatsu, J.; van der Graaf, E. R.; Van Goethem, M. -J.; van Beuzekom, M.; Klaver, T.; Visser, J.; Brandenburg, S.; Biegun, A. K.

    2016-01-01

    The quality of cancer treatment with protons critically depends on an accurate prediction of the proton stopping powers for the tissues traversed by the protons. Today, treatment planning in proton radiotherapy is based on stopping power calculations from densities of X-ray Computed Tomography (CT)

  11. Significantly Dense Two-Dimensional Hydrogen-Bond Network in a Layered Zirconium Phosphate Leading to High Proton Conductivities in Both Water-Assisted Low-Temperature and Anhydrous Intermediate-Temperature Regions.

    Science.gov (United States)

    Gui, Daxiang; Zheng, Tao; Xie, Jian; Cai, Yawen; Wang, Yaxing; Chen, Lanhua; Diwu, Juan; Chai, Zhifang; Wang, Shuao

    2016-12-19

    A highly stable layered zirconium phosphate, (NH4)2[ZrF2(HPO4)2] (ZrP-1), was synthesized by an ionothermal method and contains an extremely dense two-dimensional hydrogen-bond network that is thermally stable up to 573 K, leading to combined ultrahigh water-assisted proton conductivities of 1.45 × 10(-2) S cm(-1) at 363 K/95% relative humidity and sustainable anhydrous proton conductivity of 1.1 × 10(-5) S cm(-1) at 503 K.

  12. Characterization of creatine guanidinium proton exchange by water-exchange (WEX) spectroscopy for absolute-pH CEST imaging in vitro.

    Science.gov (United States)

    Goerke, Steffen; Zaiss, Moritz; Bachert, Peter

    2014-05-01

    Chemical exchange saturation transfer (CEST) enables indirect detection of small metabolites in tissue by MR imaging. To optimize and interpret creatine-CEST imaging we characterized the dependence of the exchange-rate constant k(sw) of creatine guanidinium protons in aqueous creatine solutions as a function of pH and temperature T in vitro. Model solutions in the low pH range (pH = 5-6.4) were measured by means of water-exchange (WEX)-filtered ¹H NMR spectroscopy on a 3 T whole-body MR tomograph. An extension of the Arrhenius equation with effective base-catalyzed Arrhenius parameters yielded a general expression for k(sw) (pH, T). The defining parameters were identified as the effective base-catalyzed rate constant k(b,eff) (298.15 K) = (3.009 ± 0.16) × 10⁹  Hz l/mol and the effective activation energy E(A,b,eff)  = (32.27 ± 7.43) kJ/mol at a buffer concentration of c(buffer)  = (1/15) M. As expected, a strong dependence of k(sw) on temperature was observed. The extrapolation of the exchange-rate constant to in vivo conditions (pH = 7.1, T = 37 °C) led to the value of the exchange-rate constant k(sw)  = 1499 Hz. With the explicit function k(sw) (pH, T) available, absolute-pH CEST imaging could be realized and experimentally verified in vitro. By means of our calibration method it is possible to adjust the guanidinium proton exchange-rate constant k(sw) to any desired value by preparing creatine model solutions with a specific pH and temperature.

  13. Local potential evolutions during proton exchange membrane fuel cell operation with dead-ended anode - Part II: Aging mitigation strategies based on water management and nitrogen crossover

    Science.gov (United States)

    Abbou, S.; Dillet, J.; Maranzana, G.; Didierjean, S.; Lottin, O.

    2017-02-01

    Proton exchange membrane (PEM) fuel cells operate with dead-ended anode in order to reduce system cost and complexity when compared with hydrogen re-circulation systems. In the first part of this work, we showed that localized fuel starvation events may occur, because of water and nitrogen accumulation in the anode side, which could be particularly damaging to the cell performance. To prevent these degradations, the anode compartment must be purged which may lead to an overall system efficiency decrease because of significant hydrogen waste. In the second part, we present several purge strategies in order to minimize both hydrogen waste and membrane-electrode assembly degradations during dead-ended anode operation. A linear segmented cell with reference electrodes was used to monitor simultaneously the current density distribution along the gas channel and the time evolution of local anode and cathode potentials. To asses MEA damages, Platinum ElectroChemical Surface Area (ECSA) and cell performance were periodically measured. The results showed that dead-end mode operation with an anode plate maintained at a temperature 5 °C hotter than the cathode plate limits water accumulation in the anode side, reducing significantly purge frequency (and thus hydrogen losses) as well as MEA damages. As nitrogen contribution to hydrogen starvation is predominant in this thermal configuration, we also tested a microleakage solution to discharge continuously most the nitrogen accumulating in the anode side while ensuring low hydrogen losses and minimum ECSA losses provided the right microleakage flow rate is chosen.

  14. DIFFUSIVE-Magnetoresistance(DMR) Proton(PMR)/Hydrogen-ion WATER: PRE-``Fert''/``Grunberg'' GMR[and CMR]: Quo-Vadis ``Honesty''???: PLAGIARISM!!!

    Science.gov (United States)

    Fart, Albart; Gruntbug, Peter; Siegel, Edward

    2011-03-01

    Proton/Hydrogen-ion Diffusive-Magnetoresistance(DMR) of Siegel[APS March-Mtgs.(70s)] based upon Siegel[Int'l. Conf. Mag.-Alloys and Oxides("ICMAO"), The Technion(77); J. Mag. Mag. Mtls. 7, 312(78)] FIRST experimental-discovery of GMR and FIRST theoretical prediction of CMR[ibid. 7, 338 (78)], facilitates NEW water production in global-warming exacerbated dry arid/semi-arid regions: Only HYDROGEN is/can be "FLYING-WATER"!!! (aka "chemical-rain-in-pipelines"). EMET/TRUTH-in-the-``SEANCES'', would-be "Sciences": C. Perelman-Corredoira [Against the Tide(07)] featuring Martin-Bradshaw ["Healing the SHAME That BINDS You"(80s)] systemic sociological-dysfunctionality(S-D), and Grigory Perelman's HEROIC ETHICS (refusal of both pure-maths Poincare-conjecture proof 2007 Fields-medal and 2010 Clay-Institute so-called/media-hyped/P.Red/spin-doctored millennium-prize million-dollar would-be award, militates as well in the current "SEANCE" of physics/maths politics/media-hype/P.R /spin-doctoring VS. Siegel FIRST experimental GMR a never-acknowledged full decade PRE-"Fert"(88) /"Grunberg(89)" ``Phales-GroPE''/Thompson-CSF/ KFZ-JEWlich 2007 physics Wolf/Japan/Nobel-prizes!!!

  15. A cost-effective nanoporous ultrathin film electrode based on nanoporous gold/IrO2 composite for proton exchange membrane water electrolysis

    Science.gov (United States)

    Zeng, Yachao; Guo, Xiaoqian; Shao, Zhigang; Yu, Hongmei; Song, Wei; Wang, Zhiqiang; Zhang, Hongjie; Yi, Baolian

    2017-02-01

    A cost-effective nanoporous ultrathin film (NPUF) electrode based on nanoporous gold (NPG)/IrO2 composite has been constructed for proton exchange membrane (PEM) water electrolysis. The electrode was fabricated by integrating IrO2 nanoparticles into NPG through a facile dealloying and thermal decomposition method. The NPUF electrode is featured in its 3D interconnected nanoporosity and ultrathin thickness. The nanoporous ultrathin architecture is binder-free and beneficial for improving electrochemical active surface area, enhancing mass transport and facilitating releasing of oxygen produced during water electrolysis. Serving as anode, a single cell performance of 1.728 V (@ 2 A cm-2) has been achieved by NPUF electrode with a loading of IrO2 and Au at 86.43 and 100.0 μg cm-2 respectively, the electrolysis voltage is 58 mV lower than that of conventional electrode with an Ir loading an order of magnitude higher. The electrolysis voltage kept relatively constant up to 300 h (@250 mA cm-2) during the course of durability test, manifesting that NPUF electrode is promising for gas evolution.

  16. Thermodynamics of Carboxyl Group′s Protonation of α -amino Acids in Water-Ethanol Mixtures at 298.15K%α-氨基酸在水-乙醇中羧基质子化热力学

    Institute of Scientific and Technical Information of China (English)

    厉刚; 林瑞森; 宗汉兴

    2000-01-01

    Enthalpy changes for the protonation of carboxyl group of four α-amino acids(glycine,L-α-alanine,L-valine and L-serine) were measured in water-ethanol mixtures (10- 70wt%) at 298.15K using LKB-2277 Bioactivity Monitor.The corresponding entropy and Gibbs energy changes were also calculated.The results show that both enthalpy changes and entropy changes are favorable to the protonation of carboxyl groups of the investigated amino acids in water-ethanol mixtures.However,the influence of the composition of ethanol in the mixed solvents on the enthalpy change and entropy changes is complicated.Both sδ and sδ ,the differences of enthalpy changes and entropy changes in mixed solvents and in pure water respectively,show a minimum approximately at xEtOH=0.1.The effects of side chains on the enthalpy change and entropy changes were also investigated using the proton transfer process between glycine and the other three amino acids.The results demonstrate that the proton transfer processes for alanine and valine are spontaneous but not for serine,which could be interpreted in terms of the electrostatic interaction between amino group and carboxyl group within the molecule and the interaction between carboxyl group and the solvent.

  17. Hydrogen Bonds in Excited State Proton Transfer

    Science.gov (United States)

    Horke, D. A.; Watts, H. M.; Smith, A. D.; Jager, E.; Springate, E.; Alexander, O.; Cacho, C.; Chapman, R. T.; Minns, R. S.

    2016-10-01

    Hydrogen bonding interactions between biological chromophores and their surrounding protein and solvent environment significantly affect the photochemical pathways of the chromophore and its biological function. A common first step in the dynamics of these systems is excited state proton transfer between the noncovalently bound molecules, which stabilizes the system against dissociation and principally alters relaxation pathways. Despite such fundamental importance, studying excited state proton transfer across a hydrogen bond has proven difficult, leaving uncertainties about the mechanism. Through time-resolved photoelectron imaging measurements, we demonstrate how the addition of a single hydrogen bond and the opening of an excited state proton transfer channel dramatically changes the outcome of a photochemical reaction, from rapid dissociation in the isolated chromophore to efficient stabilization and ground state recovery in the hydrogen bonded case, and uncover the mechanism of excited state proton transfer at a hydrogen bond, which follows sequential hydrogen and charge transfer processes.

  18. Molecular Relaxation in Liquids

    CERN Document Server

    Bagchi, Biman

    2012-01-01

    This book brings together many different relaxation phenomena in liquids under a common umbrella and provides a unified view of apparently diverse phenomena. It aligns recent experimental results obtained with modern techniques with recent theoretical developments. Such close interaction between experiment and theory in this area goes back to the works of Einstein, Smoluchowski, Kramers' and de Gennes. Development of ultrafast laser spectroscopy recently allowed study of various relaxation processes directly in the time domain, with time scales going down to picosecond (ps) and femtosecond (fs

  19. Determination of protonation constants of some tetracycline antibiotics by potentiometry and lc methods in water and acetonitrile-water binary mixtures

    National Research Council Canada - National Science Library

    Senem Şanli; Nurullah Şanli; Güleren Alsancak

    2009-01-01

    An accurate estimation of dissociation constants of tetracycline antibiotics in acetonitrile-water binary mixtures is very important for several separation techniques such as liquid chromatography and...

  20. High Temperature, Low Relative Humidity, Polymer-type Membranes Based on Disulfonated Poly(arylene ether) Block and Random Copolymers Optionally Incorporating Protonic Conducting Layered Water insoluble Zirconium Fillers

    Energy Technology Data Exchange (ETDEWEB)

    McGrath, James E.; Baird, Donald G.

    2010-06-03

    Our research group has been engaged in the past few years in the synthesis of biphenol based partially disulfonated poly(arylene ether sulfone) random copolymers as potential PEMs. This series of polymers are named as BPSH-xx, where BP stands for biphenol, S stands for sulfonated, H stands for acidified and xx represents the degree of disulfonation. All of these sulfonated copolymers phase separate to form nano scale hydrophilic and hydrophobic morphological domains. The hydrophilic phase containing the sulfonic acid moieties causes the copolymer to absorb water. Water confined in hydrophilic pores in concert with the sulfonic acid groups serve the critical function of proton (ion) conduction and water transport in these systems. Both Nafion and BPSH show high proton conductivity at fully hydrated conditions. However proton transport is especially limited at low hydration level for the BPSH random copolymer. It has been observed that the diffusion coefficients of both water and protons change with the water content of the pore. This change in proton and water transport mechanisms with hydration level has been attributed to the solvation of the acid groups and the amount of bound and bulk-like water within a pore. At low hydration levels most of the water is tightly associated with sulfonic groups and has a low diffusion coefficient. This tends to encourage isolated domain morphology. Thus, although there may be significant concentrations of protons, the transport is limited by the discontinuous morphological structure. Hence the challenge lies in how to modify the chemistry of the polymers to obtain significant protonic conductivity at low hydration levels. This may be possible if one can alter the chemical structure to synthesize nanophase separated ion containing block copolymers. Unlike the BPSH copolymers, where the sulfonic acid groups are randomly distributed along the chain, the multiblock copolymers will feature an ordered sequence of hydrophilic and

  1. Proton dynamics of two-dimensional oxalate-bridged coordination polymers.

    Science.gov (United States)

    Miyatsu, Satoshi; Kofu, Maiko; Nagoe, Atsushi; Yamada, Takeshi; Sadakiyo, Masaaki; Yamada, Teppei; Kitagawa, Hiroshi; Tyagi, Madhusudan; García Sakai, Victoria; Yamamuro, Osamu

    2014-08-28

    A two-dimensional porous coordination polymer (NH4)2{HOOC(CH2)4COOH}[Zn2(C2O4)3] (abbreviated as (NH4)2(adp)[Zn2(ox)3] (adp = adipic acid, ox = oxalate)), which accommodates water molecules between the [Zn2(ox)3] layers, is highly remarked as a new type of crystalline proton conductor. In order to investigate its phase behavior and the proton conducting mechanism, we have performed adiabatic calorimetry, neutron diffraction, and quasi-elastic neutron scattering experiments on a fully hydrated sample (NH4)2(adp)[Zn2(ox)3]·3H2O with the highest proton conductivity (8 × 10(-3) S cm(-1), 25 °C, 98% RH). Its isostructural derivative K2(adp)[Zn2(ox)3]·3H2O was also measured to investigate the role of ammonium ions. (NH4)2(adp)[Zn2(ox)3]·3H2O and K2(adp)[Zn2(ox)3]·3H2O exhibit higher order transitions at 86 K and 138 K, respectively. From the magnitude of the transition entropy, the former is of an order-disorder type while the latter is of a displacive type. (NH4)2(adp)[Zn2(ox)3]·3H2O has four Debye-type relaxations and K2(adp)[Zn2(ox)3]·3H2O has two similar relaxations above each transition temperature. The two relaxations of (NH4)2(adp)[Zn2(ox)3]·3H2O with very small activation energies (ΔEa < 5 kJ mol(-1)) are due to the rotational motions of ammonium ions and play important roles in the proton conduction mechanism. It was also found that the protons in (NH4)2(adp)[Zn2(ox)3]·3H2O are carried through a Grotthuss mechanism. We present a discussion on the proton conducting mechanism based on the present structural and dynamical information.

  2. Compaction and relaxation of biofilms

    KAUST Repository

    Valladares Linares, R.

    2015-06-18

    Operation of membrane systems for water treatment can be seriously hampered by biofouling. A better characterization of biofilms in membrane systems and their impact on membrane performance may help to develop effective biofouling control strategies. The objective of this study was to determine the occurrence, extent and timescale of biofilm compaction and relaxation (decompaction), caused by permeate flux variations. The impact of permeate flux changes on biofilm thickness, structure and stiffness was investigated in situ and non-destructively with optical coherence tomography using membrane fouling monitors operated at a constant crossflow velocity of 0.1 m s−1 with permeate production. The permeate flux was varied sequentially from 20 to 60 and back to 20 L m−2 h−1. The study showed that the average biofilm thickness on the membrane decreased after elevating the permeate flux from 20 to 60 L m−2 h−1 while the biofilm thickness increased again after restoring the original flux of 20 L m−2 h−1, indicating the occurrence of biofilm compaction and relaxation. Within a few seconds after the flux change, the biofilm thickness was changed and stabilized, biofilm compaction occurred faster than the relaxation after restoring the original permeate flux. The initial biofilm parameters were not fully reinstated: the biofilm thickness was reduced by 21%, biofilm stiffness had increased and the hydraulic biofilm resistance was elevated by 16%. Biofilm thickness was related to the hydraulic biofilm resistance. Membrane performance losses are related to the biofilm thickness, density and morphology, which are influenced by (variations in) hydraulic conditions. A (temporarily) permeate flux increase caused biofilm compaction, together with membrane performance losses. The impact of biofilms on membrane performance can be influenced (increased and reduced) by operational parameters. The article shows that a (temporary) pressure increase leads to more

  3. Water and tissue equivalence properties of biological materials for photons, electrons, protons and alpha particles in the energy region 10 keV-1 GeV: a comparative study.

    Science.gov (United States)

    Kurudirek, Murat

    2016-09-01

    To compare some biological materials in respect to the water and tissue equivalence properties for photon, electron, proton and alpha particle interactions as means of the effective atomic number (Zeff) and electron density (Ne). A Z-wise interpolation procedure has been adopted for calculation of Zeff using the mass attenuation coefficients for photons and the mass stopping powers for charged particles. At relatively low energies (100 keV-3 MeV), Zeff and Ne for photons and electrons were found to be constant while they vary much more for protons and alpha particles. In contrast, Zeff and Ne for protons and alpha particles were found to be constant after 3 MeV whereas for photons and electrons they were found to increase with the increasing energy. Also, muscle eq. liquid (with sucrose) have Zeff and Ne values close to the Muscle Skeletal (ICRP) and Muscle Striated (ICRU) within low relative differences below 9%. Muscle eq. liquid (without sucrose) have Zeff and Ne values close to the Muscle Skeletal (ICRP) and Muscle Striated (ICRU) with difference below 10%. The reported data should be useful in determining best water as well as tissue equivalent materials for photon, electron, proton and alpha particle interactions.

  4. Invasion percolation with inlet multiple injections and the water management problem in proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Ceballos, Loic; Prat, Marc [Universite de Toulouse; INPT, UPS; IMFT, Avenue Camille Soula 31400, Toulouse (France); CNRS, IMFT 31400, Toulouse (France)

    2010-02-01

    Liquid water transport in the diffusion porous layers of polymer electrolyte membrane fuel cells (PEMFC) is analyzed as a process of quasi-static invasion from multiple interfacial injection sources. From pore network simulations based on a new version of the invasion percolation algorithm it is shown that a porous layer acts as a two-phase filter: the number of breakthrough points is significantly lower that the number of injection points owing to the merging of liquid paths within the porous layer. The number of breakthrough points at the gas diffusion layer/gas channel interface obtained with this model is consistent with the available experimental observations. (author)

  5. Relationship between the crystallization rates of amorphous nifedipine, phenobarbital, and flopropione, and their molecular mobility as measured by their enthalpy relaxation and (1)H NMR relaxation times.

    Science.gov (United States)

    Aso, Y; Yoshioka, S; Kojima, S

    2000-03-01

    Isothermal crystallization of amorphous nifedipine, phenobarbital, and flopropione was studied at temperatures above and below their glass transition temperatures (T(g)). A sharp decrease in the crystallization rate with decreasing temperature was observed for phenobarbital and flopropione, such that no crystallization was observed at temperatures 20-30 degrees C lower than their T(g) within ordinary experimental time periods. In contrast, the crystallization rate of nifedipine decreased moderately with decreasing temperature, and considerable crystallization was observed at 40 degrees C below its T(g) within 4 months. The molecular mobility of these amorphous drugs was assessed by enthalpy relaxation and (1)H-NMR relaxation measurements. The enthalpy relaxation time of nifedipine was smaller than that of phenobarbital or flopropinone at the same T - T(g) values, suggesting higher molecular mobility of nifedipine. The spin-lattice relaxation time in the rotating frame (T(1rho)) decreased markedly at temperature above T(g). The slope of the Arrhenius type plot of the T(1rho) for nifedipine protons changed at about 10 degrees C below the T(g), whereas the slope for phenobarbital protons became discontinuous at about 10 degrees C above the T(g). Even at temperatures below its T(g), the spin-spin relaxation process of nifedipine could be described by the sum of its Gaussian relaxation, which is characteristic of solid protons, and its Lorentzian relaxation, which is characteristic of protons with higher mobility. In contrast, no Lorentzian relaxation was observed for phenobarbital or flopropione at temperatures below their T(g). These results also suggest that nifedipine has higher molecular mobility than phenobarbital and flopropione at temperatures below T(g). The faster crystallization of nifedipine than that of phenobarbital or flopropione observed at temperatures below its T(g) may be partly ascribed to its higher molecular mobility at these temperatures.

  6. Effect of SiO2 on relaxation phenomena and mechanism of ion conductivity of [Nafion/(SiO2)x] composite membranes.

    Science.gov (United States)

    Di Noto, Vito; Gliubizzi, Rocco; Negro, Enrico; Pace, Giuseppe

    2006-12-14

    water [(H2O)n]; (b) water solvating the oxonium ions directly interacting with sulfonic acid groups [H3O+...SO3(-)-].(H2O)n; (c) water aggregates associated with H3O+ ions [H3O+.(H2O)n]; and (d) low associated water species in dimer form [(H2O)2]. The conductivity mechanism and relaxation events were investigated by broadband dielectric spectroscopy (BDS). [Nafion/(SiO2)x] nanocomposite membranes were found to possess two different molecular relaxation phenomena which are associated with the alpha-relaxation mode of PTFE-like fluorocarbon domains and the beta-relaxation mode of acid side groups of the Nafion component. Owing to their strong coupling, both these relaxation modes are diagnostic for the interactions between the polar groups of the Nafion host polymer and the (SiO2)x oxoclusters and play a determining role in the conductivity mechanism of the membranes. The studies support the proposal that long-range proton charge transfer in [Nafion/(SiO2)x] composites takes place due to a mechanism involving exchange of the proton between the four water domains. This latter proton transfer occurs owing to a subsequent combination of domain intersections resulting from the water domain fluctuations induced by the molecular relaxation events of host Nafion polymer.

  7. Crystallographic and Computational Analysis of the Barrel Part of the PsbO Protein of Photosystem II: Carboxylate-Water Clusters as Putative Proton Transfer Relays and Structural Switches.

    Science.gov (United States)

    Bommer, Martin; Bondar, Ana-Nicoleta; Zouni, Athina; Dobbek, Holger; Dau, Holger

    2016-08-23

    In all organisms that employ oxygenic photosynthesis, the membrane-extrinsic PsbO protein is a functionally important component of photosystem II. To study the previously proposed proton antenna function of carboxylate clusters at the protein-water interface, we combined crystallography and simulations of a truncated cyanobacterial (Thermosynechococcus elongatus) PsbO without peripheral loops. We expressed the PsbO β-barrel heterologously and determined crystal structures at resolutions of 1.15-1.5 Å at 100 K at various pH values and at 297 K and pH 6. (1) Approximately half of the 177 surface waters identified at 100 K are resolved at 297 K, suggesting significant occupancy of specific water sites at room temperature, and loss of resolvable occupancy for other sites. (2) Within a loop region specific to cyanobacterial PsbO, three residues and four waters coordinating a calcium ion are well ordered even at 297 K; the ligation differs for manganese. (3) The crystal structures show water-carboxylate clusters that could facilitate fast Grotthus-type proton transfer along the protein surface and/or store protons. (4) Two carboxylate side chains, which are part of a structural motif interrupting two β-strands and connecting PsbO to photosystem II, are within hydrogen bonding distance at pH 6 (100 K). Simulations indicate coupling between protein structure and carboxylate protonation. The crystal structure determined at 100 K and pH 10 indicates broken hydrogen bonding between the carboxylates and local structural change. At pH 6 and 297 K, both conformations were present in the crystal, suggesting conformational dynamics in the functionally relevant pH regime. Taken together, crystallography and molecular dynamics underline a possible mechanism for pH-dependent structural switching.

  8. Hair Dye and Hair Relaxers

    Science.gov (United States)

    ... For Consumers Consumer Information by Audience For Women Hair Dye and Hair Relaxers Share Tweet Linkedin Pin it More sharing ... products. If you have a bad reaction to hair dyes and relaxers, you should: Stop using the ...

  9. Experimental study on the influence of clamping pressure on proton exchange membrane water electrolyzer (PEMWE) cell’s characteristics

    DEFF Research Database (Denmark)

    Al Shakhshir, Saher; Cui, Xiaoti; Kær, Søren Knudsen

    Energy transition can be led by more hydrogen production. Hydrogen offers a clean, sustainable, and flexible option for overcoming different obstacles that face the low-carbon economy [1]. PEMWE is one of the most promising candidate technologies to produce hydrogen from renewable energy sources...... temperature (70°C) and atmospheric pressure. Early results for IV curve predict that the PEMWE cell performance increases with increasing the clamping pressure at fixed temperature and current density. This can be elucidated by the EIS measurements which predict an increment in ohmic and activation resistance...... at lower clamping pressure values at the same temperature and current density. Furthermore, early results have not shown any significant change in the amount of hydrogen crossing-over from cathode to anode and water from anode to cathode. This might be attributed to the membrane properties which might...

  10. On the Experimental Investigation of the Clamping Pressure Effects on the Proton Exchange Membrane Water Electrolyser Cell Performance

    DEFF Research Database (Denmark)

    Al Shakhshir, Saher; Frensch, Steffen Henrik; Kær, Søren Knudsen

    2017-01-01

    to migrate to negatively chargedcathode, where hydrogen is reduced. Meanwhile, oxygen is produced at the anode sideelectrode and escape as a gas with the circulating water.In the recent few years, PEMWE’s R&D has inched towards; operating conditions; such asincreased operating temperature and cathode...... at different clamping pressures. All thesemeasurements are conducted at constant cell temperature (70°C) and atmospheric pressure.Furthermore, to ensure a high confidence level in the obtained data, experiments are repeatedfew times.Early results for polarization curve predict that the PEMWE cell performance...... increases withincreasing the clamping pressure at fixed temperature and current density. This can beelucidated by the EIS measurements which predict an increment in ohmic and activation...

  11. Thermodynamic evaluation and modeling of proton and water exchange associated with benzamidine and berenil binding to ß-trypsin

    Directory of Open Access Journals (Sweden)

    M.T. Pereira

    2005-11-01

    Full Text Available Serine-proteases are involved in vital processes in virtually all species. They are important targets for researchers studying the relationships between protein structure and activity, for the rational design of new pharmaceuticals. Trypsin was used as a model to assess a possible differential contribution of hydration water to the binding of two synthetic inhibitors. Thermodynamic parameters for the association of bovine ß-trypsin (homogeneous material, observed 23,294.4 ± 0.2 Da, theoretical 23,292.5 Da with the inhibitors benzamidine and berenil at pH 8.0, 25ºC and with 25 mM CaCl2, were determined using isothermal titration calorimetry and the osmotic stress method. The association constant for berenil was about 12 times higher compared to the one for benzamidine (binding constants are K = 596,599 ± 25,057 and 49,513 ± 2,732 M-1, respectively; the number of binding sites is the same for both ligands, N = 0.99 ± 0.05. Apparently the driving force responsible for this large difference of affinity is not due to hydrophobic interactions because the variation in heat capacity (DCp, a characteristic signature of these interactions, was similar in both systems tested (-464.7 ± 23.9 and -477.1 ± 86.8 J K-1 mol-1 for berenil and benzamidine, respectively. The results also indicated that the enzyme has a net gain of about 21 water molecules regardless of the inhibitor tested. It was shown that the difference in affinity could be due to a larger number of interactions between berenil and the enzyme based on computational modeling. The data support the view that pharmaceuticals derived from benzamidine that enable hydrogen bond formation outside the catalytic binding pocket of ß-trypsin may result in more effective inhibitors.

  12. Excited-state proton coupled electron transfer between photolyase and the damaged DNA through water wire: a photo-repair mechanism.

    Science.gov (United States)

    Wang, Hongjuan; Chen, Xuebo; Fang, Weihai

    2014-12-14

    The photolyase enzyme absorbs blue light to repair damaged DNA through a cyclic electron transfer reaction. A description of the underlying mechanism has proven to be a challenging issue for both experimental and theoretical studies. In the present work, combined CASPT2//CASSCF/AMBER (QM/MM) calculations have been performed for damaged DNA in photolyase. A proton-coupled electron transfer (PCET) mechanism has been determined for restoring cyclobutane pyrimidine dimer (CPD) to two normal thymine bases by irradiation of photolyase. A well-defined water wire between FADH(-) and CPD was determined as a bridge to assist the PCET process within FADH(-) and thereby trigger the forward electron transfer to CPD. The subsequent CPD splitting and the alternation of the H-bond pattern proceed in a concerted way, which makes the productive backward electron transfer occur on an ultrafast timescale. A local minimum of SCT((1)ππ*)-LMin was identified on the pathway of the futile backward electron transfer (BET), which is stabilized by the strong H-bond interaction between the water wire and CPD. As a result, the futile BET process is endothermic by ∼18.0 kcal mol(-1), which is responsible for a 2.4 ns timescale inferred experimentally for the futile BET process. Besides the unbiased interpretation for the majority of the experimental findings, the present study provides a new excited-state PCET mechanism, which leads to a significant step toward a deeper understanding of the photo-repair process of damaged-DNA by the photolyase enzyme.

  13. Interaction between reduced glutathione and PEO-PPO-PEO copolymers in aqueous solutions: studied by 1H NMR and spin-lattice relaxation.

    Science.gov (United States)

    Jia, Lianwei; Guo, Chen; Yang, Liangrong; Xiang, Junfeng; Tang, Yalin; Liu, Huizhou

    2011-03-17

    In order to investigate the effect of PEO-PPO-PEO copolymers on the glutathione (GSH)/glutathione-S-transferase (GST) detoxification system, interaction between the copolymers and GSH is studied by NMR measurements. Selective rotating-frame nuclear Overhauser effect (ROE) experiment confirms that glutamyl (Glu) α-H of GSH has spatial contact with EO methylene protons. Spin-lattice relaxation times of GSH Glu α-H show a decrease when PEO-PPO-PEO copolymers are added, and the decrease is greater with copolymers possessing more EO units. Other protons of GSH show little change in the presence of the copolymers. The addition of GSH promotes the dehydration of PEO-PPO-PEO copolymers. This results from the breaking of hydrogen bonds between water and the polymers and the forming of hydrogen bonds between Glu α-carboxylate protons and oxygen atoms of EO units. The dissociation constant between GSH and P85 copolymer is determined by spin-lattice relaxation measurements, which shows the binding is of low affinity and the two molecules are in fast dissociation kinetics. This study suggests that GSH transporting or utilizing systems may be affected by treatment of PEO-PPO-PEO copolymers.

  14. Kinetic Actviation Relaxation Technique

    CERN Document Server

    Béland, Laurent Karim; El-Mellouhi, Fedwa; Joly, Jean-François; Mousseau, Normand

    2011-01-01

    We present a detailed description of the kinetic Activation-Relaxation Technique (k-ART), an off-lattice, self-learning kinetic Monte Carlo algorithm with on-the-fly event search. Combining a topological classification for local environments and event generation with ART nouveau, an efficient unbiased sampling method for finding transition states, k-ART can be applied to complex materials with atoms in off-lattice positions or with elastic deformations that cannot be handled with standard KMC approaches. In addition to presenting the various elements of the algorithm, we demonstrate the general character of k-ART by applying the algorithm to three challenging systems: self-defect annihilation in c-Si, self-interstitial diffusion in Fe and structural relaxation in amorphous silicon.

  15. Nonlinear fractional relaxation

    Indian Academy of Sciences (India)

    A Tofighi

    2012-04-01

    We define a nonlinear model for fractional relaxation phenomena. We use -expansion method to analyse this model. By studying the fundamental solutions of this model we find that when → 0 the model exhibits a fast decay rate and when → ∞ the model exhibits a power-law decay. By analysing the frequency response we find a logarithmic enhancement for the relative ratio of susceptibility.

  16. Snapshots of Proton Accommodation at a Microscopic Water Surface: Understanding the Vibrational Spectral Signatures of the Charge Defect in Cryogenically Cooled H+(H2O)n=2 – 28 Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Fournier, Joseph A.; Wolke, Conrad T.; Johnson, Mark A.; Odbadrakh, Tuguldur T.; Jordan, Kenneth D.; Kathmann, Shawn M.; Xantheas, Sotiris S.

    2015-07-09

    In this Article, we review the role of gas-phase, size-selected protonated water clusters, H+(H2O)n, in the analysis of the microscopic mechanics responsible for the behavior of the excess proton in bulk water. We extend upon previous studies of the smaller, two-dimensional sheet-like structures to larger (n≥10) assemblies with three-dimensional cage morphologies which better mimic the bulk environment. Indeed, clusters in which a complete second solvation shell forms around a surface-embedded hydronium ion yield vibrational spectra where the signatures of the proton defect display strikingly similar positions and breadth to those observed in dilute acids. We investigate effects of the local structure and intermolecular interactions on the large red shifts observed in the proton vibrational signature upon cluster growth using various theoretical methods. We show that, in addition to sizeable anharmonic couplings, the position of the excess proton vibration can be traced to large increases in the electric field exerted on the embedded hydronium ion upon formation of the first and second solvation shells. MAJ acknowledges support from the U.S. Department of Energy under Grant No. DE-FG02- 06ER15800 as well as the facilities and staff of the Yale University Faculty of Arts and Sciences High Performance Computing Center, and by the National Science Foundation under Grant No. CNS 08-21132 that partially funded acquisition of the facilities. SMK and SSX acknowledge support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

  17. Effect of gel firmness at cutting time, pH, and temperature on rennet coagulation and syneresis: an in situ 1H NMR relaxation study.

    Science.gov (United States)

    Hansen, Christian Lyndgaard; Rinnan, Asmund; Engelsen, Søren Balling; Janhøj, Thomas; Micklander, Elisabeth; Andersen, Ulf; van den Berg, Frans

    2010-01-13

    The objective of this study was to monitor rennet-induced milk gel formation and mechanically induced gel syneresis in situ by low-field NMR. pH, temperature, and gel firmness at cutting time were varied in a factorial design. The new curve-fitting method Doubleslicing revealed that during coagulation two proton populations with distinct transverse relaxation times (T2,1=181, T2,2=465 ms) were present in fractions (f1=98.9%, f2=1.1%). Mechanical cutting of the gel in the NMR tube induced macrosyneresis, which led to the appearance of an additional proton population (T2,3=1500-2200 ms) identified as whey. On the basis of NMR quantification of whey water the syneresis rate was calculated and found to be significantly dependent on pH and temperature.

  18. Proton radiography to improve proton therapy treatment

    Science.gov (United States)

    Takatsu, J.; van der Graaf, E. R.; Van Goethem, M.-J.; van Beuzekom, M.; Klaver, T.; Visser, J.; Brandenburg, S.; Biegun, A. K.

    2016-01-01

    The quality of cancer treatment with protons critically depends on an accurate prediction of the proton stopping powers for the tissues traversed by the protons. Today, treatment planning in proton radiotherapy is based on stopping power calculations from densities of X-ray Computed Tomography (CT) images. This causes systematic uncertainties in the calculated proton range in a patient of typically 3-4%, but can become even 10% in bone regions [1,2,3,4,5,6,7,8]. This may lead to no dose in parts of the tumor and too high dose in healthy tissues [1]. A direct measurement of proton stopping powers with high-energy protons will allow reducing these uncertainties and will improve the quality of the treatment. Several studies have shown that a sufficiently accurate radiograph can be obtained by tracking individual protons traversing a phantom (patient) [4,6,10]. Our studies benefit from the gas-filled time projection chambers based on GridPix technology [2], developed at Nikhef, capable of tracking a single proton. A BaF2 crystal measuring the residual energy of protons was used. Proton radiographs of phantom consisting of different tissue-like materials were measured with a 30×30 mm2 150 MeV proton beam. Measurements were simulated with the Geant4 toolkit.First experimental and simulated energy radiographs are in very good agreement [3]. In this paper we focus on simulation studies of the proton scattering angle as it affects the position resolution of the proton energy loss radiograph. By selecting protons with a small scattering angle, the image quality can be improved significantly.

  19. PHYSICOCHEMICAL PROPERTIES OF THE WATER DEPLETED OF HEAVY ISOTOPES

    Directory of Open Access Journals (Sweden)

    Vladislav V. Goncharuk

    2012-06-01

    Full Text Available Data on physicochemical properties of the light water (deuterium concentration is reduced to the ratio D/H = 4 ppm and that of the isotope of oxygen 18 – to the ratio 18O/16O = 750 ppm have been obtained. They include the melting and boiling points, kinematic viscosity, density, the spin-spin proton relaxation time, self-diffusion coefficients, and the small-angle laser light scattering. An explanation was proposed for the detected significant changes of the light water as compared with the high-resistivity water having geochemically ordinary isotope composition.

  20. Proton movies

    CERN Multimedia

    2009-01-01

    A humorous short film made by three secondary school students received an award at a Geneva film festival. Even without millions of dollars or Hollywood stars at your disposal, it is still possible to make a good science fiction film about CERN. That is what three students from the Collège Madame de Staël in Carouge, near Geneva, demonstrated. For their amateur short film on the LHC, they were commended by the jury of the video and multimedia festival for schools organised by the "Media in education" service of the Canton of Geneva’s Public Education Department. The film is a spoof of a television news report on the LHC start-up. In sequences full of humour and imagination, the reporter conducts interviews with a very serious "Professor Sairne", some protons preparing for their voyage and even the neutrons that were rejected by the LHC. "We got the idea of making a film about CERN at the end of the summer," explains Lucinda Päsche, one of the three students. "We did o...

  1. Fluorescence Quenching of Benzaldehyde in Water by Hydrogen Atom Abstraction.

    Science.gov (United States)

    Fletcher, Katharyn; Bunz, Uwe H F; Dreuw, Andreas

    2016-09-01

    We computed the mechanism of fluorescence quenching of benzaldehyde in water through relaxed potential energy surface scans. Time-dependent density functional theory calculations along the protonation coordinate from water to benzaldehyde reveal that photoexcitation to the bright ππ* (S3 ) state is immediately followed by ultrafast decay to the nπ* (S1 ) state. Evolving along this state, benzaldehyde (BA) abstracts a hydrogen atom, resulting in a BAH(.) and OH(.) radical pair. Benzaldehyde does not act as photobase in water, but abstracts a hydrogen atom from a nearby solvent molecule. The system finally decays back to the ground state by non-radiative decay and an electron transfers back to the OH(.) radical. Proton transfer from BAH(+) to OH(-) restores the initial situation, BA in water.

  2. Experimental proposal for accurate determination of the phase relaxation time in highly excited quantum many-body systems

    CERN Document Server

    Bienert, M; Kun, S Yu

    2006-01-01

    We estimate how accurate the phase relaxation time of quantum many-body systems can be determined from data on forward peaking of evaporating protons from a compound nucleus. The angular range and accuracy of the data needed for a reliable determination of the phase relaxation time are evaluated. The general method is applied to analyze the inelastic scattering of 18 MeV protons from Pt for which previously measured double differential cross sections for two angles in the evaporating domain of the spectra show a strong forward peaking. A new experiment for an improved determination of the phase relaxation time is proposed.

  3. Determination of the cis-trans isomerization barriers of L-alanyl-L-proline in aqueous solutions and at water/hydrophobic interfaces by on-line temperature-jump relaxation HPLC and dynamic on-column reaction HPLC.

    Science.gov (United States)

    Shibukawa, Masami; Miyake, Ayaka; Eda, Sayaka; Saito, Shingo

    2015-09-15

    Proline cis-trans isomerization is known to play a key role in the rate-determining steps of protein folding. It is thus very important to understand the influence of environments, not only bulk solutions but also microenvironments such as interfaces, on the isomerization reaction of proline peptides. Here we present two HPLC methods for measurements of kinetic and equilibrium parameters for the isomerization reactions in bulk solutions and at liquid/solid interfaces. On-line temperature-jump relaxation HPLC (T-jump HPLC) allows the determination of forward and reverse rate constants of the isomerization in a bulk solution by monitoring the whole time course of conversion of pure isomers from both sides of the reaction, in contrast to other HPLC and capillary zone electrophoresis as well as spectrometric and calorimetric methods, which use a mixture of the isomers. We can then determine cis-trans isomerization barriers of the peptide at liquid/solid interfaces from the kinetic data obtained by dynamic on-column reaction HPLC and T-jump HPLC. We observed that the interconversion around the peptide bond for l-alanyl-l-proline (Ala-Pro) in water is accelerated at the surfaces of an alkyl-bonded silica and a poly(styrene-divinylbenzene) copolymer resin, and this is caused by a remarkable decrease in the enthalpy of activation. The molecular structures of the cis and trans forms of Ala-Pro estimated by quantum mechanics calculation reveal that an equilibrium shift toward the cis form as well as the rapid isomerization of Ala-Pro at the water/hydrophobic interfaces can be attributed to the lower polarity of the interfacial water at the surfaces of the hydrophobic materials compared to that of bulk water.

  4. Proton-Proton and Proton-Antiproton Colliders

    Science.gov (United States)

    Scandale, Walter

    2015-02-01

    In the last five decades, proton-proton and proton-antiproton colliders have been the most powerful tools for high energy physics investigations. They have also deeply catalyzed innovation in accelerator physics and technology. Among the large number of proposed colliders, only four have really succeeded in becoming operational: the ISR, the SppbarS, the Tevatron and the LHC. Another hadron collider, RHIC, originally conceived for ion-ion collisions, has also been operated part-time with polarized protons. Although a vast literature documenting them is available, this paper is intended to provide a quick synthesis of their main features and key performance.

  5. Challenging lanthanide relaxation theory: erbium and thulium complexes that show NMR relaxation rates faster than dysprosium and terbium analogues.

    Science.gov (United States)

    Funk, Alexander M; Harvey, Peter; Finney, Katie-Louise N A; Fox, Mark A; Kenwright, Alan M; Rogers, Nicola J; Senanayake, P Kanthi; Parker, David

    2015-07-07

    Measurements of the proton NMR paramagnetic relaxation rates for several series of isostructural lanthanide(III) complexes have been performed in aqueous solution over the field range 1.0 to 16.5 Tesla. The field dependence has been modeled using Bloch-Redfield-Wangsness theory, allowing values for the electronic relaxation time, Tle and the magnetic susceptibility, μeff, to be estimated. Anomalous relaxation rate profiles were obtained, notably for erbium and thulium complexes of low symmetry 8-coordinate aza-phosphinate complexes. Such behaviour challenges accepted theory and can be interpreted in terms of changes in Tle values that are a function of the transient ligand field induced by solvent collision and vary considerably between Ln(3+) ions, along with magnetic susceptibilities that deviate significantly from free-ion values.

  6. Heteronuclear transverse and longitudinal relaxation in AX4 spin systems: Application to 15N relaxations in 15NH4+

    Science.gov (United States)

    Werbeck, Nicolas D.; Hansen, D. Flemming

    2014-01-01

    The equations that describe the time-evolution of transverse and longitudinal 15N magnetisations in tetrahedral ammonium ions, 15NH4+, are derived from the Bloch-Wangsness-Redfield density operator relaxation theory. It is assumed that the relaxation of the spin-states is dominated by (1) the intra-molecular 15N–1H and 1H–1H dipole–dipole interactions and (2) interactions of the ammonium protons with remote spins, which also include the contribution to the relaxations that arise from the exchange of the ammonium protons with the bulk solvent. The dipole–dipole cross-correlated relaxation mechanisms between each of the 15N–1H and 1H–1H interactions are explicitly taken into account in the derivations. An application to 15N-ammonium bound to a 41 kDa domain of the protein DnaK is presented, where a comparison between experiments and simulations show that the ammonium ion rotates rapidly within its binding site with a local correlation time shorter than approximately 1 ns. The theoretical framework provided here forms the basis for further investigations of dynamics of AX4 spin systems, with ammonium ions in solution and bound to proteins of particular interest. PMID:25128779

  7. Heteronuclear transverse and longitudinal relaxation in AX4 spin systems: application to (15)N relaxations in (15)NH4(+).

    Science.gov (United States)

    Werbeck, Nicolas D; Hansen, D Flemming

    2014-09-01

    The equations that describe the time-evolution of transverse and longitudinal (15)N magnetisations in tetrahedral ammonium ions, (15)NH4(+), are derived from the Bloch-Wangsness-Redfield density operator relaxation theory. It is assumed that the relaxation of the spin-states is dominated by (1) the intra-molecular (15)N-(1)H and (1)H-(1)H dipole-dipole interactions and (2) interactions of the ammonium protons with remote spins, which also include the contribution to the relaxations that arise from the exchange of the ammonium protons with the bulk solvent. The dipole-dipole cross-correlated relaxation mechanisms between each of the (15)N-(1)H and (1)H-(1)H interactions are explicitly taken into account in the derivations. An application to (15)N-ammonium bound to a 41kDa domain of the protein DnaK is presented, where a comparison between experiments and simulations show that the ammonium ion rotates rapidly within its binding site with a local correlation time shorter than approximately 1ns. The theoretical framework provided here forms the basis for further investigations of dynamics of AX4 spin systems, with ammonium ions in solution and bound to proteins of particular interest.

  8. Proton exchange membrane fuel cells

    CERN Document Server

    Qi, Zhigang

    2013-01-01

    Preface Proton Exchange Membrane Fuel CellsFuel CellsTypes of Fuel CellsAdvantages of Fuel CellsProton Exchange Membrane Fuel CellsMembraneCatalystCatalyst LayerGas Diffusion MediumMicroporous LayerMembrane Electrode AssemblyPlateSingle CellStackSystemCell Voltage Monitoring Module (CVM)Fuel Supply Module (FSM)Air Supply Module (ASM)Exhaust Management Module (EMM)Heat Management Module (HMM)Water Management Module (WMM)Internal Power Supply Module (IPM)Power Conditioning Module (PCM)Communications Module (COM)Controls Module (CM)SummaryThermodynamics and KineticsTheoretical EfficiencyVoltagePo

  9. The search for negative amplitude components in quasi-continuous distributions of relaxation times: the example of 1H magnetization exchange in articular cartilage and hydrated collagen

    Science.gov (United States)

    Fantazzini, Paola; Galassi, Francesca; Bortolotti, Villiam; Brown, Robert J. S.; Vittur, Franco

    2011-06-01

    When inverting nuclear magnetic resonance relaxation data in order to obtain quasi-continuous distributions of relaxation times for fluids in porous media, it is common practice to impose a non-negative (NN) constraint on the distributions. While this approach can be useful in reducing the effects of data distortion and/or preventing wild oscillations in the distributions, it may give misleading results in the presence of real negative amplitude components. Here, some examples of valid negative components for articular cartilage and hydrated collagen are given. Articular cartilage is a connective tissue, consisting mainly of collagen, proteoglycans and water, which can be considered, in many aspects, as a porous medium. Separate T1 relaxation data are obtained for low-mobility ('solid') macromolecular 1H and for higher-mobility ('liquid') 1H by the separation of these components in free induction decays, with α denoting the solid/liquid 1H ratio. When quasi-continuous distributions of relaxation times (T1) of the solid and liquid signal components of cartilage or collagen are computed from experimental relaxation data without imposing the usual NN constraint, valid negative peaks may appear. The features of the distributions, in particular negative peaks, and the fact that peaks at longer times for macromolecular and water protons are at essentially the same T1, are interpreted as the result of a magnetization exchange between these two spin pools. For the only-slightly-hydrated collagen samples, with α>1, the exchange leads to small negative peaks at short T1 times for the macromolecular component. However, for the cartilage, with substantial hydration or for a strongly hydrated collagen sample, both with αLt1, the behavior is reversed, with a negative peak for water at short times. The validity of a negative peak may be accepted (dismissed) by a high (low) cost of NN in error of fit. Computed distributions for simulated data using observed signal

  10. Grueneisen relaxation photoacoustic microscopy

    Science.gov (United States)

    Wang, Lidai; Zhang, Chi; Wang, Lihong V.

    2014-01-01

    The temperature-dependent property of the Grueneisen parameter has been employed in photoacoustic imaging mainly to measure tissue temperature. Here we explore this property using a different approach and develop Grueneisen-relaxation photoacoustic microscopy (GR-PAM), a technique that images non-radiative absorption with confocal optical resolution. GR-PAM sequentially delivers two identical laser pulses with a micro-second-scale time delay. The first laser pulse generates a photoacoustic signal and thermally tags the in-focus absorbers. Owing to the temperature dependence of the Grueneisen parameter, when the second laser pulse excites the tagged absorbers within the thermal relaxation time, a photoacoustic signal stronger than the first one is produced. GR-PAM detects the amplitude difference between the two co-located photoacoustic signals, confocally imaging the non-radiative absorption. We greatly improved axial resolution from 45 µm to 2.3 µm and at the same time slightly improved lateral resolution from 0.63 µm to 0.41 µm. In addition, the optical sectioning capability facilitates the measurement of the absolute absorption coefficient without fluence calibration. PMID:25379919

  11. Transverse relaxation dispersion of the p7 membrane channel from hepatitis C virus reveals conformational breathing

    Energy Technology Data Exchange (ETDEWEB)

    Dev, Jyoti; Brüschweiler, Sven [Harvard Medical School, Department of Biological Chemistry and Molecular Pharmacology (United States); Ouyang, Bo [Chinese Academy of Sciences, State Key Laboratory of Molecular Biology, Shanghai Institute of Biochemistry and Cell Biology (China); Chou, James J., E-mail: james-chou@hms.harvard.edu [Harvard Medical School, Department of Biological Chemistry and Molecular Pharmacology (United States)

    2015-04-15

    The p7 membrane protein encoded by hepatitis C virus (HCV) assembles into a homo-hexamer that selectively conducts cations. An earlier solution NMR structure of the hexameric complex revealed a funnel-like architecture and suggests that a ring of conserved asparagines near the narrow end of the funnel are important for cation interaction. NMR based drug-binding experiments also suggest that rimantadine can allosterically inhibit ion conduction via a molecular wedge mechanism. These results suggest the presence of dilation and contraction of the funnel tip that are important for channel activity and that the action of the drug is attenuating this motion. Here, we determined the conformational dynamics and solvent accessibility of the p7 channel. The proton exchange measurements show that the cavity-lining residues are largely water accessible, consistent with the overall funnel shape of the channel. Our relaxation dispersion data show that residues Val7 and Leu8 near the asparagine ring are subject to large chemical exchange, suggesting significant intrinsic channel breathing at the tip of the funnel. Moreover, the hinge regions connecting the narrow and wide regions of the funnel show strong relaxation dispersion and these regions are the binding sites for rimantadine. Presence of rimantadine decreases the conformational dynamics near the asparagine ring and the hinge area. Our data provide direct observation of μs–ms dynamics of the p7 channel and support the molecular wedge mechanism of rimantadine inhibition of the HCV p7 channel.

  12. Proton-air and proton-proton cross sections

    Directory of Open Access Journals (Sweden)

    Ulrich Ralf

    2013-06-01

    Full Text Available Different attempts to measure hadronic cross sections with cosmic ray data are reviewed. The major results are compared to each other and the differences in the corresponding analyses are discussed. Besides some important differences, it is crucial to see that all analyses are based on the same fundamental relation of longitudinal air shower development to the observed fluctuation of experimental observables. Furthermore, the relation of the measured proton-air to the more fundamental proton-proton cross section is discussed. The current global picture combines hadronic proton-proton cross section data from accelerator and cosmic ray measurements and indicates a good consistency with predictions of models up to the highest energies.

  13. NMR paramagnetic relaxation due to the S=5/2 complex, Fe(III)-(tetra-p-sulfonatophenyl)porphyrin: central role of the tetragonal fourth-order zero-field splitting interaction.

    Science.gov (United States)

    Schaefle, Nathaniel; Sharp, Robert

    2005-05-08

    The metalloporphyrins, Me-TSPP [Me=Cr(III), Mn(III), Mn(II), Fe(III), and TSPP=meso-(tetra-p-sulfonatophenyl)porphyrin], which possess electron spins S=3/2, 2, 5/2, and 5/2, respectively, comprise an important series of model systems for mechanistic studies of NMR paramagnetic relaxation enhancement (NMR-PRE). For these S>1/2 spin systems, the NMR-PRE depends critically on the detailed form of the zero-field splitting (zfs) tensor. We report the results of experimental and theoretical studies of the NMR relaxation mechanism associated with Fe(III)-TSPP, a spin 5/2 complex for which the overall zfs is relatively large (D approximately = 10 cm(-1)). A comparison of experimental data with spin dynamics simulations shows that the primary determinant of the shape of the magnetic relaxation dispersion profile of the water proton R1 is the tetragonal fourth-order component of the zfs tensor. The relaxation mechanism, which has not previously been described, is a consequence of zfs-induced mixing of the spin eigenfunctions of adjacent Kramers doublets. We have also investigated the magnetic-field dependence of electron-spin relaxation for S=5/2 in the presence of a large zfs, such as occurs in Fe(III)-TSPP. Calculations show that field dependence of this kind is suppressed in the vicinity of the zfs limit, in agreement with observation.

  14. Molecular mechanisms for generating transmembrane proton gradients.

    Science.gov (United States)

    Gunner, M R; Amin, Muhamed; Zhu, Xuyu; Lu, Jianxun

    2013-01-01

    Membrane proteins use the energy of light or high energy substrates to build a transmembrane proton gradient through a series of reactions leading to proton release into the lower pH compartment (P-side) and proton uptake from the higher pH compartment (N-side). This review considers how the proton affinity of the substrates, cofactors and amino acids are modified in four proteins to drive proton transfers. Bacterial reaction centers (RCs) and photosystem II (PSII) carry out redox chemistry with the species to be oxidized on the P-side while reduction occurs on the N-side of the membrane. Terminal redox cofactors are used which have pKas that are strongly dependent on their redox state, so that protons are lost on oxidation and gained on reduction. Bacteriorhodopsin is a true proton pump. Light activation triggers trans to cis isomerization of a bound retinal. Strong electrostatic interactions within clusters of amino acids are modified by the conformational changes initiated by retinal motion leading to changes in proton affinity, driving transmembrane proton transfer. Cytochrome c oxidase (CcO) catalyzes the reduction of O2 to water. The protons needed for chemistry are bound from the N-side. The reduction chemistry also drives proton pumping from N- to P-side. Overall, in CcO the uptake of 4 electrons to reduce O2 transports 8 charges across the membrane, with each reduction fully coupled to removal of two protons from the N-side, the delivery of one for chemistry and transport of the other to the P-side.

  15. Magnetoviscosity and relaxation in ferrofluids

    Science.gov (United States)

    Felderhof

    2000-09-01

    The increase in viscosity of a ferrofluid due to an applied magnetic field is discussed on the basis of a phenomenological relaxation equation for the magnetization. The relaxation equation was derived earlier from irreversible thermodynamics, and differs from that postulated by Shliomis. The two relaxation equations lead to a different dependence of viscosity on magnetic field, unless the relaxation rates are related in a specific field-dependent way. Both planar Couette flow and Poiseuille pipe flow in parallel and perpendicular magnetic field are discussed. The entropy production for these situations is calculated and related to the magnetoviscosity.

  16. Protonation and structural/chemical stability of Ln{sub 2}NiO{sub 4+δ} ceramics vs. H{sub 2}O/CO{sub 2}: High temperature/water pressure ageing tests

    Energy Technology Data Exchange (ETDEWEB)

    Upasen, S. [Sorbonne Universités, UPMC Univ Paris 06, UMR 8233, MONARIS, 75005 Paris (France); CNRS-IP2CT, UMR 8233, MONARIS, F-75005 Paris (France); Batocchi, P.; Mauvy, F. [ICMCB, ICMCB-CNRS-IUT-Université de Bordeaux, 33608 Pessac Cedex (France); Slodczyk, A. [Sorbonne Universités, UPMC Univ Paris 06, UMR 8233, MONARIS, 75005 Paris (France); CNRS-IP2CT, UMR 8233, MONARIS, F-75005 Paris (France); Colomban, Ph., E-mail: philippe.colomban@upmc.fr [Sorbonne Universités, UPMC Univ Paris 06, UMR 8233, MONARIS, 75005 Paris (France); CNRS-IP2CT, UMR 8233, MONARIS, F-75005 Paris (France)

    2015-02-15

    Highlights: • High temperature/water pressure autoclave is used to study the reaction/corrosion at SOFC/HTSE electrode. • High stability of Pr{sub 2}NiO{sub 4+δ} (PNO) and Nd{sub 2}NiO{sub 4+δ} (NNO) dense ceramics vs. water pressure is demonstrated. • Protonated rare-earth nickelates retain the perovskite-type structure and their H-content is determined. • Very low laser illumination power is required to avoid RE nickelate phase transition. • Nickelates show increasing stability from La to Pr/Nd vs. CO{sub 2}-rich high temperature water vapor. - Abstract: Mixed ionic-electronic conductors (MIEC) such as rare-earth nickelates with a general formula Ln{sub 2}NiO{sub 4+δ} (Ln = La, Pr, Nd) appear as potential for energy production and storage systems: fuel cells, electrolysers and CO{sub 2} converters. Since a good electrode material should exhibit important stability in operating conditions, the structural and chemical stability of different nickelate-based, well-densified ceramics have been studied using various techniques: TGA, dilatometry, XRD, Raman scattering and IR spectroscopy. Consequently, La{sub 2}NiO{sub 4+δ} (LNO), Pr{sub 2}NiO{sub 4+δ} (PNO) and Nd{sub 2}NiO{sub 4+δ} (NNO) have been exposed during 5 days to high water vapor pressure (40 bar) at intermediate temperature (550 °C) in an autoclave device, the used water being almost free or saturated with CO{sub 2}. Such protonation process offers an accelerating stability test and allows the choice of the most pertinent composition for industrial applications requiring a selected material with important life-time. In order to understand any eventual change of crystal structure, the ceramics were investigated in as-prepared, pristine state as well as after protonation and deprotonation (due to thermal treatment till 1000 °C under dry atmosphere). The results show the presence of traces or second phases originating from undesirable hydroxylation and carbonation, detected in the near

  17. Dielectric properties of residual water in amorphous lyophilized mixtures of sugar and drug

    Energy Technology Data Exchange (ETDEWEB)

    Moznine, R El [School of Pharmacy, De Montfort University, Leiceste (United Kingdom); Smith, G [School of Pharmacy, De Montfort University, Leicester (United Kingdom); Polygalov, E [School of Pharmacy, De Montfort University, Leicester (United Kingdom); Suherman, P M [School of Pharmacy, De Montfort University, Leicester (United Kingdom); Broadhead, J [AstraZeneca Charnwood R and D, Bakewell Rd, Loughborough (United Kingdom)

    2003-02-21

    Dielectric relaxation spectroscopy was used to investigate the properties of residual water in lyophilized formulations of a proprietary tri-phosphate drug containing a sugar (trehalose, lactose or sucrose) or dextran. The dielectric properties of each formulation were determined in the frequency range (0.1 Hz-0.1 MHz) and temperature range (30 deg. C-T{sub g}). The temperature dependence of the relaxation times for all samples showed Arrhenuis behaviour, from which the activation energy was derived. Proton hopping through the hydrogen-bonded network (clusters) of water molecules was suggested as the principle mode of charge transport. Significant differences in dielectric relaxation kinetics and activation energy were observed for the different formulations, which were found to correlate with the amount of monophosphate degradation product.

  18. Water network-mediated, electron-induced proton transfer in [C{sub 5}H{sub 5}N ⋅ (H{sub 2}O){sub n}]{sup −} clusters

    Energy Technology Data Exchange (ETDEWEB)

    DeBlase, Andrew F.; Wolke, Conrad T.; Johnson, Mark A., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520 (United States); Weddle, Gary H. [Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520 (United States); Department of Chemistry, Fairfield University, 1073 North Benson Road, Fairfield, Connecticut 06824 (United States); Archer, Kaye A.; Jordan, Kenneth D., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260 (United States); Kelly, John T.; Tschumper, Gregory S.; Hammer, Nathan I., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry and Biochemistry, University of Mississippi, University, Mississippi 38677 (United States)

    2015-10-14

    The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ⋅ (H{sub 2}O){sub n=3−5}]{sup −} clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH{sup (0)}, occupying one of the primary solvation sites of the OH{sup −}. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the “solvent coordinate” at the heart of a prototypical proton-coupled electron transfer reaction.

  19. Relaxing Behavioural Inheritance

    Directory of Open Access Journals (Sweden)

    Nuno Amálio

    2013-05-01

    Full Text Available Object-oriented (OO inheritance allows the definition of families of classes in a hierarchical way. In behavioural inheritance, a strong version, it should be possible to substitute an object of a subclass for an object of its superclass without any observable effect on the system. Behavioural inheritance is related to formal refinement, but, as observed in the literature, the refinement constraints are too restrictive, ruling out many useful OO subclassings. This paper studies behavioural inheritance in the context of ZOO, an object-oriented style for Z. To overcome refinement's restrictions, this paper proposes relaxations to the behavioural inheritance refinement rules. The work is presented for Z, but the results are applicable to any OO language that supports design-by-contract.

  20. Relaxation dynamics of a protein solution investigated by dielectric spectroscopy.

    Science.gov (United States)

    Wolf, M; Gulich, R; Lunkenheimer, P; Loidl, A

    2012-05-01

    In the present work, we provide a dielectric study on two differently concentrated aqueous lysozyme solutions in the frequency range from 1MHz to 40GHz and for temperatures from 275 to 330K. We analyze the three dispersion regions, commonly found in protein solutions, usually termed β-, γ-, and δ-relaxations. The β-relaxation, occurring in the frequency range around 10MHz and the γ-relaxation around 20GHz (at room temperature) can be attributed to the rotation of the polar protein molecules in their aqueous medium and the reorientational motion of the free water molecules, respectively. The nature of the δ-relaxation, which is often ascribed to the motion of bound water molecules, is not yet fully understood. Here we provide data on the temperature dependence of the relaxation times and relaxation strengths of all three detected processes and on the dc conductivity arising from ionic charge transport. The temperature dependences of the β- and γ-relaxations are closely correlated. We found a significant temperature dependence of the dipole moment of the protein, indicating conformational changes. Moreover we find a breakdown of the Debye-Stokes-Einstein relation in this protein solution, i.e., the dc conductivity is not completely governed by the mobility of the solvent molecules. Instead it seems that the dc conductivity is closely connected to the hydration shell dynamics.

  1. Proton uptake in the H(+)-SOFC cathode material Ba(0.5)Sr(0.5)Fe(0.8)Zn(0.2)O(3-δ): transition from hydration to hydrogenation with increasing oxygen partial pressure.

    Science.gov (United States)

    Poetzsch, Daniel; Merkle, Rotraut; Maier, Joachim

    2015-01-01

    Thermogravimetric investigations on the perovskite Ba(0.5)Sr(0.5)Fe(0.8)Zn(0.2)O(3-δ) (BSFZ, with mixed hole, oxygen vacancy and proton conductivity) from water vapor can occur by acid-base reaction (hydration) or redox reaction (hydrogen uptake), depending on the oxygen partial pressure, i.e. on the material's defect concentrations. In parallel, the effective diffusion coefficient of the stoichiometry relaxation kinetics also changes. These striking observations can be rationalized in terms of a defect chemical model and transport equations for materials with three mobile carriers. Implications for the search of cathode materials with mixed electronic and protonic conductivity for application on proton conducting oxide electrolytes are discussed.

  2. Anomalous divergence of a relaxation time in discontinuous shear thickening suspensions

    CERN Document Server

    Maharjan, Rijan

    2016-01-01

    We investigated the transient relaxation of a Discontinuous Shear Thickening (DST) suspension of cornstarch in water. Starting from a steady shear in a parallel plate rheometer, we stopped the top plate rotation and measured the transient stress relaxation. We found that at low effective packing fraction $\\phi_{eff}$, the suspensions exhibited a relaxation behavior consistent with a rheometric fluid in which the relaxation is determined by the steady-state viscosity. However, for larger $\\phi_{eff}$, we find up to two exponential relaxation regimes, which both become distinct from the rheometric model. The discrepancy between the measured relaxation times and the rheometric prediction was found to be as large as 4 orders of magnitude and diverges in the limit as $\\phi_{eff} \\rightarrow \\phi_c$, corresponding to the liquid solid transition, as the measured relaxation times diverge to infinity while the rheometric prediction approaches 0. In this limit, the measured relaxation time scales are on the order of $\\...

  3. Interactions of nonprotic organic solvents with [val5]angiotensin in water.

    Science.gov (United States)

    Neuman, Robert C; Gerig, John T

    2011-02-24

    Intermolecular solvent-solute nuclear Overhauser effects have been used to explore interactions of the organic component of acetonitrile-water, acetone-water, and dimethyl sulfoxide-water mixtures with the peptide hormone [val(5)]angiotensin. As reported by the NOEs, many cross relaxation terms for interactions of these organic cosolvents are adequately accounted for using a hard spheres interaction model in which encounters of peptide and cosolvent molecules take place by mutual diffusion. However, there are indications of localized solvent-peptide interactions that are not well described by this model. In dimethyl sulfoxide-water at 0 °C, organic solvent near the C-terminal Phe8 residue and the Val3 residue produce strongly enhanced cross-relaxation terms. NOEs for all peptide N-H protons and the protons of the Tyr4 aromatic ring were significantly more positive than expected in 33% acetone-water (v/v) at 0 °C, while those for most side-chain protons were close to predictions of the hard sphere model. All peptide-organic solvent NOEs in 35% acetonitrile water (v/v) at 0 °C are consistent with the hard spheres interaction model.

  4. Magnetic relaxation in anisotropic magnets

    DEFF Research Database (Denmark)

    Lindgård, Per-Anker

    1971-01-01

    The line shape and the kinematic and thermodynamic slowing down of the critical and paramagnetic relaxation in axially anisotropic materials are discussed. Kinematic slowing down occurs only in the longitudinal relaxation function. The thermodynamic slowing down occurs in either the transverse or...

  5. Elastic proton-proton scattering at RHIC

    Energy Technology Data Exchange (ETDEWEB)

    Yip, K.

    2011-09-03

    Here we describe elastic proton+proton (p+p) scattering measurements at RHIC in p+p collisions with a special optics run of {beta}* {approx} 21 m at STAR, at the center-of-mass energy {radical}s = 200 GeV during the last week of the RHIC 2009 run. We present preliminary results of single and double spin asymmetries.

  6. Noncoplanarity in proton-proton bremsstrahlung

    NARCIS (Netherlands)

    Timmermans, RGE; Gibson, BF; Li, Y; Liou, MK

    2002-01-01

    Using the soft-photon approximation, we address the issue of the importance of noncoplanarity effects in proton-proton bremsstrahlung, We investigate the noncoplanar cross section as a function of the noncoplanarity angle (φ) over bar for the entire range of the photon polar angle psi(gamma). The (φ

  7. Water Availability as a Measure of Cellulose Hydrolysis Efficiency

    DEFF Research Database (Denmark)

    Hsieh, Chia-Wen

    Enzymatic hydrolysis involves the use of cellulases to break down cellulose in the presence of water. Therefore, not only are enzyme and substrate properties important for efficient hydrolysis, but also the hydrolysis medium, i.e. the liquid phase. The LF-NMR technique is used in this work...... to measure properties of the liquid phase, where water protons are characterized based on their mobility in the system as measured by their relaxation time. Studies of cellulose hydrolysis at low dry matter show that the contents of the liquid phase influence the final hydrolysis yield, as the presence...

  8. Proton pump inhibitors

    Science.gov (United States)

    Proton pump inhibitors (PPIs) are medicines that work by reducing the amount of stomach acid made by ... Proton pump inhibitors are used to: Relieve symptoms of acid reflux, or gastroesophageal reflux disease (GERD). This ...

  9. Proton: the particle.

    Science.gov (United States)

    Suit, Herman

    2013-11-01

    The purpose of this article is to review briefly the nature of protons: creation at the Big Bang, abundance, physical characteristics, internal components, and life span. Several particle discoveries by proton as the experimental tool are considered. Protons play important roles in science, medicine, and industry. This article was prompted by my experience in the curative treatment of cancer patients by protons and my interest in the nature of protons as particles. The latter has been stimulated by many discussions with particle physicists and reading related books and journals. Protons in our universe number ≈10(80). Protons were created at 10(-6) -1 second after the Big Bang at ≈1.37 × 10(10) years beforethe present. Proton life span has been experimentally determined to be ≥10(34) years; that is, the age of the universe is 10(-24)th of the minimum life span of a proton. The abundance of the elements is hydrogen, ≈74%; helium, ≈24%; and heavier atoms, ≈2%. Accordingly, protons are the dominant baryonic subatomic particle in the universe because ≈87% are protons. They are in each atom in our universe and thus involved in virtually every activity of matter in the visible universe, including life on our planet. Protons were discovered in 1919. In 1968, they were determined to be composed of even smaller particles, principally quarks and gluons. Protons have been the experimental tool in the discoveries of quarks (charm, bottom, and top), bosons (W(+), W(-), Z(0), and Higgs), antiprotons, and antineutrons. Industrial applications of protons are numerous and important. Additionally, protons are well appreciated in medicine for their role in radiation oncology and in magnetic resonance imaging. Protons are the dominant baryonic subatomic particle in the visible universe, comprising ≈87% of the particle mass. They are present in each atom of our universe and thus a participant in every activity involving matter. Copyright © 2013 Elsevier Inc. All

  10. Structure of Proton

    CERN Document Server

    Fayyazuddin, A

    2003-01-01

    Electron--proton scattering in elastic and highly inelastic region is reviewed in a unified approach. The importance of parity--violating scattering due to electro--weak interference in probing the structure of proton is emphasized. The importance of longitudnal spin--spin asymmetry as well as parity violating longitudnal asymmetry to extract the structure functions of proton in both regions are discussed. The recoil polarization of proton in the elastic scattering is also discussed.

  11. Pulsed NMR studies of water under extreme conditions

    Energy Technology Data Exchange (ETDEWEB)

    DeFries, Timothy Hatmaker

    1978-01-01

    The dynamic structure of water and heavy water was studied using NMR spin-lattice relaxation and self-diffusion techniques. For both compounds, the relaxation rate is proportional to the ratio of viscosity to absolute temperature at constant density. The coupling between rotational and translational motions decreases with increasing temperature and increasing density. The temperature and density dependence of the deuteron quadrupole coupling constant in D/sub 2/O was determined. The proton spin-lattice relaxation times of supercritical H/sub 2/O were measured from 400 to 700/sup 0/C and to 1 kbar. The times were found to be roughly proportional to density and were found to decrease with temperature. The angular momentum correlation times tau/sub J/ were calculated and compared with the times between collisions for a hard sphere fluid, the Enskog times, tau/sub E/. The values of tau/sub E//tau/sub J/ were roughly 6 at 400/sup 0/C and low densities. The values decreased at higher densities and higher temperatures. The proton spin-lattice relaxation times of H/sub 2/O were also measured from 90 to 350/sup 0/C up to 2 to 5 kbar. The data clearly show the change from dipolar to spin-rotation relaxation as a function of temperature and density. Both the low and the high temperature results agree with the idea that it is the strong and anisotropic intermolecular potential which causes the dynamic behavior of water to be so different from that of normal liquids.

  12. Calorimetric determination of enthalpies for the proton ionization of N,N-bis[2-hydroxyethyl]-2-aminoethanesulfonic acid (BES) and N-tris[hydroxymethyl]methyl-2-aminoethanesulfonic acid (TES) in water-methanol mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Bulos, B.N.; Jumean, F.H

    2004-02-19

    The enthalpies of proton ionization of the biochemical buffers N,N-bis[2-hydroxyethyl]-2-aminoethanesulfonic acid (BES) and N-tris[hydroxymethyl]methyl-2-aminoethanesulfonic acid (TES) were obtained in water-methanol mixtures in which the methanol mole fraction (X{sub m}) varied in the range 0-0.36. For both buffers, ionization enthalpy for the first proton ({delta}H{sub 1}) was small in all solvent media. However, upon addition of methanol, {delta}H{sub 2} increased steadily from 22.2 to a maximum of 27.2 kJ mol{sup -1} for BES, whereas for TES it varied from 30.0 to 32.4, with a minimum of 28.6 kJ mol{sup -1} at X{sub m}=0.123. It is noteworthy that this solvent composition lies within the region of maximum structure enhancement of water by methanol. The results were interpreted in terms of methanol-water interactions.

  13. Study of cross - relaxation and molecular dynamics in the solid 3-(trifluoromethyl) benzoic acid by solid state NMR off - resonance.

    Science.gov (United States)

    Woźniak-Braszak, Aneta

    2017-02-01

    Molecular dynamics of the solid 3-(trifluoromethyl) benzoic acid containing proton (1)H and fluorine (19)F nuclei was explored by the solid-state NMR off - resonance technique. Contrary to the previous experiments the proton nuclei system I relaxed in the off - resonance effective field B→e while fluorine nuclei system S was saturated for short time in comparison to the relaxation time T1I. New cross - relaxation solid - state NMR off - resonance experiments were conducted on a homebuilt pulse spectrometer operating at the on-resonance frequency of 30.2MHz, at the off - resonance frequency varied between 30.2 and 30.6MHz for protons and at the frequency of 28.411MHz for fluorines, respectively. Based on the experimental data the dispersions of the proton off - resonance spin - lattice relaxation rate ρρ(I), the fluorine off - resonance spin - lattice relaxation rate ρρ(S) and the cross - relaxation rate σρ in the rotating frame were determined. Copyright © 2016 Elsevier Inc. All rights reserved.

  14. Proton transfer pathways in Photosystem II

    Science.gov (United States)

    Ishikita, Hiroshi

    2014-03-01

    Using quantum mechanics/molecular mechanics calculations and the 1.9-Å crystal structure of Photosystem II (Umena, Y., Kawakami, K., Shen, J.-R., and Kamiya, N. (2011) Nature 473, 55-60), we investigated the H-bonding environment of the redox active tyrosine, TyrD and obtained insights that help explain its slow redox kinetics and the stability of TyrD radical. The water molecule distal to TyrD, 4 Å away from the phenolic O of TyrD (OTyrD) , corresponds to the presence of the tyrosyl radical state. The water molecule proximal to TyrD, in H-bonding distance to OTyrD, corresponds to the presence of the unoxidised tyrosine. The H+ released upon oxidation of TyrD is transferred to the proximal water, which shifts to the distal position, triggering a concerted proton transfer pathway involving D2-Arg180 and a series of waters, through which the proton reaches the aqueous phase at D2-His61. The water movement linked to the ejection of the proton from the hydrophobic environment near TyrD makes oxidation slow and quasi-irreversible, explaining the great stability of the TyrD radical. A symmetry-related proton pathway associated with TyrZ is pointed out and this is associated with one of the Cl- sites. This may represent a proton pathway functional in the water oxidation cycle.

  15. NMR Relaxation and Diffusion in Polymerized Microemulsions of HEMA and MMA

    Science.gov (United States)

    von Meerwall, E.; Chandran, S.; Slivka, J.; Lopina, S.; Cheung, M.

    2002-10-01

    In an effort to develop a class of materials for use in controlled drug delivery via implantation, we have used proton NMR T2 relaxation and pulsed-field-gradient diffusion (D) measurements to study bicontinuous microemulsions formed with methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA), polymerized and crosslinked with 4 wt. percent ethylene glycol dimethacrylate, in the presence of water containing ten percent surfactant, either the inert sodium alkyl sulfate or the polymerizable TREM-LF-40. Measurements were made at 50 deg. C over the full two-phase range (e. g., 30 to 96 percent aqueous, depending on HEMA/MMA ratio). We identify a trimodal T2 spectrum with components attributable to the semi-glassy network, adsorbed surfactant and ingested water, and the interstitial aqueous phase. In the latter, two distinct D rates are due to free water and dissolved surfactant; specimens are permeable to both. Component intensity ratios are non-monotonic in aqueous content. Results suggest a wide range of pore sizes and complex interactions between the mobile molecules and the network surfaces, pores, and swellable bulk. Surfactant reactivity seems to play a minor role. Results of other characterizations complement and support these findings.

  16. Proton magnetic resonance spectroscopy of normal human brain and glioma:a quantitive in vivo study

    Institute of Scientific and Technical Information of China (English)

    TONG Zhi-yong; YAMAKI Toshiaki; WANG Yun-jie

    2005-01-01

    Background In vivo proton magnetic resonance spectroscopy (MRS) provides a noninvasive method of examining a wide variety of cerebral metabolites in both healthy subjects and patients with various brain diseases.Absolute metabolite concentrations ha