Studies of a nitroxide radical by EPR in monocrystal: interaction of protons and electronic relaxation

International Nuclear Information System (INIS)

Alonso, A.

1986-01-01

The ESR spectra of a nitroxide radical, 4-hydroxi-2,2,6,6-tetramethylpiperidine-1-oxyl (TANOL II), introduced as impurity in a diamagnetic host, 4-hydroxi-2,6,6-tetramethylpiperedine (I), were investigated. The use of deuterated radical, 4-hydroxi-2,2,6,6 tetramethylpiperidine-d sub(17) -1, oxyl (PD-TANOL, III) improved the resolution of ESR spectra for most of orientations of magnetic field. The proton interqactions in the neighbourhood of magnetic group N-O were studied and superpyresfine tensors for two strongly coupled protons were determined. In order to study the influence of protons on electronic relaxation of radicals, the relaxation times T sub(1) and T sub(2) were estimated in the temperature range-160 sup(0)C - 25 sup(0)C for several orientations, and comparing data for protonated and deuterated radicals II and III, using the continuous wave saturation method. (author)

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects.

Science.gov (United States)

Lemke, Sonja; Handle, Philip H; Plaga, Lucie J; Stern, Josef N; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-21

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects

Science.gov (United States)

Lemke, Sonja; Handle, Philip H.; Plaga, Lucie J.; Stern, Josef N.; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W.; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-01

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Calorimetric and relaxation properties of xylitol-water mixtures

Science.gov (United States)

Elamin, Khalid; Sjöström, Johan; Jansson, Helén; Swenson, Jan

2012-03-01

We present the first broadband dielectric spectroscopy (BDS) and differential scanning calorimetry study of supercooled xylitol-water mixtures in the whole concentration range and in wide frequency (10-2-106 Hz) and temperature (120-365 K) ranges. The calorimetric glass transition, Tg, decreases from 247 K for pure xylitol to about 181 K at a water concentration of approximately 37 wt. %. At water concentrations in the range 29-35 wt. % a plentiful calorimetric behaviour is observed. In addition to the glass transition, almost simultaneous crystallization and melting events occurring around 230-240 K. At higher water concentrations ice is formed during cooling and the glass transition temperature increases to a steady value of about 200 K for all higher water concentrations. This Tg corresponds to an unfrozen xylitol-water solution containing 20 wt. % water. In addition to the true glass transition we also observed a glass transition-like feature at 220 K for all the ice containing samples. However, this feature is more likely due to ice dissolution [A. Inaba and O. Andersson, Thermochim. Acta, 461, 44 (2007)]. In the case of the BDS measurements the presence of water clearly has an effect on both the cooperative α-relaxation and the secondary β-relaxation. The α-relaxation shows a non-Arrhenius temperature dependence and becomes faster with increasing concentration of water. The fragility of the solutions, determined by the temperature dependence of the α-relaxation close to the dynamic glass transition, decreases with increasing water content up to about 26 wt. % water, where ice starts to form. This decrease in fragility with increasing water content is most likely caused by the increasing density of hydrogen bonds, forming a network-like structure in the deeply supercooled regime. The intensity of the secondary β-relaxation of xylitol decreases noticeably already at a water content of 2 wt. %, and at a water content above 5 wt. % it has been replaced by a

A study of nuclear relaxation to the electron non-Zeeman system

International Nuclear Information System (INIS)

Honten, J. van.

1979-01-01

An examination of the nuclear spin-lattice relaxation mechanism in a series of diluted copper-caesium Tutton salt crystals, containing different percentages of D 2 O in the waters of hydration, is described. Results of relaxation measurements are presented and a strong angular dependence is observed. It is proved, however, that under most experimental conditions applied, the bottleneck in the relaxation path is not the cross-relaxation but the thermal contact between the proton Zeeman system and the electron dipole-dipole interaction system. Hence the proton spin-lattice relaxation measurements have enabled determination of the time constant of this thermal contact. The microscopic coupling process which provides thermal contact, is a simultaneous transition of two electron spins and one proton spin. This so-called three-spin transition is described and calculations presented. Double resonance experiments are performed, where the resonance signal of deuterium or caesium spins is saturated and the effect on the proton resonance signal observed. (C.F.)

Preliminary study for differential diagnosis of intracranial tumors using in vivo quantitative proton MR spectroscopy with correction for T2 relaxation time

International Nuclear Information System (INIS)

Isobe, Tomonori; Yamamoto, Tetsuya; Akutsu, Hiroyoshi; Shiigai, Masanari; Shibata, Yasushi; Takada, Kenta; Masumoto, Tomohiko; Anno, Izumi; Matsumura, Akira

2015-01-01

Introduction: The intent of this study was to differentiate intracranial tumors using the metabolite concentrations obtained by quantification with correction for T2 relaxation time, and to analyze whether the spectrum peak was generated by the existence of metabolites in proton magnetic resonance spectroscopy (MRS). Methods: All proton MRS studies were performed on a clinical 1.5T MR system. 7 normal volunteers and 57 patients (gliomas, metastases, meningiomas, acoustic neuromas, and pituitary adenomas) underwent single voxel proton MRS with different echo times (TE: 68, 136, 272 ms) for T2 correction of signal derived from metabolites and tissue water. With tissue water employed as an internal reference, the concentrations of metabolite (i.e. N-acetylaspartate (NAA), total creatine (t-Cr) and choline-containing compounds (Cho)) were calculated. Moreover, proton MRS data of previously published typical literatures were critically reviewed and compared with our data. Results: Extramedullary tumors were characterized by absence of NAA compared with intramedullary tumors. High-grade glioma differed from low-grade glioma by lower t-Cr concentrations. Metastasis differed from cystic glioblastoma by higher Cho concentrations, lower t-Cr concentrations, an absence of NAA, and a prominent Lipids peak. Based on these results and review of previous reports, we suggest a clinical pathway for the differentiation of intracranial tumors. Conclusion: The metabolite concentrations obtained by quantification with correction for T2 relaxation time, and to analyze whether the spectrum peak was generated by the existence of metabolites in proton MRS is useful for the diagnosis of the intracranial tumors

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

International Nuclear Information System (INIS)

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

2001-01-01

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 T 1 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 T 1 in pure and aluminum-modified orthophosphoric acid demonstrates that the increase of T 1 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. [copyright] 2001 American Institute of Physics

Oxygen-17 relaxation in aqueous agarose gels

International Nuclear Information System (INIS)

Ablett, S.; Lillford, P.J.

1977-01-01

Nuclear magnetic relaxation of oxygen-17 in H 2 17 O enriched agarose gels shows that existing explanations of water behaviour are oversimplified. Satisfactory models must include at least three proton phases, two of which involve water molecules. (Auth.)

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

International Nuclear Information System (INIS)

Bandiera, L.; Mazzolari, A.; 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 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.)

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.)

Temperature dependence of relaxation times in proton components of fatty acids

International Nuclear Information System (INIS)

Kuroda, Kagayaki; Iwabuchi, Taku; Saito, Kensuke; Obara, Makoto; Honda, Masatoshi; Imai, Yutaka

2011-01-01

We examined the temperature dependence of relaxation times in proton components of fatty acids in various samples in vitro at 11 tesla as a standard calibration data for quantitative temperature imaging of fat. The spin-lattice relaxation time, T 1 , of both the methylene (CH 2 ) chain and terminal methyl (CH 3 ) was linearly related to temperature (r>0.98, P 2 signal for calibration and observed the signal with 18% of CH 3 to estimate temperature. These findings suggested that separating the fatty acid components would significantly improve accuracy in quantitative thermometry for fat. Use of the T 1 of CH 2 seems promising in terms of reliability and reproducibility in measuring temperature of fat. (author)

Proton NMR relaxivity of blood samples in the presence of some gadolinium and dysprosium compounds

International Nuclear Information System (INIS)

Coroiu, I.; Darabont, Al.; Bogdan, M.

1999-01-01

The use of some new compounds in MRI tissue and blood characterisation based on nuclear spin relaxation time measurements cannot be sustained until the molecular sources of these variations are understood. Tissues and blood are complex molecular systems with complex NMR properties. A better comprehension of the molecular basis of relaxation offers the possibility to predict the changes expected for a given pathology. The purpose of this contribution is to evidence the different relaxation characteristics of some gadolinium and dysprosium compounds in the presence and absence of the blood and to give a possible explanation about the molecular processes that cause occurrence of changes. Some gadolinium and dysprosium compounds such as: Gd-CIT (gadolinium citrate), Dy-DTPA (DTPA-diethylenetriamine pentaacetic acid), iron oxide - gadolinium oxide (or dysprosium oxide)- dextran complexes were prepared. The longitudinal T 1 -1 and transverse T 2 -1 'relaxation rates' measurements have been carried out as a function of molar concentrations. All measurements have been made at room temperature (about 25 deg.C) and the proton Larmor frequency ν o = 90 MHz. The pulsed NMR spectrometer utilised was a commercial Bruker SXP4/100 spectrometer. Transverse relaxation rate measurements have been made using the Carr-Purcell method, while longitudinal relaxation rate measurements using the inversion recovery pulse sequence, 180 angle-τ-90 angle. The accuracy was about 2-3% for the longitudinal relaxation rates and about 5-7% for the transverse relaxation rates. R 1 and R 2 relaxivities, in mM -1 s -1 were determined from the least square determination of the slopes of plots 1/T 1,2 versus compound molar concentration, using at least five independent measurements at several concentrations between 0 and 2 mM. Increased R 2 relaxivity observed for dysprosium compounds in the blood presence can be explained by PRE effect. The largest gain in R 2 relaxivity seems to imply a noncovalent

In-vivo measurement of proton relaxation time (T1 and T2) in paediatric brain by MRI

International Nuclear Information System (INIS)

Masumura, Michio

1986-01-01

The clinical application of MRI led to the detailed imaging of the three-dimentional structure of the brain. Thus, significant information has been obtained with respect to the diagnosis of various diseases, rating severity, evaluation of curative effects, etc. On the other hand, the proportion of the comparative length of the relaxation time to the signal intensity of the images (especially the Spin-Echo image) was not necessarily linear. Consquently, the evaluation of severity was not easy to make. However, if we can obtain T 1 and T 2 precisely as the parameters costituting the images, it will be possible to overcome the above-mentioned difficulties. Further, the usefulness of MRI in activities such as determining the water metabolism of the brain is expected to increase even more. By means of VISTA-MR (0.15 Tesla, resistive magnet ; Picker International Co.) we measured the proton relaxation time (spin-lattice relaxation time (T 1 ) and spin-spin relaxation time (T 2 )) of various intracerebral lesions in paediatric cases. As the control group, 43 children, 4 adolescents and 6 adults were used. The T 1 and T 2 in the normal infantile cases prolonged significantly as compared with adult case. Thereafter, they become shortened by aging. In the age of two or three years, they reach the normal level of adult case. In the cases of degenerative disease, brain tumor, and cerebral contusion, the remarkable prolongation of both T 1 and T 2 , compared with normal value of the same age was observed. In the cases of brain atrophy and epilepsy, T 1 and T 2 were slightly short or within normal value of the same age. In the cases of intracerebral hemorrhage, T 1 was shortened. The in-vivo proton relaxation time obtained by MRI have various limits, but they can be a noninvasive and useful index in evaluation of severity or curative effects in various cerebral diseases. (author)

Proton relaxation relationships of human and animal tissues in vitro. Changes due to autolysis and fixing

International Nuclear Information System (INIS)

Grodd, W.; Schmitt, W.G.H.

1983-01-01

The results of measurements of proton relaxation times of various tissues from rats, pigs and humans are reported; these were obtained by a resonance spectroscope at 20 MHz and 40 0 C. There were specific differences in both relaxation times (T 1 and T 2 ) of the liver and spleen. There was a difference of more than 150 ms in the longitudinal relaxation time between grey and white cerebral tissue. Autolytic changes show an increase in both relaxation times. Fixation produced a reduction in T 1 only. The significance of these findings for NMR tomography is discussed. (orig.) [de

A nuclear magnetic relaxation study on internal motion of polyelectrolytes in solution

International Nuclear Information System (INIS)

Schriever, J.

1977-01-01

The aim of this thesis is to investigate the significance and the amount of information which can be extracted from the study of frequency dependence of magnetic relaxation rates in solutions of a synthetic macromolecule. Solutions of poly(methacrylic acid), PMA, in water were chosen as the object of the present work. A short survey of nuclear magnetic relaxation in solutions of simple macromolecules is presented. Results obtained by continuous wave experiments on PMA solutions are shown (viz. the information about the transverse relaxation from line width analysis of 60 MHz proton spectra). Water enriched in 17 O is used in magnetic relaxation studies; the results of the determination of hydrogen lifetimes in aqueous solutions of acetic acid and poly(methacrylic acid) are given. The possibility of obtaining information about the dynamics of deuterons in the acid side groups of weak polyacids by measuring deuteron relaxation in heavy water solutions of those acids is considered. The use of deuteron relaxation rate experiments on solutions of selectively methylene deuterated poly(methacrylic acid), [-CD 2 -CCH 3 COOH-]n, is demonstrated and the backbone methylene C-atom motion is charachterized. The magne-tic relaxation of nuclei in the side groups of methylene deuterated PMA, viz. protons in the methyland deuterons in the acid side groups is presented

The freezing of water bonded in the wheat (Triticum aestivum L.) grain studied by means protons magnetic relaxation method

International Nuclear Information System (INIS)

Haranczyk, H.; Jasinski, G.; Strzalka, K.

1994-01-01

Some biological aspects of water freezing in the wheat grain have been studied using NMR methods. Measuring of the relaxation times for freezing and liquid water shown absence of T 2 ∼100 μs and T 2 ∼1 ms separated components what pointed for some different way of water bonding

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.

Vibrational Energy Relaxation in Water-Acetonitrile Mixtures

NARCIS (Netherlands)

Cringus, Dan; Yeremenko, Sergey; Pshenichnikov, Maxim S.; Wiersma, Douwe A.; Kobayashi, Takayoshi; Kobayashi, Tetsuro; Nelson, Keith A.; Okada, Tadashi; Silvestri, Sandro De

2004-01-01

IR pump-probe spectroscopy is used to study the effect of hydrogen bonding on the vibrational energy relaxation pathways. Hydrogen bonding accelerates the population relaxation from 12ps in diluted acetonitrile solution to 700fs in bulk water.

Temperature dependence of electron spin-lattice relaxation of radiation-produced silver atoms in polycrystalline aqueous and glassy organic matrices. Importance of relaxation by tunneling modes in disordered matrices

International Nuclear Information System (INIS)

Michalik, J.; Kevan, L.

1978-01-01

The electron spin-lattice relaxation of trapped silver atoms in polycrystalline ice matrices and in methanol, ethanol, propylene carbonate, and 2-methyltetrahydrofuran organic glasses has been directly studied as a function of temperature by the saturation-recovery method. Below 40 K the dominant electron spin-lattice relaxation mechanism involves modulation of the electron nuclear dipolar interaction with nuclei in the radical's environment by tunneling of those nuclei between two nearly equal energy configurations. This relaxation mechanism occurs with high efficiency, has a characteristic linear temperature dependence, and is typically found in highly disordered matrices. The efficiency of this relaxation mechanism seems to decrease with decreasing polarity of the matrix. Deuteration experiments show that the tunneling nuclei are protons and in methanol it is shown that the methyl protons have more tunneling modes available than the hydroxyl protons. In polycrystalline ice matrices silver atoms can be stabilized with two different orientations of surrounding water molecules; the efficiency of the tunneling relaxation reflects this difference. From these and previous results on tunneling relaxation of trapped electrons in glassy matrices it appears that tunneling relaxation may be used to distinguish models with different geometrical configurations and to determine the relative rigidity of such configurations around trapped radicals in disordered solids. (author)

The effects of bone on proton NMR relaxation times of surrounding liquids

Science.gov (United States)

Davis, C. A.; Genant, H. K.; Dunham, J. S.

1986-01-01

Preliminary attempts by our group at UCSF to assess fat content of vertebral marrow in the lumbar spine using relaxation time information demonstrated that the presence of trabecular bone affects relaxation times. The objective of this work was a thorough study of the effects of bone on NMR relaxation characteristics of surrounding liquids. Trabecular bone from autopsy specimens was ground up and sifted into a series of powders with graded densities ranging from 0.3 gm/cc to 0.8 gm/cc. Each powder was placed first in n-saline and then in cottonseed oil. With spectroscopy, spin-lattice relaxation times (T1) and effective spin-spin relaxation times (T2*) were measured for each liquid in each bone powder. As bone density and surface to volume ratio increased, T1 decreased faster for saline than for oil. T2* decreased significantly for both water and oil as the surface to volume ratio increased. It was concluded that effects of water on T1 could be explained by a surface interaction at the bone/liquid interface, which restricted rotational and translational motion of nearby molecules. The T1s of oil were not affected since oil molecules are nonpolar, do not participate in significant intermolecular hydrogen bonding, and therefore would not be expected to interact strongly with the bone surface. Effects on T2* could be explained by local magnetic field inhomogeneities created by discontinuous magnetic susceptibility near the bone surface. These preliminary results suggest that water in contact with trabecular bone in vivo will exhibit shortened relaxation times.

Xenon-Water Interaction in Bacterial Suspensions as Studied by NMR

DEFF Research Database (Denmark)

Rodin, V.; Ponomarev, Alexander; Gerasimov, Maxim

2017-01-01

suspensions of Escherichia coli in the presence of xenon using nuclear magnetic resonance (NMR). The work studied how the spin-lattice relaxation times of water protons in suspension change under xenon conditions. Xenon is able to form clathrate hydrates with water molecules at a temperature above the melting...... point of ice. The work studied NMR relaxation times which reflect the rotation freedom of water molecules in suspension. Lower relaxation times indicate reduced rotational freedom of water. Single exponential behavior of spin-lattice relaxation of protons in the suspensions of microorganisms has been...

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.

NMR relaxation induced by iron oxide particles: testing theoretical models.

Science.gov (United States)

Gossuin, Y; Orlando, T; Basini, M; Henrard, D; Lascialfari, A; Mattea, C; Stapf, S; Vuong, Q L

2016-04-15

Superparamagnetic iron oxide particles find their main application as contrast agents for cellular and molecular magnetic resonance imaging. The contrast they bring is due to the shortening of the transverse relaxation time T 2 of water protons. In order to understand their influence on proton relaxation, different theoretical relaxation models have been developed, each of them presenting a certain validity domain, which depends on the particle characteristics and proton dynamics. The validation of these models is crucial since they allow for predicting the ideal particle characteristics for obtaining the best contrast but also because the fitting of T 1 experimental data by the theory constitutes an interesting tool for the characterization of the nanoparticles. In this work, T 2 of suspensions of iron oxide particles in different solvents and at different temperatures, corresponding to different proton diffusion properties, were measured and were compared to the three main theoretical models (the motional averaging regime, the static dephasing regime, and the partial refocusing model) with good qualitative agreement. However, a real quantitative agreement was not observed, probably because of the complexity of these nanoparticulate systems. The Roch theory, developed in the motional averaging regime (MAR), was also successfully used to fit T 1 nuclear magnetic relaxation dispersion (NMRD) profiles, even outside the MAR validity range, and provided a good estimate of the particle size. On the other hand, the simultaneous fitting of T 1 and T 2 NMRD profiles by the theory was impossible, and this occurrence constitutes a clear limitation of the Roch model. Finally, the theory was shown to satisfactorily fit the deuterium T 1 NMRD profile of superparamagnetic particle suspensions in heavy water.

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.

Dielectric Relaxation of Water: Theory and Experiment

International Nuclear Information System (INIS)

Adhikari, Narayan Prasad; Paudyal, Harihar; Johri, Manoj

2010-06-01

We have studied the hydrogen bond dynamics and methods for evaluation of probability and relaxation time for hydrogen bond network. Further, dielectric relaxation time has been calculated by using a diagonalization procedure by obtaining eigen values (inverse of relaxation time) of a master equation framed on the basis of Fokker-Planck equations. Microwave cavity spectrometer has been described to make measurements of relaxation time. Slater's perturbation equations are given for the analysis of the data. A comparison of theoretical and experimental data shows that there is a need for improvements in the theoretical model and experimental techniques to provide exact information about structural properties of water. (author)

Increased CEST specificity for amide and fast-exchanging amine protons using exchange-dependent relaxation rate.

Science.gov (United States)

Zhang, Xiao-Yong; Wang, Feng; Xu, Junzhong; Gochberg, Daniel F; Gore, John C; Zu, Zhongliang

2018-02-01

Chemical exchange saturation transfer (CEST) imaging of amides at 3.5 ppm and fast-exchanging amines at 3 ppm provides a unique means to enhance the sensitivity of detection of, for example, proteins/peptides and neurotransmitters, respectively, and hence can provide important information on molecular composition. However, despite the high sensitivity relative to conventional magnetic resonance spectroscopy (MRS), in practice, CEST often has relatively poor specificity. For example, CEST signals are typically influenced by several confounding effects, including direct water saturation (DS), semi-solid non-specific magnetization transfer (MT), the influence of water relaxation times (T 1w ) and nearby overlapping CEST signals. Although several editing techniques have been developed to increase the specificity by removing DS, semi-solid MT and T 1w influences, it is still challenging to remove overlapping CEST signals from different exchanging sites. For instance, the amide proton transfer (APT) signal could be contaminated by CEST effects from fast-exchanging amines at 3 ppm and intermediate-exchanging amines at 2 ppm. The current work applies an exchange-dependent relaxation rate (R ex ) to address this problem. Simulations demonstrate that: (1) slowly exchanging amides and fast-exchanging amines have distinct dependences on irradiation powers; and (2) R ex serves as a resonance frequency high-pass filter to selectively reduce CEST signals with resonance frequencies closer to water. These characteristics of R ex provide a means to isolate the APT signal from amines. In addition, previous studies have shown that CEST signals from fast-exchanging amines have no distinct features around their resonance frequencies. However, R ex gives Lorentzian lineshapes centered at their resonance frequencies for fast-exchanging amines and thus can significantly increase the specificity of CEST imaging for amides and fast-exchanging amines. Copyright © 2017 John Wiley & Sons

Effect of cations on the hydrated proton.

Science.gov (United States)

Ottosson, Niklas; Hunger, Johannes; Bakker, Huib J

2014-09-17

We report on a strong nonadditive effect of protons and other cations on the structural dynamics of liquid water, which is revealed using dielectric relaxation spectroscopy in the frequency range of 1-50 GHz. For pure acid solutions, protons are known to have a strong structuring effect on water, leading to a pronounced decrease of the dielectric response. We observe that this structuring is reduced when protons are cosolvated with salts. This reduction is exclusively observed for combinations of protons with other ions; for all studied solutions of cosolvated salts, the effect on the structural dynamics of water is observed to be purely additive, even up to high concentrations. We derive an empirical model that quantitatively describes the nonadditive effect of cosolvated protons and cations. We argue that the effect can be explained from the special character of the proton in water and that Coulomb fields exerted by other cations, in particular doubly charged cations like Mg(2+)aq and Ca(2+)aq, induce a localization of the H(+)aq hydration structures.

Correlation between magnetic resonance image and content of water and fat in experimental tumor

International Nuclear Information System (INIS)

Sato, Tachio; Yamada, Kenji; Yamada, Susumu; Yoshioka, Seiro; Ono, Shuichi; Hishinuma, Takashi; Abe, Yoshinao; Matsuzawa, Taiju; Ogata, Yuko.

1987-01-01

Water and fat are considered to be major protons contributing to magnetic resonance (MR) signals in living tissues. This study compared proton density and T1 and T2 relaxation times with content of water and fat in tumor bearing rabbits. MR scans were performed using a Carr-Purcell-Meiboom-Gill pulse sequence with short and long repetition times. There was a strong correlation between proton density and the content of water and fat. The correlation of the content of water and fat to T1 and T2 relaxation times was not so strong as that to proton density. Viable tumor tissues had significantly shorter T2 relaxation time than the surrounding edematous tissues (p < 0.005), although the content of water and fat did not differ in the two types of tissues. T1 relaxation time did not differ in viable tumorous and edematous tissues. (Namekawa, K.)

Proton spin-lattice relaxation in a liquid crystal-Aerosil complex above the bulk isotropization temperature

Energy Technology Data Exchange (ETDEWEB)

Anoardo, E.; Grinberg, F.; Vilfan, M.; Kimmich, R

2004-02-16

We present a study of the molecular dynamics in an octylcyanobiphenyl (8CB)-Aerosil complex above the bulk isotropization temperature. Using proton nuclear magnetic relaxation experiments in the laboratory frame (T{sub 1}{sup -1}) and in the rotating-frame (T{sub 1{rho}}{sup -1}), we found a notable increase of the relaxation rates in the kHz frequency range as compared to the bulk 8CB liquid crystal at the same temperature. The field-cycling technique was used for the laboratory frame experiments while a conventional apparatus was used for the rotating frame method. The observed behavior is analyzed with the aid of Monte Carlo simulations on the basis of a two-phase fast-exchange model distinguishing surface-ordered and bulk phases. Two processes affecting the low frequency relaxation could be identified: reorientation mediated by translational displacements, accounting for molecular reorientations, and exchange losses of molecules from the surface to the bulk.

Magnetization transfer from macromolecules to water protons in murine dental tissues as revealed by 500 MHz 1H-NMR

International Nuclear Information System (INIS)

Nakamura, Koji; Era, Seiichi; Nagai, Naoki; Sogami, Masaru; Takasaki, Akihiko; Kato, Kazuo.

1997-01-01

Although much is known about magnetization transfer phenomena in biological soft tissues, little is known about those in hard tissues. Using a 500 MHz 1 H-NMR spectrometer, we studied the spin-lattice relaxation time (T 1 (H 2 O)) and the intermolecular cross-relaxation times (T IS (H 2 O)) from irradiated macromolecular protons to observed water protons in murine lower incisors (hard tissue) and compared with those in murine lens tissue (soft tissue). Mean values for the water content (%) of murine lower incisors and lens tissue were 16.02±2.39 (n=14) and 67.20±4.60 (n=15), respectively. These findings were consistent with the large different in water content between soft tissues and hard tissues. T IS (H 2 O) values obtained by f 2 -irradiation at 7.13 or -4.00 ppm showed no significant difference between lower incisors and lens tissue. Plots of 1/T IS (H 2 O) values vs. tissue dry weight (W(%)) for lower incisor tissue approximated a straight line with slope approximately equal for that obtained for lens tissue. These results suggest that the state of water in hard tissue may be similar to that in soft tissues, in spite of the significant difference in water content. Thus, saturation transfer NMR techniques such as measurement of T IS (H 2 O) values may be applicable to the study of water-macromolecule interactions in both biological soft and hard tissues. (author)

Proton exchange in systems: Glucose-water and uric acid-water

International Nuclear Information System (INIS)

Maarof, S.

2007-01-01

It is clear that formation of glucose-water and uric acid-water solutions is related in principle to interaction accepter - donor between hydrogen atom in water and oxygen atom in glucose or uric acid. The proton exchange in hydrogen bond system is an integral process and it goes by tunnel mechanism (transfer of proton within the hydrogen bridge in these structures). Proton exchange process goes very quickly at low concentrations for glucose and uric acid solutions, because these compounds are able to form more than one hydrogen bond, which helps the proton transfer within obtained structure. However, at its high concentrations, the process becomes very slow due to higher viscosity of its solutions, which result in break down of the structures, and more hydrogen bonds. (author)

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

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

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.

Thermal Fluctuations in the Magnetic Ground State of the Molecular Cluster Mn12O12 Acetate from μSR and Proton NMR Relaxation

International Nuclear Information System (INIS)

Lascialfari, A.; Borsa, F.; Carretta, P.; Jang, Z.H.; Borsa, F.; Gatteschi, D.

1998-01-01

Measurements of the spin-lattice relaxation rate are reported for muons and protons as a function of temperature for different values of the applied magnetic field in the Mn 12 O 12 molecular cluster. Strongly field dependent maxima in the relaxation rate versus temperature are observed below 50thinspthinspK. The results are explained in terms of thermal fluctuations of the total magnetization of the cluster among the different orientations with respect to the anisotropy axis. The lifetimes of the different m components of the total spin, S T =10 , of the molecule are obtained from the experiment and shown to be consistent with the ones expected from a spin-phonon coupling mechanism. No clear evidence for macroscopic quantum tunneling was observed in the field dependence of the proton relaxation rate at low T . copyright 1998 The American Physical Society

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 chemical shift titration experiments, and the CPMG derived exchange rates agree with those obtained previously from N-15 backbone relaxation measurements. Compared to measurements of backbone nuclei, C-13(epsilon 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 C-13(epsilon 1) dispersion experiments in combination with chemical shift titration experiments to obtain information on exchange dynamics of the histidine side chains...

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

International Nuclear Information System (INIS)

Lemen, L.

2015-01-01

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

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

Protein proton-proton dynamics from amide proton spin flip rates

International Nuclear Information System (INIS)

Weaver, Daniel S.; Zuiderweg, Erik R. P.

2009-01-01

Residue-specific amide proton spin-flip rates K were measured for peptide-free and peptide-bound calmodulin. K approximates the sum of NOE build-up rates between the amide proton and all other protons. This work outlines the theory of multi-proton relaxation, cross relaxation and cross correlation, and how to approximate it with a simple model based on a variable number of equidistant protons. This model is used to extract the sums of K-rates from the experimental data. Error in K is estimated using bootstrap methodology. We define a parameter Q as the ratio of experimental K-rates to theoretical K-rates, where the theoretical K-rates are computed from atomic coordinates. Q is 1 in the case of no local motion, but decreases to values as low as 0.5 with increasing domination of sidechain protons of the same residue to the amide proton flips. This establishes Q as a monotonous measure of local dynamics of the proton network surrounding the amide protons. The method is applied to the study of proton dynamics in Ca 2+ -saturated calmodulin, both free in solution and bound to smMLCK peptide. The mean Q is 0.81 ± 0.02 for free calmodulin and 0.88 ± 0.02 for peptide-bound calmodulin. This novel methodology thus reveals the presence of significant interproton disorder in this protein, while the increase in Q indicates rigidification of the proton network upon peptide binding, confirming the known high entropic cost of this process

Relaxation study of a paramagnetic ion by the observation of nuclear resonance signals

International Nuclear Information System (INIS)

Landesman, A.

1960-01-01

Dynamic polarization of protons in water containing the paramagnetic ion NO(SO 3 ) 2 was studied, both theoretically and experimentally, as a function of magnetic field. The enhancement of the proton polarization depends appreciably on the relaxation process of the electron spin and so enables us to decide which is the real relaxation process. We tried the two following processes: a) The electron spin is coupled with the nitrogen magnetic moment by hyperfine interaction; if this interaction has an anisotropic part, a relaxation process for the electronic spin will result through the Brownian motion of the ion. b) The relaxation of the electron spin takes place through spin-orbit coupling of the electron spin. Experimental results showed that the relaxation took place through the second process with the help of dynamic polarization we were able to study the relaxation of an electron spin in a liquid without using any electron resonance spectrometer, simply by observing the resonance of a nuclear spin coupled with the electron spin. Reprint of a paper published in Le Journal de Physique et le Radium, t. 20, p. 937-948, 1959 [fr

Molecular theory for nuclear magnetic relaxation in protein solutions and tissue

International Nuclear Information System (INIS)

Kimmich, R.; Nusser, W.; Gneiting, T.

1990-01-01

A model theory is presented explaining a series of striking phenomena observed with nuclear magnetic relaxation in protein systems such as solutions or tissue. The frequency, concentration and temperature dependences of proton or deuteron relaxation times of protein solutions and tissue are explained. It is concluded that the translational diffusion of water molecules along the rugged surfaces of proteins and, to a minor degree, protein backbone fluctuations are crucial processes. The rate limiting factor of macromolecular tumbling is assumed to be given by the free water content in a certain analogy to the free-volume model of Cohen ad Turnbull. There are two characteristic water mass fractions indicating the saturation of the hydration shells and the onset of protein tumbling. A closed and relatively simple set of relaxation formulas is presented. The potentially fractal nature of the diffusion of water molecules on the protein surface is discussed. (author). 43 refs.; 4 figs

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

International Nuclear Information System (INIS)

Al-Sulaiti, L.; Shipley, D.; Thomas, R.; Owen, P.; Kacperek, A.; Regan, P.H.; Palmans, H.

2012-01-01

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 ® (PW) 1 , Plastic Water ® Diagnostic Therapy (PWDT) 1 and solid water (WT1) 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: ► We study plastic-water in clinical proton beams by experiment and Monte Carlo. ► We obtain fluence correction factors for water and graphite. ► The correction factor for water was close to 1 at 60 MeV and <0.990 at 200 MeV. ► The correction factor for graphite was ∼0.5% at 60 MeV and up to 4% at 200 MeV.

Luminescence imaging of water during proton-beam irradiation for range estimation

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, Seiichi, E-mail: s-yama@met.nagoya-u.ac.jp; Okumura, Satoshi; Komori, Masataka [Radiological and Medical Laboratory Sciences, Nagoya University Graduate School of Medicine, Nagoya 461-8673 (Japan); Toshito, Toshiyuki [Department of Proton Therapy Physics, Nagoya Proton Therapy Center, Nagoya City West Medical Center, Nagoya 462-8508 (Japan)

2015-11-15

Purpose: Proton therapy has the ability to selectively deliver a dose to the target tumor, so the dose distribution should be accurately measured by a precise and efficient method. The authors found that luminescence was emitted from water during proton irradiation and conjectured that this phenomenon could be used for estimating the dose distribution. Methods: To achieve more accurate dose distribution, the authors set water phantoms on a table with a spot scanning proton therapy system and measured the luminescence images of these phantoms with a high-sensitivity, cooled charge coupled device camera during proton-beam irradiation. The authors imaged the phantoms of pure water, fluorescein solution, and an acrylic block. Results: The luminescence images of water phantoms taken during proton-beam irradiation showed clear Bragg peaks, and the measured proton ranges from the images were almost the same as those obtained with an ionization chamber. Furthermore, the image of the pure-water phantom showed almost the same distribution as the tap-water phantom, indicating that the luminescence image was not related to impurities in the water. The luminescence image of the fluorescein solution had ∼3 times higher intensity than water, with the same proton range as that of water. The luminescence image of the acrylic phantom had a 14.5% shorter proton range than that of water; the proton range in the acrylic phantom generally matched the calculated value. The luminescence images of the tap-water phantom during proton irradiation could be obtained in less than 2 s. Conclusions: Luminescence imaging during proton-beam irradiation is promising as an effective method for range estimation in proton therapy.

Luminescence imaging of water during proton-beam irradiation for range estimation

International Nuclear Information System (INIS)

Yamamoto, Seiichi; Okumura, Satoshi; Komori, Masataka; Toshito, Toshiyuki

2015-01-01

Purpose: Proton therapy has the ability to selectively deliver a dose to the target tumor, so the dose distribution should be accurately measured by a precise and efficient method. The authors found that luminescence was emitted from water during proton irradiation and conjectured that this phenomenon could be used for estimating the dose distribution. Methods: To achieve more accurate dose distribution, the authors set water phantoms on a table with a spot scanning proton therapy system and measured the luminescence images of these phantoms with a high-sensitivity, cooled charge coupled device camera during proton-beam irradiation. The authors imaged the phantoms of pure water, fluorescein solution, and an acrylic block. Results: The luminescence images of water phantoms taken during proton-beam irradiation showed clear Bragg peaks, and the measured proton ranges from the images were almost the same as those obtained with an ionization chamber. Furthermore, the image of the pure-water phantom showed almost the same distribution as the tap-water phantom, indicating that the luminescence image was not related to impurities in the water. The luminescence image of the fluorescein solution had ∼3 times higher intensity than water, with the same proton range as that of water. The luminescence image of the acrylic phantom had a 14.5% shorter proton range than that of water; the proton range in the acrylic phantom generally matched the calculated value. The luminescence images of the tap-water phantom during proton irradiation could be obtained in less than 2 s. Conclusions: Luminescence imaging during proton-beam irradiation is promising as an effective method for range estimation in proton therapy

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)

Using low-field NMR to infer the physical properties of glassy oligosaccharide/water mixtures.

Science.gov (United States)

Aeberhardt, Kasia; Bui, Quang D; Normand, Valéry

2007-03-01

Low-field NMR (LF-NMR) is usually used as an analytical technique, for instance, to determine water and oil contents. For this application, no attempt is made to understand the physical origin of the data. Here we build a physical model to explain the five fit parameters of the conventional free induction decay (FID) for glassy oligosaccharide/water mixtures. The amplitudes of the signals from low-mobility and high-mobility protons correspond to the density of oligosaccharide protons and water protons, respectively. The relaxation time of the high-mobility protons is described using a statistical model for the probability that oligosaccharide hydroxyl groups form multiple hydrogen bonds. The variation of energy of the hydrogen bond is calculated from the average bond distance and the average angle contribution. Applying the model to experimental data shows that hydrogen atoms screen the water oxygen atoms when two water molecules solvate a single hydroxyl group. Furthermore, the relaxation time of the oligosaccharide protons is independent of its molecular weight and the water content. Finally, inversion of the FID using the inverse Laplace transform gives the continuous spectrum of relaxation times, which is a fingerprint of the oligosaccharide.

Localized in vivo proton spectroscopy of the bone marrow in patients with leukemia

DEFF Research Database (Denmark)

Jensen, K E; Jensen, M; Grundtvig, P

1990-01-01

Volume selective magnetic resonance (MR) proton spectroscopy was used to investigate the haemopoietic (iliac bone) and fatty bone marrow (tibia) in patients with leukemia and polycythaemia vera. Selective measurements of the relaxation times T1 and T2 for the "water" and "fat" resonances in the b......Volume selective magnetic resonance (MR) proton spectroscopy was used to investigate the haemopoietic (iliac bone) and fatty bone marrow (tibia) in patients with leukemia and polycythaemia vera. Selective measurements of the relaxation times T1 and T2 for the "water" and "fat" resonances...... to chemotherapeutic treatment. Nine patients with polycythaemia vera and 21 normal control subjects were examined with identical methods for comparison. All patients had bone marrow biopsies performed prior to every MR examination. Significant differences could be detected in the spectral patterns from iliac bone...... decrease in marrow fat content. The T1 relaxation times of the "water" resonance in the spectra from the iliac bone marrow of the leukemic patients were significantly prolonged at diagnosis, compared to the normal controls and the patients with polycythaemia vera. After chemotherapeutic induction...

Solid state proton spin-lattice relaxation in four structurally related organic molecules

International Nuclear Information System (INIS)

Beckmann, Peter A.; Burbank, Kendra S.; Lau, Matty M.W.; Ree, Jessica N.; Weber, Tracy L.

2003-01-01

We report and interpret the temperature dependence of the proton spin-lattice relaxation rate at 8.50 and 22.5 MHz in four polycrystalline solids composed of structurally related molecules: 2-ethylanthracene, 2-t-butylanthracene, 2-ethylanthraquinone, and 2-t-butylanthraquinone. We have been unable to grow single crystals and therefore do not know the crystal structures. Hence, we use the NMR relaxometry data to make predictions about the solid state structures. As expected, we are able to conclude that the ethyl groups do not reorient in the solid state but that the t-butyl groups do. The anthraquinones have a ''simpler'' structure than the anthracenes. The best dynamical models suggest that there is a unique crystallographic site for the t-butyl groups in 2-t-butylanthraquinone and two sites, each with half the molecules, for the ethyl groups in 2-ethylanthraquinone. There are also two sites in 2-ethylanthracene, but with unequal weights, suggesting four sites in the unit cell with lower symmetry than the two anthraquinones. Finally, the observed relaxation rate data in 2-t-butylanthracene is very complex and its interpretation demonstrates the uniqueness problem that arises in interpreting relaxometry data without the knowledge of the crystal structure

Dielectric relaxation studies of some primary alcohols and their mixture with water

International Nuclear Information System (INIS)

Ahmad, S.S.; Yaqub, M.

2003-01-01

The complex dielectric constant of ethyl alcohol, methyl alcohol and 1- propanol and their mixtures with water of different concentration, (0 to 100% by weight) at the temperature of 303K has been evaluated, within the frequency range of (100KHz- 100 MHz). Moreover, the viscosity mu of each alcohol and its mixture with water have been measured at this temperature. The dielectric properties have been evaluated by Hartshorn and Ward apparatus. The purpose of this work is to study the influence of aliphatic group, size and shape on the extent of hydrogen bonding and also to obtain the thermodynamic data on hydrogen bond formation in the pure liquid state and its mixture. The width of the semicircle plot determines the distribution of average relaxation time. Dielectric relaxation time in pure alcohols and their water mixture has been calculated from the respected Cole-Cole plot and dielectric data. A single relaxation time of 117.16ps has been obtained for the molecules of pure methanol, whereas, the dielectric data of prophyl alcohol which indicates the viscosity water have been measured at the temperature 303 K. The dielectric properties in distribution of relaxation time, which is in good agreement with the Davidson-cole representation. The molecules in liquid mixture within frequency range, the mixture has more than one relaxation item, leading to the shortening of main relaxation time as compared with the pure alcohol and broadening of the complex permitivity spectra. The dependence of the dielectric relaxation on composition shows a remarkable behavior. Results are discussed in the light of H-bonded molecules. (author)

Kinetics of proton migration in liquid water.

Science.gov (United States)

Chen, Hanning; Voth, Gregory A; Agmon, Noam

2010-01-14

We have utilized multistate empirical valence bond (MS-EVB3) simulations of protonated liquid water to calculate the relative mean-square displacement (MSD) and the history-independent time correlation function, c(t), of the hydrated proton center of excess charge (CEC) with respect to the water molecule on which it has initially resided. The MSD is nonlinear for the first 15 ps, suggesting that the relative diffusion coefficient increases from a small value, D(0), at short separations to its larger bulk value, D(infinity), at large separations. With the ensuing distance-dependent diffusion coefficient, D(r), the time dependence of both the MSD and c(t) agrees quantitatively with the solution of a diffusion equation for reversible geminate recombination. This suggests that the relative motion of the CEC is not independent from the nearby water molecules, in agreement with theoretical and experimental observations that large water clusters participate in the mechanism of proton mobility.

Nuclear relaxation induced by diffusion in confined media; the case of inverted micelles

International Nuclear Information System (INIS)

Llor, Antoine

1983-01-01

This work emphasizes the specificities of molecular motions in restricted media observed by NMR. The observation of proton nuclear relaxation of small water pools in AOT reversed micelles has led to separation of dipolar contributions using substitution by deuterium. The water-water contributions to relaxation are easily explained by well-known models and show that water rotational movements are, at most, five times slower than in pure water. The other contributions display a strong frequency dependence with spectrometer frequency and, in order to explain them, a specific dipolar relaxation model was developed between two particles whose movements are restricted to the surface of a sphere and in a concentric sphere respectively. This model was generalized to all cases of diffusion movements of particles in a spherical symmetry environment. In the case of AOT micelles, this model can not explain the experimental results. An elementary discussion taking into account the polar heads specificities and their interactions with water lead to a qualitative interpretation of the experimental data. (author) [fr

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 2ppm 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 ∼10(4)s(-1) at pH 7.4 and 37°C, the activation energy, 50.2kJ/mol and its pH dependence at 1.1°C was fitted to: k (s(-1))=520+6.5×10(7)[H(+)]+3.0×10(9)[OH(-)]. Copyright © 2014. Published by Elsevier Inc.

Measurement of the relaxation rate of the magnetization in Mn12O12-acetate using proton NMR echo

Science.gov (United States)

Jang; Lascialfari; Borsa; Gatteschi

2000-03-27

We present a novel method to measure the relaxation rate W of the magnetization of Mn 12O (12)-acetate (Mn12) magnetic molecular cluster in its S = 10 ground state at low T. It is based on the observation of an exponential growth in time of the proton NMR signal during the thermal equilibration of the magnetization of the molecules. We can explain the novel effect with a simple model which relates the intensity of the proton echo signal to the microscopic reversal of the magnetization of each individual Mn12 molecule during the equilibration process. The method should find wide application in the study of magnetic molecular clusters in off-equilibrium conditions.

Proton and deuteron NMR study of PTFE ionomer membranes

Energy Technology Data Exchange (ETDEWEB)

Xu, G; Pak, Y S [Dept. of Materials Science, McMaster Univ., Hamilton, Ontario (Canada)

1992-02-01

Proton and deuteron NMR have been conducted to investigate the ionic motion in perfluorinated ionomer membranes from Dow Chemical (XUS) and DuPont (Nafion{sup R}). Two proton relaxation peaks were found in the XUS specimen absorbed with H{sub 2}O. The major (narrow) peak presented a spin-lattice relaxation time (T{sub 1}) of 107 ms while the minor (broader) one gave much longer T{sub 1}. While the former was attributed to the water molecules involved in restricted motion, the latter was expected to be associated with the protons located in the vicinity of the sulfonate groups. Similar to the previous results from the others, only a single peak was detected in Nafion{sup R} in {sup 1}H spectra, indicating that the protons in the different environments were engaging rapid exchange within NMR time scale. In contrast to the inverse proportion dependence of the linewidth on the water sorption in Nafion{sup R}, the major line of the XUS membrane exhibited insensitive linewidth dependence on the variation of H{sub 2}O concentration. The difference was attributed to the existence of narrow breaths of the pores in XUS sample, such that free water contribution to the enhancement of proton mobility was limited. The {sup 2}H spectra of Nafion{sup R} were found to possess a doublet, due to nuclear quadrupolar interaction. Dow (XUS) membrane treated in at 100% relative humidity (RH) D{sub 2}O presented a single peak with the linewidth insensitive to the amount of heavy water absorbed. An additional rise emerged on the ''shoulder'' of this single peak when treated at 33% RH. It is concluded that XUS membrane does not provide strong hydrogen bonding to eliminate the rapid motion average over the nuclear quadrupole interaction. (orig.).

Nuclear magnetic relaxation by the dipolar EMOR mechanism: General theory with applications to two-spin systems.

Science.gov (United States)

Chang, Zhiwei; Halle, Bertil

2016-02-28

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. We have embarked on a systematic program to develop, from the stochastic Liouville equation, a general and rigorous theory that can describe relaxation by the dipolar EMOR mechanism over the full range of exchange rates, dipole coupling strengths, and Larmor frequencies. Here, we present a general theoretical framework applicable to spin systems of arbitrary size with symmetric or asymmetric exchange. So far, the dipolar EMOR theory is only available for a two-spin system with symmetric exchange. Asymmetric exchange, when the spin system is fragmented by the exchange, introduces new and unexpected phenomena. Notably, the anisotropic dipole couplings of non-exchanging spins break the axial symmetry in spin Liouville space, thereby opening up new relaxation channels in the locally anisotropic sites, including longitudinal-transverse cross relaxation. Such cross-mode relaxation operates only at low fields; at higher fields it becomes nonsecular, leading to an unusual inverted relaxation dispersion that splits the extreme-narrowing regime into two sub-regimes. The general dipolar EMOR theory is illustrated here by a detailed analysis of the asymmetric two-spin case, for which we present relaxation dispersion profiles over a wide range of conditions as well as analytical results for integral relaxation rates and time-dependent spin modes in the zero-field and motional-narrowing regimes. The general theoretical framework presented here will enable a quantitative analysis of frequency-dependent water-proton longitudinal relaxation in model systems with immobilized macromolecules and, ultimately, will provide a rigorous link between relaxation-based magnetic resonance image contrast and molecular parameters.

Probing water structure and transport in proton exchange membranes

NARCIS (Netherlands)

Ling, X.

2018-01-01

Proton exchange membrane fuel cells (PEMFCs) have attracted tremendous attention as alternative energy sources because of their high energy density and practically zero greenhouse gas emission - water is their only direct by-product. Critical to the function of PEMFCs is fast proton and water

Measurement of the Relaxation Rate of the Magnetization in Mn12O12 -Acetate Using Proton NMR Echo

International Nuclear Information System (INIS)

Jang, Z. H.; Lascialfari, A.; Borsa, F.; Gatteschi, D.

2000-01-01

We present a novel method to measure the relaxation rate W of the magnetization of Mn 12 O 12 -acetate (Mn12) magnetic molecular cluster in its S=10 ground state at low T . It is based on the observation of an exponential growth in time of the proton NMR signal during the thermal equilibration of the magnetization of the molecules. We can explain the novel effect with a simple model which relates the intensity of the proton echo signal to the microscopic reversal of the magnetization of each individual Mn12 molecule during the equilibration process. The method should find wide application in the study of magnetic molecular clusters in off-equilibrium conditions. (c) 2000 The American Physical Society

Rotational dynamics account for pH-dependent relaxivities of PAMAM dendrimeric, Gd-based potential MRI contrast agents.

Science.gov (United States)

Laus, Sabrina; Sour, Angélique; Ruloff, Robert; Tóth, Eva; Merbach, André E

2005-05-06

The EPTPA5) chelate, which ensures fast water exchange in GdIII complexes, has been coupled to three different generations (5, 7, and 9) of polyamidoamine (PAMAM) dendrimers through benzylthiourea linkages (H5EPTPA = ethylenepropylenetriamine-N,N,N',N'',N''-pentaacetic acid). The proton relaxivities measured at pH 7.4 for the dendrimer complexes G5-(GdEPTPA)111, G7-(GdEPTPA)253 and G9-(GdEPTPA)1157 decrease with increasing temperature, indicating that, for the first time for dendrimers, slow water exchange does not limit relaxivity. At a given field and temperature, the relaxivity increases from G5 to G7, and then slightly decreases for G9 (r1 = 20.5, 28.3 and 27.9 mM(-1) s(-1), respectively, at 37 degrees C, 30 MHz). The relaxivities show a strong and reversible pH dependency for all three dendrimer complexes. This originates from the pH-dependent rotational dynamics of the dendrimer skeleton, which was evidenced by a combined variable-temperature and multiple-field 17O NMR and 1H relaxivity study performed at pH 6.0 and 9.9 on G5-(GdEPTPA)111. The longitudinal 17O and 1H relaxation rates of the dendrimeric complex are strongly pH-dependent, whereas they are not for the [Gd(EPTPA)(H2O)]2- monomer chelate. The longitudinal 17O and 1H relaxation rates have been analysed by the Lipari-Szabo spectral density functions and correlation times have been calculated for the global motion of the entire macromolecule (tau(gO)) and the local motion of the GdIII chelates on the surface (tau(lO)), correlated by means of an order parameter S2. The dendrimer complex G5-(GdEPTPA)111 has a considerably higher tau(gO) under acidic than under basic conditions (tau(298)gO = 4040 ps and 2950 ps, respectively), while local motions are less influenced by pH (tau(298)lO = 150 and 125 ps). The order parameter, characterizing the rigidity of the macromolecule, is also higher at pH 6.0 than at pH 9.9 (S2 = 0.43 vs 0.36, respectively). The pH dependence of the global correlation time can be

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...

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.

31-P Relaxation times of metabolic compounds in tumors grafted in nude mice

International Nuclear Information System (INIS)

Remy, C.; Benabid, A.L.; Jacrot, M.; Riondel, J.; Albrand, J.P.; Decorps, M.

1985-08-01

The observation that water proton relaxation rates were longer in tumors than in normal tissues provided a basis for the detection of human tumors by the NMR imaging technique. To evaluate the potentiality of 31-P NMR spectroscopy as a diagnostic tool of the pathological state of tissues, T1 and T2 relaxation times have been measured for the phosphates of ATP, inorganic phosphate (Pi), phosphomonoesters (PME) and phosphocreatine (PCr) in the 31-P NMR spectra obtained in vivo for normal rat brain and rat brain tumors implanted in nude mice

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.

Proton nuclear magnetic resonance study of water + t-butyl alcohol ...

African Journals Online (AJOL)

The water proton resonance initially shifts to higher frequencies (low fields) as the cosolvent is added to water, and the shift to higher frequency is strongly temperature dependent, the effect being greatly enhanced at lower temperatures. As the proportion of cosolvent increases the hydroxyl proton signals in the water + ...

Relaxation time T/sub 1/ and bound water fraction of muscle by NMR imager

Energy Technology Data Exchange (ETDEWEB)

Fukuda, N.; Ikehira, H.; Yamane, T.; Tateno, Y.; Torii, S.; Matsumura, K.

1986-05-01

In order to establish the efficacy of NMR-CT in the diagnostic investigation of muscle disorders, proton NMR-CT imaging was performed and muscle longitudinal relaxation (T1) times were measured in 20 Duchenne muscular dystrophy (DMD) patients and normal controls (NC). In addition, the bound water fraction (BWF) was calculated from the measured T1 value in appropriate cases. Results show that in DMD muscle T1 values were above normal in the early clinical stages, declined rapidly with progress of the disease, and reached the same low level as the subcutaneous fat. This decrease of T1 values was not uniform for all muscles, being most prominent in gluteus maximus and least in sartorius and gracilis. In NC muscle BWF increased with maturation under the age of 10 years, and became fixed beyond that. In the early stages of DMD, BWF was below normal.

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

Water-Protein Interactions: The Secret of Protein Dynamics

Directory of Open Access Journals (Sweden)

Silvia Martini

2013-01-01

Full Text Available Water-protein interactions help to maintain flexible conformation conditions which are required for multifunctional protein recognition processes. The intimate relationship between the protein surface and hydration water can be analyzed by studying experimental water properties measured in protein systems in solution. In particular, proteins in solution modify the structure and the dynamics of the bulk water at the solute-solvent interface. The ordering effects of proteins on hydration water are extended for several angstroms. In this paper we propose a method for analyzing the dynamical properties of the water molecules present in the hydration shells of proteins. The approach is based on the analysis of the effects of protein-solvent interactions on water protons NMR relaxation parameters. NMR relaxation parameters, especially the nonselective (R1NS and selective (R1SE spin-lattice relaxation rates of water protons, are useful for investigating the solvent dynamics at the macromolecule-solvent interfaces as well as the perturbation effects caused by the water-macromolecule interactions on the solvent dynamical properties. In this paper we demonstrate that Nuclear Magnetic Resonance Spectroscopy can be used to determine the dynamical contributions of proteins to the water molecules belonging to their hydration shells.

Dynamic and structural characterisation of micellar solutions of surfactants by spin relaxation and translational diffusion

International Nuclear Information System (INIS)

Mahieu, Nathalie

1992-01-01

The work reported in this research thesis aimed at characterizing micellar phases formed by some surfactants (sodium carboxylates) in aqueous solution. After some recalls on nuclear magnetic resonance dealing with spin relaxation (longitudinal relaxation, transverse relaxation, relaxation in the rotating coordinate system, and crossed relaxation), and comments on the dipolar mechanism responsible of relaxation phenomena, the author presents the methods used for relaxation parameter measurement and the data processing software issued from experiments. He presents experiments which allowed the self-diffusion coefficient to be measured, reports data processing, and addresses problems of special diffusion and of coherence transfers during diffusion measurements. Results of proton relaxation measurements are then presented and discussed. They are used to determine the micellar state of the studied carboxylates. The case of the oleate is also addressed. Measurements of carbon-13 relaxation times are reported, and exploited in terms of structural parameters by using the Relaxator software. An original method of the hetero-nuclear Overhauser method is presented, and used to assess the average distance between water molecules and micelle surface [fr

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...... concentrations of CuSO4 and correlating the calculated T1 and T2 values with reference values obtained by two spectrometers (corrected to MRI-proton frequency = 64 MHz) we found a maximum deviation of about 10 per cent. Measurements performed on a large water phantom in order to evaluate the homogeneity...... in the imaging plane showed a variation of less than 10 per cent within 10 cm from the centre of the magnet in all three imaging planes. Changing the gradient field strength apparently had no influence on the T2 values recorded. Consequently diffusion processes seem without significance. It is concluded...

Molecular theory for nuclear magnetic relaxation in protein solutions and tissue; Surface diffusion and free-volume analogy

Energy Technology Data Exchange (ETDEWEB)

Kimmich, R; Nusser, W; Gneiting, T [Ulm Universitaet (Federal Republic of Germany). Sektion Kernresonanzspektroskopie

1990-04-01

A model theory is presented explaining a series of striking phenomena observed with nuclear magnetic relaxation in protein systems such as solutions or tissue. The frequency, concentration and temperature dependences of proton or deuteron relaxation times of protein solutions and tissue are explained. It is concluded that the translational diffusion of water molecules along the rugged surfaces of proteins and, to a minor degree, protein backbone fluctuations are crucial processes. The rate limiting factor of macromolecular tumbling is assumed to be given by the free water content in a certain analogy to the free-volume model of Cohen ad Turnbull. There are two characteristic water mass fractions indicating the saturation of the hydration shells and the onset of protein tumbling. A closed and relatively simple set of relaxation formulas is presented. The potentially fractal nature of the diffusion of water molecules on the protein surface is discussed. (author). 43 refs.; 4 figs.

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.

Fast hydrogen exchange affects 15N relaxation measurements in intrinsically disordered proteins

International Nuclear Information System (INIS)

Kim, Seho; Wu, Kuen-Phon; Baum, Jean

2013-01-01

Unprotected amide protons can undergo fast hydrogen exchange (HX) with protons from the solvent. Generally, NMR experiments using the out-and-back coherence transfer with amide proton detection are affected by fast HX and result in reduced signal intensity. When one of these experiments, 1 H– 15 N HSQC, is used to measure the 15 N transverse relaxation rate (R 2 ), the measured R 2 rate is convoluted with the HX rate (k HX ) and has higher apparent R 2 values. Since the 15 N R 2 measurement is important for analyzing protein backbone dynamics, the HX effect on the R 2 measurement is investigated and described here by multi-exponential signal decay. We demonstrate these effects by performing 15 N R 2 CPMG experiments on α-synuclein, an intrinsically disordered protein, in which the amide protons are exposed to solvent. We show that the HX effect on R 2 CPMG can be extracted by the derived equation. In conclusion, the HX effect may be pulse sequence specific and results from various sources including the J coupling evolution, the change of steady state water proton magnetization, and the D 2 O content in the sample. To avoid the HX effect on the analysis of relaxation data of unprotected amides, it is suggested that NMR experimental conditions insensitive to the HX should be considered or that intrinsic R 2 CPMG values be obtained by methods described herein.

Kinetics of water-mediated proton transfer in our atmosphere

International Nuclear Information System (INIS)

Loerting, T.

2000-07-01

Variational transition state theory and multidimensional tunneling methods on hybrid density functional theory generated hypersurfaces have been used to investigate the temperature dependence of the reaction rate constants of water-mediated proton transfer reactions relevant to the chemistry of our atmosphere, namely the hydration of sulfur dioxide and sulfur trioxide and the decomposition of chlorine nitrate. Highly accurate reaction barriers were calculated using ab initio methods taking into account most of the electron correlation, namely CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ and G2(MP2). On comparing the determined rate constants with laboratory and atmospheric data, the following points could be established: All of the investigated reactions are highly sensitive to changes in humidity, as water acts as efficient catalyst, i.e., the barrier to the reaction is reduced drastically. Present-day atmospheric chemistry can only be explained when a limited number of water molecules is available for the formation of molecular clusters. Both in the troposphere and in the stratosphere SO 3 is hydrated rather than SO 2 . SO 2 emissions have to be oxidized, therefore, before being subject to hydration. A mechanism involving two or three water molecules is relevant for the production of sulfate aerosols, which play a decisive role in the context of global climate change and acid rain. A third water molecule has the function of assisting double-proton transfer rather than acting as active participant in triple-proton transfer in the case of the hydration of sulfur oxides. The observed ozone depletion above Arctica and Antarctica can be explained either by decomposition of chlorine nitrate in the presence of three water molecules (triple proton transfer) or by decomposition of chlorine nitrate in the presence of one molecule of HCl and one molecule of water (double proton transfer). The preassociation reaction required for homogeneous gas-phase conversion of chlorine

Quantitative pancreatic β cell MRI using manganese-enhanced Look-Locker imaging and two-site water exchange analysis.

Science.gov (United States)

Antkowiak, Patrick F; Vandsburger, Moriel H; Epstein, Frederick H

2012-06-01

Pancreatic β-cell imaging would be useful in monitoring the progression of and therapies for diabetes. The purpose of this study was to develop and evaluate quantitative β-cell MRI using manganese (Mn(2+)) labeling of β cells, T1 mapping, and a two-site water exchange model. Normal, pharmacologically-treated, and severely diabetic mice underwent injection of MnCl(2). Pancreatic water proton T1 relaxation was measured using Look-Locker MRI, and two-site water exchange analysis was used to estimate model parameters including the intracellular water proton relaxation rate constant (R1(ic)) and the intracellular fraction as indicators of β-cell function and mass, respectively. Logarithmic plots of T1 relaxation revealed two distinct proton pools relaxing with different T1s, and the two-site water exchange model fit the measured T1 relaxation data better than a monoexponential model. The intracellular R1(ic) time course revealed the kinetics of β-cell Mn(2+) labeling. Pharmacological treatments with nifedipine, tolbutamide, and diazoxide altered R1(ic), indicating that beta cell function was a determinant of Mn(2+) uptake. Intracellular fraction was significantly higher in mice with normal β cell mass than in diabetic mice (14.9% vs. 14.4%, P exchange analysis of T1 relaxation of the Mn(2+)-enhanced pancreas is a promising method for quantifying β cell volume fraction and function. Copyright © 2011 Wiley-Liss, Inc.

Measurement of the Relaxation Rate of the Magnetization in Mn{sub 12}O{sub 12} -Acetate Using Proton NMR Echo

Energy Technology Data Exchange (ETDEWEB)

Jang, Z. H. [Department of Physics and Astronomy, Ames Laboratory, Iowa State University, Ames, Iowa 50011 (United States); Lascialfari, A. [Dipartimento di Fisica ' ' A. Volta' ' e Unita' , INFM di Pavia, Via Bassi 6, 27100 Pavia, (Italy); Borsa, F. [Department of Physics and Astronomy, Ames Laboratory, Iowa State University, Ames, Iowa 50011 (United States); Dipartimento di Fisica ' ' A. Volta' ' e Unita' , INFM di Pavia, Via Bassi 6, 27100 Pavia, (Italy); Gatteschi, D. [Department of Chemistry, University of Florence, Via Maragliano 77, 50144 Firenze, (Italy)

2000-03-27

We present a novel method to measure the relaxation rate W of the magnetization of Mn{sub 12}O {sub 12} -acetate (Mn12) magnetic molecular cluster in its S=10 ground state at low T . It is based on the observation of an exponential growth in time of the proton NMR signal during the thermal equilibration of the magnetization of the molecules. We can explain the novel effect with a simple model which relates the intensity of the proton echo signal to the microscopic reversal of the magnetization of each individual Mn12 molecule during the equilibration process. The method should find wide application in the study of magnetic molecular clusters in off-equilibrium conditions. (c) 2000 The American Physical Society.

Behavior of cesium and thallium cations inside a calixarene cavity as probed by nuclear spin relaxation. Evidence of cation-pi interactions in water.

Science.gov (United States)

Cuc, Diana; Bouguet-Bonnet, Sabine; Morel-Desrosiers, Nicole; Morel, Jean-Pierre; Mutzenhardt, Pierre; Canet, Daniel

2009-08-06

We have studied the complexes formed between the p-sulfonatocalix[4]arene and cesium or thallium metal cation, first by carbon-13 longitudinal relaxation of the calixarene molecule at two values of the magnetic field B(0). From the longitudinal relaxation times of an aromatic carbon directly bonded to a proton, thus subjected essentially to the dipolar interaction with that proton, we could obtain the correlation time describing the reorientation of the CH bond. The rest of this study has demonstrated that it is also the correlation time describing the tumbling of the whole calixarene assembly. From three non-proton-bearing carbons of the aromatic cycles (thus subjected to the chemical shift anisotropy and dipolar mechanisms), we have been able to determine the variation of the chemical shift anisotropy when going from the free to the complex form of the calixarene. These variations not only provide the location of the cation inside the calixarene cavity but also constitute a direct experimental proof of the cation-pi interactions. These results are complemented by cesium and thallium relaxation measurements performed again at two values of the magnetic field B(0). An estimation of the mean distance between the cation and the calixarene protons could be obtained. These measurements have also revealed an important chemical shift anisotropy of thallium upon complexation.

Parity Nonconservation in Proton-Proton and Proton-Water Scattering at 1.5 GeV/c

Science.gov (United States)

Mischke, R. E.; Bowman, J. D.; Carlini, R.; MacArthur, D.; Nagle, D. E.; Frauenfelder, H.; Harper, R. W.; Yuan, V.; McDonald, A. B.; Talaga, R. L.

1984-07-01

Experiments searching for parity nonconservation in the scattering of 1.5 GeV/c (800 MeV) polarized protons from an unpolarized water target and a liquid hydrogen target are described. The intensity of the incident proton beam was measured upstream and downstream of the target by a pair of ionization detectors. The beam helicity was reversed at a 30-Hz rate. Auxiliary detectors monitored beam properties that could give rise to false effects. The result for the longitudinal asymmetry from the water is A{sub L} = (1.7 +- 3.3 +- 1.4) x 10{sup -7}, where the first error is statistical and the second is an estimate of systematic effects. The hydrogen data yield a preliminary result of A{sub L} = (1.0 +- 1.6) x 10{sup -7}. The systematic errors for p-p are expected to be < 1 x 10{sup -7}.

On the microscopic fluctuations driving the NMR relaxation of quadrupolar ions in water

Energy Technology Data Exchange (ETDEWEB)

Carof, Antoine; Salanne, Mathieu; Rotenberg, Benjamin, E-mail: benjamin.rotenberg@upmc.fr [Sorbonne Universités, UPMC Univ. Paris 06, CNRS, Laboratoire PHENIX, Case 51, 4 Place Jussieu, F-75005 Paris (France); Charpentier, Thibault [CEA, IRAMIS, NIMBE, LSDRM, UMR CEA-CNRS 3685, F-91191 Gif-sur-Yvette Cedex (France)

2015-11-21

Nuclear Magnetic Resonance (NMR) relaxation is sensitive to the local structure and dynamics around the probed nuclei. The Electric Field Gradient (EFG) is the key microscopic quantity to understand the NMR relaxation of quadrupolar ions, such as {sup 7}Li{sup +}, {sup 23}Na{sup +}, {sup 25}Mg{sup 2+}, {sup 35}Cl{sup −}, {sup 39}K{sup +}, or {sup 133}Cs{sup +}. Using molecular dynamics simulations, we investigate the statistical and dynamical properties of the EFG experienced by alkaline, alkaline Earth, and chloride ions at infinite dilution in water. Specifically, we analyze the effect of the ionic charge and size on the distribution of the EFG tensor and on the multi-step decay of its auto-correlation function. The main contribution to the NMR relaxation time arises from the slowest mode, with a characteristic time on the picosecond time scale. The first solvation shell of the ion plays a dominant role in the fluctuations of the EFG, all the more that the ion radius is small and its charge is large. We propose an analysis based on a simplified charge distribution around the ion, which demonstrates that the auto-correlation of the EFG, hence the NMR relaxation time, reflects primarily the collective translational motion of water molecules in the first solvation shell of the cations. Our findings provide a microscopic route to the quantitative interpretation of NMR relaxation measurements and open the way to the design of improved analytical theories for NMR relaxation for small ionic solutes, which should focus on water density fluctuations around the ion.

Effect of water-methanol mixed solvents on the ultrasonic relaxation of cadmium acetate

International Nuclear Information System (INIS)

Sree Rama Murthy, J.; Ramachandra Rao, B.

1976-01-01

Measurements of ultrasonic absorption have been made by pulse technique in 1 M solutions of cadmium acetate with water-methanol mixed solvents. Results are analysed by assuming a single relaxation mechanism. The characteristic frequency of relaxation is found to decrease with increasing composition of methanol in the solvent. It is proposed that the mechanism of relaxation may be perturbation of chemical equilibrium between complex CdAc + ions and Cd ++ , Ac - species by soundwaves. (author)

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.

The water equivalence of solid materials used for dosimetry with small proton beams

International Nuclear Information System (INIS)

Schneider, Uwe; Pemler, Peter; Besserer, Juergen; Dellert, Matthias; Moosburger, Martin; Boer, Jorrit de; Pedroni, Eros; Boehringer, Terence

2002-01-01

Various solid materials are used instead of water for absolute dosimetry with small proton beams. This may result in a dose measurement different to that in water, even when the range of protons in the phantom material is considered correctly. This dose difference is caused by the diverse cross sections for inelastic nuclear scattering in water and in the phantom materials respectively. To estimate the magnitude of this effect, flux and dose measurements with a 177 MeV proton pencil beam having a width of 0.6 cm (FWHM) were performed. The proton flux and the deposited dose in the beam path were determined behind water, lucite, polyethylene, teflon, and aluminum of diverse thicknesses. The number of out-scattered protons due to inelastic nuclear scattering was determined for water and the different materials. The ratios of the number of scattered protons in the materials relative to that in water were found to be 1.20 for lucite, 1.16 for polyethylene, 1.22 for teflon, and 1.03 for aluminum. The difference between the deposited dose in water and in the phantom materials taken in the center of the proton pencil beam, was estimated from the flux measurements, always taking the different ranges of protons in the materials into account. The estimated dose difference relative to water in 15 cm water equivalent thickness was -2.3% for lucite, -1.7% for polyethylene, -2.5% for teflon, and -0.4% for aluminum. The dose deviation was verified by a measurement using an ionization chamber. It should be noted that the dose error is larger when the effective point of measurement in the material is deeper or when the energy is higher

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.

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

Science.gov (United States)

Li, Zheng; Vendrell, Oriol

2016-01-01

The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2O)n 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. PMID:26798842

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 (applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the

Relaxation-compensated CEST-MRI at 7 T for mapping of creatine content and pH--preliminary application in human muscle tissue in vivo.

Science.gov (United States)

Rerich, Eugenia; Zaiss, Moritz; Korzowski, Andreas; Ladd, Mark E; Bachert, Peter

2015-11-01

The small biomolecule creatine is involved in energy metabolism. Mapping of the total creatine (mostly PCr and Cr) in vivo has been done with chemical shift imaging. Chemical exchange saturation transfer (CEST) allows an alternative detection of creatine via water MRI. Living tissue exhibits CEST effects from different small metabolites, including creatine, with four exchanging protons of its guanidinium group resonating about 2 ppm from the water peak and hence contributing to the amine proton CEST peak. The intermediate exchange rate (≈ 1000 Hz) of the guanidinium protons requires high RF saturation amplitude B1. However, strong B1 fields also label semi-solid magnetization transfer (MT) effects originating from immobile protons with broad linewidths (~kHz) in the tissue. Recently, it was shown that endogenous CEST contrasts are strongly affected by the MT background as well as by T1 relaxation of the water protons. We show that this influence can be corrected in the acquired CEST data by an inverse metric that yields the apparent exchange-dependent relaxation (AREX). AREX has some useful linearity features that enable preparation of both concentration, and--by using the AREX-ratio of two RF irradiation amplitudes B1--purely exchange-rate-weighted CEST contrasts. These two methods could be verified in phantom experiments with different concentration and pH values, but also varying water relaxation properties. Finally, results from a preliminary application to in vivo CEST imaging data of the human calf muscle before and after exercise are presented. The creatine concentration increases during exercise as expected and as confirmed by (31)P NMR spectroscopic imaging. However, the estimated concentrations obtained by our method were higher than the literature values: cCr,rest=24.5±3.74mM to cCr,ex=38.32±13.05mM. The CEST-based pH method shows a pH decrease during exercise, whereas a slight increase was observed by (31)P NMR spectroscopy. Copyright © 2015

R1 correction in amide proton transfer imaging: indication of the influence of transcytolemmal water exchange on CEST measurements.

Science.gov (United States)

Li, Hua; Li, Ke; Zhang, Xiao-Yong; Jiang, Xiaoyu; Zu, Zhongliang; Zaiss, Moritz; Gochberg, Daniel F; Gore, John C; Xu, Junzhong

2015-12-01

Amide proton transfer (APT) imaging may potentially detect mobile proteins/peptides non-invasively in vivo, but its specificity may be reduced by contamination from other confounding effects such as asymmetry of non-specific magnetization transfer (MT) effects and spin-lattice relaxation with rate R1 (=1/T1). Previously reported spillover, MT and R1 correction methods were based on a two-pool model, in which the existence of multiple water compartments with heterogeneous relaxation properties in real tissues was ignored. Such simple models may not adequately represent real tissues, and thus such corrections may be unreliable. The current study investigated the effectiveness and accuracy of correcting for R1 in APT imaging via simulations and in vivo experiments using tumor-bearing rats subjected to serial injections of Gd-DTPA that produced different tissue R1 values in regions of blood-brain-barrier breakdown. The results suggest that conventional measurements of APT contrast (such as APT* and MTRasym ) may be significantly contaminated by R1 variations, while the R1 -corrected metric AREX* was found to be relatively unaffected by R1 changes over a broad range (0.4-1 Hz). Our results confirm the importance of correcting for spin-lattice relaxation effects in quantitative APT imaging, and demonstrate the reliability of using the observed tissue R1 for corrections to obtain more specific and accurate measurements of APT contrast in vivo. The results also indicate that, due to relatively fast transcytolemmal water exchange, the influence of intra- and extracellular water compartments on CEST measurements with seconds long saturation time may be ignored in tumors. Copyright © 2015 John Wiley & Sons, Ltd.

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.

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

International Nuclear Information System (INIS)

Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin

2015-01-01

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

Water-Free Proton-Conducting Membranes for Fuel Cells

Science.gov (United States)

Narayanan, Sekharipuram; Yen, Shiao-Pin

2007-01-01

Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a

Fast hydrogen exchange affects {sup 15}N relaxation measurements in intrinsically disordered proteins

Energy Technology Data Exchange (ETDEWEB)

Kim, Seho; Wu, Kuen-Phon; Baum, Jean, E-mail: jean.baum@rutgers.edu [Rutgers University, Department of Chemistry and Chemical Biology (United States)

2013-03-15

Unprotected amide protons can undergo fast hydrogen exchange (HX) with protons from the solvent. Generally, NMR experiments using the out-and-back coherence transfer with amide proton detection are affected by fast HX and result in reduced signal intensity. When one of these experiments, {sup 1}H-{sup 15}N HSQC, is used to measure the {sup 15}N transverse relaxation rate (R{sub 2}), the measured R{sub 2} rate is convoluted with the HX rate (k{sub HX}) and has higher apparent R{sub 2} values. Since the {sup 15}N R{sub 2} measurement is important for analyzing protein backbone dynamics, the HX effect on the R{sub 2} measurement is investigated and described here by multi-exponential signal decay. We demonstrate these effects by performing {sup 15}N R{sub 2}{sup CPMG} experiments on {alpha}-synuclein, an intrinsically disordered protein, in which the amide protons are exposed to solvent. We show that the HX effect on R{sub 2}{sup CPMG} can be extracted by the derived equation. In conclusion, the HX effect may be pulse sequence specific and results from various sources including the J coupling evolution, the change of steady state water proton magnetization, and the D{sub 2}O content in the sample. To avoid the HX effect on the analysis of relaxation data of unprotected amides, it is suggested that NMR experimental conditions insensitive to the HX should be considered or that intrinsic R{sub 2}{sup CPMG} values be obtained by methods described herein.

Proton nuclear magnetic resonance studies on brain edema

International Nuclear Information System (INIS)

Naruse, S.; Horikawa, Y.; Tanaka, C.; Hirakawa, K.; Nishikawa, H.; Yoshizaki, K.

1982-01-01

The water in normal and edematous brain tissues of rats was studied by the pulse nuclear magnetic resonance (NMR) technique, measuring the longitudinal relaxation time (T1) and the transverse relaxation time (T2). In the normal brain, T1 and T2 were single components, both shorter than in pure water. Prolongation and separation of T2 into two components, one fast and one slow, were the characteristic findings in brain edema induced by both cold injury and triethyl tin (TET), although some differences between the two types of edema existed in the content of the lesion and in the degree of changes in T1 and T2 values. Quantitative analysis of T1 and T2 values in their time course relating to water content demonstrated that prolongation of T1 referred to the volume of increased water in tissues examined, and that two phases of T2 reflected the distribution and the content of the edema fluid. From the analysis of the slow component of T2 versus water content during edema formation, it was demonstrated that the increase in edema fluid was steady, and its content was constant during formation of TET-induced edema. On the contrary, during the formation of cold-injury edema, water-rich edema fluid increased during the initial few hours, and protein-rich edema fluid increased thereafter. It was concluded that proton NMR relaxation time measurements may provide new understanding in the field of brain edema research

Acoustic time-of-flight for proton range verification in water

Energy Technology Data Exchange (ETDEWEB)

Jones, Kevin C.; Avery, Stephen, E-mail: Stephen.Avery@uphs.upenn.edu [Department of Radiation Oncology, University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States); Vander Stappen, François [Ion Beam Applications SA, Louvain-la-Neuve 1348 (Belgium); Sehgal, Chandra M. [Department of Radiology, University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States)

2016-09-15

Purpose: Measurement of the arrival times of thermoacoustic waves induced by pulsed proton dose depositions (protoacoustics) may provide a proton range verification method. The goal of this study is to characterize the required dose and protoacoustic proton range (distance) verification accuracy in a homogeneous water medium at a hospital-based clinical cyclotron. Methods: Gaussian-like proton pulses with 17 μs widths and instantaneous currents of 480 nA (5.6 × 10{sup 7} protons/pulse, 3.4 cGy/pulse at the Bragg peak) were generated by modulating the cyclotron proton source with a function generator. After energy degradation, the 190 MeV proton pulses irradiated a water phantom, and the generated protoacoustic emissions were measured by a hydrophone. The detector position and proton pulse characteristics were varied. The experimental results were compared to simulations. Different arrival time metrics derived from acoustic waveforms were compared, and the accuracy of protoacoustic time-of-flight distance calculations was assessed. Results: A 27 mPa noise level was observed in the treatment room during irradiation. At 5 cm from the proton beam, an average maximum pressure of 5.2 mPa/1 × 10{sup 7} protons (6.1 mGy at the Bragg peak) was measured after irradiation with a proton pulse with 10%–90% rise time of 11 μs. Simulation and experiment arrival times agreed well, and the observed 2.4 μs delay between simulation and experiment is attributed to the difference between the hydrophone’s acoustic and geometric centers. Based on protoacoustic arrival times, the beam axis position was measured to within (x, y) = (−2.0,  0.5) ± 1 mm. After deconvolution of the exciting proton pulse, the protoacoustic compression peak provided the most consistent measure of the distance to the Bragg peak, with an error distribution with mean = − 4.5 mm and standard deviation = 2.0 mm. Conclusions: Based on water tank measurements at a clinical hospital-based cyclotron

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...

Proton NMR study of α-MnH 0.06

Science.gov (United States)

Soloninin, A. V.; Skripov, A. V.; Buzlukov, A. L.; Antonov, V. E.; Antonova, T. E.

2004-07-01

Proton nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates for the solid solution α-MnH 0.06 have been measured over the temperature range 11-297 K and the resonance frequency range 20-90 MHz. A considerable shift and broadening of the proton NMR line and a sharp peak of the spin-lattice relaxation rate are observed near 130 K. These effects are attributed to the onset of antiferromagnetic ordering below the Néel temperature TN≈130 K. The proton NMR line does not disappear in the antiferromagnetic phase; this suggests a small magnitude of the local magnetic fields at H-sites in α-MnH 0.06. The spin-lattice relaxation rate in the paramagnetic phase is dominated by the effects of spin fluctuations.

Optimizing Water Exchange Rates and Rotational Mobility for High-Relaxivity of a Novel Gd-DO3A Derivative Complex Conjugated to Inulin as Macromolecular Contrast Agents for MRI.

Science.gov (United States)

Granato, Luigi; Vander Elst, Luce; Henoumont, Celine; Muller, Robert N; Laurent, Sophie

2018-02-01

Thanks to the understanding of the relationships between the residence lifetime τ M of the coordinated water molecules to macrocyclic Gd-complexes and the rotational mobility τ R of these structures, and according to the theory for paramagnetic relaxation, it is now possible to design macromolecular contrast agents with enhanced relaxivities by optimizing these two parameters through ligand structural modification. We succeeded in accelerating the water exchange rate by inducing steric compression around the water binding site, and by removing the amide function from the DOTA-AA ligand [1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid mono(p-aminoanilide)] (L) previously designed. This new ligand 10[2(1-oxo-1-p-propylthioureidophenylpropyl]-1,4,7,10-tetraazacyclodecane-1,4,7-tetraacetic acid (L 1 ) was then covalently conjugated to API [O-(aminopropyl)inulin] to get the complex API-(GdL 1 )x with intent to slow down the rotational correlation time (τ R ) of the macromolecular complex. The evaluation of the longitudinal relaxivity at different magnetic fields and the study of the 17 O-NMR at variable temperature of the low-molecular-weight compound (GdL 1 ) showed a slight decrease of the τ M value (τM310 = 331 ns vs. τM310 = 450 ns for the GdL complex). Consequently to the increase of the size of the API-(GdL 1 )x complex, the rotational correlation time becomes about 360 times longer compared to the monomeric GdL 1 complex (τ R  = 33,700 ps), which results in an enhanced proton relaxivity. © 2018 Wiley-VHCA AG, Zurich, Switzerland.

Dielectric relaxation and hydrogen bonding interaction in xylitol-water mixtures using time domain reflectometry

Science.gov (United States)

Rander, D. N.; Joshi, Y. S.; Kanse, K. S.; Kumbharkhane, A. C.

2016-01-01

The measurements of complex dielectric permittivity of xylitol-water mixtures have been carried out in the frequency range of 10 MHz-30 GHz using a time domain reflectometry technique. Measurements have been done at six temperatures from 0 to 25 °C and at different weight fractions of xylitol (0 xylitol-water can be well described by Cole-Davidson model having an asymmetric distribution of relaxation times. The dielectric parameters such as static dielectric constant and relaxation time for the mixtures have been evaluated. The molecular interaction between xylitol and water molecules is discussed using the Kirkwood correlation factor ( g eff ) and thermodynamic parameter.

Water versus DNA A new deal for proton transport modeling in biological matter

International Nuclear Information System (INIS)

Champion, C; Quinto, M A; Monti, J M; Galassi, M E; Fojón, O A; Hanssen, J; Rivarola, R D; Week, P F

2015-01-01

Water vapor is a common surrogate of DNA for modeling the proton-induced ionizing processes in living tissue exposed to radiations. The present study aims at scrutinizing the validity of this approximation and then revealing new insights into proton-induced energy transfers by a comparative analysis between water and realistic biological medium. In this context, self-consistent quantum mechanical modeling of the ionization and electron capture processes is reported within the continuum distorted wave-eikonal initial state framework for both isolated water molecules and DNA components impacted by proton beams. (paper)

Ultrasonic relaxation studies associated with n-octylamine-heavy water

International Nuclear Information System (INIS)

Kor, S.K.; Singh, R.K.

1994-01-01

Ultrasonic absorption measurements have been carried out in lyotropic liquid crystalline system n-octylamine/heavy water in the frequency range 5-65 MHz and at temperatures 30 degC and 37 degC at different concentrations of heavy water in octylamine. Velocity has been measured using interferometric technique at 2 MHz at different concentrations of heavy water. Ultrasonic absorption coefficients at different concentrations in the concentration range 0.3-0.9 m.f. heavy water have been found to show a maxima in the absorption curve at critical concentration (∼0.85 m.f. heavy water). This peak has been found to shift towards lower concentrations of heavy water at higher frequencies. Results have been analysed and it has been found that single relaxation process takes place around 30 MHz and this has been attributed to aggregation of octylamine and heavy water molecules. (author). 8 refs., 6 figs., 3 tabs

Relaxation processes in aqueous solutions upon X-ray exposure. Entanglement of electronic and nuclear dynamics

Energy Technology Data Exchange (ETDEWEB)

Unger, Isaak

2017-07-01

About a decade ago new types of electronic non-radiative relaxation processes, involving the environment of an electronically excited or ionized monomer, have been predicted for van der Waals clusters and these were also the first systems where such processes have been detected experimentally. These new autoionization channels encompass the recombination of an electron and a hole, and the energy transfer to a neighboring atom or molecule. Two processes can be distinguished here. In the intermolecular Coulombic decay (ICD) the hole created upon ionization of a monomer is filled by a valence electron of the same species, and the energy released in this electron-hole recombination is used to ionize a neighboring species. In the electron transfer mediated decay (ETMD) the initial hole is filled by an electron from a neighboring species, and the energy released by this recombination is either used to ionize the same neighbor species, or to ionize a third monomer. In more recent experiments on liquid water it has been discovered that these non- local autoionization processes are strongly coupled with ultrafast nuclear dynamics. The core ionization initiates proton motion along a hydrogen donor-bond of the electronically excited water cation. This nuclear dynamics leads to the formation of transient cationic species where a proton is shared by two neighboring water molecules. Subsequent autoionization, either via Auger decay, ICD or ETMD, then occurs from any of such structure transients. This relaxation process is termed proton transfer mediated charge separation, PTM-CS. It has been found in a number of experiments that the probability of PTM-CS to occur depends on the hydrogen-bond strength between the core-ionized molecule and solvent molecules.

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

Localized water suppressed proton spectroscopy has opened up a new field of pathophysiological studies of severe brain ischemia. The signals obtained with the pulse sequences used so far are both T1 and T2 weighted. In order to evaluate the extent to which changes in metabolite signals during...... 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...... containing compounds (CHO) in a 27-ml voxel located in the affected area of the brain. Ten healthy volunteers served as controls. We found no difference in T1 or T2 of the metabolites between the patients and the normal controls. The T2 of CHO was longer than that of NAA and Cr+PCr. Our results indicate...

Complex methyl groups dynamics in [(CH3)4P]3Sb2Br9 (PBA) from low to high temperatures by proton spin-lattice relaxation and narrowing of proton NMR spectrum.

Science.gov (United States)

Latanowicz, L; Medycki, W; Jakubas, R

2009-11-01

Molecular dynamics of a polycrystalline sample of [(CH(3))(4)P](3)Sb(2)Br(9) (PBA) has been studied on the basis of the T(1) (24.7 MHz) relaxation time measurement, the proton second moment of NMR and the earlier published T(1) (90 MHz) relaxation times. The study was performed in a wide range of temperatures (30-337 K). The tunnel splitting omega(T) of the methyl groups was estimated as of low frequency (from kHz to few MHz). The proton spin pairs of the methyl group are known to perform a complex internal motion being a resultant of four components. Three of them involve mass transportation over and through the potential barrier and are characterized by the correlation times tau(3) and tau(T)of the jumps over the barrier and tunnel jumps in the threefold potential of the methyl group and tau(iso) the correlation time of isotropic rotation of the whole TMP cation. For tau(3) and tau(iso) the Arrhenius temperature dependence was assumed, while for tau(T)--the Schrödinger one. The fourth motion causes fluctuations of the tunnel splitting frequency, omega(T), and it is related to the lifetime of the methyl spin at the energy level. The correlation function for this fourth motion (tau(omega) correlation time) has been proposed by Müller-Warmuth et al. In this paper a formula for the correlation function and spectral density of the complex motion made of the above-mentioned four components was derived and used in interpretation of the T(1) relaxation time. The second moment of proton NMR line at temperatures below 50K is four times lower than its value for the rigid structure. The three components of the internal motion characterized by tau(T), tau(H), and tau(iso) were proved to reduce the second moment of the NMR line. The tunnel jumps of the methyl group reduce M(2) at almost 0K, the classical jumps over the barrier reduce M(2) in the vicinity of 50K, while the isotropic motion near 150K. Results of the study on the dynamics of CH(3) groups of TMP cation based on

Identification of structural relaxation in the dielectric response of water

DEFF Research Database (Denmark)

Hansen, Jesper Schmidt; Kisliuk, Alexander; Solokov, Alexei P.

2016-01-01

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....

Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

Energy Technology Data Exchange (ETDEWEB)

Soniat, Marielle; Rick, Steven W., E-mail: srick@uno.edu [Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70148 (United States); Kumar, Revati [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70808 (United States)

2015-07-28

The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

International Nuclear Information System (INIS)

Soniat, Marielle; Rick, Steven W.; Kumar, Revati

2015-01-01

The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface

Paramagnetic metal complexes as potential relaxation agents for NMR imaging

International Nuclear Information System (INIS)

Coroiu, Ilioara; Demco, D. E.; Darabont, Al.; Bogdan, M.

1997-01-01

The development of nuclear magnetic resonance (NMR) imaging technique as a clinical diagnostic modality has prompted the need for a new class of pharmaceuticals. These drugs must be administered to a patient in order to enhance the image contrast between the normal and diseased tissue and/or indicate the status of organ function or blood flow. Paramagnetic compounds are presently undergoing extensive evaluation as contrast agents in magnetic resonance imaging (MRI). These agents increase contrast in MRI by differentially localizing in tissue where they increase the relaxation rates of nearby water protons. The longitudinal R 1 and transverse R 2 relaxivities were measured as a function of molar concentrations for some new paramagnetic complexes like the following: dysprosium, erbium and gadolinium citrates, gadolinium methylene diphosphonate, dysprosium and gadolinium iminodiacetate, manganese para-aminobenzoate and copper nicotinate. The available theoretical approaches for quantitative understanding are presented. (authors)

MO-FG-CAMPUS-JeP1-03: Luminescence Imaging of Water During Proton Beam Irradiation for Range Estimation

International Nuclear Information System (INIS)

Yamamoto, S; Komori, M; Toshito, T; Watabe, H

2016-01-01

Purpose: Since proton therapy has the ability to selectively deliver a dose to a target tumor, the dose distribution should be accurately measured. A precise and efficient method to evaluate the dose distribution is desired. We found that luminescence was emitted from water during proton irradiation and thought this phenomenon could be used for estimating the dose distribution. Methods: For this purpose, we placed water phantoms set on a table with a spot-scanning proton-therapy system, and luminescence images of these phantoms were measured with a high-sensitivity cooled charge coupled device (CCD) camera during proton-beam irradiation. We also conducted the imaging of phantoms of pure-water, fluorescein solution and acrylic block. We made three dimensional images from the projection data. Results: The luminescence images of water phantoms during the proton-beam irradiations showed clear Bragg peaks, and the measured proton ranges from the images were almost the same as those obtained with an ionization chamber. The image of the pure-water phantom also showed almost the same distribution as the tap-water phantom, indicating that the luminescence image was not related to impurities in the water. The luminescence image of fluorescein solution had ∼3 times higher intensity than water, with the same proton range as that of water. The luminescence image of the acrylic phantom had 14.5% shorter proton range than that of water; the proton range in the acrylic phantom was relatively matched with the calculated value. The luminescence images of the tap-water phantom during proton irradiation could be obtained in less than 2 sec. Three dimensional images were successfully obtained which have more quantitative information. Conclusion: Luminescence imaging during proton-beam irradiation has the potential to be a new method for range estimations in proton therapy.

MO-FG-CAMPUS-JeP1-03: Luminescence Imaging of Water During Proton Beam Irradiation for Range Estimation

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, S; Komori, M [Nagoya University, Nagoya, Aichi (Japan); Toshito, T [Nagoya Proton Therapy Center, Nagoya, Aichi (Japan); Watabe, H [Tohoku University, Sendai, Miyagi (Japan)

2016-06-15

Purpose: Since proton therapy has the ability to selectively deliver a dose to a target tumor, the dose distribution should be accurately measured. A precise and efficient method to evaluate the dose distribution is desired. We found that luminescence was emitted from water during proton irradiation and thought this phenomenon could be used for estimating the dose distribution. Methods: For this purpose, we placed water phantoms set on a table with a spot-scanning proton-therapy system, and luminescence images of these phantoms were measured with a high-sensitivity cooled charge coupled device (CCD) camera during proton-beam irradiation. We also conducted the imaging of phantoms of pure-water, fluorescein solution and acrylic block. We made three dimensional images from the projection data. Results: The luminescence images of water phantoms during the proton-beam irradiations showed clear Bragg peaks, and the measured proton ranges from the images were almost the same as those obtained with an ionization chamber. The image of the pure-water phantom also showed almost the same distribution as the tap-water phantom, indicating that the luminescence image was not related to impurities in the water. The luminescence image of fluorescein solution had ∼3 times higher intensity than water, with the same proton range as that of water. The luminescence image of the acrylic phantom had 14.5% shorter proton range than that of water; the proton range in the acrylic phantom was relatively matched with the calculated value. The luminescence images of the tap-water phantom during proton irradiation could be obtained in less than 2 sec. Three dimensional images were successfully obtained which have more quantitative information. Conclusion: Luminescence imaging during proton-beam irradiation has the potential to be a new method for range estimations in proton therapy.

An analysis of the NMR-CT image by the measurement of proton-relaxation times in tissue

International Nuclear Information System (INIS)

Naruse, Shoji; Horikawa, Yoshiharu; Tanaka, Chuzo; Hirakawa, Kimiyoshi; Nishikawa, Hiroyasu; Shimizu, Koji; Kiri, Motosada.

1984-01-01

NMR-CT images were analyzed by measuring the proton-relaxation times in tissues. The NMR-CT images were obtained in 10 normal volunteers and 16 patients with brain tumors with a prototype superconducting magnet (Shimadzu Corp., Japan) operating at 0.2 T and 0.375 T. A smooth T 1 relaxation curve was obtained in each part of the brain and the brain tumor by the use of the data of the NMR-CT image; consequently, the in vivo T 1 value was proved to be reliable. The in vivo T 1 value showed the specific value corresponding to each region of the normal brain in all cases. Cerebral gray matter normally had the longest T 1 value, followed by the medulla oblongata, the pons, and white matter. The T 1 value of each region of the brain varied to the same degree in proportion to the strength of the static magnetic field. The in vivo T 1 values of the brain tumor varied with the histological type. All were longer than any part of the brain parenchyma, being between 480 and 780 msec at 0.2 T. The prolongation of the T 1 value does not always correspond to the degree of the malignancy in a tumor. The in vitro T 1 and T 2 values were also prolonged in all tumors. Although the absolute value of T 1 did not coincide between the in vitro and in vivo data, the tendency of the prolongation was the same between them. This result indicated that the NMR-CT images could be analysed by the use of the data of the in vitro T 1 and T 2 values in the tumor tissues. It is important to analyse the NMR-CT image by both in vivo and in vitro examinations of the relaxation times. (J.P.N.)

Thermal- and pH-Dependent Size Variable Radical Nanoparticles and Its Water Proton Relaxivity for Metal-Free MRI Functional Contrast Agents.

Science.gov (United States)

Morishita, Kosuke; Murayama, Shuhei; Araki, Takeru; Aoki, Ichio; Karasawa, Satoru

2016-09-16

For development of the metal-free MRI contrast agents, we prepared the supra-molecular organic radical, TEMPO-UBD, carrying TEMPO radical, as well as the urea, alkyl group, and phenyl ring, which demonstrate self-assembly behaviors using noncovalent bonds in an aqueous solution. In addition, TEMPO-UBD has the tertiary amine and the oligoethylene glycol chains (OEGs) for the function of pH and thermal responsiveness. By dynamic light scattering and transmission electron microscopy imaging, the resulting self-assembly was seen to form the spherical nanoparticles 10-150 nm in size. On heating, interestingly, the nanoparticles showed a lower critical solution temperature (LCST) behavior having two-step variation. This double-LCST behavior is the first such example among the supra-molecules. To evaluate of the ability as MRI contrast agents, the values of proton ((1)H) longitudinal relaxivity (r1) were determined using MRI apparatus. In conditions below and above CAC at pH 7.0, the distinguishable r1 values were estimated to be 0.17 and 0.21 mM(-1) s(1), indicating the suppression of fast tumbling motion of TEMPO moiety in a nanoparticle. Furthermore, r1 values became larger in the order of pH 7.0 > 9.0 > 5.0. Those thermal and pH dependencies indicated the possibility of metal-fee MRI functional contrast agents in the future.

Mathematical modeling of water mass balance for proton exchange membrane fuel cell

International Nuclear Information System (INIS)

Wan Ramli Wan Daud; Kamaruzzaman Sopian; Jaafar Sahari; Nik Suhaimi Mat Hassan

2006-01-01

Gas and water management are key to achieving good performance from a proton exchange membrane fuel cell (PEMFC) stack. Water plays a critical role in PEMFC. The proton conductivity is increase with the water content. In order to achieve enough hydration, water is normally introduced into the cell externally by a variety of methods such as liquid injection, steam introduction, and humidification of reactants by passing them through humidifiers before entering the cell. In this paper, mathematical modeling of water mass balance for PEMFC at anode and cathode side are proposed by using external humidification and assume that steady state, constant pressure, constant temperature and gases distribution are uniform

Stabilities of protonated water-ammonia clusters

Science.gov (United States)

Sundén, A. E. K.; Støchkel, K.; Hvelplund, P.; Brøndsted Nielsen, S.; Dynefors, B.; Hansen, K.

2018-05-01

Branching ratios of water and ammonia evaporation have been measured for spontaneous evaporation from protonated mixed clusters H+(H2O)n(NH3)m in the size range 0 ≤ n ≤ 11 and 0 ≤ m ≤ 7. Mixed clusters evaporate water except for clusters containing six or more ammonia molecules, indicating the formation of a stable core of one ammonium ion surrounded by four ammonia molecules and a second shell consisting predominantly of water. We relate evaporative branching ratios to free energy differences between the products of competing channels and determine the free energy differences for clusters with up to seven ammonia molecules. Clusters containing up to five ammonia molecules show a very strong scaling of these free energy differences.

MR spectroscopy of liver in overweight children and adolescents: Investigation of 1H T2 relaxation times at 3 T

International Nuclear Information System (INIS)

Chabanova, Elizaveta; Bille, Dorthe S.; Thisted, Ebbe; Holm, Jens-Christian; Thomsen, Henrik S.

2012-01-01

Objective: The objective was to investigate T 2 relaxation values and to optimize hepatic fat quantification using proton MR spectroscopy ( 1 H MRS) at 3 T in overweight and obese children and adolescents. Subjects: The study included 123 consecutive children and adolescents with a body mass index above the 97th percentile according to age and sex. 1 H MR spectroscopy was performed at 3.0 T using point resolved spectroscopy sequence with series TE. T 2 relaxation values and hepatic fat content corrected for the T 2 relaxation effects were calculated. Results: T 2 values for water ranged from 22 ms to 42 ms (mean value 28 ms) and T 2 values for fat ranged from 36 ms to 99 ms (mean value 64 ms). Poor correlation was observed: (1) between T 2 relaxation times of fat and T 2 relaxation times of water (correlation coefficient r = 0.038, P = 0.79); (2) between T 2 relaxation times of fat and fat content (r = 0.057, P = 0.69); (3) between T 2 relaxation times of water and fat content (r = 0.160, P = 0.26). Correlation between fat peak content and the T 2 corrected fat content decreased with increasing echo time TE: r = 0.97 for TE = 45, r = 0.93 for TE = 75, r = 0.89 for TE = 105, P 1 H MRS at 3 T is an effective technique for measuring hepatic fat content in overweight and obese children and adolescents. It is necessary to measure T 2 relaxation values and to correct the spectra for the T 2 relaxation effects in order to obtain an accurate estimate of the hepatic fat content.

Oxygen Mapping within Healthy and Acutely Infarcted Brain Tissue in Humans Using the NMR Relaxation of Lipids: A Proof-Of-Concept Translational Study.

Science.gov (United States)

Colliez, Florence; Safronova, Marta M; Magat, Julie; Joudiou, Nicolas; Peeters, André P; Jordan, Bénédicte F; Gallez, Bernard; Duprez, Thierry

2015-01-01

The clinical applicability of brain oxygenation mapping using the MOBILE (Mapping of Oxygen By Imaging Lipids relaxation Enhancement) magnetic resonance (MR) technique was assessed in the clinical setting of normal brain and of acute cerebral ischemia as a founding proof-of-concept translational study. Changes in the oxygenation level within healthy brain tissue can be detected by analyzing the spin-lattice proton relaxation ('Global T1' combining water and lipid protons) because of the paramagnetic properties of molecular oxygen. It was hypothesized that selective measurement of the relaxation of the lipid protons ('Lipids T1') would result in enhanced sensitivity of pO2 mapping because of higher solubility of oxygen in lipids than in water, and this was demonstrated in pre-clinical models using the MOBILE technique. In the present study, 12 healthy volunteers and eight patients with acute (48-72 hours) brain infarction were examined with the same clinical 3T MR system. Both Lipids R1 (R1 = 1/T1) and Global R1 were significantly different in the infarcted area and the contralateral unaffected brain tissue, with a higher statistical significance for Lipids R1 (median difference: 0.408 s-1; pbrain tissue of stroke patients were not significantly different from the R1 values calculated in the brain tissue of healthy volunteers. The main limitations of the present prototypic version of the MOBILE sequence are the long acquisition time (4 min), hampering robustness of data in uncooperative patients, and a 2 mm slice thickness precluding accurate measurements in small infarcts because of partial volume averaging effects.

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.)

Proton production, neutralisation and reduction in a floating water bridge

International Nuclear Information System (INIS)

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

2015-01-01

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. (paper)

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.

Proton-conductive nano zeolite-PVA composite film as a new water-absorbing electrolyte for water electrolysis

Directory of Open Access Journals (Sweden)

M. Nishihara

2018-03-01

Full Text Available In this study, organic-inorganic composite electrolyte membranes are developed for a novel water-absorbing porous electrolyte water electrolysis cell. As the materials of the composite electrolyte membrane, 80 wt% of a proton-conducting nano zeolite (H-MFI as an electrolyte and 20 wt% of poly(vinyl alcohol (PVA as a cross-linkable matrix are used. The nano zeolite is prepared by a milling process. The nano zeolite-PVA composite membrane precursors are prepared by spraying onto a substrate, followed by cross-linking. The resulting nano zeolite-cross-linked PVA composite films are then evaluated for their properties such as proton conductivity as electrolyte membranes for the water-absorbing porous electrolyte water electrolysis cell. It is confirmed that conventional materials such as zeolites and PVA can be used for the water electrolysis as an electrolyte.

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

International Nuclear Information System (INIS)

Poblano-Salas, C.A.; Barceinas-Sanchez, J.D.O.

2009-01-01

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.

Highly Water-Stable Lanthanide-Oxalate MOFs with Remarkable Proton Conductivity and Tunable Luminescence.

Science.gov (United States)

Zhang, Kun; Xie, Xiaoji; Li, Hongyu; Gao, Jiaxin; Nie, Li; Pan, Yue; Xie, Juan; Tian, Dan; Liu, Wenlong; Fan, Quli; Su, Haiquan; Huang, Ling; Huang, Wei

2017-09-01

Although proton conductors derived from metal-organic frameworks (MOFs) are highly anticipated for various applications including solid-state electrolytes, H 2 sensors, and ammonia synthesis, they are facing serious challenges such as poor water stability, fastidious working conditions, and low proton conductivity. Herein, we report two lanthanide-oxalate MOFs that are highly water stable, with so far the highest room-temperature proton conductivity (3.42 × 10 -3 S cm -1 ) under 100% relative humidity (RH) among lanthanide-based MOFs and, most importantly, luminescent. Moreover, the simultaneous response of both the proton conductivity and luminescence intensity to RH allows the linkage of proton conductivity with luminescence intensity. This way, the electric signal of proton conductivity variation versus RH will be readily translated to optical signal of luminescence intensity, which can be directly visualized by the naked eye. If proper lanthanide ions or even transition-metal ions are used, the working wavelengths of luminescence emissions can be further extended from visible to near infrared light for even wider-range applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nuclear magnetic resonance study of diffusion and relaxation in hydrating white cement pastes of different water content

International Nuclear Information System (INIS)

Nestle, Nikolaus; Galvosas, Petrik; Geier, Oliver; Zimmermann, Christian; Dakkouri, Marwan; Karger, Jorg

2001-01-01

While the nuclear spin relaxation time changes in hydrating cement materials have been widely studied by various groups during the last 20 years, data on the self-diffusion behavior of the pore water during hydration of a cement paste are much scarcer. Taking advantage of improved spectrometer hardware for pulsed field gradient diffusometry and a specialized pulse sequence which is designed to compensate the detrimental effects of inner magnetic field gradients in the sample we have studied the water self-diffusion behavior in pastes prepared from white cement at various water/cement ratios. For the same mixtures, studies of the transverse spin relaxation behavior were also conducted. A comparison of the results from both techniques shows that the diffusion coefficient starts to decrease only much later than the relaxation times for all pastes studied. [copyright] 2001 American Institute of Physics

Human whole-blood (1)H2O longitudinal relaxation with normal and high-relaxivity contrast reagents: influence of trans-cell-membrane water exchange.

Science.gov (United States)

Wilson, Gregory J; Woods, Mark; Springer, Charles S; Bastawrous, Sarah; Bhargava, Puneet; Maki, Jeffrey H

2014-12-01

Accurate characterization of contrast reagent (CR) longitudinal relaxivity in whole blood is required to predict arterial signal intensity in contrast-enhanced MR angiography (CE-MRA). This study measured the longitudinal relaxation rate constants (R1 ) over a concentration range for non-protein-binding and protein-binding CRs in ex vivo whole blood and plasma at 1.5 and 3.0 Tesla (T) under physiologic arterial conditions. Relaxivities of gadoteridol, gadobutrol, gadobenate, and gadofosveset were measured for [CR] from 0 to 18 mM [mmol(CR)/L(blood)]: the latter being the upper limit of what may be expected in CE-MRA. In plasma, the (1) H2 O R1 [CR]-dependence was nonlinear for gadobenate and gadofosveset secondary to CR interactions with the serum macromolecule albumin, and was well described by an analytical expression for effective 1:1 binding stoichiometry. In whole blood, the (1) H2 O R1 [CR]-dependence was markedly non-linear for all CRs, and was well-predicted by an expression for equilibrium exchange of water molecules between plasma and intracellular spaces using a priori parameter values only. In whole blood, (1) H2 O R1 exhibits a nonlinear relationship with [CR] over 0 to 18 mM CR. The nonlinearity is well described by exchange of water between erythrocyte and plasma compartments, and is particularly evident for high relaxivity CRs. © 2013 Wiley Periodicals, Inc.

Water calorimetry and ionization chamber dosimetry in an 85-MeV clinical proton beam.

Science.gov (United States)

Palmans, H; Seuntjens, J; Verhaegen, F; Denis, J M; Vynckier, S; Thierens, H

1996-05-01

In recent years, the increased use of proton beams for clinical purposes has enhanced the demand for accurate absolute dosimetry for protons. As calorimetry is the most direct way to establish the absorbed dose and because water has recently been accepted as standard material for this type of beam, the importance of water calorimetry is obvious. In this work we report water calorimeter operation in an 85-MeV proton beam and a comparison of the absorbed dose to water measured by ionometry with the dose resulting from water calorimetric measurements. To ensure a proper understanding of the heat defect for defined impurities in water for this type of radiation, a relative response study was first done in comparison with theoretical calculations of the heat defect. The results showed that pure hypoxic water and hydrogen-saturated water yielded the same response with practically zero heat defect, in agreement with the model calculations. The absorbed dose inferred from these measurements was then compared with the dose derived from ionometry by applying the European Charged Heavy Particle Dosimetry (ECHED) protocol. Restricting the comparison to chambers recommended in the protocol, the calorimeter dose was found to be 2.6% +/- 0.9% lower than the average ionometry dose. In order to estimate the significance of chamber-dependent effects in this deviation, measurements were performed using a set of ten ionization chambers of five different types. The maximum internal deviation in the ionometry results amounted to 1.1%. We detected no systematic chamber volume dependence, but observed a small but systematic effect of the chamber wall thickness. The observed deviation between calorimetry and ionometry can be attributed to a combination of the value of (Wair/e)p for protons, adopted in the ECHED protocol, the mass stopping power ratios of water to air for protons, and possibly small ionization chamber wall effects.

Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer

Science.gov (United States)

Chen, Mohan; Zheng, Lixin; Santra, Biswajit; Ko, Hsin-Yu; DiStasio, Robert A., Jr.; Klein, Michael L.; Car, Roberto; Wu, Xifan

2018-03-01

Proton transfer via hydronium and hydroxide ions in water is ubiquitous. It underlies acid-base chemistry, certain enzyme reactions, and even infection by the flu. Despite two centuries of investigation, the mechanism underlying why hydroxide diffuses slower than hydronium in water is still not well understood. Herein, we employ state-of-the-art density-functional-theory-based molecular dynamics—with corrections for non-local van der Waals interactions, and self-interaction in the electronic ground state—to model water and hydrated water ions. At this level of theory, we show that structural diffusion of hydronium preserves the previously recognized concerted behaviour. However, by contrast, proton transfer via hydroxide is less temporally correlated, due to a stabilized hypercoordination solvation structure that discourages proton transfer. Specifically, the latter exhibits non-planar geometry, which agrees with neutron-scattering results. Asymmetry in the temporal correlation of proton transfer leads to hydroxide diffusing slower than hydronium.

A proton wire and water channel revealed in the crystal structure of isatin hydrolase

DEFF Research Database (Denmark)

Bjerregaard-Andersen, Kaare; Sommer, Theis; Jensen, Jan Kristian

2014-01-01

to a novel family of metalloenzymes that include the bacterial kynurenine formamidase. The product state, mimicked by bound thioisatinate, reveals a water molecule that bridges the thioisatinate to a proton wire in an adjacent water channel and thus allows the proton released by the reaction to escape only...... when the product is formed. The functional proton wire present in IH-b represents a unique catalytic feature common to all hydrolases is here trapped and visualized for the first time. The local molecular environment required to coordinate thioisatinate allows stronger and more confident identification...

A diffusion model-free framework with echo time dependence for free-water elimination and brain tissue microstructure characterization.

Science.gov (United States)

Molina-Romero, Miguel; Gómez, Pedro A; Sperl, Jonathan I; Czisch, Michael; Sämann, Philipp G; Jones, Derek K; Menzel, Marion I; Menze, Bjoern H

2018-03-23

The compartmental nature of brain tissue microstructure is typically studied by diffusion MRI, MR relaxometry or their correlation. Diffusion MRI relies on signal representations or biophysical models, while MR relaxometry and correlation studies are based on regularized inverse Laplace transforms (ILTs). Here we introduce a general framework for characterizing microstructure that does not depend on diffusion modeling and replaces ill-posed ILTs with blind source separation (BSS). This framework yields proton density, relaxation times, volume fractions, and signal disentanglement, allowing for separation of the free-water component. Diffusion experiments repeated for several different echo times, contain entangled diffusion and relaxation compartmental information. These can be disentangled by BSS using a physically constrained nonnegative matrix factorization. Computer simulations, phantom studies, together with repeatability and reproducibility experiments demonstrated that BSS is capable of estimating proton density, compartmental volume fractions and transversal relaxations. In vivo results proved its potential to correct for free-water contamination and to estimate tissue parameters. Formulation of the diffusion-relaxation dependence as a BSS problem introduces a new framework for studying microstructure compartmentalization, and a novel tool for free-water elimination. © 2018 International Society for Magnetic Resonance in Medicine.

Dielectric relaxation in Yb-doped SrZrO3

International Nuclear Information System (INIS)

Kamishima, O; Abe, Y; Ishii, T; Kawamura, J; Hattori, T

2004-01-01

The dielectric constant of the proton conductor SrZr 1-x Yb x O 3 (x 0-0.1) was measured as a function of temperature and frequency. Two well-defined relaxation peaks were observed in SrZrO 3 doped with more than 1 mol% of Yb. The assignment of the two dielectric relaxations is discussed in terms of IR spectra and by free energy calculation for a miscibility of dopant Yb ions. The Yb concentration dependence of the relaxation strength of the two dielectric relaxations is in agreement with the results calculated from the free energy. The two relaxations can be assigned to a reorientation of a single Yb-OH dipole and of Yb-OH dipoles associated with Yb-clusters. The attractive energy for Yb-clustering in SrZrO 3 is evaluated at about -85 meV

Water interactions with varying molecular states of bovine casein: 2H NMR relaxation studies

International Nuclear Information System (INIS)

Kumosinski, T.F.; Pessen, H.; Prestrelski, S.J.; Farrell, H.M. Jr.

1987-01-01

The caseins occur in milk as spherical colloidal complexes of protein and salts with an average diameter of 1200 A, the casein micelles. Removal of Ca2+ is thought to result in their dissociation into smaller protein complexes stabilized by hydrophobic interactions and called submicelles. Whether these submicelles actually occur within the micelles as discrete particles interconnected by calcium phosphate salt bridges has been the subject of much controversy. A variety of physical measurements have shown that casein micelles contain an inordinately high amount of trapped water (2 to 7 g H 2 O/g protein). With this in mind it was of interest to determine if NMR relaxation measurements could detect the presence of this trapped water within the micelles, and to evaluate whether it is a continuum with picosecond correlation times or is associated in part with discrete submicellar structures with nanosecond motions. For this purpose the variations in 2 H NMR longitudinal and transverse relaxation rates of water with protein concentration were determined for bovine casein at various temperatures, under both submicellar and micellar conditions. D 2 O was used instead of H 2 O to eliminate cross-relaxation effects. From the protein concentration dependence of the relaxation rates, the second virial coefficient of the protein was obtained by nonlinear regression analysis. Using either an isotropic tumbling or an intermediate asymmetry model, degrees of hydration, v, and correlation times, tau c, were calculated for the caseins; from the latter parameter the Stokes radius, r, was obtained. Next, estimates of molecular weights were obtained from r and the partial specific volume. Values were in the range of those published from other methodologies for the submicelles

Stereoselective and stereospecific effects in the formation of heteronuclear tartrate complexes of 3d- and 4f-elements from proton magnetic relaxation data

International Nuclear Information System (INIS)

Sal'nikov, Yu.I.; Chevela, V.V.

1987-01-01

A new approach to identification of stereoselective and stereospecific effects in the formation of heteronuclear tartrate complexes of 3d- and 4f-elements according to proton magnetic relaxation data is developed. At the first stage comparison of experimental dependences of the property measured (relaxation efficiency coefficient, Bjerrum function etc.) on the consentrational parameters is conducted. Their different course in systems with dH 4 L (d-tartaric acid) and dlH 4 L (dl-tartaric acid) points out to the presence of stereoeffects. Then, using mathematical simulation the most true stoichiometry of complex particles is determined as well as optimized values of their stability constants and intensity factors. The method is used when investigating the following systems: Fe 3+ -dH 4 L(dlH 4 L), Ln 3+ -dH 4 L(dlH 4 L), Fe 3+ -Ln 3+ -dH 4 L(dlH 4 L)(Ln 3+ -Gd 3+ , Ho 3+ , Er 3+ , Tm 3+ )

Water in Brain Edema : Observations by the Pulsed Nuclear Magnetic Resonance Technique

NARCIS (Netherlands)

GO, KG; Edzes, HT

The state of water in three types of brain edema and in normal brain of the rat was studied by the pulsed nuclear magnetic resonance (NMR) technique. In cold-induced edema and in osmotic edema both in cortex and in white matter, the water protons have longer nuclear magnetic relaxation times than in

Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

Energy Technology Data Exchange (ETDEWEB)

Sode, Olaseni; Voth, Gregory A., E-mail: gavoth@uchicago.edu [Department of Chemistry, James Franck Institute, Institute for Biophysical Dynamics, Computation Institute, The University of Chicago, Chicago, Illinois 60637, USA and Computing, Environment and Life Sciences, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

2014-12-14

Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A{sup 2−}, a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A{sup 2-} by closing a cavity that could otherwise fill with water near the proximal Fe of the active site.

Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

International Nuclear Information System (INIS)

Sode, Olaseni; Voth, Gregory A.

2014-01-01

Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A 2− , a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A 2- by closing a cavity that could otherwise fill with water near the proximal Fe of the active site

Generation and relaxation of high rank coherences in AX3 systems in a selectively methionine labelled SH2 domain

International Nuclear Information System (INIS)

Kloiber, Karin; Fischer, Michael; Ledolter, Karin; Nagl, Michael; Schmid, Walther; Konrat, Robert

2007-01-01

The usefulness of selective isotope labelling patterns is demonstrated using the C-terminal SH2 domain of PLC-γ1 selectively 13 C labelled at methionine methyl groups. We demonstrate the generation and relaxation of coherences that are second rank in protons and first rank in carbons that derive from quadrupolar order in protons. The decay rates of second rank double quantum proton coherences are measured. These terms exhibit fewer channels for cross-correlated relaxation compared to single quantum coherences. Our results indicate the potential application of the measurement of high order proton coherences to the analysis of dynamics in methyl-bearing side chains

The freezing of water bonded in the wheat (Triticum aestivum L.) grain studied by means protons magnetic relaxation method; Zamarzanie wody zwiazanej w ziarnach pszenicy (Triticum aestivum L.) badane metoda relaksacji magnetycznej dla protonow

Energy Technology Data Exchange (ETDEWEB)

Haranczyk, H.; Jasinski, G. [Inst. Fizyki, Uniwersytet Jagiellonski, Cracow (Poland); Strzalka, K. [Inst. Biologii Molekularnej, Uniwersytet Jagiellonski, Cracow (Poland)

1994-12-31

Some biological aspects of water freezing in the wheat grain have been studied using NMR methods. Measuring of the relaxation times for freezing and liquid water shown absence of T{sub 2}{approx}100 {mu}s and T{sub 2}{approx}1 ms separated components what pointed for some different way of water bonding. 7 refs, 12 figs, 2 tabs.

Low-field one-dimensional and direction-dependent relaxation imaging of bovine articular cartilage

Science.gov (United States)

Rössler, Erik; Mattea, Carlos; Mollova, Ayret; Stapf, Siegfried

2011-12-01

The structure of articular cartilage is separated into three layers of differently oriented collagen fibers, which is accompanied by a gradient of increasing glycosaminoglycan (GAG) and decreasing water concentration from the top layer towards the bone interface. The combined effect of these structural variations results in a change of the longitudinal and transverse relaxation times as a function of the distance from the cartilage surface. In this paper, this dependence is investigated at a magnetic field strength of 0.27 T with a one-dimensional depth resolution of 50 μm on bovine hip and stifle joint articular cartilage. By employing this method, advantage is taken of the increasing contrast of the longitudinal relaxation rate found at lower magnetic field strengths. Furthermore, evidence for an orientational dependence of relaxation times with respect to an axis normal to the surface plane is given, an observation that has recently been reported using high-field MRI and that was explained by preferential orientations of collagen bundles in each of the three cartilage zones. In order to quantify the extent of a further contrast mechanism and to estimate spatially dependent glycosaminoglycan concentrations, the data are supplemented by proton relaxation times that were acquired in bovine articular cartilage that was soaked in a 0.8 mM aqueous Gd ++ solution.

Lanthanide(III) complexes of a mono(methylphosphonate) analogue of H4dota: the influence of protonation of the phosphonate moiety on the TSAP/SAP isomer ratio and the water exchange rate.

Science.gov (United States)

Rudovský, Jakub; Cígler, Petr; Kotek, Jan; Hermann, Petr; Vojtísek, Pavel; Lukes, Ivan; Peters, Joop A; Vander Elst, Luce; Muller, Robert N

2005-04-08

A monophosphonate analogue of H4dota, 1,4,7,10-tetraazacyclododecane-4,7,10-tris(carboxymethyl)-1-methylphosphonic acid (H5do3aP), and its complexes with lanthanides were synthesized. Multinuclear NMR studies reveal that, in aqueous solution, lanthanide(III) complexes of the ligand exhibit structures analogous to those of H4dota complexes. Thus, the central ion is nine-coordinate, surrounded by four nitrogen atoms, three acetate and one phosphonate oxygen atoms, and one water molecule in an apical position. For complexes of H5do3aP with Ln(III) ions in the middle of the series, the abundance of the desired twisted square-antiprismatic (TSAP) isomer is higher than for the corresponding H4dota complexes. The TSAP/square-antiprismatic (SAP) isomer ratio is highly sensitive to protonation of the phosphonate group: a higher abundance of the TSAP isomer was found in acidic solutions. The microscopic protonation constants of the TSAP isomers are higher than those of the SAP isomers. The presence of one water molecule in the first coordination sphere of the complexes in the pH region studied (pH 2.5-7.0) is confirmed by 17O NMR spectroscopy. The results of a simultaneous fit of variable-temperature 17O NMR relaxation data and 1H NMRD profiles show that the residence time of water (tauM) in the Gd(III) complex is much smaller than for [Gd(dota)(H2O)]-. The exchange rate appears to be dependent on the pH of the solution. The values of tauM are 37, 40, and 14 ns at pH 2.5, 4.7, and 7.0, respectively. These observations can be explained by an extensive second-sphere hydrogen-bonding network that varies with the state of protonation of the phosphonate moiety. Upon protonation of the complex, the second-sphere hydration probably becomes more ordered, which may result in a decrease in penetrability and an increase in tauM. The relaxivity of the Gd(III) complex is almost independent of the pH and is equal to 4.7 s(-1) mM(-1) (20 MHz, pH 7 and 37 degrees C). The solid

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.

Superconductivity and fast proton transport in nanoconfined water

Science.gov (United States)

Johnson, K. H.

2018-04-01

A real-space molecular-orbital density-wave 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 K (-43 °C).

Thermodynamics of proton binding at the alumina-water interface revisited

Energy Technology Data Exchange (ETDEWEB)

Morel, J.P.; Morel-Desrosiers, N. [Laboratoire de Thermodynamique des Solutions et des Polymeres, UMR CNRS 6003, Universite Blaise Pascal, 24 avenue des Landais, 63177 Aubiere cedex (France); Guillaud, A.; Marmier, N. [Laboratoire de Radiochimie, Sciences Analytiques et Environnement, EA 1175, Universite de Nice, 28 avenue de Valrose, 06108 Nice cedex 2 (France)

2005-07-01

Full text of publication follows: Since sorption on natural or synthetic materials can attenuate the migration of the radionuclides, sorption reactions have to be taken into account in repository performance assessment models. In order to check these models at different temperatures, experimental data such as the enthalpies of sorption are thus required. Highly sensitive micro-calorimeters can now be used to determine the heat effects accompanying the sorption of radionuclides on oxide-water interfaces, but enthalpies of sorption cannot be extracted from microcalorimetric data without a clear knowledge of the thermodynamics of protonation and deprotonation of the oxide surface. However, the values reported in the literature show large discrepancies and one must conclude that, amazingly, this fundamental problem of proton binding is not yet resolved. We have thus undertaken to measure by titration micro-calorimetry the heat effects accompanying proton exchange at the alumina-water interface at 25 deg. C. Based on (i) the surface sites speciation provided by a surface complexation model (built from acid-base titrations at 25 deg. C), and (ii) results of the microcalorimetric experiments, calculations have been made to extract the enthalpy variations associated respectively to protonation and deprotonation of the alumina surface. In a second step, the protonation and deprotonation enthalpy values have been used to calculate the alumina surface acidity constants at 60 deg. C via the Van't Hoff equation. Then, a theoretical titration curve at 60 deg. C has been calculated and compared to the experimental alumina surface titration curve. A good agreement between the predicted acid-base titration curve and the experimental one was observed. (authors)

Thermodynamics of proton binding at the alumina-water interface revisited

International Nuclear Information System (INIS)

Morel, J.P.; Morel-Desrosiers, N.; Guillaud, A.; Marmier, N.

2005-01-01

Full text of publication follows: Since sorption on natural or synthetic materials can attenuate the migration of the radionuclides, sorption reactions have to be taken into account in repository performance assessment models. In order to check these models at different temperatures, experimental data such as the enthalpies of sorption are thus required. Highly sensitive micro-calorimeters can now be used to determine the heat effects accompanying the sorption of radionuclides on oxide-water interfaces, but enthalpies of sorption cannot be extracted from microcalorimetric data without a clear knowledge of the thermodynamics of protonation and deprotonation of the oxide surface. However, the values reported in the literature show large discrepancies and one must conclude that, amazingly, this fundamental problem of proton binding is not yet resolved. We have thus undertaken to measure by titration micro-calorimetry the heat effects accompanying proton exchange at the alumina-water interface at 25 deg. C. Based on (i) the surface sites speciation provided by a surface complexation model (built from acid-base titrations at 25 deg. C), and (ii) results of the microcalorimetric experiments, calculations have been made to extract the enthalpy variations associated respectively to protonation and deprotonation of the alumina surface. In a second step, the protonation and deprotonation enthalpy values have been used to calculate the alumina surface acidity constants at 60 deg. C via the Van't Hoff equation. Then, a theoretical titration curve at 60 deg. C has been calculated and compared to the experimental alumina surface titration curve. A good agreement between the predicted acid-base titration curve and the experimental one was observed. (authors)

Leading coordinate analysis of reaction pathways in proton chain transfer: Application to a two-proton transfer model for the green fluorescent protein

International Nuclear Information System (INIS)

Wang Sufan; Smith, Sean C.

2006-01-01

The 'leading coordinate' approach to computing an approximate reaction pathway, with subsequent determination of the true minimum energy profile, is applied to a two-proton chain transfer model based on the chromophore and its surrounding moieties within the green fluorescent protein (GFP). Using an ab initio quantum chemical method, a number of different relaxed energy profiles are found for several plausible guesses at leading coordinates. The results obtained for different trial leading coordinates are rationalized through the calculation of a two-dimensional relaxed potential energy surface (PES) for the system. Analysis of the 2-D relaxed PES reveals that two of the trial pathways are entirely spurious, while two others contain useful information and can be used to furnish starting points for successful saddle-point searches. Implications for selection of trial leading coordinates in this class of proton chain transfer reactions are discussed, and a simple diagnostic function is proposed for revealing whether or not a relaxed pathway based on a trial leading coordinate is likely to furnish useful information

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

Rotational and translational dynamics and their relation to hydrogen bond lifetimes in an ionic liquid by means of NMR relaxation time experiments and molecular dynamics simulation

Science.gov (United States)

Strate, Anne; Neumann, Jan; Overbeck, Viviane; Bonsa, Anne-Marie; Michalik, Dirk; Paschek, Dietmar; Ludwig, Ralf

2018-05-01

We report a concerted theoretical and experimental effort to determine the reorientational dynamics as well as hydrogen bond lifetimes for the doubly ionic hydrogen bond +OH⋯O- in the ionic liquid (2-hydroxyethyl)trimethylammonium bis(trifluoromethylsulfonyl)imide [Ch][NTf2] by using a combination of NMR relaxation time experiments, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations. Due to fast proton exchange, the determination of rotational correlation times is challenging. For molecular liquids, 17O-enhanced proton relaxation time experiments have been used to determine the rotational correlation times for the OH vectors in water or alcohols. As an alternative to those expensive isotopic substitution experiments, we employed a recently introduced approach which is providing access to the rotational dynamics from a single NMR deuteron quadrupolar relaxation time experiment. Here, the deuteron quadrupole coupling constants (DQCCs) are obtained from a relation between the DQCC and the δ1H proton chemical shifts determined from a set of DFT calculated clusters in combination with experimentally determined proton chemical shifts. The NMR-obtained rotational correlation times were compared to those obtained from MD simulations and then related to viscosities for testing the applicability of popular hydrodynamic models. In addition, hydrogen bond lifetimes were derived, using hydrogen bond population correlation functions computed from MD simulations. Here, two different time domains were observed: The short-time contributions to the hydrogen lifetimes and the reorientational correlation times have roughly the same size and are located in the picosecond range, whereas the long-time contributions decay with relaxation times in the nanosecond regime and are related to rather slow diffusion processes. The computed average hydrogen bond lifetime is dominated by the long-time process, highlighting the importance and longevity of

Relaxation Time of High-Density Amorphous Ice

Science.gov (United States)

Handle, Philip H.; Seidl, Markus; Loerting, Thomas

2012-06-01

Amorphous water plays a fundamental role in astrophysics, cryoelectron microscopy, hydration of matter, and our understanding of anomalous liquid water properties. Yet, the characteristics of the relaxation processes taking place in high-density amorphous ice (HDA) are unknown. We here reveal that the relaxation processes in HDA at 110-135 K at 0.1-0.2 GPa are of collective and global nature, resembling the alpha relaxation in glassy material. Measured relaxation times suggest liquid-like relaxation characteristics in the vicinity of the crystallization temperature at 145 K. By carefully relaxing pressurized HDA for several hours at 135 K, we produce a state that is closer to the ideal glass state than all HDA states discussed so far in literature.

Methyl group rotation and nuclear relaxation at low temperatures

International Nuclear Information System (INIS)

Zweers, A.E.

1976-01-01

This thesis deals with the proton spin-lattice relaxation of some methyl group compounds at liquid helium temperatures. In these molecular crystals, an energy difference between the ground and first rotational state of the methyl group occurs, the so-called tunnelling splitting, which is of the order of a few degrees Kelvin. This means that the high temperature approximation is inappropriate for the description of the occupation densities of the two lowest rotational levels. A description of the properties of the methyl group in connection with relaxation

SU-C-207A-04: Accuracy of Acoustic-Based Proton Range Verification in Water

International Nuclear Information System (INIS)

Jones, KC; Sehgal, CM; Avery, S; Vander Stappen, F

2016-01-01

Purpose: To determine the accuracy and dose required for acoustic-based proton range verification (protoacoustics) in water. Methods: Proton pulses with 17 µs FWHM and instantaneous currents of 480 nA (5.6 × 10 7 protons/pulse, 8.9 cGy/pulse) were generated by a clinical, hospital-based cyclotron at the University of Pennsylvania. The protoacoustic signal generated in a water phantom by the 190 MeV proton pulses was measured with a hydrophone placed at multiple known positions surrounding the dose deposition. The background random noise was measured. The protoacoustic signal was simulated to compare to the experiments. Results: The maximum protoacoustic signal amplitude at 5 cm distance was 5.2 mPa per 1 × 10 7 protons (1.6 cGy at the Bragg peak). The background random noise of the measurement was 27 mPa. Comparison between simulation and experiment indicates that the hydrophone introduced a delay of 2.4 µs. For acoustic data collected with a signal-to-noise ratio (SNR) of 21, deconvolution of the protoacoustic signal with the proton pulse provided the most precise time-of-flight range measurement (standard deviation of 2.0 mm), but a systematic error (−4.5 mm) was observed. Conclusion: Based on water phantom measurements at a clinical hospital-based cyclotron, protoacoustics is a potential technique for measuring the proton Bragg peak range with 2.0 mm standard deviation. Simultaneous use of multiple detectors is expected to reduce the standard deviation, but calibration is required to remove systematic error. Based on the measured background noise and protoacoustic amplitude, a SNR of 5.3 is projected for a deposited dose of 2 Gy.

Magnetic-relaxation method of analysis of inorganic substances

International Nuclear Information System (INIS)

Popel', A.A.

1978-01-01

The magnetic-relaxation method is considered of the quantitative analysis of inorganic substances based on time dependence of magnetic nuclei relaxation on the quantity of paramagnetic centres in a solution. The characteristic is given of some methods of measuring nuclear magnetic relaxation times: method of weak oscillation generator and pulse methods. The effect of temperature, general solution viscosity, diamagnetic salt concentration, medium acidity on nuclear relaxation velocity is described. The determination sensitivity is estimated and the means of its increase definable concentration intervals and method selectivity are considered. The method application when studying complexing in the solution is described. A particular attention is given to the investigation of heteroligand homocentre, heterocentre and protonated complexes as well as to the problems of particle exchange of the first coordination sphere with particles from the mass of solution. The equations for equilibrium constant calculation in different systems are given. Possibilities of determining diamagnetic ions by the magnetic-relaxation method using paramagnetic indicators are confirmed by the quantitative analysis of indium, gallium, thorium and scandium in their salt solutions

Effect of glycidyl methacrylate (GMA) incorporation on water uptake and conductivity of proton exchange membranes

Science.gov (United States)

Sproll, Véronique; Schmidt, Thomas J.; Gubler, Lorenz

2018-03-01

The aim of this work was to investigate how hygroscopic moieties like hydrolyzed glycidyl methacrylate (GMA) influence the properties of sulfonated polysytrene based proton exchange membranes (PEM). Therefore, several membranes were synthesized by electron beam treatment of the ETFE (ethylene-alt-tetrafluoroethylene) base film with a subsequent co-grafting of styrene and GMA at different ratios. The obtained membranes were sulfonated to introduce proton conducting groups and the epoxide moiety of the GMA unit was hydrolyzed for a better water absorption. The PEM was investigated regarding its structural composition, water uptake and through-plane conductivity. It could be shown that the density of sulfonic acid groups has a higher influence on the proton conductivity of the PEM than an increased water uptake.

Transverse water relaxation in whole blood and erythrocytes at 3T, 7T, 9.4T, 11.7T and 16.4T; determination of intracellular hemoglobin and extracellular albumin relaxivities.

Science.gov (United States)

Grgac, Ksenija; Li, Wenbo; Huang, Alan; Qin, Qin; van Zijl, Peter C M

2017-05-01

Blood is a physiological substance with multiple water compartments, which contain water-binding proteins such as hemoglobin in erythrocytes and albumin in plasma. Knowing the water transverse (R 2 ) relaxation rates from these different blood compartments is a prerequisite for quantifying the blood oxygenation level-dependent (BOLD) effect. Here, we report the Carr-Purcell-Meiboom-Gill (CPMG) based transverse (R 2CPMG ) relaxation rates of water in bovine blood samples circulated in a perfusion system at physiological temperature in order to mimic blood perfusion in humans. R 2CPMG values of blood plasma, lysed packed erythrocytes, lysed plasma/erythrocyte mixtures, and whole blood at 3 T, 7 T, 9.4 T, 11.7 T and 16.4 T were measured as a function of hematocrit or hemoglobin concentration, oxygenation, and CPMG inter-echo spacing (τ cp ). R 2CPMG in lysed cells showed a small τ cp dependence, attributed to the water exchange rate between free and hemoglobin-bound water to be much faster than τ cp . This was contrary to the tangential dependence in whole blood, where a much slower exchange between cells and blood plasma applies. Whole blood data were fitted as a function of τ cp using a general tangential correlation time model applicable for exchange as well as diffusion contributions to R 2CPMG , and the intercept R 20blood at infinitely short τ cp was determined. The R 20blood values at different hematocrit and the R 2CPMG values of lysed erythrocyte/plasma mixtures at different hemoglobin concentration were used to determine the relaxivity of hemoglobin inside the erythrocyte (r 2Hb ) and albumin (r 2Alb ) in plasma. The r 2Hb values obtained from lysed erythrocytes and whole blood were comparable at full oxygenation. However, while r 2Hb determined from lysed cells showed a linear dependence on oxygenation, this dependence became quadratic in whole blood. This possibly suggests an additional relaxation effect inside intact cells, perhaps due to hemoglobin

Which Density Functional Should Be Used to Describe Protonated Water Clusters?

Science.gov (United States)

Shi, Ruili; Huang, Xiaoming; Su, Yan; Lu, Hai-Gang; Li, Si-Dian; Tang, Lingli; Zhao, Jijun

2017-04-27

Protonated water cluster is one of the most important hydrogen-bond network systems. Finding an appropriate DFT method to study the properties of protonated water clusters can substantially improve the economy in computational resources without sacrificing the accuracy compared to high-level methods. Using high-level MP2 and CCSD(T) methods as well as experimental results as benchmark, we systematically examined the effect of seven exchange-correlation GGA functionals (with BLYP, B3LYP, X3LYP, PBE0, PBE1W, M05-2X, and B97-D parametrizations) in describing the geometric parameters, interaction energies, dipole moments, and vibrational properties of protonated water clusters H + (H 2 O) 2-9,12 . The overall performance of all these functionals is acceptable, and each of them has its advantage in certain aspects. X3LYP is the best to describe the interaction energies, and PBE0 and M05-2X are also recommended to investigate interaction energies. PBE0 gives the best anharmonic frequencies, followed by PBE1W, B97-D and BLYP methods. PBE1W, B3LYP, B97-D, and X3LYP can yield better geometries. The capability of B97-D to distinguish the relative energies between isomers is the best among all the seven methods, followed by M05-2X and PBE0.

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.

Proton transfer dynamics in a polar nanodroplet: ESIPT of 4'-n,n-dimethylamino-3-hydroxyflavone in AOT/alkane/water reverse micelles

Energy Technology Data Exchange (ETDEWEB)

Ghosh, Deborin [Department of Chemistry, University College of Science & Technology, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009 (India); Batuta, Shaikh; Begum, Naznin Ara [Bio-Organic Chemistry Lab, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235 (India); Mandal, Debabrata, E-mail: dmandal.chemistry@gmail.com [Department of Chemistry, University College of Science & Technology, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009 (India)

2017-04-15

The excited state intramolecular proton transfer (ESIPT) of the well-known fluorophore 4'-N,N-Dimethylamino-3-hydroxyflavone (DMA3HF) was studied in AOT/n-heptane/water reverse micelle solutions. For DMA3HF molecules located inside the AOT encapsulated polar nanodroplets, ESIPT from excited enol (E*) to tautomer (T*) forms was markedly inhibited, yielding time-constants of ≥100 ps, and followed the same trend as solvent relaxation when the ratio W= [H{sub 2}O]/[AOT] was varied. At W=0, the DMA3HF molecules were attached to the ionic AOT headgroups via strong intermolecular H-bonding, which hindered ESIPT. Addition of water changes the situation radically: water molecules form stronger H-bonds with AOT headgroups, displacing the DMA3HF, which are instead engaged in intermolecular H-bonded complexes of the type [DMA3HF···water]. ESIPT of these complex-bound fluorophores involves substantial rearrangement of H-bonding, and is coupled to solvation dynamics. With increasing W-value, solvation becomes faster, and so does ESIPT, reducing the yield of E* species. At the same time, the local environment within the nanodroplets become more more polar with gradual accumulation of water, which causes a monotonic red-shift of the E* emission peak.

Protons and how they are transported by proton pumps

DEFF Research Database (Denmark)

Buch-Pedersen, Morten Jeppe; Pedersen, Bjørn Panyella; Nissen, Poul

2008-01-01

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....

Relaxation dynamics following transition of solvated electrons

International Nuclear Information System (INIS)

Barnett, R.B.; Landman, U.; Nitzan, A.

1989-01-01

Relaxation dynamics following an electronic transition of an excess solvated electron in clusters and in bulk water is studied using an adiabatic simulation method. In this method the solvent evolves classically and the electron is constrained to a specified state. The coupling between the solvent and the excess electron is evaluated via the quantum expectation value of the electron--water molecule interaction potential. The relaxation following excitation (or deexcitation) is characterized by two time scales: (i) a very fast (/similar to/20--30 fs) one associated with molecular rotations in the first solvation shell about the electron, and (ii) a slower stage (/similar to/200 fs), which is of the order of the longitudinal dielectric relaxation time. The fast relaxation stage exhibits an isotope effect. The spectroscopical consequences of the relaxation dynamics are discussed

Towards quantitative measurements of relaxation times and other parameters in the brain

International Nuclear Information System (INIS)

Tofts, P.S.; Du Boulay, E.P.G.H.

1990-01-01

The nature and physical significance of the relaxation times T1 and T2 and of proton density are described. Methods of measuring T1 and T2 are discussed with emphasis on the establishment of precision and the maintenance of accuracy. Reported standards of success are briefly reviewed. We expect sensitivities of the order of 1% to be achievable in serial studies. Although early hopes of disease diagnosis by tissue characterisation were not realised, strict scientific method and careful calibration have made it pracitcable to apply relaxation time measurement to research into disease process. Serial measurements in patients and correlation with similar studies in animal models, biopsy results and autopsy material taken together have provided new knowledge about cerebral oedema, water compartmentation, alcoholism and the natural history of multiple sclerosis. There are prospects of using measurement to monitor treatment in other diseases with diffuse brain abnormalities invisible on the usual images. Secondarily derived parameters and notably the quantification of blood-brain barrier defect after injection of Gadolinium-DTPA also offer prospects of valuable data. (orig.)

Thermodynamic stability and relaxation studies of small, triaza-macrocyclic Mn(II) chelates.

Science.gov (United States)

de Sá, Arsénio; Bonnet, Célia S; Geraldes, Carlos F G C; Tóth, Éva; Ferreira, Paula M T; André, João P

2013-04-07

Due to its favorable relaxometric properties, Mn(2+) is an appealing metal ion for magnetic resonance imaging (MRI) contrast agents. This paper reports the synthesis and characterization of three new triazadicarboxylate-type ligands and their Mn(2+) chelates (NODAHep, 1,4,7-triazacyclononane-1,4-diacetate-7-heptanil; NODABA, 1,4,7-triazacyclononane-1,4-diacetate-7-benzoic acid; and NODAHA, 1,4,7-triazacyclononane-1,4-diacetate-7-hexanoic acid). The protonation constants of the ligands and the stability constants of the chelates formed with Mn(2+) and the endogenous Zn(2+) ion have been determined by potentiometry. In overall, the thermodynamic stability of the chelates is lower than that of the corresponding NOTA analogues (NOTA = 1,4,7-triazacyclononane-1,4,7-triacetate), consistent with the decreased number of coordinating carboxylate groups. Variable temperature (1)H NMRD and (17)O NMR measurements have been performed on the paramagnetic chelates to provide information on the water exchange rates and the rotational dynamics. The values of the (17)O chemical shifts are consistent with the presence of one water molecule in the first coordination sphere of Mn(2+). The three complexes are in the slow to intermediate regime for the water exchange rate, and they all display relatively high rotational correlation times, which explain the relaxivity values between 4.7 and 5.8 mM(-1) s(-1) (20 MHz and 298 K). These relaxivities are higher than expected for Mn(2+) chelates of such size and comparable to those of small monohydrated Gd(3+) complexes. The amphiphilic [Mn(NODAHep)] forms micelles above 22 mM (its critical micellar concentration was determined by relaxometry and fluorescence), and interacts with HSA via its alkylic carbon chain providing a 60% relaxivity increase at 20 MHz due to a longer tumbling time.

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

Science.gov (United States)

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

2004-05-01

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

Proton Resonance Lines of Water in Heulandite, Mordenite and Clinoptilolite

International Nuclear Information System (INIS)

Cruz Inclan, C.; Diaz Quintanilla, D.; Diaz Ruano, A.

1986-01-01

It is reported for the first time the proton magnetic resonance spectra of the clinoptilolite and mordenite between 220 K and 440 K. In mordenite it was observed that all water molecules have so an intensive diffusive movement, that they are completely delocalized. In clinoptilolite below 390 K, only a part of the water molecules are completely delocalized. Over 390 K all water molecules become delocalized. This particular behavior of the water molecules in clinoptilolite and mordenite is confronted with those structural models proposed by D.W. Breck. The concept of non-localized quantum state is introduced in order to explain the difference observed with the structural models. (author)

Study of aqueous complexes of uranium (IV) in an acid medium by nuclear magnetic resonance

International Nuclear Information System (INIS)

Kiener, C.; Folcher, G.; Rigny, P.; Virlet, J.

1976-01-01

The hydration of tetravalent uranium in acid solutions has been studied by proton magnetic resonance. Longitudinal and transversal relaxation rates of water are reported as a function of temperature, acidity, and added ions. The relaxation rates observed in perchloric solutions at high temperature are governed by the exchange process of water molecules between the inner coordination sphere of uranium(IV) and the bulk water. The bound proton's lifetime lies between 10 ms and 1 s. At pH > 0, the exchange rate depends upon acidity according to a simple expression. At high concentrations of diamagnetic ions the exchange rate depends linearly upon water activity. At low temperature, the proton relaxation rates are dominated by an outer sphere effect and the electronic relaxation time of uranium(IV) is found to be about 10 -13 s. No signal is observed from protons of the water molecules in the first sphere, firmly bound to uranium(IV), which undergo rapid relaxation. The chemical shift of the proton absorption signal in hydrochloric solutions arise from tightly bound water molecules in paramagnetic interaction with uranium(IV) in a second sphere, and in fast exchange with the bulk water. Above a chlorine concentration of 6 M, the monochloro complex of uranium(IV) contributes to the chemical shift. (author)

Adsorption of phospholipids at oil/water interfaces during emulsification is controlled by stress relaxation and diffusion.

Science.gov (United States)

Hildebrandt, Ellen; Nirschl, Hermann; Kok, Robbert Jan; Leneweit, Gero

2018-05-16

Adsorption of phosphatidylcholines at oil/water interfaces strongly deviates from spread monolayers at air/water surfaces. Understanding its nature and consequences could vastly improve applications in medical nanoemulsions and biotechnologies. Adsorption kinetics at interfaces of water with different oil phases were measured by profile analysis tensiometry. Adsorption kinetics for 2 different phospholipids, DPPC and POPC, as well as 2 organic phases, squalene and squalane, show that formation of interfacial monolayers is initially dominated by stress-relaxation in the first minutes. Diffusion only gradually contributes to a decrease in interfacial tension at later stages of time and higher film pressures. The results can be applied for the optimization of emulsification protocols using mechanical treatments. Emulsions using phospholipids with unsaturated fatty acids are dominated much more strongly by stress-relaxation and cover interfaces very fast compared to those with saturated fatty acids. In contrast, phospholipid layers consisting of saturated fatty acids converge faster towards the equilibrium than those with unsaturated fatty acids.

Spin-locking vs. 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

2010-01-01

Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of non-equivalent 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 metabolites 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. 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 (MTRasym) is highly dependent on the choice of saturation pulse power. In the intermediate exchange regime, MTRasym becomes complicated and should be interpreted with care. PMID:21500270

Vibrational and Rotational Energy Relaxation in Liquids

DEFF Research Database (Denmark)

Petersen, Jakob

Vibrational and rotational energy relaxation in liquids are studied by means of computer simulations. As a precursor for studying vibrational energy relaxation of a solute molecule subsequent to the formation of a chemical bond, the validity of the classical Bersohn-Zewail model for describing......, 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...

Parity Nonconservation in Proton-water Scattering at 800 MeV

Science.gov (United States)

Nagle, D. E.; Bowman, J. D.; Carlini, R.; Mischke, R. E.; Frauenfelder, H.; Harper, R. W.; Yuan, V.; McDonald, A. B.; Talaga, R.

1982-01-01

A search has been made for parity nonconservation in the scattering of 800 MeV polarized protons from an unpolarized water target. The result is for the longitudinal asymmetry, A{sub L} = +(6.6 +- 3.2) x 10{sup -7}. Control runs with Pb, using a thickness which gave equivalent beam broadening from Coulomb multiple scattering, but a factor of ten less nuclear interactions than the water target, gave A{sub L} = -(0.5 +- 6.0) x 10{sup -7}.

Estimation and correction of produced light from prompt gamma photons on luminescence imaging of water for proton therapy dosimetry

Science.gov (United States)

Yabe, Takuya; Komori, Masataka; Toshito, Toshiyuki; Yamaguchi, Mitsutaka; Kawachi, Naoki; Yamamoto, Seiichi

2018-02-01

Although the luminescence images of water during proton-beam irradiation using a cooled charge-coupled device camera showed almost the same ranges of proton beams as those measured by an ionization chamber, the depth profiles showed lower Bragg peak intensities than those measured by an ionization chamber. In addition, a broad optical baseline signal was observed in depths that exceed the depth of the Bragg peak. We hypothesize that this broad baseline signal originates from the interaction of proton-induced prompt gamma photons with water. These prompt gamma photons interact with water to form high-energy Compton electrons, which may cause luminescence or Cherenkov emission from depths exceeding the location of the Bragg peak. To clarify this idea, we measured the luminescence images of water during the irradiations of protons in water with minimized parallax errors, and also simulated the produced light by the interactions of prompt gamma photons with water. We corrected the measured depth profiles of the luminescence images by subtracting the simulated distributions of the produced light by the interactions of prompt gamma photons in water. Corrections were also conducted using the estimated depth profiles of the light of the prompt gamma photons, as obtained from the off-beam areas of the luminescence images of water. With these corrections, we successfully obtained depth profiles that have almost identical distributions as the simulated dose distributions for protons. The percentage relative height of the Bragg peak with corrections to that of the simulation data increased to 94% from 80% without correction. Also, the percentage relative offset heights of the deeper part of the Bragg peak with corrections decreased to 0.2%-0.4% from 4% without correction. These results indicate that the luminescence imaging of water has potential for the dose distribution measurements for proton therapy dosimetry.

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.

PREFACE: Transport phenomena in proton conducting media Transport phenomena in proton conducting media

Science.gov (United States)

Eikerling, Michael

2011-06-01

Proton transport phenomena are of paramount importance for acid-base chemistry, energy transduction in biological organisms, corrosion processes, and energy conversion in electrochemical systems such as polymer electrolyte fuel cells. The relevance for such a plethora of materials and systems, and the ever-lasting fascination with the highly concerted nature of underlying processes drive research across disciplines in chemistry, biology, physics and chemical engineering. A proton never travels alone. Proton motion is strongly correlated with its environment, usually comprised of an electrolyte and a solid or soft host material. For the transport in nature's most benign proton solvent and shuttle, water that is, insights from ab initio simulations, matured over the last 15 years, have furnished molecular details of the structural diffusion mechanism of protons. Excess proton movement in water consists of sequences of Eigen-Zundel-Eigen transitions, triggered by hydrogen bond breaking and making in the surrounding water network. Nowadays, there is little debate about the validity of this mechanism in water, which bears a stunning resemblance to the basic mechanistic picture put forward by de Grotthuss in 1806. While strong coupling of an excess proton with degrees of freedom of solvent and host materials facilitates proton motion, this coupling also creates negative synergies. In general, proton mobility in biomaterials and electrochemical proton conducting media is highly sensitive to the abundance and structure of the proton solvent. In polymer electrolyte membranes, in which protons are bound to move in nano-sized water-channels, evaporation of water or local membrane dehydration due to electro-osmotic coupling are well-known phenomena that could dramatically diminish proton conductivity. Contributions in this special issue address various vital aspects of the concerted nature of proton motion and they elucidate important structural and dynamic effects of solvent

Ultrahigh relaxivity and safe probes of manganese oxide nanoparticles for in vivo imaging.

Science.gov (United States)

Xiao, J; Tian, X M; Yang, C; Liu, P; Luo, N Q; Liang, Y; Li, H B; Chen, D H; Wang, C X; Li, L; Yang, G W

2013-12-05

Mn-based nanoparticles (NPs) have emerged as new class of probes for magnetic resonance imaging due to the impressive contrast ability. However, the reported Mn-based NPs possess low relaxivity and there are no immunotoxicity data regarding Mn-based NPs as contrast agents. Here, we demonstrate the ultrahigh relaxivity of water protons of 8.26 mM(-1) s(-1) from the Mn3O4 NPs synthesized by a simple and green technique, which is twice higher than that of commercial gadolinium (Gd)-based contrast agents (4.11 mM(-1) s(-1)) and the highest value reported to date for Mn-based NPs. We for the first time demonstrate these Mn3O4 NPs biocompatibilities both in vitro and in vivo are satisfactory based on systematical studies of the intrinsic toxicity including cell viability of human nasopharyngeal carcinoma cells, normal nasopharyngeal epithelium, apoptosis in cells and in vivo immunotoxicity. These findings pave the way for the practical clinical diagnosis of Mn based NPs as safe probes for in vivo imaging.

Structural and dynamical characterization of piroxicam by 1H- and 13C-NMR relaxation studies

International Nuclear Information System (INIS)

Rossi, C.; Casini, A.; Picchi, M.P.; Laschi, F.; Calabria, A.; Marcolongo, R.

1987-01-01

Carbon spin-lattice relaxation rates of anti-inflammatory drug, piroxicam, have been measured. These results have been used in determining the reorientational rates of the proton carbon vectors. An analysis of internal motions within the pyridinyl moiety of piroxicam was carried out. Selective proton-carbon nuclear Overhauser effect (NOE) measurements were made in order to determine the solution structure of piroxicam. The effect of indirect NOE arising from exchangeable protons has been analyzed and considered. 20 refs.; 4 figs.; 3 tabs

Nuclear magnetic relaxation in aqueous praseodymium and europium solutions

International Nuclear Information System (INIS)

Lopez, J.L.; Diaz, D.

1991-01-01

A general theory for the relaxation of the nuclear spin in paramagnetic complexes where the electronic spin is within a slow-movement regime was presented by Benetis et al. and applied to d-group elements (Ni 2+ , Co 2+ ). This paper show the possibility to apply such formalism to f-group elements and it was developed for S=3(Eu 3+ ). A group of magnitudes characterizing the microstructure and dynamics of these solutions is reported with the approximations used. The dispersion of the nuclear magnetic relaxation (NMRD) for the proton of the variable field was also assessed which had a similar behaviour to what was experimentally reported

Cross-relaxation imaging:methods, challenges and applications

International Nuclear Information System (INIS)

Stikov, Nikola

2010-01-01

An overview of quantitative magnetization transfer (qMT) is given, with focus on cross relaxation imaging (CRI) as a fast method for quantifying the proportion of protons bound to complex macromolecules in tissue. The procedure for generating CRI maps is outlined, showing examples in the human brain and knee, and discussing the caveats and challenges in generating precise and accurate CRI maps. Finally, several applications of CRI for imaging tissue microstructure are presented.(Author)

Radiation damage to uracil and water by proton and electron impact

International Nuclear Information System (INIS)

Scheier, P.; Hanel, G.; Denifl, S; Gstir, B.; Maerk, T.D.; Farizon, B.; Farizon, M.; Coupier, B.

2002-01-01

Full text: The inelastic interaction of protons (in the energy range from 20 keV to 150 keV) and electrons (from thermal energies up to 20 eV) with water and uracil, the latter a building block of the RNA has been studied in two laboratories with specially designed experimental setups. These measurements are motivated from a present lack of understanding how on a molecular level damage to living cells and organisms is caused. A unique way of simultaneous detection of the product ions after swift proton (or hydrogen) impact and the analysis of the charge state of the projectile after the collision allows to distinguish between direct ionization (e.g., projectile remains a proton) and electron capture events (e.g., proton becomes neutralized). The latter process turns out to be more destructive, i.e. leads to a higher yield of fragmentation. For electrons both the formation of positively and negatively charged ions has been investigated. We discovered that already thermal electrons lead with a rather large cross section to a dissociation of the uracil molecule producing an anion and a fast hydrogen radical. (author)

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. Copyright © 2010 Wiley-Liss, Inc.

Interfacial Water-Transport Effects in Proton-Exchange Membranes

Energy Technology Data Exchange (ETDEWEB)

Kienitz, Brian; Yamada, Haruhiko; Nonoyama, Nobuaki; Weber, Adam

2009-11-19

It is well known that the proton-exchange membrane is perhaps the most critical component of a polymer-electrolyte fuel cell. Typical membranes, such as Nafion(R), require hydration to conduct efficiently and are instrumental in cell water management. Recently, evidence has been shown that these membranes might have different interfacial morphology and transport properties than in the bulk. In this paper, experimental data combined with theoretical simulations will be presented that explore the existence and impact of interfacial resistance on water transport for Nafion(R) 21x membranes. A mass-transfer coefficient for the interfacial resistance is calculated from experimental data using different permeation cells. This coefficient is shown to depend exponentially on relative humidity or water activity. The interfacial resistance does not seem to exist for liquid/membrane or membrane/membrane interfaces. The effect of the interfacial resistance is to flatten the water-content profiles within the membrane during operation. Under typical operating conditions, the resistance is on par with the water-transport resistance of the bulk membrane. Thus, the interfacial resistance can be dominant especially in thin, dry membranes and can affect overall fuel-cell performance.

Hydrogen bond network relaxation in aqueous polyelectrolyte solutions: the effect of temperature

International Nuclear Information System (INIS)

Sarti, S; Bordi, F; Truzzolillo, D

2012-01-01

Dielectric spectroscopy data over the range 100 MHz-40 GHz allow for a reliable analysis of two of the major relaxation phenomena for polyelectrolytes (PE) in water. Within this range, the dielectric relaxation of pure water is dominated by a near-Debye process at ν = 18.5 GHz corresponding to a relaxation time of τ = 8.4 ps at 25 °C. This mode is commonly attributed to the cooperative relaxation specific to liquids forming a hydrogen bond network (HBN) and arising from long range H-bond-mediated dipole-dipole interactions. The presence of charged polymers in water partially modifies the dielectric characteristics of the orientational water molecule relaxation due to a change of the dielectric constant of water surrounding the charges on the polyion chain. We report experimental results on the effect of the presence of a standard flexible polyelectrolyte (sodium polyacrylate) on the HBN relaxation in water for different temperatures, showing that the HBN relaxation time does not change by increasing the polyelectrolyte density in water, even if relatively high concentrations are reached (0.02 monomol l -1 ≤ C ≤ 0.4 monomol l -1 ). We also find that the effect of PE addition on the HBN relaxation is not even a broadening of its distribution, rather a decrease of the spectral weight that goes beyond the pure volume fraction effect. This extra decrease is larger at low T and less evident at high T, supporting the idea that the correlation length of the water is less affected by the presence of charged flexible chains at high temperatures. (paper)

Coupling fast water exchange to slow molecular tumbling in Gd3+ chelates: why faster is not always better.

Science.gov (United States)

Avedano, Stefano; Botta, Mauro; Haigh, Julian S; Longo, Dario L; Woods, Mark

2013-08-05

The influence of dynamics on solution state structure is a widely overlooked consideration in chemistry. Variations in Gd(3+) chelate hydration with changing coordination geometry and dissociative water exchange kinetics substantially impact the effectiveness (or relaxivity) of monohydrated Gd(3+) chelates as T1-shortening contrast agents for MRI. Theory shows that relaxivity is highly dependent upon the Gd(3+)-water proton distance (rGdH), and yet this distance is almost never considered as a variable in assessing the relaxivity of a Gd(3+) chelate as a potential contrast agent. The consequence of this omission can be seen when considering the relaxivity of isomeric Gd(3+) chelates that exhibit different dissociative water exchange kinetics. The results described herein show that the relaxivity of a chelate with "optimal" dissociative water exchange kinetics is actually lower than that of an isomeric chelate with "suboptimal" dissociative water exchange. When the rate of molecular tumbling of these chelates is slowed, an approach that has long been understood to increase relaxivity, the observed difference in relaxivity is increased with the more rapidly exchanging ("optimal") chelate exhibiting lower relaxivity than the "suboptimally" exchanging isomer. The difference between the chelates arises from a non-field-dependent parameter: either the hydration number (q) or rGdH. For solution state Gd(3+) chelates, changes in the values of q and rGdH are indistinguishable. These parametric expressions simply describe the hydration state of the chelate--i.e., the number and position of closely associating water molecules. The hydration state (q/rGdH(6)) of a chelate is intrinsically linked to its dissociative water exchange rate kex, and the interrelation of these parameters must be considered when examining the relaxivity of Gd(3+) chelates. The data presented herein indicate that the changes in the hydration parameter (q/rGdH(6)) associated with changing dissociative

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...... are brought into the framework of quantum mechanical PT theory in condensed media. Both the nature of the elementary act and the reaction coordinates are, however, different for the two types of PT clusters. The corresponding rate constants are calculated and compared with MD simulations. Within the framework...

Water equivalence of various materials for clinical proton dosimetry by experiment and Monte Carlo simulation

International Nuclear Information System (INIS)

Al-Sulaiti, Leena; Shipley, David; Thomas, Russell; Kacperek, Andrzej; Regan, Patrick; Palmans, Hugo

2010-01-01

The accurate conversion of dose to various materials used in clinical proton dosimetry to dose-to-water is based on fluence correction factors, accounting for attenuation of primary protons and production of secondary particles due to non-elastic nuclear interactions. This work aims to investigate the depth dose distribution and the fluence correction with respect to water or graphite at water equivalent depths (WED) in different target materials relevant for dosimetry such as polymethyl methacrylate (PMMA), graphite, A-150, aluminium and copper at 60 and 200 MeV. This was done through a comparison between Monte Carlo simulation using MCNPX 2.5.0, analytical model calculations and experimental measurements at Clatterbridge Centre of Oncology (CCO) in a 60 MeV modulated and un-modulated proton beam. MCNPX simulations indicated small fluence corrections for all materials with respect to graphite and water in 60 and 200 MeV except for aluminium. The analytical calculations showed an increase in the fluence correction factor to a few percent for all materials with respect to water at 200 MeV. The experimental measurements for 60 MeV un-modulated beam indicated a good agreement with MCNPX. For the modulated beam the fluence correction factor was found to be decreasing below unity by up to few percent with depth for aluminium and copper but almost constant and unity for A-150.

Similarities between intra- and intermolecular hydrogen bonds in RNA kissing complexes found by means of cross-correlated relaxation

International Nuclear Information System (INIS)

Dittmer, Jens; Kim, Chul-Hyun; Bodenhausen, Geoffrey

2003-01-01

The bond lengths and dynamics of intra- and intermolecular hydrogen bonds in an RNA kissing complex have been characterized by determining the NMR relaxation rates of various double- and triple-quantum coherences that involve an imino proton and two neighboring nitrogen-15 nuclei belonging to opposite bases. New experiments allow one to determine the chemical shift anisotropy of the imino protons. The bond lengths derived from dipolar relaxation and the lack of modulations of the nitrogen chemical shifts indicate that the intermolecular hydrogen bonds which hold the kissing complex together are very similar to the intramolecular hydrogen bonds in the double-stranded stem of the RNA

Water versus DNA: new insights into proton track-structure modelling in radiobiology and radiotherapy.

Science.gov (United States)

Champion, C; Quinto, M A; Monti, J M; Galassi, M E; Weck, P F; Fojón, O A; Hanssen, J; Rivarola, R D

2015-10-21

Water is a common surrogate of DNA for modelling the charged particle-induced ionizing processes in living tissue exposed to radiations. The present study aims at scrutinizing the validity of this approximation and then revealing new insights into proton-induced energy transfers by a comparative analysis between water and realistic biological medium. In this context, a self-consistent quantum mechanical modelling of the ionization and electron capture processes is reported within the continuum distorted wave-eikonal initial state framework for both isolated water molecules and DNA components impacted by proton beams. Their respective probability of occurrence-expressed in terms of total cross sections-as well as their energetic signature (potential and kinetic) are assessed in order to clearly emphasize the differences existing between realistic building blocks of living matter and the controverted water-medium surrogate. Consequences in radiobiology and radiotherapy will be discussed in particular in view of treatment planning refinement aiming at better radiotherapy strategies.

Proton permeation of lipid bilayers.

Science.gov (United States)

Deamer, D W

1987-10-01

Proton permeation of the lipid bilayer barrier has two unique features. First, permeability coefficients measured at neutral pH ranges are six to seven orders of magnitude greater than expected from knowledge of other monovalent cations. Second, proton conductance across planar lipid bilayers varies at most by a factor of 10 when pH is varied from near 1 to near 11. Two mechanisms have been proposed to account for this anomalous behavior: proton conductance related to contaminants of lipid bilayers, and proton translocation along transient hydrogen-bonded chains (tHBC) of associated water molecules in the membrane. The weight of evidence suggests that trace contaminants may contribute to proton conductance across planar lipid membranes at certain pH ranges, but cannot account for the anomalous proton flux in liposome systems. Two new results will be reported here which were designed to test the tHBC model. These include measurements of relative proton/potassium permeability in the gramicidin channel, and plots of proton flux against the magnitude of pH gradients. (1) The relative permeabilities of protons and potassium through the gramicidin channel, which contains a single strand of hydrogen-bonded water molecules, were found to differ by at least four orders of magnitude when measured at neutral pH ranges. This result demonstrates that a hydrogen-bonded chain of water molecules can provide substantial discrimination between protons and other cations. It was also possible to calculate that if approximately 7% of bilayer water was present in a transient configuration similar to that of the gramicidin channel, it could account for the measured proton flux. (2) The plot of proton conductance against pH gradient across liposome membranes was superlinear, a result that is consistent with one of three alternative tHBC models for proton conductance described by Nagle elsewhere in this volume.

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

International Nuclear Information System (INIS)

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

Proton nuclear magnetic resonance spectroscopy of plasma lipoproteins in malignancy

International Nuclear Information System (INIS)

Nabholtz, J.M.; Rossignol, A.; Farnier, M.; Gambert, P.; Tremeaux, J.C.; Friedman, S.; Guerrin, J.

1988-01-01

A recent study described a method of detecting malignant tumors by water-supressed proton nuclear magnetic resonance (1 H NMR) study of plasma. We performed a similar study of the W 1/2, a mean of the full width at half height of the resonances of the methyl and methylene groups of the lipids of plasma lipoproteins which is inversely related to the spin-spin apparent relaxation time (T 2 * ). W 1/2 values were measured at a fixed baseline width of 310 Hz. The study was prospective and blinded and comprised 182 subjects consisting of 40 controls, 68 patients with untreated malignancies, 45 with malignant tumors undergoing therapy and 29 benign tumor patients. No differences were seen between any groups that could serve as a basis for a useful clinical test. The major difficulty in the determination of W 1/2 was due to interference of metabolite protons (particularly lactate) within the lipoprotein resonance signal. Triglyceride level was seen to correlate inversely with W 1/2 within malignant patient groups. These discrepant results may be related to differing triglyceride-rich very low density lipoprotein (VLDL) levels in the ;atient populations of each study. We conclude that the water-suppressed 1H NMR of plasma lipoproteins is not a valid measurement for assessing malignancy. (orig.)

High-Relaxivity MRI Contrast Agents: Where Coordination Chemistry Meets Medical Imaging

Energy Technology Data Exchange (ETDEWEB)

Werner, Eric J.; Datta, Ankona; Jocher, Christoph J.; Raymond, Kenneth N.

2008-01-15

The desire to improve and expand the scope of clinical magnetic resonance imaging (MRI) has prompted the search for contrast agents of higher efficiency. The development of better agents requires consideration of the fundamental coordination chemistry of the gadolinium(III) ion and the parameters that affect its efficacy as a proton relaxation agent. In optimizing each parameter, other practical issues such as solubility and in vivo toxicity must also be addressed, making the attainment of safe, high-relaxivity agents a challenging goal. Here we present recent advances in the field, with an emphasis on the hydroxypyridinone family of Gd{sup III} chelates.

Calculation of the protons stopping power in water using dielectric formalism in the MELF-GOS approach

International Nuclear Information System (INIS)

Ribeiro, Franciane; Mazer, Amanda Cristina; Hormaza, Joel Mesa

2016-01-01

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)

Precise determination of the Bragg peak position of proton beams in liquid water

International Nuclear Information System (INIS)

Marouane, Abdelhak; Ouaskit, Said; Inchaouh, Jamal

2011-01-01

The influence of water molecules on the surrounding biological molecules during irradiation with protons is currently a major subject in radiation science. Proton collisions with the water molecules are estimated around the Bragg peak region, taking into account ionization, excitation, charge-changing processes, and energetic secondary electron behavior. The Bragg peak profile and position was determined by adopting a new approach involving discretization, incrementation, and dividing the target into layers, the thickness of each layer being selected randomly from a distribution weighted by the values of the total interaction cross section, from excitation up to ionization of the target and the incident projectile charge exchange. The calculation was carried out by a Monte-Carlo simulation in the energy range 20 ≤ E ≤ 10 8 eV, including the relativistic corrections.

Computation of transverse muon-spin relaxation functions including trapping-detrapping reactions, with application to electron-irradiated tantalum

International Nuclear Information System (INIS)

Doering, K.P.; Aurenz, T.; Herlach, D.; Schaefer, H.E.; Arnold, K.P.; Jacobs, W.; Orth, H.; Haas, N.; Seeger, A.; Max-Planck-Institut fuer Metallforschung, Stuttgart

1986-01-01

A new technique for the economical evaluation of transverse muon spin relaxation functions in situations involving μ + trapping at and detrapping from crystal defects is applied to electron-irradiated Ta exhibiting relaxation maxima at about 35 K, 100 K, and 250 K. The long-range μ + diffusion is shown to be limted by traps over the entire temperature range investigated. The (static) relaxation rates for several possible configurations of trapped muons are discussed, including the effect of the simultaneous presence of a proton in a vacancy. (orig.)

Nuclear magnetic relaxation of methyl group in liquids

International Nuclear Information System (INIS)

Blicharska, B.

1986-01-01

The theoretical description of the relaxation process of methyl group in liquids and some results of the measurements of relaxation function and relaxation times for cryoprotective solutions are presented. Starting from the application of the operator formalism the general equation for spin operators e.g. components of the nuclear spin and magnetization is founded. Next, the spin Hamiltonian is presented as contraction of the symmetry adapted spherical tensors as well as the correlation functions and spectral densities. On the basis of extended and modified Woessner model of motion the correlation functions and spectral densities are calculated for methyl group in liquids. Using these functions the relaxation matrix elements, the spin-spin and spin-lattice relaxation times can be expressed. The prediction of the theory agrees with author's previous experiments on cryoprotective solutions. The observed dependence on temperature, frequency and isotopic dilution in methanol-water, methanol-dimethyl sulfoxide (DMSO) and DMSO-water solutions is in a satisfactory agreement with theoretical equations. 34 refs. (author)

Local mechanical stress relaxation of Gunn diodes irradiated by protons

International Nuclear Information System (INIS)

Gradoboev, A V; Tesleva, E P

2017-01-01

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)·10 2 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. (paper)

Proton transport facilitating water-oxidation: the role of second sphere ligands surrounding the catalytic metal cluster.

Science.gov (United States)

Bao, Han; Dilbeck, Preston L; Burnap, Robert L

2013-10-01

The ability of PSII to extract electrons from water, with molecular oxygen as a by-product, is a remarkable biochemical and evolutionary innovation. From an evolutionary perspective, the invention of PSII approximately 2.7 Ga led to the accelerated accumulation of biomass in the biosphere and the accumulation of oxygen in the atmosphere, a combination that allowed for the evolution of a much more complex and extensive biosphere than would otherwise have been possible. From the biochemical and enzymatic perspective, PSII is remarkable because of the thermodynamic and kinetic obstacles that needed to have been overcome to oxidize water as the ultimate photosynthetic electron donor. This article focuses on how proton release is an integral part of how these kinetic and thermodynamic obstacles have been overcome: the sequential removal of protons from the active site of H2O-oxidation facilitates the multistep oxidation of the substrate water at the Mn4CaOx, the catalytic heart of the H2O-oxidation reaction. As noted previously, the facilitated deprotonation of the Mn4CaOx cluster exerts a redox-leveling function preventing the accumulation of excess positive charge on the cluster, which might otherwise hinder the already energetically difficult oxidation of water. Using recent results, including the characteristics of site-directed mutants, the role of the second sphere of amino acid ligands and the associated network of water molecules surrounding the Mn4CaOx is discussed in relation to proton transport in other systems. In addition to the redox-leveling function, a trapping function is assigned to the proton release step occurring immediately prior to the dioxygen chemistry. This trapping appears to involve a yet-to-be clarified gating mechanism that facilitates to coordinated release of a proton from the neighborhood of the active site thereby insuring that the backward charge-recombination reaction does not out-compete the forward reaction of dioxygen chemistry

Protonic charge defect structures in floating water bridges observed as Zundel and Eigen solvation arrangements

Science.gov (United States)

Teschke, Omar; de Castro, Jose Roberto; Valente Filho, Juracyr Ferraz; Soares, David Mendez

2017-10-01

Protonic arrangements were detected in water bridge structures using confocal Raman microscopy, and the spectra show two formed structures. The measured Raman spectra were modified using the voltage applied to the bridge structure, which changed the proportion of these two species. Initially, for a 6.3 kV applied voltage, there was a measurable increase in the bridge current above the Ohmic contribution and the observed Raman spectrum of this new injected specie corresponded to the computed spectrum for the Zundel protonic arrangement. As the voltage further increases a contribution from the Eigen proton solvation specie is added to the measured spectrum.

Short echo time proton spectroscopy of the brain in healthy volunteers using an insert gradient head coil

DEFF Research Database (Denmark)

Gideon, P; Danielsen, E R; Schneider, M

1995-01-01

An insert gradient head coil with built-in X, Y, and Z gradients was used for localized proton spectroscopy in the brain of healthy volunteers, using short echo time stimulated echo acquisition mode (STEAM) sequences. Volume of interest size was 3.4 ml, repetition time was 6.0 s, and echo times...... were 10 and 20 ms, respectively. Good quality proton spectra with practically no eddy current artefacts were acquired allowing observation of strongly coupled compounds, and compounds with short T2 relaxation times. The gradient head coil thus permits further studies of compounds such as glutamine....../glutamate and myo-inositols. These compounds were more prominent within grey matter than within white matter. Rough estimations of metabolite concentrations using water as an internal standard were in good agreement with previous reports....

31P and 1H NMR studies of the structure of enzyme-bound substrate complexes of lobster muscle arginine kinase: Relaxation measurements with Mn(II) and Co(II)

International Nuclear Information System (INIS)

Jarori, G.K.; Ray, B.D.; Rao, B.D.N.

1989-01-01

The paramagnetic effects of Mn(II) and Co(II) on the spin-lattice relaxation rates of 31 P nuclei of ATP and ADP and of Mn(II) on the spin-lattice relaxation rate of the δ protons of arginine bound to arginine kinase from lobster tail muscle have been measured. Temperature variation of 31 P relaxation rates in E-MnADP and E-MnATP yields activation energies (ΔE) in the range 6-10 kcal/mol. Thus, the 31 P relaxation rates in these complexes are exchange limited and cannot provide structural information. However, the relaxation rates in E-CoADP and E-CoATP exhibit frequency dependence and ΔE values in the range 1-2 kcal/mol; i.e., these rates depend upon 31 P-Co(II) distances. These distances were calculated to be in the range 3.2-4.5 angstrom, appropriate for direct coordination between Co(II) and the phosphoryl groups. The paramagnetic effect of Mn(II) on the 1 H spin-lattice relaxation rate of the δ protons of arginine in the E-MnADP-Arg complex was also measured at three frequencies. From the frequency dependence of the relaxation rate an effective τ C of 0.6 ns has also been calculated, which is most likely to be the electron spin relaxation rate (τ S1 ) for Mn(II) in this complex. The distance estimated on the basis of the reciprocal sixth root of the average relaxation rate of the δ protons was 10.9 ± 0.3 angstrom

Relaxation to equilibrium following photoacid dissociation in mineral acids and buffer solutions

International Nuclear Information System (INIS)

Pines, D; Nibbering, E T J; Pines, E

2007-01-01

The relaxation to the dissociation equilibrium of a weak acid undergoing a transient pK a change in the presence of a strong mineral acid has been the subject of considerable interest both experimentally and theoretically. Here we compare this process with the analogue event taking place in a buffer solution of a weak carboxylic acid. The comparison has been performed in identical pH and ionic strength conditions and at a sufficiently short timescale where the buffer can only affect the weak acid relaxation by proton scavenging. Although the two relaxation processes have been found to differ in their temporal behaviour, they have both resulted in identical equilibrium amplitudes of the photoacid. This observation reassures the well-known chemical wisdom that pK a values measured in buffer solutions do not depend on the specific chemical reactivity of the buffer. We analyse the essentially many-body relaxation problem in terms of a re-normalized geminate recombination reaction which persists over longer times than the exponential relaxation to equilibrium of homogenously distributed populations of the reactants

Effect of cholesterol solubilised in membranes on the interfacial water structure

International Nuclear Information System (INIS)

Maitra, A.; Patanjali, P.

1987-01-01

Cholesterol solubilised in the reverse micellar system of Aerosol OT in isooctane has been found to decrease the hydrophilicity of the surfactant molecule. This has been studied in detail by water proton NMR relaxation measurements in water-Aerosol OT-isooctane with and without cholesterol. It is concluded that the intermolecular hydrogen bonding between the 3β-OH group of cholesterol and the carbonyl ester of Aerosol OT is responsible for the decrease in hydrogen bonding capacity of the latter. (author). 23 refs.; 2 figs

Calculations and measurements of the scintillator-to-water stopping power ratio of liquid scintillators for use in proton radiotherapy

International Nuclear Information System (INIS)

Scott Ingram, W.; Robertson, Daniel; Beddar, Sam

2015-01-01

Liquid scintillators are a promising detector for high-resolution three-dimensional proton therapy dosimetry. Because the scintillator comprises both the active volume of the detector and the phantom material, an ideal scintillator will exhibit water equivalence in its radiological properties. One of the most fundamental of these is the scintillator’s stopping power. The objective of this study was to compare calculations and measurements of scintillator-to-water stopping power ratios to evaluate the suitability of the liquid scintillators BC-531 and OptiPhase HiSafe 3 for proton dosimetry. We also measured the relative scintillation output of the two scintillators. Both calculations and measurements show that the linear stopping power of OptiPhase is significantly closer to water than that of BC-531. BC-531 has a somewhat higher scintillation output. OptiPhase can be mixed with water at high concentrations, which further improves its scintillator-to-water stopping power ratio. However, this causes the solution to become cloudy, which has a negative impact on the scintillation output and spatial resolution of the detector. OptiPhase is preferred over BC-531 for proton dosimetry because its density and scintillator-to-water stopping power ratio are more water equivalent

NMR relaxation times of natural rubber latex

International Nuclear Information System (INIS)

Harun, S.; Aziz, H.; Basir, Z.

1994-01-01

NMR relaxation times T sub 1 and T sub 2 of natural rubber latex have been measured at 25 degree C on a pulsed NMR spectrometer. The work focuses on the variation of the relaxation times with the amount of water content from 0% to 50%. The water content was adjusted by centrifuging and removing a certain amount of water from the sample. The data were analysed using a biexponential fitting procedure which yields simultaneously either T sub 1a and T sub 1b or T sub 2a and T sub 2b. The amount of solid was compared with the known amount of dry rubber content

Spatial characterization of T1 and T2 relaxation times and the water apparent diffusion coefficient in rabbit Achilles tendon subjected to tensile loading.

Science.gov (United States)

Wellen, J; Helmer, K G; Grigg, P; Sotak, C H

2005-03-01

Tendons exhibit viscoelastic mechanical behavior under tensile loading. The elasticity arises from the collagen chains that form fibrils, while the viscous response arises from the interaction of the water with the solid matrix. Therefore, an understanding of the behavior of water in response to the application of a load is crucial to the understanding of the origin of the viscous response. Three-dimensional MRI mapping of rabbit Achilles tendons was performed at 2.0 T to characterize the response of T(1) and T(2) relaxation times and the apparent diffusion coefficient (ADC) of water to tensile loading. The ADC was measured in directions both parallel (ADC( parallel)) and perpendicular (ADC( perpendicular)) to the long axis of the tendon. At a short diffusion time (5.8 ms) MR parameter maps showed the existence of two regions, here termed "core" and "rim", that exhibited statistically significant differences in T(1), T(2), and ADC( perpendicular) under the baseline loading condition. MR parameter maps were also generated at a second loading condition of approximately 1 MPa. At a diffusion time of 5.8 ms, there was a statistically significant increase in the rim region for both ADC( perpendicular) (57.5%) and ADC( parallel) (20.5%) upon tensile loading. The changes in core ADC(( perpendicular), ( parallel)), as well as the relaxation parameters in both core and rim regions, were not statistically significant. The effect of diffusion time on the ADC(( perpendicular), ( parallel)) values was investigated by creating maps at three additional diffusion times (50.0, 125.0, 250.0 ms) using a diffusion-weighted, stimulated-echo (DW-STE) pulse sequence. At longer diffusion times, ADC(( perpendicular), ( parallel)) values increased rather than approaching a constant value. This observation was attributed to T(1) spin-editing during the DW-STE pulse sequence, which resulted in the loss of short-T(1) components (with correspondingly lower ADCs) at longer diffusion times

NMR relaxation times in human brain tumors (preliminary results)

International Nuclear Information System (INIS)

Benoist, L.; Certaines, J. de; Chatel, M.; Menault, F.

1981-01-01

Since the early work of Damadian in 1971, proton NMR studies of tumors has been well documented. Present study concerns the spin-lattice T 1 and spin-spin T 2 relaxation times of normal dog brain according to the histological differentiation and of 35 human benignant or malignant tumors. The results principally show T 2 important variations between white and gray substance in normal brain but no discrimination between malignant and benignant tumors [fr

Vibrational and orientational dynamics of water in aqueous hydroxide solutions.

Science.gov (United States)

Hunger, Johannes; Liu, Liyuan; Tielrooij, Klaas-Jan; Bonn, Mischa; Bakker, Huib

2011-09-28

We report the vibrational and orientational dynamics of water molecules in isotopically diluted NaOH and NaOD solutions using polarization-resolved femtosecond vibrational spectroscopy and terahertz time-domain dielectric relaxation measurements. We observe a speed-up of the vibrational relaxation of the O-D stretching vibration of HDO molecules outside the first hydration shell of OH(-) from 1.7 ± 0.2 ps for neat water to 1.0 ± 0.2 ps for a solution of 5 M NaOH in HDO:H(2)O. For the O-H vibration of HDO molecules outside the first hydration shell of OD(-), we observe a similar speed-up from 750 ± 50 fs to 600 ± 50 fs for a solution of 6 M NaOD in HDO:D(2)O. The acceleration of the decay is assigned to fluctuations in the energy levels of the HDO molecules due to charge transfer events and charge fluctuations. The reorientation dynamics of water molecules outside the first hydration shell are observed to show the same time constant of 2.5 ± 0.2 ps as in bulk liquid water, indicating that there is no long range effect of the hydroxide ion on the hydrogen-bond structure of liquid water. The terahertz dielectric relaxation experiments show that the transfer of the hydroxide ion through liquid water involves the simultaneous motion of ~7 surrounding water molecules, considerably less than previously reported for the proton. © 2011 American Institute of Physics

Nuclear relaxation and critical fluctuations in membranes containing cholesterol

Science.gov (United States)

McConnell, Harden

2009-04-01

Nuclear resonance frequencies in bilayer membranes depend on lipid composition. Our calculations describe the combined effects of composition fluctuations and diffusion on nuclear relaxation near a miscibility critical point. Both tracer and gradient diffusion are included. The calculations involve correlation functions and a correlation length ξ =ξ0T/(T -Tc), where T -Tc is temperature above the critical temperature and ξ0 is a parameter of molecular length. Several correlation functions are examined, each of which is related in some degree to the Ising model correlation function. These correlation functions are used in the calculation of transverse deuterium relaxation rates in magic angle spinning and quadrupole echo experiments. The calculations are compared with experiments that report maxima in deuterium and proton nuclear relaxation rates at the critical temperature [Veatch et al., Proc. Nat. Acad. Sci. U.S.A. 104, 17650 (2007)]. One Ising-model-related correlation function yields a maximum 1/T2 relaxation rate at the critical temperature for both magic angle spinning and quadrupole echo experiments. The calculated rates at the critical temperature are close to the experimental rates. The rate maxima involve relatively rapid tracer diffusion in a static composition gradient over distances of up to 10-100 nm.

Solution conformation and dynamics of a tetrasaccharide related to the LewisX antigen deduced by NMR relaxation measurements

International Nuclear Information System (INIS)

Poveda, Ana; Asensio, Juan Luis; Martin-Pastor, Manuel; Jimenez-Barbero, Jesus

1997-01-01

1 H-NMR cross-relaxation rates and nonselective longitudinal relaxation times have been obtained at two magnetic fields (7.0 and 11.8 T) and at a variety of temperatures for the branched tetrasaccharide methyl 3-O-α-N-acetyl-galactosaminyl-β-galactopyranosyl-(1 → 4)[3-O-α-fucosyl] -glucopyranoside (1), an inhibitor of astrocyte growth. In addition, 13 C-NMR relaxation data have also been recorded at both fields. The 1 H-NMR relaxation data have been interpreted using different motional models to obtain proton-proton correlation times. The results indicate that the GalNAc and Fuc rings display more extensive local motion than the two inner Glc and Gal moieties, since those present significantly shorter local correlation times. The 13 C-NMR relaxation parameters have been interpreted in terms of the Lipari-Szabo model-free approach. Thus, order parameters and internal motion correlation times have been deduced. As obtained for the 1 H-NMR relaxation data, the two outer residues possess smaller order parameters than the two inner rings. Internal correlation times are in the order of 100 ps. The hydroxymethyl groups have also different behaviour,with the exocyclic carbon on the glucopyranoside unit showing the highestS 2 . Molecular dynamics simulations using a solvated system have also been performed and internal motion correlation functions have been deduced from these calculations. Order parameters and interproton distances have been compared to those inferred from the NMR measurements. The obtained results are in fair agreement with the experimental data

Monitoring of organic contaminants in sediments using low field proton nuclear magnetic resonance

Science.gov (United States)

Zhang, Chi; Rupert, Yuri

2016-04-01

The effective monitoring of soils and groundwater contaminated with organic compounds is an important goal of many environmental restoration efforts. Recent geophysical methods such as electrical resistivity, complex conductivity, and ground penetrating radar have been successfully applied to characterize organic contaminants in the subsurface and to monitor remediation process both in laboratory and in field. Low field proton nuclear magnetic resonance (NMR) is a geophysical tool sensitive to the molecular-scale physical and chemical environment of hydrogen-bearing fluids in geological materials and shows promise as a novel method for monitoring contaminant remediation. This laboratory research focuses on measurements on synthetic samples to determine the sensitivity of NMR to the presence of organic contaminants and improve understanding of relationships between NMR observables, hydrological properties of the sediments, and amount and state of contaminants in porous media. Toluene, a light non-aqueous phase liquid (LNAPL) has been selected as a representative organic contaminant. Three types of porous media (pure silica sands, montmorillonite clay, and various sand-clay mixtures with different sand/clay ratios) were prepared as synthetic sediments. NMR relaxation time (T2) and diffusion-relaxation (D - T2) correlation measurements were performed in each sediment saturated with water and toluene mixed fluid at assorted concentrations (0% toluene and 100% water, 1% toluene and 99% water, 5% toluene and 95% water, 25% toluene and 75% water, and 100% toluene and 0% water) to 1) understand the effect of different porous media on the NMR responses in each fluid mixture, 2) investigate the role of clay content on T2 relaxation of each fluid, 3) quantify the amount hydrocarbons in the presence of water in each sediment, and 4) resolve hydrocarbons from water in D - T2 map. Relationships between the compositions of porous media, hydrocarbon concentration, and hydraulic

Accelerating proton spin diffusion in perdeuterated proteins at 100 kHz MAS

Energy Technology Data Exchange (ETDEWEB)

Wittmann, Johannes J.; Agarwal, Vipin; Hellwagner, Johannes; Lends, Alons; Cadalbert, Riccardo; Meier, Beat H., E-mail: beme@ethz.ch; Ernst, Matthias, E-mail: maer@ethz.ch [ETH Zurich, Physical Chemistry (Switzerland)

2016-12-15

Fast magic-angle spinning (>60 kHz) has many advantages but makes spin-diffusion-type proton–proton long-range polarization transfer inefficient and highly dependent on chemical-shift offset. Using 100%-HN-[{sup 2}H,{sup 13}C,{sup 15}N]-ubiquitin as a model substance, we quantify the influence of the chemical-shift difference on the spin diffusion between proton spins and compare two experiments which lead to an improved chemical-shift compensation of the transfer: rotating-frame spin diffusion and a new experiment, reverse amplitude-modulated MIRROR. Both approaches enable broadband spin diffusion, but the application of the first variant is limited due to fast spin relaxation in the rotating frame. The reverse MIRROR experiment, in contrast, is a promising candidate for the determination of structurally relevant distance restraints. The applied tailored rf-irradiation schemes allow full control over the range of recoupled chemical shifts and efficiently drive spin diffusion. Here, the relevant relaxation time is the larger longitudinal relaxation time, which leads to a higher signal-to-noise ratio in the spectra.

Magnetic relaxation in analytical, coordination and bioinorganic chemistry

International Nuclear Information System (INIS)

Mikhajlov, O.

1982-01-01

Nuclear magnetic relaxation is a special type of nuclear magnetic resonance in which the rate is measured of energy transfer between the excited nuclei and their molecular medium (spin-lattice relaxation) or the whole nuclear spin system (spin-spin relaxation). Nuclear magnetic relaxation relates to nuclei with a spin of 1/2, primarily H 1 1 , and is mainly measured in water solutions. It is suitable for (1) analytical chemistry because the relaxation time rapidly reduces in the presence of paramagnetic ions, (2) the study of complex compounds, (3) the study of biochemical reactions in the presence of different metal ions. It is also suitable for testing the composition of a flowing liquid. Its disadvantage is that it requires complex and expensive equipment. (Ha)

NMR mechanisms in gel dosimetry

International Nuclear Information System (INIS)

Schreiner, L J

2009-01-01

Nuclear magnetic resonance was critical to the development of gel dosimetry, as it established the potential for three dimensional dosimetry with chemical dosimeter systems through magnetic resonance imaging [1]. In the last two decades MRI has served as the gold standard for imaging, while NMR relaxometry has played an important role in the development and understanding of the behaviour of new gel dosimetry systems. Therefore, an appreciation of the relaxation mechanisms determining the NMR behaviour of irradiated gel dosimeters is important for a full comprehension of a considerable component of the literature on gel dosimetry. A number of excellent papers have presented this important theory, this brief review will highlight some of the salient points made previously [1-5]. The spin relaxation of gel dosimeters (which determines the dose dependence in most conventional MR imaging) is determined principally by the protons on water molecules in the system. These water protons exist in different environments, or groups (see Figure 1): on bulk water, on water hydrating the chemical species that are being modified under irradiation, and on water hydrating the gel matrix used to spatially stabilize the dosimeter (e.g., gelatin, agarose, etc). The spin relaxation depends on the inherent relaxation rate of each spin group, that is, on the relaxation rate which would be observed for the specific group if it were isolated. Also, the different water environments are not isolated from each other, and the observed relaxation rate also depends on the rate of exchange of magnetization between the groups, and on the fraction of protons in each group. In fact, the water exchanges quickly between the environments, so that relaxation is in what is usually termed the fast exchange regime. In the limit of fast exchange, the relaxation of the water protons is well characterized by a single exponential and hence by a single apparent relaxation rate. In irradiated gel dosimeters this

Nuclear spin relaxation due to hydrogen diffusion in b.c.c. metals

International Nuclear Information System (INIS)

Faux, D.A.; Hall, C.K.

1989-01-01

We present Monte Carlo simulation results for the proton-proton contribution to the T 1 -1 relaxation rate for hydrogen spins diffusing on the tetrahedral sites of a b.c.c. metal. It is assumed that each hydrogen blocks all sites to the zeroth (no multiple-occupancy), second or third neighbour and that longer-range interactions may be neglected. Comparisons are made to the BPP and Torrey models. It is found that both the BPP and Torrey models give reasonable values for the peak height but that their predictions for the peak position and the high- and low-temperature limit are in error, particularly for large blocking distances. (orig.)

Wall relaxation and the driving forces for cell expansive growth

Science.gov (United States)

Cosgrove, D. J.

1987-01-01

When water uptake by growing cells is prevented, the turgor pressure and the tensile stress in the cell wall are reduced by continued wall loosening. This process, termed in vivo stress relaxation, provides a new way to study the dynamics of wall loosening and to measure the wall yield threshold and the physiological wall extensibility. Stress relaxation experiments indicate that wall stress supplies the mechanical driving force for wall yielding. Cell expansion also requires water absorption. The driving force for water uptake during growth is created by wall relaxation, which lowers the water potential of the expanding cells. New techniques for measuring this driving force show that it is smaller than believed previously; in elongating stems it is only 0.3 to 0.5 bar. This means that the hydraulic resistance of the water transport pathway is small and that rate of cell expansion is controlled primarily by wall loosening and yielding.

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

Energy Technology Data Exchange (ETDEWEB)

Guerrero, A. F., E-mail: afguerreror@uqvirtual.edu.co [Departamento de Física, Universidad Del Quindío Cra 15 # 12N Armenia, Quindío (Colombia); Mesa, J., E-mail: jmesa@ibb.unesp.br [Instituto de Biociências de Botucatu da UNESP Distrito de Rubião Jr. s/n°, 18618-000, Botucatu, SP (Brazil)

2016-07-07

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 10{sup 1} eV - 10{sup 10} eV taking into account all the charge states is calculated.

Hydrogen-1 NMR relaxation time studies in membrane: anesthetic systems

International Nuclear Information System (INIS)

Pinto, L.M.A.; Fraceto, L.; Paula, E. de; Franzoni, L.; Spisni, A.

1997-01-01

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 1 H-NMR longitudinal relaxation times (T 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 1 in this system than in isotropic phases, reflecting LA immobilization caused by insertion in the membrane. T 1 values for the lipid protons in the presence of LA were analyzed, in an attempt to identify specific LA:lipid contact regions. (author)

Investigation of water distribution in proton exchange membrane fuel cells via Terahertz imaging

International Nuclear Information System (INIS)

Thamboon, P.; Buaphad, P.; Thongbai, C.; Saisud, J.; Kusoljariyakul, K.; Rhodes, M.W.; Vilaithong, T.

2011-01-01

Coherent transition radiation in a THz regime generated from a femtosecond electron bunch is explored for its potential use in imaging applications. Due to water sensitivity, the THz imaging experiment is performed on a proton exchange membrane fuel cell (PEMFC) to assess the ability to quantify water in the flow field of the cell. In this investigation, the PEMFC design and the experimental setup for the THz imaging is described. The results of the THz images in the flow field are also discussed.

An experimental study on MRI signal intensity vs concentration of water-soluble contrast media

International Nuclear Information System (INIS)

Lee, Ghi Jai; Han, Chang Yul; Chang, Kee Hyun; Han, Moon Hee; Han, Man Chung

1991-01-01

There has been only one report that water-soluble contrast media containing iodine and used in conventional X -ray radiography reduce T1-and T2-relaxation times. We evaluated the relationship between signal intensity (relative signal intensity to normal saline) and T2-relaxation time of MRI and the concentration of 3 water-soluble contrast media [meglumine ioxithalamate (Telebrix 30), iopromide (Ultravist 300), iotrolan (Isovist 300)] through the phantom study, using both 2.0T and 0.5T MR units. We found that the signal intensity increased significantly on the T1-weighted images as the concentration of contrast media increased. The degree of the increase was larger on 0.5T MR than on 2.0T MR. The signal intensity on proton density image showed no significant difference at various concentrations. However, there were significant decreases of both signal intensity on the T2-weighted images and T2-relaxation time as the concentration of contrast media increased, which was more prominent on 2.0T MR than 0.5T MR. Between the contrast media of the same concentration, there was no significant difference in signal intensity and T2-relaxation time

Characterization of water in hydrated Bombyx mori silk fibroin fiber and films by 2H NMR relaxation and 13C solid state NMR.

Science.gov (United States)

Asakura, Tetsuo; Isobe, Kotaro; Kametani, Shunsuke; Ukpebor, Obehi T; Silverstein, Moshe C; Boutis, Gregory S

2017-03-01

The mechanical properties of Bombyx mori silk fibroin (SF), such as elasticity and tensile strength, change remarkably upon hydration. However, the microscopic interaction with water is not currently well understood on a molecular level. In this work, the dynamics of water molecules interacting with SF was studied by 2 H solution NMR relaxation and exchange measurements. Additionally, the conformations of hydrated [3- 13 C]Ala-, [3- 13 C]Ser-, and [3- 13 C]Tyr-SF fibers and films were investigated by 13 C DD/MAS NMR. Using an inverse Laplace transform algorithm, we were able to identify four distinct components in the relaxation times for water in SF fiber. Namely, A: bulk water outside the fiber, B: water molecules trapped weakly on the surface of the fiber, C: bound water molecules located in the inner surface of the fiber, and D: bound water molecules located in the inner part of the fiber were distinguishable. In addition, four components were also observed for water in the SF film immersed in methanol for 30s, while only two components for the film immersed in methanol for 24h. The effects of hydration on the conformation of Ser and Tyr residues in the site-specific crystalline and non-crystalline domains of 13 C selectively labeled SF, respectively, could be determined independently. Our measurements provide new insight relating the characteristics of water and the hydration structure of silk, which are relevant in light of current interest in the design of novel silk-based biomaterials. The mechanical properties of Bombyx mori silk fibroin (SF) change remarkably upon hydration. However, the microscopic interaction between SF and water is not currently well understood on a molecular level. We were able to identify four distinct components in the relaxation times for water in SF fiber by 2 H solution NMR relaxation and exchange measurements. In addition, the effects of hydration on the conformation of Ser and Tyr residues in the site-specific crystalline and

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.

Proton and aluminum binding properties of organic acids in surface waters of the northeastern U.S.

Science.gov (United States)

Fakhraei, Habibollah; Driscoll, Charles T

2015-03-03

A variety of mathematical estimators have been used to quantify the degree of protonation of naturally occurring organic acids. These estimators range from monoprotic, diprotic, and triprotic analog models to the discrete and continuous (Gaussian) distributions of a single proton binding-dissociation. Natural water samples from two long-term monitoring programs in the northeastern U.S. were used to quantify proton- and aluminum-binding properties of naturally occurring organic matter. Water chemistry observations were clustered into 0.05 pH intervals (over 3.75-7.35 pH range) and fit to a triprotic analog model. The model optimization indicates that about 5% of dissolved organic carbon participates in ion binding, and organic acids are composed of both strong and weak acids (i.e., pKa1 = 2.54, pKa2 = 6.19, and pKa3 = 7.52 for Adirondack samples). Binding between organic acids and aluminum can substantially influence the acid behavior of dissolved organic matter and the availability of the toxic form of aluminum (i.e., inorganic monomeric aluminum).

Solution conformation and dynamics of a tetrasaccharide related to the Lewis{sup X} antigen deduced by NMR relaxation measurements

Energy Technology Data Exchange (ETDEWEB)

Poveda, Ana [Universidad Autonoma de Madrid, Servicio Interdepartamental de Investigacion (Spain); Asensio, Juan Luis; Martin-Pastor, Manuel; Jimenez-Barbero, Jesus [Instituto de Quimica Organica, CSIC, Grupo de Carbohidratos (Spain)

1997-07-15

{sup 1}H-NMR cross-relaxation rates and nonselective longitudinal relaxation times have been obtained at two magnetic fields (7.0 and 11.8 T) and at a variety of temperatures for the branched tetrasaccharide methyl 3-O-{alpha}-N-acetyl-galactosaminyl-{beta}-galactopyranosyl-(1{sup {yields}}4)[3-O-{alpha}-fucosyl] -glucopyranoside (1), an inhibitor of astrocyte growth. In addition, {sup 13}C-NMR relaxation data have also been recorded at both fields. The {sup 1}H-NMR relaxation data have been interpreted using different motional models to obtain proton-proton correlation times. The results indicate that the GalNAc and Fuc rings display more extensive local motion than the two inner Glc and Gal moieties, since those present significantly shorter local correlation times. The{sup 13}C-NMR relaxation parameters have been interpreted in terms of the Lipari-Szabo model-free approach. Thus, order parameters and internal motion correlation times have been deduced. As obtained for the{sup 1}H-NMR relaxation data, the two outer residues possess smaller order parameters than the two inner rings. Internal correlation times are in the order of 100 ps. The hydroxymethyl groups have also different behaviour,with the exocyclic carbon on the glucopyranoside unit showing the highestS{sup 2}. Molecular dynamics simulations using a solvated system have also been performed and internal motion correlation functions have been deduced from these calculations. Order parameters and interproton distances have been compared to those inferred from the NMR measurements. The obtained results are in fair agreement with the experimental data.

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.

Pressure control of a proton beam-irradiated water target through an internal flow channel-induced thermosyphon.

Science.gov (United States)

Hong, Bong Hwan; Jung, In Su

2017-07-01

A water target was designed to enhance cooling efficiency using a thermosyphon, which is a system that uses natural convection to induce heat exchange. Two water targets were fabricated: a square target without any flow channel and a target with a flow channel design to induce a thermosyphon mechanism. These two targets had the same internal volume of 8 ml. First, visualization experiments were performed to observe the internal flow by natural convection. Subsequently, an experiment was conducted to compare the cooling performance of both water targets by measuring the temperature and pressure. A 30-MeV proton beam with a beam current of 20 μA was used to irradiate both targets. Consequently, the target with an internal flow channel had a lower mean temperature and a 50% pressure drop compared to the target without a flow channel during proton beam irradiation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Automated processing for proton spectroscopic imaging using water reference deconvolution.

Science.gov (United States)

Maudsley, A A; Wu, Z; Meyerhoff, D J; Weiner, M W

1994-06-01

Automated formation of MR spectroscopic images (MRSI) is necessary before routine application of these methods is possible for in vivo studies; however, this task is complicated by the presence of spatially dependent instrumental distortions and the complex nature of the MR spectrum. A data processing method is presented for completely automated formation of in vivo proton spectroscopic images, and applied for analysis of human brain metabolites. This procedure uses the water reference deconvolution method (G. A. Morris, J. Magn. Reson. 80, 547(1988)) to correct for line shape distortions caused by instrumental and sample characteristics, followed by parametric spectral analysis. Results for automated image formation were found to compare favorably with operator dependent spectral integration methods. While the water reference deconvolution processing was found to provide good correction of spatially dependent resonance frequency shifts, it was found to be susceptible to errors for correction of line shape distortions. These occur due to differences between the water reference and the metabolite distributions.

T1 and T2 relaxivity of intracellular and extracellular USPIO at 1.5T and 3T clinical MR scanning

International Nuclear Information System (INIS)

Simon, Gerhard H.; Bauer, Jan; Saborovski, Olaf; Fu, Yanjun; Wendland, Michael F.; Daldrup-Link, Heike E.; Corot, Claire

2006-01-01

In this study we evaluated the effects of intracellular compartmentalization of the ultrasmall superparamagnetic iron oxide (USPIO) ferumoxtran-10 on its proton T1 and T2 relaxivities at 1.5 and 3T. Monocytes were labeled with ferumoxtran-10 by simple incubation. Decreasing quantities of ferumoxtran-10-labeled cells (2.5 x 10 7 -0.3 x 10 7 cells/ml) and decreasing concentrations of free ferumoxtran-10 (without cells) in Ficoll solution were evaluated with 1.5 and 3T clinical magnetic resonance (MR) scanners. Pulse sequences comprised axial spin echo (SE) sequences with multiple TRs and fixed TE and SE sequences with fixed TR and increasing TEs. Signal intensity measurements were used to calculate T1 and T2 relaxation times of all samples, assuming a monoexponential signal decay. The iron content in all samples was determined by inductively coupled plasma atomic emission spectrometry and used for calculating relaxivities. Measurements at 1.5T and 3T showed higher T1 and T2 relaxivity values of free extracellular ferumoxtran-10 as opposed to intracellularly compartmentalized ferumoxtran-10, under the evaluated conditions of homogeneously dispersed contrast agents/cells in Ficoll solution and a cell density of up to 2.5 x 10 7 cells/ml. At 3T, differences in T1-relaxivities between intra- and extracellular USPIO were smaller, while differences in USPIO T2-relaxivities were similar compared with 1.5T. In conclusion, cellular compartmentalization of ferumoxtran-10 changes proton relaxivity. (orig.)

Nuclear magnetic resonance studies on brain edema. Time course of /sup 1/H-NMR relaxation times

Energy Technology Data Exchange (ETDEWEB)

Naruse, S; Horikawa, Y; Tanaka, C; Hirakawa, K; Nishikawa, H [Kyoto Prefectural Univ. of Medicine (Japan)

1981-06-01

1. The state of water in normal and edematous brain tissue was studied by measurement of proton longitudinal (T/sub 1/) and transverse (T/sub 2/) relaxation times using pulsed nuclear magnetic resonance (NMR) technique. 2. In control rats, T/sub 1/ and T/sub 2/ of water showed one component, which was more fast in white matter. Those values displayed 1.07 - 1.18 sec. of T/sub 1/ and 75 - 76 msec. of T/sub 2/. 3. When rat brain was injured by cold, T/sub 1/ was observed to become longer (1.18 - 1.27 sec.), and T/sub 2/ was observed be separated into two components, the faster T/sub 2/ (45 - 50 msec.) and slower T/sub 2/ (100 - 105 msec.), in both gray and white matter of the injured side. 4. In triethyltin (TET) induced brain edema, elongation of T/sub 1/ (1.2 sec.) and remarkable separation of T/sub 2/, faster T/sub 2/ (75 msec.) and slower T/sub 2/ (400 - 450 msec.), were observed in white matter. 5. In both cold and TET induced edema, slower T/sub 2/ fraction is suggested to be the extracellular space and faster T/sub 2/ fraction, intracellular. 6. T/sub 2/ changes precede the water content changes in cold injury, and parallel in TET induced edema. Those changes of relaxation times are reversible. 7. T/sub 2/ changes of water is more sensitive than the T/sub 1/ for the detection of production and disappearance of brain edema. 8. These results disclose the dynamic movements of water during the course of brain edema and offered significant information of the clinical application of NMR-CT.

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

Water permeability of acinar cell membranes in the isolated perfused rabbit mandibular salivary gland.

Science.gov (United States)

Steward, M C; Seo, Y; Rawlings, J M; Case, R M

1990-01-01

1. The diffusive water permeability of epithelial cell membranes in the perfused rabbit mandibular salivary gland was measured at 37 degrees C by a 1H nuclear magnetic resonance relaxation method using an extracellular relaxation reagent, gadolinium diethylenetriaminepentaacetic acid (Gd(DTPA)). 2. In glands perfused with a HEPES-buffered solution containing 10 mmol l-1 Gd(DTPA), the spin-lattice (T1) relaxation of the water protons showed two exponential components. The water compartment responsible for the slower component corresponded in magnitude to 71 +/- 5% of the wet weight of the gland, and was attributed to the exchangeable intracellular water of the acinar cells. 3. The rate constant for water efflux from the cells was estimated to be 4.1 +/- 0.1 s-1 which would be consistent with a diffusive membrane permeability (Pd) of approximately 3 x 10(-3) cm s-1. Stimulation with acetylcholine (10(-6) mol l-1) did not cause any detectable change in membrane water permeability. 4. Since the basolateral membrane probably provides the main pathway for water efflux, the osmotic water permeability of this barrier (expressed per gland) was estimated to be less than 6.2 cm3 s-1. This would be insufficient to account for the generation of a near-isosmotic fluid at the flow rates observed during secretion, and suggests that a substantial fraction of the flow of water occurs via a paracellular route. PMID:1966053

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.

Effects of the Relaxation of Upwelling-Favorable Winds on the Diurnal and Semidiurnal Water Temperature Fluctuations in the Santa Barbara Channel, California

Science.gov (United States)

Aristizábal, María. F.; Fewings, Melanie R.; Washburn, Libe

2017-10-01

In the Santa Barbara Channel, California, and around the Northern Channel Islands, water temperature fluctuations in the diurnal and semidiurnal frequency bands are intermittent, with amplitudes that vary on time scales of days to weeks. The cause of this intermittency is not well understood. We studied the effects of the barotropic tide, vertical stratification, propagation of coastal-trapped waves, regional wind relaxations, and diurnal-band winds on the intermittency of the temperature fluctuations during 1992-2015. We used temperature data from 43 moorings in 10-200 m water depth and wind data from two buoys and one land station. Subtidal-frequency changes in vertical stratification explain 20-40% of the intermittency in diurnal and semidiurnal temperature fluctuations at time scales of days to weeks. Along the mainland north of Point Conception and at the Northern Channel Islands, the relaxation of upwelling-favorable winds substantially increases vertical stratification, accounting for up to 55% of the subtidal-frequency variability in stratification. As a result of the enhanced stratification, wind relaxations enhance the diurnal and semidiurnal temperature fluctuations at those sites, even though the diurnal-band wind forcing decreases during wind relaxation. A linear model where the background stratification is advected vertically explains a substantial fraction of the temperature fluctuations at most sites. The increase of vertical stratification and subsequent increase in diurnal and semidiurnal temperature fluctuations during wind relaxation is a mechanism that can supply nutrients to the euphotic zone and kelp forests in the Channel in summer when upwelling is weak.

Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: longitudinal relaxation dispersion for spin I = 1.

Science.gov (United States)

Nilsson, Tomas; Halle, Bertil

2012-08-07

The frequency dependence of the longitudinal relaxation rate, known as the magnetic relaxation dispersion (MRD), can provide a frequency-resolved characterization of molecular motions in complex biological and colloidal systems on time scales ranging from 1 ns to 100 μs. The conformational dynamics of immobilized proteins and other biopolymers can thus be probed in vitro or in vivo by exploiting internal water molecules or labile hydrogens that exchange with a dominant bulk water pool. Numerous water (1)H and (2)H MRD studies of such systems have been reported, but the widely different theoretical models currently used to analyze the MRD data have resulted in divergent views of the underlying molecular motions. We have argued that the essential mechanism responsible for the main dispersion is the exchange-mediated orientational randomization (EMOR) of anisotropic nuclear (electric quadrupole or magnetic dipole) couplings when internal water molecules or labile hydrogens escape from orientationally confining macromolecular sites. In the EMOR model, the exchange process is thus not just a means of mixing spin populations but it is also the direct cause of spin relaxation. Although the EMOR theory has been used in several studies to analyze water (2)H MRD data from immobilized biopolymers, the fully developed theory has not been described. Here, we present a comprehensive account of a generalized version of the EMOR theory for spin I = 1 nuclides like (2)H. As compared to a previously described version of the EMOR theory, the present version incorporates three generalizations that are all essential in applications to experimental data: (i) a biaxial (residual) electric field gradient tensor, (ii) direct and indirect effects of internal motions, and (iii) multiple sites with different exchange rates. In addition, we describe and assess different approximations to the exact EMOR theory that are useful in various regimes. In particular, we consider the experimentally

Paraffin molecule mobility in channel clathrates of urea on spectroscopic NMR relaxation data

CERN Document Server

Kriger, Y G; Chekhova, G N

2001-01-01

The temperature dependences of the protons spin-lattice relaxation time (T sub I) in the channel clathrates of urea with paraffins are measured. The data on the T sub I are interpreted within the frames of the model of the paraffins molecules and their fragments orientation in the clathrate channels. The dynamics peculiarities are connected with the disproportion effects of these compounds

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; Christensen, Erik

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...

Anisotropy of the proton spin--lattice relaxation time in the superconducting intercalation complex TaS2(NH3): Structural and bonding implications

International Nuclear Information System (INIS)

Gamble, F.R.; Silbernagel, B.G.

1975-01-01

The nature of the interaction responsible for the formation of molecular intercalation complexes between Lewis bases and layered transition metal dichalcogenides is not well understood. To some extent this is due to a lack of structural information. A prototype of these complexes is TaS 2 (NH 3 ), in which monolayers of ammonia are inserted between the metallic, superconducting layers of TaS 2 . The compound is crystalline and stoichiometric. Measurement of the anisotropy of the proton spin--lattice relaxation time at 300 degreeK indicates that the molecular threefold symmetry axis is not perpendicular to the disulfide layers as suggested by other workers, but is parallel to the layers. This orientation precludes direct interaction between the molecular lone pair orbital and the transition metal atoms. The interactions governing the structure of this complex may be similar to those obtaining in the intercalation complexes between TaS 2 and a number of substituted pyridines, in which complexes the axis of the lone pair orbital is also parallel to the layers

Studying the destruction of various fluoropolymers caused by gamma - irradiation and MeV protons

International Nuclear Information System (INIS)

Allayarov, S.R.; Ol'khov, Yu.A.; Gordon, D.A.; Muntele, C.I.; Muntele, I.C.; Ila, D.; Dixon, D.A.; Kispert, L.D.; Nikolskij, V.G.

2007-01-01

While fluoropolymers are normally used as anti-adherent coating, they are intensely investigated for potential use in various radiation dosimeter applications as well as space technology. In order to understand the discrepancy between high chemical and thermal stability and low radiation stability of various fluoropolymers, we are bombarding them with 1 MeV protons to fluences up to 2·10 15 protons/cm 2 as well as subjected some of them to gamma-irradiation by dose of 10 kGy. During bombardment we are monitoring the emission of chemical species with a residual gas analyzer. Gamma-irradiated samples were tested by radio thermoluminescence method. The results we present here are a good indicator that material damage happens much earlier than 2·10 15 protons/cm 2 and that further work should be addressed at much smaller exposures. Radio thermoluminescence also can be used at small doses of irradiation (10-30 kGy). The thermomechanical curve of radiation-free polyvinyledenefluoride (PVDF) is characteristic for topologically di-block amorphous polymer of quasi-crossing structure. In the temperature range of from 173 K up to 228 K polymer is vitrified. The vitrification temperature of PVDF is 228 K. All molecular-relaxation and quantitative characteristics of PVDF were determined before and after its irradiation by protons. Protons caused significant changes in PVDF. From di-block amorphous it transformed in to amorphous-crystalline structure. An appreciable influence of dose at proton irradiation of polymer was revealed both on topological level and on molecular-relaxation one. (authors)

Feasibility of proton-activated implantable markers for proton range verification using PET

Science.gov (United States)

Cho, Jongmin; Ibbott, Geoffrey; Gillin, Michael; Gonzalez-Lepera, Carlos; Titt, Uwe; Paganetti, Harald; Kerr, Matthew; Mawlawi, Osama

2013-11-01

Proton beam range verification using positron emission tomography (PET) currently relies on proton activation of tissue, the products of which decay with a short half-life and necessitate an on-site PET scanner. Tissue activation is, however, negligible near the distal dose fall-off region of the proton beam range due to their high interaction energy thresholds. Therefore Monte Carlo simulation is often supplemented for comparison with measurement; however, this also may be associated with systematic and statistical uncertainties. Therefore, we sought to test the feasibility of using long-lived proton-activated external materials that are inserted or infused into the target volume for more accurate proton beam range verification that could be performed at an off-site PET scanner. We irradiated samples of ≥98% 18O-enriched water, natural Cu foils, and >97% 68Zn-enriched foils as candidate materials, along with samples of tissue-equivalent materials including 16O water, heptane (C7H16), and polycarbonate (C16H14O3)n, at four depths (ranging from 100% to 3% of center of modulation (COM) dose) along the distal fall-off of a modulated 160 MeV proton beam. Samples were irradiated either directly or after being embedded in Plastic Water® or balsa wood. We then measured the activity of the samples using PET imaging for 20 or 30 min after various delay times. Measured activities of candidate materials were up to 100 times greater than those of the tissue-equivalent materials at the four distal dose fall-off depths. The differences between candidate materials and tissue-equivalent materials became more apparent after longer delays between irradiation and PET imaging, due to the longer half-lives of the candidate materials. Furthermore, the activation of the candidate materials closely mimicked the distal dose fall-off with offsets of 1 to 2 mm. Also, signals from the foils were clearly visible compared to the background from the activated Plastic Water® and balsa wood

Curie-type paramagnetic NMR relaxation in the aqueous solution of Ni(II).

Science.gov (United States)

Mareš, Jiří; Hanni, Matti; Lantto, Perttu; Lounila, Juhani; Vaara, Juha

2014-04-21

Ni(2+)(aq) has been used for many decades as a model system for paramagnetic nuclear magnetic resonance (pNMR) relaxation studies. More recently, its magnetic properties and also nuclear magnetic relaxation rates have been studied computationally. We have calculated electron paramagnetic resonance and NMR parameters using quantum-mechanical (QM) computation of molecular dynamics snapshots, obtained using a polarizable empirical force field. Statistical averages of hyperfine coupling, g- and zero-field splitting tensors, as well as the pNMR shielding terms, are compared to the available experimental and computational data. In accordance with our previous work, the isotropic hyperfine coupling as well as nuclear shielding values agree well with experimental measurements for the (17)O nuclei of water molecules in the first solvation shell of the nickel ion, whereas larger deviations are found for (1)H centers. We report, for the first time, the Curie-type contribution to the pNMR relaxation rate using QM calculations together with Redfield relaxation theory. The Curie relaxation mechanism is analogous to chemical shift anisotropy relaxation, well-known in diamagnetic NMR. Due to the predominance of other types of paramagnetic relaxation mechanisms for this system, it is possible to extract the Curie term only computationally. The Curie mechanism alone would result in around 16 and 20 s(-1) of relaxation rates (R1 and R2 respectively) for the (1)H nuclei of water molecules bonded to the Ni(2+) center, in a magnetic field of 11.7 T. The corresponding (17)O relaxation rates are around 33 and 38 s(-1). We also report the Curie contribution to the relaxation rate for molecules beyond the first solvation shell in a 1 M solution of Ni(2+) in water.

The impact of fibre orientation on T1-relaxation and apparent tissue water content in white matter.

Science.gov (United States)

Schyboll, Felix; Jaekel, Uwe; Weber, Bernd; Neeb, Heiko

2018-02-20

Recent MRI studies have shown that the orientation of nerve fibres relative to the main magnetic field affects the R 2 *(= 1/T 2 *) relaxation rate in white matter (WM) structures. The underlying physical causes have been discussed in several studies but are still not completely understood. However, understanding these effects in detail is of great importance since this might serve as a basis for the development of new diagnostic tools and/or improve quantitative susceptibility mapping techniques. Therefore, in addition to the known angular dependence of R 2 *, the current study investigates the relationship between fibre orientation and the longitudinal relaxation rate, R 1 (= 1/T 1 ), as well as the apparent water content. For a group of 16 healthy subjects, a series of gradient echo, echo-planar and diffusion weighted images were acquired at 3T from which the decay rates, the apparent water content and the diffusion direction were reconstructed. The diffusion weighted data were used to determine the angle between the principle fibre direction and the main magnetic field to examine the angular dependence of R 1 and apparent water content. The obtained results demonstrate that both parameters depend on the fibre orientation and exhibit a positive correlation with the angle between fibre direction and main magnetic field. These observations could be helpful to improve and/or constrain existing biophysical models of brain microstructure by imposing additional constraints resulting from the observed angular dependence R 1 and apparent water content in white matter.

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)

Energizing porters by proton-motive force.

Science.gov (United States)

Nelson, N

1994-11-01

It is generally accepted that the chemistry of water was the most crucial determinant in shaping life on earth. Among the more important chemical features of water is its dissociation into protons and hydroxyl ions. The presence of relatively high proton concentrations in the ambient solution resulted in the evolution of proton pumps during the dawn of life on earth. These proton pumps maintained neutral pH inside the cells and generated electrochemical gradients of protons (proton-motive force) across their membranes. The existence of proton-motive force enabled the evolution of porters driven by it that are most probably among the more primitive porters in the world. The directionality of the substrate transport by the porters could be to both sides of the membranes because they can serve as proton symporters or antiporters. One of the most important subjects of this meeting is the mechanism by which proton-motive and other ion-motive forces drive the transport processes through porters. Is there a common mechanism of action for all proton-driven porters? Is there some common partial reaction by which we can identify the way that porters are energized by proton-motive force? Is there a common coupling between proton movement and uptake or secretion of certain molecules? Even a partial answer to one of these questions would advance our knowledge... or confusion. As my mentor Efraim Racker used to say: 'If you are not totally confused you do not understand the issue'.

Proton affinities in water of maingroup-element Hydrides - Effects of hydration and methyl substitution

NARCIS (Netherlands)

Swart, M.; Rosler, E.; Bickelhaupt, F.M.

2007-01-01

We have computed the proton affinities in water of archetypal anionic and neutral bases across the periodic table using the generalized gradient approximation (GGA) of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. The main purpose of this work is to provide an intrinsically consistent set

1H NMR relaxometry as an indicator of setting and water depletion during cement hydration

International Nuclear Information System (INIS)

Wang, Biyun; Faure, Paméla; Thiéry, Mickaël; Baroghel-Bouny, Véronique

2013-01-01

Proton nuclear magnetic resonance relaxometry has been used to detect setting and microstructure evolution during cement hydration. NMR measurements were performed since casting, during setting and until hardening (from 0 to 3 days). The mobility of water molecules was assessed by an analysis focused on the diagram of longitudinal relaxation time T 1 generated by an Inversion Recovery sequence. The initial stiffening of the solid network was identified by an analysis of the relaxation rate 1/T 1 . The kinetics of water depletion was investigated by using a simple one-pulse acquisition sequence. In parallel, conventional techniques (Vicat needle and temperature monitoring), as well as numerical simulations of hydration, were used to complement and validate these NMR results. Cement pastes and mortars with different water-to-cement ratios made of grey or white OPCs were tested. Furthermore, the effects of the addition of sand, super-plasticizer and silica fume on the hydration kinetics were investigated

Influence of different environments on the excited-state proton transfer and dual fluorescence of fisetin

Science.gov (United States)

Guharay, Jayanti; Dennison, S. Moses; Sengupta, Pradeep K.

1999-05-01

The influence of different protic and aprotic solvent environments on the excited-state intramolecular proton transfer (ESIPT) leading to a dual fluorescence behaviour of a biologically important, naturally occurring, polyhydroxyflavone, fisetin (3,3',4',7-tetrahydroxyflavone), has been investigated. The normal fluorescence band, in particular, is extremely sensitive to solvent polarity with νmax shifting from 24 510 cm -1 in dioxane ( ET(30)=36.0) to 20 790 cm -1 in methanol ( ET(30)=55.5). This is rationalized in terms of solvent dipolar relaxation process, which also accounts for the red edge excitation shifts (REES) observed in viscous environments such as glycerol at low temperatures. Significant solvent dependence of the tautomer fluorescence properties ( νmax, yield and decay kinetics) reveals the influence of external hydrogen bonding perturbation on the internal hydrogen bond of the molecule. These excited-state relaxation phenomena and their relevant parameters have been used to probe the microenvironment of fisetin in a membrane mimetic system, namely AOT reverse micelles in n-heptane at different water/surfactant molar ratio ( w0).

Proton beam monitor chamber calibration

International Nuclear Information System (INIS)

Gomà, C; Meer, D; Safai, S; Lorentini, S

2014-01-01

The first goal of this paper is to clarify the reference conditions for the reference dosimetry of clinical proton beams. A clear distinction is made between proton beam delivery systems which should be calibrated with a spread-out Bragg peak field and those that should be calibrated with a (pseudo-)monoenergetic proton beam. For the latter, this paper also compares two independent dosimetry techniques to calibrate the beam monitor chambers: absolute dosimetry (of the number of protons exiting the nozzle) with a Faraday cup and reference dosimetry (i.e. determination of the absorbed dose to water under IAEA TRS-398 reference conditions) with an ionization chamber. To compare the two techniques, Monte Carlo simulations were performed to convert dose-to-water to proton fluence. A good agreement was found between the Faraday cup technique and the reference dosimetry with a plane-parallel ionization chamber. The differences—of the order of 3%—were found to be within the uncertainty of the comparison. For cylindrical ionization chambers, however, the agreement was only possible when positioning the effective point of measurement of the chamber at the reference measurement depth—i.e. not complying with IAEA TRS-398 recommendations. In conclusion, for cylindrical ionization chambers, IAEA TRS-398 reference conditions for monoenergetic proton beams led to a systematic error in the determination of the absorbed dose to water, especially relevant for low-energy proton beams. To overcome this problem, the effective point of measurement of cylindrical ionization chambers should be taken into account when positioning the reference point of the chamber. Within the current IAEA TRS-398 recommendations, it seems advisable to use plane-parallel ionization chambers—rather than cylindrical chambers—for the reference dosimetry of pseudo-monoenergetic proton beams. (paper)

Menstrual variation of breast volume and T2 relaxation times in cyclical mastalgia

International Nuclear Information System (INIS)

Hussain, Zainab; Brooks, Jonathan; Percy, Dave

2008-01-01

Purpose: Hormonal activity causes breast volume to change during the menstrual cycle. One possible cause of this volume change is thought to be due to water retention or oedema within the tissues. We used magnetic resonance imaging (MRI) to study the variation in breast volume and 1 H Magnetic Resonance Spectroscopy (MRS) to measure T 2 relaxation times which are known to increase with increasing tissue water content. We hypothesised that an increase in breast volume will elevate T 2 relaxation due to the presence of an increased water content within the breast. T 2 Relaxation time and volume were studied in fifteen control subjects and in a cohort of eight patients with cyclical mastalgia in order to determine whether changes in breast volume and T 2 relaxation times differed in controls and patients during menses, ovulation and premenses. Method: Breast volume was determined by the Cavalieri method in combination with point counting techniques on MR images and T 2 relaxation times of the water and fat in a voxel of breast tissue were obtained using 1 H Magnetic Resonance Spectroscopy (MRS). Results: Statistical analysis (ANOVA) demonstrated highly significant differences in breast volume between the three stages of the cycle (p 2 of fat or water did not depend on stage of cycle. T-tests demonstrated no significant differences in T 2 of water or fat between patient and control groups. The average T 2 relaxation time of water was lowest in the patient and control groups during ovulation and highest in the patient group during premenses. Conclusion: We have performed the first combined volumetric and spectroscopic study of women with cyclical mastalgia and demonstrated that the global changes in volumes and T 2 were not significantly different from normal menstrual variations

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

Proton spectroscopic imaging of polyacrylamide gel dosimeters for absolute radiation dosimetry

International Nuclear Information System (INIS)

Murphy, P.S.; Schwarz, A.J.; Leach, M.O.

2000-01-01

Proton spectroscopy has been evaluated as a method for quantifying radiation induced changes in polyacrylamide gel dosimeters. A calibration was first performed using BANG-type gel samples receiving uniform doses of 6 MV photons from 0 to 9 Gy in 1 Gy intervals. The peak integral of the acrylic protons belonging to acrylamide and methylenebisacrylamide normalized to the water signal was plotted against absorbed dose. Response was approximately linear within the range 0-7 Gy. A large gel phantom irradiated with three, coplanar 3x3cm square fields to 5.74 Gy at isocentre was then imaged with an echo-filter technique to map the distribution of monomers directly. The image, normalized to the water signal, was converted into an absolute dose map. At the isocentre the measured dose was 5.69 Gy (SD = 0.09) which was in good agreement with the planned dose. The measured dose distribution elsewhere in the sample shows greater errors. A T 2 derived dose map demonstrated a better relative distribution but gave an overestimate of the dose at isocentre of 18%. The data indicate that MR measurements of monomer concentration can complement T 2 -based measurements and can be used to verify absolute dose. Compared with the more usual T 2 measurements for assessing gel polymerization, monomer concentration analysis is less sensitive to parameters such as gel pH and temperature, which can cause ambiguous relaxation time measurements and erroneous absolute dose calculations. (author)

Water Adsorption on Clean and Defective Anatase TiO2 (001) Nanotube Surfaces: A Surface Science Approach.

Science.gov (United States)

Kenmoe, Stephane; Lisovski, Oleg; Piskunov, Sergei; Bocharov, Dmitry; Zhukovskii, Yuri F; Spohr, Eckhard

2018-04-11

We use ab initio molecular dynamics simulations to study the adsorption of thin water films with 1 and 2 ML coverage on anatase TiO 2 (001) nanotubes. The nanotubes are modeled as 2D slabs, which consist of partially constrained and partially relaxed structural motifs from nanotubes. The effect of anion doping on the adsorption is investigated by substituting O atoms with N and S impurities on the nanotube slab surface. Due to strain-induced curvature effects, water adsorbs molecularly on defect-free surfaces via weak bonds on Ti sites and H bonds to surface oxygens. While the introduction of an S atom weakens the interaction of the surface with water, which adsorbs molecularly, the presence of an N impurity renders the surface more reactive to water, with a proton transfer from the water film and the formation of an NH group at the N site. At 2 ML coverage, a further surface-assisted proton transfer takes place in the water film, resulting in the formation of an OH - group and an NH 2 + cationic site on the surface.

Chemical dynamics of the first proton-coupled electron transfer of water oxidation on TiO2 anatase.

Science.gov (United States)

Chen, Jia; Li, Ye-Fei; Sit, Patrick; Selloni, Annabella

2013-12-18

Titanium dioxide (TiO2) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO2. We use a periodic model of the TiO2/water interface that includes a slab of anatase TiO2 and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer.

The Effect of Isotopic Substitution on Quantum Proton Transfer Across Short Water Bridges in Biological Systems

Science.gov (United States)

Blazejewski, Jacob; Schultz, Chase; Mazzuca, James

2015-03-01

Many biological systems utilize water chains to transfer charge over long distances by means of an excess proton. This study examines how quantum effects impact these reactions in a small model system. The model consists of a water molecule situated between an imidazole donor and acceptor group, which simulate a fixed amino acid backbone. A one dimensional energy profile is evaluated using density functional theory at the 6-31G*/B3LYP level, which generates a barrier with a width of 0.6 Å and a height of 20.7 kcal/mol. Quantum transmission probability is evaluated by solving the time dependent Schrödinger equation on a grid. Isotopic effects are examined by performing calculations with both hydrogen and deuterium. The ratio of hydrogen over the deuterium shows a 130-fold increase in transmission probability at low temperatures. This indicates a substantial quantum tunneling effect. The study of higher dimensional systems as well as increasing the number of water molecules in the chain will be necessary to fully describe the proton transfer process. Alma College Provost's Office.

Hydrogen-bond dynamics and proton transfer in nanoconfinement

NARCIS (Netherlands)

van der Loop, T.H.

2015-01-01

Proton transfer is of fundamental importance to both biology and chemistry. Much is known about proton transfer in large water volumes but often proton transfer reactions take place in very small nanometer sized volumes for example between lipid layers and in proton channels in mitochondria and

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.

Changes in the Zero-Point Energy of the Protons as the Source of the Binding Energy of Water to A-Phase DNA

International Nuclear Information System (INIS)

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

2010-01-01

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 Angst .

Proton exchange membranes from sulfonated polyetheretherketone and sulfonated polyethersulfone-cardo blends: Conductivity, water sorption and permeation properties

International Nuclear Information System (INIS)

Li, Yongli; Nguyen, Quang Trong; Schaetzel, Pierre; Lixon-Buquet, Camille; Colasse, Laurent; Ratieuville, Vincent

2013-01-01

Five blend membranes were prepared by solvent evaporation from solutions of the synthesized sulfonated polyetheretherketone (SPEEK) and sulfonated polyethersulfone-cardo (SPESc). Their ion exchange capacity and degree of sulfonation determined by acid–base titration and by thermogravimetric analysis were consistent. The blends glass transition behavior obtained by differential scanning calorimetry suggests that the two sulfonated polymers are compatible in the whole composition range. The values of the activation energy for proton transport determined by conductivity measurements on the SPEEK-based blend membranes were in the range of 13–34 kJ mol −1 , which suggest a mixed transport mechanism that involves both proton jumps on ionic sites and water of hydration and diffusion of proton–water complex in hydrophilic domains. The water vapor sorption in the membranes exhibits sigmoid-shape isotherms which were well fitted by the “new dual mode sorption” model, and the fitted parameters values were successfully used to model the change in the water permeation flux with the upstream water activity using the first Fick's diffusion equation. The fast increase in the permeation flux beyond a critical value of activity (0.5) was owing to the exponential concentration-dependent diffusion coefficient. These modelings allowed us to show a strong increase in the limit diffusion coefficient of water and a decrease in the water-diffusion plasticization coefficient with the SPEEK content in the polymer blends

Water-induced charge transport in tablets of microcrystalline cellulose of varying density: dielectric spectroscopy and transient current measurements

International Nuclear Information System (INIS)

Nilsson, Martin; Alderborn, Goeran; Stroemme, Maria

2003-01-01

Room temperature dielectric frequency response data taken over 13 decades in frequency on microcrystalline cellulose (MCC) tablets of varying density are presented. The frequency response shows on three different processes: the first one is a high-frequency relaxation process whose magnitude increases and reaches a plateau as the tablet density increases. This process is associated with orientational motions of local chain segments via glycosidic bonds. The second relaxation process, related to the presence of water in the MCC matrix, is insensitive to changes in tablet density. At lower frequencies, dc-like imperfect charge transport dominates the dielectric spectrum. The dc conductivity was found to decrease with increasing tablet density and increase exponentially with increasing humidity. Transient current measurements indicated that two different ionic species, protons and OH - ions, lied behind the observed conductivity. At ambient humidity of 22%, only one in a billion of the water molecules present in the tablet matrix participated in long range dc conduction. The diffusion coefficient of the protons and OH - ions were found to be of the order of 10 -9 cm 2 /s, which is the same as for small salt building ions in MCC. This shows that ionic drugs leaving a tablet matrix may diffuse in the same manner as the constituent ions of water and, thus, elucidates the necessity to understand the water transport properties of excipient materials to be able to tailor the drug release process from pharmaceutical tablets

Variational formulation of relaxed and multi-region relaxed magnetohydrodynamics

Science.gov (United States)

Dewar, R. L.; Yoshida, Z.; Bhattacharjee, A.; Hudson, S. R.

2015-12-01

> Ideal magnetohydrodynamics (IMHD) is strongly constrained by an infinite number of microscopic constraints expressing mass, entropy and magnetic flux conservation in each infinitesimal fluid element, the latter preventing magnetic reconnection. By contrast, in the Taylor relaxation model for formation of macroscopically self-organized plasma equilibrium states, all these constraints are relaxed save for the global magnetic fluxes and helicity. A Lagrangian variational principle is presented that leads to a new, fully dynamical, relaxed magnetohydrodynamics (RxMHD), such that all static solutions are Taylor states but also allows state with flow. By postulating that some long-lived macroscopic current sheets can act as barriers to relaxation, separating the plasma into multiple relaxation regions, a further generalization, multi-region relaxed magnetohydrodynamics (MRxMHD) is developed.

Doppler-shift proton fraction measurement on a CW proton injector

International Nuclear Information System (INIS)

Kamperschroer, J.H.; Sherman, J.D.; Zaugg, T.J.; Arvin, A.H.; Bolt, A.S.; Richards, M.C.

1998-01-01

A spectrometer/Optical Multi-channel Analyzer has been used to measure the proton fraction of the cw proton injector developed for the Accelerator Production of Tritium (APT) and the Low Energy Demonstration Accelerator (LEDA) at Los Alamos. This technique, pioneered by the Lawrence Berkeley National Laboratory (LBNL), was subsequently adopted by the international fusion community as the standard for determining the extracted ion fractions of neutral beam injectors. Proton fractions up to 95 ± 3% have been measured on the LEDA injector. These values are in good agreement with results obtained by magnetically sweeping the ion beam, collimated by a slit, across a Faraday cup. Since the velocity distribution of each beam species is measured, it also can be used to determine beam divergence. While divergence has not yet been ascertained due to the wide slit widths in use, non-Gaussian distributions have been observed during operation above the design-matched perveance. An additional feature is that the presence of extracted water ions can be observed. During ion source conditioning at 75 kV, an extracted water fraction > 30% was briefly observed

Pair plasma relaxation time scales.

Science.gov (United States)

Aksenov, A G; Ruffini, R; Vereshchagin, G V

2010-04-01

By numerically solving the relativistic Boltzmann equations, we compute the time scale for relaxation to thermal equilibrium for an optically thick electron-positron plasma with baryon loading. We focus on the time scales of electromagnetic interactions. The collisional integrals are obtained directly from the corresponding QED matrix elements. Thermalization time scales are computed for a wide range of values of both the total-energy density (over 10 orders of magnitude) and of the baryonic loading parameter (over 6 orders of magnitude). This also allows us to study such interesting limiting cases as the almost purely electron-positron plasma or electron-proton plasma as well as intermediate cases. These results appear to be important both for laboratory experiments aimed at generating optically thick pair plasmas as well as for astrophysical models in which electron-positron pair plasmas play a relevant role.

Conceptual design of proton beam window

International Nuclear Information System (INIS)

Teraoku, Takuji; Kaminaga, Masanori; Terada, Atsuhiko; Ishikura, Syuichi; Kinoshita, Hidetaka; Hino, Ryutaro

2001-01-01

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)

Proton T2 relaxation effect of superparamagnetic iron oxide. Comparison between fast spin echo and conventional spin echo sequence

International Nuclear Information System (INIS)

Tanimoto, Akihiro; Satoh, Yoshinori; Higuchi, Nobuya; Izutsu, Mutsumu; Yuasa, Yuji; Hiramatsu, Kyoichi

1995-01-01

Superparamagnetic iron oxide (SPIO) particles have been known to show a great T 2 relaxation effect in the liver, which contributes to significant liver signal decrease and detection of hepatic neoplasms. Recently, fast spin echo (FSE) sequence with less scanning time than conventional spin echo (SE) sequence has been rapidly introduced in clinical MR imaging. To investigate whether SPIO would show decreased T 2 relaxation effect on FSE, we obtained T 2 relaxivity (R2) of SPIO in vitro and liver signal decrease caused by SPIO in vivo. SPIO showed 20% less R2 on Carr-Purcell-Meiboom-Gill (CPMG) sequence than on SE. Relative liver signal-to-noise ratio (SNR) decrease caused by SPIO was significantly smaller (p 2 relaxation effect on FSE than on SE. However, further studies will be required to assess the diagnostic capability of SPIO on FSE, in the detection of hepatic neoplasms. (author)

Ground-state magnetization of the molecular cluster Mn12O12-acetate as seen by proton NMR

International Nuclear Information System (INIS)

Furukawa, Y.; Watanabe, K.; Kumagai, K.; Jang, Z. H.; Lascialfari, A.; Borsa, F.; Gatteschi, D.

2000-01-01

1 H nuclear magnetic resonance (NMR) measurements have been carried out in Mn 12 O 12 -acetate clusters at low temperature in order to investigate microscopically the static and dynamic magnetic properties of the molecule in its high-spin S=10 ground state. Below liquid helium temperature it is found that the local hyperfine fields at the proton sites are static as expected for the very slow superparamagnetic relaxation of Mn 12 O 12 at low temperature. The magnitude and distribution of the hyperfine fields can be reproduced to a good approximation by considering only the dipolar interaction of protons with the local Mn magnetic moments and by assigning the magnitude and orientation of the local moments of the different Mn 3+ and Mn 4+ ions according to an accepted coupling scheme for the total S=10 ground state. The relaxation time of the macroscopic magnetization of the cluster was measured by monitoring the change of the intensity of the 1 H-NMR shifted lines following inversion of the applied magnetic field. This is possible because the sudden change of the field orientation changes the sign of the shift of the NMR lines in the proton spectrum. Although important differences are noticed, the relaxation time of the magnetization as measured indirectly by the 1 H-NMR method is comparable to the one obtained directly with a superconducting quantum interference device magnetometer. In particular we could reproduce the minima in the relaxation time as a function of magnetic field at the fields for level crossing, minima which are considered to be a signature of the quantum tunneling of the magnetization

Gd-HOPO Based High Relaxivity MRI Contrast Agents

Energy Technology Data Exchange (ETDEWEB)

Datta, Ankona; Raymond, Kenneth

2008-11-06

Tris-bidentate HOPO-based ligands developed in our laboratory were designed to complement the coordination preferences of Gd{sup 3+}, especially its oxophilicity. The HOPO ligands provide a hexadentate coordination environment for Gd{sup 3+} in which all he donor atoms are oxygen. Because Gd{sup 3+} favors eight or nine coordination, this design provides two to three open sites for inner-sphere water molecules. These water molecules rapidly exchange with bulk solution, hence affecting the relaxation rates of bulk water olecules. The parameters affecting the efficiency of these contrast agents have been tuned to improve contrast while still maintaining a high thermodynamic stability for Gd{sup 3+} binding. The Gd- HOPO-based contrast agents surpass current commercially available agents ecause of a higher number of inner-sphere water molecules, rapid exchange of inner-sphere water molecules via an associative mechanism, and a long electronic relaxation time. The contrast enhancement provided by these agents is at least twice that of commercial contrast gents, which are based on polyaminocarboxylate ligands.

An investigation of proton conductivity of binary matrices sulfonated ...

Indian Academy of Sciences (India)

to their potential applications in proton exchange membrane fuel cells (PEMFCs) ... is highly sulfonated and has high water uptake property.11,12 The proton conductivity ... SPSU membranes have lower gas permeability and liquid. (water and ...

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.

Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy

International Nuclear Information System (INIS)

Horner, D.A.

1984-08-01

The nuclear magnetic relaxation times of oxygen-17 have been measured in aqueous sodium bisulfite solutions in the pH range from 2.5 to 5 as a function of temperature, pH, and S(IV) concentration, at an ionic strength of 1.0 m. The rate law for oxygen exchange between bisulfite ion and water was obtained from an analysis of the data, and is consistent with oxygen exchange occurring via the reaction SO 2 + H 2 O right reversible H + + SHO 3 - . The value of k/sub -1/ is in agreement with relaxation measurements. Direct spectroscopic evidence was found for the existence of two isomers of bisulfite ion: one with the proton bonded to the sulfur (HSO 3 - ) and the other with the proton bonded to an oxygen (SO 3 H - ). (The symbol SHO 3 - in the above chemical equation refers to both isomeric forms of bisulfite ion.) The relative amounts of the two isomers were determined as a function of temperature, and the rate and mechanism of oxygen exchange between the two was investigated. One of the two isomers, presumably SO 3 H - , exchanges oxygens with water much more rapidly than does the other. A two-pulse sequence was developed which greatly diminished the solvent peak in the NMR spectrum

Acceleration of protons to above 6 MeV using H2O 'snow' nanowire targets

International Nuclear Information System (INIS)

Pomerantz, I.; Schleifer, E.; Nahum, E.; Eisenmann, S.; Botton, M.; Gordon, D.; Sprangel, P.; Zigler, A.

2012-01-01

A scheme is presented for using H 2 O 'snow' nanowire targets for the generation of fast protons. This novel method may relax the requirements for very high laser intensities, thus reducing the size and cost of laser based ion acceleration system.

Rapid simultaneous high-resolution mapping of myelin water fraction and relaxation times in human brain using BMC-mcDESPOT.

Science.gov (United States)

Bouhrara, Mustapha; Spencer, Richard G

2017-02-15

A number of central nervous system (CNS) diseases exhibit changes in myelin content and magnetic resonance longitudinal, T 1 , and transverse, T 2 , relaxation times, which therefore represent important biomarkers of CNS pathology. Among the methods applied for measurement of myelin water fraction (MWF) and relaxation times, the multicomponent driven equilibrium single pulse observation of T 1 and T 2 (mcDESPOT) approach is of particular interest. mcDESPOT permits whole brain mapping of multicomponent T 1 and T 2 , with data acquisition accomplished within a clinically realistic acquisition time. Unfortunately, previous studies have indicated the limited performance of mcDESPOT in the setting of the modest signal-to-noise range of high-resolution mapping, required for the depiction of small structures and to reduce partial volume effects. Recently, we showed that a new Bayesian Monte Carlo (BMC) analysis substantially improved determination of MWF from mcDESPOT imaging data. However, our previous study was limited in that it did not discuss determination of relaxation times. Here, we extend the BMC analysis to the simultaneous determination of whole-brain MWF and relaxation times using the two-component mcDESPOT signal model. Simulation analyses and in-vivo human brain studies indicate the overall greater performance of this approach compared to the stochastic region contraction (SRC) algorithm, conventionally used to derive parameter estimates from mcDESPOT data. SRC estimates of the transverse relaxation time of the long T 2 fraction, T 2,l , and the longitudinal relaxation time of the short T 1 fraction, T 1,s , clustered towards the lower and upper parameter search space limits, respectively, indicating failure of the fitting procedure. We demonstrate that this effect is absent in the BMC analysis. Our results also showed improved parameter estimation for BMC as compared to SRC for high-resolution mapping. Overall we find that the combination of BMC analysis

Tunneling splitting of magnetic levels in Fe8 detected by 1H NMR cross relaxation

Science.gov (United States)

Furukawa, Y.; Aizawa, K.; Kumagai, K.; Ullu, R.; Lascialfari, A.; Borsa, F.

2003-05-01

Measurements of proton NMR and the spin lattice relaxation rate 1/T1 in the octanuclear iron (III) cluster [Fe8(N3C6H15)6O2(OH)12]ṡ[Br8ṡ9H2O], in short Fe8, have been performed at 1.5 K in a powder sample aligned along the main anisotropy z axis, as a function of a transverse magnetic field (i.e., perpendicular to the main easy axis z). A big enhancement of 1/T1 is observed over a wide range of fields (2.5-5 T), which can be attributed to the tunneling dynamics; in fact, when the tunneling splitting of the pairwise degenerate m=±10 states of the Fe8 molecule becomes equal to the proton Larmor frequency a very effective spin lattice relaxation channel for the nuclei is opened. The experimental results are explained satisfactorily by considering the distribution of tunneling splitting resulting from the distribution of the angles in the hard xy plane for the aligned powder, and the results of the direct diagonalization of the model Hamiltonian.

Electro-activity of cobalt and nickel complexes for the reduction of protons into di-hydrogen. Application to PEM water electrolysis

International Nuclear Information System (INIS)

Pantani, O.; Anxolabehere, E.; Aukauloo, A.; Millet, P.

2006-01-01

Proton exchange membrane (PEM) water electrolysis is a safe and efficient way to perform water splitting into di-hydrogen and di-oxygen. In a PEM water electrolyser, platinum is commonly used as electro-catalyst on the cathodic side of the cells, mostly because of its efficiency for hydrogen evolution. But for cost considerations, there is a need to find alternative low-cost electrocatalysts. Molecular chemistry offers the possibility of synthesizing new compounds for this purpose, such as transition metal complexes. Results obtained with nickel- and cobalt-oximes compounds are presented in this paper. They have been chemically (1H NMR, EPR) and electrochemically (voltametry, spectro-electrochemistry) characterized. Their ability to electrochemically reduce protons into di-hydrogen when they are either dissolved in solution or immobilized at the surface of a solid electrode is discussed. (authors)

Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study.

Science.gov (United States)

Wilhelm, Florian; Schmickler, Wolfgang; Spohr, Eckhard

2010-05-05

A recently developed empirical valence bond (EVB) model for proton transfer on Pt(111) electrodes (Wilhelm et al 2008 J. Phys. Chem. C 112 10814) has been applied in molecular dynamics (MD) simulations of a water film in contact with a charged Pt surface. A total of seven negative surface charge densities σ between -7.5 and -18.9 µC cm(-2) were investigated. For each value of σ, between 30 and 84 initial conditions of a solvated proton within a water slab were sampled, and the trajectories were integrated until discharge of a proton occurred on the charged surfaces. We have calculated the mean rates for discharge and for adsorption of solvated protons within the adsorbed water layer in contact with the metal electrode as a function of surface charge density. For the less negative values of σ we observe a Tafel-like exponential increase of discharge rate with decreasing σ. At the more negative values this exponential increase levels off and the discharge process is apparently transport limited. Mechanistically, the Tafel regime corresponds to a stepwise proton transfer: first, a proton is transferred from the bulk into the contact water layer, which is followed by transfer of a proton to the charged surface and concomitant discharge. At the more negative surface charge densities the proton transfer into the contact water layer and the transfer of another proton to the surface and its discharge occur almost simultaneously.

NMR relaxation in natural soils: Fast Field Cycling and T1-T2 Determination by IR-MEMS

Science.gov (United States)

Haber-Pohlmeier, S.; Pohlmeier, A.; Stapf, S.; van Dusschoten, D.

2009-04-01

Soils are natural porous media of highest importance for food production and sustainment of water resources. For these functions, prominent properties are their ability of water retainment and transport, which are mainly controlled by pore size distribution. The latter is related to NMR relaxation times of water molecules, of which the longitudinal relaxation time can be determined non-invasively by fast-field cycling relaxometry (FFC) and both are obtainable by inversion recovery - multi-echo- imaging (IR-MEMS) methods. The advantage of the FFC method is the determination of the field dependent dispersion of the spin-lattice relaxation rate, whereas MRI at high field is capable of yielding spatially resolved T1 and T2 times. Here we present results of T1- relaxation time distributions of water in three natural soils, obtained by the analysis of FFC data by means of the inverse Laplace transformation (CONTIN)1. Kaldenkirchen soil shows relatively broad bimodal distribution functions D(T1) which shift to higher relaxation rates with increasing relaxation field. These data are compared to spatially resolved T1- and T2 distributions, obtained by IR-MEMS. The distribution of T1 corresponds well to that obtained by FFC.

SU-F-I-63: Relaxation Times of Lipid Resonances in NAFLD Animal Model Using Enhanced Curve Fitting

Energy Technology Data Exchange (ETDEWEB)

Song, K-H; Yoo, C-H; Lim, S-I; Choe, B-Y [Department of Biomedical Engineering, and Research Institute of Biomedical Engineering, The Catholic University of Korea College of Medicine, Seoul (Korea, Republic of)

2016-06-15

Purpose: The objective of this study is to evaluate the relaxation time of methylene resonance in comparison with other lipid resonances. Methods: The examinations were performed on a 3.0T MRI scanner using a four-channel animal coil. Eight more Sprague-Dawley rats in the same baseline weight range were housed with ad libitum access to water and a high-fat (HF) diet (60% fat, 20% protein, and 20% carbohydrate). In order to avoid large blood vessels, a voxel (0.8×0.8×0.8 cm{sup 3}) was placed in a homogeneous area of the liver parenchyma during free breathing. Lipid relaxations in NC and HF diet rats were estimated at a fixed repetition time (TR) of 6000 msec, and multi echo time (TEs) of 40–220 msec. All spectra for data measurement were processed using the Advanced Method for Accurate, Robust, and Efficient Spectral (AMARES) fitting algorithm of the Java-based Magnetic Resonance User Interface (jMRUI) package. Results: The mean T2 relaxation time of the methylene resonance in normal-chow diet was 37.1 msec (M{sub 0}, 2.9±0.5), with a standard deviation of 4.3 msec. The mean T2 relaxation time of the methylene resonance was 31.4 msec (M{sub 0}, 3.7±0.3), with a standard deviation of 1.8 msec. The T2 relaxation times of methylene protons were higher in normal-chow diet rats than in HF rats (p<0.05), and the extrapolated M{sub 0} values were higher in HF rats than in NC rats (p<0.005). The excellent linear fit with R{sup 2}>0.9971 and R{sup 2}>0.9987 indicates T2 relaxation decay curves with mono-exponential function. Conclusion: In in vivo, a sufficient spectral resolution and a sufficiently high signal-to-noise ratio (SNR) can be achieved, so that the data measured over short TE values can be extrapolated back to TE = 0 to produce better estimates of the relative weights of the spectral components. In the short term, treating the effective decay rate as exponential is an adequate approximation.

Proton transfer events in GFP.

Science.gov (United States)

Di Donato, Mariangela; van Wilderen, Luuk J G W; Van Stokkum, Ivo H M; Stuart, Thomas Cohen; Kennis, John T M; Hellingwerf, Klaas J; van Grondelle, Rienk; Groot, Marie Louise

2011-09-28

Proton transfer is one of the most important elementary processes in biology. Green fluorescent protein (GFP) serves as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. Illumination initiates proton transfer through a 'proton-wire', formed by the chromophore (the proton donor), water molecule W22, Ser205 and Glu222 (the acceptor), on a picosecond time scale. To obtain a more refined view of this process, we have used a combined approach of time resolved mid-infrared spectroscopy and visible pump-dump-probe spectroscopy to resolve with atomic resolution how and how fast protons move through this wire. Our results indicate that absorption of light by GFP induces in 3 ps (10 ps in D(2)O) a shift of the equilibrium positions of all protons in the H-bonded network, leading to a partial protonation of Glu222 and to a so-called low barrier hydrogen bond (LBHB) for the chromophore's proton, giving rise to dual emission at 475 and 508 nm. This state is followed by a repositioning of the protons on the wire in 10 ps (80 ps in D(2)O), ultimately forming the fully deprotonated chromophore and protonated Glu222.

Effect of water and gluten on physico-chemical properties and stability of ready to eat shelf-stable pasta.

Science.gov (United States)

Diantom, Agoura; Carini, Eleonora; Curti, Elena; Cassotta, Fabrizio; D'Alessandro, Alessandro; Vittadini, Elena

2016-03-15

A multi-analytical and multi-dimensional approach was used to investigate the effect of moisture and gluten on physico-chemical properties of shelf-stable ready to eat (RTE) pasta. Moisture and frozen water contents were not affected by formulation nor storage time. Hardness and retrograded amylopectin significantly increased during storage in all samples, more markedly in pasta with the lowest moisture content. Higher amounts of water and gluten reduced pasta hardening and contributed to control RTE pasta quality. (1)H FID became steeper in all samples during storage, but no effect of high moisture and gluten levels was observed on the mobility of these protons. Three proton T2 populations were observed (population C, population D and population E). Population C and D were not resolved during all storage. (1)H T2 relaxation time of the most abundant population (population E) shifted to shorter times and the amount of protons increased during storage, more importantly in the samples with lower moisture and gluten content. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: longitudinal relaxation dispersion for a dipole-coupled spin-1/2 pair.

Science.gov (United States)

Chang, Zhiwei; Halle, Bertil

2013-10-14

In complex biological or colloidal samples, magnetic relaxation dispersion (MRD) experiments using the field-cycling technique can characterize molecular motions on time scales ranging from nanoseconds to microseconds, provided that a rigorous theory of nuclear spin relaxation is available. In gels, cross-linked proteins, and biological tissues, where an immobilized macromolecular component coexists with a mobile solvent phase, nuclear spins residing in solvent (or cosolvent) species relax predominantly via exchange-mediated orientational randomization (EMOR) of anisotropic nuclear (electric quadrupole or magnetic dipole) couplings. The physical or chemical exchange processes that dominate the MRD typically occur on a time scale of microseconds or longer, where the conventional perturbation theory of spin relaxation breaks down. There is thus a need for a more general relaxation theory. Such a theory, based on the stochastic Liouville equation (SLE) for the EMOR mechanism, is available for a single quadrupolar spin I = 1. Here, we present the corresponding theory for a dipole-coupled spin-1/2 pair. To our knowledge, this is the first treatment of dipolar MRD outside the motional-narrowing regime. Based on an analytical solution of the spatial part of the SLE, we show how the integral longitudinal relaxation rate can be computed efficiently. Both like and unlike spins, with selective or non-selective excitation, are treated. For the experimentally important dilute regime, where only a small fraction of the spin pairs are immobilized, we obtain simple analytical expressions for the auto-relaxation and cross-relaxation rates which generalize the well-known Solomon equations. These generalized results will be useful in biophysical studies, e.g., of intermittent protein dynamics. In addition, they represent a first step towards a rigorous theory of water (1)H relaxation in biological tissues, which is a prerequisite for unravelling the molecular basis of soft

Production and characterization of protonated molecular clusters containing a given number of water molecules with the DIAM set-up

International Nuclear Information System (INIS)

Bruny, G.

2010-01-01

nano-scale characterization of irradiation in bio-molecular systems requires observation of novel features which are now achievable with the recent technical progress. This work is a central part in the development of DIAM which is a new experimental set-up devoted to irradiation of bio-molecular clusters at the Institut de Physique Nucleaire de Lyon. The development of the cluster source and of a double focusing mass spectrometer leads to the production of intense beams of mass selected protonated molecular clusters. Combined with this mass selected cluster beams an innovative detection technique is demonstrated in collision induced dissociation experiments. The results contribute to the knowledge of the stability and the structure of the small protonated water clusters and mixed clusters of water and pyridine. (author)

Menstrual variation of breast volume and T{sub 2} relaxation times in cyclical mastalgia

Energy Technology Data Exchange (ETDEWEB)

Hussain, Zainab [Department of Medical Imaging, University of Liverpool, Johnstone Building, Brownlow Hill, P.O. Box 147, Liverpool, Merseyside L69 3GB (United Kingdom); Magnetic Resonance and Image Analysis Research Centre, University of Liverpool, Johnstone Building, Brownlow Hill, P.O. Box 147, Liverpool, Merseyside L69 3GB (United Kingdom)], E-mail: zay@liverpool.ac.uk; Brooks, Jonathan [Magnetic Resonance and Image Analysis Research Centre, University of Liverpool, Johnstone Building, Brownlow Hill, P.O. Box 147, Liverpool, Merseyside L69 3GB (United Kingdom); Department of Human Anatomy and Genetics, University of Oxford, Oxford (United Kingdom); Percy, Dave [Centre for Operational Research and Applied Statistics, University of Salford, Salford, Greater Manchester M5 4WT (United Kingdom)

2008-02-15

Purpose: Hormonal activity causes breast volume to change during the menstrual cycle. One possible cause of this volume change is thought to be due to water retention or oedema within the tissues. We used magnetic resonance imaging (MRI) to study the variation in breast volume and {sup 1}H Magnetic Resonance Spectroscopy (MRS) to measure T{sub 2} relaxation times which are known to increase with increasing tissue water content. We hypothesised that an increase in breast volume will elevate T{sub 2} relaxation due to the presence of an increased water content within the breast. T{sub 2} Relaxation time and volume were studied in fifteen control subjects and in a cohort of eight patients with cyclical mastalgia in order to determine whether changes in breast volume and T{sub 2} relaxation times differed in controls and patients during menses, ovulation and premenses. Method: Breast volume was determined by the Cavalieri method in combination with point counting techniques on MR images and T{sub 2} relaxation times of the water and fat in a voxel of breast tissue were obtained using {sup 1}H Magnetic Resonance Spectroscopy (MRS). Results: Statistical analysis (ANOVA) demonstrated highly significant differences in breast volume between the three stages of the cycle (p < 0.0005) with breast volume being greatest premenstrually. Patients did not exhibit an increase in volume premenstrually, significantly above controls. T{sub 2} of fat or water did not depend on stage of cycle. T-tests demonstrated no significant differences in T{sub 2} of water or fat between patient and control groups. The average T{sub 2} relaxation time of water was lowest in the patient and control groups during ovulation and highest in the patient group during premenses. Conclusion: We have performed the first combined volumetric and spectroscopic study of women with cyclical mastalgia and demonstrated that the global changes in volumes and T{sub 2} were not significantly different from normal

Electron spin-lattice relaxation mechanisms of radiation produced trapped electrons and hydrogen atoms in aqueous and organic glassy matrices. Modulation of electron nuclear dipolar interaction by tunnelling modes in a glassy matrix. [. gamma. rays

Energy Technology Data Exchange (ETDEWEB)

Bowman, M K; Kevan, L [Wayne State Univ., Detroit, Mich. (USA). Dept. of Chemistry

1977-01-01

The spin lattice relaxation of trapped electrons in aqueous and organic glasses and trapped hydrogen atoms in phosphoric acid glass has been directly studied as a function of temperature by the saturation recovery method. Below 50 to 100 K, the major spin lattice relaxation mechanism involves modulation of the electron nuclear dipolar (END) interaction with nuclei in the radical's environment by tunnelling of those nuclei between two or more positions. This relaxation mechanism occurs with high efficiency and has a characteristic linear temperature dependence. The tunnelling nuclei around trapped electrons do not seem to involve the nearest neighbor nuclei which are oriented by the electron in the process of solvation. Instead the tunnelling nuclei typically appear to be next nearest neighbors to the trapped electron. The identities of the tunnelling nuclei have been deduced by isotopic substitution and are attributed to: Na in 10 mol dm/sup -3/ NaOH aqueous glass, ethyl protons in ethanol glass, methyl protons in methanol glass and methyl protons in MTHF glass. For trapped hydrogen atoms in phosphoric acid, the phosphorus nuclei appear to be the effective tunnelling nuclei. Below approximately 10 K the spin lattice relaxation is dominated by a temperature independent cross relaxation term for H atoms in phosphoric acid glass and for electrons in 10 mol dm/sup -3/ NaOH aqueous glass, but not for electrons in organic glasses. This is compared with recent electron-electron double resonance studies of cross relaxation in these glasses. The spin lattice relaxation of O/sup -/ formed in 10 mol dm/sup -3/ NaOH aqueous glass was also studied and found to be mainly dominated by a Raman process with an effective Debye temperature of about 100 K.

IRMA iterative relaxation matrix approach for NMR structure determination application to DNA fragments

International Nuclear Information System (INIS)

Koning, M.M.G.

1990-01-01

The subject of this thesis is the structure determination of DNA molecules in solution with the use of NMR. For this purpose a new relaxation matrix approach is introduced. The emphasis is on the interpretation of nuclear Overhauser effects (NOEs) in terms of proton-proton distances and related three dimensional structures. The DNA molecules studied are obligonucleotides, unmodifief as well as modified molecules bu UV radiation. From comparison with unmodified molecules it turned out that UV irradiation scarcely influences the helical structure of the DNA string. At one place of the string a nucleotide is rotated towards the high-ANTI conformation which results in a slight unwinding of the DNA string but sufficient for blocking of the normal reading of genetic information. (H.W.). 456 refs.; 50 figs.; 30 tabs

Muon spin relaxation by electronic excitations moving in one dimension

International Nuclear Information System (INIS)

Jestaedt, Th.; Sivia, D.S.; Cox, S.F.J.

1997-01-01

The manner in which an electronic spin, executing a linear random walk, e.g. along a polymer chain, depolarizes a muon (or proton) probe spin, is investigated by computer simulation. The essential features of the model are the assumptions of a contact hyperfine interaction with limited range and of loss of coherence between successive encounters. The low dimensionality of the motion is reflected in the shape of the relaxation functions generated, which depart significantly from simple exponentials. Fits to various functional forms are examined for different combinations of hop rate and chain length, hyperfine constant and applied magnetic field

Accurate Quantitation of Water-amide Proton Exchange Rates Using the Phase-Modulated CLEAN Chemical EXchange (CLEANEX-PM) Approach with a Fast-HSQC (FHSQC) Detection Scheme

International Nuclear Information System (INIS)

Hwang, Tsang-Lin; Zijl, Peter C.M. van; Mori, Susumu

1998-01-01

Measurement of exchange rates between water and NH protons by magnetization transfer methods is often complicated by artifacts, such as intramolecular NOEs, and/or TOCSY transfer from Cα protons coincident with the water frequency, or exchange-relayed NOEs from fast exchanging hydroxyl or amine protons. By applying the Phase-Modulated CLEAN chemical EXchange (CLEANEX-PM) spin-locking sequence, 135 o (x) 120 o (-x) 110 o (x) 110 o (-x) 120 o (x) 135 o (-x) during the mixing period, these artifacts can be eliminated, revealing an unambiguous water-NH exchange spectrum. In this paper, the CLEANEX-PM mixing scheme is combined with Fast-HSQC (FHSQC) detection and used to obtain accurate chemical exchange rates from the initial slope analysis for a sample of 15N labeled staphylococcal nuclease. The results are compared to rates obtained using Water EXchange filter (WEX) II-FHSQC, and spin-echo-filtered WEX II-FHSQC measurements, and clearly identify the spurious NOE contributions in the exchange system

Magnetic resonance in food science

International Nuclear Information System (INIS)

Hills, B.P.

1994-01-01

Imaging protocols suitable for obtaining quantitative maps of NMR parameters in heterogenous food materials are first considered; it is followed by a discussion of the interpretation of the NMR parameter maps in terms of mass and heat transport and associated physico-chemical changes in the food material, leading to an analysis of the effect of food microstructure on water proton relaxation and diffusion and of the molecular mechanisms of water proton relaxation in biopolymer systems. Finally, high resolution NMR protocols suitable for following composition changes in food materials are discussed. 13 fig., 86 ref

Unveiling the water-associated conformational mobility in the active site of ascorbate peroxidase.

Science.gov (United States)

Chao, Wei-Chih; Lin, Li-Ju; Lu, Jyh-Feng; Wang, Jinn-Shyan; Lin, Tzu-Chieh; Chen, Yi-Han; Chen, Yi-Ting; Yang, Hsiao-Ching; Chou, Pi-Tai

2018-03-01

We carried out comprehensive spectroscopic studies of wild type and mutants of ascorbate peroxidase (APX) to gain understanding of the conformational mobility of the active site. In this approach, three unnatural tryptophans were applied to replace the distal tryptophan (W41) in an aim to probe polarity/water environment near the edge of the heme-containing active site. 7-azatryptophan ((7-aza)Trp) is sensitive to environment polarity, while 2,7-azatryptophan ((2,7-aza)Trp) and 2,6-diazatryptophan ((2,6-aza)Trp) undergo excited-state water-catalyzed double and triple proton transfer, respectively, and are sensitive to the water network. The combination of their absorption, emission bands and the associated relaxation dynamics of these fluorescence probes, together with the Soret-band difference absorption and resonance Raman spectroscopy, lead us to unveil the water associated conformational mobility in the active site of APX. The results are suggestive of the existence of equilibrium between two different environments surrounding W41 in APX, i.e., the water-rich and water-scant forms with distinct fluorescence relaxation. Our results thus demonstrate for the first time the power of integrating multiple sensors (7-aza)Trp, (2,7-aza)Trp and (2,6-aza)Trp in probing the water environment of a specifically targeted Trp in proteins. Copyright © 2017 Elsevier B.V. All rights reserved.

Sulfonated poly(fluorenyl ether ketone nitrile) electrolyte membrane with high proton conductivity and low water uptake

Energy Technology Data Exchange (ETDEWEB)

Tian, S.H.; Wang, S.J.; Xiao, M.; Meng, Y.Z. [State Key Laboratory of Optoelectronic Materials and Technologies/Institute of Optoelectronic and Functional Composite Materials, Sun Yat-sen University, Guangzhou 510275 (China); Shu, D. [School of Chemistry and Environmental, South China Normal University, Guangzhou 510006 (China)

2010-01-01

High molecular weight sulfonated poly(fluorenyl ether ketone nitrile)s with different equivalent weight (EW) from 681 to 369 g mequiv.{sup -1} are synthesized by the nucleophilic substitution polycondensation of various amounts of sulfonated difluorobenzophenone (SDFBP) and 2,6-difluorobenzonitrile (DFBN) with bisphenol fluorene (BPF). The synthesized copolymers are characterized by {sup 1}H NMR, FT-IR, TGA, and DSC techniques. The membranes cast from the corresponding copolymers exhibit superior thermal stability, good oxidative stability and high proton conductivity, but low water uptake due to the strong nitrile dipole interchain interactions that combine to limit swelling. Among all the membranes, the membrane with EW of 441 g mequiv.{sup -1} shows optimum properties of both high proton conductivity of 41.9 mS cm{sup -1} and low water uptake of 42.6%. Accordingly, That membrane is fabricated into a membrane electrode assembly (MEA) and evaluated in a single proton exchange membrane fuel cell (PEMFC). The experimental results indicate its similar cell performance as that of Nafion {sup registered} 117 at 70 C, but much better cell performance at higher temperatures. At the potential of 0.6 V, the current density of fuel cell using the prepared membrane and Nafion {sup registered} 117 is 0.46 and 0.25 A cm{sup -2}, respectively. The highest current density of the former reaches as high as 1.25 A cm{sup -2}. (author)

Three-way modelling of NMR relaxation profiles from thawed cod muscle

DEFF Research Database (Denmark)

Jensen, Kristina Nedenskov; Guldager, Helle Skov; Jørgensen, Bo Munk

2002-01-01

Low-field 1H nuclear magnetic resonance transverse relaxation was used to measure water mobility and distribution in cod stored at -20°C or -30°C for up to 12 months and subsequently from 0 to 21 days in modified atmosphere at +2°C. The relaxation profiles were decomposed by parallel factor analy...

Prospects for very large, sensitive water Cherenkov detectors for proton decay and neutrino oscillations search

International Nuclear Information System (INIS)

Cline, D.B.

1982-01-01

We discuss the possibility of constructing large water Cherenkov detectors with mass 10 5 to 10 6 tons that would be sensitive to a few hundred MeV - few GeV energy release. The 10 5 ton detector would be suitable for a search for certain proton decay modes whereas the 10 6 ton detector would act as an active shield for the proton decay detector and as a nu/sub e/, nu/sub μ/ and possibly nu/sub tau/ interaction detector. The neutrino physics would include a sensitive search for neutrino oscillations using atmospheric neutrinos. The location of this detector could be in the deep ocean near Hawaii or in a deep trench between Cuba and Haiti or perhaps deep lakes like Superior or Baikal if flexible containers are used

Paramagnetic relaxation effects in perturbed angular correlations for arbitrary electronic relaxation time

International Nuclear Information System (INIS)

Chopin, C.; Spanjaard, D.; Hartmann-Boutron, F.

1975-01-01

Previous perturbation treatments of paramagnetic relaxation effects in γγ PAC were limited to the case of very short electronic relaxation times. This limitation is circumvented by invoking a new perturbation theory recently elaborated by Hirst and others for handling relaxation effects in Moessbauer spectra. Under the assumption of spherical electronic relaxation the perturbation factors are computed as functions of certain relaxation parameters which are directly related to the microscopic relaxation Hamiltonian. The results are compared to those of the stochastic theory of Scherer and Blume [fr

Noninvasive evaluation of adult onset myopathy from carnitine palmitoyl transferase II deficiency using proton magnetic resonance spectroscopy.

Science.gov (United States)

Videen, J S; Haseler, L J; Karpinski, N C; Terkeltaub, R A

1999-08-01

The adult onset metabolic myopathy of carnitine palmitoyl transferase II (CPT II) deficiency is under-recognized, in part due to variable degrees of enzyme deficiency and symptomatology, as well as limitations in means for noninvasive evaluation. We describe a proton magnetic resonance spectroscopy (MRS) technique, using a standard clinical magnetic resonance imaging scanner, to diagnose and help monitor the response to therapy in adult CPT II deficiency. A 53-year-old woman presented with a long standing history of diffuse aching and fatigue provoked by high fat intake, fasting, or prolonged exertion. Muscle biopsy revealed myopathic features and a deficiency (33% of control) of CPT II activity with elevated palmitoyl carnitine. Proton MRS of the soleus muscle was performed using a 1.5 Tesla scanner before and during dietary therapy. Proton MRS revealed shortening of the transverse relaxation time (T2), consistent with increased acetylation of the carnitine pool. The symptoms resolved completely by treatment with frequent feedings of a high carbohydrate diet low in long chain fatty acids supplemented with medium chain triglycerides and L-carnitine. Recovery of normal muscle MRS and carnitine T2 relaxation was documented by the third month of therapy. Proton MRS is a novel, potentially useful, and readily available adjunct in the diagnosis and therapeutic monitoring of muscle CPT II deficiency.

Metal Phosphates as Intermediate Temperature Proton Conducting Electrolytes

DEFF Research Database (Denmark)

Huang, Yunjie; Li, Q.F.; Pan, Chao

2012-01-01

A series of metal phosphates were synthesized and screened as potential proton conductor electrolytes for fuel cells and electrolysers operational at intermediate temperatures. Among the selected, niobium and bismuth phosphates exhibited a proton conductivity of 10-2 and 10-7 S cm-1, respectively......, under the anhydrous atmosphere at 250 °C, showing close correlation with the presence of hydroxyl groups in the phosphate phases. At the water partial pressure of above 0.6 atm, both phosphates possessed a proton conductivity to a level of above 3 x 10-2 S cm-1. Reasonable stability of the proton...... conductivity was observed under either a constant low water partial pressure or under a humidity cycling test within a period of more than 80 hours....

Resonances in field-cycling NMR on molecular crystals. (reversible) Spin dynamics or (irreversible) relaxation?; Resonanzen in Field-Cycling-NMR an Molekuelkristallen. (reversible) Spindynamik oder (irreversible) Relaxation?

Energy Technology Data Exchange (ETDEWEB)

Tacke, Christian

2015-07-01

Multi spin systems with spin 1/2 nuclei and dipolar coupled quadrupolar nuclei can show so called ''quadrupolar dips''. There are two main reasons for this behavior: polarization transfer and relaxation. They look quite alike and without additional research cannot be differentiated easily in most cases. These two phenomena have quite different physical and theoretical backgrounds. For no or very slow dynamics, polarization transfer will take place, which is energy conserving inside the spin system. This effect can entirely be described using quantum mechanics on the spin system. Detailed knowledge about the crystallography is needed, because this affects the relevant hamiltonians directly. For systems with fast enough dynamics, relaxation takes over, and the energy flows from the spin system to the lattice; thus a more complex theoretical description is needed. This description has to include a dynamic model, usually in the form of a spectral density function. Both models should include detailed modelling of the complete spin system. A software library was developed to be able to model complex spin systems. It allows to simulate polarization transfer or relaxation effects. NMR measurements were performed on the protonic conductor K{sub 3}H(SO{sub 4}){sub 2}. A single crystal shows sharp quadrupolar dips at room temperature. Dynamics could be excluded using relaxation measurements and literature values. Thus, a polarization transfer analysis was used to describe those dips with good agreement. As a second system, imidazolium based molecular crystals were analyzed. The quadrupolar dips were expected to be caused by polarization transfer; this was carefully analyzed and found not to be true. A relaxation based analysis shows good agreement with the measured data in the high temperature area. It leverages a two step spectral density function, which indicates two distinct dynamic processes happening in this system.

Incoherent quasielastic neutron scattering from water in supercooled regime

International Nuclear Information System (INIS)

Chen, S.; Teixeira, J.; Nicklow, R.

1982-01-01

Measurements of the quasielastic spectra have been made with a three-axis neutron spectrometer at constant-Q mode in a temperature range from 38 0 C down to -20 0 C. Two energy resolutions both high (δE = 100 μ eV) and low (δE = 800 μ eV) were used to identify and separate a sharp component from a broad one. As temperature is decreased below zero the spectrum shows an increasing sharp component standing out on top of the broad one. The broad component is attributed to rotational motions of water molecules. A preliminary analysis of the linewidths gives a Q-independent relaxation time which has the same magnitude as the rotational relaxation time measured by nuclear magnetic resonance. The Q dependence of the sharp line is analyzed by a Q-dependent diffusion coefficient. A temperature-independent characteristic length l 0 = 0.5 A is obtained. We then attempt to relate this length to local geometry of protons associated with hydrogen bonding

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.

Dielectric properties of water in Triton X-100 (nonionic detergent)-water mixtures

International Nuclear Information System (INIS)

Asami, Koji

2007-01-01

Dielectric measurements were carried out for mixtures of Triton X-100 (TX, a nonionic detergent with a poly(ethylene oxide) chain) and water with or without electrolytes over a frequency range of 1 MHz to 10 GHz to study the structure and dynamics of water molecules in the mixtures. Dielectric relaxation was found above 100 MHz, being assigned to the dielectric relaxation of water. The intensity of the dielectric relaxation was proportional to the water content above 0 deg. C. Below the freezing temperature of bulk water, the relaxation intensity decreased at TX concentrations (C TX ) below 50 wt% at -10 deg. Cand below 60 wt% at -20 deg. Cbecause frozen water shifts the dielectric relaxation to a frequency region far below 1 MHz. This indicated that there is no bulk water at C TX above 50 wt% and that at least two water molecules per ethylene oxide (EO) unit are tightly associated with the ethylene oxide chain. The low-frequency conductivity of the mixtures of TX and electrolyte solutions was well represented by Bruggeman's mixture equation at C TX below 40 wt%, if two water molecules per EO unit form an insulating shell surrounding TX micelles

On the Effect of Clamping Pressure and Method on the Current Mapping of Proton Exchange Membrane Water Electrolysis

DEFF Research Database (Denmark)

Al Shakhshir, Saher; Zhou, Fan; Kær, Søren Knudsen

The degradation of the electrochemical reaction of the proton exchange membrane water electrolysis (PEMWE) can be characterized using in-situ current mapping measurements (CMM). CMM is significantly affected by the amount of clamping pressure and method. In this work the current is mapped...

Optimization of transversal relaxation of nitroxides for pulsed electron-electron double resonance spectroscopy in phospholipid membranes.

Science.gov (United States)

Dastvan, Reza; Bode, Bela E; Karuppiah, Muruga Poopathi Raja; Marko, Andriy; Lyubenova, Sevdalina; Schwalbe, Harald; Prisner, Thomas F

2010-10-28

Pulsed electron-electron double resonance (PELDOR) spectroscopy is increasingly applied to spin-labeled membrane proteins. However, after reconstitution into liposomes, spin labels often exhibit a much faster transversal relaxation (T(m)) than in detergent micelles, thus limiting application of the method in lipid bilayers. In this study, the main reasons for enhanced transversal relaxation in phospholipid membranes were investigated systematically by use of spin-labeled derivatives of stearic acid and phosphatidylcholine as well as spin-labeled derivatives of the channel-forming peptide gramicidin A under the conditions typically employed for PELDOR distance measurements. Our results clearly show that dephasing due to instantaneous diffusion that depends on dipolar interaction among electron spins is an important contributor to the fast echo decay in cases of high local concentrations of spin labels in membranes. The main difference between spin labels in detergent micelles and membranes is their local concentration. Consequently, avoiding spin clustering and suppressing instantaneous diffusion is the key step for maximizing PELDOR sensitivity in lipid membranes. Even though proton spin diffusion is an important relaxation mechanism, only in samples of low local concentrations does deuteration of acyl chains and buffer significantly prolong T(m). In these cases, values of up to 7 μs have been achieved. Furthermore, our study revealed that membrane composition and labeling position in the membrane can also affect T(m), either by promoting the segregation of spin-labeled species or by altering their exposure to matrix protons. Effects of other experimental parameters including temperature (<50 K), presence of oxygen, and cryoprotectant type are negligible under our experimental conditions.

A combined molecular dynamics and Monte Carlo simulation of the spatial distribution of energy deposition by proton beams in liquid water

Energy Technology Data Exchange (ETDEWEB)

Garcia-Molina, Rafael [Departamento de Fisica, Centro de Investigacion en Optica y Nanofisica (CIOyN), Universidad de Murcia, E-30100 Murcia (Spain); Abril, Isabel [Departament de Fisica Aplicada, Universitat d' Alacant, E-03080 Alacant (Spain); Heredia-Avalos, Santiago [Departament de Fisica, Enginyeria de Sistemes i Teoria del Senyal, Universitat d' Alacant, E-03080 Alacant (Spain); Kyriakou, Ioanna; Emfietzoglou, Dimitris, E-mail: rgm@um.es [Medical Physics Laboratory, University of Ioannina Medical School, GR-45110 Ioannina (Greece)

2011-10-07

We have evaluated the spatial distribution of energy deposition by proton beams in liquid water using the simulation code SEICS (Simulation of Energetic Ions and Clusters through Solids), which combines molecular dynamics and Monte Carlo techniques and includes the main interaction phenomena between the projectile and the target constituents: (i) the electronic stopping force due to energy loss to target electronic excitations, including fluctuations due to the energy-loss straggling, (ii) the elastic scattering with the target nuclei, with their corresponding energy loss and (iii) the dynamical changes in projectile charge state due to electronic capture and loss processes. An important feature of SEICS is the accurate account of the excitation spectrum of liquid water, based on a consistent solid-state description of its energy-loss-function over the whole energy and momentum space. We analyse how the above-mentioned interactions affect the depth distribution of the energy delivered in liquid water by proton beams with incident energies of the order of several MeV. Our simulations show that the position of the Bragg peak is determined mainly by the stopping power, whereas its width can be attributed to the energy-loss straggling. Multiple elastic scattering processes contribute slightly only at the distal part of the Bragg peak. The charge state of the projectiles only changes when approaching the end of their trajectories, i.e. near the Bragg peak. We have also simulated the proton-beam energy distribution at several depths in the liquid water target, and found that it is determined mainly by the fluctuation in the energy loss of the projectile, evaluated through the energy-loss straggling. We conclude that a proper description of the target excitation spectrum as well as the inclusion of the energy-loss straggling is essential in the calculation of the proton beam depth-dose distribution.

A combined molecular dynamics and Monte Carlo simulation of the spatial distribution of energy deposition by proton beams in liquid water

International Nuclear Information System (INIS)

Garcia-Molina, Rafael; Abril, Isabel; Heredia-Avalos, Santiago; Kyriakou, Ioanna; Emfietzoglou, Dimitris

2011-01-01

We have evaluated the spatial distribution of energy deposition by proton beams in liquid water using the simulation code SEICS (Simulation of Energetic Ions and Clusters through Solids), which combines molecular dynamics and Monte Carlo techniques and includes the main interaction phenomena between the projectile and the target constituents: (i) the electronic stopping force due to energy loss to target electronic excitations, including fluctuations due to the energy-loss straggling, (ii) the elastic scattering with the target nuclei, with their corresponding energy loss and (iii) the dynamical changes in projectile charge state due to electronic capture and loss processes. An important feature of SEICS is the accurate account of the excitation spectrum of liquid water, based on a consistent solid-state description of its energy-loss-function over the whole energy and momentum space. We analyse how the above-mentioned interactions affect the depth distribution of the energy delivered in liquid water by proton beams with incident energies of the order of several MeV. Our simulations show that the position of the Bragg peak is determined mainly by the stopping power, whereas its width can be attributed to the energy-loss straggling. Multiple elastic scattering processes contribute slightly only at the distal part of the Bragg peak. The charge state of the projectiles only changes when approaching the end of their trajectories, i.e. near the Bragg peak. We have also simulated the proton-beam energy distribution at several depths in the liquid water target, and found that it is determined mainly by the fluctuation in the energy loss of the projectile, evaluated through the energy-loss straggling. We conclude that a proper description of the target excitation spectrum as well as the inclusion of the energy-loss straggling is essential in the calculation of the proton beam depth-dose distribution.

How the shape of an H-bonded network controls proton-coupled water activation in HONO formation.

Science.gov (United States)

Relph, Rachael A; Guasco, Timothy L; Elliott, Ben M; Kamrath, Michael Z; McCoy, Anne B; Steele, Ryan P; Schofield, Daniel P; Jordan, Kenneth D; Viggiano, Albert A; Ferguson, Eldon E; Johnson, Mark A

2010-01-15

Many chemical reactions in atmospheric aerosols and bulk aqueous environments are influenced by the surrounding solvation shell, but the precise molecular interactions underlying such effects have rarely been elucidated. We exploited recent advances in isomer-specific cluster vibrational spectroscopy to explore the fundamental relation between the hydrogen (H)-bonding arrangement of a set of ion-solvating water molecules and the chemical activity of this ensemble. We find that the extent to which the nitrosonium ion (NO+)and water form nitrous acid (HONO) and a hydrated proton cluster in the critical trihydrate depends sensitively on the geometrical arrangement of the water molecules in the network. Theoretical analysis of these data details the role of the water network in promoting charge delocalization.

Proton beam characterization by proton-induced acoustic emission: simulation studies

International Nuclear Information System (INIS)

Jones, K C; Witztum, A; Avery, S; Sehgal, C M

2014-01-01

Due to their Bragg peak, proton beams are capable of delivering a targeted dose of radiation to a narrow volume, but range uncertainties currently limit their accuracy. One promising beam characterization technique, protoacoustic range verification, measures the acoustic emission generated by the proton beam. We simulated the pressure waves generated by proton radiation passing through water. We observed that the proton-induced acoustic signal consists of two peaks, labeled α and γ, with two originating sources. The α acoustic peak is generated by the pre-Bragg peak heated region whereas the source of the γ acoustic peak is the proton Bragg peak. The arrival time of the α and γ peaks at a transducer reveals the distance from the beam propagation axis and Bragg peak center, respectively. The maximum pressure is not observed directly above the Bragg peak due to interference of the acoustic signals. Range verification based on the arrival times is shown to be more effective than determining the Bragg peak position based on pressure amplitudes. The temporal width of the α and γ peaks are linearly proportional to the beam diameter and Bragg peak width, respectively. The temporal separation between compression and rarefaction peaks is proportional to the spill time width. The pressure wave expected from a spread out Bragg peak dose is characterized. The simulations also show that acoustic monitoring can verify the proton beam dose distribution and range by characterizing the Bragg peak position to within ∼1 mm. (paper)

pH-Dependent Regulation of the Relaxation Rate of the Radical Anion of the Secondary Quinone Electron Acceptor QB in Photosystem II As Revealed by Fourier Transform Infrared Spectroscopy.

Science.gov (United States)

Nozawa, Yosuke; Noguchi, Takumi

2018-05-15

Photosystem II (PSII) is a protein complex that performs water oxidation using light energy during photosynthesis. In PSII, electrons abstracted from water are eventually transferred to the secondary quinone electron acceptor, Q B , and upon double reduction, Q B is converted to quinol by binding two protons. Thus, excess electron transfer in PSII increases the pH of the stroma. In this study, to investigate the pH-dependent regulation of the electron flow in PSII, we have estimated the relaxation rate of the Q B - radical anion in the pH region between 5 and 8 by direct monitoring of its population using light-induced Fourier transform infrared difference spectroscopy. The decay of Q B - by charge recombination with the S 2 state of the water oxidation center in PSII membranes was shown to be accelerated at higher pH, whereas that of Q A - examined in the presence of a herbicide was virtually unaffected at pH ≤7.5 and slightly slowed at pH 8. These observations were consistent with the previous studies that included rather indirect monitoring of the Q B - and Q A - decays using fluorescence detection. The accelerated relaxation of Q B - was explained by the shift of a redox equilibrium between Q A - and Q B - to the Q A - side due to the decrease in the redox potential of Q B at higher pH, which is induced by deprotonation of a single amino acid residue near Q B . It is proposed that this pH-dependent Q B - relaxation is one of the mechanisms of electron flow regulation in PSII for its photoprotection.

Mitigating IPMC back relaxation through feedforward and feedback control of patterned electrodes

International Nuclear Information System (INIS)

Fleming, Maxwell J; Leang, Kam K; Kim, Kwang J

2012-01-01

With low driving voltage ( < 5 V) and the ability to be operated in aqueous environments, ionic polymer–metal composite (IPMC) materials are quickly gaining attention for use in many applications including soft bio-inspired actuators and sensors. There are, however, drawbacks to IPMC actuators, including the ‘back relaxation’ effect. Specifically, when subjected to an excessively slow input, the IPMC actuator will slowly relax back toward its original position. There is debate over the physical mechanism of back relaxation, although one prevalent theory describes an initial current, caused by the electrostatic forces of the charging electrodes, which drives water molecules across the ion exchange membrane and deforms the IPMC. Once the electrodes are fully charged, however, the dominant element of the motion is the osmotic pressure, driving the water molecules back to equilibrium, thus causing back relaxation. A new method to mitigate back relaxation is proposed, taking advantage of controlled activation of patterned (sectored) electrodes on the IPMC. By actuating sectors in opposing directions, back relaxation can be effectively canceled out. An integrated feedforward and feedback controller is employed based on this concept, and is shown to minimize back relaxation, while reducing the input voltage required, as compared to the case of the non-sectored IPMC. Experimental results show nearly an order of magnitude reduction in the tracking error compared to the uncompensated case, and that the IPMC’s position can be maintained over a period of 60 and 1200 s with minimal evidence of back relaxation. (paper)

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......-hoc and real time electrical signal of the fuel cell water balance by employing hot wire anemometry. The hot wire sensor is placed into a binary mixture of hydrogen and water vapour, and the voltage signal received gives valuable insight into heat and mass transfer phenomena in a PEMFC. A central question...

Neutron scattering from polarised proton domains

CERN Document Server

Van den Brandt, B; Kohbrecher, J; Konter, J A; Mango, S; Glattli, H; Leymarie, E; Grillo, I; May, R P; Jouve, H; Stuhrmann, H B; Stuhrmann, H B; Zimmer, O

2002-01-01

Time-dependent small-angle polarised neutron scattering from domains of polarised protons has been observed at the onset of dynamic nuclear polarisation in a frozen solution of 98% deuterated glycerol-water at 1 K containing a small concentration of paramagnetic centres (EHBA-Cr sup V). Simultaneous NMR measurements show that the observed scattering arises from protons around the Cr sup V -ions which are polarised to approx 10% in a few seconds, much faster than the protons in the bulk. (authors)

Complete relaxation and conformational exchange matrix (CORCEMA) analysis of intermolecular saturation transfer effects in reversibly forming ligand-receptor complexes.

Science.gov (United States)

Jayalakshmi, V; Krishna, N Rama

2002-03-01

A couple of recent applications of intermolecular NOE (INOE) experiments as applied to biomolecular systems involve the (i) saturation transfer difference NMR (STD-NMR) method and (ii) the intermolecular cross-saturation NMR (ICS-NMR) experiment. STD-NMR is a promising tool for rapid screening of a large library of compounds to identify bioactive ligands binding to a target protein. Additionally, it is also useful in mapping the binding epitopes presented by a bioactive ligand to its target protein. In this latter application, the STD-NMR technique is essentially similar to the ICS-NMR experiment, which is used to map protein-protein or protein-nucleic acid contact surfaces in complexes. In this work, we present a complete relaxation and conformational exchange matrix (CORCEMA) theory (H. N. B. Moseley et al., J. Magn. Reson. B 108, 243-261 (1995)) applicable for these two closely related experiments. As in our previous work, we show that when exchange is fast on the relaxation rate scale, a simplified CORCEMA theory can be formulated using a generalized average relaxation rate matrix. Its range of validity is established by comparing its predictions with those of the exact CORCEMA theory which is valid for all exchange rates. Using some ideal model systems we have analyzed the factors that influence the ligand proton intensity changes when the resonances from some protons on the receptor protein are saturated. The results show that the intensity changes in the ligand signals in an intermolecular NOE experiment are very much dependent upon: (1) the saturation time, (2) the location of the saturated receptor protons with respect to the ligand protons, (3) the conformation of the ligand-receptor interface, (4) the rotational correlation times for the molecular species, (5) the kinetics of the reversibly forming complex, and (6) the ligand/receptor ratio. As an example of a typical application of the STD-NMR experiment we have also simulated the STD effects for a

The role of the umbrella inversion mode in proton diffusion

Science.gov (United States)

Hassanali, Ali A.; Giberti, Federico; Sosso, Gabriele C.; Parrinello, Michele

2014-04-01

Here, using ab initio molecular dynamics (AIMD) simulations, we elucidate the role of the umbrella inversion mode of the hydronium in proton transfer (PT) in liquid water. The hydrophobic face of the hydronium oxygen experiences asymmetries in the solvent potential along the inversion coordinate and this has a rather drastic effect on the barrier for proton transfer. This behavior is coupled to the fluctuations of voids or cavities in the vicinity of the hydronium in the water network. The peculiar inversion mode can either trap or release the proton from different parts of the water network.

WE-EF-303-10: Single- Detector Proton Radiography as a Portal Imaging Equivalent for Proton Therapy

Energy Technology Data Exchange (ETDEWEB)

Doolan, P [University College London Hospital, London (United Kingdom); Bentefour, E [Ion Beam Applications, Louvain-la-Neuve (Belgium); Testa, M; Cascio, E; Lu, H [Massachussetts General Hospital, Boston, MA (United States); Royle, G [University College London, London (United Kingdom); Gottschalk, B [Harvard University, Cambridge, MA (United States)

2015-06-15

Purpose: In proton therapy, patient alignment is of critical importance due to the sensitivity of the proton range to tissue heterogeneities. Traditionally proton radiography is used for verification of the water-equivalent path length (WEPL), which dictates the depth protons reach. In this work we propose its use for alignment. Additionally, many new proton centers have cone-beam computed tomography in place of beamline X-ray imaging and so proton radiography offers a unique patient alignment verification similar to portal imaging in photon therapy. Method: Proton radiographs of a CIRS head phantom were acquired using the Beam Imaging System (BIS) (IBA, Louvain-la-Neuve) in a horizontal beamline. A scattered beam was produced using a small, dedicated, range modulator (RM) wheel fabricated out of aluminum. The RM wheel was rotated slowly (20 sec/rev) using a stepper motor to compensate for the frame rate of the BIS (120 ms). Dose rate functions (DRFs) over two RM wheel rotations were acquired. Calibration was made with known thicknesses of homogeneous solid water. For each pixel the time width, skewness and kurtosis of the DRFs were computed. The time width was used to compute the object WEPL. In the heterogeneous phantom, the excess skewness and excess kurtosis (i.e. difference from homogeneous cases) were computed and assessed for suitability for patient set up. Results: The technique allowed for the simultaneous production of images that can be used for WEPL verification, showing few internal details, and excess skewness and kurtosis images that can be used for soft tissue alignment. These latter images highlight areas where range mixing has occurred, correlating with phantom heterogeneities. Conclusion: The excess skewness and kurtosis images contain details that are not visible in the WET images. These images, unique to the time-resolved proton radiographic method, could be used for patient set up according to soft tissues.

Carbon Nitride Materials as Efficient Catalyst Supports for Proton Exchange Membrane Water Electrolyzers

Directory of Open Access Journals (Sweden)

Ana Belen Jorge

2018-06-01

Full Text Available Carbon nitride materials with graphitic to polymeric structures (gCNH were investigated as catalyst supports for the proton exchange membrane (PEM water electrolyzers using IrO2 nanoparticles as oxygen evolution electrocatalyst. Here, the performance of IrO2 nanoparticles formed and deposited in situ onto carbon nitride support for PEM water electrolysis was explored based on previous preliminary studies conducted in related systems. The results revealed that this preparation route catalyzed the decomposition of the carbon nitride to form a material with much lower N content. This resulted in a significant enhancement of the performance of the gCNH-IrO2 (or N-doped C-IrO2 electrocatalyst that was likely attributed to higher electrical conductivity of the N-doped carbon support.

Temperature dependence of 1H NMR relaxation time, T2, for intact and neoplastic plant tissues

Science.gov (United States)

Lewa, Czesław J.; Lewa, Maria

Temperature dependences of the spin-spin proton relaxation time, T2, have been shown for normal and tumorous tissues collected from kalus culture Nicotiana tabacum and from the plant Kalanchoe daigremontiana. For neoplastic plant tissues, time T2 was increased compared to that for intact plants, a finding similar to that for animal and human tissues. The temperature dependences obtained were compared to analogous relations observed with animal tissues.

New load cycling strategy for enhanced durability of high temperature proton exchange membrane fuel cell

DEFF Research Database (Denmark)

Thomas, Sobi; Jeppesen, Christian; Steenberg, Thomas

2017-01-01

The objective of this paper is to develop a new operational strategy to increase the lifetime of a high temperature proton exchange membrane (HT-PEMFCs) fuel cell system by using load cycling patterns to reduce the phosphoric acid loss from the fuel cell. Four single cells were operated under.......8 Acm-2 for the higher end, were selected for the load cycling operation. The relaxation time, which is the period of time spent at low current density operation, is varied to understand how the performance over prolonged period behaves. The duration of the high current density operation is selected...... based on the relaxation time in order to have the same average current density of (0.55 Acm-2 ) for all the cells. Cell 5, with a relaxation time of 2 min performs best and shows lower degradation rate of 36 μVh-1 compared to other load cycling cells with smaller relaxation times. The cell operated...

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

energy sources. The proton exchange membrane water electrolyser(PEMWE) is the most candidate technology to produce hydrogen from renewable energysources. PEMWE cell splits water into hydrogen and oxygen when an electric current is passedthrough it. Electrical current forces the positively charged ions...... 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...

Time resolved infrared spectroscopy of femtosecond proton dynamics in the liquid phase

International Nuclear Information System (INIS)

Amir, W.

2003-12-01

This work of thesis aims to understand the strong mobility of protons in water. Water is fundamental to life and mediates many chemical and biological processes. However this liquid is poorly understood at the molecular level. The richness of interdisciplinary sciences allows us to study the properties which make it so unique. The technique used for this study was the femtosecond time resolved vibrational spectroscopy. Several experiments were carried out to characterize the femtosecond proton dynamics in water. The visualization of the rotation of water molecules obtained by anisotropy measurements will be presented. This experiment is carried out in isotopic water HDO/D 2 O for reasons of experimental and theoretical suitability. However this is not water. Pure water H 2 O was also studied without thermal effects across vibrations modes. An intermolecular energy resonant transfer was observed. Finally the localized structure of the proton in water (called Eigen form) was clearly experimentally observed. This molecule is implicated in the abnormal mobility of the proton in water (Grotthuss mechanism). (author)

Hydration of DNA by tritiated water and isotope distribution: a study by 1H, 2H, and 3H NMR spectroscopy

International Nuclear Information System (INIS)

Mathur-De Vre, R.; Grimee-Declerck, R.; Lejeune, P.; Bertinchamps, A.J.

1982-01-01

The hydration layer of DNA (0.75%) in tritiated water represents 3.5% of solvent 3 HHO. The combined effects of temperature (-6 to -40 0 C) and H 2 O/ 2 H 2 O solvent composition on the spin-lattice relaxation times of water protons and deuterons suggest selective distribution of isotopes in the hydration layer. The ''hydration isotope'' effect and the localization of tritiated water molecules in the hydration layer of DNA have important implications in describing the radiobiological effects of tritiated water because the initial molecular damage caused by 3 HHO (internal radiation source) localizes close to 3 H due to the short range and low energy of 3 H β rays

An analysis of hydrated proton diffusion in ab initio molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Tse, Ying-Lung Steve; Voth, Gregory A., E-mail: gavoth@uchicago.edu [Department of Chemistry, James Franck Institute, and Computation Institute, University of Chicago, Chicago, Illinois 60637 (United States); Knight, Chris [Leadership Computing Facility, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

2015-01-07

A detailed understanding of the inherently multiscale proton transport process raises a number of scientifically challenging questions. For example, there remain many (partially addressed) questions on the molecular mechanism for long-range proton migration and the potential for the formation of long-lived traps giving rise to burst-and-rest proton dynamics. Using results from a sizeable collection of ab initio molecular dynamics (AIMD) simulations (totaling ∼2.7 ns) with various density functional approximations (Becke-Lee-Yang-Parr (BLYP), BLYP–D3, Hamprecht-Cohen-Tozer-Handy, B3LYP) and temperatures (300–330 K), equilibrium and dynamical properties of one excess proton and 128 water molecules are studied. Two features in particular (concerted hops and weak hydrogen-bond donors) are investigated to identify modes in the system that are strongly correlated with the onset of periods of burst-and-rest dynamics. The question of concerted hops seeks to identify those time scales over which long-range proton transport can be classified as a series of sequential water hopping events or as a near-simultaneous concerted process along compressed water wires. The coupling of the observed burst-and-rest dynamics with motions of a fourth neighboring water molecule (a weak hydrogen-bond donor) solvating the protonated water molecule is also investigated. The presence (absence) of hydrogen bonds involving this fourth water molecule before and after successful proton hopping events is found to be strongly correlated with periods of burst (rest) dynamics (and consistent with pre-solvation concepts). By analyzing several realizations of the AIMD trajectories on the 100-ps time scale, convergence of statistics can be assessed. For instance, it was observed that the probability for a fourth water molecule to approach the hydronium, if not already proximal at the beginning of the lifetime of the hydronium, is very low, indicative of the formation of stable void regions

Rare earth(III) complexes for the development of new magnetic and luminescent probes

International Nuclear Information System (INIS)

Nonat, A.

2007-10-01

The simultaneous optimisation of the molecular parameters determining the relaxivity (number of coordinated water molecules, water-exchange, rotation dynamics of the whole complex, electronic relaxation, Gd(III)-proton distance) is essential to prepare efficient contrast agents. The aim of this work is on the one hand to design and study complexes with a high number of bound water molecules and to understand the influence of the coordination sphere on the stability and on the electronic relaxation and on the other hand, to use the ligand as a chromophore for the development of luminescent probes for biomedical imaging. We present the structure, the stability and the relaxivity of Gd(III) complexes of two series of tripodal ligands containing picolinate units based either on the 1,4,7-tri-aza-cyclononane ring or on a tertiary amine. These complexes show high relaxivity in water and in serum and can establish a non covalent interaction with serum albumin. The interpretation of the water proton relaxivity with the help of new relaxometric methods based on an auxiliary probe solute has allowed us to show that both the presence of the picolinate groups and the 1,4,7-tri-aza-cyclononane framework can lead to Gd(III) complexes with favourable electronic relaxation properties. This ligands have also been used for Eu(III) and Tb(III) complexation leading to strong luminescence in visible light. Other complexes derived from 8-hydroxyquinoline unit which display a very high luminescence in infrared are also studied. (author)

Rare earth(III) complexes for the development of new magnetic and luminescent probes; Complexes de lanthanides(III) pour le developpement de nouvelles sondes magnetiques et luminescentes

Energy Technology Data Exchange (ETDEWEB)

Nonat, A

2007-10-15

The simultaneous optimisation of the molecular parameters determining the relaxivity (number of coordinated water molecules, water-exchange, rotation dynamics of the whole complex, electronic relaxation, Gd(III)-proton distance) is essential to prepare efficient contrast agents. The aim of this work is on the one hand to design and study complexes with a high number of bound water molecules and to understand the influence of the coordination sphere on the stability and on the electronic relaxation and on the other hand, to use the ligand as a chromophore for the development of luminescent probes for biomedical imaging. We present the structure, the stability and the relaxivity of Gd(III) complexes of two series of tripodal ligands containing picolinate units based either on the 1,4,7-tri-aza-cyclononane ring or on a tertiary amine. These complexes show high relaxivity in water and in serum and can establish a non covalent interaction with serum albumin. The interpretation of the water proton relaxivity with the help of new relaxometric methods based on an auxiliary probe solute has allowed us to show that both the presence of the picolinate groups and the 1,4,7-tri-aza-cyclononane framework can lead to Gd(III) complexes with favourable electronic relaxation properties. This ligands have also been used for Eu(III) and Tb(III) complexation leading to strong luminescence in visible light. Other complexes derived from 8-hydroxyquinoline unit which display a very high luminescence in infrared are also studied. (author)

Dynamic behavior of liquid water transport in a tapered channel of a proton exchange membrane fuel cell cathode

NARCIS (Netherlands)

Akhtar, N.; Kerkhof, P.J.A.M.

2011-01-01

A numerical model of a proton exchange membrane fuel cell (PEMFC) cathode with a tapered channel design has been developed in order to examine the dynamic behavior of liquid water transport. Three-dimensional, transient simulations employing the level-set method (available in COMSOL 3.5a, a

Predicting liquid water saturation through differently structured cathode gas diffusion media of a proton exchange Membrane Fuel Cell

NARCIS (Netherlands)

Akhtar, N.; Kerkhof, P.J.A.M.

2012-01-01

The role of gas diffusion media with differently structured properties have been examined with emphasis on the liquid water saturation within the cathode of a proton exchange membrane fuel cell (PEMFC). The cathode electrode consists of a gas diffusion layer (GDL), a micro-porous layer and a

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 infrared absorption spectrum of the protonated water dimer (H5O2+) is simulated in full dimensionality (15 dimensional) in the spectral range of 0-4000 cm(-1). The calculations are performed using the multiconfiguration time-dependent Hartree (MCTDH) method for propagation of wavepackets. All...

Stress relaxation in quasi-two-dimensional self-assembled nanoparticle monolayers

Science.gov (United States)

Boucheron, Leandra S.; Stanley, Jacob T.; Dai, Yeling; You, Siheng Sean; Parzyck, Christopher T.; Narayanan, Suresh; Sandy, Alec R.; Jiang, Zhang; Meron, Mati; Lin, Binhua; Shpyrko, Oleg G.

2018-05-01

We experimentally probed the stress relaxation of a monolayer of iron oxide nanoparticles at the water-air interface. Upon drop-casting onto a water surface, the nanoparticles self-assembled into islands of two-dimensional hexagonally close packed crystalline domains surrounded by large voids. When compressed laterally, the voids gradually disappeared as the surface pressure increased. After the compression was stopped, the surface pressure (as measured by a Wilhelmy plate) evolved as a function of the film aging time with three distinct timescales. These aging dynamics were intrinsic to the stressed state built up during the non-equilibrium compression of the film. Utilizing x-ray photon correlation spectroscopy, we measured the characteristic relaxation time (τ ) of in-plane nanoparticle motion as a function of the aging time through both second-order and two-time autocorrelation analysis. Compressed and stretched exponential fitting of the intermediate scattering function yielded exponents (β ) indicating different relaxation mechanisms of the films under different compression stresses. For a monolayer compressed to a lower surface pressure (between 20 mN/m and 30 mN/m), the relaxation time (τ ) decreased continuously as a function of the aging time, as did the fitted exponent, which transitioned from being compressed (>1 ) to stretched (stress release through crystalline domain reorganization. However, for a monolayer compressed to a higher surface pressure (around 40 mN/m), the relaxation time increased continuously and the compressed exponent varied very little from a value of 1.6, suggesting that the system may have been highly stressed and jammed. Despite the interesting stress relaxation signatures seen in these samples, the structural ordering of the monolayer remained the same over the sample lifetime, as revealed by grazing incidence x-ray diffraction.

Earth's field NMR detection of oil under arctic ice-water suppression

Science.gov (United States)

Conradi, Mark S.; Altobelli, Stephen A.; Sowko, Nicholas J.; Conradi, Susan H.; Fukushima, Eiichi

2018-03-01

Earth's field NMR has been developed to detect oil trapped under or in Arctic sea-ice. A large challenge, addressed here, is the suppression of the water signal that dominates the oil signal. Selective suppression of water is based on relaxation time T1 because of the negligible chemical shifts in the weak earth's magnetic field, making all proton signals overlap spectroscopically. The first approach is inversion-null recovery, modified for use with pre-polarization. The requirements for efficient inversion over a wide range of B1 and subsequent adiabatic reorientation of the magnetization to align with the static field are stressed. The second method acquires FIDs at two durations of pre-polarization and cancels the water component of the signal after the data are acquired. While less elegant, this technique imposes no stringent requirements. Similar water suppression is found in simulations for the two methods. Oil detection in the presence of water is demonstrated experimentally with both techniques.

Distribution of water in fresh cod

DEFF Research Database (Denmark)

Andersen, Charlotte Møller; Rinnan, A.

2002-01-01

Low-field (1)H nuclear magnetic resonance (NMR) transverse relaxation was used to measure water mobility and distribution of water in fresh cod fillets. The NMR relaxations were analysed with the so-called SLICING method giving uni-exponential profiles from which the transverse relaxation time (T(2......)-values) and the relative sizes of the water populations were calculated. Two water populations with the T(2)-values of 50 and 94 ms were obtained. The shortest relaxation time was primarily found near the head, and water with the longest relaxation time was primarily found near the tail. This variation...... can he explained by the smaller muscle cells and muscle fibers in the tail, which may influence the distributions of water into the different pools. The amount of one of the water populations was correlated to the overall water content with a correlation coefficient of -0.94. (C) 2002 Elsevier Science...

Proton-counting radiography for proton therapy: a proof of principle using CMOS APS technology

International Nuclear Information System (INIS)

Poludniowski, G; Esposito, M; Evans, P M; Allinson, N M; Anaxagoras, T; Green, S; Parker, D J; Price, T; Manolopoulos, S; Nieto-Camero, J

2014-01-01

Despite the early recognition of the potential of proton imaging to assist proton therapy (Cormack 1963 J. Appl. Phys. 34 2722), the modality is still removed from clinical practice, with various approaches in development. For proton-counting radiography applications such as computed tomography (CT), the water-equivalent-path-length that each proton has travelled through an imaged object must be inferred. Typically, scintillator-based technology has been used in various energy/range telescope designs. Here we propose a very different alternative of using radiation-hard CMOS active pixel sensor technology. The ability of such a sensor to resolve the passage of individual protons in a therapy beam has not been previously shown. Here, such capability is demonstrated using a 36 MeV cyclotron beam (University of Birmingham Cyclotron, Birmingham, UK) and a 200 MeV clinical radiotherapy beam (iThemba LABS, Cape Town, SA). The feasibility of tracking individual protons through multiple CMOS layers is also demonstrated using a two-layer stack of sensors. The chief advantages of this solution are the spatial discrimination of events intrinsic to pixelated sensors, combined with the potential provision of information on both the range and residual energy of a proton. The challenges in developing a practical system are discussed. (paper)

Proton-counting radiography for proton therapy: a proof of principle using CMOS APS technology.

Science.gov (United States)

Poludniowski, G; Allinson, N M; Anaxagoras, T; Esposito, M; Green, S; Manolopoulos, S; Nieto-Camero, J; Parker, D J; Price, T; Evans, P M

2014-06-07

Despite the early recognition of the potential of proton imaging to assist proton therapy (Cormack 1963 J. Appl. Phys. 34 2722), the modality is still removed from clinical practice, with various approaches in development. For proton-counting radiography applications such as computed tomography (CT), the water-equivalent-path-length that each proton has travelled through an imaged object must be inferred. Typically, scintillator-based technology has been used in various energy/range telescope designs. Here we propose a very different alternative of using radiation-hard CMOS active pixel sensor technology. The ability of such a sensor to resolve the passage of individual protons in a therapy beam has not been previously shown. Here, such capability is demonstrated using a 36 MeV cyclotron beam (University of Birmingham Cyclotron, Birmingham, UK) and a 200 MeV clinical radiotherapy beam (iThemba LABS, Cape Town, SA). The feasibility of tracking individual protons through multiple CMOS layers is also demonstrated using a two-layer stack of sensors. The chief advantages of this solution are the spatial discrimination of events intrinsic to pixelated sensors, combined with the potential provision of information on both the range and residual energy of a proton. The challenges in developing a practical system are discussed.

Proton and O sup(2-) ion diffusion studied by γ-γ angular correlation and by impedance spectroscopy

International Nuclear Information System (INIS)

Oliveira Damasceno, O. de.

1988-01-01

The interaction of sup(181) Ta quadrupole momentum with electric field gradient was measured by perturbed angular correlation spectroscopy in polycrystalline samples of hafnium hydride and hafnium oxide. The measurements were done as function of the temperature, in cubic and tetragonal phases of hafnium hydride. In the cubic phase, spin relaxation effects related to proton diffusion with activation energy of 0.43 ± 0.05eV were observed, and in the tetragonal phase, the interaction was purely static. The hafnium oxide was studied in cubic phase stabilized by addition of calcium oxide or magnesium oxide. Relaxation effects probably due to O sup(2-) ion diffusion were verified. The protonic conduction in K H sub(2) PO sub(4) was studied by impedance spectroscopy, in pellets prepared by melting or powder compression using silver and platinum electrodes. In the case of silver electrodes, in the low frequency region, the impedance spectrum tends to a 45 sup(0) typical line of the diffusion process. It was attributed to hydrogen injection in the electrode. Heating k H sub(2) PO sub(4) at about 230 sup(0)C modifies significantly the electric properties. Two relaxation annealing reduced conductivities to constant values independently of preparation method. (author)

Electrical spectroscopy studies of two new siloxanic proton conducting membranes

International Nuclear Information System (INIS)

Di Noto, Vito; Vittadello, Michele; Zago, Vanni; Pace, Giuseppe; Vidali, Maurizio

2006-01-01

This contribution is focused on the conductivity study and the protonic transfer investigation of two new siloxanic membranes. The conductivity of the systems has been studied within the temperature range 5 deg. C ≤ T ≤ 145 deg. C, both for pristine and hydrated membranes. Membrane A has been hydrated up to 33.12% in weight, while in B up to 27.76%. The conductivity of these membranes has shown a temperature dependence of the Arrhenius type variable in the interval 1.6 x 10 -4 ≤ σ A ≤ 2.3 x 10 -3 S cm -1 and 1.3 x 10 -5 ≤ σ B ≤ 2.9 x 10 -4 S cm -1 , respectively, for A and B. In particular, conductivities of 2 x 10 -3 S cm -1 (A) and of 2 x 10 -4 S cm -1 (B) at 125 deg. C were observed. The conductivity mechanism was investigated by using broad band electrical spectroscopy in the region between 40 Hz and 10 MHz. This study, for both the materials has shown the presence at low frequencies (10 2 ≤ f β ≤ 10 4 Hz) of β relaxations related to the sulphonic side chain dynamics. The activation energy measured for this molecular dynamics is about ≅30 kJ mol -1 and corresponds to the typical interaction energy associated with hydrogen bonding. Furthermore, it was observed that the activation energies determined from the conductivity measurements are 12 and 14 kJ mol -1 , respectively, for A and B. This shows that the protonic conductivity is strongly influenced by the side chain dynamics and that the charge migration occurs through an ion hopping mechanism between different regions, consisting of micro-clusters of hydration water coordinated with the polar sulphonic groups of the side chains. The comparable activation energies and the values of the conductivity demonstrate that in these systems the conductivity is proportional to the concentration of the sulphonic groups. This shows also that these kinds of membranes, with a high concentration of SO 3 H are necessary in order to obtain materials with a high protonic conductivity with the capacity to

SU-E-J-63: Feasibility Study of Proton Digital Tomosynthesis in Proton Beam Therapy.

Science.gov (United States)

Min, B; Kwak, J; Lee, J; Cho, S; Park, S; Yoo, S; Chung, K; Cho, S; Lim, Y; Shin, D; Lee, S; Kim, J

2012-06-01

We investigated the feasibility of proton tomosynthesis as daily positioning of patients and compared the results with photon tomosynthesis as an alternative to conventional portal imaging or on-board cone-beam computed tomography. Dedicated photon-like proton beam using the passively scattered proton beams by the cyclotron was generated for proton imaging. The eleven projections were acquired over 30 degree with 3 degree increment in order to investigate the performance of proton tomosynthesis. The cylinder blocks and resolution phantom were used to evaluate imaging performance. Resolution phantom of a cylinder of diameter 12 cm was used to investigate the reconstructed imaging characteristics. Electron density cylinder blocks with diameter of 28 mm and height of 70 mm were employed to assess the imaging quality. The solid water, breast, bone, adipose, lung, muscle, and liver, which were tissue equivalent inserts, were positioned around the resolution phantom. The images were reconstructed by projection onto convex sets (POCS) algorithm and total variation minimization (TVM) methods. The Gafchromic EBT films were utilized for measuring the photon-like proton beams as a proton detector. In addition, the photon tomosynthesis images were obtained for a comparison with proton tomosynthesis images. The same angular sampling data were acquired for both proton and photon tomosynthesis. In the resolution phantom image obtained proton tomosynthesis, down to 1.6 mm diameter rods were resolved visually, although the separation between adjacent rods was less distinct. In contrast, down to 1.2 mm diameter rods were resolved visually in the reconstructed image obtained photon tomosynthesis. Both proton and photon tomosynthesis images were similar in intensities of different density blocks. Our results demonstrated that proton tomosynthesis could make it possible to provide comparable tomography imaging to photon tomosynthesis for positioning as determined by manual registration

Relaxation characteristics of hastelloy X

International Nuclear Information System (INIS)

Suzuki, Kazuhiko

1980-02-01

Relaxation diagrams of Hastelloy X (relaxation curves, relaxation design diagrams, etc.) were generated from the creep constitutive equation of Hastelloy X, using inelastic stress analysis code TEPICC-J. These data are in good agreement with experimental relaxation data of ORNL-5479. Three typical inelastic stress analyses were performed for various relaxation behaviors of the high-temperature structures. An attempt was also made to predict these relaxation behaviors by the relaxation curves. (author)

Time resolved infrared spectroscopy of femtosecond proton dynamics in the liquid phase; Spectroscopie infrarouge resolue en temps pour l'etude de la dynamique femtoseconde du proton en phase liquide

Energy Technology Data Exchange (ETDEWEB)

Amir, W

2003-12-15

This work of thesis aims to understand the strong mobility of protons in water. Water is fundamental to life and mediates many chemical and biological processes. However this liquid is poorly understood at the molecular level. The richness of interdisciplinary sciences allows us to study the properties which make it so unique. The technique used for this study was the femtosecond time resolved vibrational spectroscopy. Several experiments were carried out to characterize the femtosecond proton dynamics in water. The visualization of the rotation of water molecules obtained by anisotropy measurements will be presented. This experiment is carried out in isotopic water HDO/D{sub 2}O for reasons of experimental and theoretical suitability. However this is not water. Pure water H{sub 2}O was also studied without thermal effects across vibrations modes. An intermolecular energy resonant transfer was observed. Finally the localized structure of the proton in water (called Eigen form) was clearly experimentally observed. This molecule is implicated in the abnormal mobility of the proton in water (Grotthuss mechanism). (author)

Corroborative evidences of TV γ -scaling of the α-relaxation originating from the primitive relaxation/JG β relaxation

Science.gov (United States)

Ngai, K. L.; Paluch, M.

2017-12-01

Successful thermodynamic scaling of the structural alpha-relaxation time or transport coefficients of glass-forming liquids determined at various temperatures T and pressures P means the data conform to a single function of the product variable TVgamma, where V is the specific volume and gamma is a material specific constant. In the past two decades we have witnessed successful TVgamma-scaling in many molecular, polymeric, and even metallic glass-formers, and gamma is related to the slope of the repulsive part of the intermolecular potential. The advances made indicate TVgamma-scaling is an important aspect of the dynamic and thermodynamic properties of glass-formers. In this paper we show the origin of TVgamma-scaling is not from the structural alpha-relaxation time. Instead it comes from its precursor, the Johari-Goldstein beta-relaxation or the primitive relaxation of the Coupling Model and their relaxation times or tau_0 respectively. It is remarkable that all relaxation times are functions of TVgamma with the same gama, as well as the fractional exponent of the Kohlrausch correlation function of the structural alpha-relaxation. We arrive at this conclusion convincingly based on corroborative evidences from a number of experiments and molecular dynamics simulations performed on a wide variety of glass-formers and in conjunction with consistency with the predictions of the Coupling Model.

Differential saturation study of radial and angular modulation mechanisms of electron spin--lattice relaxation for trapped hydrogen atoms in sulfuric acid glasses. [X radiation

Energy Technology Data Exchange (ETDEWEB)

Plonka, A; Kevan, L

1976-11-01

A differential ESR saturation study of allowed transitions and forbidden proton spin-flip satellite transitions for trapped hydrogen atoms in sulfuric acid glasses indicates that angular modulation dominates the spin-lattice relaxation mechanisms and suggests that the modulation arises from motion of the H atom.

Transverse relaxation dispersion of the p7 membrane channel from hepatitis C virus reveals conformational breathing

International Nuclear Information System (INIS)

Dev, Jyoti; Brüschweiler, Sven; Ouyang, Bo; Chou, James J.

2015-01-01

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

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.

Structural design study of a proton beam window for a 1-MW spallation neutron source

CERN Document Server

Teraoku, T; Ishikura, S; Kaminaga, M; Maekawa, F; Meigo, S I; Terada, A

2003-01-01

A 1-MW spallation neutron source aiming at materials and life science researches will be constructed under the JAERI-KEK High-intensity Proton Accelerator Project (J-PARC). A proton beam passes through a proton beam window, and be injected into a target of the neutron source. The proton beam window functions as a boundary wall between a high vacuum area in the proton beam line and a helium atmosphere at about atmospheric pressure in a helium vessel which contains the target and moderators. The proton beam window is cooled by light water because high heat-density is generated in the window material by interactions with the proton beam. Then, uniformity of the water flow is requested at the window to suppress a hot-spot that causes excessive thermal stress and cooling water boiling. Also, the window has to be strong enough in its structure for inner stress due to water pressure and thermal stress due to heat generation. In this report, we propose two types of proton beam windows; one flat-type that is easy to m...

Capturing molecular multimode relaxation processes in excitable gases based on decomposition of acoustic relaxation spectra

Science.gov (United States)

Zhu, Ming; Liu, Tingting; Wang, Shu; Zhang, Kesheng

2017-08-01

Existing two-frequency reconstructive methods can only capture primary (single) molecular relaxation processes in excitable gases. In this paper, we present a reconstructive method based on the novel decomposition of frequency-dependent acoustic relaxation spectra to capture the entire molecular multimode relaxation process. This decomposition of acoustic relaxation spectra is developed from the frequency-dependent effective specific heat, indicating that a multi-relaxation process is the sum of the interior single-relaxation processes. Based on this decomposition, we can reconstruct the entire multi-relaxation process by capturing the relaxation times and relaxation strengths of N interior single-relaxation processes, using the measurements of acoustic absorption and sound speed at 2N frequencies. Experimental data for the gas mixtures CO2-N2 and CO2-O2 validate our decomposition and reconstruction approach.

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

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.

On the nuclear halo of a proton pencil beam stopping in water

International Nuclear Information System (INIS)

Gottschalk, Bernard; Cascio, Ethan W; Daartz, Juliane; Wagner, Miles S

2015-01-01

The dose distribution of a proton beam stopping in water has components due to basic physics and may have others from beam contamination. We propose the concise terms core for the primary beam, halo (see Pedroni et al 2005 Phys. Med. Biol. 50 541–61) for the low dose region from charged secondaries, aura for the low dose region from neutrals, and spray for beam contamination.We have measured the dose distribution in a water tank at 177 MeV under conditions where spray, therefore radial asymmetry, is negligible. We used an ADCL calibrated thimble chamber and a Faraday cup calibrated integral beam monitor so as to obtain immediately the absolute dose per proton. We took depth scans at fixed distances from the beam centroid rather than radial scans at fixed depths. That minimizes the signal range for each scan and better reveals the structure of the core and halo.Transitions from core to halo to aura are already discernible in the raw data. The halo has components attributable to coherent and incoherent nuclear reactions. Due to elastic and inelastic scattering by the nuclear force, the Bragg peak persists to radii larger than can be accounted for by Molière single scattering. The radius of the incoherent component, a dose bump around midrange, agrees with the kinematics of knockout reactions.We have fitted the data in two ways. The first is algebraic or model dependent (MD) as far as possible, and has 25 parameters. The second, using 2D cubic spline regression, is model independent. Optimal parameterization for treatment planning will probably be a hybrid of the two, and will of course require measurements at several incident energies.The MD fit to the core term resembles that of the PSI group (Pedroni et al 2005), which has been widely emulated. However, we replace their T(w), a mass stopping power which mixes electromagnetic (EM) and nuclear effects, with one that is purely EM, arguing that protons that do not undergo hard single scatters continue to lose energy

On the nuclear halo of a proton pencil beam stopping in water

Science.gov (United States)

Gottschalk, Bernard; Cascio, Ethan W.; Daartz, Juliane; Wagner, Miles S.

2015-07-01

The dose distribution of a proton beam stopping in water has components due to basic physics and may have others from beam contamination. We propose the concise terms core for the primary beam, halo (see Pedroni et al 2005 Phys. Med. Biol. 50 541-61) for the low dose region from charged secondaries, aura for the low dose region from neutrals, and spray for beam contamination. We have measured the dose distribution in a water tank at 177 MeV under conditions where spray, therefore radial asymmetry, is negligible. We used an ADCL calibrated thimble chamber and a Faraday cup calibrated integral beam monitor so as to obtain immediately the absolute dose per proton. We took depth scans at fixed distances from the beam centroid rather than radial scans at fixed depths. That minimizes the signal range for each scan and better reveals the structure of the core and halo. Transitions from core to halo to aura are already discernible in the raw data. The halo has components attributable to coherent and incoherent nuclear reactions. Due to elastic and inelastic scattering by the nuclear force, the Bragg peak persists to radii larger than can be accounted for by Molière single scattering. The radius of the incoherent component, a dose bump around midrange, agrees with the kinematics of knockout reactions. We have fitted the data in two ways. The first is algebraic or model dependent (MD) as far as possible, and has 25 parameters. The second, using 2D cubic spline regression, is model independent. Optimal parameterization for treatment planning will probably be a hybrid of the two, and will of course require measurements at several incident energies. The MD fit to the core term resembles that of the PSI group (Pedroni et al 2005), which has been widely emulated. However, we replace their T(w), a mass stopping power which mixes electromagnetic (EM) and nuclear effects, with one that is purely EM, arguing that protons that do not undergo hard single scatters continue to lose

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...... operation. The water balance indicates how much of the product water leaves at the anode side versus the cathode side. Previous methods of determining the fuel cell water balance often relied on condensing the water in the exhaust gas streams and weighing the accumulated mass which is a time consuming...... process that has limited accuracy. Currently, our group is developing a novel method to accurately determine the water balance in a PEMFC in real time by employing hot-wire anemometry. The amount of heat transferred from the wire to the anode exhaust stream can be translated into a voltage signal which...

WE-EF-303-09: Proton-Acoustic Range Verification in Proton Therapy

Energy Technology Data Exchange (ETDEWEB)

Ahmad, M; Xing, L [Stanford University School of Medicine, Stanford, CA (United States); Xiang, L [University of Oklahoma (OK), Norman, OK (United States)

2015-06-15

Purpose: We investigated proton-acoustic signals detection for range verification with current ultrasound instruments in typical clinical scenarios. Using simulations that included a realistic noise model, we determined the theoretical minimum dose required to generate detectable proton-acoustic signals. Methods: An analytical model was used to calculate the dose distributions and local pressure rise (per proton) for beams of different energy (100 and 160 MeV) and spot widths (1, 5, and 10 mm) in a water phantom. The acoustic waves propagating from the Bragg peak were modeled by the general 3D pressure wave equation and convolved with Gaussian kernels to simulate various proton pulse widths (0.1 – 10 ms). A realistic PZT ultrasound transducer (5 cm diameter) was simulated with a Butterworth band-pass filter, and ii) randomly generated noise based on a model of thermal noise in the transducer. The signal-to-noise ratio was calculated, determining the minimum number of protons and dose required per pulse. The maximum spatial resolution was also estimated from the signal spectrum. Results: The calculated noise in the transducer was 12–28 mPa, depending on the transducer center frequency (70–380 kHz). The minimum number of protons were on the order of 0.6–6 million per pulse, leading to 3–110 mGy dose per pulse at the Bragg peak, depending on the spot size. The acoustic signal consisted of lower frequencies for wider pulses, leading to lower noise levels, but also worse spatial resolution. The resolution was 1-mm for a 0.1-µs pulse width, but increased to 5-mm for a 10-µs pulse width. Conclusion: We have established minimum dose detection limits for proton-acoustic range validation. These limits correspond to a best case scenario with a large detector with no losses and only detector thermal noise. Feasible proton-acoustic range detection will require at least 10{sup 7} protons per pulse and pulse widths ≤ 1-µs.

Proton transport in additives to the polymer electrolyte membrane for fuel cell application

Energy Technology Data Exchange (ETDEWEB)

Toelle, Pia

2011-03-21

The enhancement of proton transport in polymer electrolyte membranes is an important issue for the development of fuel cell technology. The objective is a material providing proton transport at a temperature range of 350 K to 450 K independent from a purely water based mechanism. To enhance the PEM properties of standard polymer materials, a class of additives is studied by means of atomistic simulations consisting of functionalised mesoporous silicon dioxide particles. The functional molecules are imidazole or sulphonic acid, covalently bound to the surface via a carbon chain with a surface density of about 1.0 nm{sup -2} groups. At first, the proton transport mechanism is explored in a system of functional molecules in vacuum. The molecules are constrained by the terminal carbon groups according to the geometric arrangement in the porous silicon dioxide. The proton transport mechanism is characterised by structural properties obtained from classical molecular dynamics simulations and consists of the aggregation of two or more functional groups, a barrier free proton transport between these groups followed by the separation of the groups and formation of new aggregates due to fluctuations in the hydrogen bond network and movement of the carbon chain. For the different proton conducting groups, i.e. methyl imidazole, methyl sulphonic acid and water, the barrier free proton transport and the formation of protonated bimolecular complexes were addressed by potential energy calculations of the density functional based tight binding method (DFTB). For sulphonic acid even at a temperature of 450 K, relatively stable aggregates are formed, while most imidazole groups are isolated and the hydrogen bond fluctuations are high. However, high density of groups and elevated temperatures enhance the proton transport in both systems. Besides the anchorage and the density of the groups, the influence of the chemical environment on the proton transport was studied. Therefore, the

Rotational dynamics in supercooled water from nuclear spin relaxation and molecular simulations.

Science.gov (United States)

Qvist, Johan; Mattea, Carlos; Sunde, Erik P; Halle, Bertil

2012-05-28

Structural dynamics in liquid water slow down dramatically in the supercooled regime. To shed further light on the origin of this super-Arrhenius temperature dependence, we report high-precision (17)O and (2)H NMR relaxation data for H(2)O and D(2)O, respectively, down to 37 K below the equilibrium freezing point. With the aid of molecular dynamics (MD) simulations, we provide a detailed analysis of the rotational motions probed by the NMR experiments. The NMR-derived rotational correlation time τ(R) is the integral of a time correlation function (TCF) that, after a subpicosecond librational decay, can be described as a sum of two exponentials. Using a coarse-graining algorithm to map the MD trajectory on a continuous-time random walk (CTRW) in angular space, we show that the slowest TCF component can be attributed to large-angle molecular jumps. The mean jump angle is ∼48° at all temperatures and the waiting time distribution is non-exponential, implying dynamical heterogeneity. We have previously used an analogous CTRW model to analyze quasielastic neutron scattering data from supercooled water. Although the translational and rotational waiting times are of similar magnitude, most translational jumps are not synchronized with a rotational jump of the same molecule. The rotational waiting time has a stronger temperature dependence than the translation one, consistent with the strong increase of the experimentally derived product τ(R) D(T) at low temperatures. The present CTRW jump model is related to, but differs in essential ways from the extended jump model proposed by Laage and co-workers. Our analysis traces the super-Arrhenius temperature dependence of τ(R) to the rotational waiting time. We present arguments against interpreting this temperature dependence in terms of mode-coupling theory or in terms of mixture models of water structure.

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.

Optimized co-solute paramagnetic relaxation enhancement for the rapid NMR analysis of a highly fibrillogenic peptide

International Nuclear Information System (INIS)

Oktaviani, Nur Alia; Risør, Michael W.; Lee, Young-Ho; Megens, Rik P.; Jong, Djurre H. de; Otten, Renee; Scheek, Ruud M.; Enghild, Jan J.; Nielsen, Niels Chr.; Ikegami, Takahisa; Mulder, Frans A. A.

2015-01-01

Co-solute paramagnetic relaxation enhancement (PRE) is an attractive way to speed up data acquisition in NMR spectroscopy by shortening the T 1 relaxation time of the nucleus of interest and thus the necessary recycle delay. Here, we present the rationale to utilize high-spin iron(III) as the optimal transition metal for this purpose and characterize the properties of its neutral chelate form Fe(DO3A) as a suitable PRE agent. Fe(DO3A) effectively reduces the T 1 values across the entire sequence of the intrinsically disordered protein α-synuclein with negligible impact on line width. The agent is better suited than currently used alternatives, shows no specific interaction with the polypeptide chain and, due to its high relaxivity, is effective at low concentrations and in ‘proton-less’ NMR experiments. By using Fe(DO3A) we were able to complete the backbone resonance assignment of a highly fibrillogenic peptide from α 1 -antitrypsin by acquiring the necessary suite of multidimensional NMR datasets in 3 h

Optimized co-solute paramagnetic relaxation enhancement for the rapid NMR analysis of a highly fibrillogenic peptide

Energy Technology Data Exchange (ETDEWEB)

Oktaviani, Nur Alia [University of Groningen, Groningen Biomolecular Sciences and Biotechnology Institute (Netherlands); Risør, Michael W. [University of Aarhus, Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry (Denmark); Lee, Young-Ho [Osaka University, Institute for Protein Research (Japan); Megens, Rik P. [University of Groningen, Stratingh Institute for Chemistry (Netherlands); Jong, Djurre H. de; Otten, Renee; Scheek, Ruud M. [University of Groningen, Groningen Biomolecular Sciences and Biotechnology Institute (Netherlands); Enghild, Jan J. [University of Aarhus, Interdisciplinary Nanoscience Center (iNANO) and Department of Molecular Biology and Genetics (Denmark); Nielsen, Niels Chr. [University of Aarhus, Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry (Denmark); Ikegami, Takahisa [Yokohama City University, Graduate School of Medical Life Science (Japan); Mulder, Frans A. A., E-mail: fmulder@chem.au.dk [University of Groningen, Groningen Biomolecular Sciences and Biotechnology Institute (Netherlands)

2015-06-15

Co-solute paramagnetic relaxation enhancement (PRE) is an attractive way to speed up data acquisition in NMR spectroscopy by shortening the T{sub 1} relaxation time of the nucleus of interest and thus the necessary recycle delay. Here, we present the rationale to utilize high-spin iron(III) as the optimal transition metal for this purpose and characterize the properties of its neutral chelate form Fe(DO3A) as a suitable PRE agent. Fe(DO3A) effectively reduces the T{sub 1} values across the entire sequence of the intrinsically disordered protein α-synuclein with negligible impact on line width. The agent is better suited than currently used alternatives, shows no specific interaction with the polypeptide chain and, due to its high relaxivity, is effective at low concentrations and in ‘proton-less’ NMR experiments. By using Fe(DO3A) we were able to complete the backbone resonance assignment of a highly fibrillogenic peptide from α{sub 1}-antitrypsin by acquiring the necessary suite of multidimensional NMR datasets in 3 h.

Proton Conductivity of Proton Exchange Membrane Synergistically Promoted by Different Functionalized Metal-Organic Frameworks.

Science.gov (United States)

Rao, Zhuang; Tang, Beibei; Wu, Peiyi

2017-07-12

In this study, two functionalized metal-organic frameworks (MOFs), UiO-66-SO 3 H and UiO-66-NH 2 , were synthesized. Then, different composite proton exchange membranes (PEMs) were prepared by single doping and codoping of these two MOFs, respectively. It was found that codoping of these two MOFs with suitable sizes was more conducive to the proton conductivity enhancement of the composite PEM. A synergistic effect between these two MOFs led to the the formation of more consecutive hydration channels in the composite PEM. It further greatly promoted the proton conductivity of the composite PEM. The proton conductivity of the codoped PEM reached up to 0.256 S/cm under 90 °C, 95% RH, which was ∼1.17 times higher than that of the recast Nafion (0.118 S/cm). Besides, the methanol permeability of the codoped PEM was prominently decreased owing to the methanol trapping effect of the pores of these two MOFs. Meanwhile, the high water and thermal stabilities of these two MOFs were beneficial to the high proton conductivity stability of the codoped PEM under high humidity and high temperature. The proton conductivity of the codoped PEM was almost unchanged throughout 3000 min of testing under 90 °C, 95% RH. This work provides a valuable reference for designing different functionalized MOFs to synergistically promote the proton conductivities of PEMs.

Moving protons with pendant amines: proton mobility in a nickel catalyst for oxidation of hydrogen.

Science.gov (United States)

O'Hagan, Molly; Shaw, Wendy J; Raugei, Simone; Chen, Shentan; Yang, Jenny Y; Kilgore, Uriah J; DuBois, Daniel L; Bullock, R Morris

2011-09-14

Proton transport is ubiquitous in chemical and biological processes, including the reduction of dioxygen to water, the reduction of CO(2) to formate, and the production/oxidation of hydrogen. In this work we describe intramolecular proton transfer between Ni and positioned pendant amines for the hydrogen oxidation electrocatalyst [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+) (P(Cy)(2)N(Bn)(2) = 1,5-dibenzyl-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane). Rate constants are determined by variable-temperature one-dimensional NMR techniques and two-dimensional EXSY experiments. Computational studies provide insight into the details of the proton movement and energetics of these complexes. Intramolecular proton exchange processes are observed for two of the three experimentally observable isomers of the doubly protonated Ni(0) complex, [Ni(P(Cy)(2)N(Bn)(2)H)(2)](2+), which have N-H bonds but no Ni-H bonds. For these two isomers, with pendant amines positioned endo to the Ni, the rate constants for proton exchange range from 10(4) to 10(5) s(-1) at 25 °C, depending on isomer and solvent. No exchange is observed for protons on pendant amines positioned exo to the Ni. Analysis of the exchange as a function of temperature provides a barrier for proton exchange of ΔG(‡) = 11-12 kcal/mol for both isomers, with little dependence on solvent. Density functional theory calculations and molecular dynamics simulations support the experimental observations, suggesting metal-mediated intramolecular proton transfers between nitrogen atoms, with chair-to-boat isomerizations as the rate-limiting steps. Because of the fast rate of proton movement, this catalyst may be considered a metal center surrounded by a cloud of exchanging protons. The high intramolecular proton mobility provides information directly pertinent to the ability of pendant amines to accelerate proton transfers during catalysis of hydrogen oxidation. These results may also have broader implications for proton movement in

DINS measurements on VESUVIO in the Resonance Detector configuration: proton mean kinetic energy in water

Science.gov (United States)

Pietropaolo, Antonino; Andreani, Carla; Filabozzi, Alessandra; Senesi, Roberto; Gorini, Giuseppe; Perelli-Cippo, Enrico; Tardocchi, Marco; Rhodes, Nigel J.; Schooneveld, Erik M.

2006-04-01

Deep Inelastic Neutron Scattering (DINS) measurements have been performed on a liquid water sample at two different temperatures and pressures. The experiments were carried out using the VESUVIO spectrometer at the ISIS spallation neutron source. This experiment represents the first DINS measurement from water using the Resonance Detector configuration, employing yttrium-aluminum-perovskite scintillator and a 238U analyzer foil. The maximum energy of the scattered neutrons was about 70 eV, allowing to access an extended kinematic space with energy and wave vector transfers at the proton recoil peak in the range 1 eV <= hbarω <= 20 eV and 25 Å-1 <= q <= 90 Å-1, respectively. Comparison with DINS measurements on water performed in the standard Resonance Filter configuration indicates the potential advantages offered by the use of Resonance Detector approach for DINS measurements at forward scattering angles.

The effects of some parameters on the calculated 1H NMR relaxation times of cell water

International Nuclear Information System (INIS)

Koivula, A.; Suominen, K.; Kiviniitty, K.

1976-01-01

The effect of some parameters on the longitudinal and transverse relaxation times is calculated and a comparison between the calculated relaxation times with the results of different measurements is made. (M.S.)

Polarization reversal of proton spins in solid-state targets by superradiance effects

International Nuclear Information System (INIS)

Reichertz, L.A.

1991-02-01

Scattering experiments with polarized targets are prepared at the Bonn accelerator ELSA. The new Bonn frozen spin target (BOFROST) developed for real photon experiments at the PHOENICS detector has been tested in the laboratory. Proton polarization values of -99% and +94% in ammonia, -96% and +90% in butanol have been achieved at a magnetic field of 3.5 Tesla. At a temperature of 70 mK and a magnetic field of 0.35 Tesla a very fast spontaneous polarization reversal has been observed. This effect occured at negative polarization only and has been identified as a self-induced superradiance effect in the proton spin system. This work describes the polarization and relaxation measurements at BOFROST and detailed experiments concerning the superradiance effect. (orig.) [de

Evaluation of self-water-removal in a dead-ended proton exchange membrane fuel cell

International Nuclear Information System (INIS)

Wan, Zhongmin; Liu, Jing; Luo, Zhiping; Tu, Zhengkai; Liu, Zhichun; Liu, Wei

2013-01-01

Highlights: ► Operation characteristics in a dead-ended PEM fuel cell were addressed. ► Modified flow channel was used to realize water removal. ► A novel method by condensing the moisture in the stack end was introduced. - Abstract: In this paper, the operation characteristic of a dead-ended proton exchange membrane fuel cell (PEMFC) placed with vertical orientation is investigated. The relationship between the channel geometry and the wettability of the gas diffusion layer (GDL) surface is theoretically analyzed. Based on the theoretical analysis, straight flow channels with 2.0 mm width and 1.0 mm depth are used for the experimental investigation and the moisture is condensed at the stack end to improve water removal. The results show that the designed fuel cell can operate for about 1 h at 800 mA cm −2 and the performance of the cell decreases with the increase in the operation temperature. Moreover, the recovered liquid water is corresponded closely to the theoretical values

A Water-Stable Proton-Conductive Barium(II)-Organic Framework for Ammonia Sensing at High Humidity.

Science.gov (United States)

Guo, Kaimeng; Zhao, Lili; Yu, Shihang; Zhou, Wenyan; Li, Zifeng; Li, Gang

2018-06-07

In view of environmental protection and the need for early prediction of major diseases, it is necessary to accurately monitor the change of trace ammonia concentration in air or in exhaled breath. However, the adoption of proton-conductive metal-organic frameworks (MOFs) as smart sensors in this field is limited by a lack of ultrasensitive gas-detecting performance at high relative humidity (RH). Here, the pellet fabrication of a water-stable proton-conductive MOF, Ba( o-CbPhH 2 IDC)(H 2 O) 4 ] n (1) ( o-CbPhH 4 IDC = 2-(2-carboxylphenyl)-1 H-imidazole-4,5-dicarboxylic acid) is reported. The MOF 1 displays enhanced sensitivity and selectivity to NH 3 gas at high RHs (>85%) and 30 °C, and the sensing mechanism is suggested. The electrochemical impedance gas sensor fabricated by MOF 1 is a promising sensor for ammonia at mild temperature and high RHs.

Evaluation of human thyroid tumors by proton nuclear magnetic resonance

International Nuclear Information System (INIS)

deCertaines, J.; Herry, J.Y.; Lancien, G.; Benoist, L.; Bernard, A.M.; LeClech, G.

1982-01-01

Proton nuclear magnetic resonance (NMR) was used in a study of 40 patients with thyroid tumors following partial or total thyroidectomy. Three patient groups were considered: those with nodules showing increased uptake, those with solitary nodules with decreased uptake, and those with multinodular goiters. Spin-lattice and spin-spin relaxation times (T 1 and T 2 ) were measured on samples of nodular and extranodular tissue from each patient. Increased T 1 and T 2 were observed for benign cold nodules, an increase in T 1 alone for nodules with increased uptake, and a wide fluctuation in T 1 and T 2 for multinodular goiters. The four cancers in the series did not show a distinctive proton NMR pattern in comparison with the other nodular structures studied. The results point to the feasibility of applying NMR techniques to the detection of thyroid disease

Structural design study of a proton beam window for a 1-MW spallation neutron source

Energy Technology Data Exchange (ETDEWEB)

Teraoku, Takuji; Terada, Atsuhiko; Maekawa, Fujio; Meigo, Shin-ichiro; Kaminaga, Masanori; Ishikura, Syuichi; Hino, Ryutaro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

2003-03-01

A 1-MW spallation neutron source aiming at materials and life science researches will be constructed under the JAERI-KEK High-intensity Proton Accelerator Project (J-PARC). A proton beam passes through a proton beam window, and be injected into a target of the neutron source. The proton beam window functions as a boundary wall between a high vacuum area in the proton beam line and a helium atmosphere at about atmospheric pressure in a helium vessel which contains the target and moderators. The proton beam window is cooled by light water because high heat-density is generated in the window material by interactions with the proton beam. Then, uniformity of the water flow is requested at the window to suppress a hot-spot that causes excessive thermal stress and cooling water boiling. Also, the window has to be strong enough in its structure for inner stress due to water pressure and thermal stress due to heat generation. In this report, we propose two types of proton beam windows; one flat-type that is easy to manufacture, and the other, curved-type that has high stress resistivity. As a part of design study for the windows, evaluation of strength of structure and thermal hydraulic analysis were conducted. As a result, it was found that sufficient heat removal was assured with uniform water flow at the window, and stress caused by internal water pressure and thermal stress could be maintained below allowable stress values. Accordingly, it was confirmed that the proton beam window designs were feasible. (author)

Advantages of Chemical Exchange-Sensitive Spin-Lock (CESL) Over Saturation Transfer (CEST) for Hydroxyl- and Amine-Water Proton Exchange Studies

Science.gov (United States)

Jin, Tao; Kim, Seong-Gi

2014-01-01

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 (IMEX) processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, its sensitivity is not optimal, and more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the property of CEST signals is compared to a CE-sensitive spin-locking (CESL) technique irradiating at the labile proton frequency. Firstly, using a higher power and shorter irradiation in CE-MRI yields i) increasing selectivity to faster chemical exchange rates by higher sensitivity to faster exchanges and less sensitivity to slower CE and magnetization transfer processes, and ii) decreasing 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. Secondly, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with asymmetric population approximation (CEAPA), which can be used for quantitative CE-MRI, and validated by simulations of Bloch-McConnell equations and phantom experiments. Lastly, in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 of 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 IMEX protons. PMID:25199631

Proton NMR for Measuring Quantum Level Crossing in the Magnetic Molecular Ring Fe10

International Nuclear Information System (INIS)

Julien, M.; Jang, Z.H.; Borsa, F.; Julien, M.; Lascialfari, A.; Borsa, F.; Horvatic, M.; Caneschi, A.; Gatteschi, D.

1999-01-01

The proton nuclear spin-lattice relaxation rate 1/T 1 has been measured as a function of temperature and magnetic field (up to 15thinspthinspT) in the molecular magnetic ring Fe 10 ( OCH 3 ) 20 (O 2 CCH 2 Cl) 10 (Fe10). Striking enhancement of 1/T 1 is observed around magnetic field values corresponding to a crossing between the ground state and the excited states of the molecule. We propose that this is due to a cross-relaxation effect between the nuclear Zeeman reservoir and the reservoir of the Zeeman levels of the molecule. This effect provides a powerful tool to investigate quantum dynamical phenomena at level crossing. copyright 1999 The American Physical Society

Proton-proton bremsstrahlung

International Nuclear Information System (INIS)

Fearing, H.W.

1990-01-01

We summarize some of the information about the nucleon-nucleon force which has been obtained by comparing recent calculations of proton-proton bremsstrahlung with cross section and analyzing power data from the new TRIUMF bremsstrahlung experiment. Some comments are made as to how these results can be extended to neutron-proton bremsstrahlung. (Author) 17 refs., 6 figs

The generation of absorbed dose profiles of proton beam in water using Geant4 code

International Nuclear Information System (INIS)

Christovao, Marilia T.; Campos, Tarcisio Passos R. de

2007-01-01

The present article approaches simulations on the proton beam radiation therapy, using an application based on the code GEANT4, with Open GL as a visualization drive and JAS3 (Java Analysis Studio) analysis data tools systems, implementing the AIDA interfaces. The proton radiotherapy is adapted to treat cancer or other benign tumors that are close to sensitive structures, since it allows precise irradiation of the target with high doses, while the health tissues adjacent to vital organs and tissues are preserved, due to physical property of dose profile. GEANT4 is a toolkit for simulating the transport of particles through matter, in complex geometries. Taking advantage of the object-oriented project features, the user can adapt or extend the tool in all domain, due to the flexibility of the code, providing a subroutine's group for materials definition, geometries and particles properties in agreement with the user's needs to generate the Monte Carlo simulation. In this paper, the parameters of beam line used in the simulation possess adjustment elements, such as: the range shifter, composition and dimension; the beam line, energy, intensity, length, according with physic processes applied. The simulation result is the depth dose profiles on water, dependent on the various incident beam energy. Starting from those profiles, one can define appropriate conditions for proton radiotherapy in ocular region. (author)

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...... and increased degradation rates. Clearly, a fundamental understanding of all aspects of water management in PEMFC is imperative. This includes the fuel cell water balance, i.e. which fraction of the product water leaves the fuel cell via the anode channels versus the cathode channel. Our research group...... signal received gives valuable insight into heat and mass transfer phenomena in a PEMFC....

Atmospheric Wind Relaxations and the Oceanic Response in the California Current Large Marine Ecosystem

Science.gov (United States)

Fewings, M. R.; Dorman, C. E.; Washburn, L.; Liu, W.

2010-12-01

On the West Coast of North America in summer, episodic relaxation of the upwelling-favorable winds causes warm water to propagate northward from southern to central California, against the prevailing currents [Harms and Winant 1998, Winant et al. 2003, Melton et al. 2009]. Similar wind relaxations are an important characteristic of coastal upwelling ecosystems worldwide. Although these wind relaxations have an important influence on coastal ocean dynamics, no description exists of the regional atmospheric patterns that lead to wind relaxations in southern California, or of the regional ocean response. We use QuikSCAT wind stress, North American Regional Reanalysis atmospheric pressure products, water temperature and velocity from coastal ocean moorings, surface ocean currents from high-frequency radars, and MODIS satellite sea-surface temperature and ocean color images to analyze wind relaxation events and the ocean response. We identify the events based on an empirical index calculated from NDBC buoy winds [Melton et al. 2009]. We describe the regional evolution of the atmosphere from the Gulf of Alaska to Baja California over the few days leading up to wind relaxations, and the coastal ocean temperature, color, and current response off southern and central California. We analyze ~100 wind relaxation events in June-September during the QuikSCAT mission, 1999-2009. Our results indicate south-central California wind relaxations in summer are tied to mid-level atmospheric low-pressure systems that form in the Gulf of Alaska and propagate southeastward over 3-5 days. As the low-pressure systems reach southern California, the atmospheric pressure gradient along the coast weakens, causing the surface wind stress to relax to near zero. The weak wind signal appears first at San Diego and propagates northward. QuikSCAT data indicate the relaxed winds extend over the entire Southern California Bight and up to 200 km offshore of central California. Atmospheric dynamics in

Mozart versus new age music: relaxation states, stress, and ABC relaxation theory.

Science.gov (United States)

Smith, Jonathan C; Joyce, Carol A

2004-01-01

Smith's (2001) Attentional Behavioral Cognitive (ABC) relaxation theory proposes that all approaches to relaxation (including music) have the potential for evoking one or more of 15 factor-analytically derived relaxation states, or "R-States" (Sleepiness, Disengagement, Rested / Refreshed, Energized, Physical Relaxation, At Ease/Peace, Joy, Mental Quiet, Childlike Innocence, Thankfulness and Love, Mystery, Awe and Wonder, Prayerfulness, Timeless/Boundless/Infinite, and Aware). The present study investigated R-States and stress symptom-patterns associated with listening to Mozart versus New Age music. Students (N = 63) were divided into three relaxation groups based on previously determined preferences. Fourteen listened to a 28-minute tape recording of Mozart's Eine Kleine Nachtmusik and 14 listened to a 28-minute tape of Steven Halpern's New Age Serenity Suite. Others (n = 35) did not want music and instead chose a set of popular recreational magazines. Participants engaged in their relaxation activity at home for three consecutive days for 28 minutes a session. Before and after each session, each person completed the Smith Relaxation States Inventory (Smith, 2001), a comprehensive questionnaire tapping 15 R-States as well as the stress states of somatic stress, worry, and negative emotion. Results revealed no differences at Session 1. At Session 2, those who listened to Mozart reported higher levels of At Ease/Peace and lower levels of Negative Emotion. Pronounced differences emerged at Session 3. Mozart listeners uniquely reported substantially higher levels of Mental Quiet, Awe and Wonder, and Mystery. Mozart listeners reported higher levels, and New Age listeners slightly elevated levels, of At Ease/Peace and Rested/Refreshed. Both Mozart and New Age listeners reported higher levels of Thankfulness and Love. In summary, those who listened to Mozart's Eine Kleine Nachtmusik reported more psychological relaxation and less stress than either those who listened to

Study of micellar solutions of the 'sodium lauryl sulphate-heavy water' system by using pulsed NMR

International Nuclear Information System (INIS)

Fouchet, C.

1972-01-01

This research thesis reports the study of the nuclear magnetic resonance of protons contained by micellar solutions of sodium lauryl sulphate and heavy water. Relaxation times have been measured with respect to various parameters: concentration, temperature, frequency. The author presents the main properties of micellar solutions and indicate the various possible movements. Then, he addresses the implemented technique, and shows that NMR is sensitive to short range interactions, and allows micellar movements to be studied over an extended rate range. Experimental results are then presented and interpreted [fr

Mechanical relaxation in glasses

International Nuclear Information System (INIS)

Hiki, Y.

2004-01-01

The basic properties of glasses and the characteristics of mechanical relaxation in glasses were briefly reviewed, and then our studies concerned were presented. Experimental methods adopted were viscosity, internal friction, ultrasonic attenuation, and Brillouin scattering measurements. The specimens used were several kinds of inorganic, organic, and metallic glasses. The measurements were mainly carried out from the room temperature up to the glass transition temperature, and the relaxation time was determined as a function of temperature. The 'double relaxation' composed of two Arrhenius-type relaxations was observed in many materials. In both relaxations, the 'compensation effect' showing a correlation of the pre-exponential factor and the activation energy was observed. These results were explained by considering the 'complex relaxation' due to cooperative motions of atoms or group of atoms. Values of activation energy near the glass transition determined by the various experimental methods were compared with each other

Proton movement and coupling in the POT family of peptide transporters.

Science.gov (United States)

Parker, Joanne L; Li, Chenghan; Brinth, Allete; Wang, Zhi; Vogeley, Lutz; Solcan, Nicolae; Ledderboge-Vucinic, Gregory; Swanson, Jessica M J; Caffrey, Martin; Voth, Gregory A; Newstead, Simon

2017-12-12

POT transporters represent an evolutionarily well-conserved family of proton-coupled transport systems in biology. An unusual feature of the family is their ability to couple the transport of chemically diverse ligands to an inwardly directed proton electrochemical gradient. For example, in mammals, fungi, and bacteria they are predominantly peptide transporters, whereas in plants the family has diverged to recognize nitrate, plant defense compounds, and hormones. Although recent structural and biochemical studies have identified conserved sites of proton binding, the mechanism through which transport is coupled to proton movement remains enigmatic. Here we show that different POT transporters operate through distinct proton-coupled mechanisms through changes in the extracellular gate. A high-resolution crystal structure reveals the presence of ordered water molecules within the peptide binding site. Multiscale molecular dynamics simulations confirm proton transport occurs through these waters via Grotthuss shuttling and reveal that proton binding to the extracellular side of the transporter facilitates a reorientation from an inward- to outward-facing state. Together these results demonstrate that within the POT family multiple mechanisms of proton coupling have likely evolved in conjunction with variation of the extracellular gate. Copyright © 2017 the Author(s). Published by PNAS.

Proton disorder in cubic ice: Effect on the electronic and optical properties

International Nuclear Information System (INIS)

Garbuio, Viviana; Pulci, Olivia; Cascella, Michele; Kupchak, Igor; Seitsonen, Ari Paavo

2015-01-01

The proton disorder in ice has a key role in several properties such as the growth mode, thermodynamical properties, and ferroelectricity. While structural phase transitions from proton disordered to proton ordered ices have been extensively studied, much less is known about their electronic and optical properties. Here, we present ab initio many body perturbation theory-based calculations of the electronic and optical properties of cubic ice at different levels of proton disorder. We compare our results with those from liquid water, that acts as an example of a fully (proton- and oxygen-)disordered system. We find that by increasing the proton disorder, a shrinking of the electronic gap occurs in ice, and it is smallest in the liquid water. Simultaneously, the excitonic binding energy decreases, so that the final optical gaps result to be almost independent on the degree of proton disorder. We explain these findings as an interplay between the local dipolar disorder and the electronic correlation

Solvent Exchange Rates of Side-chain Amide Protons in Proteins

International Nuclear Information System (INIS)

Rajagopal, Ponni; Jones, Bryan E.; Klevit, Rachel E.

1998-01-01

Solvent exchange rates and temperature coefficients for Asn/Gln side-chain amide protons have been measured in Escherichia coli HPr. The protons of the eight side-chain amide groups (two Asn and six Gln) exhibit varying exchange rates which are slower than some of the fast exchanging backbone amide protons. Differences in exchange rates of the E and Z protons of the same side-chain amide group are obtained by measuring exchange rates at pH values > 8. An NOE between a side-chain amide proton and a bound water molecule was also observed

Sup(1)H n.m.r. relaxation of radiation induced crosslinking in polyester-styrene systems

International Nuclear Information System (INIS)

Andreis, M.; Veksli, Z.; Ranogajec, F.; Hedvig, P.

1989-01-01

The structure and dynamics of a network formed by radiation induced crosslinking of polyesters based on 1,6-hexane diol and 1,2-propylene glycol and maleic anhydride (HDF and PGF, respectively) with styrene is studied by proton pulsed n.m.r. spectroscopy. The dependence of spin-lattice, T 1 , and spin-spin, T 2 , relaxation times on the structure of polyester chain, molar ratios of styrene to polyester unsaturations and the radiation doses are analysed in terms of network formation and structure, and their effect on molecular motion. Above the gel point, at temperatures above the glass transition, the presence of two T 2 components reflects the heterogeneity of the network structure in both resins. Parallel with the n.m.r. relaxation measurements the crosslink density was determined from the extracted gel phase or double bonds (fumaric and styrene) participating in the crosslinking process. (author)

Local electronic environment of protons in VHsub(x) alloys

International Nuclear Information System (INIS)

Kazama, Shigeo; Fukai, Yuh

1977-01-01

The Knight shift (Ksub(H)) and the spin-lattice relaxation time T 1 of protons have been measured in vanadium-hydrogen alloys (VHsub(x)) with hydrogen concentration x=0.042 -- 0.736, at temperatures between 100 0 and 200 0 C. The resolution of +-1 ppm in the shift was attained by using a high-resolution spectrometer, and the effect of demagnetizing field was isolated by using a single sheet of foil as a specimen. This allowed the simultaneous determination of Ksub(H) and the bulk magnetic susceptibility. Ksub(H) measured relative to bare protons was found to be negative and change little with hydrogen concentration. No temperature dependence of the shift was observed, even across the phase transition. These results are interpreted in terms of a contact interaction with the uniform spin-polarization in the interstitial region and some additional contributions from H-induced states. An evidence for the electron-electron interaction in VHsub(x) is derived from comparison of Ksub(H) and T 1 . (auth.)

Corrosion of target and structural materials in water irradiated by an 800 MeV proton beam

International Nuclear Information System (INIS)

Butt, D.P.; Kanner, G.S.; Lillard, R.S.

1996-01-01

Radiation enhanced, aqueous corrosion of solid neutron-targets such as tungsten or tantalum, or target cladding or structural materials such as superalloys and stainless steels, is a significant concern in accelerator-driven transmutation technologies. In this paper we briefly describe our current methods for control and in situ monitoring of corrosion in accelerator cooling water loops. Using floating, electrochemical impedance spectroscopy (EIS), we have measured the corrosion rates of aluminum 6061, copper, Inconel 718, and 304L stainless steel in the flow loop of a water target irradiated by a μamp, 800 MeV proton beam. Impedance spectroscopy allows us to model the corrosion process of a material as an equivalent electrical circuit. Thus the polarization resistance, which is inversely proportional to the corrosion rate, can be extracted from the frequency response of a metal specimen. During a three month period, without the use of corrosion mitigation techniques, we observed increases of several orders of magnitude in the water conductivity and the corrosion rates. The increase in corrosion is at least partially attributed to a build up of peroxide in our pseudo-closed loop system. In this paper we also briefly describe our second generation experiments, scheduled to begin in late 1996. In these experiments we plan to measure the corrosion rates of tungsten, tantalum, Inconel 718, 316L and 304L stainless steel, HT-9 austenitic stainless steel, and aluminum 5053. Two or three electrode probes of each material are being placed directly in the proton beam, in a high neutron flux region, or a significant distance from the high radiation area. We will be measuring corrosion rates, changes in pH and conductivity, and we will be establishing parameters for filtration and mitigation of corrosion. We will also discuss our ideas for making in situ measurements of water radiolysis using optical and laser diagnostic techniques

Musculoskeletal MRI at 3.0 T and 7.0 T: a comparison of relaxation times and image contrast.

Science.gov (United States)

Jordan, Caroline D; Saranathan, Manojkumar; Bangerter, Neal K; Hargreaves, Brian A; Gold, Garry E

2013-05-01

The purpose of this study was to measure and compare the relaxation times of musculoskeletal tissues at 3.0 T and 7.0 T, and to use these measurements to select appropriate parameters for musculoskeletal protocols at 7.0 T. We measured the T₁ and T₂ relaxation times of cartilage, muscle, synovial fluid, bone marrow and subcutaneous fat at both 3.0 T and 7.0 T in the knees of five healthy volunteers. The T₁ relaxation times were measured using a spin-echo inversion recovery sequence with six inversion times. The T₂ relaxation times were measured using a spin-echo sequence with seven echo times. The accuracy of both the T₁ and T₂ measurement techniques was verified in phantoms at both magnetic field strengths. We used the measured relaxation times to help design 7.0 T musculoskeletal protocols that preserve the favorable contrast characteristics of our 3.0 T protocols, while achieving significantly higher resolution at higher SNR efficiency. The T₁ relaxation times in all tissues at 7.0 T were consistently higher than those measured at 3.0 T, while the T₂ relaxation times at 7.0 T were consistently lower than those measured at 3.0 T. The measured relaxation times were used to help develop high resolution 7.0 T protocols that had similar fluid-to-cartilage contrast to that of the standard clinical 3.0 T protocols for the following sequences: proton-density-weighted fast spin-echo (FSE), T₂-weighted FSE, and 3D-FSE-Cube. The T₁ and T₂ changes were within the expected ranges. Parameters for musculoskeletal protocols at 7.0 T can be optimized based on these values, yielding improved resolution in musculoskeletal imaging with similar contrast to that of standard 3.0 T clinical protocols. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Musculoskeletal MRI at 3.0 T and 7.0 T: A comparison of relaxation times and image contrast

International Nuclear Information System (INIS)

Jordan, Caroline D.; Saranathan, Manojkumar; Bangerter, Neal K.; Hargreaves, Brian A.; Gold, Garry E.

2013-01-01

Objective: The purpose of this study was to measure and compare the relaxation times of musculoskeletal tissues at 3.0 T and 7.0 T, and to use these measurements to select appropriate parameters for musculoskeletal protocols at 7.0 T. Materials and methods: We measured the T 1 and T 2 relaxation times of cartilage, muscle, synovial fluid, bone marrow and subcutaneous fat at both 3.0 T and 7.0 T in the knees of five healthy volunteers. The T 1 relaxation times were measured using a spin-echo inversion recovery sequence with six inversion times. The T 2 relaxation times were measured using a spin-echo sequence with seven echo times. The accuracy of both the T 1 and T 2 measurement techniques was verified in phantoms at both magnetic field strengths. We used the measured relaxation times to help design 7.0 T musculoskeletal protocols that preserve the favorable contrast characteristics of our 3.0 T protocols, while achieving significantly higher resolution at higher SNR efficiency. Results: The T 1 relaxation times in all tissues at 7.0 T were consistently higher than those measured at 3.0 T, while the T 2 relaxation times at 7.0 T were consistently lower than those measured at 3.0 T. The measured relaxation times were used to help develop high resolution 7.0 T protocols that had similar fluid-to-cartilage contrast to that of the standard clinical 3.0 T protocols for the following sequences: proton-density-weighted fast spin-echo (FSE), T 2 -weighted FSE, and 3D-FSE-Cube. Conclusion: The T 1 and T 2 changes were within the expected ranges. Parameters for musculoskeletal protocols at 7.0 T can be optimized based on these values, yielding improved resolution in musculoskeletal imaging with similar contrast to that of standard 3.0 T clinical protocols

Changes in seed water status as characterized by NMR in developing soybean seed grown under moisture stress conditions

International Nuclear Information System (INIS)

Krishnan, P.; Singh, Ravender; Verma, A.P.S.; Joshi, D.K.; Singh, Sheoraj

2014-01-01

Highlights: • In developing soybean seeds, moisture stress resulted in more proportion of water to bound state. • These changes are further corroborated by concomitant changes in seed metabolites. • Thus there exists a moisture stress and development stage dependence of seed tissue water status. - Abstract: Changes in water status of developing seeds of Soybean (Glycine max L. Merrill.) grown under different moisture stress conditions were characterized by proton nuclear magnetic resonance (NMR)- spin–spin relaxation time (T 2 ). A comparison of the seed development characteristics, composition and physical properties indicated that, characteristics like seed weight, seed number/ear, rate of seed filling increased with development stages but decreased with moisture stress conditions. The NMR- spin–spin relaxation (T 2 ) component like bound water increased with seed maturation (40–50%) but decreased with moisture stress conditions (30–40%). The changes in seed water status to increasing levels of moisture stress and seed maturity indicates that moisture stress resulted in more proportion of water to bound state and intermediate state and less proportion of water in free-state. These changes are further corroborated by significant changes in protein and starch contents in seeds under high moisture stress treatments. Thus seed water status during its development is not only affected by development processes but also by moisture stress conditions. This study strongly indicated a clear moisture stress and development stage dependence of seed tissue water status in developing soybean seeds

Changes in seed water status as characterized by NMR in developing soybean seed grown under moisture stress conditions

Energy Technology Data Exchange (ETDEWEB)

Krishnan, P., E-mail: pkrishnan@iari.res.in; Singh, Ravender; Verma, A.P.S.; Joshi, D.K.; Singh, Sheoraj

2014-02-21

Highlights: • In developing soybean seeds, moisture stress resulted in more proportion of water to bound state. • These changes are further corroborated by concomitant changes in seed metabolites. • Thus there exists a moisture stress and development stage dependence of seed tissue water status. - Abstract: Changes in water status of developing seeds of Soybean (Glycine max L. Merrill.) grown under different moisture stress conditions were characterized by proton nuclear magnetic resonance (NMR)- spin–spin relaxation time (T{sub 2}). A comparison of the seed development characteristics, composition and physical properties indicated that, characteristics like seed weight, seed number/ear, rate of seed filling increased with development stages but decreased with moisture stress conditions. The NMR- spin–spin relaxation (T{sub 2}) component like bound water increased with seed maturation (40–50%) but decreased with moisture stress conditions (30–40%). The changes in seed water status to increasing levels of moisture stress and seed maturity indicates that moisture stress resulted in more proportion of water to bound state and intermediate state and less proportion of water in free-state. These changes are further corroborated by significant changes in protein and starch contents in seeds under high moisture stress treatments. Thus seed water status during its development is not only affected by development processes but also by moisture stress conditions. This study strongly indicated a clear moisture stress and development stage dependence of seed tissue water status in developing soybean seeds.

Advanced Proton Conducting Polymer Electrolytes for Electrochemical Capacitors

Science.gov (United States)

Gao, Han

Research on solid electrochemical energy storage devices aims to provide high performance, low cost, and safe operation solutions for emerging applications from flexible consumer electronics to microelectronics. Polymer electrolytes, minimizing device sealing and liquid electrolyte leakage, are key enablers for these next-generation technologies. In this thesis, a novel proton-conducing polymer electrolyte system has been developed using heteropolyacids (HPAs) and polyvinyl alcohol for electrochemical capacitors. A thorough understanding of proton conduction mechanisms of HPAs together with the interactions among HPAs, additives, and polymer framework has been developed. Structure and chemical bonding of the electrolytes have been studied extensively to identify and elucidate key attributes affecting the electrolyte properties. Numerical models describing the proton conduction mechanism have been applied to differentiate those attributes. The performance optimization of the polymer electrolytes through additives, polymer structural modifications, and synthesis of alternative HPAs has achieved several important milestones, including: (a) high proton mobility and proton density; (b) good ion accessibility at electrode/electrolyte interface; (c) wide electrochemical stability window; and (d) good environmental stability. Specifically, high proton mobility has been addressed by cross-linking the polymer framework to improve the water storage capability at normal-to-high humidity conditions (e.g. 50-80% RH) as well as by incorporating nano-fillers to enhance the water retention at normal humidity levels (e.g. 30-60% RH). High proton density has been reached by utilizing additional proton donors (i.e. acidic plasticizers) and by developing different HPAs. Good ion accessibility has been achieved through addition of plasticizers. Electrochemical stability window of the electrolyte system has also been investigated and expanded by utilizing HPAs with different heteroatoms

Sparse-view proton computed tomography using modulated proton beams

Energy Technology Data Exchange (ETDEWEB)

Lee, Jiseoc; Kim, Changhwan; Cho, Seungryong, E-mail: scho@kaist.ac.kr [Department of Nuclear and Quantum Engineering, Korea Advanced Institute of Science and Technology, Daejon 305-701 (Korea, Republic of); Min, Byungjun [Department of Radiation Oncology, Kangbuk Samsung Hospital, 110–746 (Korea, Republic of); Kwak, Jungwon [Department of Radiation Oncology, Asan Medical Center, 138–736 (Korea, Republic of); Park, Seyjoon; Lee, Se Byeong [Proton Therapy Center, National Cancer Center, 410–769 (Korea, Republic of); Park, Sungyong [Proton Therapy Center, McLaren Cancer Institute, Flint, Michigan 48532 (United States)

2015-02-15

Purpose: Proton imaging that uses a modulated proton beam and an intensity detector allows a relatively fast image acquisition compared to the imaging approach based on a trajectory tracking detector. In addition, it requires a relatively simple implementation in a conventional proton therapy equipment. The model of geometric straight ray assumed in conventional computed tomography (CT) image reconstruction is however challenged by multiple-Coulomb scattering and energy straggling in the proton imaging. Radiation dose to the patient is another important issue that has to be taken care of for practical applications. In this work, the authors have investigated iterative image reconstructions after a deconvolution of the sparsely view-sampled data to address these issues in proton CT. Methods: Proton projection images were acquired using the modulated proton beams and the EBT2 film as an intensity detector. Four electron-density cylinders representing normal soft tissues and bone were used as imaged object and scanned at 40 views that are equally separated over 360°. Digitized film images were converted to water-equivalent thickness by use of an empirically derived conversion curve. For improving the image quality, a deconvolution-based image deblurring with an empirically acquired point spread function was employed. They have implemented iterative image reconstruction algorithms such as adaptive steepest descent-projection onto convex sets (ASD-POCS), superiorization method–projection onto convex sets (SM-POCS), superiorization method–expectation maximization (SM-EM), and expectation maximization-total variation minimization (EM-TV). Performance of the four image reconstruction algorithms was analyzed and compared quantitatively via contrast-to-noise ratio (CNR) and root-mean-square-error (RMSE). Results: Objects of higher electron density have been reconstructed more accurately than those of lower density objects. The bone, for example, has been reconstructed

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

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...

Breathing and Relaxation

Science.gov (United States)

... Find a Doctor Relaxation is the absence of tension in muscle groups and a minimum or absence ... Drill Meditation Progressive Muscle Relaxation Minimizing Shortness of Breath Visualization This information has been approved by Shelby ...

Temperature Dependence of Logarithmic-like Relaxational Dynamics of Hydrated tRNA.

Science.gov (United States)

Chu, Xiang-Qiang; Mamontov, Eugene; O'Neill, Hugh; Zhang, Qiu

2013-03-21

The dynamics of RNA within the β-relaxation region of 10 ps to 1 ns is crucial to its biological function. Because of its simpler chemical building blocks and the lack of the side methyl groups, faster relaxational dynamics of RNA compared to proteins can be expected. However, the situation is actually opposite. In this work, the relaxational dynamics of tRNA is measured by quasielastic neutron scattering and analyzed using the mode coupling theory, originally developed for glass-forming liquids. Our results reveal that the dynamics of tRNA follows a log-decay within the β-relaxation region, which is an important trait demonstrated by the dynamics of proteins. The dynamics of hydrated tRNA and lysozyme compared in the time domain further demonstrate that the slower dynamics of tRNA relative to proteins originates from the difference in the folded states of tRNA and proteins, as well as the influence of their hydration water.

An S-N2-model for proton transfer in hydrogen-bonded systems

DEFF Research Database (Denmark)

Kuznetsov, A.M.; Ulstrup, Jens

2004-01-01

A new mechanism of proton transfer in donor-acceptor complexes with long hydrogen bonds is suggested. The transition is regarded as totally adiabatic. Two closest water molecules that move synchronously by hindered translation to and from the reaction complex are crucial. The water molecules induce...... a shift of the proton from the donor to the acceptor with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. Expressions for the activation barrier and kinetic hydrogen isotope effect are derived. The general scheme is illustrated with the use...... of model molecular potentials, and with reference to the excess proton conductivity in aqueous solution....

Quantification of Protein Hydration, Glass Transitions, and Structural Relaxations of Aqueous Protein and Carbohydrate-Protein Systems.

Science.gov (United States)

Roos, Yrjö H; Potes, Naritchaya

2015-06-11

Water distribution and miscibility of carbohydrate and protein components in biological materials and their structural contributions in concentrated solids are poorly understood. In the present study, structural relaxations and a glass transition of protein hydration water and antiplasticization of the hydration water at low temperatures were measured using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) for bovine whey protein (BWP), aqueous glucose-fructose (GF), and their mixture. Thermal transitions of α-lactalbumin and β-lactoglobulin components of BWP included water-content-dependent endothermic but reversible dehydration and denaturation, and exothermic and irreversible aggregation. An α-relaxation assigned to hydration water in BWP appeared at water-content-dependent temperatures and increased to over the range of 150-200 K at decreasing water content and in the presence of GF. Two separate glass transitions and individual fractions of unfrozen water of ternary GF-BWP-water systems contributed to uncoupled α-relaxations, suggesting different roles of protein hydration water and carbohydrate vitrification in concentrated solids during freezing and dehydration. Hydration water in the BWP fraction of GF-BWP systems was derived from equilibrium water sorption and glass transition data of the GF fraction, which gave a significant universal method to quantify (i) protein hydration water and (ii) the unfrozen water in protein-carbohydrate systems for such applications as cryopreservation, freezing, lyophilization, and dehydration of biological materials. A ternary supplemented phase diagram (state diagram) established for the GF-BWP-water system can be used for the analysis of the water distribution across carbohydrate and protein components in such applications.

Proton-beam radiation therapy dosimetry standardization

International Nuclear Information System (INIS)

Gall, K.P.

1995-01-01

Beams of protons have been used for radiation therapy applications for over 40 years. In the last decade the number of facilities treating patients and the total number of patients being treated has begun go grow rapidly. Due to the limited and experimental nature of the early programs, dosimetry protocols tended to be locally defined. With the publication of the AAPM Task Group 20 report open-quotes Protocol for Dosimetry of Heavy Charged Particlesclose quotes and the open-quotes European Code of Practice for Proton-Beam Dosimetryclose quotes the practice of determining dose in proton-beam therapy was somewhat unified. The ICRU has also recently commissioned a report on recommendations for proton-beam dosimetry. There have been three main methods of determining proton dose; the Faraday cup technique, the ionization chamber technique, and the calorimeter technique. For practical reasons the ionization chamber technique has become the most widely used. However, due to large errors in basic parameters (e.g., W-value) is also has a large uncertainty for absolute dose. It has been proposed that the development of water calorimeter absorbed dose standards would reduce the uncertainty in absolute proton dose as well as the relative dose between megavoltage X-ray beams and proton beams. The advantages and disadvantages are discussed

SU-F-J-56: The Connection Between Cherenkov Light Emission and Radiation Absorbed Dose in Proton Irradiated Phantoms

Energy Technology Data Exchange (ETDEWEB)

Darafsheh, A; Kassaee, A; Finlay, J [University of Pennsylvania, Philadelphia, PA (United States); Taleei, R [UT Southwestern Medical Center, Dallas, TX (United States)

2016-06-15

Purpose: Range verification in proton therapy is of great importance. Cherenkov light follows the photon and electron energy deposition in water phantom. The purpose of this study is to investigate the connection between Cherenkov light generation and radiation absorbed dose in a water phantom irradiated with proton beams. Methods: Monte Carlo simulation was performed by employing FLUKA Monte Carlo code to stochastically simulate radiation transport, ionizing radiation dose deposition, and Cherenkov radiation in water phantoms. The simulations were performed for proton beams with energies in the range 50–600 MeV to cover a wide range of proton energies. Results: The mechanism of Cherenkov light production depends on the initial energy of protons. For proton energy with 50–400 MeV energy that is below the threshold (∼483 MeV in water) for Cherenkov light production directly from incident protons, Cherenkov light is produced mainly from the secondary electrons liberated as a result of columbic interactions with the incident protons. For proton beams with energy above 500 MeV, in the initial depth that incident protons have higher energy than the Cherenkov light production threshold, the light has higher intensity. As the slowing down process results in lower energy protons in larger depths in the water phantom, there is a knee point in the Cherenkov light curve vs. depth due to switching the Cherenkov light production mechanism from primary protons to secondary electrons. At the end of the depth dose curve the Cherenkov light intensity does not follow the dose peak because of the lack of high energy protons to produce Cherenkov light either directly or through secondary electrons. Conclusion: In contrast to photon and electron beams, Cherenkov light generation induced by proton beams does not follow the proton energy deposition specially close to the end of the proton range near the Bragg peak.

Sleep, Stress & Relaxation: Rejuvenate Body & Mind

Science.gov (United States)

Sleep, Stress & Relaxation: Rejuvenate Body & Mind; Relieve Stress; best ways to relieve stress; best way to relieve stress; different ways to relieve stress; does smoking relieve stress; does tobacco relieve stress; how can I relieve stress; how can you relieve stress; how do I relieve stress; reduce stress; does smoking reduce stress; how can I reduce stress; how to reduce stress; reduce stress; reduce stress levels; reducing stress; smoking reduce stress; smoking reduces stress; stress reducing techniques; techniques to reduce stress; stress relief; best stress relief; natural stress relief; need stress relief; relief for stress; relief from stress; relief of stress; smoking and stress relief; smoking for stress relief; smoking stress relief; deal with stress; dealing with stress; dealing with anger; dealing with stress; different ways of dealing with stress; help dealing with stress; how to deal with anger; how to deal with stress; how to deal with stress when quitting smoking; stress management; free stress management; how can you manage stress; how do you manage stress; how to manage stress; manage stress; management of stress; management stress; managing stress; strategies for managing stress; coping with stress; cope with stress; copeing with stress; coping and stress; coping skills for stress; coping strategies for stress; coping strategies with stress; coping strategy for stress; coping with stress; coping with stress and anxiety; emotional health; emotional health; emotional health article; emotional health articles; deep relaxation; deep breathing relaxation techniques; deep muscle relaxation; deep relaxation; deep relaxation meditation; deep relaxation technique; deep relaxation techniques; meditation exercises; mindful exercises; mindful meditation exercises; online relaxation exercises; relaxation breathing exercises; relaxation exercise; relaxation exercises; stress relaxation; methods of relaxation for stress; relax stress; relax techniques stress

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

International Nuclear Information System (INIS)

Hosseinzadeh, Elham; Rokni, Masoud; Rabbani, Abid; Mortensen, Henrik Hilleke

2013-01-01

Highlights: ► Developing a general zero dimensional Proton Exchange Membrane Fuel Cell (PEMFC) model for a forklift. ► System performance with different cooling fluids. ► Water and thermal management of fuel cell system. ► Effect of inlet temperature, outlet temperature and temperature gradient on system performance. - Abstract: 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 stack and BOP has been investigated in this study. The results show that humidification of the inlet air is of great importance. By decreasing the relative humidity of inlet air from 95% to 25%, the voltage can drop by 29%. In addition, elevated stack temperature can lead to a higher average 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. The system can then be started up at about −25 °C with negligible change in the efficiency

Quantitative Study of Longitudinal Relaxation (T 1) Contrast Mechanisms in Brain MRI

Science.gov (United States)

Jiang, Xu

Longitudinal relaxation (T1) contrast in MRI is important for studying brain morphology and is widely used in clinical applications. Although MRI only detects signals from water hydrogen ( 1H) protons (WPs), T1 contrast is known to be influenced by other species of 1H protons, including those in macromolecules (MPs), such as lipids and proteins, through magnetization transfer (MT) between WPs and MPs. This complicates the use and quantification of T1 contrast for studying the underlying tissue composition and the physiology of the brain. MT contributes to T1 contrast to an extent that is generally dependent on MT kinetics, as well as the concentration and NMR spectral properties of MPs. However, the MP spectral properties and MT kinetics are both difficult to measure directly, as the signal from MPs is generally invisible to MRI. Therefore, to investigate MT kinetics and further quantify T1 contrast, we first developed a reliable way to indirectly measure the MP fraction and their exchange rate with WPs, with minimal dependence on the spectral properties of MPs. For this purpose, we used brief, highpower radiofrequency (RF) NMR excitation pulses to almost completely saturate the magnetization of MPs. Based on this, both MT kinetics and the contribution of MPs to T1 contrast through MT were studied. The thus obtained knowledge allowed us to subsequently infer the spectral properties of MPs by applying low-power, frequencyselective off-resonance RF pulses and measuring the offset-frequency dependent effect of MPs on the WP MRI signal. A two-pool exchange model was used in both cases to account for direct effects of the RF pulse on WP magnetization. Consistent with earlier works using MRI at low-field and post-mortem analysis of brain tissue, our novel measurement approach found that MPs constitute an up to 27% fraction of the total 1H protons in human brain white matter, and their spectrum follows a super-Lorentzian line with a T2 of 9.6+/-0.6 mus and a resonance

Fast neutron spectroscopy by gas proton-recoil methods at the light water reactor pressure vessel simulator

International Nuclear Information System (INIS)

Rogers, J.W.

1980-10-01

Fast neutron spectrum measurements were made in a Light Water Reactor (LWR) Pressure Vessel Simulator (PVS) to provide neutron spectral definition required to appropriately perform and interpret neutron dosimetry measurements related to fast neutron damage in LWR-PV steels. Proton-recoil proportional counter methods using hydrogen and methane gas-filled detectors were applied to obtain the proton spectra from which the neutron spectra were derived. Cylindrical and spherical geometry detectors were used to cover the neutron energy range between 50 keV and 2 MeV. Results show that the neutron spectra shift in energy distribution toward lower energy between the front and back of a PVS. The relative neutron flux densities increase in this energy range with increasing thickness of the steel. Neutron spectrum fine structure shapes and changes are observed. These results should assist in the generation of more accurate effective cross sections and fluences for use in LWR-PV fast neutron dosimetry and materials damage analyses

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....... Furthermore, the presence of irreducible liquid water is taken into account. In order to account for compression, porous media morphology variations are specified based on the gas diffusion layer (GDL) through-plane strain and intrusion which are stated as a function of compression. These morphology...... variations affect gas and liquid water transport, and hence liquid water distribution and the risk of blocking active sites. Hence, water transport is studied under GDL compression in order to investigate the qualitative effects. Two simulation cases are compared; one with and one without compression....