Unlocking the Sugar ‘Steric Gate’ of DNA Polymerases†

OpenAIRE

Brown, Jessica A.; Suo, Zucai

2011-01-01

To maintain genomic stability, ribonucleotide incorporation during DNA synthesis is controlled predominantly at the DNA polymerase level. A steric clash between the 2′-hydroxyl of an incoming ribonucleotide and a bulky active site residue, known as the ‘steric gate’, establishes an effective mechanism for most DNA polymerases to selectively insert deoxyribonucleotides. Recent kinetic, structural, and in vivo studies have illuminated novel features about ribonucleotide exclusion and the mechan...

Sustainable steric stabilization of colloidal titania nanoparticles

Science.gov (United States)

Elbasuney, Sherif

2017-07-01

A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180-240 °C to ensure DDSA ring opening and binding to titania nanoparticles. Organic-modified titania demonstrated complete change in surface properties from hydrophilic to hydrophobic and exhibited phase transfer from the aqueous phase to the organic phase. Exclusive surface modification in the reactor was found to be an effective approach; it demonstrated surfactant loading level 2.2 times that of post synthesis surface modification. Titania was also stabilized in aqueous media using poly acrylic acid (PAA) as polar polymeric dispersant. PAA-titania nanoparticles demonstrated a durable amorphous polymeric layer of 2 nm thickness. This

Remote Steric Effect as a Facile Strategy for Improving the Efficiency of Exciplex-Based OLEDs.

Science.gov (United States)

Hung, Wen-Yi; Wang, Ting-Chih; Chiang, Pin-Yi; Peng, Bo-Ji; Wong, Ken-Tsung

2017-03-01

This work reports a new strategy of introducing remote steric effect onto the electron donor for giving the better performance of the exciplex-based organic light-emitting device (OLED). The bulky triphenylsilyl group (SiPh 3 ) was introduced onto the fluorene bridge of 4,4'-(9H-fluorene-9,9-diyl)bis(N,N-di-p-tolylaniline) (DTAF) to create remote steric interactions for increasing the possibility of effective contacts between electron-donating chromophores and acceptor molecules, rendering the resulting exciplex to have a higher photoluminescence quantum yield (PLQY). The green exciplex device based on DSDTAF:3N-T2T (1:1) as an emitting layer exhibits a low turn-on voltage of 2.0 V, high maximum efficiencies (13.2%, 42.9 cd A -1 , 45.5 lm W -1 ), which are higher than the device employed DTAF (without SiPh 3 groups) (11.6%, 35.3 cd A -1 , 41.3 lm W -1 ) as donor under the same device structure. This strategy was further examined for blue exciplex, where the EQE was enhanced from 9.5% to 12.5% as the electron acceptor PO-T2T mixed with a tert-butyl group substituted carbazole-based donor (CPTBF) as the emitting exciplex in device. This strategy is simple and useful for developing high performance exciplex OLEDs.

On the nature of the electronic effect of multiple hydroxyl groups in the 6-membered ring - the effects are additive but steric hindrance plays a role too

DEFF Research Database (Denmark)

Pedersen, Christian Marcus; Bols, Mikael

2017-01-01

Research during the last two decades has shown a remarkable directional component of the substituent effects of hydroxy groups, which has a profound effect on the properties of hydroxylated compounds such as carbohydrates. While the epimerisation of a single hydroxyl function is well studied...... synthesized and their pKa and conformation were studied. The results show that the large difference in the electronic effect between the axial and equatorial hydroxyls is partially cancelled by counteracting steric hindrance from 1,3-diaxial interactions. Hydrogen bonding does not appear to play any role...

Poisson-Nernst-Planck equations with steric effects - non-convexity and multiple stationary solutions

Science.gov (United States)

Gavish, Nir

2018-04-01

We study the existence and stability of stationary solutions of Poisson-Nernst-Planck equations with steric effects (PNP-steric equations) with two counter-charged species. We show that within a range of parameters, steric effects give rise to multiple solutions of the corresponding stationary equation that are smooth. The PNP-steric equation, however, is found to be ill-posed at the parameter regime where multiple solutions arise. Following these findings, we introduce a novel PNP-Cahn-Hilliard model, show that it is well-posed and that it admits multiple stationary solutions that are smooth and stable. The various branches of stationary solutions and their stability are mapped utilizing bifurcation analysis and numerical continuation methods.

Multiple solutions of steady-state Poisson–Nernst–Planck equations with steric effects

International Nuclear Information System (INIS)

Lin, Tai-Chia; Eisenberg, Bob

2015-01-01

Experiments measuring currents through single protein channels show unstable currents. Channels switch between ‘open’ or ‘closed’ states in a spontaneous stochastic process called gating. Currents are either (nearly) zero or at a definite level, characteristic of each type of protein, independent of time, once the channel is open. The steady state Poisson–Nernst–Planck equations with steric effects (PNP-steric equations) describe steady current through the open channel quite well, in a wide variety of conditions. Here we study the existence of multiple solutions of steady state PNP-steric equations to see if they themselves, without modification or augmentation, can describe two levels of current. We prove that there are two steady state solutions of PNP-steric equations for (a) three types of ion species (two types of cations and one type of anion) with a positive constant permanent charge, and (b) four types of ion species (two types of cations and their counter-ions) with a constant permanent charge but no sign condition. The excess currents (due to steric effects) associated with these two steady state solutions are derived and expressed as two distinct formulas. Our results indicate that PNP-steric equations may become a useful model to study spontaneous gating of ion channels. Spontaneous gating is thought to involve small structural changes in the channel protein that perhaps produce large changes in the profiles of free energy that determine ion flow. Gating is known to be modulated by external structures. Both can be included in future extensions of our present analysis. (paper)

Atropisomerism about aryl-Csp(3) bonds: the electronic and steric influence of ortho-substituents on conformational exchange in cannabidiol and linderatin derivatives.

Science.gov (United States)

Berber, Hatice; Lameiras, Pedro; Denhez, Clément; Antheaume, Cyril; Clayden, Jonathan

2014-07-03

Terpenylation reactions of substituted phenols were used to prepare cannabidiol and linderatin derivatives, and their structure and conformational behavior in solution were investigated by NMR and, for some representative examples, by DFT. VT-NMR spectra and DFT calculations were used to determine the activation energies of the conformational change arising from restricted rotation about the aryl-Csp(3) bond that lead to two unequally populated rotameric epimers. The NBO calculation was applied to explain the electronic stabilization of one conformer over another by donor-acceptor charge transfer interactions. Conformational control arises from a combination of stereoelectronic and steric effects between substituents in close contact with each other on the two rings of the endocyclic epoxide atropisomers. This study represents the first exploration of the stereoelectronic origins of atropisomerism around C(sp(2))-C(sp(3)) single bonds through theoretical calculations.

Uncertainties in Steric Sea Level Change Estimation During the Satellite Altimeter Era: Concepts and Practices

Science.gov (United States)

MacIntosh, C. R.; Merchant, C. J.; von Schuckmann, K.

2017-01-01

This article presents a review of current practice in estimating steric sea level change, focussed on the treatment of uncertainty. Steric sea level change is the contribution to the change in sea level arising from the dependence of density on temperature and salinity. It is a significant component of sea level rise and a reflection of changing ocean heat content. However, tracking these steric changes still remains a significant challenge for the scientific community. We review the importance of understanding the uncertainty in estimates of steric sea level change. Relevant concepts of uncertainty are discussed and illustrated with the example of observational uncertainty propagation from a single profile of temperature and salinity measurements to steric height. We summarise and discuss the recent literature on methodologies and techniques used to estimate steric sea level in the context of the treatment of uncertainty. Our conclusions are that progress in quantifying steric sea level uncertainty will benefit from: greater clarity and transparency in published discussions of uncertainty, including exploitation of international standards for quantifying and expressing uncertainty in measurement; and the development of community "recipes" for quantifying the error covariances in observations and from sparse sampling and for estimating and propagating uncertainty across spatio-temporal scales.

Understanding the Steric Height Long Term Variability at the Bermuda Atlantic Time-Series Study (BATS) Site with a Neutral Density Approach

Science.gov (United States)

Goncalves Neto, A.; Johnson, R. J.; Bates, N. R.

2016-02-01

Rising sea level is one of the main concerns for human life in a scenario with global atmosphere and ocean warming, which is of particular concern for oceanic islands. Bermuda, located in the center of the Sargasso Sea, provides an ideal location to investigate sea level rise since it has a long term tide gauge (1933-present) and is in close proximity to deep ocean time-series sites, namely, Hydrostation `S' (1954-present) and the Bermuda Atlantic Time-Series Study site (1988-present). In this study, we use the monthly CTD deep casts at BATS to compute the contribution of steric height (SH) to the local sea surface height (SSH) for the past 24 years. To determine the relative contribution from the various water masses we first define 8 layers (Surface Layer, Upper Thermocline, Subtropical Mode-Water, Lower Thermocline, Antarctic Intermediate Water, Labrador Sea Water, Iceland-Scotland Overflow Water, Denmark Strait Overflow Water) based on neutral density criteria for which SH is computed. Additionally, we calculate the thermosteric and halosteric components for each of the defined neutral density layers. Surprisingly, the results show that, despite a 3.3mm/yr sea level rise observed at the Bermuda tide gauge, the steric contribution to the SSH at BATS has decreased at a rate of -1.1mm/yr during the same period. The thermal component is found to account for the negative trend in the steric height (-4.4mm/yr), whereas the halosteric component (3.3mm/yr) partially compensates the thermal signal and can be explained by an overall cooling and freshening at the BATS site. Although the surface layer and the upper thermocline waters are warming, all the subtropical and polar water masses, which represent most of the local water column, are cooling and therefore drive the overall SH contribution to the local SSH. Hence, it suggests that the mass contribution to the local SSH plays an important role in the sea level rise, for which we investigate with GRACE data.

Zirconium bisamidinate complexes with sterically demanding ligands : structure, solution dynamics, and reactivity

NARCIS (Netherlands)

Otten, Edwin; Dijkstra, Peter; Visser, Cindy; Meetsma, Auke; Hessen, Bart

2005-01-01

Bisamidinate zirconium dichloride and dimethyl complexes with the sterically demanding amidinate ligands [PhC(NAr)(2))](-) (A) and [PhC(NAr)(NAr')](-) (B) (Ar = 2,6-(Pr2C6H3)-Pr-i; Ar' = 2,6-Me2C6H3) were prepared. The steric demand of ligand A induces the unusual trans geometry in

Unlocking the Sugar ‘Steric Gate’ of DNA Polymerases†

Science.gov (United States)

Brown, Jessica A.; Suo, Zucai

2011-01-01

To maintain genomic stability, ribonucleotide incorporation during DNA synthesis is controlled predominantly at the DNA polymerase level. A steric clash between the 2′-hydroxyl of an incoming ribonucleotide and a bulky active site residue, known as the ‘steric gate’, establishes an effective mechanism for most DNA polymerases to selectively insert deoxyribonucleotides. Recent kinetic, structural, and in vivo studies have illuminated novel features about ribonucleotide exclusion and the mechanistic consequences of ribonucleotide misincorporation on downstream events, such as the bypass of a ribonucleotide in a DNA template and the subsequent extension of the DNA lesion bypass product. These important findings are summarized in this review article. PMID:21226515

The cyclin-dependent kinase 8 module sterically blocks Mediator interactions with RNA polymerase II

DEFF Research Database (Denmark)

Elmlund, Hans; Baraznenok, Vera; Lindahl, Martin

2006-01-01

CDK8 (cyclin-dependent kinase 8), along with CycC, Med12, and Med13, form a repressive module (the Cdk8 module) that prevents RNA polymerase II (pol II) interactions with Mediator. Here, we report that the ability of the Cdk8 module to prevent pol II interactions is independent of the Cdk8......-dependent kinase activity. We use electron microscopy and single-particle reconstruction to demonstrate that the Cdk8 module forms a distinct structural entity that binds to the head and middle region of Mediator, thereby sterically blocking interactions with pol II....

Steric Stabilization of “Charge-Free” Cellulose Nanowhiskers by Grafting of Poly(ethylene glycol

Directory of Open Access Journals (Sweden)

Jun Araki

2014-12-01

Full Text Available A sterically stabilized aqueous suspension of “charge-free” cellulose nanowhiskers was prepared by hydrochloric acid hydrolysis of cotton powders and subsequent surface grafting of monomethoxy poly(ethylene glycol (mPEG. The preparation scheme included carboxylation of the terminal hydroxyl groups in mPEG via oxidation with silica gel particles carrying 2,2,6,6-tetramethyl-1-pyperidinyloxyl (TEMPO moieties and subsequent esterification between terminal carboxyls in mPEG and surface hydroxyl groups of cellulose nanowhiskers, mediated by 1,1'-carbonyldiimidazole (CDI in dimethyl sulfoxide or dimethylacetamide. Some of the prepared PEG-grafted samples showed remarkable flow birefringence and enhanced stability after 24 h, even in 0.1 M NaCl, suggesting successful steric stabilization by efficient mPEG grafting. Actual PEG grafting via ester linkages was confirmed by attenuated total reflectance-Fourier transform infrared spectrometry. In a typical example, the amount of grafted mPEG was estimated as ca. 0.3 g/g cellulose by two measurements, i.e., weight increase after grafting and weight loss after alkali cleavage of ester linkages. Transmission electron microscopy indicated unchanged nanowhisker morphology after mPEG grafting.

Sustainable steric stabilization of colloidal titania nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Elbasuney, Sherif, E-mail: sherif_basuney2000@yahoo.com

2017-07-01

Graphical abstract: Controlled surface properties of titania nanoparticles via surface modification, flocculation from aqueous phase (a), stabilization in aqueous phase (b), extraction to organic phase (c). - Highlights: • Complete change in surface properties of titania nanoparticles from hydrophilic to hydrophobic. • Harvesting the formulated nanoparticles from the aqueous phase to the organic phase. • Exclusive surface modification in the reactor during nanoparticle synthesis. • Sustainable stabilization of titania nanoparticles in aqueous media with polar polymeric dispersant. - Abstract: A route to produce a stable colloidal suspension is essential if mono-dispersed particles are to be successfully synthesized, isolated, and used in subsequent nanocomposite manufacture. Dispersing nanoparticles in fluids was found to be an important approach for avoiding poor dispersion characteristics. However, there is still a great tendency for colloidal nanoparticles to flocculate over time. Steric stabilization can prevent coagulation by introducing a thick adsorbed organic layer which constitutes a significant steric barrier that can prevent the particle surfaces from coming into direct contact. One of the main features of hydrothermal synthesis technique is that it offers novel approaches for sustainable nanoparticle surface modification. This manuscript reports on the sustainable steric stabilization of titanium dioxide nanoparticles. Nanoparticle surface modification was performed via two main approaches including post-synthesis and in situ surface modification. The tuneable hydrothermal conditions (i.e. temperature, pressure, flow rates, and surfactant addition) were optimized to enable controlled steric stabilization in a continuous fashion. Effective post synthesis surface modification with organic ligand (dodecenyl succinic anhydride (DDSA)) was achieved; the optimum surface coating temperature was reported to be 180–240 °C to ensure DDSA ring opening

Elimination reactions. V. Steric effects in Hofmann elimination

International Nuclear Information System (INIS)

Coke, J.L.; Smith, G.D.; Britton, G.H. Jr.

1975-01-01

Earlier Hofmann elimination studies were extended, and the percent syn eliminations in several ring systems have been correlated using cis-d 1 and trans-d 1 models. The measurements of several syn and anti k/sub H//k/sub D/ kinetic isotope effects are reported. Results indicate that Hofmann elimination of N,N,N-trimethyl-3,3-dimethylcyclopentylammonium hydroxide goes by 97 percent syn mechanism to give 3,3-dimethylcyclopentene and by 70 + - 6 percent syn mechanism to give 4,4-dimethylcyclopentene. There appears to be severe steric interactions in the anti mechanism in the 3,3-dimethylcyclopentyl system. Results indicate that, for Hofmann pyrolysis of trimethylammonium hydroxides, cyclopentene is formed by a 39 +- 7 percent syn mechanism, cyclohexene is formed by a 2 + - 2 percent syn mechanism, and cycloheptene is formed by a 30 +- 2 percent syn mechanism. Steric effects on isotope effects and mechanisms are discussed. (U.S.)

Fisher information and steric effect: study of the internal rotation barrier of ethane.

Science.gov (United States)

Esquivel, Rodolfo O; Liu, Shubin; Angulo, Juan Carlos; Dehesa, Jesús S; Antolín, Juan; Molina-Espíritu, Moyocoyani

2011-05-05

On the basis of a density-based quantification of the steric effect [Liu, S. B. J. Chem. Phys.2007, 126, 244103], the origin of the internal rotation barrier between the eclipsed and staggered conformers of ethane is systematically investigated in this work from an information-theoretical point of view by using the Fisher information measure in conjugated spaces. Two kinds of computational approaches are considered in this work: adiabatic (with optimal structure) and vertical (with fixed geometry). The analyses are performed systematically by following, in each case, the conformeric path by changing the dihedral angle from 0 to 180° . This is calculated at the HF, MP2, B3LYP, and CCSD(T) levels of theory and with several basis sets. Selected descriptors of the densities are utilized to support the observations. Our results show that in the adiabatic case the eclipsed conformer possesses a larger steric repulsion than the staggered conformer, but in the vertical cases the staggered conformer retains a larger steric repulsion. Our results verify the plausibility for defining and computing the steric effect in the post-Hartree-Fock level of theory according to the scheme proposed by Liu.

Estimating the magnitude of steric effects in rigid systems by NMR

International Nuclear Information System (INIS)

Yoneda, Julliane Diniz; Seidl, Peter Rudolf; Leal, Katia Zaccur

2008-01-01

The rapid advance of supramolecular chemistry has led to a better understanding of the forces and interactions that are responsible for many different phenomena. Among these, steric effects play an important role in determining the constraints to association between the species involved. Although the role of steric effects has been recognized for a long time, quantitative information has been mainly related to the comparison of these effects on a chemical reaction or conformational equilibrium rather than the properties of the group of atoms that is responsible for their manifestation. This situation has been changing with the increase in power of computational methods and the accumulation of data on model compounds that can be used for the purpose of comparison. Here we present a short review of our recent work on NMR of rigid carbocyclic systems and apply this type of approach to di- and triamantane systems. Our results show how NMR can be used to locate the segment of a molecule that is subjected to steric effects and evaluate the degree to which these effects will distort its geometry. (author)

Estimating the magnitude of steric effects in rigid systems by NMR

Energy Technology Data Exchange (ETDEWEB)

Yoneda, Julliane Diniz [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Programa Pos-Graduacao em Quimica Organica; Seidl, Peter Rudolf [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica; Leal, Katia Zaccur, E-mail: pseidl@eq.ufrj.br [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Fisico-Quimica. Programa de Pos-Graduacao em Quimica Organica

2008-07-01

The rapid advance of supramolecular chemistry has led to a better understanding of the forces and interactions that are responsible for many different phenomena. Among these, steric effects play an important role in determining the constraints to association between the species involved. Although the role of steric effects has been recognized for a long time, quantitative information has been mainly related to the comparison of these effects on a chemical reaction or conformational equilibrium rather than the properties of the group of atoms that is responsible for their manifestation. This situation has been changing with the increase in power of computational methods and the accumulation of data on model compounds that can be used for the purpose of comparison. Here we present a short review of our recent work on NMR of rigid carbocyclic systems and apply this type of approach to di- and triamantane systems. Our results show how NMR can be used to locate the segment of a molecule that is subjected to steric effects and evaluate the degree to which these effects will distort its geometry. (author)

Solution NMR characterization of magnetic/electronic properties of azide and cyanide-inhibited substrate complexes of human heme oxygenase: implications for steric ligand tilt.

Science.gov (United States)

Peng, Dungeng; Ogura, Hiroshi; Ma, Li-Hua; Evans, John P; de Montellano, Paul R Ortiz; La Mar, Gerd N

2013-04-01

Solution 2D (1)H NMR was carried out on the azide-ligated substrate complex of human heme oxygenase, hHO, to provide information on the active site molecular structure, chromophore electronic/magnetic properties, and the distal H-bond network linked to the exogenous ligand by catalytically relevant oriented water molecules. While 2D NMR exhibited very similar patterns of two-dimensional nuclear Overhauser spectroscopy cross peaks of residues with substrate and among residues as the previously characterized cyanide complex, significant, broadly distributed chemical shift differences were observed for both labile and non-labile protons. The anisotropy and orientation of the paramagnetic susceptibility tensor, χ, were determined for both the azide and cyanide complexes. The most significant difference observed is the tilt of the major magnetic axes from the heme normal, which is only half as large for the azide than cyanide ligand, with each ligand tilted toward the catalytically cleaved α-meso position. The difference in chemical shifts is quantitatively correlated with differences in dipolar shifts in the respective complexes for all but the distal helix. The necessity of considering dipolar shifts, and hence determination of the orientation/anisotropy of χ, in comparing chemical shifts involving paramagnetic complexes, is emphasized. The analysis shows that the H-bond network cannot detect significant differences in H-bond acceptor properties of cyanide versus azide ligands. Lastly, significant retardation of distal helix labile proton exchange upon replacing cyanide with azide indicates that the dynamic stability of the distal helix is increased upon decreasing the steric interaction of the ligand with the distal helix. Copyright © 2013. Published by Elsevier Inc.

Crystal structures of three sterically congested disilanes

Directory of Open Access Journals (Sweden)

Kothanda Rama Pichaandi

2017-03-01

Full Text Available In the three sterically congested silanes, C24H38Si2 (1 (1,1,2,2-tetraisopropyl-1,2-diphenyldisilane, C24H34Br4Si2 (2 [1,1,2,2-tetrakis(2-bromopropan-2-yl-1,2-diphenyldisilane] and C32H38Si2 (3 (1,2-di-tert-butyl-1,1,2,2-tetraphenyldisilane, the Si—Si bond length is shortest in (1 and longest in (2, with (3 having an intermediate value, which parallels the increasing steric congestion. A comparison of the two isopropyl derivatives, (1 and 2, shows a significant increase in the Si—C(ipso distance with the introduction of bromine. Also, in the brominated compound 2, attractive intermolecular Br...Br interactions exist with Br...Br separations ca 0.52 Å shorter than the sum of the van der Waals radii. In compound 2, one of the bromoisopropyl groups is rotationally disordered in an 0.8812 (9:0.1188 (9 ratio. Compound 3 exhibits `whole molecule' disorder in a 0.9645 (7:0.0355 (7 ratio with the Si—Si bonds in the two components making an angle of ca 66°.

Quinoidal Oligo(9,10-anthryl)s with Chain-Length-Dependent Ground States: A Balance between Aromatic Stabilization and Steric Strain Release

KAUST Repository

Lim, Zhenglong

2015-11-12

Quinoidal π-conjugated polycyclic hydrocarbons have attracted intensive research interest due to their unique optical/electronic properties and possible magnetic activity, which arises from a thermally excited triplet state. However, there is still lack of fundamental understanding on the factors that determine the electronic ground states. Herein, by using quinoidal oligo(9,10-anthryl)s, it is demonstrated that both aromatic stabilisation and steric strain release play balanced roles in determining the ground states. Oligomers with up to four anthryl units were synthesised and their ground states were investigated by electronic absorption and electron spin resonance (ESR) spectroscopy, assisted by density functional theory (DFT) calculations. The quinoidal 9,10-anthryl dimer 1 has a closed-shell ground state, whereas the tri- (2) and tetramers (3) both have an open-shell diradical ground state with a small singlet-triplet gap. Such a difference results from competition between two driving forces: the large steric repulsion between the anthryl/phenyl units in the closed-shell quinoidal form that drives the molecule to a flexible open-shell diradical structure, and aromatic stabilisation due to the gain of more aromatic sextet rings in the closed-shell form, which drives the molecule towards a contorted quinoidal structure. The ground states of these oligomers thus depend on the overall balance between these two driving forces and show chain-length dependence. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrons in water radiolysis

International Nuclear Information System (INIS)

Laverne, J.A.; Pimblott, S.M.

2006-01-01

The hydrated electron is the main reducing species produced in the radiolysis of water. Many studies have examined its reactivity using pulsed radiolysis techniques and competition kinetics. Data bases list hundreds of rate coefficients for reaction of the hydrated electron with substances ranging from inorganic ions like nitrate to biopolymers like DNA. Although the chemistry of the hydrated electron is often examined, its mechanism of formation and variation in yield are considerable less known, especially under extreme conditions such as in high temperature water or with heavy ion radiolysis. This work will examine various aspects of the radiation chemistry of the hydrated electron beginning with the generation of secondary electrons in primary energy loss events during the passage of ionizing radiation to the radiolytic yields of the hydrated electron produced by different types of radiation. Ion radiation is a 'white light source.' Energy losses range from the minimum excitation energy of the medium up to the kinematic maximum determined by the collision parameters. However, certain energy loss events are more probable than others. The dipole oscillator strength distributions of media essentially give the probability of energy loss events in collisions with no momentum transfer. Dipole oscillator distributions have been constructed from experimental data for a wide variety of materials including all the phases of water. Calculations using cross sections based on dipole oscillator distributions show that the most probable energy loss event in water is only about 20 eV with an average value closer to 60 eV. The preponderance of energy loss events of less than 100 eV means that many low energy electrons are formed by the passage of a single ion. Low energy electrons have short mean free paths and they remain in the vicinity of the primary energy loss events. The spatial distribution of these low energy electrons defines the radial track structure of the incident

Retinal Photoisomerization in Rhodopsin: Electrostatic and Steric Catalysis

International Nuclear Information System (INIS)

Tomasello, Gaia; Altoe, Piero; Stenta, Marco; Olaso-Gonzalez, Gloria; Garavelli, Marco; Orlandi, Giorgio

2007-01-01

Excited state QM(CASPT2//CASSCF)/MM(GAFF) calculations, by our recently developed code COBRAMM (Computations at Bologna Relating Ab-initio and Molecular Mechanic Methods), were carried out in rhodopsin to investigate on the steric and electrostatic effects in retinal photoisomerization catalysis due to the β-ionone ring and glutammate 181 (GLU 181), respectively. The excited state photoisomerization channel has been mapped and a new christallographyc structure (2.2 Aa resolution) has been used for this purpose. Two different set-ups have been used to evaluate the electrostatic effects of GLU 181 (which is very close to the central double bond of the chromophore): the first with a neutral GLU 181 (as commonly accepted), the second with a negatively charged (i.e. deprotonated) GLU 181 (as very recent experimental findings seem to suggest). On the other hand, β-ionone ring steric effects were evaluated by calculating the photoisomerization path of a modified chromophore, where the ring double bond has been saturated. Spectroscopic properties were calculated and compared with the available experimental data

Study of first electronic transition and hydrogen bonding state of ultra-thin water layer of nanometer thickness on an α-alumina surface by far-ultraviolet spectroscopy

Science.gov (United States)

Goto, Takeyoshi; Kinugasa, Tomoya

2018-05-01

The first electronic transition (A˜ ← X˜) and the hydrogen bonding state of an ultra-thin water layer of nanometer thickness between two α-alumina surfaces (0.5-20 nm) were studied using far-ultraviolet (FUV) spectroscopy in the wavelength range 140-180 nm. The ultra-thin water layer of nanometer thickness was prepared by squeezing a water droplet ( 1 μL) between a highly polished α-alumina prism and an α-alumina plate using a high pressure clamp ( 4.7 MPa), and the FUV spectra of the water layer at different thicknesses were measured using the attenuated total reflection method. As the water layer became thinner, the A˜ ← X˜ bands were gradually shifted to higher or lower energy relative to that of bulk water; at thicknesses smaller than 4 nm, these shifts were substantial (0.1-0.2 eV) in either case. The FUV spectra of the water layer with thickness lost at thicknesses below 4 nm, because of steric hydration forces between the α-alumina surfaces.

Steric Pressure among Membrane-Bound Polymers Opposes Lipid Phase Separation.

Science.gov (United States)

Imam, Zachary I; Kenyon, Laura E; Carrillo, Adelita; Espinoza, Isai; Nagib, Fatema; Stachowiak, Jeanne C

2016-04-19

Lipid rafts are thought to be key organizers of membrane-protein complexes in cells. Many proteins that interact with rafts have bulky polymeric components such as intrinsically disordered protein domains and polysaccharide chains. Therefore, understanding the interaction between membrane domains and membrane-bound polymers provides insights into the roles rafts play in cells. Multiple studies have demonstrated that high concentrations of membrane-bound polymeric domains create significant lateral steric pressure at membrane surfaces. Furthermore, our recent work has shown that lateral steric pressure at membrane surfaces opposes the assembly of membrane domains. Building on these findings, here we report that membrane-bound polymers are potent suppressors of membrane phase separation, which can destabilize lipid domains with substantially greater efficiency than globular domains such as membrane-bound proteins. Specifically, we created giant vesicles with a ternary lipid composition, which separated into coexisting liquid ordered and disordered phases. Lipids with saturated tails and poly(ethylene glycol) (PEG) chains conjugated to their head groups were included at increasing molar concentrations. When these lipids were sparse on the membrane surface they partitioned to the liquid ordered phase. However, as they became more concentrated, the fraction of GUVs that were phase-separated decreased dramatically, ultimately yielding a population of homogeneous membrane vesicles. Experiments and physical modeling using compositions of increasing PEG molecular weight and lipid miscibility phase transition temperature demonstrate that longer polymers are the most efficient suppressors of membrane phase separation when the energetic barrier to lipid mixing is low. In contrast, as the miscibility transition temperature increases, longer polymers are more readily driven out of domains by the increased steric pressure. Therefore, the concentration of shorter polymers required

Steric and Stereochemical Modulation in Pyridyl- and Quinolyl-Containing Ligands

Directory of Open Access Journals (Sweden)

Zhaohua Dai

2016-12-01

Full Text Available Nitrogen-containing pyridine and quinoline are outstanding platforms on which excellent ionophores and sensors for metal ions can be built. Steric and stereochemical effects can be used to modulate the affinity and selectivity of such ligands toward different metal ions on the coordination chemistry front. On the signal transduction front, such effects can also be used to modulate optical responses of these ligands in metal sensing systems. In this review, steric modulation of achiral ligands and stereochemical modulation in chiral ligands, especially ionophores and sensors for zinc, copper, silver, and mercury, are examined using published structural and spectral data. Although it might be more challenging to construct chiral ligands than achiral ones, isotropic and anisotropic absorption signals from a single chiroptical fluorescent sensor provide not only detection but also differentiation of multiple analytes with high selectivity.

Synthesis and structural characterization of PHP[(C(5)Me(4))(2)], a monodentate chiral phosphine derived from intramolecular C-C coupling of tetramethylcyclopentadienyl groups: an evaluation of steric and electronic properties.

Science.gov (United States)

Shin, J H; Bridgewater, B M; Churchill, D G; Parkin, G

2001-10-22

The chiral monodentate phosphine PhP[(C(5)Me(4))(2)] is readily obtained by oxidation of the lithium complex Li(2)[PhP(C(5)Me(4))(2)] with I(2), which couples the two cyclopentadienyl groups to form a five-membered heterocyclic ring. The steric and electronic properties of PhP[(C(5)Me(4))(2)] have been evaluated by X-ray diffraction and IR spectroscopic studies on a variety of derivatives, including Ph[(C(5)Me(4))(2)]PE (E = S, Se), Cp*MCl(4)[P[(C(5)Me(4))(2)]Ph] (M = Mo, Ta), Ir[P[(C(5)Me(4))(2)]Ph](2)(CO)Cl, and CpFe(CO)[PhP[(C(5)Me(4))(2)

Reversible Redox-Induced Modulation of Sterics in an α-Diimine Ligand Coordinated to Gallium

Energy Technology Data Exchange (ETDEWEB)

Zarkesh, Ryan A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Foster, Michael E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Ichimura, Andrew S. [San Francisco State Univ., CA (United States); Anstey, Mitchell R. [Davidson College, Davidson, NC (United States)

2017-07-01

The ability to tune the steric envelope through redox events post-synthetically or in tandem with other chemical processes is a powerful tool that could assist in enabling new catalytic methodologies and understanding potential pitfalls in ligand design. The α-diimine ligand, dmp-BIAN, exhibits the peculiar and previously unreported feature of varying steric profiles depending on oxidation state when paired with a main group element. A study of the factors that give rise to this behaviour as well as its impact on the incorporation of other ligands is performed.

Cobalamins uncovered by modern electronic structure calculations

DEFF Research Database (Denmark)

Kepp, Kasper Planeta; Ryde, Ulf

2009-01-01

electronic-structure calculations, in particular density functional methods, the understanding of the molecular mechanism of cobalamins has changed dramatically, going from a dominating view of trans-steric strain effects to a much more complex view involving an arsenal of catalytic strategies. Among...... these are cis-steric distortions, electrostatic stabilization of radical products, the realization that nucleotide units can serve as polar handles, and the careful design of the active sites, with polar residues in the radical enzymes and non-polar residues in the transferases. Together, these strategies...

Substituent effects in heterogeneous catalysis--5. The steric hindrance of bulky alkyl substituents in cyclohexanone hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Chihara, T; Tanaka, K

1979-02-01

The steric hindrance of bulky alkyl substituents in cyclohexanone hydrogenation was demonstrated by the reactivities of 2-isopropyl and 2-tert.-butyl cyclohexanone relative to cyclohexanone in individual and competitive hydrogenation at 30/sup 0/C over alumina-supported ruthenium, rhodium, and platinum catalysts. The results indicate that the ketone adsorption onto the catalyst is sterically hindered by the alkyl substitution significantly more than the surface reaction which follows the adsorption.

Picking a Fight with Water, and Water Lost ... an Electron

Science.gov (United States)

Herr, Jonathan D.

The global need for energy is increasing, as is the importance of producing energy by green and renewable methodologies. This document outlines a research program dedicated to investigating a possible source for this form of energy generation and storage: solar fuels. The photon-induced splitting of water into molecular hydrogen and oxygen is currently hindered by large overpotentials from the oxidation half-reaction of water-splitting. This study concentrated on fundamental models of water-spitting chemistry, using a physical and computational chemistry analysis. The oxidation was first explored via ab initio electronic structure calculations of bare cationic water clusters, comprised of 2 to 21 molecules, in order to determine key electronic interactions that facilitate oxidation. Deeper understanding of these interactions could serve as guides for the development of viable water oxidation catalysts (WOC) designed to reduce overpotentials. The cationic water cluster study was followed by an investigation into hydrated copper (I) clusters, which acted as precursor models for real WOCs. Analyzing how the copper ion perturbed the properties of water clusters led to important electronic considerations for the development of WOCs, such as copper-water interactions that go beyond simple electrostatics. The importance of diagnostic thermodynamic properties, as well as anharmonic characteristics being persistent throughout oxidized water clusters, necessitated the use of quantum and classical molecular dynamics (MD) routines. Therefore, two new methods for accelerating computationally demanding classical and quantum MD methods were developed to increase their accessibility. The first method utilized a new form of electronic extrapolation - a linear prediction routine incorporating a Burg minimization - to decrease the iterations required for solving the electronic equations throughout the dynamics. The second method utilized a multiple-timestepping description of the

Electron localization in water clusters

International Nuclear Information System (INIS)

Landman, U.; Barnett, R.N.; Cleveland, C.L.; Jortner, J.

1987-01-01

Electron attachment to water clusters was explored by the quantum path integral molecular dynamics method, demonstrating that the energetically favored localization mode involves a surface state of the excess electron, rather than the precursor of the hydrated electron. The cluster size dependence, the energetics and the charge distribution of these novel electron-cluster surface states are explored. 20 refs., 2 figs., 1 tab

Intramolecular inverse electron demand Diels-Alder reactions of pyrimidines

NARCIS (Netherlands)

Frissen, A.E.

1990-01-01

This thesis deals with the intramolecular inverse electron demand Diels-Alder reaction of pyrimidines. The main objective of the study was to investigate the synthetic applicability of this reaction and to get more insight in the electronic and steric effects which determine the reactivity

A novel steric effect-regulated isothermal exponential amplification technology for the one-step homogeneous sensing of proteins.

Science.gov (United States)

Wu, Wanghua; Pan, Wufan; Yu, Dongdong; Yuan, Zhen; Qin, Yazhou; Lu, Yuxiang; Zhang, Tao; Zhou, Jianguang

2018-02-12

A simple and homogeneous technology, the steric effect-regulated isothermal exponential amplification reaction (SER-EXPAR), was developed to sense proteins. By using a small molecule linked DNA nanostructure, termed enzyme-binding hairpin (EBH), the protein-small molecule binding events could be readily sensed by utilizing the steric effect generated between the protein and enzyme. It set free the enzyme to be active again, thus regulating the amplification rate of EXPAR.

13C and 1H nuclear magnetic resonance of methyl-substituted acetophenones and methyl benzoates: steric hindrance and inhibited conjugation.

Science.gov (United States)

Budesínský, Milos; Kulhánek, Jirí; Böhm, Stanislav; Cigler, Petr; Exner, Otto

2004-10-01

The 1H and 13C NMR spectra of 14 methyl-substituted acetophenones and 14 methyl-substituted methyl benzoates were assigned and interpreted with respect to the conformation of the C(ar)-C(O) bond. The substituent effects are proportional in the two series and can be divided into polar and steric: each has different effects on the 13C SCS of the individual atoms. In the case of C atoms C(O), C(1) and CH3(CO), the steric effects were quantitatively separated by comparing SCS in the ortho and para positions. The steric effects are proportional for the individual C atoms and also to steric effects estimated from other physical quantities. However, they do not depend simply on the angle of torsion phi of the functional group as anticipated hitherto. A better description distinguishes two classes of compounds: sterically not hindered or slightly hindered planar molecules and strongly sterically hindered, markedly non-planar. In order to confirm this reasoning without empirical correlations, the J(C,C) coupling constants were measured for three acetophenone derivatives labeled with 13C in the acetyl methyl group. The constants confirm unambiguously the conformation of 2-methylacetophenone; their zero values are in accord with the conformation of 2,6-dimethylacetophenone. The zero values in the unsubstituted acetophenone are at variance with previous erroneous report but all J(C,C) values are in accord with calculations at the B3LYP/6-311++G(2d,2p)//B3LYP/6-311+G(d,p) level. Copyright 2004 John Wiley & Sons, Ltd.

Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO(2 π/2) with He

International Nuclear Information System (INIS)

Wiskerke, Arjan E.; de Lange, Marc J.L.; Stolte, Steven; Taatjes, Craig A.; van der Avoird, Ad; Klos, Jacek

2004-01-01

coupled-cluster methods including single, double, and noniterated triple excitations (J. Klos, G. Chalasinski, M. T. Berry, R. Bukowski, and S. M. Cybulski, J. Chem. Phys. 112, 2195 (2000)) and correlated electron-pair approximation (M. Yang and M. H. Alexander, J. Chem. Phys. 103, 6973 (1995)) potential energy surfaces. The calculated steric asymmetry S i # yields# f of the inelastic cross sections at E tr = 514 cm -1 is in reasonable agreement with that derived from the present experimental measurements for both spin-manifold conserving (F 1 → F 1 ) and spin-manifold changing (F 1 → F 2 ) collisions, except that the overall sign of the effect is opposite. Additionally, calculated field-free integral cross sections for collisions at E tr = 508 cm -1 are compared to the experimental data of Joswig et al. (J. Chem. Phys. 85, 1904 (1986)). Finally, the calculated differential cross section for collision energy E tr = 491 cm -1 is compared to experimental data of Westley et al. (J. Chem. Phys. 114, 2669 (2001)) for the spin-orbit conserving transition F 1 (j = 0.5) → F 1 f(j(prime) = 3.5)

Steric Maps to Evaluate the Role of Steric Hindrance on the IPr NHC Ligand

KAUST Repository

Poater, Albert

2013-06-01

Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) (IPr) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes effect the metal environment and therefore the related catalytic behaviour by simple steric maps. Bearing in mind that there is a significant structural difference between IPr and IPr* ligands, that translated in different reactivity for several olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. Furthermore, this communication endeavours to modify further the skeleton of the IPr NHC ligand. The optimization of these bulky new systems go to the limits of the DFT computational method.

Synthesis of zinc phthalocyanine with large steric hindrance and its photovoltaic performance for dye-sensitized solar cells.

Science.gov (United States)

Lin, Li; Peng, Bosi; Shi, Wenye; Guo, Yingying; Li, Renjie

2015-03-28

A zinc phthalocyanine (ZnPc) derivative (Zn-tri-PcNc-8) containing tri-benzonaphtho-condensed porphyrazine with one carboxylic and six diphenylphenoxy peripheral substitutions was designed and synthesized as a sensitizer for dye-sensitized solar cells (DSSCs). For the purpose of extending the absorption spectra while minimizing the formation of ZnPc molecular aggregates, bulky 2,6-diphenylphenoxy groups were used as electron donor moieties, and the carboxylic group as an anchoring group to graft the sensitizer onto the semiconductor. It was found that a TiO2-based solar cell sensitized by Zn-tri-PcNc-8 shows a maximum incident photon-to-current conversion efficiency in the red/near-IR light range (650-750 nm), and a solar cell sensitized at near room temperature (30 °C) for 48 h exhibits the best efficiency (3.01%). The efficiency was much higher than that (1.96%) for a solar cell sensitized by its analogue (Zn-tri-PcNc-2) having one carboxyl and three tert-butyl groups without chenodeoxycholic acid (CDCA), indicating that the introduction of six bulky diphenylphenoxy substitutions with large steric hindrance in the ZnPc macrocycle can effectively suppress the molecular aggregates, thus resulting in an improved conversion efficiency. The present results shed light on an effective solution to adjust the ZnPc property via chemical modification such as changing the "push-pull" effect and adding large steric hindrance substituents to further improve the efficiency of the phthalocyanine-sensitized solar cell.

Steric parameters and excess properties of hydroxamic acids

International Nuclear Information System (INIS)

Patre, Sandhya; Thakur, Piyush; Pande, Rama

2012-01-01

Graphical abstract: Plot of excess molar volume, V E , vs X 2 of (A) PBHA in DMF, (B) PMNHA in DMF, and (C) PNHA in DMF, at (■), 298.15 K; (▪), 303.15 K; (▪), 308.15 K; and (▪), 313.15 K. Highlights: ► Apparent molar volume indicates greater solute–solvent interactions. ► Excess properties show higher dispersion force in solution than pure solvent. ► Excess parameters suggest strong solute–solvent and solute–solute interactions. ► Limiting apparent molar expansibilities instigate highly hydrophobic characters. ► Hepler’s constant suggest the structure promoter nature of hydroxamic acids. - Abstract: Steric parameters of N-phenylbenzo-, N-phenyl-4-methyl-3-nitrobenzo-, and N-phenyl-4-nitrobenzo-, hydroxamic acids were measured in N,N-dimethylformamide (DMF) as a function of their concentrations at T = (298.15, 303.15, 308.15, and 313.15) K. The apparent molar volume (V φ ), limiting apparent molar volume (V φ 0 ) at infinite dilution and the slope (S V ∗ ) are calculated from the experimental values of density (ρ) by applying the Masson’s equation. The apparent molar expansibility at infinite dilution (φ E 0 ), molar volume (V) and the excess molar volume (V E ) are also computed. The refractive indices (n) have been used to calculate the steric parameters, viz. molar refraction (R M ), polarizability (α) and excess molar refraction (R) of these molecules. The results show the strong solute–solvent interactions present in the system and thus, help to explore the molecular structure.

Peptide Probes Reveal a Hydrophobic Steric Ratchet in the Anthrax Toxin Protective Antigen Translocase.

Science.gov (United States)

Colby, Jennifer M; Krantz, Bryan A

2015-11-06

Anthrax toxin is a tripartite virulence factor produced by Bacillus anthracis during infection. Under acidic endosomal pH conditions, the toxin's protective antigen (PA) component forms a transmembrane channel in host cells. The PA channel then translocates its two enzyme components, lethal factor and edema factor, into the host cytosol under the proton motive force. Protein translocation under a proton motive force is catalyzed by a series of nonspecific polypeptide binding sites, called clamps. A 10-residue guest/host peptide model system, KKKKKXXSXX, was used to functionally probe polypeptide-clamp interactions within wild-type PA channels. The guest residues were Thr, Ala, Leu, Phe, Tyr, and Trp. In steady-state translocation experiments, the channel blocked most tightly with peptides that had increasing amounts of nonpolar surface area. Cooperative peptide binding was observed in the Trp-containing peptide sequence but not the other tested sequences. Trp substitutions into a flexible, uncharged linker between the lethal factor amino-terminal domain and diphtheria toxin A chain expedited translocation. Therefore, peptide-clamp sites in translocase channels can sense large steric features (like tryptophan) in peptides, and while these steric interactions may make a peptide translocate poorly, in the context of folded domains, they can make the protein translocate more rapidly presumably via a hydrophobic steric ratchet mechanism. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

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.

Electron beam sterilization of water discharged from sewage

International Nuclear Information System (INIS)

Miyata, Teijiro; Arai, Hidehiko; Tokunaga, Okihiro; Machi, Sueo; Kondo, Masaki; Minemura, Takashi; Nakao, Akio; Seike, Yasuhiko.

1989-01-01

At present, the water treated at city sewerages is discharged to rivers after the chlorine sterilization, but it was clarified recently that this chlorine treatment produces carcinogenic organic chlorine compounds, and residual chlorine exerts harmful effect to aquatics, therefore, it is desirable to develop the sterilization techniques substituting for chlorine treatment. Already many reports elucidated that irradiation is effective for the sterilization of the water discharged from sewerage. However, as the technical subject for putting radiation process in practical use, the treatment of large quantity was a problem. Recently by the progress of the technology of manufacturing electron accelerators, the equipment with large power output which can treat in large quantity was developed, and it has become applicable also to sewage treatment. Therefore, the authors examined the practicality of electron beam process as the substitute technology for chlorine sterilizaiton. In the case of using electron beam, though the power output of accelerators is large, the flight range of electron beam in water is short. The comparison of the sterilization effect of electron beam with that of Co-60 gamma ray, the effects of water depth, discharged water quality and water velocity on the sterilization effect and so on were experimentally examined. (K.I.)

Dye stability and performances of dye-sensitized solar cells with different nitrogen additives at elevated temperatures - Can sterically hindered pyridines prevent dye degradation?

Energy Technology Data Exchange (ETDEWEB)

Tuyet Nguyen, Phuong; Lund, Torben [Department of Science, Systems and Models, Roskilde University, 4000 Roskilde (Denmark); Rand Andersen, Anders [University of Southern Denmark, Institute of Sensors, Signals and Electrotechnics (SENSE), Niels Bohrs Alle 1, 5230 Odense M (Denmark); Danish Technological Institute, Plastics Technology, Gregersensvej 2630 Taastrup (Denmark); Morten Skou, Eivind [University of Southern Denmark, Department of Chemical Engineering, Biotechnology and Enviromental Technology, Niels Bohrs Alle 1, 5230 Odense M (Denmark)

2010-10-15

The homogeneous kinetics of the nucleophilic substitution reactions between the ruthenium dye N719 and eight pyridines and 1-methylbenzimidazole have been investigated in 3-methoxypropionitrile at 100 C. The half lives of N719 with the additives 4-tert-butylpyridine (0.5 M) and 1-methylbenzimidazole (0.5 M) were 57 and 160 h, respectively. Sterically hindered pyridines like 2,6-lutidine did not react with N719. The efficiencies of dye-sensitized solar cells (DSC, area=8.0 cm{sup 2}) prepared with 1-methylbenzimidazole (MBI), 4-tert-butylpyridine (4-TBP), 2,6-lutidine and without any additive were 7.1%, 6.2%, 6.0% and 4.8%, respectively. The cells were stored in dark at 85 C and their I-V curves and impedance spectra were measured at regular time intervals. The N719 dye degradation in the cells were monitored by a new dye extraction protocol combined with analysis of the dye extract by HPLC coupled to mass spectrometry. After 300 h storage in dark at 85 C 40% of the initial amount of N719 dye was degraded in DSC cells prepared with MBI and the efficiency was decreased to 40% of its initial value. DSC cells prepared with 2,6-lutidine or no additives showed smaller thermal dye and efficiency stability at elevated temperatures than DSC cells prepared with the none sterically hindered additives MBI and 4-TBP. In the cells prepared with 2,6-lutidine or no additive higher contents of the iodo products [RuL{sub 2}(NCS)(iodide)]{sup +} and [RuL{sub 2}(3-MPN)(iodide)]{sup +} were found than in cells prepared with 4-TBP and MBI. It is suggested that sterically hindered pyridines have smaller complexation constants with I{sub 3}{sup -} than unsterically hindered additives. This may explain the observed faster nucleophilic substitution rates of uncomplexed I{sub 3}{sup -} with N719 in DSC cells prepared with sterically hindered pyridines. The EIS analysis showed that the lifetime of the injected electrons in the TiO{sub 2}{tau}{sub eff} is reduced by a thermally induced change

The water-water cycle as alternative photon and electron sinks.

OpenAIRE

Asada, K

2000-01-01

The water-water cycle in chloroplasts is the photoreduction of dioxygen to water in photosystem I (PS I) by the electrons generated in photosystem II (PS II) from water. In the water-water cycle, the rate of photoreduction of dioxygen in PS I is several orders of magnitude lower than those of the disproportionation of superoxide catalysed by superoxide dismutase, the reduction of hydrogen peroxide to water catalysed by ascorbate peroxidase, and the reduction of the resulting oxidized forms of...

Electronic and steric influences of pendant amine groups on the protonation of molybdenum bis (dinitrogen) complexes

Energy Technology Data Exchange (ETDEWEB)

Labios, Liezel A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Heiden, Zachariah M. [Washington State Univ., Pullman, WA (United States); Mock, Michael T. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2015-05-04

The synthesis of a series of P^EtP^NRR' (P^EtP^NRR' = Et₂PCH₂CH₂P(CH₂NRR')₂, R = H, R' = Ph or 2,4-difluorophenyl; R = R' = Ph or ⁱPr) diphosphine ligands containing mono- and disubstituted pendant amine groups, and the preparation of their corresponding molybdenum bis(dinitrogen) complexes trans-Mo(N₂)₂(PMePh₂)₂(P^EtP^NRR') is described. In situ IR and multinuclear NMR spectroscopic studies monitoring the stepwise addition of (HOTf) to trans-Mo(N₂)₂(PMePh₂)₂(P^EtP^NRR') complexes in THF at -40 °C show that the electronic and steric properties of the R and R' groups of the pendant amines influence whether the complexes are protonated at Mo, a pendant amine, a coordinated N2 ligand, or a combination of these sites. For example, complexes containing mono-aryl substituted pendant amines are protonated at Mo and pendant amine to generate mono- and dicationic Mo–H species. Protonation of the complex containing less basic diphenyl-substituted pendant amines exclusively generates a monocationic hydrazido (Mo(NNH₂)) product, indicating preferential protonation of an N₂ ligand. Addition of HOTf to the complex featuring more basic diisopropyl amines primarily produces a monocationic product protonated at a pendant amine site, as well as a trace amount of dicationic Mo(NNH₂) product that contain protonated pendant amines. In addition, trans-Mo(N₂)₂(PMePh₂)₂(depe) (depe = Et₂PCH₂CH₂PEt₂) without a pendant amine was synthesized and treated with HOTf, generating a monocationic Mo(NNH₂) product. Protonolysis experiments conducted on select complexes in the series afforded trace amounts of NH₄⁺. Computational analysis of the series of trans-Mo(N₂)₂(PMePh₂)₂(P^EtP^NRR') complexes provides further insight into the proton affinity values of the metal center, N�

Effects of the steric hindrance of micropores in the hyper-cross-linked polymeric adsorbent on the adsorption of p-nitroaniline in aqueous solution

International Nuclear Information System (INIS)

Xiao, Guqing; Wen, Ruimin; Wei, Dongmei; Wu, Dan

2014-01-01

Graphical abstract: The hyper-cross-linked polymeric adsorbents (GQ-05 and GQ-03) with different steric hindrance of micropores were designed. The adsorption capacity and adsorption rate of PNA onto the two adsorbents followed the order GQ-05 > GQ-03. The steric hindrance of micropores was a crucial factor for the adsorption capacity and adsorption rate order. - Highlights: • Two adsorbents with different steric hindrance of micropores were designed. • The adsorption capacity and adsorption rate followed the order GQ-05 > GQ-03. • The steric hindrance of micropores was a crucial factor for the order. - Abstract: A hyper-cross-linked polymeric adsorbent with “-CH 2 -phenol-CH 2 -” as the cross-linked bridge (denoted GQ-05), and another hyper-cross-linked polymeric adsorbent with “-CH 2 -p-cresol-CH 2 -” as the cross-linked bridge (denoted GQ-03) were synthesized to reveal the effect of the steric hindrance of micropores in the hyper-cross-linked polymeric adsorbent on adsorption capacity and adsorption rate of p-nitroaniline (PNA) from aqueous solution. The results of adsorption kinetics indicated the order of the adsorption rate GQ-05 > GQ-03. The pseudo-first-order rate equation could describe the entire adsorption process of PNA onto GQ-05 while the equation characterized the adsorption process of GQ-03 in two stages. The order of the adsorption capacity GQ-05 > GQ-03 was demonstrated by thermodynamic analysis and dynamic adsorption. The steric hindrance of micropores in the hyper-cross-linked polymeric adsorbent was a crucial factor for the order of the adsorption capacity and adsorption rate

Electronic and steric effects in regioselective tritiation of anilides

Energy Technology Data Exchange (ETDEWEB)

OOhashi, Kunio; Udo, Masato (Chiba Univ. (Japan). Coll. of Arts and Sciences)

1992-07-01

Acetanilide, propionanilide and isobutyranilide were tritiated at the ortho positions with very high regioselectivity by heating with HTO in the presence of RhCl[sub 3][center dot]3H[sub 2]O in N, N-dimethylformamide (DMF). In this reaction for pivalanilide the specific activity alone was determined, because attempts to establish the regioselectivity were unsuccessful. The extent of tritium incorporation decreased with increasing bulkiness of the alkyl groups. Only slight tritium was introduced by the same reaction for trifluoroacetanilide, which would probably be attributed to a strong electron-attracting property of the trifluoromethyl group. The above findings give support to the previous suggestion that the present isotope exchange reaction proceeds via an initial coordination of the nitrogen atom of anilides to the rhodium (III) chloride trihydrate catalyst. (author).

Hydrophilic luminescent silicon nanoparticles in steric colloidal solutions: their size, agglomeration and toxicity

Czech Academy of Sciences Publication Activity Database

Herynková, Kateřina; Šimáková, Petra; Cibulka, Ondřej; Fučíková, Anna; Kalbáčová, M.H.

2017-01-01

Roč. 14, č. 12 (2017), s. 1-4, č. článku 1700195. ISSN 1862-6351 Grant - others:AV ČR(CZ) DAAD-16-18 Program:Bilaterální spolupráce Institutional support: RVO:68378271 Keywords : silicon nanocrystals * colloidal solutions * steric stabilization * cytotoxicity Subject RIV: BO - Biophysics OBOR OECD: Biophysics

SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps

KAUST Repository

Falivene, Laura; Credendino, Raffaele; Poater, Albert; Petta, Andrea; Serra, Luigi; Oliva, Romina; Scarano, Vittorio; Cavallo, Luigi

2016-01-01

Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.

SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps

KAUST Repository

Falivene, Laura

2016-06-27

Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.

A Steric-inhibition model for regulation of nucleotide exchange via the Dock180 family of GEFs.

Science.gov (United States)

Lu, Mingjian; Kinchen, Jason M; Rossman, Kent L; Grimsley, Cynthia; Hall, Matthew; Sondek, John; Hengartner, Michael O; Yajnik, Vijay; Ravichandran, Kodi S

2005-02-22

CDM (CED-5, Dock180, Myoblast city) family members have been recently identified as novel, evolutionarily conserved guanine nucleotide exchange factors (GEFs) for Rho-family GTPases . They regulate multiple processes, including embryonic development, cell migration, apoptotic-cell engulfment, tumor invasion, and HIV-1 infection, in diverse model systems . However, the mechanism(s) of regulation of CDM proteins has not been well understood. Here, our studies on the prototype member Dock180 reveal a steric-inhibition model for regulating the Dock180 family of GEFs. At basal state, the N-terminal SH3 domain of Dock180 binds to the distant catalytic Docker domain and negatively regulates the function of Dock180. Further studies revealed that the SH3:Docker interaction sterically blocks Rac access to the Docker domain. Interestingly, ELMO binding to the SH3 domain of Dock180 disrupted the SH3:Docker interaction, facilitated Rac access to the Docker domain, and contributed to the GEF activity of the Dock180/ELMO complex. Additional genetic rescue studies in C. elegans suggested that the regulation of the Docker-domain-mediated GEF activity by the SH3 domain and its adjoining region is evolutionarily conserved. This steric-inhibition model may be a general mechanism for regulating multiple SH3-domain-containing Dock180 family members and may have implications for a variety of biological processes.

Mechanochemical Preparation of Stable Sub-100 nm γ-Cyclodextrin:Buckminsterfullerene (C60) Nanoparticles by Electrostatic or Steric Stabilization.

Science.gov (United States)

Van Guyse, Joachim F R; de la Rosa, Victor R; Hoogenboom, Richard

2018-02-21

Buckminster fullerene (C 60 )'s main hurdle to enter the field of biomedicine is its low bioavailability, which results from its extremely low water solubility. A well-known approach to increase the water solubility of C 60 is by complexation with γ-cyclodextrins. However, the formed complexes are not stable in time as they rapidly aggregate and eventually precipitate due to attractive intermolecular forces, a common problem in inclusion complexes of cyclodextrins. In this study we attempt to overcome the attractive intermolecular forces between the complexes by designing custom γ-cyclodextrin (γCD)-based supramolecular hosts for C 60 that inhibit the aggregation found in native γCD-C 60 complexes. The approach entails the introduction of either repulsive electrostatic forces or increased steric hindrance to prevent aggregation, thus enhancing the biomedical application potential of C 60 . These modifications have led to new sub-100 nm nanostructures that show long-term stability in solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium

OpenAIRE

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; Mcinnes, Eric; Tuna, Floriana; Wooles, Ashley; Maron, Laurent; Liddle, Stephen

2017-01-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido compl...

A Hybrid System Based on an Electronic Nose Coupled with an Electronic Tongue for the Characterization of Moroccan Waters

Directory of Open Access Journals (Sweden)

Z. Haddi

2014-05-01

Full Text Available A hybrid multisensor system combined with multivariate analysis was applied to the characterization of different kinds of Moroccan waters. The proposed hybrid system based on an electronic nose coupled with an electronic tongue consisted of metal oxide semiconductors and potentiometric sensors respectively. Five Taguchi Gas Sensors were implemented in the electronic nose for the discrimination between mineral, natural, sparkling, river and tap waters. Afterwards, the electronic tongue, based on series of Ion-Selective-Electrodes was applied to the analysis of the same waters. Multisensor responses obtained from the waters were processed by two chemometrics: Principal Component Analysis (PCA and Linear Discriminant Analysis (LDA. PCA results using electronic nose data depict all of the potable water samples in a separate group from the samples that were originated from river. Furthermore, PCA and LDA analysis on electronic tongue data permitted clear and rapid recognizing of the different waters due to the concentration changes of the chemical parameters from source to another.

Sterically demanding diphosphonite ligands - synthesis and application in nickel-catalyzed isomerization of 2-methyl-3-butenenitrile

NARCIS (Netherlands)

Vlugt, van der J.I.; Hewat, A.C.; Neto, S.; Sablong, R.J.; Mills, A.M.; Lutz, M.; Spek, A.L.; Müller, C.; Vogt, D.

2004-01-01

The synthesis of a novel class of sterically demanding diphosphonites 1-8, based on rigid backbones, is described. The starting materials are all commercially available and the methodology allows for a modular approach. All ligands have been fully characterized, including an X-ray crystal structure

Electron beam destruction of contaminant gasoline additives in water

International Nuclear Information System (INIS)

Mezyk, S.P.; Jones, J.; Cooper, W.J.; O'Shea, K.E.; Fim, D.K.

2003-01-01

The U.S. phase-out of tetraethyl lead in the 1970's resulted in ever-increasing amounts of high-octane compounds, notably methyl tert-butyl ether (MTBE), being added to gasoline to give cleaner burning fuel. However, the 1990 Clean Air Act oxygenate requirements led refiners to more than double the amount of these chemicals being blended into gasoline, and this combination of large scale use, high water solubility, low soil adsorption, and only minor biodegradability under normal aquifer conditions has now resulted in large-scale MTBE contamination occurring in natural, ground, and drinking water systems. The remediation of gasoline oxygenate contaminated ground and drinking water remains a pressing environmental problem. Studies of MTBE-contaminated water have shown that conventional air stripping and carbon adsorption are not viable technologies. Therefore Advanced Oxidation (and Reduction) Processes (AOPs) are expected to be required for these remediations. These technologies are defined as those that use the hydroxyl radical (and hydrated electron) and include H 2 O 2 /UV, H 2 O 2 /Fe(II), H 2 O 2 /O 3 , TiO 2 /UV, sonolysis, and electron beam treatment of contaminated waters. The water decontamination of current and potential gasoline oxygenates (MTBE, ethyl tert-butyl ether (ETBE), tert-butyl alcohol (TBA), ethanol, and tert-amyl ether (TAME)) using free radicals produced by the electron beam irradiation AOP has been studied. Kinetic studies have been used to determine rate constants for the reaction of these ethers and alcohols with hydroxyl radicals, hydrated electrons and hydrogen atoms, and also the subsequent formation and decay of their corresponding peroxyl radicals. These kinetic data have been combined with mechanistic degradation and product distribution information to construct a computer kinetic model that can predict the removal of these contaminants under a variety of water conditions. This model was used to compare the predicted MTBE removal

Steric sea level variability (1993-2010) in an ensemble of ocean reanalyses and objective analyses

Science.gov (United States)

Storto, Andrea; Masina, Simona; Balmaseda, Magdalena; Guinehut, Stéphanie; Xue, Yan; Szekely, Tanguy; Fukumori, Ichiro; Forget, Gael; Chang, You-Soon; Good, Simon A.; Köhl, Armin; Vernieres, Guillaume; Ferry, Nicolas; Peterson, K. Andrew; Behringer, David; Ishii, Masayoshi; Masuda, Shuhei; Fujii, Yosuke; Toyoda, Takahiro; Yin, Yonghong; Valdivieso, Maria; Barnier, Bernard; Boyer, Tim; Lee, Tony; Gourrion, Jérome; Wang, Ou; Heimback, Patrick; Rosati, Anthony; Kovach, Robin; Hernandez, Fabrice; Martin, Matthew J.; Kamachi, Masafumi; Kuragano, Tsurane; Mogensen, Kristian; Alves, Oscar; Haines, Keith; Wang, Xiaochun

2017-08-01

Quantifying the effect of the seawater density changes on sea level variability is of crucial importance for climate change studies, as the sea level cumulative rise can be regarded as both an important climate change indicator and a possible danger for human activities in coastal areas. In this work, as part of the Ocean Reanalysis Intercomparison Project, the global and regional steric sea level changes are estimated and compared from an ensemble of 16 ocean reanalyses and 4 objective analyses. These estimates are initially compared with a satellite-derived (altimetry minus gravimetry) dataset for a short period (2003-2010). The ensemble mean exhibits a significant high correlation at both global and regional scale, and the ensemble of ocean reanalyses outperforms that of objective analyses, in particular in the Southern Ocean. The reanalysis ensemble mean thus represents a valuable tool for further analyses, although large uncertainties remain for the inter-annual trends. Within the extended intercomparison period that spans the altimetry era (1993-2010), we find that the ensemble of reanalyses and objective analyses are in good agreement, and both detect a trend of the global steric sea level of 1.0 and 1.1 ± 0.05 mm/year, respectively. However, the spread among the products of the halosteric component trend exceeds the mean trend itself, questioning the reliability of its estimate. This is related to the scarcity of salinity observations before the Argo era. Furthermore, the impact of deep ocean layers is non-negligible on the steric sea level variability (22 and 12 % for the layers below 700 and 1500 m of depth, respectively), although the small deep ocean trends are not significant with respect to the products spread.

Steric effects in release of amides from linkers in solid-phase synthesis. Molecular mechanics modeling of key step in peptide and combinatorial chemistry

DEFF Research Database (Denmark)

Norrby, Per-Ola; Jensen, Knud Jørgen

2006-01-01

Acidolytic release of an amide from a solid support by C-N bond cleavage is all ubiquitous and crucial step in many solid-phase syntheses. We have used molecular modeling of a pseudo-equilibrium to explore substituent and steric effects in the release of peptides. The high acid-lability of the ba......Acidolytic release of an amide from a solid support by C-N bond cleavage is all ubiquitous and crucial step in many solid-phase syntheses. We have used molecular modeling of a pseudo-equilibrium to explore substituent and steric effects in the release of peptides. The high acid......-lability of the backbone amide linkage (BAL), which releases sec. amides, compared to C-terminal amide anchoring, which releases primary amides, was rationalized by steric relief upon cleavage. Thus, the relative stability of the carbenium ion formed from the linker in the acidolytic release is an insufficient measure...

Micro-flow synthesis and structural analysis of sterically crowded diimine ligands with five aryl rings

Directory of Open Access Journals (Sweden)

Shinichiro Fuse

2013-11-01

Full Text Available Sterically crowded diimine ligands with five aryl rings were prepared in one step in good yields using a micro-flow technique. X-ray crystallographic analysis revealed the detailed structure of the bulky ligands. The nickel complexes prepared from the ligands exerted high polymerization activity in the ethylene homopolymerization and copolymerization of ethylene with polar monomers.

Anomalous Ground State of the Electrons in Nano-confined Water

Science.gov (United States)

2016-06-13

Anomalous ground state of the electrons in nano -confined water G. F. Reiter1*, Aniruddha Deb2*, Y. Sakurai3, M. Itou3, V. G. Krishnan4, S. J...electronic ground state of nano -confined water must be responsible for these anomalies but has so far not been investigated. We show here for the first time...using x-ray Compton scattering and a computational model, that the ground state configuration of the valence electrons in a particular nano

Revealing climate modes in steric sea levels: lessons learned from satellite geodesy, objective analyses and ocean reanalyses

Science.gov (United States)

Pfeffer, J.; Tregoning, P.; Purcell, A. P.

2017-12-01

Due to increased greenhouse gases emissions, the oceans are accumulating heat. In response to the ocean circulation and atmospheric forcing, the heat is irregularly redistributed within the oceans, causing sea level to rise at variable rates in space and time. These rates of steric expansion are extremely difficult to assess because of the sparsity of in-situ hydrographic observations available within the course of the 20th century. We compare here three methods to reconstruct the steric sea levels over the past 13, 25 and 58 years based on satellite geodesy, objective analyses and ocean reanalyses. The interannual to decadal variability of each dataset is explored with a model merging six climate indices representative of the natural variability of the ocean and climate system. Consistent regional patterns are identified for the Pacific Decadal Oscillation (PDO) and El Niño Southern Oscillation (ENSO) in all datasets at all timescales. Despite the short time coverage (13 years), the combination of satellite geodetic data (altimetry and GRACE) also reveals significant steric responses to the North Pacific Gyre Oscillation (NPGO), Indian Dipole (IOD) and Indian ocean basinwide (IOBM) mode. The richer information content in the ocean reanalyses allows us to recover the regional fingerprints of the PDO, ENSO, NPGO, IOD and IOBM, but also of the Atlantic Multidecadal Oscillation (AMO) acting over longer time scales (40 to 60 years). Therefore, ocean reanalyses, coupled with climate mode analyses, constitute innovative and promising tools to investigate the mechanisms triggering the variability of sea level rise over the past decades.

Passivating ligand and solvent contribution to the electronics properties of semiconductor nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Tretiak, Sergei [Los Alamos National Laboratory; Crotty, Angela [Los Alamos National Laboratory; Fischer, Sean [Los Alamos National Laboratory; Kilina, Svetlana [NON LANL

2010-10-04

Expanding on previous work, we examine in detail the impact passivating ligands have on the electronic properties of CdSe quantum dots (QDs). We also explore the importance of the inclusion of solvent in simulating passivated QDs. Most ligand states are found well removed from the band edges, with pyridine being the exception and contributing states that sit right on the conduction band edge. Localized trap states are found for trimethylphosphine and pyridine capped QDs, with solvent helping to eliminate these. The effect of losing a ligand on the electronic properties of the system is observed to vary in proportion with the binding energy and steric bulk of the ligand. More disruption of the electronic properties is seen for tight-binding, sterically large ligands. We also look at the validity of using the single-particle Kohn-Sham (KS) representation to approximate optical absorption spectra. Besides a systematic blue-shift relative to the time-dependent density functional theory spectra, the KS spectra are in very good agreement with the more accurate method for these systems. Such agreement here justifies the use of the KS approach for calculating absorption spectra of QD systems.

Measurements of absorbed energy distributions in water from pulsed electron beams

International Nuclear Information System (INIS)

Devanney, J.A.

1974-01-01

An evaluation of the use of a holographic interferometer to measure the energy deposition as a function of depth in water from pulsed electron beams, together with a brief description of the interferometer and the technique of generating a hologram are presented. The holographic interferometer is used to measure the energy deposition as a function of depth in water from various pulsed beams of monoenergetic electrons in the energy range from 1.0 to 2.5 MeV. These results are compared to those computed by using a Monte Carlo radiation transport code, ETRAN-15, for the same electron energies. After the discrepancies between the measured and computed results are evaluated, reasonable agreement is found between the measured and computed absorbed energy distributions as a function of depth in water. An evalutation of the response of the interferometer as a function of electron intensities is performed. A comparison among four energy deposition curves that result from the irradiation of water with pulsed electron beams from a Febetron accelerator, model 705, is presented. These pulsed beams were produced by the same vacuum diode with the same charging voltage. The results indicate that the energy distribution of the electrons in the pulsed beam is not always constant. A comparison of the energy deposition curves that result from the irradiation of water with electron pulses from different vacuum diodes but the same charging voltage is presented. These results indicate again that the energy distribution of the electrons in the pulsed beam may vary between vacuum diodes. These differences would not be realized by using a totally absorbing metal calorimeter and Faraday Cup

Electronic Polarizability and the Effective Pair Potentials of Water

Science.gov (United States)

Leontyev, I. V.; Stuchebrukhov, A. A.

2014-01-01

Employing the continuum dielectric model for electronic polarizability, we have developed a new consistent procedure for parameterization of the effective nonpolarizable potential of liquid water. The model explains the striking difference between the value of water dipole moment μ~3D reported in recent ab initio and experimental studies with the value μeff~2.3D typically used in the empirical potentials, such as TIP3P or SPC/E. It is shown that the consistency of the parameterization scheme can be achieved if the magnitude of the effective dipole of water is understood as a scaled value μeff=μ∕εel, where εel =1.78 is the electronic (high-frequency) dielectric constant of water, and a new electronic polarization energy term, missing in the previous theories, is included. The new term is evaluated by using Kirkwood - Onsager theory. The new scheme is fully consistent with experimental data on enthalpy of vaporization, density, diffusion coefficient, and static dielectric constant. The new theoretical framework provides important insights into the nature of the effective parameters, which is crucial when the computational models of liquid water are used for simulations in different environments, such as proteins, or for interaction with solutes. PMID:25383062

Targeted Sterically Stabilized Phospholipid siRNA Nanomedicine for Hepatic and Renal Fibrosis

Directory of Open Access Journals (Sweden)

Fatima Khaja

2016-01-01

Full Text Available Since its discovery, small interfering RNA (siRNA has been considered a potent tool for modulating gene expression. It has the ability to specifically target proteins via selective degradation of messenger RNA (mRNA not easily accessed by conventional drugs. Hence, RNA interference (RNAi therapeutics have great potential in the treatment of many diseases caused by faulty protein expression such as fibrosis and cancer. However, for clinical application siRNA faces a number of obstacles, such as poor in vivo stability, and off-target effects. Here we developed a unique targeted nanomedicine to tackle current siRNA delivery issues by formulating a biocompatible, biodegradable and relatively inexpensive nanocarrier of sterically stabilized phospholipid nanoparticles (SSLNPs. This nanocarrier is capable of incorporating siRNA in its core through self-association with a novel cationic lipid composed of naturally occuring phospholipids and amino acids. This overall assembly protects and delivers sufficient amounts of siRNA to knockdown over-expressed protein in target cells. The siRNA used in this study, targets connective tissue growth factor (CTGF, an important regulator of fibrosis in both hepatic and renal cells. Furthermore, asialoglycoprotein receptors are targeted by attaching the galactosamine ligand to the nanocarries which enhances the uptake of nanoparticles by hepatocytes and renal tubular epithelial cells, the major producers of CTGF in fibrosis. On animals this innovative nanoconstruct, small interfering RNA in sterically stabilized phospholipid nanoparticles (siRNA-SSLNP, showed favorable pharmacokinetic properties and accumulated mostly in hepatic and renal tissues making siRNA-SSLNP a suitable system for targeting liver and kidney fibrotic diseases.

Abaxial growth and steric constraints guide leaf folding and shape in Acer pseudoplatanus.

Science.gov (United States)

Couturier, Etienne; Brunel, Nicole; Douady, Stéphane; Nakayama, Naomi

2012-08-01

How leaf shape is regulated is a long-standing question in botany. For diverse groups of dicotyledon species, lamina folding along the veins and geometry of the space available for the primordia can explain the palmate leaf morphology. Dubbed the kirigami theory, this hypothesis of fold-dependent leaf shape regulation has remained largely theoretical. Using Acer pseudoplatanus, we investigated the mechanisms behind the two key processes of kirigami leaf development. Cytological examination and quantitative analyses were used to examine the course of the vein-dependent lamina folding. Surgical ablation and tissue culturing were employed to test the effects of physical constraints on primordia growth. The final morphology of leaves growing without steric constraints were predicted mathematically. The cytological examination showed that the lamina's abaxial side along the veins grows substantially more than the adaxial side. The abaxial hypergrowth along the veins and the lamina extension correlated with the lamina folding. When a primordium was released from the physical constraints imposed by the other primordia, it rapidly grew into the newly available space, while maintaining the curvature inward. The morphology of such a leaf was predicted to lack symmetry in the lobe shapes. The enhanced growth on the abaxial side of the lamina along the veins is likely to drive lamina folding. The surgical ablation provided clear support for the space-filling nature of leaf growth; thus, steric constraints play a role in determination of the shapes of folded leaves and probably also of the final leaf morphology.

Model potentials in liquid water ionization by fast electron impact

International Nuclear Information System (INIS)

De Sanctis, M L; Stia, C R; Fojón, O A; Politis, M-F; Vuilleumier, R

2015-01-01

We study the ionization of water molecules in liquid phase by fast electron impact. We use our previous first-order model within an independent electron approximation that allows the reduction of the multielectronic problem into a monoelectronic one. The initial molecular states of the liquid water are represented in a realistic way through a Wannier orbital formalism. We complete our previous study by taking into account approximately the influence of the passive electrons of the target by means of different model potentials. We compute multiple differential cross sections for the most external orbital 1B 1 and compare them with other results

Ab initio calculation of the electronic absorption spectrum of liquid water

International Nuclear Information System (INIS)

Martiniano, Hugo F. M. C.; Galamba, Nuno; Cabral, Benedito J. Costa

2014-01-01

The electronic absorption spectrum of liquid water was investigated by coupling a one-body energy decomposition scheme to configurations generated by classical and Born-Oppenheimer Molecular Dynamics (BOMD). A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies in the liquid phase were calculated with the equation of motion coupled cluster with single and double excitations method. Molecular dynamics configurations were generated by different approaches. Classical MD were carried out with the TIP4P-Ew and AMOEBA force fields. The BLYP and BLYP-D3 exchange-correlation functionals were used in BOMD. Theoretical and experimental results for the electronic absorption spectrum of liquid water are in good agreement. Emphasis is placed on the relationship between the structure of liquid water predicted by the different models and the electronic absorption spectrum. The theoretical gas to liquid phase blue-shift of the peak positions of the electronic absorption spectrum is in good agreement with experiment. The overall shift is determined by a competition between the O–H stretching of the water monomer in liquid water that leads to a red-shift and polarization effects that induce a blue-shift. The results illustrate the importance of coupling many-body energy decomposition schemes to molecular dynamics configurations to carry out ab initio calculations of the electronic properties in liquid phase

Electron stimulated reactions of methyl iodide coadsorbed with amorphous solid water

International Nuclear Information System (INIS)

Perry, C. C.; Faradzhev, N. S.; Madey, T. E.; Fairbrother, D. H.

2007-01-01

The electron stimulated reactions of methyl iodide (MeI) adsorbed on and suspended within amorphous solid water (ice) were studied using a combination of postirradiation temperature programmed desorption and reflection absorption infrared spectroscopy. For MeI adsorbed on top of amorphous solid water (ice), electron beam irradiation is responsible for both structural and chemical transformations within the overlayer. Electron stimulated reactions of MeI result principally in the formation of methyl radicals and solvated iodide anions. The cross section for electron stimulated decomposition of MeI is comparable to the gas phase value and is only weakly dependent upon the local environment. For both adsorbed MeI and suspended MeI, reactions of methyl radicals within MeI clusters lead to the formation of ethane, ethyl iodide, and diiodomethane. In contrast, reactions between the products of methyl iodide and water dissociation are responsible for the formation of methanol and carbon dioxide. Methane, formed as a result of reactions between methyl radicals and either parent MeI molecules or hydrogen atoms, is also observed. The product distribution is found to depend on the film's initial chemical composition as well as the electron fluence. Results from this study highlight the similarities in the carbon-containing products formed when monohalomethanes coadsorbed with amorphous solid water are irradiated by either electrons or photons

Sterically controlled mechanochemistry under hydrostatic pressure

Science.gov (United States)

Yan, Hao; Yang, Fan; Pan, Ding; Lin, Yu; Hohman, J. Nathan; Solis-Ibarra, Diego; Li, Fei Hua; Dahl, Jeremy E. P.; Carlson, Robert M. K.; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Galli, Giulia; Mao, Wendy L.; Shen, Zhi-Xun; Melosh, Nicholas A.

2018-02-01

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. However, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistry through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain. We engineer molecules with mechanically heterogeneous components—a compressible (‘soft’) mechanophore and incompressible (‘hard’) ligands. In these ‘molecular anvils’, isotropic stress leads to relative motions of the rigid ligands, anisotropically deforming the compressible mechanophore and activating bonds. Conversely, rigid ligands in steric contact impede relative motion, blocking reactivity. We combine experiments and computations to demonstrate hydrostatic-pressure-driven redox reactions in metal-organic chalcogenides that incorporate molecular elements that have heterogeneous compressibility, in which bending of bond angles or shearing of adjacent chains activates the metal-chalcogen bonds, leading to the formation of the elemental metal. These results reveal an unexplored reaction mechanism and suggest possible strategies for high-specificity mechanosynthesis.

Determination of the Electronics Charge--Electrolysis of Water Method.

Science.gov (United States)

Venkatachar, Arun C.

1985-01-01

Presents an alternative method for measuring the electronic charge using data from the electrolysis of acidified distilled water. The process (carried out in a commercially available electrolytic cell) has the advantage of short completion time so that students can determine electron charge and mass in one laboratory period. (DH)

SAXS Study of Sterically Stabilized Lipid Nanocarriers Functionalized by DNA

Science.gov (United States)

Angelov, Borislav; Angelova, Angelina; Filippov, Sergey; Karlsson, Göran; Terrill, Nick; Lesieur, Sylviane; Štěpánek, Petr

2012-03-01

The structure of novel spontaneously self-assembled plasmid DNA/lipid complexes is investigated by means of synchrotron radiation small-angle X-ray scattering (SAXS) and Cryo-TEM imaging. Liquid crystalline (LC) hydrated lipid systems are prepared using the non-ionic lipids monoolein and DOPE-PEG2000 and the cationic amphiphile CTAB. The employed plasmid DNA (pDNA) is encoding for the human protein brain-derived neurotrophic factor (BDNF). A coexistence of nanoparticulate objects with different LC inner organizations is established. A transition from bicontinuous membrane sponges, cubosome intermediates and unilamelar liposomes to multilamellar vesicles, functionalized by pDNA, is favoured upon binding and compaction of pBDNF onto the cationic PEGylated lipid nanocarriers. The obtained sterically stabilized multicompartment nanoobjects, with confined supercoiled plasmid DNA (pBDNF), are important in the context of multicompartment lipid nanocarriers of interest for gene therapy of neurodegenerative diseases.

SAXS Study of Sterically Stabilized Lipid Nanocarriers Functionalized by DNA

International Nuclear Information System (INIS)

Angelov, Borislav; Filippov, Sergey; Štepánek, Petr; Angelova, Angelina; Lesieur, Sylviane; Karlsson, Göran; Terrill, Nick

2012-01-01

The structure of novel spontaneously self-assembled plasmid DNA/lipid complexes is investigated by means of synchrotron radiation small-angle X-ray scattering (SAXS) and Cryo-TEM imaging. Liquid crystalline (LC) hydrated lipid systems are prepared using the non-ionic lipids monoolein and DOPE-PEG 2000 and the cationic amphiphile CTAB. The employed plasmid DNA (pDNA) is encoding for the human protein brain-derived neurotrophic factor (BDNF). A coexistence of nanoparticulate objects with different LC inner organizations is established. A transition from bicontinuous membrane sponges, cubosome intermediates and unilamelar liposomes to multilamellar vesicles, functionalized by pDNA, is favoured upon binding and compaction of pBDNF onto the cationic PEGylated lipid nanocarriers. The obtained sterically stabilized multicompartment nanoobjects, with confined supercoiled plasmid DNA (pBDNF), are important in the context of multicompartment lipid nanocarriers of interest for gene therapy of neurodegenerative diseases.

Steric restrictions of RISC in RNA interference identified with size-expanded RNA nucleobases.

Science.gov (United States)

Hernández, Armando R; Peterson, Larryn W; Kool, Eric T

2012-08-17

Understanding the interactions between small interfering RNAs (siRNAs) and the RNA-induced silencing complex (RISC), the key protein complex of RNA interference (RNAi), is of great importance to the development of siRNAs with improved biological and potentially therapeutic function. Although various chemically modified siRNAs have been reported, relatively few studies with modified nucleobases exist. Here we describe the synthesis and hybridization properties of siRNAs bearing size-expanded RNA (xRNA) nucleobases and their use as a novel and systematic set of steric probes in RNAi. xRNA nucleobases are expanded by 2.4 Å using benzo-homologation and retain canonical Watson-Crick base-pairing groups. Our data show that the modified siRNA duplexes display small changes in melting temperature (+1.4 to -5.0 °C); substitutions near the center are somewhat destabilizing to the RNA duplex, while substitutions near the ends are stabilizing. RNAi studies in a dual-reporter luciferase assay in HeLa cells revealed that xRNA nucleobases in the antisense strand reduce activity at some central positions near the seed region but are generally well tolerated near the ends. Most importantly, we observed that xRNA substitutions near the 3'-end increased activity over that of wild-type siRNAs. The data are analyzed in terms of site-dependent steric effects in RISC. Circular dichroism experiments show that single xRNA substitutions do not significantly distort the native A-form helical structure of the siRNA duplex, and serum stability studies demonstrated that xRNA substitutions protect siRNAs against nuclease degradation.

Direct measurement of electron beam quality conversion factors using water calorimetry.

Science.gov (United States)

Renaud, James; Sarfehnia, Arman; Marchant, Kristin; McEwen, Malcolm; Ross, Carl; Seuntjens, Jan

2015-11-01

In this work, the authors describe an electron sealed water calorimeter (ESWcal) designed to directly measure absorbed dose to water in clinical electron beams and its use to derive electron beam quality conversion factors for two ionization chamber types. A functioning calorimeter prototype was constructed in-house and used to obtain reproducible measurements in clinical accelerator-based 6, 9, 12, 16, and 20 MeV electron beams. Corrections for the radiation field perturbation due to the presence of the glass calorimeter vessel were calculated using Monte Carlo (MC) simulations. The conductive heat transfer due to dose gradients and nonwater materials was also accounted for using a commercial finite element method software package. The relative combined standard uncertainty on the ESWcal dose was estimated to be 0.50% for the 9-20 MeV beams and 1.00% for the 6 MeV beam, demonstrating that the development of a water calorimeter-based standard for electron beams over such a wide range of clinically relevant energies is feasible. The largest contributor to the uncertainty was the positioning (Type A, 0.10%-0.40%) and its influence on the perturbation correction (Type B, 0.10%-0.60%). As a preliminary validation, measurements performed with the ESWcal in a 6 MV photon beam were directly compared to results derived from the National Research Council of Canada (NRC) photon beam standard water calorimeter. These two independent devices were shown to agree well within the 0.43% combined relative uncertainty of the ESWcal for this beam type and quality. Absorbed dose electron beam quality conversion factors were measured using the ESWcal for the Exradin A12 and PTW Roos ionization chambers. The photon-electron conversion factor, kecal, for the A12 was also experimentally determined. Nonstatistically significant differences of up to 0.7% were found when compared to the calculation-based factors listed in the AAPM's TG-51 protocol. General agreement between the relative

Multicomponent synthesis of unsymmetrical unsaturated N-heterocyclic carbene precursors and their related transition-metal complexes

KAUST Repository

Queval, Pierre

2013-12-04

A low-cost, modular, and easily scalable multicomponent procedure affording access in good yields and excellent selectivity (up to 93 %) to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl-imidazolium salts is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron donor ability, high steric discrimination, and modular steric demand. A low-cost, modular, and easily scalable multicomponent procedure, affording access to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl- imidazolium salts in good yields and excellent selectivities, is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron-donor ability, high steric discrimination, and modular steric demand. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of Steric Hindrance in the Crystal Packing of Z′ = 4 Superstructure of Trimethyltin Hydroxide

KAUST Repository

Dey, S.

2018-01-22

The roomerature crystal structure of trimethyltin hydroxide, (CH)SnOH, has been described by Anderson et al. [Cryst. Growth Des. 2011, 11, 820-826] as a 2a × 2b × 8c, 32-fold superstructure. We report a a × b × 8c, eight-fold superstructure with orthorhombic P2cn symmetry and Z′ = 4. Structured diffuse scattering observed at the positions of presumed superlattice reflections along a∗ and b∗ might have appeared as Bragg reflections in the experiment by Anderson et al. Alternatively, Anderson et al. and the present work might have studied different polymorphs of (CH)SnOH. Crystalline (CH)SnOH constitutes polymeric chains arranged parallel to c. In the eight-fold superstructure at 220 K, the polymeric chains possess a distorted zigzag arrangement of linked linear O-Sn-O units with bent angle at oxygen of ∼139.2°. This structure is essentially different from the 8-helical arrangement in the published 32-fold superstructure model. The origin of the distorted zigzag structure is explained by steric hindrance between hydrogen atoms of adjacent hydroxy groups and (CH)Sn groups. Frustration in the packing of the chains is determined by steric hindrance between methyl groups of neighboring chains, which prevents the formation of interchain C-H···O hydrogen bonds.

Different Steric-Twist-Induced Ternary Memory Characteristics in Nonconjugated Copolymers with Pendant Naphthalene and 1,8-Naphthalimide Moieties.

Science.gov (United States)

Wang, Ming; Li, Zhuang; Li, Hua; He, Jinghui; Li, Najun; Xu, Qingfeng; Lu, Jianmei

2017-10-18

Herein, novel random copolymers PMNN and PMNB were designed and synthesized, and the memory devices Al/PMNN and PMNB/ITO both exhibited ternary memory performance. The switching voltages of the OFF-ON1 and ON1-ON2 transitions for both memory devices are around -2.0 and -3.5 V, respectively, and the ON1/OFF, ON2/ON1 current ratios are both up to 10 3 . The observed tristable electrical conductivity switching could be attributed to field-induced conformational ordering of the naphthalene rings in the side chains, and subsequent charge trapping by 1,8-naphthalimide moieties. More interestingly, by adjusting the connection sites of 1,8-naphthalimide moieties to tune the steric-twist effect, different memory properties were achieved (PMNN showed nonvolatile write once, read many (WORM) memory behavior, whereas PMNB showed volatile static RAM (SRAM) memory behavior). This result will offer a guideline for the design of different high-performance multilevel memory devices by tuning the steric effects of the chemical moieties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Steric and electrostatic interactions govern nanofiltration of amino acids.

Science.gov (United States)

Shim, Yongki; Chellam, Shankararaman

2007-10-01

Crossflow nanofiltration experiments were performed to investigate the factors influencing the removal of amino acids by a commercially available polymeric thin-film composite membrane. The removals of five monoprotic (Ala, Val, Leu, Gly, and Thr), one diprotic (Asp), and one dibasic (Arg) amino acids in a range of permeate fluxes, feed pH values, and ionic strengths were analyzed using a phenomenological model of membrane transport. At any given pH and ionic strength, reflection coefficients (rejection at asymptotically infinite flux) of monoprotic amino acids increased with molar radius demonstrating the role of steric interactions on their removal. Additionally, consistent with Donnan exclusion, higher reflection coefficients were obtained when the membrane and the amino acids both carried the same nature of charge (positive or negative). In other words, both co-ion repulsion and molecular size determined amino acids removal. Importantly, the removal of effectively neutral amino acids were significantly higher than neutral sugars and alcohols of similar size demonstrating that even near their isoelectric point, zwitterionic characteristics preclude them from being considered as strictly neutral. (c) 2007 Wiley Periodicals, Inc.

Direct measurement of electron beam quality conversion factors using water calorimetry

Energy Technology Data Exchange (ETDEWEB)

Renaud, James, E-mail: james.renaud@mail.mcgill.ca; Seuntjens, Jan [Medical Physics Unit, McGill University, Montréal, Québec H3G 1A4 (Canada); Sarfehnia, Arman [Medical Physics Unit, McGill University, Montréal, Québec H3G 1A4, Canada and Department of Radiation Oncology, University of Toronto, Toronto, Ontario M5S 3E2 (Canada); Marchant, Kristin [Allan Blair Cancer Centre, Saskatchewan Cancer Agency, Regina, Saskatchewan S4T 7T1, Canada and Department of Oncology, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5A1 (Canada); McEwen, Malcolm; Ross, Carl [Ionizing Radiation Standards, National Research Council of Canada, Ottawa, Ontario K1A 0R6 (Canada)

2015-11-15

Purpose: In this work, the authors describe an electron sealed water calorimeter (ESWcal) designed to directly measure absorbed dose to water in clinical electron beams and its use to derive electron beam quality conversion factors for two ionization chamber types. Methods: A functioning calorimeter prototype was constructed in-house and used to obtain reproducible measurements in clinical accelerator-based 6, 9, 12, 16, and 20 MeV electron beams. Corrections for the radiation field perturbation due to the presence of the glass calorimeter vessel were calculated using Monte Carlo (MC) simulations. The conductive heat transfer due to dose gradients and nonwater materials was also accounted for using a commercial finite element method software package. Results: The relative combined standard uncertainty on the ESWcal dose was estimated to be 0.50% for the 9–20 MeV beams and 1.00% for the 6 MeV beam, demonstrating that the development of a water calorimeter-based standard for electron beams over such a wide range of clinically relevant energies is feasible. The largest contributor to the uncertainty was the positioning (Type A, 0.10%–0.40%) and its influence on the perturbation correction (Type B, 0.10%–0.60%). As a preliminary validation, measurements performed with the ESWcal in a 6 MV photon beam were directly compared to results derived from the National Research Council of Canada (NRC) photon beam standard water calorimeter. These two independent devices were shown to agree well within the 0.43% combined relative uncertainty of the ESWcal for this beam type and quality. Absorbed dose electron beam quality conversion factors were measured using the ESWcal for the Exradin A12 and PTW Roos ionization chambers. The photon-electron conversion factor, k{sub ecal}, for the A12 was also experimentally determined. Nonstatistically significant differences of up to 0.7% were found when compared to the calculation-based factors listed in the AAPM’s TG-51 protocol

Models for the transport of low energy electrons in water and the yield of hydrated electrons at early times

International Nuclear Information System (INIS)

Brenner, D.J.; Miller, J.H.; Ritchie, R.H.; Bichsel, H.

1985-01-01

An insulator model with four experimental energy bands was used to fit the optical properties of liquid water and to extend these data to non-zero momentum transfer. Inelastic mean free paths derived from this dielectric response function provided the basic information necessary to degrade high energy electrons to the subexcitation energy domain. Two approaches for the transport of subexcitation electrons were investigated. (i) Gas phase cross sections were used to degrade subexcitation electrons to thermal energy and the thermalization lengths were scaled to unit density. (ii) Thermalization lengths were estimated by age-diffusion theory with a stopping power deduced from the data on liquid water and transport cross sections derived from elastic scattering in water vapor. Theoretical ranges were compared to recent experimental results. A stochastic model was used to calculate the rapid diffusion and reaction of hydrated electrons with other radiolysis products. The sensitivity of the calculated yields to the model assumptions and comparison with experimental data are discussed

Influence of steric hindrance on enantioseparation of Dns-amino acids and pesticides on terguride based chiral selectors in capillary electrophoresis

Czech Academy of Sciences Publication Activity Database

Honzátko, Aleš; Cvak, Jan; Vaingátová, Silvie; Flieger, Miroslav

2005-01-01

Roč. 28, - (2005), s. 673-677 ISSN 1615-9306 R&D Projects: GA ČR GA203/02/0933 Institutional research plan: CEZ:AV0Z50200510 Keywords : steric hindrance * capillary electrophoresis * pesticides Subject RIV: EE - Microbiology, Virology Impact factor: 1.829, year: 2005

Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors.

Science.gov (United States)

Tsuruoka, Nozomu; Sadakane, Takuya; Hayashi, Rika; Tsujimura, Seiya

2017-03-10

The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH) from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus . At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k ₂ values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors

Directory of Open Access Journals (Sweden)

Nozomu Tsuruoka

2017-03-01

Full Text Available The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus. At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k2 values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

Steric and mass-induced Mediterranean sea level trends from 14 years of altimetry data

Science.gov (United States)

Criado-Aldeanueva, Francisco; Del Río Vera, Jorge; García-Lafuente, Jesús

2008-02-01

Long-term series of almost 14 years of altimetry data (1992-2005) have been analysed along with Sea Surface Temperature (SST) and temperature and salinity profiles to investigate sea level trends over the Mediterranean Sea. Although sea level variations are mainly driven by the steric contribution, the mass-induced component plays some role in modulating its oscillation. A spatially averaged positive trend of 2.1 ± 0.6 mm/year has been observed, but a change in sign in 2001 seems to appear. Steric effects (mainly on thermal origin) account for ˜ 55% of sea level trend. Although Mediterranean Sea is a semi-enclosed basin, this value is comparable to that reported for the global ocean. Sea level rise is particularly important in the Levantine basin south of Crete with values up to 10 ± 1 mm/year. Other areas of sea level rise are localised throughout the Levantine basin and in the Adriatic and Alboran Seas, with more moderate values. Sea level drop areas are localised in the Algerian basin, between the Balearic Islands and the African coasts and, particularly, in the Ionian basin. In this area, negative trends as high as - 10 ± 0.8 mm/year are detected mainly due to the mass-induced contribution, which suggests decadal changes of surface circulation. The inferred sea level trends have been correlated with North Atlantic Oscillation (NAO) indices and a low but significant correlation has been detected between sea level in the Levantine and Balearic basins and NAO index.

Quinoidal Oligo(9,10-anthryl)s with Chain-Length-Dependent Ground States: A Balance between Aromatic Stabilization and Steric Strain Release

KAUST Repository

Lim, Zhenglong; Zheng, Bin; Huang, Kuo-Wei; Liu, Ye; Wu, Jishan

2015-01-01

: the large steric repulsion between the anthryl/phenyl units in the closed-shell quinoidal form that drives the molecule to a flexible open-shell diradical structure, and aromatic stabilisation due to the gain of more aromatic sextet rings in the closed

Electron drift velocities in He and water mixtures: Measurements and an assessment of the water vapour cross-section sets

International Nuclear Information System (INIS)

Urquijo, J. de; Juárez, A. M.; Basurto, E.; Ness, K. F.; Robson, R. E.; White, R. D.; Brunger, M. J.

2014-01-01

The drift velocity of electrons in mixtures of gaseous water and helium is measured over the range of reduced electric fields 0.1–300 Td using a pulsed-Townsend technique. Admixtures of 1% and 2% water to helium are found to produce negative differential conductivity (NDC), despite NDC being absent from the pure gases. The measured drift velocities are used as a further discriminative assessment on the accuracy and completeness of a recently proposed set of electron-water vapour cross-sections [K. F. Ness, R. E. Robson, M. J. Brunger, and R. D. White, J. Chem. Phys. 136, 024318 (2012)]. A refinement of the momentum transfer cross-section for electron-water vapour scattering is presented, which ensures self-consistency with the measured drift velocities in mixtures with helium to within approximately 5% over the range of reduced fields considered

Diazo Reagents with Small Steric Footprints for Simultaneous Arming/SAR Studies of Alcohol-Containing Natural Products via O–H Insertion

Science.gov (United States)

Chamni, Supakarn; He, Qing-Li; Dang, Yongjun; Bhat, Shridhar; Liu, Jun O.; Romo, Daniel

2011-01-01

Natural products are essential tools for basic cellular studies leading to the identification of medically relevant protein targets and the discovery of potential therapeutic leads. The development of methods that enable mild and selective derivatization of natural products continues to be of significant interest for mining their information-rich content. Herein, we describe novel diazo reagents for simultaneous arming and structure-activity relationship (SAR) studies of alcohol-containing natural products with a small steric footprint, namely an α-trifluoroethyl (HTFB) substituted reagent. The Rh(II)-catalyzed O–H insertion reaction of several natural products, including the potent translation inhibitor lactimidomycin, was investigated and useful reactivity and both chemo- and site (chemosite) selectivities were observed. Differential binding to the known protein targets of both FK506 and fumagillol was demonstrated, validating the advantage of the smaller steric footprint of trifluoroethyl derivatives. A p-azidophenyl diazo reagent is also described that will prove useful for photoaffinity labeling of low affinity small molecule protein receptors. PMID:21894934

Electron-induced hydrogen loss in uracil in a water cluster environment

International Nuclear Information System (INIS)

Smyth, M.; Kohanoff, J.; Fabrikant, I. I.

2014-01-01

Low-energy electron-impact hydrogen loss due to dissociative electron attachment (DEA) to the uracil and thymine molecules in a water cluster environment is investigated theoretically. Only the A ′ -resonance contribution, describing the near-threshold behavior of DEA, is incorporated. Calculations are based on the nonlocal complex potential theory and the multiple scattering theory, and are performed for a model target with basic properties of uracil and thymine, surrounded by five water molecules. The DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster. This growth is due to two effects: the increase of the resonance lifetime and the negative shift in the resonance position due to interaction of the intermediate negative ion with the surrounding water molecules. A similar effect was earlier found in DEA to chlorofluorocarbons

Electron Density Dropout Near Enceladus in the Context of Water-Vapor and Water-Ice

Science.gov (United States)

Farrell, W. M.; Kurth, W. S.; Gurnett, D. A.; Johnson, R. E.; Kaiser, M. L.; Wahlund, J.-E.; Waite, J. H., Jr.

2009-01-01

On 12 March 2008, the Cassini spacecraft made a close encounter with the Saturnian moon Enceladus, passing within 52 km of the moon. The spacecraft trajectory was intentionally-oriented in a southerly direction to create a close alignment with the intense water-dominated plumes emitted from the south polar region. During the passage, the Cassini Radio and Plasma Wave System (RPWS) detected two distinct radio signatures: 1) Impulses associated with small water-ice dust grain impacts and 2) an upper hybrid (UH) resonance emission that both intensified and displayed a sharp frequency decrease in the near-vicinity of the moon. The frequency decrease of the UH emission is associated with an unexpectedly sharp decrease in electron density from approximately 90 el/cubic cm to below 20 el/cubic cm that occurs on a time scale of a minute near the closest encounter with the moon. In this work, we consider a number of scenarios to explain this sharp electron dropout, but surmise that electron absorption by ice grains is the most likely process.

Unconventional exo selectivity in thermal normal-electron-demand Diels-Alder reactions

Science.gov (United States)

Ho, Guo-Ming; Huang, Ci-Jhang; Li, Elise Yu-Tzu; Hsu, Sheng-Kai; Wu, Ti; Zulueta, Medel Manuel L.; Wu, Kevin Binchia; Hung, Shang-Cheng

2016-10-01

The Diels-Alder reaction is a useful tool for generating functionalized chiral molecules through the concerted cycloaddition of dienes and dienophiles leading to six-membered rings. Traditionally, the selective predictions of the products rely heavily on consideration of the secondary orbital interactions that stabilize the endo pathway. However, there remain some basic examples defying this notion and produce the exo-isomer as major product. Here we systematically evaluated of the structural features driving exo selectivity in thermal normal-electron-demand Diels-Alder reactions. Substitution at the Cβ position and the size and electronegativity of the electron-withdrawing group of the dienophile are contributing factors. Experimental and computational studies both point toward the steric and electrostatic forces between the substituents in both the diene and the dienophile that increase the likelihood of the exo pathway. For these substrates, the dominance of the endo pathway is reduced by transition state distortions and poor structural alignments of the reacting partners. We also noted the tilt of the dienophile with respect to the diene causing steric strain on the functionalities at the more advanced bond forming carbon-carbon position of the endo transition state. Insights into such factors may benefit synthetic planning and asserting control over this important named reaction.

Redox regulation of protein tyrosine phosphatase 1B (PTP1B): Importance of steric and electronic effects on the unusual cyclization of the sulfenic acid intermediate to a sulfenyl amide

Science.gov (United States)

Sarma, Bani Kanta

2013-09-01

The redox regulation of protein tyrosine phosphatase 1B (PTP1B) via the unusual transformation of its sulfenic acid (PTP1B-SOH) to a cyclic sulfenyl amide intermediate is studied by using small molecule chemical models. These studies suggest that the sulfenic acids derived from the H2O2-mediated reactions o-amido thiophenols do not efficiently cyclize to sulfenyl amides and the sulfenic acids produced in situ can be trapped by using methyl iodide. Theoretical calculations suggest that the most stable conformer of such sulfenic acids are stabilized by nO → σ*S-OH orbital interactions, which force the -OH group to adopt a position trans to the S⋯O interaction, leading to an almost linear arrangement of the O⋯S-O moiety and this may be the reason for the slow cyclization of such sulfenic acids to their corresponding sulfenyl amides. On the other hand, additional substituents at the 6-position of o-amido phenylsulfenic acids that can induce steric environment and alter the electronic properties around the sulfenic acid moiety by S⋯N or S⋯O nonbonded interactions destabilize the sulfenic acids by inducing strain in the molecule. This may lead to efficient the cyclization of such sulfenic acids. This model study suggests that the amino acid residues in the close proximity of the sulfenic acid moiety in PTP1B may play an important role in the cyclization of PTP1B-SOH to produce the corresponding sulfenyl amide.

Steric effects in the dynamics of electrolytes at large applied voltages. II. Modified Poisson-Nernst-Planck equations.

Science.gov (United States)

Kilic, Mustafa Sabri; Bazant, Martin Z; Ajdari, Armand

2007-02-01

In situations involving large potentials or surface charges, the Poisson-Boltzman (PB) equation has shortcomings because it neglects ion-ion interactions and steric effects. This has been widely recognized by the electrochemistry community, leading to the development of various alternative models resulting in different sets "modified PB equations," which have had at least qualitative success in predicting equilibrium ion distributions. On the other hand, the literature is scarce in terms of descriptions of concentration dynamics in these regimes. Here, adapting strategies developed to modify the PB equation, we propose a simple modification of the widely used Poisson-Nernst-Planck (PNP) equations for ionic transport, which at least qualitatively accounts for steric effects. We analyze numerical solutions of these modified PNP equations on the model problem of the charging of a simple electrolyte cell, and compare the outcome to that of the standard PNP equations. Finally, we repeat the asymptotic analysis of Bazant, Thornton, and Ajdari [Phys. Rev. E 70, 021506 (2004)] for this new system of equations to further document the interest and limits of validity of the simpler equivalent electrical circuit models introduced in Part I [Kilic, Bazant, and Ajdari, Phys. Rev. E 75, 021502 (2007)] for such problems.

Electron-induced hydrogen loss in uracil in a water cluster environment

Energy Technology Data Exchange (ETDEWEB)

Smyth, M.; Kohanoff, J. [Atomistic Simulation Centre, Queen' s University Belfast, Belfast BT7 1NN, Northern Ireland (United Kingdom); Fabrikant, I. I., E-mail: ifabrikant1@unl.edu [Department of Physics and Astronomy, University of Nebraska, Lincoln, Nebraska 68588, USA and Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom)

2014-05-14

Low-energy electron-impact hydrogen loss due to dissociative electron attachment (DEA) to the uracil and thymine molecules in a water cluster environment is investigated theoretically. Only the A{sup ′}-resonance contribution, describing the near-threshold behavior of DEA, is incorporated. Calculations are based on the nonlocal complex potential theory and the multiple scattering theory, and are performed for a model target with basic properties of uracil and thymine, surrounded by five water molecules. The DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster. This growth is due to two effects: the increase of the resonance lifetime and the negative shift in the resonance position due to interaction of the intermediate negative ion with the surrounding water molecules. A similar effect was earlier found in DEA to chlorofluorocarbons.

Evaluation of some water - equivalent plastics as phantom materials for electron dosimetry

International Nuclear Information System (INIS)

Mihailescu, D.; Borcia, C.

2005-01-01

In the International Code of Practice for Dosimetry TRS-398 published by the International Atomic Energy Agency (IAEA), water is recommended as the reference medium for the determination of absorbed dose for high-energy electron beams. Plastic phantoms may be used under certain circumstances (electron energy below 10 MeV, R 50 2 ) for electron beam dosimetry. In this case, a depth-scaling factor is required for the conversion of depth in solid phantoms to depth in water. A fluence-scaling factor is also necessary for converting ionization chamber readings in plastic phantom to readings in water. The aim of this paper is to calculate, using Monte Carlo simulations, the depth-scaling factors c pl and fluence-scaling factors h pl of some commercially available water substitute solid phantoms in order to evaluate their water equivalency. Two sets of calculations were performed: one for electron pencil beams and another for 10 x 10 cm 2 parallel beams, both of which are normally incident on water and solid phantoms. We used only mono-energetic beams of 6, 9, 12, 15, and 18 MeV. The results were compared with TRS-398 recommended values. In the case of pencil beams, we found that by applying the TRS-398 protocol, unacceptable uncertainties (up to 10%) were introduced in the dose distribution calculations. By contrast, TRS-398 can safely be used for 10 x 10 cm 2 beams (reference beams). In this case, uncertainties lower than 1% were obtained, what was in agreement with other published data. (authors)

Steric Interference of Adhesion Supports In-Vitro Chondrogenesis of Mesenchymal Stem Cells on Hydrogels for Cartilage Repair

OpenAIRE

Goldshmid, Revital; Cohen, Shlomit; Shachaf, Yonatan; Kupershmit, Ilana; Sarig-Nadir, Offra; Seliktar, Dror; Wechsler, Roni

2015-01-01

Recent studies suggest the presence of cell adhesion motifs found in structural proteins can inhibit chondrogenesis. In this context, the current study aims to determine if a polyethylene glycol (PEG)-modified fibrinogen matrix could support better chondrogenesis of human bone marrow mesenchymal stem cells (BM-MSC) based on steric interference of adhesion, when compared to a natural fibrin matrix. Hydrogels used as substrates for two-dimensional (2D) BM-MSC cultures under chondrogenic conditi...

Steric hindrances create a discrete linear Dy4 complex exhibiting SMM behaviour.

Science.gov (United States)

Lin, Shuang-Yan; Zhao, Lang; Ke, Hongshan; Guo, Yun-Nan; Tang, Jinkui; Guo, Yang; Dou, Jianmin

2012-03-21

Two linear tetranuclear lanthanide complexes of general formula [Ln(4)(L)(2)(C(6)H(5)COO)(12)(MeOH)(4)], where HL = 2,6-bis((furan-2-ylmethylimino)methyl)-4-methylphenol, () and Ln(III) = Dy(III) (1) and Gd(III) (2), have been synthesized and characterized. The crystal structural analysis demonstrates that two Schiff-base ligands inhibit the growth of benzoate bridged 1D chains, leading to the isolation of discrete tetranuclear complexes due to their steric hindrances. Every Ln(III) ion is coordinated by eight donor atoms in a distorted bicapped trigonal-prismatic arrangement. Alternating current (ac) susceptibility measurements of complex 1 reveal a frequency- and temperature-dependent out-of-phase signal under zero dc field, typical of single-molecule magnet (SMM) behaviour with an anisotropic barrier Δ(eff) = 17.2 K.

The general properties of water - nitrobenzene - crown - bis-1,2-dicarbollylcobaltate extraction systems

International Nuclear Information System (INIS)

Vanura, P.

2003-01-01

The extraction and stability constants in the system water - nitrobenzene have been collected and general rules valid for water - nitrobenzene - crown - bis-1,2-dicarbollylcobaltate extraction system have been found. The main principles are size compatibility of ion diameter and crown cavity diameters, the flexibility of crown, the basicity of crown and the steric factor of both the ligand and the extracted ion. The extraction in the system water - mineral acid or salt polyoxyethylene compound - bis-1,2-dicarbollylcobaltate - nitrobenzene is more complicated than can be expected from usually used ion diameter - crown cavity diameter compatibility principle. The other important factors are the basicity and the deformability of crown, steric aspect and the angles of bonds of extracted ion. The binuclear 'sandwich' complexes with H + ion and Sr 2+ or Ba 2+ ions have been proved for dibenzo-18-crown-6 (DB18C6). On the other hand, only SrL 2 and BaL 2 (L = 15C5) complexes are formed in nitrobenzene saturated with water. The addition of polyoxyethylene compound usually increases the distribution ratio of alkali earth metal ions and the selectivity of its mutual separation. (authors)

Brownian dynamics simulations of an order-disorder transition in sheared sterically stabilized colloidal suspensions

International Nuclear Information System (INIS)

Rigos, A.A.; Wilemski, G.

1992-01-01

The shear thinning behavior of a sterically stabilized nonaqueous colloidal suspension was investigated using nonequilibrium Brownian dynamics simulations of systems with 108 and 256 particles. At a volume fraction of 0.4, the suspension is thixotropic: it has a reversible shear thinning transition from a disordered state to an ordered, lamellar state with triangularly packed strings of particles. The time scale for the transition is set by the free particle diffusion constant. For the smaller system, the transition occurs gradually with increasing shear rate. For the larger system, the transition is sharp and discontinuous shear thinning is found. 34 refs., 9 figs., 1 tab

In vitro circumvention of cisplatin resistance by the novel sterically hindered platinum complex AMD473.

Science.gov (United States)

Holford, J.; Sharp, S. Y.; Murrer, B. A.; Abrams, M.; Kelland, L. R.

1998-01-01

A novel sterically hindered platinum complex, AMD473 [cis-aminedichloro(2-methylpyridine) platinum (II)], has been selected for phase I clinical trials due to commence in 1997. AMD473 was rationally designed to react preferentially with nucleic acids over sulphur ligands such as glutathione. This report documents the in vitro circumvention of acquired cisplatin resistance mechanisms in human ovarian carcinoma (HOC) cell lines by AMD473. In a panel of 11 HOC cell lines, AMD473 showed intermediate growth inhibition potency (mean IC50 of 8.1 microM) in comparison to cisplatin (mean IC50 of 2.6 microM) and carboplatin (mean IC50 of 20.3 microM). AMD473 showed only a 30.7-fold increase in IC50 value from the most sensitive to the most resistant HOC cell line, whereas for cisplatin it was 117.9-fold and for carboplatin 119.7-fold. AMD473 also showed significantly (P or = 14 h for AMD473) after equitoxic doses were exposed to HOC cells for 2 h. AMD473 ICLs in the CH1 HOC cell line were slowly formed and showed no visible signs of being repaired 24 h after removal of drug. This was paralleled by a slower, longer lasting induction of p53 protein by equitoxic doses of AMD473 in HOC cell lines with wild-type p53. This new class of sterically hindered platinum compound, selected for clinical trial in 1997, may therefore elicit improved clinical response in intrinsically and acquired cisplatin-resistant tumours in the clinic. Images Figure 9 PMID:9472630

A multi water bag model of drift kinetic electron plasma

International Nuclear Information System (INIS)

Morel, P.; Dreydemy Ghiro, F.; Berionni, V.; Gurcan, O.D.; Coulette, D.; Besse, N.

2014-01-01

A Multi Water Bag model is proposed for describing drift kinetic plasmas in a magnetized cylindrical geometry, relevant for various experimental devices, solar wind modeling... The Multi Water Bag (MWB) model is adapted to the description of a plasma with kinetic electrons as well as an arbitrary number of kinetic ions. This allows to describe the kinetic dynamics of the electrons, making possible the study of electron temperature gradient (ETG) modes, in addition to the effects of non adiabatic electrons on the ion temperature gradient (ITG) modes, that are of prime importance in the magnetized plasmas micro-turbulence [X. Garbet, Y. Idomura, L. Villard, T.H. Watanabe, Nucl. Fusion 50, 043002 (2010); J.A. Krommes, Ann. Rev. Fluid Mech. 44, 175 (2012)]. The MWB model is shown to link kinetic and fluid descriptions, depending on the number of bags considered. Linear stability of the ETG modes is presented and compared to the existing results regarding cylindrical ITG modes [P. Morel, E. Gravier, N. Besse, R. Klein, A. Ghizzo, P. Bertrand, W. Garbet, Ph. Ghendrih, V. Grandgirard, Y. Sarazin, Phys. Plasmas 14, 112109 (2007)]. (authors)

Unfavorable regions in the ramachandran plot: Is it really steric hindrance? The interacting quantum atoms perspective.

Science.gov (United States)

Maxwell, Peter I; Popelier, Paul L A

2017-11-05

Accurate description of the intrinsic preferences of amino acids is important to consider when developing a biomolecular force field. In this study, we use a modern energy partitioning approach called Interacting Quantum Atoms to inspect the cause of the φ and ψ torsional preferences of three dipeptides (Gly, Val, and Ile). Repeating energy trends at each of the molecular, functional group, and atomic levels are observed across both (1) the three amino acids and (2) the φ/ψ scans in Ramachandran plots. At the molecular level, it is surprisingly electrostatic destabilization that causes the high-energy regions in the Ramachandran plot, not molecular steric hindrance (related to the intra-atomic energy). At the functional group and atomic levels, the importance of key peptide atoms (O i -1 , C i , N i , N i +1 ) and some sidechain hydrogen atoms (H γ ) are identified as responsible for the destabilization seen in the energetically disfavored Ramachandran regions. Consistently, the O i -1 atoms are particularly important for the explanation of dipeptide intrinsic behavior, where electrostatic and steric destabilization unusually complement one another. The findings suggest that, at least for these dipeptides, it is the peptide group atoms that dominate the intrinsic behavior, more so than the sidechain atoms. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.

Gauche effect in 1,2-difluoroethane. Hyperconjugation, bent bonds, steric repulsion.

Science.gov (United States)

Goodman, Lionel; Gu, Hongbing; Pophristic, Vojislava

2005-02-17

Natural bond orbital deletion calculations show that whereas the gauche preference arises from vicinal hyperconjugative interaction between anti C-H bonds and C-F* antibonds, the cis C-H/C-F* interactions are substantial (approximately 25% of the anti interaction). The established significantly >60 degrees FCCF dihedral angle for the equilibrium conformer can then be rationalized in terms of the hyperconjugation model alone by taking into account both anti interactions that maximize near 60 degrees and the smaller cis interactions that maximize at a much larger dihedral angle. This explanation does not invoke repulsive forces to rationalize the 72 degrees equilibrium conformer angle. The relative minimum energy for the trans conformer is the consequence of a balance between decreasing hyperconjugative stabilization and decreasing steric destabilization as the FCCF torsional angle approaches 180 degrees . The torsional coordinate is predicted to be strongly contaminated by CCF bending, with the result that approximately half of the trans --> gauche stabilization energy stems from mode coupling.

Holographic Measurements of Electron-Beam Dose Distributions Around Inhomogeneities in Water

DEFF Research Database (Denmark)

Miller, Arne; McLaughlin, W. L.

1976-01-01

Dose distribution measurements made in a small quartz cell filled with water, and with an Al rod placed in the water are reported. The cell was irradiated vertically from above with monoenergetic 3 MeV electrons from a Van de Graaff accelerator. The holographic interferometric method previously...

Sterically Bulky NHC Adducts of GaMe3 and InMe3 for H2 Activation and Lactide Polymerization

Directory of Open Access Journals (Sweden)

Anaëlle Bolley

2018-01-01

Full Text Available The sterically bulky Ga(III and In(III (IPr*MMe3 adducts (1 and 2 and (SItBuMMe3 adducts (3 and 4 (M = Ga, In; IPr* = 1,3-bis{2,6-bis(diphenylmethyl-4-methylphenyl}-1,3-dihydro- imidazol-2-ylidene; SItBu = 1,3-bis(1,1-dimethylethyl-imidazolidin-2-ylidene were prepared and structurally characterized, allowing an estimation of the steric hindrance of such Lewis pairs (yields in 1–4: 92%, 90%, 73%, and 42%, respectively. While the IPr* adducts 1 and 2 are robust species, the more severely congested SItBu adducts 3 and 4 are more reactive and exhibit a limited stability in solution. Adduct (SItBuGaMe3 (3 reacts quickly with H2 at room temperature to afford the corresponding aminal product, 1,3-di-tert-butylimidazolidine (5, along with free GaMe3. Such Frustrated Lewis Pair (FLP reactivity constitutes the first instance of a H2 activation involving a simple trialkyl GaR3 species. Adduct 3 also mediates the ring-opening polymerization (ROP of rac-lactide at room temperature to afford cyclic polylactide (PLA.

Comparative study of PBI Cross Linked Utilizing Agents of Varying Steric Configurations

DEFF Research Database (Denmark)

Kirkebcek, Andreas; Aili, David; Li, Qingfeng

2016-01-01

ionic or covalent cross linking. When considering such, little attention is devoted to explore the effect of the sterical configuration of the cross linking agent. In this contribution three different cross linking agents are utilized to evaluate how these affects final membrane properties.......The high thermal and chemical stability of poly[2,2'-(m-phenylene)-5,5' bibenzimidazole] (PBI) accounts for its wise spread use in high temperature polymer electrolyte membrane fuel cells (HT- PEMFC). By doping the membrane with phosphoric acid (PA) ionic conductivity is obtained. Thus conductivity...... is dependent on the amount of PA present within the membrane. However mechanical properties are reduced are significantly reduced due to the plasticizing effect shown by PA [1]. This effect is due to PBI chain displacement. This effect can be lessened by use of cross linking [2-4]. This can be obtained using...

Modeling water flux and salt rejection of mesoporous γ-alumina and microporous organosilica membranes

NARCIS (Netherlands)

Farsi, A.; Boffa, V.; Qureshi, H.F.; Nijmeijer, Arian; Winnubst, Aloysius J.A.; Lykkegaard Christensen, M.

2014-01-01

The water and ion transport through a mesoporous γ-alumina membrane and a microporous organosilica membrane was simulated using the extended Nernst Planck equation combined with models for Donnan, steric and dielectric interfacial exclusion mechanisms. Due to the surface charge within the pore, the

Effect of Gamma and Electron Beam Irradiation on Textile Waste Water

International Nuclear Information System (INIS)

Selambakkannu, S.; Khomsaton Abu Bakar; Ting, T.M.

2011-01-01

In this studies gamma and electron beam irradiation was used to treat textile waste water. Comparisons between both types of irradiation in terms of effectiveness to degrade the pollutants present in textile waste water was done. Prior to irradiation, the raw wastewater was diluted using distilled water to a target concentration of COD 400 mg/l. The sample was irradiated at selected doses between the ranges of 10 kGy to 100 kGy. The results showed that irradiation has significantly contributed in the reduction of the highly colored refractory organic pollutants. The COD removal at the lowest dose, 10 kGy, was reduced to 390 mg/l for gamma and 400 mg/l for electron beam. Meanwhile, at the highest dose, 100 kGy, the COD was reduced to 125 mg/l for gamma and 144 mg/l for electron beam. The degree of removal is influenced by the dose introduced during the treatment process. As the dose increased, the higher the removal of organic pollutant was recorded. However, gamma irradiation is more effective although the differences are not significant between gamma and electron beam irradiation. On the other hand, other properties of the wastewater such as pH, turbidity, suspended solid, BOD and color also shows a gradual decrease as the dose increases for both types of irradiation. (author)

Use of an Electronic Tongue System and Fuzzy Logic to Analyze Water Samples

Science.gov (United States)

Braga, Guilherme S.; Paterno, Leonardo G.; Fonseca, Fernando J.

2009-05-01

An electronic tongue (ET) system incorporating 8 chemical sensors was used in combination with two pattern recognition tools, namely principal component analysis (PCA) and Fuzzy logic for discriminating/classification of water samples from different sources (tap, distilled and three brands of mineral water). The Fuzzy program exhibited a higher accuracy than the PCA and allowed the ET to classify correctly 4 in 5 types of water. Exception was made for one brand of mineral water which was sometimes misclassified as tap water. On the other hand, the PCA grouped water samples in three clusters, one with the distilled water; a second with tap water and one brand of mineral water, and the third with the other two other brands of mineral water. Samples in the second and third clusters could not be distinguished. Nevertheless, close grouping between repeated tests indicated that the ET system response is reproducible. The potential use of the Fuzzy logic as the data processing tool in combination with an electronic tongue system is discussed.

A structural study of [CpM(CO)3H] (M = Cr, Mo and W) by single-crystal X-ray diffraction and DFT calculations: sterically crowded yet surprisingly flexible molecules.

Science.gov (United States)

Burchell, Richard P L; Sirsch, Peter; Decken, Andreas; McGrady, G Sean

2009-08-14

The single-crystal X-ray structures of the complexes [CpCr(CO)3H] 1, [CpMo(CO)3H] 2 and [CpW(CO)3H] 3 are reported. The results indicate that 1 adopts a structure close to a distorted three-legged piano stool geometry, whereas a conventional four-legged piano stool arrangement is observed for 2 and 3. Further insight into the equilibrium geometries and potential energy surfaces of all three complexes was obtained by DFT calculations. These show that in the gas phase complex 1 also prefers a geometry close to a four-legged piano stool in line with its heavier congeners, and implying strong packing forces at work for 1 in the solid state. Comparison with their isolelectronic group 7 tricarbonyl counterparts [CpM(CO)3] (M = Mn 4 and Re 5) illustrates that 1, 2 and 3 are sterically crowded complexes. However, a surprisingly soft bending potential is evident for the M-H moiety, whose order (1 approximately = 2 < 3) correlates with the M-H bond strength rather than with the degree of congestion at the metal centre, indicating electronic rather than steric control of the potential. The calculations also reveal cooperative motions of the hydride and carbonyl ligands in the M(CO)3H unit, which allow the M-H moiety to move freely, in spite of the closeness of the four basal ligands, helping to explain the surprising flexibility of the crowded coordination sphere observed for this family of high CN complexes.

Ceramic membrane fouling during ultrafiltration of oil/water emulsions: roles played by stabilization surfactants of oil droplets.

Science.gov (United States)

Lu, Dongwei; Zhang, Tao; Ma, Jun

2015-04-07

Oil/water (O/W) emulsion stabilized by surfactants is the part of oily wastewater that is most difficult to handle. Ceramic membrane ultrafiltration presently is an ideal process to treat O/W emulsions. However, little is known about the fouling mechanism of the ceramic membrane during O/W emulsion treatment. This paper investigated how stabilization surfactants of O/W emulsions influence the irreversible fouling of ceramic membranes during ultrafiltration. An unexpected phenomenon observed was that irreversible fouling was much less when the charge of the stabilization surfactant of O/W emulsions is opposite to the membrane. The less ceramic membrane fouling in this case was proposed to be due to a synergetic steric effect and demulsification effect which prevented the penetration of oil droplets into membrane pores and led to less pore blockage. This proposed mechanism was supported by cross section images of fouled and virgin ceramic membranes taken with scanning electron microscopy, regression results of classical fouling models, and analysis of organic components rejected by the membrane. Furthermore, this mechanism was also verified by the existence of a steric effect and demulsification effect. Our finding suggests that ceramic membrane oppositely charged to the stabilization surfactant should be applied in ultrafiltration of O/W emulsions to alleviate irreversible membrane fouling. It could be a useful rule for ceramic membrane ultrafiltration of oily wastewater.

Ceramic membrane fouling during ultrafiltration of oil/water emulsions: Roles played by stabilization surfactants of oil droplets

KAUST Repository

Lu, Dongwei

2015-04-07

Oil/water (O/W) emulsion stabilized by surfactants is the part of oily wastewater that is most difficult to handle. Ceramic membrane ultrafiltration presently is an ideal process to treat O/W emulsions. However, little is known about the fouling mechanism of the ceramic membrane during O/W emulsion treatment. This paper investigated how stabilization surfactants of O/W emulsions influence the irreversible fouling of ceramic membranes during ultrafiltration. An unexpected phenomenon observed was that irreversible fouling was much less when the charge of the stabilization surfactant of O/W emulsions is opposite to the membrane. The less ceramic membrane fouling in this case was proposed to be due to a synergetic steric effect and demulsification effect which prevented the penetration of oil droplets into membrane pores and led to less pore blockage. This proposed mechanism was supported by cross section images of fouled and virgin ceramic membranes taken with scanning electron microscopy, regression results of classical fouling models, and analysis of organic components rejected by the membrane. Furthermore, this mechanism was also verified by the existence of a steric effect and demulsification effect. Our finding suggests that ceramic membrane oppositely charged to the stabilization surfactant should be applied in ultrafiltration of O/W emulsions to alleviate irreversible membrane fouling. It could be a useful rule for ceramic membrane ultrafiltration of oily wastewater. © 2015 American Chemical Society.

Ozone/electron beam process for water treatment: design, limitations and economic considerations

International Nuclear Information System (INIS)

Gehringer, P.; Eschweiler, H.

1996-01-01

Electron beam irradiation of water is the easiest way to generate OH free radicals but the efficiency of the irradiation process as advanced oxidation process (AOP) is deteriorated by reducing species formed simultaneously with the OH free radicals. Addition of ozone to the water before or during irradiation improves the efficiency essentially by converting the reducing species into OH free radicals and turning by that the irradiation process into a full AOP. The main reaction pathways of the primary species formed by the action of ionizing radiation on water in a natural groundwater with and without the presence of ozone are reviewed. Based on these data an explanation of both the dose rate effect and the ozone effect is attempted. New data is presented which illustrates the effect of alkalinity on the way in which ozone is introduced into the water, and the impact of both water matrix and chemical structure of the pollutants to the efficacy of the ozone/electron beam process. (author)

Black sea annual and inter-annual water mass variations from space

DEFF Research Database (Denmark)

Yildiz, H.; Andersen, Ole Baltazar; Simav, M.

2011-01-01

influenced by the leakage of hydrological signals from the surrounding land. After applying the corresponding correction, we found a good agreement with water mass variations derived from steric-corrected satellite altimetry observations. Both GRACE and altimetry show significant annual water mass variations......This study evaluates the performance of two widely used GRACE solutions (CNES/GRGS RL02 and CSR RL04) in deriving annual and inter-annual water mass variations in the Black Sea for the period 2003–2007. It is demonstrated that the GRACE derived water mass variations in the Black Sea are heavily...

Degradation of pollutants and elimination of pathogens of waste water by adsorption of accelerated electrons

International Nuclear Information System (INIS)

Martinez M, I.

1991-10-01

This report presents a position of the pollutants degradation of the industrial residual waters, it intends a method that consists on making pass residual water, treated biologically by a packed column with activated carbon. The carbon retains the pollutants and the water goes out with a purity that allows the reuse. In simultaneous form to the adsorption of pollutants are made pass electrons through the column of carbon, the electrons will destroy to the polluting adsorbed in the carbon; the pollutants degrade until CO 2 that escapes as gas. The active sites of the carbon are empty and clever to be occupied by other pollutants. This process is continuous and it is repeated while water is passing by the column and electrons through this. (Author)

Electron beam absorption in solid and in water phantoms: depth scaling and energy-range relations

International Nuclear Information System (INIS)

Grosswendt, B.; Roos, M.

1989-01-01

In electron dosimetry energy parameters are used with values evaluated from ranges in water. The electron ranges in water may be deduced from ranges measured in solid phantoms. Several procedures recommended by national and international organisations differ both in the scaling of the ranges and in the energy-range relations for water. Using the Monte Carlo method the application of different procedures for electron energies below 10 MeV is studied for different phantom materials. It is shown that deviations in the range scaling and in the energy-range relations for water may accumulate to give energy errors of several per cent. In consequence energy-range relations are deduced for several solid phantom materials which enable a single-step energy determination. (author)

Evaluation of two water-equivalent phantom materials for output calibration of photon and electron beams

International Nuclear Information System (INIS)

Liu Lizhong; Prasad, Satish C.; Bassano, Daniel A.

2003-01-01

Two commercially available water-equivalent solid phantom materials were evaluated for output calibration in both photon (6-15 MV) and electron (6-20 MeV) beams. The solid water 457 and virtual water materials have the same chemical composition but differ in manufacturing process and density. A Farmer-type ionization chamber was used for measuring the output of the photon beams at 5- and 10-cm depth and electron beams at maximum buildup depth in the solid phantoms and in natural water. The water-equivalency correction factor for the solid materials is defined as the ratio of the chamber reading in natural water to that in the solid at the same linear depth. For photon beams, the correction factor was found to be independent of depth and was 0.987 and 0.993 for 6- and 15-MV beams, respectively, for solid water. For virtual water, the corresponding correction factors were 0.993 and 0.998 for 6- and 15-MV beams, respectively. For electron beams, the correction factors ranged from 1.013 to 1.007 for energies of 6 to 20 MeV for both solid materials. This indicated that the water-equivalency of these materials is within ± 1.3%, making them suitable substitutes for natural water in both photon and electron beam output measurements over a wide energy range. These correction factors are slightly larger than the manufacturers' advertised values (± 1.0% for solid water and ± 0.5% for virtual water). We suggest that these corrections are large enough in most cases and should be applied in the calculation of beam outputs

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

Science.gov (United States)

Naghavi, S Shahab; Emery, Antoine A; Hansen, Heine A; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

Dynamic Low-Vacuum Scanning Electron Microscope Freeze Drying Observation for Fresh Water Algae

International Nuclear Information System (INIS)

Mohsen, H.T.; Ghaly, W.A.; Zahran, N.F.; Helal, A.I.

2010-01-01

A new perpetration method for serving in dynamic examinations of the fresh water algae is developed in connection with the Low-Vacuum Scanning Electron Microscope (LV-SEM) freeze drying technique. Specimens are collected from fresh water of Ismailia channel then transferred directly to freeze by liquid nitrogen and dried in the chamber of the scanning electron microscope in the low vacuum mode. Scanning electron micrographs revealed that the drying method presented the microstructure of algae. Dehydration in a graded ethanol series is not necessary in the new method. Dried algae specimen is observed in SEM high vacuum mode after conductive coating at higher resolution. Low-vacuum SEM freeze drying technique is a simple, time-saving and reproducible method for scanning electron microscopy that is applicable to various aquatic microorganisms covered with soft tissues.

Water soluble and metal-containing electron beam resist poly(sodium 4-styrenesulfonate)

International Nuclear Information System (INIS)

Abbas, Arwa Saud; Alqarni, Sondos; Shokouhi, Babak Baradaran; Yavuz, Mustafa; Cui, Bo

2014-01-01

Popular electron beam resists such as PMMA, ZEP and HSQ all use solvent or base solutions for processing, which may attack the sub-layers or substrate that are made out of organic semiconducting materials. In this study we show that water soluble poly(sodium 4-styrenesulfonate), or sodium PSS, can be used as a negative electron beam resist developed in water. Moreover, since PSS contains metal sodium, its dry etching resistance is much higher than PMMA. It is notable that sodium PSS’s sensitivity and contrast is still far inferior to organic resists such as PMMA, thus it is not suitable for patterning dense and high-resolution structures. Nevertheless, feature size down to 40 nm was achieved for sparse patterns. Lastly, using very low energy (here 2 keV) electron beam lithography and liftoff process using water only, patterning of metal layer on an organic conductive material P3HT was achieved. The metallization of an organic conducting material may find applications in organic semiconductor devices such as OLED. (paper)

The HKS model for electron production in liquid water by light ions

International Nuclear Information System (INIS)

Bernal, M.A.; Liendo, J.A.

2006-01-01

The HKS model developed to determine ionization cross sections (ICS) for the interaction of non-relativistic ions with matter, is used for 0.5 MeV protons impinging on liquid water and some inconsistencies between the single (SDCS) and double (DDCS) differential cross section values predicted by the formalism are found. To overcome this problem, new SDCS and DDCS formulas are determined analytically by use of the transition probabilities published by Hansen and Kocbach [J.P. Hansen, L. Kocbach, J. Phys. B 22 (1989) L71]. The new cross section expressions applied to the 0.5 MeV proton on liquid water case, give perfectly consistent SDCS and DDCS values. Furthermore, SDCS and DDCS values predicted from the new formulas for ionization of liquid water by protons (0.5-4.2 MeV/u) and alpha particles (0.3-0.5 MeV/u) are compared with corresponding experimental cross section values reported in the literature for water vapor ionization. Despite of the simplicity of the HKS model, accurate secondary electron energy distributions can be obtained, even for electron energies as low as 10 eV. Although the same accuracy cannot be achieved for electron angular distributions, the HKS formalism can still be used when these distributions are not critical

Inversion of electron-water elastic scattering data

International Nuclear Information System (INIS)

Lun, A.; Chen, X.J.; Allen, L.J.; Amos, K.

1994-01-01

Fixed energy inverse scattering theory has been used to analyse the differential cross-sections for the elastic scattering of electrons from water molecules. Both semiclassical (WKB) and fully quantal inversion methods have been used with data taken in the energy range 100 to 1000 eV. Constrained to be real, the local inversion potentials are found to be energy dependent; a dependence that can be interpreted as the local equivalence of true nonlocality in the actual interaction. 14 refs., 4 tabs., 8 figs

Direct access to highly crystalline mesoporous nano TiO2 using sterically bulky organic acid templates

Science.gov (United States)

Bakre, Pratibha V.; Tilve, S. G.

2018-05-01

Sterically bulky monocarboxylic acid templates pivalic acid and phenoxyacetic acid are reported for the first time as organic templates in the sol-gel synthesis of TiO2. Mesoporous nanoparticulates of pure anatase phase and of well defined size were synthesized. The characterization of the materials prepared was done by various methods such as XRD, SEM, TEM, FTIR, UV-DRS, BET, etc. The prepared TiO2 samples were evaluated for the day light photodegradation of methylene blue by comparing with Degussa P25 and templates free synthesized TiO2 and were found to be more efficient.

Nanometer-resolution electron microscopy through micrometers-thick water layers

Energy Technology Data Exchange (ETDEWEB)

Jonge, Niels de, E-mail: niels.de.jonge@vanderbilt.edu [Vanderbilt University Medical Center, Department of Molecular Physiology and Biophysics, Nashville, TN 37232-0615 (United States); Oak Ridge National Laboratory, Materials Science and Technology Division, Oak Ridge, TN 37831-6064 (United States); Poirier-Demers, Nicolas; Demers, Hendrix [Universite de Sherbrooke, Electrical and Computer Engineering, Sherbrooke, Quebec J1K 2R1 (Canada); Peckys, Diana B. [Oak Ridge National Laboratory, Materials Science and Technology Division, Oak Ridge, TN 37831-6064 (United States); University of Tennessee, Center for Environmental Biotechnology, Knoxville, TN 37996-1605 (United States); Drouin, Dominique [Universite de Sherbrooke, Electrical and Computer Engineering, Sherbrooke, Quebec J1K 2R1 (Canada)

2010-08-15

Scanning transmission electron microscopy (STEM) was used to image gold nanoparticles on top of and below saline water layers of several micrometers thickness. The smallest gold nanoparticles studied had diameters of 1.4 nm and were visible for a liquid thickness of up to 3.3 {mu}m. The imaging of gold nanoparticles below several micrometers of liquid was limited by broadening of the electron probe caused by scattering of the electron beam in the liquid. The experimental data corresponded to analytical models of the resolution and of the electron probe broadening as function of the liquid thickness. The results were also compared with Monte Carlo simulations of the STEM imaging on modeled specimens of similar geometry and composition as used for the experiments. Applications of STEM imaging in liquid can be found in cell biology, e.g., to study tagged proteins in whole eukaryotic cells in liquid and in materials science to study the interaction of solid:liquid interfaces at the nanoscale.

Quantitative Determination of Spring Water Quality Parameters via Electronic Tongue

Directory of Open Access Journals (Sweden)

Noèlia Carbó

2017-12-01

Full Text Available The use of a voltammetric electronic tongue for the quantitative analysis of quality parameters in spring water is proposed here. The electronic voltammetric tongue consisted of a set of four noble electrodes (iridium, rhodium, platinum, and gold housed inside a stainless steel cylinder. These noble metals have a high durability and are not demanding for maintenance, features required for the development of future automated equipment. A pulse voltammetry study was conducted in 83 spring water samples to determine concentrations of nitrate (range: 6.9–115 mg/L, sulfate (32–472 mg/L, fluoride (0.08–0.26 mg/L, chloride (17–190 mg/L, and sodium (11–94 mg/L as well as pH (7.3–7.8. These parameters were also determined by routine analytical methods in spring water samples. A partial least squares (PLS analysis was run to obtain a model to predict these parameter. Orthogonal signal correction (OSC was applied in the preprocessing step. Calibration (67% and validation (33% sets were selected randomly. The electronic tongue showed good predictive power to determine the concentrations of nitrate, sulfate, chloride, and sodium as well as pH and displayed a lower R2 and slope in the validation set for fluoride. Nitrate and fluoride concentrations were estimated with errors lower than 15%, whereas chloride, sulfate, and sodium concentrations as well as pH were estimated with errors below 10%.

Understanding the Role of Water on Electron-Initiated Processes and Radical Chemistry

Energy Technology Data Exchange (ETDEWEB)

Garrett, Bruce C [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Colson, Steven D [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Laufer, Allan H [US Department of Energy Office of Science Office of Basic Energy Sciences; Ray, Douglas [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2003-06-10

On September 26–28, 2002, a workshop entitled “Understanding the Role of Water on Electron-Initiated Processes and Radical Chemistry” was held to assess new research opportunities in electron-driven processes and radical chemistry in aqueous systems. Of particular interest was the unique and complex role that the structure of water plays in influencing these processes. Novel experimental and theoretical approaches to solving long-standing problems in the field were explored. A broad selection of participants from universities and the national laboratories contributed to the workshop, which included scientific and technical presentations and parallel sessions for discussions and report writing.

Steric congestion at, and proximity to, a ferrous center leads to hydration of α-nitrile substituents forming coordinated carboxamides.

Science.gov (United States)

Thallaj, Nasser K; Orain, Pierre-Yves; Thibon, Aurore; Sandroni, Martina; Welter, Richard; Mandon, Dominique

2014-08-04

The question of the conversion of nitrile groups into amides (nitrile hydration) by action of water in mild and eco-compatible conditions and in the presence of iron is addressed in this article. We come back to the only known example of hydration of a nitrile function into carboxamide by a ferrous [Fe(II)] center in particularly mild conditions and very efficiently and demonstrate that these unusual conditions result from the occurrence of steric stress at the reaction site and formation of a more stable end product. Two bis(cyano-substituted) (tris 2-pyridyl methyl amine) ligands have been prepared, and the structures of the corresponding FeCl2 complexes are reported, both in the solid state and in solution. These two ligands only differ by the position of the nitrile group on the tripod in the α and β position, respectively, with respect to the pyridine nitrogen. In any case, intramolecular coordination is impossible. Upon action of water, the nitrile groups are hydrated however only if they are located in the α position. The fact that the β-substituted β-(NC)2TPAFeCl2 complex is not water sensitive suggests that the reaction proceeds in an intramolecular way at the vicinity of the metal center. In the bis α-substituted α-(NC)2TPAFeCl2 complex, both functions are converted in a very clean fashion, pointing out that this complex exhibits ligand flexibility and is not deactivated after the first hydration. At a preparative scale, this reaction allows the one-pot conversion of the bis(cyano-substituted) tripod into a bis(amido-substituted) one in particularly mild conditions with a very good yield. Additionally, the XRD structure of a ferric compound in which the two carboxamido ligands are bound to the metal in a seven-coordinate environment is reported.

A voltammetric electronic tongue as tool for water quality monitoring in wastewater treatment plants.

Science.gov (United States)

Campos, Inmaculada; Alcañiz, Miguel; Aguado, Daniel; Barat, Ramón; Ferrer, José; Gil, Luis; Marrakchi, Mouna; Martínez-Mañez, Ramón; Soto, Juan; Vivancos, José-Luis

2012-05-15

The use of a voltammetric electronic tongue as tool for the prediction of concentration levels of certain water quality parameters from influent and effluent wastewater from a Submerged Anaerobic Membrane Bioreactor pilot plant applied to domestic wastewater treatment is proposed here. The electronic tongue consists of a set of noble (Au, Pt, Rh, Ir, and Ag) and non-noble (Ni, Co and Cu) electrodes that were housed inside a stainless steel cylinder which was used as the body of the electronic tongue system. As a previous step an electrochemical study of the response of the ions sulphate, orthophosphate, acetate, bicarbonate and ammonium was carried out in water using the electrodes contained in the electronic tongue. The second part of the work was devoted to the application of the electronic tongue to the characterization of the influent and effluent waters from the wastewater treatment plant. Partial Least Squares analysis was used to obtain a correlation between the data from the tongue and the pollution parameters measured in the laboratory such as soluble chemical oxygen demand (CODs), soluble biological oxygen demand (BODs), ammonia (NH(4)-N), orthophosphate (PO(4)-P), Sulphate (SO(4)-S), acetic acid (HAC) and alkalinity (Alk). A total of 28 and 11 samples were used in the training and the validation steps, respectively, for both influent and effluent water samples. The electronic tongue showed relatively good predictive power for the determination of BOD, COD, NH(4)-N, PO(4)-P, SO(4)-S, and Alk. Copyright © 2012 Elsevier Ltd. All rights reserved.

Primary processes of the electron-protic species coupling in pure aqueous phases: - femtosecond laser spectroscopy study; - quantum approach of the electron-water interaction

International Nuclear Information System (INIS)

Pommeret, Stanislas

1991-01-01

This thesis work deals with the coupling mechanisms between an electron, water molecules or protic species (hydronium ion, hydroxyl radical). Two complementary studies have been carry out in pure aqueous phases. The first one is concerned with the structural aspect of the hydrated electron which is studied via a semi-quantum approach Splitting Operator Method. The results indicates the importance of the second hydration shell in the localisation of an electron at 77 and 300 Kelvin. The second part of this work relates to the dynamic of the primary processes in light or heavy water at room temperature: the ion-molecule reaction, radical pair formation, geminate recombination of the hydrated electron with the hydronium ion and the hydroxyl radical. The dynamic of these reactions is studied by time resolved absorption spectroscopy from the near infrared to the near ultraviolet with a few tens femto-seconds temporal precision. The analysis of the primary processes takes into account the protic properties of water molecules. (author) [fr

Time Resolved Broadband Terahertz Relaxation Dynamics of Electron in Water

DEFF Research Database (Denmark)

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

We investigated the transient response of the solvated electron in water ejected by photodetachment from potassium ferrocyanide using time resolved terahertz spectroscopy (TSTS). Ultrabroadband THz transients are generated and detected by a two-color femtosecond-induced air plasma and air biased...

Quantum mechanical force field for water with explicit electronic polarization.

Science.gov (United States)

Han, Jaebeom; Mazack, Michael J M; Zhang, Peng; Truhlar, Donald G; Gao, Jiali

2013-08-07

A quantum mechanical force field (QMFF) for water is described. Unlike traditional approaches that use quantum mechanical results and experimental data to parameterize empirical potential energy functions, the present QMFF uses a quantum mechanical framework to represent intramolecular and intermolecular interactions in an entire condensed-phase system. In particular, the internal energy terms used in molecular mechanics are replaced by a quantum mechanical formalism that naturally includes electronic polarization due to intermolecular interactions and its effects on the force constants of the intramolecular force field. As a quantum mechanical force field, both intermolecular interactions and the Hamiltonian describing the individual molecular fragments can be parameterized to strive for accuracy and computational efficiency. In this work, we introduce a polarizable molecular orbital model Hamiltonian for water and for oxygen- and hydrogen-containing compounds, whereas the electrostatic potential responsible for intermolecular interactions in the liquid and in solution is modeled by a three-point charge representation that realistically reproduces the total molecular dipole moment and the local hybridization contributions. The present QMFF for water, which is called the XP3P (explicit polarization with three-point-charge potential) model, is suitable for modeling both gas-phase clusters and liquid water. The paper demonstrates the performance of the XP3P model for water and proton clusters and the properties of the pure liquid from about 900 × 10(6) self-consistent-field calculations on a periodic system consisting of 267 water molecules. The unusual dipole derivative behavior of water, which is incorrectly modeled in molecular mechanics, is naturally reproduced as a result of an electronic structural treatment of chemical bonding by XP3P. We anticipate that the XP3P model will be useful for studying proton transport in solution and solid phases as well as across

Studing electronic structure of water molecules in aquocomplexes by the method of pions minus capture by hydrogen

International Nuclear Information System (INIS)

Dezhi, I.; Krumshtejn, Z.V.; Molnar, B.; Petrukhin, V.I.; Rybakov, V.N.; Suvorov, V.M.; Khorvat, D.; Tsisek, Z.; Yutlandov, I.A.

1980-01-01

Using the effect of electron shell state on π-meson capture by chemically bound hydrogen studied has been change of electron density in hydrogen atoms of water molecules bound into aquocomplexes. The fact of depression of π-meson capture probability by hydrogen of water in aquocomplexes has been established. The magnitudes of depression indicate essential decrease of electron density in a hydrogen atom of coordinated water. Interaction of ligands with oxygen-containing anions also essentially contributes to a magnitude of depression

Two-state model of excess electron relaxation and geminate recombination in water and aqueous solutions

International Nuclear Information System (INIS)

Fedorenko, S.G.

2010-01-01

Graphical abstract: After photo-induced ionization a free electron suffers a quick conversion to a solvated state, and then recombines with the parent atom or ion. However, high mobility and reactivity of a free electron can allow the electron to delocalize and recombine in the free state. The theory of two channel processes of geminate electron recombination is developed and applied to the experiment of three-pulse generation of excess electrons in water. - Abstract: After photo-induced ionization a free electron suffers a quick conversion to a solvated state, and then can recombine with the parent atom or ion. However, high mobility and reactivity of a free electron can allow the electron to delocalize and recombine in the free state. The theory of two channel processes of geminate electron recombination is developed here for the general type of the Markovian motion of reactants. A contact model is used for analytical solution of the problem of geminate recombination of neutral and charged reactants. The theory is applied to the experiment of three-pulse generation of excess electrons in water.

Advanced Oxidation Treatment of Drinking Water and Wastewater Using High-energy Electron Beam Irradiation

Directory of Open Access Journals (Sweden)

Abbas Behjat

2007-03-01

Full Text Available Application of electron beam as a strong oxidation method for disinfection of drinking water and wastewater has been investigated. Drinking water samples were prepared from wells in rock zones in Yazd Province. Wastewater samples were collected from Yazd Wastewater Treatment Plant. Samples were irradiated by 10 MeV electron beam accelerator at Yazd Radiation Processing Center. The irradiation dose range varied from 0.5-5 kGy. Biological parameters and microbial agents such as aerobic mesophiles and coliforms including E. coli count before and after irradiation versus irradiation dose were obtained using MPN method. The data obtained from irradiated water and wastewater were compared with un-irradiated (control samples. The results showed a removal of 90% of all microorganisms at irradiation doses below 5 kGy, suggesting electron beam irradiation as an effective method for disinfection of wastewater.

Effect of electron beam irradiation on fisheries water

International Nuclear Information System (INIS)

Sarala Selambakkannu; Khomsaton Abu Bakar; Jamaliah Shariff; Suhairi Alimon

2012-01-01

This paper studies about water obtained from fish pond of fisheries research centre. Usual water quality parameters such as pH, COD, Turbidity and Ammonia content were analyzed before and after irradiation. Electron beam irradiation was used to irradiate the water with the dose 100 kGy, 200 kGy and 300 kGy. Only high dose was applied on this water as only a limited amount of samples was supplied. All the parameters indicated a slight increase after irradiation except for the ammonia content, which showed a gradual decrease as irradiation dose increases. Sample condition was changed before irradiation in order to obtain more effective results in the following batch. The water sample from fisheries was diluted with distilled water to the ratio of 1:1.This was followed with irradiation at 100 kGy, 200 kGy and 300 kGy. The results still showed an increase in all parameters after irradiation except for ammonia content. For the following irradiation batch, the pH of the sample was adjusted to pH 4 and pH 8 before irradiation. For this sample the irradiation dose selected was only 100 kGy. A higher value of ammonia was observed for the sample with pH 4 after irradiation. Other parameters were almost the same as the first two batches. (author)

Electron driven water formation from oxyhydrogen clusters in superfluid helium nanodroplets

International Nuclear Information System (INIS)

Renzler, Michael; Kranabetter, Lorenz; Barwa, Erik; Scheier, Paul; Illenberger, Eugen

2015-01-01

Helium nanodroplets provide an enviroment that allow studies of chemical reactions at ultracold temperatures. We use these droplets as a matrix to study the formation of water upon electron bombardment of oxyhydrogen clusters (paper)

Disinfection of sludge and waste-water by irradiation with electrons of low accelerating voltage

International Nuclear Information System (INIS)

Holl, P.; Schneider, H.

1975-01-01

From the point of view of hygiene, sewage sludge and water accumulating in ever increasing quantities, some of which is used in agriculture, represent a potential threat to the health of man and beast, as well as to the environment. It is known that these chains of infection can be broken up by ionizing radiation. The use of natural ionizing radiation or electron radiation with high accelerating voltage has not been accepted in practice because the radiation cannot be cut off and the investment cost for electron accelerators with an accelerating voltage of more than 1 MV is very high. These disadvantages may be overcome by using an electron accelerator with low accelerating voltage. Complex experiments have shown that it is not necessary to adapt the thickness of sewage sludge or water layer to the range of electrons. The layer to be irradiated may be much thicker if the substrate is revolved during irradiation. The advantages of this method are low accelerating voltage for the electrons and hence less costly radiation shielding, complete absorption of the radiated energy by the substrate, and low investment and operating cost. The sterilizing effect of the process can be explained by the secondary reactions that take place in the water, in addition to the primary reactions, when irradiating with high specific ionizing density. It is known from experiments carried out by Muenzner that water irradiated with electrons of high specific ionization density, when added to bacterial cultures, will destroy them. This is explained by the Weiss radical theory of water, with reaction products such as H 2 , O 2 and H 2 O 2 . The success of this process is shown by experiments with Escherichia coli, tap water to which Salmonella senftenberg were added, and by the content of Enterobacteriaceae in various sludges as a function of the irradiation period, as well as by the rate at which various invariable species of strongilide larvae, eggs of Ascaris suum, Fasciola hepatica and

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

OXYGEN 18 EXCHANGE REACTIONS OF ALDEHYDES AND KETONES

Energy Technology Data Exchange (ETDEWEB)

Byrn, Marianne; Calvin, Melvin

1965-12-01

Using infra-red spectroscopy, the equilibrium exchange times have been determined for a series of ketones, aromatic aldehydes, and {beta}-ketoesters reacting with oxygen 18 enriched water. These exchange times have been evaluated in terms of steric and electronic considerations, and applied to a discussion of the exchange times of chlorophylls a and b and chlorophyll derivatives.

An unusually stable chlorophosphite: What makes BIFOP–Cl so robust against hydrolysis?

Directory of Open Access Journals (Sweden)

Roberto Blanco Trillo

2015-03-01

Full Text Available Two chlorophosphites, the biphenyl-based BIFOP–Cl and the diphenyl ether-based O–BIFOP–Cl, exhibit striking differences regarding their reaction with water. While BIFOP–Cl is nearly completely unreactive, its oxo-derivative O–BIFOP–Cl reacts instantly with water, yielding a tricyclic hydrocarbon unit after rearrangement. The analysis of the crystal structure of O–BIFOP–Cl and BIFOP–Cl revealed that the large steric demand of encapsulating fenchane units renders the phosphorus atom nearly inaccessible by nucleophilic reagents, but only for BIFOP–Cl. In addition to the steric effect, a hypervalent P(III–O interaction as well as an electronic conjugation effect causes the high reactivity of O–BIFOP–Cl. A DFT study of the hydrolysis in BIFOP–Cl verifies a higher repulsive interaction to water and a decreased leaving tendency of the chloride nucleofuge, which is caused by the fenchane units. This high stability of BIFOP–Cl against nucleophiles supports its application as a chiral ligand, for example, in Pd catalysts.

Monte Carlo electron-photon transport using GPUs as an accelerator: Results for a water-aluminum-water phantom

Energy Technology Data Exchange (ETDEWEB)

Su, L.; Du, X.; Liu, T.; Xu, X. G. [Nuclear Engineering Program, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States)

2013-07-01

An electron-photon coupled Monte Carlo code ARCHER - Accelerated Radiation-transport Computations in Heterogeneous Environments - is being developed at Rensselaer Polytechnic Institute as a software test bed for emerging heterogeneous high performance computers that utilize accelerators such as GPUs. In this paper, the preliminary results of code development and testing are presented. The electron transport in media was modeled using the class-II condensed history method. The electron energy considered ranges from a few hundred keV to 30 MeV. Moller scattering and bremsstrahlung processes above a preset energy were explicitly modeled. Energy loss below that threshold was accounted for using the Continuously Slowing Down Approximation (CSDA). Photon transport was dealt with using the delta tracking method. Photoelectric effect, Compton scattering and pair production were modeled. Voxelised geometry was supported. A serial ARHCHER-CPU was first written in C++. The code was then ported to the GPU platform using CUDA C. The hardware involved a desktop PC with an Intel Xeon X5660 CPU and six NVIDIA Tesla M2090 GPUs. ARHCHER was tested for a case of 20 MeV electron beam incident perpendicularly on a water-aluminum-water phantom. The depth and lateral dose profiles were found to agree with results obtained from well tested MC codes. Using six GPU cards, 6x10{sup 6} histories of electrons were simulated within 2 seconds. In comparison, the same case running the EGSnrc and MCNPX codes required 1645 seconds and 9213 seconds, respectively, on a CPU with a single core used. (authors)

Bacillus cereus as indicator in the sterilization of residual water with high energy electrons

International Nuclear Information System (INIS)

Mejia Z, E.

2000-01-01

One of the main causes of water pollution is the presence of microorganisms that provoke infections, moreover of chemical substances. The processes of residual water treatment finally require of the disinfection for its use or final disposition. The radiation technology for the residual water treatment by mean of electron beams is an innovator process because as well as decomposing the chemical substance or to degrade them, also it provokes a disinfection by which this is proposed as alternative for disinfection of residual water, with the purpose in reusing the water treated in the agriculture, recreation and industry among others secondary activities, solving environmental or health problems. The objective of this work is to evaluate the use of Bacillus cereus as biological indicator in the disinfection by radiation, using High Energy Electrons. To fulfil with this objective, the work was developed in three stages, the first one consisted in the acquisition, propagation and conservation of the Bacillus cereus stumps, considering Escherichia coli and Salmonella typhimurium as pathogenic germs present in residual water. Moreover, the inocule standardization and the conditions of the Electron accelerator Type Pelletron. In the second stage it was performed the irradiation of aqueous samples of the microorganisms simulating biological pollution and the application to problem samples of a treatment plant sited in the Lerma River zone of mixed residual water. And in the third stage was performed a regression analysis to the reported survival for each kind of microorganisms. The results obtained show that with the use of Electron beams was reduced 6 logarithmic units de E. coli at 129 Gy, for S. typhimurium it was reduced 8 logarithmic units at 383 Gy and the B. cereus at 511 Gy was reduced 6.8 logarithmic units. Of the problem samples irradiated at 500 Gy, the concentration of the total account diminished from 8.70 x 10 7 UFC/ml to 550 UFC/ml, the presence of B. Cereus

Steric exclusion and protein conformation determine the localization of plasma membrane transporters.

Science.gov (United States)

Bianchi, Frans; Syga, Łukasz; Moiset, Gemma; Spakman, Dian; Schavemaker, Paul E; Punter, Christiaan M; Seinen, Anne-Bart; van Oijen, Antoine M; Robinson, Andrew; Poolman, Bert

2018-02-05

The plasma membrane (PM) of Saccharomyces cerevisiae contains membrane compartments, MCC/eisosomes and MCPs, named after the protein residents Can1 and Pma1, respectively. Using high-resolution fluorescence microscopy techniques we show that Can1 and the homologous transporter Lyp1 are able to diffuse into the MCC/eisosomes, where a limited number of proteins are conditionally trapped at the (outer) edge of the compartment. Upon addition of substrate, the immobilized proteins diffuse away from the MCC/eisosomes, presumably after taking a different conformation in the substrate-bound state. Our data indicate that the mobile fraction of all integral plasma membrane proteins tested shows extremely slow Brownian diffusion through most of the PM. We also show that proteins with large cytoplasmic domains, such as Pma1 and synthetic chimera of Can1 and Lyp1, are excluded from the MCC/eisosomes. We hypothesize that the distinct localization patterns found for these integral membrane proteins in S. cerevisiae arises from a combination of slow lateral diffusion, steric exclusion, and conditional trapping in membrane compartments.

Effects of water on fingernail electron paramagnetic resonance dosimetry.

Science.gov (United States)

Zhang, Tengda; Zhao, Zhixin; Zhang, Haiying; Zhai, Hezheng; Ruan, Shuzhou; Jiao, Ling; Zhang, Wenyi

2016-09-01

Electron paramagnetic resonance (EPR) is a promising biodosimetric method, and fingernails are sensitive biomaterials to ionizing radiation. Therefore, kinetic energy released per unit mass (kerma) can be estimated by measuring the level of free radicals within fingernails, using EPR. However, to date this dosimetry has been deficient and insufficiently accurate. In the sampling processes and measurements, water plays a significant role. This paper discusses many effects of water on fingernail EPR dosimetry, including disturbance to EPR measurements and two different effects on the production of free radicals. Water that is unable to contact free radicals can promote the production of free radicals due to indirect ionizing effects. Therefore, varying water content within fingernails can lead to varying growth rates in the free radical concentration after irradiation-these two variables have a linear relationship, with a slope of 1.8143. Thus, EPR dosimetry needs to be adjusted according to the water content of the fingernails of an individual. When the free radicals are exposed to water, the eliminating effect will appear. Therefore, soaking fingernail pieces in water before irradiation, as many researchers have previously done, can cause estimation errors. In addition, nails need to be dehydrated before making accurately quantitative EPR measurements. © The Author 2016. Published by Oxford University Press on behalf of The Japan Radiation Research Society and Japanese Society for Radiation Oncology.

Full scale electron beam systems for treatment of water, wastewater and medical waste

International Nuclear Information System (INIS)

Waite, T.D.; Kurucz, C.N.; Cooper, W.J.; Brown, D.

1998-01-01

High energy electron accelerators have been used in numerous applications for several decades. In the early 1980's several attempts to use electron accelerators for the disinfection of sludge proved that the technology could be used for that application. One such facility was designed, built and tested for one year at the Miami-Dade Virginia Key Wastewater Treatment Plant. The process successfully disinfected anaerobically digested sludge. However, due to changing local regulations the process was never implemented. Now this process may provide a viable alternative for the ultimate destruction of toxic and hazardous organic chemicals from water and sludges. When high energy electrons impact an aqueous solution, with or without particulate matter present, reactive transient species are formed. The three transient species of most interest are the aqueous electron, e - aq, hydrogen radical, H·, and the hydroxyl radical, ·OH. The relative concentration of these radicals in an irradiated solution of pure water is 44, 10 and 46%, respectively. The absolute concentration of the radicals is dose and water quality dependent, but is in excess of mM levels in potable, raw and secondary wastewater effluent at our facility. This paper describes the facilities at the Electron Beam Research Facility (EBRF) in Miami, FL. The accelerator is a 1.5 MeV, 50 mA insulated core transformer type. Several areas of research have been the focus of the studies with an interdisciplinary team of faculty and students in engineering and science. The areas included are, inactivation of bacteria in raw and chlorinated and unchlorinated secondary wastewater and the changes in biochemical oxygen demand and chemical oxygen demand in the raw and unchlorinated secondary wastewater. The removal of toxic chemicals has also been studied in some detail. These studies have been conducted both at the EBRF and using 60 Co gamma irradiation. To examine the effect of water quality on the destruction of the

Steric control of the donor/acceptor interface: Implications in organic photovoltaic charge generation

KAUST Repository

Holcombe, Thomas W.; Norton, Joseph E.; Rivnay, Jonathan; Woo, Claire; Goris, Ludwig J.; Piliego, Claudia; Griffini, Gianmarco; Sellinger, Alan; Bré das, Jean Luc; Salleo, Alberto; Frechet, Jean

2011-01-01

The performance of organic photovoltaic (OPV) devices is currently limited by modest short-circuit current densities. Approaches toward improving this output parameter may provide new avenues to advance OPV technologies and the basic science of charge transfer in organic semiconductors. This work highlights how steric control of the charge separation interface can be effectively tuned in OPV devices. By introducing an octylphenyl substituent onto the investigated polymer backbones, the thermally relaxed charge-transfer state, and potentially excited charge-transfer states, can be raised in energy. This decreases the barrier to charge separation and results in increased photocurrent generation. This finding is of particular significance for nonfullerene OPVs, which have many potential advantages such as tunable energy levels and spectral breadth, but are prone to poor exciton separation efficiencies. Computational, spectroscopic, and synthetic methods were combined to develop a structure-property relationship that correlates polymer substituents with charge-transfer state energies and, ultimately, device efficiencies. © 2011 American Chemical Society.

Steric control of the donor/acceptor interface: Implications in organic photovoltaic charge generation

KAUST Repository

Holcombe, Thomas W.

2011-08-10

The performance of organic photovoltaic (OPV) devices is currently limited by modest short-circuit current densities. Approaches toward improving this output parameter may provide new avenues to advance OPV technologies and the basic science of charge transfer in organic semiconductors. This work highlights how steric control of the charge separation interface can be effectively tuned in OPV devices. By introducing an octylphenyl substituent onto the investigated polymer backbones, the thermally relaxed charge-transfer state, and potentially excited charge-transfer states, can be raised in energy. This decreases the barrier to charge separation and results in increased photocurrent generation. This finding is of particular significance for nonfullerene OPVs, which have many potential advantages such as tunable energy levels and spectral breadth, but are prone to poor exciton separation efficiencies. Computational, spectroscopic, and synthetic methods were combined to develop a structure-property relationship that correlates polymer substituents with charge-transfer state energies and, ultimately, device efficiencies. © 2011 American Chemical Society.

Use of an Electronic Tongue to Detect Geosmin in Distilled Water

Science.gov (United States)

Braga, Guilherme S.; Paterno, Leonardo G.; Fonseca, Fernando J.

2011-11-01

An electronic tongue (ET) system consisting of conducting polymer sensors was employed to detect geosmin (GSM) in distilled water. GSM is a tainting compound and known to cause undesirable tastes and odors in water and aquaculture farming. Diluted solutions of GSM were prepared in distilled water at different concentrations. The electrical response (capacitance) of the sensors was analyzed using principal analysis component (PCA). The data obtained were separated into different clusters indicating a good sensibility of the ET system to this compound in distilled water. The ET showed signal saturation for concentrations higher than 300 ng.L-1. So far, the detection limit of our system is 25 ng.L-1. Nevertheless, close grouping between repeated tests indicated that the ET system response is reproducible.

Solution 1H NMR investigation of the active site molecular and electronic structures of substrate-bound, cyanide-inhibited HmuO, a bacterial heme oxygenase from Corynebacterium diphtheriae.

Science.gov (United States)

Li, Yiming; Syvitski, Ray T; Chu, Grace C; Ikeda-Saito, Masao; Mar, Gerd N La

2003-02-28

The molecular structure and dynamic properties of the active site environment of HmuO, a heme oxygenase (HO) from the pathogenic bacterium Corynebacterium diphtheriae, have been investigated by (1)H NMR spectroscopy using the human HO (hHO) complex as a homology model. It is demonstrated that not only the spatial contacts among residues and between residues and heme, but the magnetic axes that can be related to the direction and magnitude of the steric tilt of the FeCN unit are strongly conserved in the two HO complexes. The results indicate that very similar contributions of steric blockage of several meso positions and steric tilt of the attacking ligand are operative. A distal H-bond network that involves numerous very strong H-bonds and immobilized water molecules is identified in HmuO that is analogous to that previously identified in hHO (Li, Y., Syvitski, R. T., Auclair, K., Wilks, A., Ortiz de Montellano, P. R., and La Mar, G. N. (2002) J. Biol. Chem. 277, 33018-33031). The NMR results are completely consistent with the very recent crystal structure of the HmuO.substrate complex. The H-bond network/ordered water molecules are proposed to orient the distal water molecule near the catalytically key Asp(136) (Asp(140) in hHO) that stabilizes the hydroperoxy intermediate. The dynamic stability of this H-bond network in HmuO is significantly greater than in hHO and may account for the slower catalytic rate in bacterial HO compared with mammalian HO.

Structural and functional significance of water permeation through cotransporters

DEFF Research Database (Denmark)

Zeuthen, Thomas; Gorraitz, Edurne; Her, Ka

2016-01-01

Membrane transporters, in addition to their major role as specific carriers for ions and small molecules, can also behave as water channels. However, neither the location of the water pathway in the protein nor their functional importance is known. Here, we map the pathway for water and urea...... through the intestinal sodium/glucose cotransporter SGLT1. Molecular dynamics simulations using the atomic structure of the bacterial transporter vSGLT suggest that water permeates the same path as Na+ and sugar. On a structural model of SGLT1, based on the homology structure of vSGLT, we identified...... to be due to alterations in steric hindrance to water and urea, and/or changes in protein folding caused by mismatching of side chains in the water pathway. Water permeation through SGLT1 and other transporters bears directly on the structural mechanism for the transport of polar solutes through...

Multifaceted catalytic hydrogenation of amides via diverse activation of a sterically confined bipyridine-ruthenium framework.

Science.gov (United States)

Miura, Takashi; Naruto, Masayuki; Toda, Katsuaki; Shimomura, Taiki; Saito, Susumu

2017-05-16

Amides are ubiquitous and abundant in nature and our society, but are very stable and reluctant to salt-free, catalytic chemical transformations. Through the activation of a "sterically confined bipyridine-ruthenium (Ru) framework (molecularly well-designed site to confine adsorbed H 2 in)" of a precatalyst, catalytic hydrogenation of formamides through polyamide is achieved under a wide range of reaction conditions. Both C=O bond and C-N bond cleavage of a lactam became also possible using a single precatalyst. That is, catalyst diversity is induced by activation and stepwise multiple hydrogenation of a single precatalyst when the conditions are varied. The versatile catalysts have different structures and different resting states for multifaceted amide hydrogenation, but the common structure produced upon reaction with H 2 , which catalyzes hydrogenation, seems to be "H-Ru-N-H."

Electron beam water calorimetry measurements to obtain beam quality conversion factors.

Science.gov (United States)

Muir, Bryan R; Cojocaru, Claudiu D; McEwen, Malcolm R; Ross, Carl K

2017-10-01

To provide results of water calorimetry and ion chamber measurements in high-energy electron beams carried out at the National Research Council Canada (NRC). There are three main aspects to this work: (a) investigation of the behavior of ionization chambers in electron beams of different energies with focus on long-term stability, (b) water calorimetry measurements to determine absorbed dose to water in high-energy beams for direct calibration of ion chambers, and (c) using measurements of chamber response relative to reference ion chambers, determination of beam quality conversion factors, k Q , for several ion chamber types. Measurements are made in electron beams with energies between 8 MeV and 22 MeV from the NRC Elekta Precise clinical linear accelerator. Ion chamber measurements are made as a function of depth for cylindrical and plane-parallel ion chambers over a period of five years to investigate the stability of ion chamber response and for indirect calibration. Water calorimetry measurements are made in 18 MeV and 22 MeV beams. An insulated enclosure with fine temperature control is used to maintain a constant temperature (drifts less than 0.1 mK/min) of the calorimeter phantom at 4°C to minimize effects from convection. Two vessels of different designs are used with calibrated thermistor probes to measure radiation induced temperature rise. The vessels are filled with high-purity water and saturated with H 2 or N 2 gas to minimize the effect of radiochemical reactions on the measured temperature rise. A set of secondary standard ion chambers are calibrated directly against the calorimeter. Finally, several other ion chambers are calibrated in the NRC 60 Co reference field and then cross-calibrated against the secondary standard chambers in electron beams to realize k Q factors. The long-term stability of the cylindrical ion chambers in electron beams is better (always <0.15%) than plane-parallel chambers (0.2% to 0.4%). Calorimetry measurements

Steric control of redox events in organo-uranium chemistry: synthesis and characterisation of U(V) oxo and nitrido complexes

OpenAIRE

Tsoureas, Nikolaos; Kilpatrick, Alexander; Inman, Christopher; Cloke, Frederick Geoffrey

2016-01-01

The synthesis and molecular structures of a U(V) neutral terminal oxo complex and a U(V) sodium uranium nitride contact ion pair are described. The synthesis of the former is achieved by the use of tBuNCO as a mild oxygen transfer reagent, whilst that of the latter is via the reduction of NaN3. Both mono-uranium complexes are stabilised by the presence of bulky silyl substituents on the ligand framework that facilitate a 2e- oxidation of a single U(III) centre. In contrast, when steric hindra...

Water swelling properties of the electron beam irradiated PVA-g-AAc hydrogels

Energy Technology Data Exchange (ETDEWEB)

Wang, Qingguo, E-mail: qwang@qust.edu.cn [Key Laboratory of Rubber-Plastics of Ministry of Education, Qingdao University of Science and Technology, Qingdao 266042 (China); Shandong Provincial Key Laboratory of Rubber-Plastics, Qingdao 266042 (China); Zhou, Xue; Zeng, Jinxia; Wang, Jizeng [Key Laboratory of Rubber-Plastics of Ministry of Education, Qingdao University of Science and Technology, Qingdao 266042 (China)

2016-02-01

In this paper, the electron beam irradiation technology being more suitable for the industry application is explored to fabricate the acrylic acid (AAc) monomer-grafted polyvinyl alcohol (PVA-g-AAc) hydrogels. ATR-IR spectra of the PVA-g-AAc hydrogels shows an obvious absorption peak of the −C=O group at 1701 cm{sup −1}, indicating that the AAc monomers were grafted onto the PVA macromolecules. This paper also studied some effects of the mass ratio of PVA/AAc, pH of buffer solution and irradiation dosage on the water swelling properties of the electron beam irradiated PVA-g-AAc hydrogels. The water swelling ratio of PVA-g-AAc hydrogels decreases with increased irradiation dosage and mass ratio of PVA/AAc, whereas swelling ratio increases with increased pH of buffer solution and soaking time. The water-swelling behavior of PVA-g-AAc hydrogels occurred easily in an alkaline environment, particularly in a buffer solution with pH 9.2. Both PVA-g-AAc hydrogels (PVA/AAc = 1/5, w/w) irradiated with 5 kilogray (kGy) and PVA-g-AAc hydrogels (PVA/AAc = 1/1, w/w) irradiated with 15 kGy could easily absorb water and lead to high water swelling ratios (up to about 600%), which are potential candidates to meet the requirements for some biomedical applications.

Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

Science.gov (United States)

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

2017-12-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

Extraction of UO22+ by two highly sterically hindered (X1) (X2) PO(OH) extractants from an aqueous chloride phase

International Nuclear Information System (INIS)

Mason, G.W.; Lewey, S.M.; Gilles, D.M.; Peppard, D.F.

1978-01-01

The comparative extraction behaviour of tracer-level UO 2 2+ into benzene solutions of two highly sterically hindered extractants, di(2,6-di-iso-propylphenyl) phosphoric acid, HD(2,6-i-PPHI)P and di-tertiary-butyl phosphinic acid, H[Dt-BP], vs an aqueous 1.0 F (NaCl + HCl) phase was studied. The extraction of UO 2 2+ in both systems is directly second-power dependent upon extractant concentration and inversely second-power dependent upon hydrogen ion concentration, the stoichiometry of extraction being UOsub(2A) 2+ + 2(HY)sub(2O) = UO 2 (HY 2 )sub(2O) + 2Hsub(A) + . The expression for the distribution ratio, K is K = Ksub(s)F 2 /[H + ] 2 the general expression for the extraction of any metallic species being K - Ksub(s)Fsup(a)/[H + ]sup(b) where Ksub(s) is a constant characteristic of the system, F the concentration in formality units of extractant in the organic phase, [H + ] the concentration of hydrogen ion in the aqueous phase, and a and b the respective extractant and hydrogen-ion dependencies. Both extractants have a high degree of steric hindrance. The HD(2,6-i-PPHI)P is the more highly acidic, the pKsub(A) value, in 75% ethanol, being 3.2. The pKsub(A), previously reported, for H[Dt-BP] is 6.26. The Ksub(s) for UO 2 2+ in the system HY in benzene diluent vs an aqueous 1.0 F (NaCl + HCl) phase is 2 x 10 4 for H[Dt-BP] and 3 x 10 -1 for HD(2,6-i-PPHI)P; the ratio of the Ksub(s) values nearly 7 x 10 3 , favours the less acidic extractant. For comparative purposes, the Ksub(s) values for UO 2 2+ and for Am 3+ and Eu 3+ in other (X 1 )(X 2 )PO(OH), in benzene diluent, vs 1.0 F (NaCl + HCl) systems are presented. The variations are discussed in terms of the pKsub(A) of the extractant and the steric hindrance within the extractant. (author)

Electronic structure effects in liquid water studied by photoelectron spectroscopy and density functional theory

Energy Technology Data Exchange (ETDEWEB)

Nordlund, Dennis; Odelius, Michael; Bluhm, Hendrik; Ogasawara, Hirohito; Pettersson, Lars G.M.; Nilsson, Anders

2008-04-29

We present valence photoelectron emission spectra of liquid water in comparison with gas-phase water, ice close to the melting point, low temperature amorphous and crystalline ice. All aggregation states have major electronic structure changes relative to the free molecule, with rehybridization and development of bonding and anti-bonding states accompanying the hydrogen bond formation. Sensitivity to the local structural order, most prominent in the shape and splitting of the occupied 3a{sub 1} orbital, is understood from the electronic structure averaging over various geometrical structures, and reflects the local nature of the orbital interaction.

Utilization of high energy electron beam in the treatment of drinking and waste water

International Nuclear Information System (INIS)

Oliveira Sampa, M.H. de; Borrely, S.I.; Morita, D.M.

1991-08-01

Samples of drinking water and waste water were irradiated using high energy electron beam with doses from 0.37kGy to 100kGy. Preliminary data show the removal of about 100% tri halomethanes (THM) in drinking water (concentration from 2.7 μg/1 to 45μg/1, 90% of the color of the Public Owned Wastewater Treatment Plant effluent and 87% of oil and grease of the cutting fluid waste water. (author)

Waste water treatment by ionizing radiations. Removal of biological and chemical risks by water and sludge treatment with electron beams. Orientation 10 July 2002

International Nuclear Information System (INIS)

2002-01-01

This report aims at analysing the reliability of the application of electron ionizing radiation in the treatment of waste waters and effluents, and at identifying possible fields of application and associated technological and economic implications. After some recalls on physics, electrochemistry, radiolysis, and water pollution, the report proposes an overview of the technique of irradiation of waters, with its scientific background (water radiolysis, chemical and biological effects), its process (recovery cycle and possible interventions, processed pollutants), the case of irradiation by electrons (power, rate, flexibility), an overview of benefits and drawbacks, and a brief history of this practice and an overview of current researches. After a recall of regulatory and political requirements, the report discusses possible fields of application: waste water treatment plants, domestic, agricultural and urban sewage wasters, hospital and medical wastes, liquid food industry products, industrial waters. The choice of accelerator parameters and components is then discussed

13C nuclear magnetic resonance data of lanosterol derivatives—Profiling the steric topology of the steroid skeleton via substituent effects on its 13C NMR

Science.gov (United States)

Dias, Jerry Ray; Gao, Hongwu

2009-12-01

The 13C NMR spectra of over 24 tetracyclic triterpenoid derivatives have been structurally analyzed. The 13C NMR chemical shifts allow one to probe the steric topology of the rigid steroid skeleton and inductive effects of its substituents. Use of deuterium labeling in chemical shift assignment and B-ring aromatic terpenoids are also featured.

Simulation of electronic circuit sensitivity towards humidity using electrochemical data on water layer

DEFF Research Database (Denmark)

Joshy, Salil; Verdingovas, Vadimas; Jellesen, Morten Stendahl

2015-01-01

Climatic conditions like temperature and humidity have direct influence on the operation of electronic circuits. The effects of temperature on the operation of electronic circuits have been widely investigated, while the effect of humidity and solder flux residues are not well understood including...... the effect on circuit and PCBA (printed circuit board assembly) layout design. This paper elucidates a methodology for analyzing the sensitivity of an electronic circuit based on parasitic circuit analysis using data on electrical property of the water layer formed under humid as well as contaminated...

Photoelectron spectroscopy of liquid water and aqueous solution: Electron effective attenuation lengths and emission-angle anisotropy

Energy Technology Data Exchange (ETDEWEB)

Ottosson, Niklas [Department of Physics, Uppsala University, SE-75121 Uppsala (Sweden); Faubel, Manfred [Max-Planck-Institut fuer Dynamik und Selbstorganisation, Bunsenstrasse 10, D-37073 Goettingen (Germany); Bradforth, Stephen E. [Department of Chemistry, University of Southern California, Los Angeles, CA 90089 (United States); Jungwirth, Pavel [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, and Center for Biomolecules and Complex Molecular Systems, Flemingovo nam. 2, 16610 Prague 6 (Czech Republic); Winter, Bernd, E-mail: winter@bessy.d [Helmholtz-Zentrum Berlin fuer Materialien und Energie, and BESSY, Albert-Einstein-Strasse 15, D-12489 Berlin (Germany); Max-Born-Institut, Max-Born-Strasse 2A, D-12489 Berlin (Germany)

2010-03-15

Photoelectron (PE) spectroscopy measurements from liquid water and from a 4 m NaI aqueous solution are performed using a liquid microjet in combination with soft X-ray synchrotron radiation. From the oxygen 1s PE signal intensity from liquid water, measured as a function of photon energy (up to 1500 eV), we quantitatively determine relative electron inelastic effective attenuation lengths (EAL) for (photo)electron kinetic energies in the 70-900 eV range. In order to determine the absolute electron escape depths a calibration point is needed, which is not directly accessible by experiment. This information can instead be indirectly derived by comparing PE experiments and molecular dynamics (MD) simulations of an aqueous solution interface where density profiles of water, anions, and cations are distinctively different. We have chosen sodium iodide in water because iodide has a considerable propensity for the solution surface, whereas the sodium cation is repelled from the surface. By measuring the intensities of photoelectrons emitted from different orbitals of different symmetries from each aqueous ion we also evaluate whether gas-phase ionization cross sections and asymmetry parameters can describe the photoemission from ions at and near the aqueous solution/vapor interface. We show that gas-phase data reproduce surprisingly well the experimental observations for hydrated ions as long as the photon energy is sufficiently far above the ionization threshold. Electrons detected at the higher photon energies originate predominantly from deeper layers, suggesting that bulk-solution electron elastic scattering is relatively weak.

Structural, vibrational, electronic investigations and quantum chemical studies of 2-amino-4-methoxybenzothiazole

Science.gov (United States)

Arjunan, V.; Raj, Arushma; Santhanam, R.; Marchewka, M. K.; Mohan, S.

2013-02-01

Extensive vibrational investigations of 2-amino-4-methoxybenzothiazole have been carried out with FTIR and FT-Raman spectral techniques. The electronic structure of the molecule has been analysed by UV-Visible and NMR spectroscopies. The DFT studies were carried out with B3LYP and HF methods utilising 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets to determine the structural, thermodynamical, vibrational, electronic characteristics of the compound and also to understand the electronic and steric influence of the methoxy amino groups on the skeletal frequencies. The mixing of the fundamental modes was determined with the help of total energy distribution (TED). The energies of the frontier molecular orbitals have also been determined. The kinetic and thermodynamic stability and chemical hardness of the molecule have been determined. Complete NBO analysis was also carried out to find out the intramolecular electronic interactions and their stabilisation energy. 1H and 13C NMR chemical shifts and the electronic transitions of the molecule are also discussed.

Structural, vibrational, electronic investigations and quantum chemical studies of 2-amino-4-methoxybenzothiazole.

Science.gov (United States)

Arjunan, V; Raj, Arushma; Santhanam, R; Marchewka, M K; Mohan, S

2013-02-01

Extensive vibrational investigations of 2-amino-4-methoxybenzothiazole have been carried out with FTIR and FT-Raman spectral techniques. The electronic structure of the molecule has been analysed by UV-Visible and NMR spectroscopies. The DFT studies were carried out with B3LYP and HF methods utilising 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets to determine the structural, thermodynamical, vibrational, electronic characteristics of the compound and also to understand the electronic and steric influence of the methoxy amino groups on the skeletal frequencies. The mixing of the fundamental modes was determined with the help of total energy distribution (TED). The energies of the frontier molecular orbitals have also been determined. The kinetic and thermodynamic stability and chemical hardness of the molecule have been determined. Complete NBO analysis was also carried out to find out the intramolecular electronic interactions and their stabilisation energy. (1)H and (13)C NMR chemical shifts and the electronic transitions of the molecule are also discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

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

One- or two-electron water oxidation, hydroxyl radical, or H_2O_2 evolution

International Nuclear Information System (INIS)

Siahrostami, Samira; Li, Guo-Ling; Viswanathan, Venkatasubramanian; Nørskov, Jens K.

2017-01-01

Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H_2O_2) or hydroxyl radicals (•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O_2 evolution. Here, we develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to •OH, H_2O_2, and O_2.

Interplay of alternative conjugated pathways and steric interactions on the electronic and optical properties of donor-acceptor conjugated polymers

KAUST Repository

Lima, Igo T.; Risko, Chad; Aziz, Saadullah Gary; Da Silva Filho, Demé trio A Da Silva; Bredas, Jean-Luc

2014-01-01

Donor-acceptor π-conjugated copolymers are of interest for a wide range of electronic applications, including field-effect transistors and solar cells. Here, we present a density functional theory (DFT) study of the impact of varying the conjugation pathway on the geometric, electronic, and optical properties of donor-acceptor systems. We consider both linear ("in series"), traditional conjugation among the donor-acceptor moieties versus structures where the acceptor units are appended orthogonally to the linear, donor-only conjugated backbone. Long-range-corrected hybrid functionals are used in the investigation with the values of the tuned long-range separation parameters providing an estimate of the extent of conjugation as a function of the oligomer architecture. Considerable differences in the electronic and optical properties are determined as a function of the nature of the conjugation pathway, features that should be taken into account in the design of donor-acceptor copolymers.

Thermalisation of high energy electrons and positrons in water vapour

Science.gov (United States)

Munoz, A.; Blanco, F.; Limao-Vieira, P.; Thorn, P. A.; Brunger, M. J.; Buckman, S. J.; Garcia, G.

2008-07-01

In this study we describe a method to simulate single electron tracks of electrons in molecular gases, particularly in water vapour, from relatively high energies, where Born (Inokuti 1971) approximation is supposed to be valid, down to thermal energies paying special attention to the low energy secondary electrons which are abundantly generated along the energy degradation procedure. Experimental electron scattering cross sections (Munoz et al. 2007) and energy loss spectra (Thorn et al. 2007) have been determined, where possible, to be used as input parameters of the simulating program. These experimental data have been complemented with optical potential calculation (Blanco and Garcia 2003) providing a complete set of interaction probability functions for each type of collision which could take place in the considered energy range: elastic, ionization, electronic excitation, vibrational and rotational excitation. From the simulated track structure (Munoz et al. 2005) information about energy deposition and radiation damage at the molecular level can be derived. A similar procedure is proposed to the study of single positron tracks in gases. Due to the lack of experimental data for positron interaction with molecules, especially for those related to energy loss and excitation cross sections, some distribution probability data have been derived from those of electron scattering by introducing positron characteristics as positroniun formation. Preliminary results for argon are presented discussing also the utility of the model to biomedical applications based on positron emitters.

Sterics level the rates of proton transfer to [Ni(XPh){PhP(CH₂CH₂PPh₂)₂}]⁺ (X = O, S or Se).

Science.gov (United States)

Alwaaly, Ahmed; Henderson, Richard A

2014-09-04

Rates of proton transfers between lutH(+) (lut = 2,6-dimethylpyridine) and [Ni(XPh)(PhP{CH2CH2PPh2}2)](+) (X = O, S or Se) are slow and show little variation (k(O) : k(S) : k(Se) = 1 : 12 : 9). This unusual behaviour is a consequence of sterics affecting the optimal interaction between the reactants prior to proton transfer.

Improving the water solubility of Monascus pigments under acidic conditions with gum arabic.

Science.gov (United States)

Jian, Wenjie; Sun, Yuanming; Wu, Jian-Yong

2017-07-01

Monascus pigments (Mps) are natural food colorants and their stability in acidic solutions is important for application in the food industry. This study aimed to evaluate the use of gum arabic (GA) as a stabilizer for maintaining the solubility of Mps in an acidic aqueous solution exposed to a high temperature, and to analyze the molecular interactions between GA and Mps. Mps dispersed (0.2 g kg -1 ) in deionized water at pH 3.0-4.0 without GA formed precipitates but remained in a stable solution in the presence of GA (1 g kg -1 ). The significant improvement of Mps water solubility under acidic conditions was attributed to the formation of Mps-GA complexes, as indicated by a sharp increase in the fluorescence intensity. The results on particle size, zeta potential, and transmission electron microscopy further suggested that molecular binding of Mps to GA, electrostatic repulsion, and steric hindrance of GA were contributing factors to preventing the aggregation of Mps in acidic solutions. A mechanistic model was presented for GA-Mps interactions and complex structures. GA was proven to be an effective stabilizer of natural food colorants in acidic solutions. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Characterization of the phantom material virtual water in high-energy photon and electron beams.

Science.gov (United States)

McEwen, M R; Niven, D

2006-04-01

The material Virtual Water has been characterized in photon and electron beams. Range-scaling factors and fluence correction factors were obtained, the latter with an uncertainty of around 0.2%. This level of uncertainty means that it may be possible to perform dosimetry in a solid phantom with an accuracy approaching that of measurements in water. Two formulations of Virtual Water were investigated with nominally the same elemental composition but differing densities. For photon beams neither formulation showed exact water equivalence-the water/Virtual Water dose ratio varied with the depth of measurement with a difference of over 1% at 10 cm depth. However, by using a density (range) scaling factor very good agreement (water and Virtual Water at all depths was obtained. In the case of electron beams a range-scaling factor was also required to match the shapes of the depth dose curves in water and Virtual Water. However, there remained a difference in the measured fluence in the two phantoms after this scaling factor had been applied. For measurements around the peak of the depth-dose curve and the reference depth this difference showed some small energy dependence but was in the range 0.1%-0.4%. Perturbation measurements have indicated that small slabs of material upstream of a detector have a small (<0.1% effect) on the chamber reading but material behind the detector can have a larger effect. This has consequences for the design of experiments and in the comparison of measurements and Monte Carlo-derived values.

Synergy of licorice extract and pea protein hydrolysate for oxidative stability of soybean oil-in-water emulsions.

Science.gov (United States)

Zhang, Xin; Xiong, Youling L; Chen, Jie; Zhou, Lirong

2014-08-13

Previously developed radical-scavenging pea protein hydrolysates (PPHs) prepared with Flavourzyme (Fla-PPH) and Protamex (Pro-PPH) were used as cosurfactants with Tween 20 to produce soybean oil-in-water (O/W) emulsions, and the suppression of lipid oxidation was investigated. Both PPHs significantly retarded oxidation (P < 0.05) of the emulsions when stored at 37 °C for 14 days. Electron microscopy revealed an interfacial peptidyl membrane around oil droplets, which afforded steric restrictions to oxidation initiators. When licorice extract (LE) was also used in emulsion preparation, a remarkable synergistic oxidation inhibition was observed with both PPHs. LE adsorbed onto oil droplets either directly or through associating with PPH to produce a thick and compact interfacial membrane enabling the defense against oxygen species. Liquiritin apioside, neolicuroside, glabrene, and 18β-glycyrrhetic acid were the predominant phenolic derivatives partitioning at the interface and most likely the major contributors to the notable synergistic antioxidant activity when coupled with PPHs.

Comparison of measurements of absorbed dose to water using a water calorimeter and ionization chambers for clinical radiotherapy photon and electron beams

International Nuclear Information System (INIS)

Marles, A.E.M.

1981-01-01

With the development of the water calorimeter direct measurement of absorbed dose in water becomes possible. This could lead to the establishment of an absorbed dose rather than an exposure related standard for ionization chambers for high energy electrons and photons. In changing to an absorbed dose standard it is necessary to investigate the effect of different parameters, among which are the energy dependence, the air volume, wall thickness and material of the chamber. The effect of these parameters is experimentally studied and presented for several commercially available chambers and one experimental chamber, for photons up to 25 MV and electrons up to 20 MeV, using a water calorimeter as the absorbed dose standard and the most recent formalism to calculate the absorbed dose with ion chambers. For electron beams, the dose measured with the calorimeter was 1% lower than the dose calculated with the chambers, independent of beam energy and chamber. For photon beams, the absorbed dose measured with the calorimeter was 3.8% higher than the absorbed dose calculated from the chamber readings. Such differences were found to be chamber and energy independent. The results for the photons were found to be statistically different from the results with the electron beams. Such difference could not be attributed to a difference in the calorimeter response

Dynamical electron-phonon coupling, G W self-consistency, and vertex effect on the electronic band gap of ice and liquid water

Science.gov (United States)

Ziaei, Vafa; Bredow, Thomas

2017-06-01

We study the impact of dynamical electron-phonon (el-ph) effects on the electronic band gap of ice and liquid water by accounting for frequency-dependent Fan contributions in the el-ph mediated self-energy within the many-body perturbation theory (MBPT). We find that the dynamical el-ph coupling effects greatly reduce the static el-ph band-gap correction of the hydrogen-rich molecular ice crystal from-2.46 to -0.23 eV in great contrast to the result of Monserrat et al. [Phys. Rev. B 92, 140302 (2015), 10.1103/PhysRevB.92.140302]. This is of particular importance as otherwise the static el-ph gap correction would considerably reduce the electronic band gap, leading to considerable underestimation of the intense peaks of optical absorption spectra of ice which would be in great disagreement to experimental references. By contrast, the static el-ph gap correction of liquid water is very moderate (-0.32 eV), and inclusion of dynamical effects slightly reduces the gap correction to -0.19 eV. Further, we determine the diverse sensitivity of ice and liquid water to the G W self-consistency and show that the energy-only self-consistent approach (GnWn ) exhibits large implicit vertex character in comparison to the quasiparticle self-consistent approach, for which an explicit calculation of vertex corrections is necessary for good agreement with experiment.

Finite-bias electronic transport of molecules in a water solution

KAUST Repository

Rungger, Ivan

2010-06-04

The effects of water wetting conditions on the transport properties of molecular nanojunctions are investigated theoretically by using a combination of empirical-potential molecular-dynamics and first-principles electronic-transport calculations. These are at the level of the nonequilibrium Green’s-function method implemented for self-interaction corrected density-functional theory. We find that water effectively produces electrostatic gating to the molecular junction with a gating potential determined by the time-averaged water dipole field. Such a field is large for the polar benzene-dithiol molecule, resulting in a transmission spectrum shifted by about 0.6 eV with respect to that of the dry junction. The situation is drastically different for carbon nanotubes (CNTs). In fact, because of their hydrophobic nature the gating is almost negligible so that the average transmission spectrum of wet Au/CNT/Au junctions is essentially the same as that in dry conditions. This suggests that CNTs can be used as molecular interconnects also in water-wet situations, for instance, as tips for scanning tunnel microscopy in solution or in biological sensors.

Finite-bias electronic transport of molecules in a water solution

KAUST Repository

Rungger, Ivan; Chen, X.; Sanvito, Stefano; Schwingenschlö gl, Udo

2010-01-01

The effects of water wetting conditions on the transport properties of molecular nanojunctions are investigated theoretically by using a combination of empirical-potential molecular-dynamics and first-principles electronic-transport calculations. These are at the level of the nonequilibrium Green’s-function method implemented for self-interaction corrected density-functional theory. We find that water effectively produces electrostatic gating to the molecular junction with a gating potential determined by the time-averaged water dipole field. Such a field is large for the polar benzene-dithiol molecule, resulting in a transmission spectrum shifted by about 0.6 eV with respect to that of the dry junction. The situation is drastically different for carbon nanotubes (CNTs). In fact, because of their hydrophobic nature the gating is almost negligible so that the average transmission spectrum of wet Au/CNT/Au junctions is essentially the same as that in dry conditions. This suggests that CNTs can be used as molecular interconnects also in water-wet situations, for instance, as tips for scanning tunnel microscopy in solution or in biological sensors.

Radiobiological application of simulation of low-energy electron transport in liquid water

International Nuclear Information System (INIS)

Eudaldo Puell, Teresa.

1979-01-01

A Monte-Carlo transport simulation method, so-called event-after-event method provide results about trajectories of low-energy electrons, slowing-down in liquid water. A radiosensitive target model constituted by water cylindrical volumes, like the ones which surround the DNA molecule, is taken into consideration. The results characterizing the primary physical stage of radiation action, such as, space ionization distributions, interionization distance distributions ..., are obtained in some configurations constituted by single or several targets, in order to approach the biological reality [fr

Metal coordination by sterically hindered heterocyclic ligands, including 2-vinylpyridine, assessed by investigation of cobaloximes.

Science.gov (United States)

Siega, Patrizia; Randaccio, Lucio; Marzilli, Patricia A; Marzilli, Luigi G

2006-04-17

Structural and 1H NMR data have been obtained for cobaloximes with the bulkiest substituted pyridines reported so far. We have isolated in noncoordinating solvents the complexes CH3Co(DH)2L (methylcobaloxime, where DH = the monoanion of dimethylglyoxime) with L = sterically hindered N-donor ligands: quinoline, 4-CH3quinoline, 2,4-(CH3)2pyridine, and 2-R-pyridine (R = CH3, OCH3, CH2CH3, CH=CH2). We have found that the Co-N(ax) bond is very long in the structurally characterized complexes. In particular, CH3Co(DH)2(4-CH3quinoline) has a longer Co-N(ax) bond (2.193(3) A) than any reported for methylcobaloximes. The main cause of the long bonds is unambiguously identified as the steric bulk of L by the fairly linear relationship found for Co-N(ax) distance vs CCA (calculated cone angle, CCA, a computed measure of bulk) over an extensive series of methylcobaloximes. The linear relationship improves if L basicity (quantified by pKa) is taken into account. In anhydrous CDCl3 at 25 degrees C, all complexes except the 2-aminopyridine adduct exhibit 1H NMR spectra consistent with partial dissociation of L to form the methylcobaloxime dimer. 1H NMR experiments at -20 degrees C allowed us to assess qualitatively the relative binding ability of L as follows: 2,4-(CH3)2pyridine > 4-CH3quinoline approximately = quinoline approximately = 2-CH3pyridine > 2-CH3Opyridine > 2-CH3CH2pyridine > 2-CH2=CHpyridine. The broadness of the 1H NMR signals at 25 degrees C suggests a similar order for the ligand exchange rate. The lack of dissociation by 2-aminopyridine is attributed to an intramolecular hydrogen bond between the NH2 group and an oxime O atom. The weaker than expected binding of 2-vinylpyridine relative to the Co-N(ax) bond length is attributed to rotation of the 2-vinyl group required for this bulky ligand to bind to the metal center, a conclusion supported by pronounced changes in 2-vinylpyridine signals upon coordination.

Degradation of pollutants and elimination of pathogens of waste water by adsorption of accelerated electrons; Degradacion de contaminantes y eliminacion de patogenos de aguas residuales por adsorcion de electrones acelerados

Energy Technology Data Exchange (ETDEWEB)

Martinez M, I

1991-10-15

This report presents a position of the pollutants degradation of the industrial residual waters, it intends a method that consists on making pass residual water, treated biologically by a packed column with activated carbon. The carbon retains the pollutants and the water goes out with a purity that allows the reuse. In simultaneous form to the adsorption of pollutants are made pass electrons through the column of carbon, the electrons will destroy to the polluting adsorbed in the carbon; the pollutants degrade until CO{sub 2} that escapes as gas. The active sites of the carbon are empty and clever to be occupied by other pollutants. This process is continuous and it is repeated while water is passing by the column and electrons through this. (Author)

A nuclear magnetic resonance and electron spin resonance study on the dynamics of pentacoordinated organophosphorus compounds

International Nuclear Information System (INIS)

Keijzer, A.E.H. de.

1988-01-01

In this thesis the role of the steric and electronic effects on the fundamental dynamic behaviour of pentacoordinated phosporus compounds is further elaborated. In chapter 2 a variable temperature 13 C NMR study, performed on a series of monocyclic oxyphosphoranes, is presented. The investigations were carried out to determine the influence of the conformational transmission effect on the barriers to pseudorotation in pentacoordinated phosphorus compounds. Chapter 3 also comprises a variable temperature 13 C NMR study on pentacoordinated phosphorus compounds. In this chapter, however, an additional high-resolution 1 H NMR study on the conformational equilibria around the P-O-C-C-O fragments is included. These studies were performed in order to determine whether the enhancement of the reorganization rates around phosphorus is brought about by accelerated pseudorotation or by the involvement of hexacoordinated zwitterionic phosphorus intermediates. In chapter 4, a 31 P NMR study on the solvolysis rate of several phosphinate esters is described. This study was performed in order to determine the influence of the conformational transmission effect on the solvolysis rate of phosphate esters. A number of phosphates is examined in which, during the course of the solvolysis reaction, the conformational transmission effect is bound to be present or absent respectively. Moreover, it is discussed in which way the concept of conformational transmission induced differences in solvolysis rates can be used as a probe to examine the reactions of biologically important phosphate esters. In chapters 5 and 6 ESR studies on the influence of steric and electronic factors on phosphoranyl formation in solution, and on the intramolecular electron transfer in phosphoranyl radicals are presented. (author). 121 refs.; 33 figs.; 17 figs

Near field resonant inductive coupling to power electronic devices dispersed in water

NARCIS (Netherlands)

Kuipers, J.; Bruning, H.; Bakker, S.; Rijnaarts, H.H.M.

2012-01-01

The purpose of this research was to investigate inductive coupling as a way to wirelessly power electronic devices dispersed in water. The most important parameters determining this efficiency are: (1) the coupling between transmitting and receiving coils, (2) the quality factors of the transmitting

Pulse radiolysis study on solvated electrons in ionic liquid with controlling water content

International Nuclear Information System (INIS)

Yang Jinfeng; Kondoh, T.; Yoshida, Y.; Nagaishi, R.

2006-01-01

Room-temperature ionic liquids, which are nonvolatile and nonflammable, have been proposed as 'green solvents' for new applications in chemical synthesis, separation chemistry, electrochemistry and other areas. In the separation chemistry, the hydrophobic ionic liquids have been practically expected to be alternative to traditional organic solvents for solvent extraction of 4f and 5f elements from the viewpoints of the immiscibility in water, especially in the spent nuclear fuel reprocessing. However, the chemical reaction or kinetics studies are important to apply the ionic liquids for various processes. To understand the effects of ionic liquids on chemical reactions, pulse radiolysis studies of ionic liquid have been carried out on nanosecond scale by using a 27 MeV electron beam and an analyzing light source of xenon lamp. In the experiment, a hydrophobic ionic liquid of diethylmethyl(2-methoxy)ammonium-bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI) salt was used. The ionic liquid of DEMMA-TFSI was prepared by reacting equimolar amounts of diethylmethyl(2-methoxy)ammonium chloride (C 10 H 20 F 6 N 2 O 5 S 2 Cl, >98%, Nisshinbo) with lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 , SynQuest Labs., Inc.) in aqueous solutions at room temperature. The ionic liquid was separated from the aqueous phase, purified by repeated extractions with water to LiCl and excess reagent, and finally dried at 110 degree C under vacuum. The transient absorptions of the ionic liquid were measured at wavelengths from 350 to 1400 nm, in which two photodiodes of silicon ( 1000 nm) were used. The spectrum of solvated electrons in the ionic liquid of DEMMA-TFSI was obtained with an absorption peak of 1060 nm and a wide bandwidth of about 600 nm (FWHM). The decay constant of the solvated electrons in the ionic liquid was 1.54 x 10 7 s -1 , which is independent on the wavelength. The absorption peak of the spectrum was blue-shifted from 1060 to 780 nm with increasing water

Three-dimensional machining of carbon nanotube forests using water-assisted scanning electron microscope processing

Energy Technology Data Exchange (ETDEWEB)

Rajabifar, Bahram; Maschmann, Matthew R., E-mail: MaschmannM@missouri.edu [Department of Mechanical and Aerospace Engineering, University of Missouri, Columbia, Missouri 65211 (United States); Kim, Sanha; Hart, A. John [Department of Mechanical Engineering and Laboratory for Manufacturing and Productivity, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Slinker, Keith [Materials and Manufacturing Directorate, AFRL/RX, Air Force Research Lab, Ohio 45433 (United States); Universal Technology Corporation, Beavercreek, Ohio 45424 (United States); Ehlert, Gregory J. [Materials and Manufacturing Directorate, AFRL/RX, Air Force Research Lab, Ohio 45433 (United States)

2015-10-05

We demonstrate that vertically aligned carbon nanotubes (CNTs) can be precisely machined in a low pressure water vapor ambient using the electron beam of an environmental scanning electron microscope. The electron beam locally damages the irradiated regions of the CNT forest and also dissociates the water vapor molecules into reactive species including hydroxyl radicals. These species then locally oxidize the damaged region of the CNTs. The technique offers material removal capabilities ranging from selected CNTs to hundreds of cubic microns. We study how the material removal rate is influenced by the acceleration voltage, beam current, dwell time, operating pressure, and CNT orientation. Milled cuts with depths between 0–100 microns are generated, corresponding to a material removal rate of up to 20.1 μm{sup 3}/min. The technique produces little carbon residue and does not disturb the native morphology of the CNT network. Finally, we demonstrate direct machining of pyramidal surfaces and re-entrant cuts to create freestanding geometries.

Three-dimensional machining of carbon nanotube forests using water-assisted scanning electron microscope processing

Science.gov (United States)

Rajabifar, Bahram; Kim, Sanha; Slinker, Keith; Ehlert, Gregory J.; Hart, A. John; Maschmann, Matthew R.

2015-10-01

We demonstrate that vertically aligned carbon nanotubes (CNTs) can be precisely machined in a low pressure water vapor ambient using the electron beam of an environmental scanning electron microscope. The electron beam locally damages the irradiated regions of the CNT forest and also dissociates the water vapor molecules into reactive species including hydroxyl radicals. These species then locally oxidize the damaged region of the CNTs. The technique offers material removal capabilities ranging from selected CNTs to hundreds of cubic microns. We study how the material removal rate is influenced by the acceleration voltage, beam current, dwell time, operating pressure, and CNT orientation. Milled cuts with depths between 0-100 microns are generated, corresponding to a material removal rate of up to 20.1 μm3/min. The technique produces little carbon residue and does not disturb the native morphology of the CNT network. Finally, we demonstrate direct machining of pyramidal surfaces and re-entrant cuts to create freestanding geometries.

Probing the electronic structure of liquid water with many-body perturbation theory

Science.gov (United States)

Pham, Tuan Anh; Zhang, Cui; Schwegler, Eric; Galli, Giulia

2014-03-01

We present a first-principles investigation of the electronic structure of liquid water based on many-body perturbation theory (MBPT), within the G0W0 approximation. The liquid quasiparticle band gap and the position of its valence band maximum and conduction band minimum with respect to vacuum were computed and it is shown that the use of MBPT is crucial to obtain results that are in good agreement with experiment. We found that the level of theory chosen to generate molecular dynamics trajectories may substantially affect the electronic structure of the liquid, in particular, the relative position of its band edges and redox potentials. Our results represent an essential step in establishing a predictive framework for computing the relative position of water redox potentials and the band edges of semiconductors and insulators. Work supported by DOE/BES (Grant No. DE-SC0008938). Work at LLNL was performed under Contract DE-AC52-07NA27344.

Biocatalytic photosynthesis with water as an electron donor.

Science.gov (United States)

Ryu, Jungki; Nam, Dong Heon; Lee, Sahng Ha; Park, Chan Beum

2014-09-15

Efficient harvesting of unlimited solar energy and its conversion into valuable chemicals is one of the ultimate goals of scientists. With the ever-increasing concerns about sustainable growth and environmental issues, numerous efforts have been made to develop artificial photosynthetic process for the production of fuels and fine chemicals, thus mimicking natural photosynthesis. Despite the research progress made over the decades, the technology is still in its infancy because of the difficulties in kinetic coupling of whole photocatalytic cycles. Herein, we report a new type of artificial photosynthesis system that can avoid such problems by integrally coupling biocatalytic redox reactions with photocatalytic water splitting. We found that photocatalytic water splitting can be efficiently coupled with biocatalytic redox reactions by using tetracobalt polyoxometalate and Rh-based organometallic compound as hole and electron scavengers, respectively, for photoexcited [Ru(bpy)3](2+). Based on these results, we could successfully photosynthesize a model chiral compound (L-glutamate) using a model redox enzyme (glutamate dehydrogenase) upon in situ photoregeneration of cofactors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio theoretical calculations of the electronic excitation energies of small water clusters.

Science.gov (United States)

Tachikawa, Hiroto; Yabushita, Akihiro; Kawasaki, Masahiro

2011-12-14

A direct ab initio molecular dynamics method has been applied to a water monomer and water clusters (H(2)O)(n) (n = 1-3) to elucidate the effects of zero-point energy (ZPE) vibration on the absorption spectra of water clusters. Static ab initio calculations without ZPE showed that the first electronic transitions of (H(2)O)(n), (1)B(1)←(1)A(1), are blue-shifted as a function of cluster size (n): 7.38 eV (n = 1), 7.58 eV (n = 2) and 8.01 eV (n = 3). The inclusion of the ZPE vibration strongly affects the excitation energies of a water dimer, and a long red-tail appears in the range of 6.42-6.90 eV due to the structural flexibility of a water dimer. The ultraviolet photodissociation of water clusters and water ice surfaces is relevant to these results.

Single-Step versus Stepwise Two-Electron Reduction of Polyarylpyridiniums: Insights from the Steric Switching of Redox Potential Compression

Czech Academy of Sciences Publication Activity Database

Fortage, J.; Peltier, C.; Perruchot, Ch.; Takemoto, Y.; Teki, Y.; Bedioui, F.; Marvand, V.; Dupeyre, G.; Pospíšil, Lubomír; Adamo, C.; Hromadová, Magdaléna; Ciofini, I.; Lainé, P. P.

2012-01-01

Roč. 134, č. 5 (2012), s. 2691-2705 ISSN 0002-7863 Institutional research plan: CEZ:AV0Z40400503 Keywords : FUNCTIONALIZED TERPYRIDYL LIGANDS * GATED PHOTOINDUCED PROCESSES * ONE-ELECTRON REDUCTION Subject RIV: CG - Electrochemistry Impact factor: 10.677, year: 2012

The use of electron beam accelerator for the treatment of drinking water and wastewater in Brazil

International Nuclear Information System (INIS)

Sampa, M.H.O.; Borrely, S.I.; Silva, B.L.

1995-01-01

Brazil started a research program using high-energy electrons from accelerators for treating drinking water and wastewater in 1991. The objective is to study the potential use of this technique for disinfection of domestic wastewater, chemical degradation of dyes, phenols, oils and greases in industrial wastewater and reduction of trihalomethanes (THM's) concentration in drinking water. An Electron Beam Accelerator, 1.5MeV - 25mA from Radiation Dynamics Inc., was used for all experiments. A pilot plant designed to treat up to 3m 3 /h was built. (author)

The use of electron beam accelerator for the treatment of drinking water and wastewater in Brazil

International Nuclear Information System (INIS)

Sampa, M.H.O.; Borrely, S.I.; Silva, B.L.

1995-01-01

Brazil started a research program using high-energy electrons from accelerators for treating drinking water and wastewater in 1991. The objective is to study the potential use of this technique for disinfection of domestic wastewater, chemical degradation of dyes, phenols, oils and greases in industrial wastewater and reduction of trihalomethanes (THM's) concentration in drinking water. An Electron Beam Accelerator, 1.5MeV -25mA from Radiation Dynamics Inc., was used for all experiments. A pilot plant designed to treat up to 3m 3 /h was built. (author)

The use of electron beam accelerator for the treatment of drinking water and wastewater in Brazil

Science.gov (United States)

Sampa, M. H. O.; Borrely, S. I.; Silva, B. L.; Vieira, J. M.; Rela, P. R.; Calvo, W. A. P.; Nieto, R. C.; Duarte, C. L.; Perez, H. E. B.; Somessari, E. S.; Lugão, A. B.

1995-09-01

Brazil started a research program using high-energy electrons from accelerators for treating drinking water and wastewater in 1991. The objective is to study the potential use of this technique for disinfection of domestic wastewater, chemical degradation of dyes, phenols, oils and greases in industrial wastewater and reduction of trihalomethanes (THM's) concentration in drinking water. An Electron Beam Accelerator, 1.5MeV-25mA from Radiation Dynamics Inc., was used for all experiments. A pilot plant designed to treat up to 3m3/h was built.

Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

Science.gov (United States)

Varenyk, O. V.; Silibin, M. V.; Kiselev, D. A.; Eliseev, E. A.; Kalinin, S. V.; Morozovska, A. N.

2015-08-01

The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. The obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers, which are of potential interest for flexible and high-density non-volatile memory devices.

Self-consistent modelling of electrochemical strain microscopy in mixed ionic-electronic conductors: Nonlinear and dynamic regimes

Energy Technology Data Exchange (ETDEWEB)

Varenyk, O. V.; Morozovska, A. N., E-mail: sergei2@ornl.gov, E-mail: anna.n.morozovska@gmail.com [Institute of Physics, National Academy of Sciences of Ukraine, 46, pr. Nauky, 03028 Kyiv (Ukraine); Silibin, M. V. [National Research University of Electronic Technology “MIET,” 124498 Moscow (Russian Federation); Kiselev, D. A. [National University of Science and Technology “MISiS,” 119049 Moscow, Leninskiy pr. 4 (Russian Federation); Eliseev, E. A. [Institute for Problems of Materials Science, NAS of Ukraine, Krjijanovskogo 3, 03142 Kyiv (Ukraine); Kalinin, S. V., E-mail: sergei2@ornl.gov, E-mail: anna.n.morozovska@gmail.com [The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States)

2015-08-21

The frequency dependent Electrochemical Strain Microscopy (ESM) response of mixed ionic-electronic conductors is analyzed within the framework of Fermi-Dirac statistics and the Vegard law, accounting for steric effects from mobile donors. The emergence of dynamic charge waves and nonlinear deformation of the surface in response to bias applied to the tip-surface junction is numerically explored. The 2D maps of the strain and concentration distributions across the mixed ionic-electronic conductor and bias-induced surface displacements are calculated. The obtained numerical results can be applied to quantify the ESM response of Li-based solid electrolytes, materials with resistive switching, and electroactive ferroelectric polymers, which are of potential interest for flexible and high-density non-volatile memory devices.

Diffusion of ionic and non-ionic contrast agents in articular cartilage with increased cross-linking--contribution of steric and electrostatic effects.

Science.gov (United States)

Kulmala, K A M; Karjalainen, H M; Kokkonen, H T; Tiitu, V; Kovanen, V; Lammi, M J; Jurvelin, J S; Korhonen, R K; Töyräs, J

2013-10-01

To investigate the effect of threose-induced collagen cross-linking on diffusion of ionic and non-ionic contrast agents in articular cartilage. Osteochondral plugs (Ø=6mm) were prepared from bovine patellae and divided into two groups according to the contrast agent to be used in contrast enhanced computed tomography (CECT) imaging: (I) anionic ioxaglate and (II) non-ionic iodixanol. The groups I and II contained 7 and 6 sample pairs, respectively. One of the paired samples served as a reference while the other was treated with threose to induce collagen cross-linking. The equilibrium partitioning of the contrast agents was imaged after 24h of immersion. Fixed charge density (FCD), water content, contents of proteoglycans, total collagen, hydroxylysyl pyridinoline (HP), lysyl pyridinoline (LP) and pentosidine (Pent) cross-links were determined as a reference. The equilibrium partitioning of ioxaglate (group I) was significantly (p=0.018) lower (-23.4%) in threose-treated than control samples while the equilibrium partitioning of iodixanol (group II) was unaffected by the threose-treatment. FCD in the middle and deep zones of the cartilage (pionic iodixanol showed no changes in partition after cross-linking, in contrast to anionic ioxaglate, we conclude that the cross-linking induced changes in charge distribution have greater effect on diffusion compared to the cross-linking induced changes in steric hindrance. Copyright © 2013 IPEM. Published by Elsevier Ltd. All rights reserved.

The technology and economics of treating waste water with electron beam radiation

International Nuclear Information System (INIS)

Cleland, M.R.

1976-01-01

The use of ionizing radiation from electron beam accelerators is considered in this paper for the disinfection of waste water. Combinations of radiation with oxygen, chlorine, heat and retention media are discussed as possible methods to reduce the dosage requirements and the treatment costs. The production of ozone by the irradiation of oxygen is also evaluated as an alternative method of using this form of energy. The capital and operating costs for large electron beam facilities are analyzed to show the favorable trends with rising power levels. Cost comparisons between conventional disinfection processes and two radiation processes are presented and discussed. The results of these cost analyses support the premise that electron beam radiation should be evaluated as a likely competitor to ozonation or carbon filtration for large sewage treatment plants. (author)

The technology and economics of treating waste water with electron beam radiation

International Nuclear Information System (INIS)

Cleland, M.R.

1976-01-01

The use of ionizing radiation from electron beam accelerators is considered in this paper for the disinfection of waste water. Combinations of radiation with oxygen, chlorine, heat and retention media are discussed as possible methods to reduce the dosage requirements and the treatment costs. The production of ozone by the irradiation of oxygen is also evaluated as an alternative method of using this form of energy. The capital and operating costs for large electron beam facilities are analyzed to show the favorable trends with rising power levels. Cost comparisons between 'conventional' disinfection processes and two radiation processes are presented and discussed. The results of these cost analyses support the premise that electron beam radiation should be evaluated as a likely competitor to ozonation or carbon filtration for large sewage treatment plants. (orig.) [de

Geant4-DNA simulation of electron slowing-down spectra in liquid water

Energy Technology Data Exchange (ETDEWEB)

Incerti, S., E-mail: sebastien.incerti@tdt.edu.vn [Division of Nuclear Physics, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Faculty of Applied Sciences, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Univ. Bordeaux, CENBG, UMR 5797, F-33170, Gradignan (France); CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Kyriakou, I. [Medical Physics Laboratory, University of Ioannina Medical School, 45110 Ioannina (Greece); Tran, H.N. [Division of Nuclear Physics, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Faculty of Applied Sciences, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam)

2017-04-15

This work presents the simulation of monoenergetic electron slowing-down spectra in liquid water by the Geant4-DNA extension of the Geant4 Monte Carlo toolkit (release 10.2p01). These spectra are simulated for several incident energies using the most recent Geant4-DNA physics models, and they are compared to literature data. The influence of Auger electron production is discussed. For the first time, a dedicated Geant4-DNA example allowing such simulations is described and is provided to Geant4 users, allowing further verification of Geant4-DNA track structure simulation capabilities.

Electron spin resonance of the solvation of radiation-produced silver atoms in alcohol-water mixtures

International Nuclear Information System (INIS)

Li, A.S.W.; Kevan, L.

1982-01-01

Frozen solutions of silver salts exposed to 60 Co γ-irradiation form silver atoms by reaction of radiation-produced electrons with the silver ion. At 4 K the silver atoms are initially produced in a nonequilibrium or presolvated state and upon brief thermal excitation to 77 K the first solvation shell geometry changes towards an equilibrium or solvated silver atom. This is most pronounced in water but also occurs in methanol, ethanol and n-propanol matrices. The changes in the electron spin resonance magnetic parameters upon silver atom solvation have been determined. In alcohol-water mixtures Ag 0 is preferentially solvated by polycrystalline water at low alcohol concentration. Above a particular alcohol mole percent Ag 0 suddenly changes its environment to a glassy alcohol one. This sudden change occurs at 17, 13 and 6 mol % methanol, ethanol and n-propanol, respectively. These mole percents correlate with the minimum of the excess enthalpy of mixing and with the hydrogen atom trapping ability of these alcohol-water mixtures. The results also suggest that the local environmental disorder around Ag 0 increases with alcohol chain length in alcohol-water frozen solutions. (author)

Detection of water and its derivatives on individual nanoparticles using vibrational electron energy-loss spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Crozier, Peter A., E-mail: crozier@asu.edu [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States); Aoki, Toshihiro [LeRoy Eyring Center for Solid State Science, Arizona State University, Tempe, AZ 85287-1704 (United States); Liu, Qianlang [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States)

2016-10-15

Understanding the role of water, hydrate and hydroxyl species on nanoparticle surfaces and interfaces is very important in both physical and life sciences. Detecting the presence of oxygen-hydrogen species with nanometer resolution is extremely challenging at present. Here we show that the recently developed vibrational electron energy-loss spectroscopy using subnanometer focused electron beams can be employed to spectroscopically identify the local presence and variation of OH species on nanoscale surfaces. The hydrogen-oxygen fingerprint can be correlated with highly localized structural and morphological information obtained from electron imaging. Moreover, the current approach exploits the aloof beam mode of spectral acquisition which does not require direct electron irradiation of the sample thus greatly reducing beam damage to the OH bond. These findings open the door for using electron microscopy to probe local hydroxyl and hydrate species on nanoscale organic and inorganic structures. - Highlights: • High spatial resolution spectroscopic detection of water related species in nanoparticles. • Detection of OH stretch modes with vibrational EELS. • Differentiation between hydrate and hydroxide species on or on nanoparticles. • Detection of hydrate on a single 60 nm oxide nanoparticle of MgO. • Use of aloof beam EELS to minimize radiation damage.

Pre-feasibility study of electron beam irradiation of fresh water

International Nuclear Information System (INIS)

Finshi V, Silvia.

1997-01-01

A technical/economic evaluation of electron beam irradiation for the decontamination of liquids in the country is presented. Irradiation of fresh water is evaluated for the production of drinking water as a replacement for chlorine disinfection, which can lead to the formation of tri halo methanes. that are carcinogenic compounds. The technical literature states that the percentage of microorganisms removed by electro beam irradiation is high and similar to that found with chlorine disinfection. From an economic point of view, irradiation technology is not presently competitive as an alternative to conventional chlorination in terms of processing costs (US$0.23/m 3 ) instead of US$0.013/m 3 for conventional chlorination. Nevertheless, irradiation costs decreased sharply when unit costs for the accelerator machine are decreased with a resulting drop in capital costs

NHC-Copper(I) Halide-Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water

KAUST Repository

Czerwiński, Paweł

2016-05-04

An efficient and easily scalable NHC-copper(I) halide-catalyzed addition of terminal alkynes to 1,1,1-trifluoromethyl ketones, carried out on water for the first time, is reported. A series of addition reactions were performed with as little as 0.1-2.0mol% of [(NHC)CuX] (X=Cl, Br, I, OAc, OTf) complexes, providing tertiary propargylic trifluoromethyl alcohols in high yields and with excellent chemoselectivity from a broad range of aryl- and more challenging alkyl-substituted trifluoromethyl ketones (TFMKs). DFT calculations were performed to rationalize the correlation between the yield of catalytic alkynylation and the sterics of N-heterocyclic carbenes (NHCs), expressed as buried volume (%VBur), indicating that steric effects dominate the yield of the reaction. Additional DFT calculations shed some light on the differential reactivity of [(NHC)CuX] complexes in the alkynylation of TFMKs. The first enantioselective version of a direct alkynylation in the presence of C1-symmetric NHC-copper(I) complexes is also presented. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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)

Electron beam irradiation enhances the digestibility and fermentation yield of water-soaked lignocellulosic biomass

Directory of Open Access Journals (Sweden)

Jin Seop Bak

2014-12-01

Full Text Available In order to overcome the limitation of commercial electron beam irradiation (EBI, lignocellulosic rice straw (RS was pretreated using water soaking-based electron beam irradiation (WEBI. This environment-friendly pretreatment, without the formation (or release of inhibitory compounds (especially hydroxymethylfurfural and furfural, significantly increased the enzymatic hydrolysis and fermentation yields of RS. Specifically, when water-soaked RS (solid:liquid ratio of 100% was treated with WEBI doses of 1 MeV at 80 kGy, 0.12 mA, the glucose yield after 120 h of hydrolysis was 70.4% of the theoretical maximum. This value was predominantly higher than the 29.5% and 52.1% measured from untreated and EBI-treated RS, respectively. Furthermore, after simultaneous saccharification and fermentation for 48 h, the ethanol concentration, production yield, and productivity were 9.3 g/L, 57.0% of the theoretical maximum, and 0.19 g/L h, respectively. Finally, scanning electron microscopy images revealed that WEBI induced significant ultrastructural changes to the surface of lignocellulosic fibers.

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

International Nuclear Information System (INIS)

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

2012-01-01

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

DFT and time-resolved IR investigation of electron transfer between photogenerated 17- and 19-electron organometallic radicals

Energy Technology Data Exchange (ETDEWEB)

Cahoon, James B.; Kling, Matthias F.; Sawyer, Karma R.; Andersen, Lars K.; Harris, Charles B.

2008-04-30

The photochemical disproportionation mechanism of [CpW(CO){sub 3}]{sub 2} in the presence of Lewis bases PR{sub 3} was investigated on the nano- and microsecond time-scales with Step-Scan FTIR time-resolved infrared spectroscopy. 532 nm laser excitation was used to homolytically cleave the W-W bond, forming the 17-electron radicals CpW(CO){sub 3} and initiating the reaction. With the Lewis base PPh{sub 3}, disproportionation to form the ionic products CpW(CO){sub 3}PPh{sub 3}{sup +} and CpW(CO){sub 3}{sup -} was directly monitored on the microsecond time-scale. Detailed examination of the kinetics and concentration dependence of this reaction indicates that disproportionation proceeds by electron transfer from the 19-electron species CpW(CO){sub 3}PPh{sub 3} to the 17-electron species CpW(CO){sub 3}. This result is contrary to the currently accepted disproportionation mechanism which predicts electron transfer from the 19-electron species to the dimer [CpW(CO){sub 3}]{sub 2}. With the Lewis base P(OMe){sub 3} on the other hand, ligand substitution to form the product [CpW(CO){sub 2}P(OMe){sub 3}]{sub 2} is the primary reaction on the microsecond time-scale. Density Functional Theory (DFT) calculations support the experimental results and suggest that the differences in the reactivity between P(OMe){sub 3} and PPh{sub 3} are due to steric effects. The results indicate that radical-to-radical electron transfer is a previously unknown but important process for the formation of ionic products with the organometallic dimer [CpW(CO){sub 3}]{sub 2} and may also be applicable to the entire class of organometallic dimers containing a single metal-metal bond.

Overcoming double-step CO2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg2(dobpdc)† †Electronic supplementary information (ESI) available: Additional experimental details, and full characterization (powder X-ray diffraction, infrared spectra, diamine loadings, dry N2 decomposition profiles, and CO2 adsorption data) for all new adsorbents. CCDC 1577354. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04266c

Science.gov (United States)

Milner, Phillip J.; Martell, Jeffrey D.; Siegelman, Rebecca L.; Gygi, David; Weston, Simon C.

2017-01-01

Alkyldiamine-functionalized variants of the metal–organic framework Mg2(dobpdc) (dobpdc4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) are promising for CO2 capture applications owing to their unique step-shaped CO2 adsorption profiles resulting from the cooperative formation of ammonium carbamate chains. Primary,secondary (1°,2°) alkylethylenediamine-appended variants are of particular interest because of their low CO2 step pressures (≤1 mbar at 40 °C), minimal adsorption/desorption hysteresis, and high thermal stability. Herein, we demonstrate that further increasing the size of the alkyl group on the secondary amine affords enhanced stability against diamine volatilization, but also leads to surprising two-step CO2 adsorption/desorption profiles. This two-step behavior likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg2(dobpdc) and leads to decreased CO2 working capacities and increased water co-adsorption under humid conditions. To minimize these unfavorable steric interactions, we targeted diamine-appended variants of the isoreticularly expanded framework Mg2(dotpdc) (dotpdc4– = 4,4′′-dioxido-[1,1′:4′,1′′-terphenyl]-3,3′′-dicarboxylate), reported here for the first time, and the previously reported isomeric framework Mg-IRMOF-74-II or Mg2(pc-dobpdc) (pc-dobpdc4– = 3,3′-dioxidobiphenyl-4,4′-dicarboxylate, pc = para-carboxylate), which, in contrast to Mg2(dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg2(pc-dobpdc) with large diamines such as N-(n-heptyl)ethylenediamine results in optimal adsorption behavior, highlighting the advantage of tuning both the pore shape and the diamine size for the development

Ionization of liquid water by fast electron impact: multiple differential cross sections for the 1B1 orbital

International Nuclear Information System (INIS)

Fojon, O A; De Sanctis, M L; Stia, C R; Vuilleumier, R; Politis, M-F

2011-01-01

We present a theoretical study of single ionization of water molecules in liquid phase by impact of fast electrons in a coplanar geometry. Multiple differential cross sections are obtained through a first order model obtained within the framework of an independent electron approximation in which relaxation of the target is not taken into account. The wavefunctions for a single water molecule in the liquid phase are obtained through a Wannier orbital formalism and the ejected electron is described by means of Coulomb functions. We also present averaged calculations over all molecular orientations. A comparison with previous theoretical and experimental results, the latter corresponding to water in gaz phase, shows a good agreement. The main physical features of the reaction (such as binary and recoil peaks) present in measurements for vapor are also observed in the present theoretical predictions.

Forming mechanism and avoiding measures of blue-ring on electronic beam welding sample after water corrosion

International Nuclear Information System (INIS)

Ren Defang; Luo Xiandian; Tong Shenxiu; Guo Xulin; Peng Haiqing

2001-01-01

After water corrosion in compliance with ASTM G2, the blue ring appears on the nuclear fuel rod samples of AFA 2G welded by using a Big Chamber Electron Beam Welder made in Russia. The characteristics, appearance, chemical composition, microstructure of b lue ring a nd some condition test are described. The mechanism of forming blue ring may be depicted as following: welding metal vapor and the splash produced by secondary and scatter electrons on metal clamp and gun body deposit in the area between HAZ and substrate because of the water cooling down effects on the clamp; these deposits, after water corrosion, appears as blue ring on the fuel rod surface. Avoiding measure is that the side of the clamp closing to weld seal is chamfered, while making the welding chamber cleaner

Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

Science.gov (United States)

2016-06-03

Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9681 Calculation of Vibrational and Electronic Excited -State Absorption Spectra...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited -State Absorption Spectra of Arsenic-Water Complexes Using...Unclassified Unlimited Unclassified Unlimited 59 Samuel G. Lambrakos (202) 767-2601 Calculations are presented of vibrational and electronic excited -state

Simulation of energy deposit distribution in water for 10 and 25 MeV electron beams

International Nuclear Information System (INIS)

Borrell Carbonell, Maria de los Angeles.

1977-01-01

The Monte Carlo method was applied to transport simulation of electron beams from the exit window of a linear accelerator till the absorption by a water phantom. The distribution of energy deposit is calculated for ideal apparatus and experimental conditions. Calculations are made for a distance window-water surface of one meter, for 10 and 25 MeV monoenergetic incident electrons, and for different fields (15x15 cm 2 to 4x4 cm 2 ). Comparisons with experimental measurements obtained in comparable conditions with a Sagittaire accelerator (C.G.R.-MeV), show a good agreement concerning radial distribution and depth distribution around isodose 100%. However a certain disagreement appears in the end of depth penetration [fr

CGR MeV program for water and liquid sludges treatment with high-energy electron beams. Pt. 1

International Nuclear Information System (INIS)

Gallien, C.L.; Icre, P.; Levaillant, C.; Montiel, A.

1976-01-01

Research on the application of high-energy electron beams treatment to water and liquid sludges is described. Topics discussed include limitations of conventional methods of water treatment, dosimetry, biological assays with Pleurodeles waltlii, radioactivity measurement, chemical and bacteriological analysis. (author)

TH-CD-201-06: Experimental Characterization of Acoustic Signals Generated in Water Following Clinical Photon and Electron Beam Irradiation

International Nuclear Information System (INIS)

Hickling, S; El Naqa, I

2016-01-01

Purpose: Previous work has demonstrated the detectability of acoustic waves induced following the irradiation of high density metals with radiotherapy linac photon beams. This work demonstrates the ability to experimentally detect such acoustic signals following both photon and electron irradiation in a more radiotherapy relevant material. The relationship between induced acoustic signal properties in water and the deposited dose distribution is explored, and the feasibility of exploiting such signals for radiotherapy dosimetry is demonstrated. Methods: Acoustic waves were experimentally induced in a water tank via the thermoacoustic effect following a single pulse of photon or electron irradiation produced by a clinical linac. An immersion ultrasound transducer was used to detect these acoustic waves in water and signals were read out on an oscilloscope. Results: Peaks and troughs in the detected acoustic signals were found to correspond to the location of gradients in the deposited dose distribution following both photon and electron irradiation. Signal amplitude was linearly related to the dose per pulse deposited by photon or electron beams at the depth of detection. Flattening filter free beams induced large acoustic signals, and signal amplitude decreased with depth after the depth of maximum dose. Varying the field size resulted in a temporal shift of the acoustic signal peaks and a change in the detected signal frequency. Conclusion: Acoustic waves can be detected in a water tank following irradiation by linac photon and electron beams with basic electronics, and have characteristics related to the deposited dose distribution. The physical location of dose gradients and the amount of dose deposited can be inferred from the location and magnitude of acoustic signal peaks. Thus, the detection of induced acoustic waves could be applied to photon and electron water tank and in vivo dosimetry. This work was supported in part by CIHR grants MOP-114910 and MOP

Water-clear cell adenoma of the parathyroid. A case report with immunohistochemistry and electron microscopy.

Science.gov (United States)

Grenko, R T; Anderson, K M; Kauffman, G; Abt, A B

1995-11-01

We report a water-clear cell adenoma of the parathyroid gland, a lesion which to our knowledge has not been described previously. Like its rare but well-described hyperplastic counterpart, water-clear cell hyperplasia, this adenoma is composed of cells with abundant foamy-to-granular cytoplasm and mild nuclear pleomorphism. The cells form glandular structures and cell nests separated by fine fibrovascular septae. The tumor cells stain positively with anti-parathyroid hormone and show characteristic glassy and flocculate material by electron microscopy. Unlike water-clear cell hyperplasia, water-clear cell adenoma is a solitary lesion that compresses the residual nonneoplastic parathyroid gland.

Seasonal variability of the Red Sea, from satellite gravity, radar altimetry, and in situ observations

Science.gov (United States)

Wahr, John; Smeed, David A.; Leuliette, Eric; Swenson, Sean

2014-08-01

Seasonal variations of sea surface height (SSH) and mass within the Red Sea are caused mostly by exchange of heat with the atmosphere and by flow through the strait opening into the Gulf of Aden to the south. That flow involves a net mass transfer into the Red Sea during fall and out during spring, though in summer there is an influx of cool water at intermediate depths. Thus, summer water in the south is warmer near the surface due to higher air temperatures, but cooler at intermediate depths. Summer water in the north experiences warming by air-sea exchange only. The temperature affects water density, which impacts SSH but has no effect on mass. We study this seasonal cycle by combining GRACE mass estimates, altimeter SSH measurements, and steric contributions derived from the World Ocean Atlas temperature climatology. Among our conclusions are: mass contributions are much larger than steric contributions; the mass is largest in winter, consistent with winds pushing water into the Red Sea in fall and out during spring; the steric signal is largest in summer, consistent with surface warming; and the cool, intermediate-depth water flowing into the Red Sea in spring has little impact on the steric signal, because contributions from the lowered temperature are offset by effects of decreased salinity. The results suggest that the combined use of altimeter and GRACE measurements can provide a useful alternative to in situ data for monitoring the steric signal.

A low-cost electronic tensiometer system for continuous monitoring of soil water potential

Directory of Open Access Journals (Sweden)

Martin Thalheimer

2013-12-01

Full Text Available A low cost system for measuring soil water potential and data logging was developed on the basis of an Arduino microcontroller board, electronic pressure transducers and water-filled tensiometers. The assembly of this system requires only minimal soldering, limited to the wiring of the power supply and the pressure sensors to the microcontroller board. The system presented here is, therefore, not only inexpensive, but also suited for easy reproduction by users with only basic technical skills. The utility and reliability of the system was tested in a commercial apple orchard.

Effects of Surface Dipole Lengths on Evaporation of Tiny Water Aggregation

International Nuclear Information System (INIS)

Wang Shen; Wan Rongzheng; Fang Haiping; Tu Yusong

2013-01-01

Using molecular dynamics simulation, we compared evaporation behavior of a tiny amount of water molecules adsorbed on solid surfaces with different dipole lengths, including surface dipole lengths of 1 fold, 2 folds, 4 folds, 6 folds and 8 folds of 0.14 nm and different charges from 0.1e to 0.9e. Surfaces with short dipole lengths (1-fold system) can always maintain hydrophobic character and the evaporation speeds are not influenced, whether the surface charges are enhanced or weakened; but when surface dipole lengths get to 8 folds, surfaces become more hydrophilic as the surface charge increases, and the evaporation speeds increase gradually and monotonically. By tuning dipole lengths from 1-fold to 8-fold systems, we confirmed non-monotonic variation of the evaporation flux (first increases, then decreases) in 4 fold system with charges (0.1e–0.7e), reported in our previous paper [S. Wang, et al., J. Phys. Chem. B 116 (2012) 13863], and also show the process from the enhancement of this unexpected non-monotonic variation to its vanishment with surface dipole lengths increasing. Herein, we demonstrated two key factors to influence the evaporation flux of a tiny amount of water molecules adsorbed on solid surfaces: the exposed surficial area of water aggregation from where the water molecules can evaporate directly and the attraction potential from the substrate hindering the evaporation. In addition, more interestingly, we showed extra steric effect of surface dipoles on further increase of evaporation flux for 2-folds, 4-folds, 6-folds and 8-folds systems with charges around larger than 0.7e. (The steric effect is first reported by parts of our authors [C. Wang, et al., Sci. Rep. 2 (2012) 358]). This study presents a complete physical picture of the influence of surface dipole lengths on the evaporation behavior of the adsorbed tiny amount of water. (condensed matter: structural, mechanical, and thermal properties)

Characterization of the phantom material Virtual WaterTM in high-energy photon and electron beams

International Nuclear Information System (INIS)

McEwen, M.R.; Niven, D.

2006-01-01

The material Virtual Water TM has been characterized in photon and electron beams. Range-scaling factors and fluence correction factors were obtained, the latter with an uncertainty of around 0.2%. This level of uncertainty means that it may be possible to perform dosimetry in a solid phantom with an accuracy approaching that of measurements in water. Two formulations of Virtual Water TM were investigated with nominally the same elemental composition but differing densities. For photon beams neither formulation showed exact water equivalence--the water/Virtual Water TM dose ratio varied with the depth of measurement with a difference of over 1% at 10 cm depth. However, by using a density (range) scaling factor very good agreement ( TM at all depths was obtained. In the case of electron beams a range-scaling factor was also required to match the shapes of the depth dose curves in water and Virtual Wate TM . However, there remained a difference in the measured fluence in the two phantoms after this scaling factor had been applied. For measurements around the peak of the depth-dose curve and the reference depth this difference showed some small energy dependence but was in the range 0.1%-0.4%. Perturbation measurements have indicated that small slabs of material upstream of a detector have a small (<0.1% effect) on the chamber reading but material behind the detector can have a larger effect. This has consequences for the design of experiments and in the comparison of measurements and Monte Carlo-derived values

Molecular engineering of D-A-π-A dyes with 2-(1,1-dicyanomethylene)rhodanine as an electron-accepting and anchoring group for dye-sensitized solar cells

International Nuclear Information System (INIS)

Mao, Jiangyi; Zhang, Xiaoyu; Liu, Shih-Hung; Shen, Zhongjin; Li, Xing; Wu, Wenjun; Chou, Pi-Tai; Hua, Jianli

2015-01-01

Graphical abstract: We designed and synthesized two new D-A-π-A dyes (RD-III and RD-IV) with 2-(1,1-dicyanomethylene) rhodanine (DCRD) as an electron-accepting and anchoring group. The theoretical calculation of dye/(TiO 2 ) 38 displayed that the angle between the molecule of RD-III and the surface of TiO 2 was only 31.84 0 in contrast to 97.16 0 for CA-III. This adsorption state can facilitate dye aggregation and charge recombination, resulting in a decrease of short circuit current density (J sc ) and open circuit voltage (V oc ). Further improvement has been successfully made by adding long alkoxy chains with large steric hindrance. After introducing the alkoxy chains of the benzothiadiazole unit, the dihedral angle between RD-IV and TiO 2 increased to 42.61 0 and the steric hindrance can inhibit dye aggregation and charge recombination. Therefore, higher photoelectric conversion efficiency of 5.53% was obtained with RD-IV in DSSC devices compared with 4.51% for DSSC based on RD-III. - Highlights: • We obtained two D-A-π-A dyes with 2-(1,1-dicyanomethylene) rhodanine as acceptor. • Introduction of octyloxy groups can increase the angle of dye/TiO 2 . • Octyloxy groups can inhibit dye aggregation and charge recombination effectively. • Higher power conversion efficiency of 5.53% was obtained with dye octyloxy group. - Abstract: The electron-accepting and anchoring group plays a significant role on the optical and electrochemical properties of an organic dye. They also affect the intramolecular charge transfer, the electron injection processes and the adsorption mode, hence the photostability of the dye on TiO 2 films. In this study, we have designed and synthesized two new D-A-π-A dyes (RD-III and RD-IV) with 2-(1,1-dicyanomethylene) rhodanine (DCRD) as electron-accepting and anchoring group. For comparison, an analogue of RD-III, namely CA-III, with cyanoacrylic acid (CA) as the acceptor was also prepared. We have carefully examined their optical and

Bonded exciplex formation: electronic and stereoelectronic effects.

Science.gov (United States)

Wang, Yingsheng; Haze, Olesya; Dinnocenzo, Joseph P; Farid, Samir; Farid, Ramy S; Gould, Ian R

2008-12-18

As recently proposed, the singlet-excited states of several cyanoaromatics react with pyridine via bonded-exciplex formation, a novel concept in photochemical charge transfer reactions. Presented here are electronic and steric effects on the quenching rate constants, which provide valuable support for the model. Additionally, excited-state quenching in poly(vinylpyridine) is strongly inhibited both relative to that in neat pyridine and also to conventional exciplex formation in polymers, consistent with a restrictive orientational requirement for the formation of bonded exciplexes. Examples of competing reactions to form both conventional and bonded exciplexes are presented, which illustrate the delicate balance between these two processes when their reaction energetics are similar. Experimental and computational evidence is provided for the formation of a bonded exciplex in the reaction of the singlet excited state of 2,6,9,10-tetracyanoanthracene (TCA) with an oxygen-substituted donor, dioxane, thus expanding the scope of bonded exciplexes.

The water-water cycle in leaves is not a major alternative electron sink for dissipation of excess excitation energy when CO2 assimilation is restricted

NARCIS (Netherlands)

Driever, S.M.; Baker, N.R.

2011-01-01

Electron flux from water via photosystem II (PSII) and PSI to oxygen (water–water cycle) may provide a mechanism for dissipation of excess excitation energy in leaves when CO2 assimilation is restricted. Mass spectrometry was used to measure O2 uptake and evolution together with CO2 uptake in leaves

Effects of water stress on photosynthetic electron transport, photophosphorylation, and metabolite levels of Xanthium strumarium mesophyll cells.

Science.gov (United States)

Sharkey, T D; Badger, M R

1982-12-01

Several component processes of photosynthesis were measured in osmotically stressed mesophyll cells of Xanthium strumarium L. The ribulose-1,5-bisphosphate regeneration capacity was reduced by water stress. Photophoshorylation was sensitive to water stress but photosynthetic electron transport was unaffected by water potentials down to-40 bar (-4 MPa). The concentrations of several intermediates of the photosynthetic carbon-reduction cycle remained relatively constant and did not indicate that ATP supply was limiting photosynthesis in the water-stressed cells.

Electron density in surface barrier discharge emerging at argon/water interface: quantification for streamers and leaders

Science.gov (United States)

Cvetanović, Nikola; Galmiz, Oleksandr; Synek, Petr; Zemánek, Miroslav; Brablec, Antonín; Hoder, Tomáš

2018-02-01

Optical emission spectroscopy, fast intensified CCD imaging and electrical measurements were applied to investigate the basic plasma parameters of surface barrier discharge emerging from a conductive water electrode. The discharge was generated at the triple-line interface of atmospheric pressure argon gas and conductive water solution at the fused silica dielectrics using a sinusoidal high-voltage waveform. The spectroscopic methods of atomic line broadening and molecular spectroscopy were used to determine the electron densities and the gas temperature in the active plasma. These parameters were obtained for both applied voltage polarities and resolved spatially. Two different spectral signatures were identified in the spatially resolved spectra resulting in electron densities differing by two orders of magnitude. It is shown that two discharge mechanisms take a place: the streamer and the leader one, with electron densities of 1014 and 1016 cm-3, respectively. This spectroscopic evidence is supported by the combined diagnostics of electrical current measurements and phase-resolved intensified CCD camera imaging.

Ab initio calculations of dissociative excitation of water and methane molecules upon electron impact at low energies

International Nuclear Information System (INIS)

Gil, T.J.; McCurdy, C.W.; Rescigno, T.N.; Lengsfield, B.H. III

1994-01-01

The authors are reporting results of ab-initio calculations of electron-impact excitation of water and methane occurring at scattering energies up to 60 eV. The authors consider dissociative excited states of both systems since the understanding of their chemistry has considerable importance in plasma technology and atmospheric research. In the case of methane the authors are dealing with the promotion of a valence electron into Rydberg orbitals, while in water the excited states have one electron in an antibonding unoccupied valence orbital and support Feshbach resonances. The authors discuss issues related to convergence of the close-coupling expansion in the case of Rydberg excitation, where the authors have coupled up to 16 channels. The practical realization of the calculation within the framework of the complex Kohn variational principle represents merging of quantum chemistry and quantum scattering theory and is also discussed

Characterization of Emulsions of Fish Oil and Water by Cryo Scanning Electron Microscopy

DEFF Research Database (Denmark)

Jensen, Louise Helene Søgaard; Horn, Anna Frisenfeldt; Jacobsen, Charlotte

Addition of fish oil to industrially prepared food products is attractive to the food industry because of the well-documented health effects of the omega 3 fatty acids in the fish oil [1]. Polyunsaturated Fatty Acids including omega 3 fatty acids are highly susceptible to lipid oxidation due...... to the many double bonds. Emulsions of fish oil in water are potential candidates for a delivery system of fish oil to food products. It has been suggested that oxidation of oil-in-water emulsions is initiated at the interface between oil and water. It has also been proposed that oxidation is to some extent...... is to characterize fish oil in water emulsions with respect to oil droplet size, distribution, and ultimately to view the structure and thickness of the interface layer. A freeze-fractured surface viewed at low temperatures under the scanning electron microscope is a promising strategy to reveal variations...

Bacillus cereus as indicator in the sterilization of residual water with high energy electrons; Bacillus cereus como indicador en la desinfeccion de aguas residuales con electrones de alta energia

Energy Technology Data Exchange (ETDEWEB)

Mejia Z, E

2000-07-01

One of the main causes of water pollution is the presence of microorganisms that provoke infections, moreover of chemical substances. The processes of residual water treatment finally require of the disinfection for its use or final disposition. The radiation technology for the residual water treatment by mean of electron beams is an innovator process because as well as decomposing the chemical substance or to degrade them, also it provokes a disinfection by which this is proposed as alternative for disinfection of residual water, with the purpose in reusing the water treated in the agriculture, recreation and industry among others secondary activities, solving environmental or health problems. The objective of this work is to evaluate the use of Bacillus cereus as biological indicator in the disinfection by radiation, using High Energy Electrons. To fulfil with this objective, the work was developed in three stages, the first one consisted in the acquisition, propagation and conservation of the Bacillus cereus stumps, considering Escherichia coli and Salmonella typhimurium as pathogenic germs present in residual water. Moreover, the inocule standardization and the conditions of the Electron accelerator Type Pelletron. In the second stage it was performed the irradiation of aqueous samples of the microorganisms simulating biological pollution and the application to problem samples of a treatment plant sited in the Lerma River zone of mixed residual water. And in the third stage was performed a regression analysis to the reported survival for each kind of microorganisms. The results obtained show that with the use of Electron beams was reduced 6 logarithmic units de E. coli at 129 Gy, for S. typhimurium it was reduced 8 logarithmic units at 383 Gy and the B. cereus at 511 Gy was reduced 6.8 logarithmic units. Of the problem samples irradiated at 500 Gy, the concentration of the total account diminished from 8.70 x 10{sup 7} UFC/ml to 550 UFC/ml, the presence of B

Pulse radiolysis of liquid water using picosecond electron pulses produced by a table-top terawatt laser system

International Nuclear Information System (INIS)

Saleh, Ned; Flippo, Kirk; Nemoto, Koshichi; Umstadter, Donald; Crowell, Robert A.; Jonah, Charles D.; Trifunac, Alexander D.

2000-01-01

A laser based electron generator is shown, for the first time, to produce sufficient charge to conduct time resolved investigations of radiation induced chemical events. Electron pulses generated by focussing terawatt laser pulses into a supersonic helium gas jet are used to ionize liquid water. The decay of the hydrated electrons produced by the ionizing electron pulses is monitored with 0.3 μs time resolution. Hydrated electron concentrations as high as 22 μM were generated. The results show that terawatt lasers offer both an alternative to linear accelerators and a means to achieve subpicosecond time resolution for pulse radiolysis studies. (c) 2000 American Institute of Physics

The impact of intramolecular π-coupling and steric flexibility on the ordering of organic films at solid/liquid-interfaces

Science.gov (United States)

Saracino, Martino; Breuer, Stephan; Barati, Gholamreza; Sak, Emilia; Hingerl, Kurt; Müller, Ute; Müller, Manfred; Höger, Sigurd; Wandelt, Klaus

2013-01-01

In the present work the effect of the intramolecular steric flexibility on the structural self-assembly of organic cations and their redox activity at a chloride precovered Cu(100) electrode is investigated. In particular the adsorption of 1,1‧-dibenzyl-4,4‧-(propane-1,3-diyl)dipyridinium (C3-DBDP) is studied by means of cyclic voltametry (CV), in situ scanning tunneling microscopy (EC-STM) and ex situ X-ray photoelectron spectroscopy (XPS) and the experimental results are compared to previously published findings on related bipyridinium (“viologen”) molecules. The CV measurements reveal a loss of the redox activity of the more flexible C3-DBDP2 + compared to dibenzylviologen (DBV2 +), as the first electron reduction step of C3-DBDP2 + does not appear within the potential window of the Cu(100), but is shifted below the hydrogen evolution regime. This reduced redox activity is the result of the lifting of the extended π-system of the bipyridinium core by introducing the propyl chain between the two pyridinium rings. In agreement with this result, XP spectra prove that the C3-DBDP2 + cations retain their initial dicationic charge within the entire potential window in solution but also upon adsorption on the Cl-c(2x2)/Cu(100) substrate, where they are found to form an inter-linked stripe phase. The building blocks of each stripe are attributed to one pyridinium-benzyl moiety, which represents half of one C3-DBDP2 + molecule. The resulting consecutive arrangement of half C3-DBDP2 + molecules along one stripe is stabilized by electrostatic attraction between the positively charged pyridinium rings and the negatively charged π-system of the benzyl rings.

Probing the structural and dynamical properties of liquid water with models including non-local electron correlation

International Nuclear Information System (INIS)

Del Ben, Mauro; Hutter, Jürg; VandeVondele, Joost

2015-01-01

Water is a ubiquitous liquid that displays a wide range of anomalous properties and has a delicate structure that challenges experiment and simulation alike. The various intermolecular interactions that play an important role, such as repulsion, polarization, hydrogen bonding, and van der Waals interactions, are often difficult to reproduce faithfully in atomistic models. Here, electronic structure theories including all these interactions at equal footing, which requires the inclusion of non-local electron correlation, are used to describe structure and dynamics of bulk liquid water. Isobaric-isothermal (NpT) ensemble simulations based on the Random Phase Approximation (RPA) yield excellent density (0.994 g/ml) and fair radial distribution functions, while various other density functional approximations produce scattered results (0.8-1.2 g/ml). Molecular dynamics simulation in the microcanonical (NVE) ensemble based on Møller-Plesset perturbation theory (MP2) yields dynamical properties in the condensed phase, namely, the infrared spectrum and diffusion constant. At the MP2 and RPA levels of theory, ice is correctly predicted to float on water, resolving one of the anomalies as resulting from a delicate balance between van der Waals and hydrogen bonding interactions. For several properties, obtaining quantitative agreement with experiment requires correction for nuclear quantum effects (NQEs), highlighting their importance, for structure, dynamics, and electronic properties. A computed NQE shift of 0.6 eV for the band gap and absorption spectrum illustrates the latter. Giving access to both structure and dynamics of condensed phase systems, non-local electron correlation will increasingly be used to study systems where weak interactions are of paramount importance

The effects of conformational constraints and steric bulk in the amino acid moiety of philanthotoxins on AMPAR antagonism

DEFF Research Database (Denmark)

Jørgensen, Malene; Olsen, Christian A; Mellor, Ian R

2005-01-01

, establishing general protocols for philanthotoxin solution- and solid-phase synthesis (39-90% and 42-54% overall yields, respectively). The analogues were tested for their ability to antagonize kainate-induced currents of 2-amino-3-(3-hydroxy-5-methyl-4-isoxazoyl)propanoic acid receptors (AMPAR) expressed...... in Xenopus oocytes from rat brain mRNA. This showed that steric bulk in the amino acid moiety is well tolerated and suggests that binding to AMPAR does not involve the alpha-NHCO group as a donor in hydrogen bonding.......Philanthotoxin-343 (PhTX-343), a synthetic analogue of wasp toxin PhTX-433, is a noncompetitive antagonist at ionotropic receptors (e.g., AChR or iGluR). To determine possible effects of variations of the amino acid side chain, a library consisting of seventeen PhTX-343 analogues was prepared. Thus...

Giant onsite electronic entropy enhances the performance of ceria for water splitting

DEFF Research Database (Denmark)

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine Anton

2017-01-01

lanthanides, and reaches a maximum value of ≈4.7 kB per oxygen vacancy for Ce4+/Ce3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has...... a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions....

Electron scavenging in ethylene glycol-water glass at 4 and 77 K: scavenging of trapped vs mobile electrons. [. gamma. -rays, x radiation

Energy Technology Data Exchange (ETDEWEB)

Lin, D P; Kevan, L [Wayne State Univ., Detroit, Mich. (USA). Dept. of Chemistry; Steen, H B

1976-01-01

Electron scavenging efficiencies have been measured at 77 and 4 K in ethylene glycol-water glass for the following scavengers which span a 250-fold range of scavenger efficiencies at 77 K: HCl, NaNO/sub 3/ and K/sub 2/Cr0/sub 4/. The range of scavenging efficiencies decreases to 62 at 4 K with the largest relative change occurring for the less efficient scavengers. These results are suggested to be most consistent with a model in which scavenging occurs by tunneling from shallowly and deeply trapped electrons at 4 and 77 K, respectively.

Theoretical analysis of the rotational barrier of ethane.

Science.gov (United States)

Mo, Yirong; Gao, Jiali

2007-02-01

The understanding of the ethane rotation barrier is fundamental for structural theory and the conformational analysis of organic molecules and requires a consistent theoretical model to differentiate the steric and hyperconjugation effects. Due to recently renewed controversies over the barrier's origin, we developed a computational approach to probe the rotation barriers of ethane and its congeners in terms of steric repulsion, hyperconjugative interaction, and electronic and geometric relaxations. Our study reinstated that the conventional steric repulsion overwhelmingly dominates the barriers.

Overcoming double-step CO2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg2(dobpdc).

Science.gov (United States)

Milner, Phillip J; Martell, Jeffrey D; Siegelman, Rebecca L; Gygi, David; Weston, Simon C; Long, Jeffrey R

2018-01-07

Alkyldiamine-functionalized variants of the metal-organic framework Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising for CO 2 capture applications owing to their unique step-shaped CO 2 adsorption profiles resulting from the cooperative formation of ammonium carbamate chains. Primary , secondary (1°,2°) alkylethylenediamine-appended variants are of particular interest because of their low CO 2 step pressures (≤1 mbar at 40 °C), minimal adsorption/desorption hysteresis, and high thermal stability. Herein, we demonstrate that further increasing the size of the alkyl group on the secondary amine affords enhanced stability against diamine volatilization, but also leads to surprising two-step CO 2 adsorption/desorption profiles. This two-step behavior likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg 2 (dobpdc) and leads to decreased CO 2 working capacities and increased water co-adsorption under humid conditions. To minimize these unfavorable steric interactions, we targeted diamine-appended variants of the isoreticularly expanded framework Mg 2 (dotpdc) (dotpdc 4- = 4,4''-dioxido-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate), reported here for the first time, and the previously reported isomeric framework Mg-IRMOF-74-II or Mg 2 (pc-dobpdc) (pc-dobpdc 4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate, pc = para -carboxylate), which, in contrast to Mg 2 (dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO 2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg 2 (pc-dobpdc) with large diamines such as N -( n -heptyl)ethylenediamine results in optimal adsorption behavior, highlighting the advantage of tuning both the pore shape and the diamine size for the development of

Spatial distribution of bremsstrahlung in water and water-iron by 22-MeV electron bombardment measured with activation detectors

International Nuclear Information System (INIS)

Nakamura, Takashi; Nishimoto, Takanao; Hirayama, Hideo.

1977-01-01

The spatial distributions of bremsstrahlung in water (1 m thick) and water (60 cm thick)-iron (6.3 cm thick) bombarded by 22-MeV electrons were measured by using a new activation method which we developed. These informations are useful for studying shielding, residual activity and radiation damage of accelerator and target materials. From the measured activities, the bremsstrahlung spectra in water were evaluated with the LYRA and the SAND-II unfolding codes. The evaluated spectra were in good agreement with the analytical calculation by the DIBRE code, except for the higher energy ends. The longitudinal and the lateral distributions of bremsstrahlung flux in water were obtained by integrating the evaluated spectra above 8 MeV. The agreement of the experimental and the calculated flux distributions was very good except for a large angle to beam direction. The total photon number crossing a plane normal to the beam axis attenuates exponentially along the axial depth. The iso-flux contour of bremsstrahlung flux was given by interpolating the flux distribution curves. Only the saturated activities of gold detectors were obtained for water-iron in good experimental accuracy. The spatial distribution of gold saturated activities in water-iron clearly shows the attenuating effect due to strong absorption in iron. (auth.)

NCEI ocean heat content, temperature anomalies, salinity anomalies, thermosteric sea level anomalies, halosteric sea level anomalies, and total steric sea level anomalies from 1955 to present calculated from in situ oceanographic subsurface profile data (NCEI Accession 0164586)

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — This accession contains ocean heat content change, oceanic temperature and salinity changes, and steric sea level change (change in volume without change in mass),...

Band resolution of optical spectra of solvated electrons in water, alcohols, and tetrahydrofuran

International Nuclear Information System (INIS)

Jou, F.-Y.; Freeman, G.R.

1979-01-01

The optical absorption spectra of solvated electrons in water, alcohols, and tetrahydrofuran are empirically resolved into two Gaussian bands and a continuum tail. The first Gaussian band covers most of the low energy side of the spectrum. The second Gaussian band lies at an energy slightly above that of the absorption maximum of the total spectrum. With the exception of tert-butyl alcohol, in water and alcohols the following were observed: (a) the first Gaussian bands have the same half-width, but the oscillator strength in water is about double that in an alcohol; (b) the second Gaussian bands have similar half-widths and oscillator strengths; (c) the continuum tails have similar half-widths, yet that in water possesses only about one third as much oscillator strength as the one in alcohol. In tert-butyl alcohol and tetrahydrofuran the first Gaussian band and the continuum tail each carry nearly half of the total oscillator strength. (author)

The role of atomic level steric effects and attractive forces in protein folding.

Science.gov (United States)

Lammert, Heiko; Wolynes, Peter G; Onuchic, José N

2012-02-01

Protein folding into tertiary structures is controlled by an interplay of attractive contact interactions and steric effects. We investigate the balance between these contributions using structure-based models using an all-atom representation of the structure combined with a coarse-grained contact potential. Tertiary contact interactions between atoms are collected into a single broad attractive well between the C(β) atoms between each residue pair in a native contact. Through the width of these contact potentials we control their tolerance for deviations from the ideal structure and the spatial range of attractive interactions. In the compact native state dominant packing constraints limit the effects of a coarse-grained contact potential. During folding, however, the broad attractive potentials allow an early collapse that starts before the native local structure is completely adopted. As a consequence the folding transition is broadened and the free energy barrier is decreased. Eventually two-state folding behavior is lost completely for systems with very broad attractive potentials. The stabilization of native-like residue interactions in non-perfect geometries early in the folding process frequently leads to structural traps. Global mirror images are a notable example. These traps are penalized by the details of the repulsive interactions only after further collapse. Successful folding to the native state requires simultaneous guidance from both attractive and repulsive interactions. Copyright © 2011 Wiley Periodicals, Inc.

Electron Beam-Induced Immobilization of Laccase on Porous Supports for Waste Water Treatment Applications

Directory of Open Access Journals (Sweden)

Elham Jahangiri

2014-08-01

Full Text Available The versatile oxidase enzyme laccase was immobilized on porous supports such as polymer membranes and cryogels with a view of using such biocatalysts in bioreactors aiming at the degradation of environmental pollutants in wastewater. Besides a large surface area for supporting the biocatalyst, the aforementioned porous systems also offer the possibility for simultaneous filtration applications in wastewater treatment. Herein a “green” water-based, initiator-free, and straightforward route to highly reactive membrane and cryogel-based bioreactors is presented, where laccase was immobilized onto the porous polymer supports using a water-based electron beam-initiated grafting reaction. In a second approach, the laccase redox mediators 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS and syringaldehyde were cross-linked instead of the enzyme via electron irradiation in a frozen aqueous poly(acrylate mixture in a one pot set-up, yielding a mechanical stable macroporous cryogel with interconnected pores ranging from 10 to 50 µm in size. The membranes as well as the cryogels were characterized regarding their morphology, chemical composition, and catalytic activity. The reactivity towards waste- water pollutants was demonstrated by the degradation of the model compound bisphenol A (BPA. Both membrane- and cryogel-immobilized laccase remained highly active after electron beam irradiation. Apparent specific BPA removal rates were higher for cryogel- than for membrane-immobilized and free laccase, whereas membrane-immobilized laccase was more stable with respect to maintenance of enzymatic activity and prevention of enzyme leakage from the carrier than cryogel-immobilized laccase. Cryogel-immobilized redox mediators remained functional in accelerating the laccase-catalyzed BPA degradation, and especially ABTS was found to act more efficiently in immobilized than in freely dissolved state.

Initial electron energy spectra in water irradiated by photons with energies to 1 GeV

International Nuclear Information System (INIS)

Todo, A.S.; Hiromoto, G.; Turner, J.E.; Hamm, R.N.; Wright, H.A.

1984-02-01

This work was undertaken to provide basic physical data for use in the dosimetry of high-energy photons. Present and future sources of such photons are described, and the relevant literature is reviewed and summarized. Calculations were performed with a Monte Carlo computer code, PHOEL-3, which is also described. Tables of initial electron and positron energies are presented for monoenergetic photons undergoing single interactions in water. Photon energies to 1 GeV are treated. The code treats explicitly the production of electron-positron pairs, Compton scattering, photoelectric absorption, and the emission of Auger electrons following the occurrence of K-shell vacancies in oxygen. The tables give directly the information needed to specify the absolute single-collision kerma in water, which approximates tissue, at each photon energy. Results for continuous photon energy spectra can be obtained by using linear interpolation with the tables. (Continuous spectra can also be used directly in PHOEL-3.) The conditions under whch first-collision kerma approximate absorbed dose are discussed. A formula is given for estimating bremsstrahlung energy loss, one of the principal differences between kerma and absorbed dose in practical cases. 31 references, 4 figures, 18 tables

Quantitative nanoscale water mapping in frozen-hydrated skin by low-loss electron energy-loss spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Yakovlev, Sergey [Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, Hoboken, NJ 07030 (United States); Misra, Manoj; Shi, Shanling [Unilever Research and Development, Trumbull, CT 06611 (United States); Firlar, Emre [Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, Hoboken, NJ 07030 (United States); Libera, Matthew, E-mail: mlibera@stevens.edu [Department of Chemical Engineering and Materials Science, Stevens Institute of Technology, Hoboken, NJ 07030 (United States)

2010-06-15

Spatially resolved low-loss electron energy-loss spectroscopy (EELS) is a powerful method to quantitatively determine the water distribution in frozen-hydrated biological materials at high spatial resolution. However, hydrated tissue, particularly its hydrophilic protein-rich component, is very sensitive to electron radiation. This sensitivity has traditionally limited the achievable spatial resolution because of the relatively high noise associated with low-dose data acquisition. We show that the damage caused by high-dose data acquisition affects the accuracy of a multiple-least-squares (MLS) compositional analysis because of inaccuracies in the reference spectrum used to represent the protein. Higher spatial resolution combined with more accurate compositional analysis can be achieved if a reference spectrum is used that better represents the electron-beam-damaged protein component under frozen-hydrated conditions rather than one separately collected from dry protein under low-dose conditions. We thus introduce a method to extract the best-fitting protein reference spectrum from an experimental spectrum dataset. This method can be used when the MLS-fitting problem is sufficiently constrained so that the only unknown is the reference spectrum for the protein component. We apply this approach to map the distribution of water in cryo-sections obtained from frozen-hydrated tissue of porcine skin. The raw spectral data were collected at doses up to 10{sup 5} e/nm{sup 2} despite the fact that observable damage begins at doses as low as 10{sup 3} e/nm{sup 2}. The resulting spatial resolution of 10 nm is 5-10 times better than that in previous studies of frozen-hydrated tissue and is sufficient to resolve sub-cellular water fluctuations as well as the inter-cellular lipid-rich regions of skin where water-mediated processes are believed to play a significant role in the phenotype of keratinocytes in the stratum corneum.

Quantitative nanoscale water mapping in frozen-hydrated skin by low-loss electron energy-loss spectroscopy

International Nuclear Information System (INIS)

Yakovlev, Sergey; Misra, Manoj; Shi, Shanling; Firlar, Emre; Libera, Matthew

2010-01-01

Spatially resolved low-loss electron energy-loss spectroscopy (EELS) is a powerful method to quantitatively determine the water distribution in frozen-hydrated biological materials at high spatial resolution. However, hydrated tissue, particularly its hydrophilic protein-rich component, is very sensitive to electron radiation. This sensitivity has traditionally limited the achievable spatial resolution because of the relatively high noise associated with low-dose data acquisition. We show that the damage caused by high-dose data acquisition affects the accuracy of a multiple-least-squares (MLS) compositional analysis because of inaccuracies in the reference spectrum used to represent the protein. Higher spatial resolution combined with more accurate compositional analysis can be achieved if a reference spectrum is used that better represents the electron-beam-damaged protein component under frozen-hydrated conditions rather than one separately collected from dry protein under low-dose conditions. We thus introduce a method to extract the best-fitting protein reference spectrum from an experimental spectrum dataset. This method can be used when the MLS-fitting problem is sufficiently constrained so that the only unknown is the reference spectrum for the protein component. We apply this approach to map the distribution of water in cryo-sections obtained from frozen-hydrated tissue of porcine skin. The raw spectral data were collected at doses up to 10 5 e/nm 2 despite the fact that observable damage begins at doses as low as 10 3 e/nm 2 . The resulting spatial resolution of 10 nm is 5-10 times better than that in previous studies of frozen-hydrated tissue and is sufficient to resolve sub-cellular water fluctuations as well as the inter-cellular lipid-rich regions of skin where water-mediated processes are believed to play a significant role in the phenotype of keratinocytes in the stratum corneum.

Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

Science.gov (United States)

Zhu, Di; Zhang, Linghong; Ruther, Rose E; Hamers, Robert J

2013-09-01

The photocatalytic reduction of N₂ to NH₃ is typically hampered by poor binding of N₂ to catalytic materials and by the very high energy of the intermediates involved in this reaction. Solvated electrons directly introduced into the reactant solution can provide an alternative pathway to overcome such limitations. Here we demonstrate that illuminated hydrogen-terminated diamond yields facile electron emission into water, thus inducing reduction of N₂ to NH₃ at ambient temperature and pressure. Transient absorption measurements at 632 nm reveal the presence of solvated electrons adjacent to the diamond after photoexcitation. Experiments using inexpensive synthetic diamond samples and diamond powder show that photocatalytic activity is strongly dependent on the surface termination and correlates with the production of solvated electrons. The use of diamond to eject electrons into a reactant liquid represents a new paradigm for photocatalytic reduction, bringing electrons directly to reactants without requiring molecular adsorption to the surface.

Population Shift between the Open and Closed States Changes the Water Permeability of an Aquaporin Z Mutant

DEFF Research Database (Denmark)

Xin, Lin; Helix Nielsen, Claus; Su, Haibin

2012-01-01

gate in the triple mutant with R189 as the primary steric gate in both mutant and WT AqpZ. The double gates (R189 and W43-F183) result in a high population of the closed conformation in the mutant. Occasionally an open state, with diffusive water permeability very close to that of WT AqpZ, was observed...... be modulated and may further point to how aquaporin function can be optimized for biomimetic membrane applications....

Eco-friendly electron beam lithography using water-developable resist material derived from biomass

Science.gov (United States)

Takei, Satoshi; Oshima, Akihiro; Wakabayashi, Takanori; Kozawa, Takahiro; Tagawa, Seiichi

2012-07-01

We investigated the eco-friendly electron beam (EB) lithography using a high-sensitive negative type of water-developable resist material derived from biomass on hardmask layer for tri-layer processes. A water developable, non-chemically amplified, high sensitive, and negative tone resist material in EB lithography was developed for environmental affair, safety, easiness of handling, and health of the working people, instead of the common developable process of trimethylphenylammonium hydroxide. The images of 200 nm line and 800 nm space pattern with exposure dose of 7.0 μC/cm2 and CF4 etching selectivity of 2.2 with hardmask layer were provided by specific process conditions.

Suitability of olive oil washing water as an electron donor in a feed batch operating bio-electrochemical system

International Nuclear Information System (INIS)

Fermoso, F.G.; Fernández-Rodríguez, M.J.; Jiménez-Rodríguez, A.; Serrano, A.; Borja, R.

2017-01-01

Olive oil washing water derived from the two-phase manufacturing process was assessed as an electron donor in a bio-electrochemical system (BES) operating at 35 ºC. Start-up was carried out by using acetate as a substrate for the BES, reaching a potential of around +680 mV. After day 54, BES was fed with olive oil washing water. The degradation of olive oil washing water in the BES generated a maximum voltage potential of around +520 mV and a Chemical Oxygen Demand (COD) removal efficiency of 41%. However, subsequent loads produced a decrease in the COD removal, while current and power density diminished greatly. The deterioration of these parameters could be a consequence of the accumulation of recalcitrant or inhibitory compounds, such as phenols. These results demonstrated that the use of olive oil washing water as an electron donor in a BES is feasible, although it has to be further investigated in order to make it more suitable for a real application. [es

Sensory evaluation and electronic tongue for sensing flavored mineral water taste attributes.

Science.gov (United States)

Sipos, László; Gere, Attila; Szöllősi, Dániel; Kovács, Zoltán; Kókai, Zoltán; Fekete, András

2013-10-01

In this article a trained sensory panel evaluated 6 flavored mineral water samples. The samples consisted of 3 different brands, each with 2 flavors (pear-lemon grass and josta berry). The applied sensory method was profile analysis. Our aim was to analyze the sensory profiles and to investigate the similarities between the sensitivity of the trained human panel and an electronic tongue device. Another objective was to demonstrate the possibilities for the prediction of sensory attributes from electronic tongue measurements using a multivariate statistical method (Partial Least Squares regression [PLS]). The results showed that the products manufactured under different brand name but with the same aromas had very similar sensory profiles. The panel performance evaluation showed that it is appropriate (discrimination ability, repeatability, and panel consensus) to compare the panel's results with the results of the electronic tongue. The samples can be discriminated by the electronic tongue and an accurate classification model can be built. Principal Component Analysis BiPlot diagrams showed that Brand A and B were similar because the manufacturers use the same aroma brands for their products. It can be concluded that Brand C was quite different compared to the other samples independently of the aroma content. Based on the electronic tongue results good prediction models can be obtained with high correlation coefficient (r(2) > 0.81) and low prediction error (RMSEP sensory evaluation from 0 to 100). © 2013 Institute of Food Technologists®

Detour factors in water and plastic phantoms and their use for range and depth scaling in electron-beam dosimetry

International Nuclear Information System (INIS)

Fernandez-Varea, J.M.; Andreo, P.; Tabata, T.

1996-01-01

Average penetration depths and detour factors of 1-50 MeV electrons in water and plastic materials have been computed by means of analytical calculation, within the continuous-slowing-down approximation and including multiple scattering, and using the Monte Carlo codes ITS and PENELOPE. Results are compared to detour factors from alternative definitions previously proposed in the literature. Different procedures used in low-energy electron-beam dosimetry to convert ranges and depths measured in plastic phantoms into water-equivalent ranges and depths are analysed. A new simple and accurate scaling method, based on Monte Carlo-derived ratios of average electron penetration depths and thus incorporating the effect of multiple scattering, is presented. Data are given for most plastics used in electron-beam dosimetry together with a fit which extends the method to any other low-Z plastic material. A study of scaled depth - dose curves and mean energies as a function of depth for some plastics of common usage shows that the method improves the consistency and results of other scaling procedures in dosimetry with electron beams at therapeutic energies. (author)

Controlled and Efficient Polymerization of Conjugated Polar Alkenes by Lewis Pairs Based on Sterically Hindered Aryloxide-Substituted Alkylaluminum

Directory of Open Access Journals (Sweden)

Xiaojun Wang

2018-02-01

Full Text Available Reported herein is the development of an effective strategy for controlled and efficient Lewis pair polymerization of conjugated polar alkenes, including methyl methacrylate (MMA, n-butyl methacrylate (nBuMA, and γ-methyl-α-methylene-γ-butyrolactone (γMMBL, by the utilization of sterically encumbered Al(BHT2Me (BHT: 2,6-di-tert-butyl-4-methylphenol as a Lewis acid that shuts down intramolecular backbiting termination. In combination with a selected N-heterocyclic carbene (NHC as a Lewis base, the polymerization of MMA exhibited activity up to 3000 h−1 TOF and an acceptable initiation efficiency of 60.6%, producing polymers with high molecular weight (Mn up to 130 kg/mol and extremely narrow dispersity (Đ = 1.06~1.13. This controlled polymerization with a living characteristic has been evidenced by chain-extension experiments and chain-end analysis, and enabled the synthesis of well-defined diblock copolymers.

The role of PEG conformation in mixed layers: from protein corona substrate to steric stabilization avoiding protein adsorption

Directory of Open Access Journals (Sweden)

Joan Comenge

2015-03-01

Full Text Available Although nanoparticles (NPs have been traditionally modified with a single ligand layer, mixture of ligands might help to combine different functionalities and to further engineer the NP surface. A detailed study of the competition between an alkanethiol (11-mercaptoundecanoic acid and SH-PEG for the surface of AuNPs and the resultant behaviors of this model nanoconjugate is presented here. As a result, the physicochemical properties of these conjugates can be progressively tuned by controlling the composition and especially the conformation of the mixed monolayer. This has implications in the physiological stability. The controlled changes on the SH-PEG conformation rather than its concentration induce a change in the stabilization mechanism from electrostatic repulsion to steric hindrance, which changes the biological fate of NPs. Importantly, the adsorption of proteins on the conjugates can be tailored by tuning the composition and conformation of the mixed layer.

Evaluation of thermoluminescent dosimeters using water equivalent phantoms for application in clinical electrons beams dosimetry

International Nuclear Information System (INIS)

Bravim, Amanda

2010-01-01

The dosimetry in Radiotherapy provides the calibration of the radiation beam as well as the quality control of the dose in the clinical routine. Its main objective is to determine with greater accuracy the dose absorbed by the tumor. This study aimed to evaluate the behavior of three thermoluminescent dosimeters for the clinical electron beam dosimetry. The performance of the calcium sulfate detector doped with dysprosium (CaSO 4 : Dy) produced by IPEN was compared with two dosimeters commercially available by Harshaw. Both are named TLD-100, however they differ in their dimensions. The dosimeters were evaluated using water, solid water (RMI-457) and PMMA phantoms in different exposure fields for 4, 6, 9, 12 and 16 MeV electron beam energies. It was also performed measurements in photon beams of 6 and 15 MV (2 and 5 MeV) only for comparison. The dose-response curves were obtained for the 60 Co gamma radiation in air and under conditions of electronic equilibrium, both for clinical beam of photons and electrons in maximum dose depths. The sensitivity, reproducibility, intrinsic efficiency and energy dependence response of dosimeters were studied. The CaSO 4 : Dy showed the same behavior of TLD-100, demonstrating only an advantage in the sensitivity to the beams and radiation doses studied. Thus, the dosimeter produced by IPEN can be considered a new alternative for dosimetry in Radiotherapy departments. (author)

Microscopic solvation of a lithium atom in water-ammonia mixed clusters: solvent coordination and electron localization in presence of a counterion.

Science.gov (United States)

Pratihar, Subha; Chandra, Amalendu

2008-07-14

The microsolvation structures and energetics of water-ammonia mixed clusters containing a lithium atom, i.e., Li(H(2)O)(n)(NH(3)), n = 1-5, are investigated by means of ab initio theoretical calculations. Several structural aspects such as the solvent coordination to the metal ion and binding motifs of the free valence electron of the metal are investigated. We also study the energetics aspects such as the dependence of vertical ionization energies on the cluster size, and all these structural and energetics aspects are compared to the corresponding results of previously studied anionic water-ammonia clusters without a metal ion. It is found that the Li-O and Li-N interactions play a very important role in stabilizing the lithium-water-ammonia clusters, and the presence of these metal ion-solvent interactions also affect the characteristics of electron solvation in these clusters. This is seen from the spatial distribution of the singly occupied molecular orbital (SOMO) which holds the ejected valence electron of the Li atom. For very small clusters, SOMO electron density is found to exist mainly at the vicinity of the Li atom, whereas for larger clusters, it is distributed outside the first solvation shell. The free dangling hydrogens of water and ammonia molecules are involved in capturing the SOMO electron density. In some of the conformers, OH{e}HO and OH{e}HN types of interactions are found to be present. The presence of the metal ion at the center of the cluster ensures that the ejected electron is solvated at a surface state only, whereas both surface and interiorlike states were found for the free electron in the corresponding anionic clusters without a metal ion. The vertical ionization energies of the present clusters are found to be higher than the vertical detachment energies of the corresponding anionic clusters which signify a relatively stronger binding of the free electron in the presence of the positive metal counterion. The shifts in different

Quantitative conformational analysis of the core region of N-glycans using residual dipolar couplings, aqueous molecular dynamics, and steric alignment

International Nuclear Information System (INIS)

Almond, Andrew; Duus, Jens O.

2001-01-01

A method is described for quantitatively investigating the dynamic conformation of small oligosaccharides containing an α(1 → 6) linkage. It was applied to the oligosaccharide Man-α(1 → 3) {Man-α (1 → 6)}Man-α-O-Me, which is a core region frequently observed in N-linked glycans. The approach tests an aqueous molecular dynamics simulation, capable of predicting microscopic dynamics, against experimental residual dipolar couplings, by assuming that alignment is caused purely by steric hindrance. The experimental constraints were heteronuclear and homonuclear residual dipolar couplings, and in particular those within the α(1 → 6) linkage itself. Powerful spin-state-selective pulse sequences and editing schemes were used to obtain the most relevant couplings for testing the model. Molecular dynamics simulations in water over a period of 50 ns were not able to predict the correct rotamer population at the α(1 → 6) linkage to agree with the experimental data. However, this sampling problem could be corrected using a simple maximum likelihood optimisation, indicating that the simulation was modelling local dynamics correctly. The maximum likelihood prediction of the residual dipolar couplings was found to be an almost equal population of the gg and gt rotamer conformations at the α(1 → 6) linkage, and the tg conformation was predicted to be unstable and unpopulated in aqueous solution. In this case all twelve measured residual dipolar couplings could be satisfied. This conformer population could also be used to make predictions of scalar couplings with the use of a previously derived empirical equation, and is qualitatively in agreement with previous predictions based on NMR, X-ray crystallography and optical data

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

International Nuclear Information System (INIS)

Faradzhev, N.S.; Perry, C.C.; Kusmierek, D.O.; Fairbrother, D.H.; Madey, T.E.

2004-01-01

The kinetics of decomposition and subsequent chemistry of adsorbed CF 2 Cl 2 , activated by low-energy electron irradiation, have been examined and compared with CCl 4 . These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF 2 Cl 2 and CCl 4 dissociation increase in an H 2 O (D 2 O) environment (2-3x), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H 2 O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2x10 -15 cm 2 for CF 2 Cl 2 and 2.5±0.2x10 -15 cm 2 for CCl 4 . RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl - and F - anions in the halocarbon/water films and production of H 3 O + , CO 2 , and intermediate compounds COF 2 (for CF 2 Cl 2 ) and COCl 2 , C 2 Cl 4 (for CCl 4 ) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation

Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical

International Nuclear Information System (INIS)

Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide

2016-01-01

In this work we achieve three milestones: (1) we present a subsystem DFT method capable of running ab-initio molecular dynamics simulations accurately and efficiently. (2) In order to rid the simulations of inter-molecular self-interaction error, we exploit the ability of semilocal frozen density embedding formulation of subsystem DFT to represent the total electron density as a sum of localized subsystem electron densities that are constrained to integrate to a preset, constant number of electrons; the success of the method relies on the fact that employed semilocal nonadditive kinetic energy functionals effectively cancel out errors in semilocal exchange–correlation potentials that are linked to static correlation effects and self-interaction. (3) We demonstrate this concept by simulating liquid water and solvated OH • radical. While the bulk of our simulations have been performed on a periodic box containing 64 independent water molecules for 52 ps, we also simulated a box containing 256 water molecules for 22 ps. The results show that, provided one employs an accurate nonadditive kinetic energy functional, the dynamics of liquid water and OH • radical are in semiquantitative agreement with experimental results or higher-level electronic structure calculations. Our assessments are based upon comparisons of radial and angular distribution functions as well as the diffusion coefficient of the liquid.

Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical.

Science.gov (United States)

Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

2016-06-21

In this work we achieve three milestones: (1) we present a subsystem DFT method capable of running ab-initio molecular dynamics simulations accurately and efficiently. (2) In order to rid the simulations of inter-molecular self-interaction error, we exploit the ability of semilocal frozen density embedding formulation of subsystem DFT to represent the total electron density as a sum of localized subsystem electron densities that are constrained to integrate to a preset, constant number of electrons; the success of the method relies on the fact that employed semilocal nonadditive kinetic energy functionals effectively cancel out errors in semilocal exchange-correlation potentials that are linked to static correlation effects and self-interaction. (3) We demonstrate this concept by simulating liquid water and solvated OH(•) radical. While the bulk of our simulations have been performed on a periodic box containing 64 independent water molecules for 52 ps, we also simulated a box containing 256 water molecules for 22 ps. The results show that, provided one employs an accurate nonadditive kinetic energy functional, the dynamics of liquid water and OH(•) radical are in semiquantitative agreement with experimental results or higher-level electronic structure calculations. Our assessments are based upon comparisons of radial and angular distribution functions as well as the diffusion coefficient of the liquid.

Analysis of 3D models of octopus estrogen receptor with estradiol: evidence for steric clashes that prevent estrogen binding.

Science.gov (United States)

Baker, Michael E; Chandsawangbhuwana, Charlie

2007-09-28

Relatives of the vertebrate estrogen receptor (ER) are found in Aplysia californica, Octopus vulgaris, Thais clavigera, and Marisa cornuarietis. Unlike vertebrate ERs, invertebrate ERs are constitutively active and do not bind estradiol. To investigate the molecular basis of the absence of estrogen binding, we constructed a 3D model of the putative steroid-binding domain on octopus ER. Our 3D model indicates that binding of estradiol to octopus ER is prevented by steric clashes between estradiol and amino acids in the steroid-binding pocket. In this respect, octopus ER resembles vertebrate estrogen-related receptors (ERR), which have a ligand-binding pocket that cannot accommodate estradiol. Like ERR, octopus ER also may have the activation function 2 domain (AF2) in a configuration that can bind to coactivators in the absence of estrogens, which would explain constitutive activity of octopus ER.

Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

Energy Technology Data Exchange (ETDEWEB)

Robinson, Jerome R.; Gordon, Zachary; Booth, Corwin H.; Carroll, Patrick J.; Walsh, Patrick J.; Schelter, Eric J.

2014-06-24

Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1'-BINOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses of functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.

Evaluation of three electronic report processing systems for preparing hydrologic reports of the U.S Geological Survey, Water Resources Division

Science.gov (United States)

Stiltner, G.J.

1990-01-01

In 1987, the Water Resources Division of the U.S. Geological Survey undertook three pilot projects to evaluate electronic report processing systems as a means to improve the quality and timeliness of reports pertaining to water resources investigations. The three projects selected for study included the use of the following configuration of software and hardware: Ventura Publisher software on an IBM model AT personal computer, PageMaker software on a Macintosh computer, and FrameMaker software on a Sun Microsystems workstation. The following assessment criteria were to be addressed in the pilot studies: The combined use of text, tables, and graphics; analysis of time; ease of learning; compatibility with the existing minicomputer system; and technical limitations. It was considered essential that the camera-ready copy produced be in a format suitable for publication. Visual improvement alone was not a consideration. This report consolidates and summarizes the findings of the electronic report processing pilot projects. Text and table files originating on the existing minicomputer system were successfully transformed to the electronic report processing systems in American Standard Code for Information Interchange (ASCII) format. Graphics prepared using a proprietary graphics software package were transferred to all the electronic report processing software through the use of Computer Graphic Metafiles. Graphics from other sources were entered into the systems by scanning paper images. Comparative analysis of time needed to process text and tables by the electronic report processing systems and by conventional methods indicated that, although more time is invested in creating the original page composition for an electronically processed report , substantial time is saved in producing subsequent reports because the format can be stored and re-used by electronic means as a template. Because of the more compact page layouts, costs of printing the reports were 15% to 25

A new approach to solvent extraction: Electronic pulses shatter water droplets

International Nuclear Information System (INIS)

Anon.

1991-01-01

Researchers in the Chemical Technology Division of Oak Ridge National Laboratory (ORNL) have invented a device that represents a significant improvement in the area of solvent extraction, which is a widely used technique to recover valuable materials from a liquid stream. Known as the Emulsion Phase Contactor (EPC), the technology uses a pulsed electrical field to enhance recovery of chemicals (either valuable products or pollutants) that are dissolved in water. Because of its higher efficiency, the recovery method can be accomplished in much smaller vessels than those used in conventional solvent extractors, which use mechanical processes to recover chemicals. When water droplets carrying the substance to be extracted are introduced into the EPC, they are shattered by electronic pulses that produce water particles in the 1- to 5-micron size range. These water particles are up to 100 times smaller than those created by mechanical agitation. These tiny particles produce a much greater surface area than can be achieved using chemical agitators, enabling the chemical solvent to extract more material from the water base. In addition, the EPC uses much less power than mechanical methods and has no moving parts; therefore, servicing requirements for the extraction apparatus are expected to be significantly reduced. ORNL researchers initially tested the technology at a very small scale, and evaluated its capabilities in extracting high-value substances such as isotopes, pharmaceuticals, and precious metals. Further work has indicated that the EPC can be applied on a much larger scale to handle more common chemical substances

Novel Structures for the Excess Electron State of the Water Hexamer and the Interaction Forces Governing the Structures

International Nuclear Information System (INIS)

Lee, S.; Kim, J.; Lee, S.J.; Kim, K.S.

1997-01-01

The geometrical and electronic structures of partially hydrated electron systems, in particular, the water hexamer, which have been controversial for decades, have been clarified by an exhaustive search for possible low-lying energy structures. Several competing interaction forces governing the conformation have been examined for the first time. The low-lying energy structures are hybrid (or partially internal and partially surface) excess electron states. Our prediction is evidenced from excellent agreements with available experimental data. The vertical electron-detachment energies are mainly determined by the number of dangling H atoms (H d ) . copyright 1997 The American Physical Society

Pumping experiment of water on B and LaB6 films with electron beam evaporator

International Nuclear Information System (INIS)

Mori, Takahiro; Hanaoka, Yutaka; Akaishi, Kenya; Kubota, Yusuke; Motojima, Osamu; Mushiaki, Motoi; Funato, Yasuyuki.

1992-10-01

Pumping characteristics of water vapor on boron and lanthanum hexaboride films formed with an electron beam evaporator have been investigated in high vacuum of a pressure region between 10 -4 and 10 -3 Pa. Measured initial maximum pumping speeds of water for fresh B and LaB 6 films on substrates with a deposition amount from 2.3 x 10 21 to 6.7 x 10 21 molecules·m -2 are 3.2 ∼ 4.9 m 3 ·s -1 ·m -2 , and maximum saturation amounts of adsorbed water on these films are 2.9 x 10 20 ∼ 1.3 x 10 21 H 2 O molecules·m -2 . (author)

Suitability of olive oil washing water as an electron donor in a feed batch operating bio-electrochemical system

Directory of Open Access Journals (Sweden)

F. G. Fermoso

2017-06-01

Full Text Available Olive oil washing water derived from the two-phase manufacturing process was assessed as an electron donor in a bio-electrochemical system (BES operating at 35 ºC. Start-up was carried out by using acetate as a substrate for the BES, reaching a potential of around +680 mV. After day 54, BES was fed with olive oil washing water. The degradation of olive oil washing water in the BES generated a maximum voltage potential of around +520 mV and a Chemical Oxygen Demand (COD removal efficiency of 41%. However, subsequent loads produced a decrease in the COD removal, while current and power density diminished greatly. The deterioration of these parameters could be a consequence of the accumulation of recalcitrant or inhibitory compounds, such as phenols. These results demonstrated that the use of olive oil washing water as an electron donor in a BES is feasible, although it has to be further investigated in order to make it more suitable for a real application.

Application of electron beam irradiation. 4. Treatment of pollutants by electron beam irradiation

International Nuclear Information System (INIS)

Tokunaga, Okihiro; Arai, Hidehiko

1994-01-01

Electron beam irradiation is capable of dissolving and removing pollutants, such as sulfur oxides, nitrogen oxides, and organic compounds, by easy production of OH radicals in flue gas and water. This paper deals with current status in the search for techniques for treating flue gas and waste water, using electron beam irradiation. Pilot tests have been conducted during the period 1991-1994 for the treatment of flue gas caused by coal and garbage burning and road tunnels. Firstly, techniques for cleaning flue gas with electron beams are outlined, with special reference to their characteristics and process of research development. Secondly, the application of electron beam irradiation in the treatment of waste water is described in terms of the following: (1) disinfection of sewage, (2) cleaning of water polluted with toxic organic compounds, (3) treatment for eliminating sewage sludge, (4) promotion of sewage sludge sedimentation, (5) disinfection and composting of sewage sludge, and (6) regeneration of activated carbon used for the treatment of waste water. (N.K.)

Volumetric and steric properties of hydroxamic acids in ethanol at different temperatures

International Nuclear Information System (INIS)

Yadav, Sushama Singh; Pande, Rama; Khare, Deepesh; Tripathi, Manorama

2012-01-01

Highlights: ► Density, ρ and refractive index, n of PBHA and o-TBHA are measured in ethanol at different temperatures. ► From the experimental value of ρ and n, V φ , V φ 0 , S V ∗ , φ E 0 , V, R M , R S and α are calculated. ► Excess properties such as V E , R M E , n E are also computed. ► The behaviour of these parameters suggests that PBHA and o-TBHA act as structure maker in ethanol. - Abstract: Physical properties, such as density, ρ and refractive index, n of two hydroxamic acids (N-Phenylbenzo, C 6 H 5 NOH·C 6 H 5 C=O and N-o-tolylbenzo, o-CH 3 ·C 6 H 4 NOH·C 6 H 5 C=O) have been measured in ethanol as a function of concentration at T = (298.15, 303.15, and 308.15) K. The apparent molar volume, V φ , apparent molar volume at infinite dilution, V φ 0 and the slope, S V ∗ are calculated from the experimental value of density, ρ by applying the Masson’s equation. The apparent molar expansibility at infinite dilution, φ E 0 , molar volume, V and the excess molar volume, V E are also computed. The refractive index, n, data have been used to calculate the steric parameters viz. molar refraction, R M , excess refractive index, n E , excess molar refraction, R M E and polarizability, α of these molecules. The results obtained have been qualitatively used to interpret the solute–solute and solute–solvent interactions between hydroxamic acids and ethanol.

Toxicity reduction for pharmaceuticals mixture in water by electron beam irradiation

International Nuclear Information System (INIS)

Boiani, Nathalia Fonseca; Tominaga, Flavio Kiyoshi; Borrely, Sueli Ivone

2015-01-01

The incorrect disposal of products is committing the environment quality once the aquatic environment is the main vehicle for dispersion of pollutants. Among the highlighted contaminants there are the pharmaceuticals, which are also released to the aquatic environment through the domestic sewage, hospitals and effluents. The monitoring of these pharmaceuticals in the environment has grown, showing many of them as persistent pollutants. Pharmaceuticals from different therapeutic classes have been detected in domestic sewage, surface water and groundwater around the world. Several studies evidenced Fluoxetine Hydrochloride residues in waters. Another important product is the Propranolol, used for heart disease treatments as far as fluoxetine is applied for treating mental diseases. The objective of this study was to apply the radiation processing for the abatement of pollutant in waters. Electron beam accelerator was used during irradiation of the mixture (Propranolol + Fluoxetine Hydrochloride) in aqueous solution. Acute toxicity assays were carried out for Vibrio fischeri marine bacterium, 15 minutes exposure. The results showed that irradiation (2.5kGy and 5.0kGy) enhanced the average effective concentration of the mixture, which means reduction of toxicity (56.34%, 55.70% respectively). Inverse effect was obtained with 7.5 kGy and 10 kGy. (author)

Toxicity reduction for pharmaceuticals mixture in water by electron beam irradiation

Energy Technology Data Exchange (ETDEWEB)

Boiani, Nathalia Fonseca; Tominaga, Flavio Kiyoshi; Borrely, Sueli Ivone, E-mail: flavio_tominaga@hotmail.com, E-mail: sborrely@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2015-07-01

The incorrect disposal of products is committing the environment quality once the aquatic environment is the main vehicle for dispersion of pollutants. Among the highlighted contaminants there are the pharmaceuticals, which are also released to the aquatic environment through the domestic sewage, hospitals and effluents. The monitoring of these pharmaceuticals in the environment has grown, showing many of them as persistent pollutants. Pharmaceuticals from different therapeutic classes have been detected in domestic sewage, surface water and groundwater around the world. Several studies evidenced Fluoxetine Hydrochloride residues in waters. Another important product is the Propranolol, used for heart disease treatments as far as fluoxetine is applied for treating mental diseases. The objective of this study was to apply the radiation processing for the abatement of pollutant in waters. Electron beam accelerator was used during irradiation of the mixture (Propranolol + Fluoxetine Hydrochloride) in aqueous solution. Acute toxicity assays were carried out for Vibrio fischeri marine bacterium, 15 minutes exposure. The results showed that irradiation (2.5kGy and 5.0kGy) enhanced the average effective concentration of the mixture, which means reduction of toxicity (56.34%, 55.70% respectively). Inverse effect was obtained with 7.5 kGy and 10 kGy. (author)

Electron spin echo envelope modulation (ESEEM) reveals water and phosphate interactions with the KcsA potassium channel

OpenAIRE

Cieslak, John A.; Focia, Pamela J.; Gross, Adrian

2010-01-01

Electron spin-echo envelope modulation (ESEEM) spectroscopy is a well-established technique for the study of naturally occurring paramagnetic metal centers. The technique has been used to study copper complexes, hemes, enzyme mechanisms, micellar water content, and water permeation profiles in membranes, among other applications. In the present study, we combine ESEEM spectroscopy with site-directed spin labeling (SDSL) and X-ray crystallography in order to evaluate the technique's potential ...

Clearance and Biodistribution of Liposomally Encapsulated Nitroxides: A Model for Targeted Delivery of Electron Paramagnetic Resonance Imaging Probes to Tumors

Science.gov (United States)

Burks, Scott R.; Legenzov, Eric A.; Rosen, Gerald M.

2011-01-01

Electron paramagnetic resonance (EPR) imaging using nitroxides as molecular probes is potentially a powerful tool for the detection and physiological characterization of micrometastatic lesions. Encapsulating nitroxides in anti-HER2 immunoliposomes at high concentrations to take advantage of the “self-quenching” phenomenon of nitroxides allows generation of robust EPR signals in HER2-overexpressing breast tumor cells with minimal background from indifferent tissues or circulating liposomes. We investigated the in vivo pharmacological properties of nitroxides encapsulated in sterically stabilized liposomes designed for long circulation times. We show that circulation times of nitroxides can be extended from hours to days; this increases the proportion of liposomes in circulation to enhance tumor targeting. Furthermore, nitroxides encapsulated in sterically stabilized anti-HER2 immunoliposomes can be delivered to HER2-overexpressing tumors at micromolar concentrations, which should be imageable by EPR. Lastly, after in vivo administration, liposomally encapsulated nitroxide signal also appears in the liver, spleen, and kidneys. Although these organs are spatially distinct and would not hinder tumor imaging in our model, understanding nitroxide signal retention in these organs is essential for further improvements in EPR imaging contrast between tumors and other tissues. These results lay the foundation to use liposomally delivered nitroxides and EPR imaging to visualize tumor cells in vivo. PMID:21737567

Data needs for the track structure of alpha particles and electrons in water

International Nuclear Information System (INIS)

Pagnamenta, A.

1983-01-01

We have made calculations of the ionization spectra for alpha particle and electron tracks in water. We have also computed the number of ions created per micrometre of track length, the energy distribution of the secondaries, and the energy expended per ion pair created. Our aim is less toward theoretical derivations than to obtain a numerically accurate description of the track structure at all energies in a form suitable for biomedical applications. 13 references

Electron scattering in large water clusters from photoelectron imaging with high harmonic radiation.

Science.gov (United States)

Gartmann, Thomas E; Hartweg, Sebastian; Ban, Loren; Chasovskikh, Egor; Yoder, Bruce L; Signorell, Ruth

2018-06-06

Low-energy electron scattering in water clusters (H2O)n with average cluster sizes of n < 700 is investigated by angle-resolved photoelectron spectroscopy using high harmonic radiation at photon energies of 14.0, 20.3, and 26.5 eV for ionization from the three outermost valence orbitals. The measurements probe the evolution of the photoelectron anisotropy parameter β as a function of cluster size. A remarkably steep decrease of β with increasing cluster size is observed, which for the largest clusters reaches liquid bulk values. Detailed electron scattering calculations reveal that neither gas nor condensed phase scattering can explain the cluster data. Qualitative agreement between experiment and simulations is obtained with scattering calculations that treat cluster scattering as an intermediate case between gas and condensed phase scattering.

Contribution of climate-driven change in continental water storage to recent sea-level rise

Science.gov (United States)

Milly, P. C. D.; Cazenave, A.; Gennero, C.

2003-01-01

Using a global model of continental water balance, forced by interannual variations in precipitation and near-surface atmospheric temperature for the period 1981–1998, we estimate the sea-level changes associated with climate-driven changes in storage of water as snowpack, soil water, and ground water; storage in ice sheets and large lakes is not considered. The 1981–1998 trend is estimated to be 0.12 mm/yr, and substantial interannual fluctuations are inferred; for 1993–1998, the trend is 0.25 mm/yr. At the decadal time scale, the terrestrial contribution to eustatic (i.e., induced by mass exchange) sea-level rise is significantly smaller than the estimated steric (i.e., induced by density changes) trend for the same period, but is not negligibly small. In the model the sea-level rise is driven mainly by a downtrend in continental precipitation during the study period, which we believe was generated by natural variability in the climate system. PMID:14576277

Transport coefficients and cross sections for electrons in water vapour: Comparison of cross section sets using an improved Boltzmann equation solution

Science.gov (United States)

Ness, K. F.; Robson, R. E.; Brunger, M. J.; White, R. D.

2012-01-01

This paper revisits the issues surrounding computation of electron transport properties in water vapour as a function of E/n0 (the ratio of the applied electric field to the water vapour number density) up to 1200 Td. We solve the Boltzmann equation using an improved version of the code of Ness and Robson [Phys. Rev. A 38, 1446 (1988)], facilitating the calculation of transport coefficients to a considerably higher degree of accuracy. This allows a correspondingly more discriminating test of the various electron-water vapour cross section sets proposed by a number of authors, which has become an important issue as such sets are now being applied to study electron driven processes in atmospheric phenomena [P. Thorn, L. Campbell, and M. Brunger, PMC Physics B 2, 1 (2009)] and in modeling charged particle tracks in matter [A. Munoz, F. Blanco, G. Garcia, P. A. Thorn, M. J. Brunger, J. P. Sullivan, and S. J. Buckman, Int. J. Mass Spectrom. 277, 175 (2008)].

Dosimetric characteristics of water equivalent for two solid water phantoms

International Nuclear Information System (INIS)

Wang Jianhua; Wang Xun; Ren Jiangping

2011-01-01

Objective: To investigate the water equivalent of two solid water phantoms. Methods: The X-ray and electron beam depth-ion curves were measured in water and two solid water phantoms, RW3 and Virtual Water. The water-equivalency correction factors for the two solid water phantoms were compared. We measured and calculated the range sealing factors and the fluence correction factors for the two solid water phantoms in the case of electron beams. Results: The average difference between the measured ionization in solid water phantoms and water was 0.42% and 0.16% on 6 MV X-ray (t=-6.15, P=0.001 and t=-1.65, P=0.419) and 0.21% and 0.31% on 10 MV X-ray (t=1.728, P=0.135 and t=-2.296, P=0.061), with 17.4% and 14.5% on 6 MeV electron beams (t=-1.37, P=0.208 and t=-1.47, P=0.179) and 7.0% and 6.0% on 15 MeV electron beams (t=-0.58, P=0.581 and t=-0.90, P=0.395). The water-equivalency correction factors for the two solid water phantoms varied slightly largely, F=58.54, P=0.000 on 6 MV X-ray, F=0.211, P=0.662 on 10 MV X-ray, F=0.97, P=0.353 on 6 MeV electron beams, F=0.14, P=0.717 on 15 MeV electron beams. However, they were almost equal to 1 near the reference depths. The two solid water phantoms showed a similar tread of C pl increasing (F=26.40, P=0.014) and h pl decreasing (F=7.45, P=0.072) with increasing energy. Conclusion: The solid water phantom should undergo a quality control test before being clinical use. (authors)

Post-mining water treatment. Nanofiltration of uranium-contaminated drainage. Experiments and modeling

Energy Technology Data Exchange (ETDEWEB)

Hoyer, Michael

2017-07-01

Nanofiltration of real uranium-contaminated mine drainage was successfully discussed in experiments and modeling. For the simulation a renowned model was adapted that is capable of describing multi-component solutions. Although the description of synthetic multi-component solutions with a limited number of components was performed before ([Garcia-Aleman2004], [Geraldes2006], [Bandini2003]) the results of this work show that the adapted model is capable of describing the very complex solution. The model developed here is based on: The Donnan-Steric Partitioning Pore Model incorporating Dielectric Exclusion - DSPM and DE ref. [Bowen1997], [Bandini2003], [Bowen2002], [Vezzani2002]. The steric, electric, and dielectric exclusion model - SEDE ref. [Szymczyk2005]. The developed modeling approach is capable of describing multi-component transport, and is based on the pore radius, membrane thickness, and volumetric membrane charge density as physically relevant membrane parameters instead of mere fitting parameters which allows conclusions concerning membrane modification or process design. The experiments involve typical commercially available membranes in combination with a water sample of industrial relevance in the mining sector. Furthermore, it has been shown experimentally that uranium speciation influences its retention. Hence, all experiments consider the speciation of uranium when assessing its charge and size. In the simulation 10 different ionic components have been taken into account. By freely fitting 4 parameters in parallel (pore radius, membrane thickness, membrane charge, relative permittivity of the oriented water layer at the pore wall) an excellent agreement between experiment and simulation was obtained. Moreover, the determined membrane thickness and pore radius is in close agreement with the values obtained by independent membrane characterization using pure water permeability and glucose retention. On the other hand, the fitted and the literature

Post-mining water treatment. Nanofiltration of uranium-contaminated drainage. Experiments and modeling

International Nuclear Information System (INIS)

Hoyer, Michael

2017-01-01

Nanofiltration of real uranium-contaminated mine drainage was successfully discussed in experiments and modeling. For the simulation a renowned model was adapted that is capable of describing multi-component solutions. Although the description of synthetic multi-component solutions with a limited number of components was performed before ([Garcia-Aleman2004], [Geraldes2006], [Bandini2003]) the results of this work show that the adapted model is capable of describing the very complex solution. The model developed here is based on: The Donnan-Steric Partitioning Pore Model incorporating Dielectric Exclusion - DSPM and DE ref. [Bowen1997], [Bandini2003], [Bowen2002], [Vezzani2002]. The steric, electric, and dielectric exclusion model - SEDE ref. [Szymczyk2005]. The developed modeling approach is capable of describing multi-component transport, and is based on the pore radius, membrane thickness, and volumetric membrane charge density as physically relevant membrane parameters instead of mere fitting parameters which allows conclusions concerning membrane modification or process design. The experiments involve typical commercially available membranes in combination with a water sample of industrial relevance in the mining sector. Furthermore, it has been shown experimentally that uranium speciation influences its retention. Hence, all experiments consider the speciation of uranium when assessing its charge and size. In the simulation 10 different ionic components have been taken into account. By freely fitting 4 parameters in parallel (pore radius, membrane thickness, membrane charge, relative permittivity of the oriented water layer at the pore wall) an excellent agreement between experiment and simulation was obtained. Moreover, the determined membrane thickness and pore radius is in close agreement with the values obtained by independent membrane characterization using pure water permeability and glucose retention. On the other hand, the fitted and the literature

Theoretical perspectives on electron transfer and charge separation events in photochemical water cleavage systems

International Nuclear Information System (INIS)

Kozak, J.J.; Lenoir, P.M.; Musho, M.K.; Tembe, B.L.

1984-01-01

We study in this paper the dynamics induced by models for photochemical water cleavage systems, focusing on the spatial and temporal factors influencing electron transfer and charge separation processes in such systems. The reaction-diffusion theory is formulated in full generality and the consequences explored in a number of spatio-temporal regimes, viz. the spatially homogeneous system in the long-time limit (i.e. the steady state for a well-stirred system), the spatially homogeneous system in evolution, and the spatially inhomogeneous system in evolution (where, in the latter study, we consider electron transfer at the cluster surface to be governed by a rate constant that reflects the localized nature of such processes). The results of numerical simulations are presented for all three cases and used to highlight the importance of heterogeneous environments in enhancing the cage escape yield of charge separated species, and to demonstrate the dependence of the hydrogen yield on the localization of electron-transfer processes in the vicinity of the microcatalyst surface

Kinetic measurements of the hydrolytic degradation of cefixime: effect of Captisol complexation and water-soluble polymers.

Science.gov (United States)

Mallick, Subrata; Mondal, Arijit; Sannigrahi, Santanu

2008-07-01

We have taken kinetic measurements of the hydrolytic degradation of cefixime, and have studied the effect of Captisol complexation and water-soluble polymers on that degradation. The phase solubility of cefixime in Captisol was determined. Kinetic measurements were carried out as a function of pH and temperature. High-performance liquid chromatography (HPLC) was performed to assay all the samples of phase-solubility analysis and kinetic measurements. Chromatographic separation of the degradation products was also performed by HPLC. FT-IR spectroscopy was used to investigate the presence of any interaction between cefixime and Captisol and soluble polymer. The phase-solubility study showed A(L)-type behaviour. The pH-rate profile of cefixime exhibited a U-shaped profile whilst the degradation of cefixime alone was markedly accelerated with elevated temperature. A strong stabilizing influence of the cefixime-Captisol complexation and hypromellose was observed against aqueous mediated degradation, as compared with povidone and macrogol. The unfavourable effect of povidone and macrogol may have been due to the steric hindrance, which prevented the guest molecule from entering the cyclodextrin cavity, whereas hypromellose did not produce any steric hindrance.

Identification and measurement of chlorinated organic pesticides in water by electron-capture gas chromatography

Science.gov (United States)

Lamar, William L.; Goerlitz, Donald F.; Law, LeRoy M.

1965-01-01

Pesticides, in minute quantities, may affect the regimen of streams, and because they may concentrate in sediments, aquatic organisms, and edible aquatic foods, their detection and their measurement in the parts-per-trillion range are considered essential. In 1964 the U.S. Geological Survey at Menlo Park, Calif., began research on methods for monitoring pesticides in water. Two systems were selected--electron-capture gas chromatography and microcoulometric-titration gas chromatography. Studies on these systems are now in progress. This report provides current information on the development and application of an electron-capture gas chromatographic procedure. This method is a convenient and extremely sensitive procedure for the detection and measurement of organic pesticides having high electron affinities, notably the chlorinated organic pesticides. The electron-affinity detector is extremely sensitive to these substances but it is not as sensitive to many other compounds. By this method, the chlorinated organic pesticide may be determined on a sample of convenient size in concentrations as low as the parts-per-trillion range. To insure greater accuracy in the identifications, the pesticides reported were separated and identified by their retention times on two different types of gas chromatographic columns.

Utilization of the high energy electrons beams generated in accelerator for treatment of drinking water and wastewater

International Nuclear Information System (INIS)

Oliveira Sampa, M.H. de; Borrely, S.I.; Morita, D.M.

1991-01-01

Samples of drinking water and wastewater were irradiated using high energy electron beam with doses from 0.37kGy to 100kGy. Preliminary data show the removal of about 100% of trihalomethanes (THM) in drinking water (concentration from 2.7μg/l to 45μg/l, 90% of the color of the Public Owned Wastewater Treatment Plant effluent and 87% of oil and grease of the cutting fluid wastewater. (author)

A Non-Exploding Alkali Metal Drop on Water: From Blue Solvated Electrons to Bursting Molten Hydroxide

Czech Academy of Sciences Publication Activity Database

Mason, Philip E.; Buttersack, T.; Bauerecker, S.; Jungwirth, Pavel

2016-01-01

Roč. 55, č. 42 (2016), s. 13019-13022 ISSN 1433-7851 R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388963 Keywords : sodium potassium alloy * water * hydrated electrons Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 11.994, year: 2016

76 FR 36919 - Proof of Concept Demonstration for Electronic Reporting of Clean Water Act Compliance Monitoring...

Science.gov (United States)

2011-06-23

... reporting services to the regulated community for the NPDES program (e.g., NPDES permitted facilities). This open platform model would likely be similar to the Internal Revenue Service (IRS) model for electronic... Federal and state levels, to strengthen that performance, and to transform EPA's water quality and...

One-electron oxidation of DNA: mechanism and consequences.

Science.gov (United States)

Schuster, Gary B

2009-01-01

All living organisms store the information necessary to maintain life in their DNA. Any process that damages DNA and causes loss or corruption of that information threatens the viability of the organism. One-electron oxidation is such a process. Loss of an electron from DNA generates a radical cation that is located primarily on its nucleobases. The radical cation migrates reversibly through duplex DNA by hopping until it is eventually trapped in an irreversible chemical reaction. The particular sequence of nucleobases in a DNA oligomer determines both the efficiency of hopping and the specific location and nature of the damaging chemical reaction. In its normal aqueous solutions, DNA is a polyanion because of the negative charge carried by its phosphate groups. Counter ions (typically Na(+)) to the phosphate groups play an important role in facilitating both the migration of the radical cation and in its eventual reaction with H(2)O. Irreversible reaction of a radical cation with H(2)O in duplex DNA occurs preferentially at the most reactive site. In normal DNA that is comprised of the four common DNA nucleobases, reaction occurs most commonly at a guanine and results in its conversion primarily to 8-oxo-7,8-dihydroguanine (8-OxoG). Both electronic and steric effects control the outcome of this process. If the DNA oligomer does not contain a suitable guanine, then reaction of the radical cation occurs at the thymine of a TT step primarily by a tandem process. The general outcomes revealed in the one-electron oxidation of DNA oligomers in solution appear to be generally valid also for more complex DNA structures and for the cellular DNA of living organisms.

Highly water-dispersible, mixed ionic-electronic conducting, polymer acid-doped polyanilines as ionomers for direct methanol fuel cells.

Science.gov (United States)

Murthy, Arun; Manthiram, Arumugam

2011-06-28

Highly water-dispersible polymer acid-doped polyanilines have been synthesized and evaluated as an alternative for expensive Nafion ionomers in the anode of direct methanol fuel cells (DMFC). These polymers as ionomers lead to higher performance in single cell DMFC compared to Nafion ionomers due to mixed ionic-electronic conduction, water dispersibility, and co-catalytic activity. This journal is © The Royal Society of Chemistry 2011

Impact of potassium and water on the electronic properties of InN(0001) surfaces

International Nuclear Information System (INIS)

Reiss, S.; Eisenhardt, A.; Krischok, S.; Himmerlich, M.

2014-01-01

In this work we investigate the interaction of potassium and water with 2 x 2 reconstructed InN(0001) surfaces prepared by plasma-assisted molecular beam epitaxy. The influence of adsorbate-substrate-interaction on surface properties is characterized in-situ by photoelectron spectroscopy. Potassium exposure leads to a strong reduction in the work function Φ to 1.6 eV revealing a charge transfer from the adsorbate to the InN surface. In parallel, a reduction of the surface downward band bending by 0.2 eV and hence a reduced electron accumulation density is observed. While interaction of water with clean InN(0001)-2 x 2 surfaces induces only minor changes in the surface band bending, water adsorption at potassium covered InN(0001) leads to a reversal of the K-induced reduction in surface band bending and a slight increase of Φ to 2.4 eV. These results show that surrounding water modifies the interaction of potassium with InN(0001) surfaces. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Inverse-Electron-Demand Diels-Alder Reactions: Principles and Applications.

Science.gov (United States)

Png, Zhuang Mao; Zeng, Huining; Ye, Qun; Xu, Jianwei

2017-09-05

Inverse-electron-demand Diels-Alder (iEDDA) reactions are an intriguing class of cycloaddition reactions that have attracted increasing attention for their application in bioorthogonal chemistry, the total synthesis of natural products, and materials science. In many cases, the application of the iEDDA reaction has been demonstrated as an innovative approach to achieve target structures. The theoretical aspects of this class of reactions are of particular interest for scientists as a means to understand the various factors, such as steric strain and electron density of the attached groups, that govern the reaction and thus to elucidate the reaction mechanism. This review aims to summarize both theoretical investigations and application-driven research work on the iEDDA reaction. First, the historical aspects and the theoretical basis of the reaction, especially recent advances in time-dependent density functional theory (TD-DFT) calculations, as well as catalysis strategies will be highlighted and discussed. Second, the applications of this novel reaction in the context of materials science, bioorthogonal chemistry, and total synthesis of natural products will be elaborated with selected recent examples. The challenges and opportunities of the iEDDA reaction will be highlighted to give more insight into its potential applications in many other research areas. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Prediction of Water Binding to Protein Hydration Sites with a Discrete, Semiexplicit Solvent Model.

Science.gov (United States)

Setny, Piotr

2015-12-08

Buried water molecules are ubiquitous in protein structures and are found at the interface of most protein-ligand complexes. Determining their distribution and thermodynamic effect is a challenging yet important task, of great of practical value for the modeling of biomolecular structures and their interactions. In this study, we present a novel method aimed at the prediction of buried water molecules in protein structures and estimation of their binding free energies. It is based on a semiexplicit, discrete solvation model, which we previously introduced in the context of small molecule hydration. The method is applicable to all macromolecular structures described by a standard all-atom force field, and predicts complete solvent distribution within a single run with modest computational cost. We demonstrate that it indicates positions of buried hydration sites, including those filled by more than one water molecule, and accurately differentiates them from sterically accessible to water but void regions. The obtained estimates of water binding free energies are in fair agreement with reference results determined with the double decoupling method.

Radiolysis of liquid water: an attempt to reconcile Monte-Carlo calculations with new experimental hydrated electron yield data at early times

International Nuclear Information System (INIS)

Muroya, Y.; Meesungnoen, J.; Jay-Gerin, J.-P.; Filali-Mouhim, A.; Goulet, T.; Katsumura, Y.; Mankhetkorn, S.

2002-01-01

A re-examination of our Monte-Carlo modeling of the radiolysis of liquid water by low linear-energy-transfer (LET ∼ 0.3 keV μm -1 ) radiation is undertaken herein in an attempt to reconcile the results of our simulation code with recently revised experimental hydrated electron (e aq - ) yield data at early times. The thermalization distance of subexcitation electrons, the recombination cross section of the electrons with their water parent cations prior to thermalization, and the branching ratios of the different competing mechanisms in the dissociative decay of vibrationally excited states of water molecules were taken as adjustable parameters in our simulations. Using a global-fit procedure, we have been unable to find a set of values for those parameters to simultaneously reproduce (i) the revised e aq - yield of 4.0 ± 0.2 molecules per 100 eV at 'time zero' (that is, a reduction of ∼20% over the hitherto accepted value of 4.8 molecules per 100 eV), (ii) the newly measured e aq - decay kinetic profile from 100 ps to 10 ns, and (iii) the time-dependent yields of the other radiolytic species H . , . OH, H 2 , and H 2 O 2 (up to ∼1 μs). The lowest possible limiting 'time-zero' yield of e aq - that we could in fact obtain, while ensuring an acceptable agreement between all computed and experimental yields, was ∼4.4 to 4.5 molecules per 100 eV. Under these conditions, the mean values of the electron thermalization distance and of the geminate electron-cation recombination probability, averaged over the subexcitation electron 'entry spectrum,' are found to be equal to ∼139 A and ∼18%, respectively. These values are to be compared with those obtained in our previous simulations of liquid water radiolysis, namely ∼88 A and ∼5.5%, respectively. Our average electron thermalization distance is also to be compared with the typical size (∼64-80 A) of the initial hydrated electron distributions estimated in current deterministic models of 'spur' chemistry

Laser-assisted electron scattering in strong-field ionization of dense water vapor by ultrashort laser pulses

International Nuclear Information System (INIS)

Wilke, M; Al-Obaidi, R; Moguilevski, A; Kothe, A; Engel, N; Metje, J; Kiyan, I Yu; Aziz, E F

2014-01-01

We report on strong-field ionization of dense water gas in a short infrared laser pulse. By employing a unique combination of photoelectron spectroscopy with a liquid micro-jet technique, we observe how the character of electron emission at high kinetic energies changes with the increase of the medium density. This change is associated with the process of laser-assisted electron scattering (LAES) on neighboring particles, which becomes a dominant mechanism of hot electron emission at higher medium densities. The manifestation of this mechanism is found to require densities that are orders of magnitude lower than those considered for heating the laser-generated plasmas via the LAES process. The experimental results are supported by simulations of the LAES yield with the use of the Kroll–Watson theory. (paper)

The electronic encapsulation of knowledge in hydraulics, hydrology and water resources

Science.gov (United States)

Abbott, Michael B.

The rapidly developing practice of encapsulating knowledge in electronic media is shown to lead necessarily to the restructuring of the knowledge itself. The consequences of this for hydraulics, hydrology and more general water-resources management are investigated in particular relation to current process-simulation, real-time control and advice-serving systems. The generic properties of the electronic knowledge encapsulator are described, and attention is drawn to the manner in which knowledge 'goes into hiding' through encapsulation. This property is traced in the simple situations of pure mathesis and in the more complex situations of taxinomia using one example each from hydraulics and hydrology. The consequences for systems architectures are explained, pointing to the need for multi-agent architectures for ecological modelling and for more general hydroinformatics systems also. The relevance of these developments is indicated by reference to ongoing projects in which they are currently being realised. In conclusion, some more general epistemological aspects are considered within the same context. As this contribution is so much concerned with the processes of signification and communication, it has been partly shaped by the theory of semiotics, as popularised by Eco ( A Theory of Semiotics, Indiana University, Bloomington, 1977).

Inelastic cross-sections for electron transport in liquid water: a comparison of dielectric models

International Nuclear Information System (INIS)

Emfietzoglou, D.

2003-01-01

Various methodologies for constructing inelastic cross-sections for low-energy (<10 keV) electron transport in liquid water are presented and compared. They are all based on an optical-data model which provides the dependence on energy loss, and a dispersion algorithm which incorporates the momentum-transfer dependence. A Drude dielectric model was used to analytically represent the optical data. Various dispersion schemes were examined: the Bethe approximation, the δ-oscillator models of Ashley and Liljequist, and two forms of Ritchie's extended-Drude model. They all have been used in Monte-Carlo (MC) codes for analog electron transport in the condensed phase. Results in the form of differential and total inelastic cross-sections are presented. Where possible, comparisons with results of other studies are made. It was found that, despite the application of general constraints (e.g. sum rules), the optical model has a notable influence on the single-collision energy loss spectrum. In addition, both the shape and peak position of the total and differential cross-section distributions depend strongly on the dispersion model adopted. The work is particularly relevant to the development of event-by-event MC transport codes for liquid water, as well as, to the calculations of stopping-powers below the range of applicability of Bethe's formula

Density Functional Study of Stacking Structures and Electronic Behaviors of AnE-PV Copolymer.

Science.gov (United States)

Dong, Chuan-Ding; Beenken, Wichard J D

2016-10-10

In this work, we report an in-depth investigation on the π-stacking and interdigitating structures of poly(p-anthracene-ethynylene)-alt-poly(p-phenylene-vinylene) copolymer with octyl and ethyl-hexyl side chains and the resulting electronic band structures using density functional theory calculations. We found that in the π-stacking direction, the preferred stacking structure, determined by the steric effect of the branched ethyl-hexyl side chains, is featured by the anthracene-ethynylene units stacking on the phenylene-vinylene units of the neighboring chains and vice versa. This stacking structure, combined with the interdigitating structure where the branched side chains of the laterally neighboring chains are isolated, defines the energetically favorable structure of the ordered copolymer phase, which provides a good compromise between light absorption and charge-carrier transport.

Electron fluence correction factors for various materials in clinical electron beams

International Nuclear Information System (INIS)

Olivares, M.; Blois, F. de; Podgorsak, E.B.; Seuntjens, J.P.

2001-01-01

Relative to solid water, electron fluence correction factors at the depth of dose maximum in bone, lung, aluminum, and copper for nominal electron beam energies of 9 MeV and 15 MeV of the Clinac 18 accelerator have been determined experimentally and by Monte Carlo calculation. Thermoluminescent dosimeters were used to measure depth doses in these materials. The measured relative dose at d max in the various materials versus that of solid water, when irradiated with the same number of monitor units, has been used to calculate the ratio of electron fluence for the various materials to that of solid water. The beams of the Clinac 18 were fully characterized using the EGS4/BEAM system. EGSnrc with the relativistic spin option turned on was used to optimize the primary electron energy at the exit window, and to calculate depth doses in the five phantom materials using the optimized phase-space data. Normalizing all depth doses to the dose maximum in solid water stopping power ratio corrected, measured depth doses and calculated depth doses differ by less than ±1% at the depth of dose maximum and by less than 4% elsewhere. Monte Carlo calculated ratios of doses in each material to dose in LiF were used to convert the TLD measurements at the dose maximum into dose at the center of the TLD in the phantom material. Fluence perturbation correction factors for a LiF TLD at the depth of dose maximum deduced from these calculations amount to less than 1% for 0.15 mm thick TLDs in low Z materials and are between 1% and 3% for TLDs in Al and Cu phantoms. Electron fluence ratios of the studied materials relative to solid water vary between 0.83±0.01 and 1.55±0.02 for materials varying in density from 0.27 g/cm3 (lung) to 8.96 g/cm3 (Cu). The difference in electron fluence ratios derived from measurements and calculations ranges from -1.6% to +0.2% at 9 MeV and from -1.9% to +0.2% at 15 MeV and is not significant at the 1σ level. Excluding the data for Cu, electron fluence

The METAS absorbed dose to water calibration service for high energy photon and electron beam radiotherapy

International Nuclear Information System (INIS)

Stucki, G.; Muench, W.; Quintel, H.

2002-01-01

Full text: The Swiss Federal Office of Metrology and Accreditation (METAS) provides an absorbed dose to water calibration service for reference dosimeters using 60 Co γ radiation, ten X-ray beam qualities between TPR 20,10 =0.639 and 0.802 and ten electron beam qualities between R 50 =1.75 gcm -2 and 8.54 gcm -2 . A 22 MeV microtron accelerator with a conventional treatment head is used as radiation source for the high energy photon and electron beams. The treatment head produces clinical beams. The METAS absorbed dose calibration service for high energy photons is based on a primary standard sealed water calorimeter of the Domen type, that is used to calibrate several METAS transfer standards of type NE2611A and NE2571A in terms of absorbed dose to water in the energy range from 60 Co to TPR 20,10 = 0.802. User reference dosimeters are compared with the transfer standards to give calibration factors in absorbed dose to water with an uncertainty of 1.0% for 60 Co γ radiation and 1.4% for higher energies (coverage factor k=2). The calibration service was launched in 1997. The calibration factors measured by METAS have been compared with those derived from the Code of Practice of the International Atomic Energy Agency using the calculated k Q factors listed in table 14. The comparison showed a maximum difference of 0.8% for the NE25611A and NE 2571A chambers. At 60 Co γ radiation the METAS primary standard of absorbed dose to water was bilaterally compared with the primary standards of the Bureau International des Poids et Mesures BIPM (Sevres) as well as of the National Research Council NRC (Canada). In either case the standards were in agreement within the comparison uncertainties. The METAS absorbed dose calibration service for high energy electron beams is based on a primary standard chemical dosimeter. A monoenergetic electron beam of precisely known particle energy and beam charge is totally absorbed in Fricke solution (ferrous ammonium sulphate) of a given

Penetration depth measurement of a 6 MeV electron beam in water by magnetic resonance imaging

Directory of Open Access Journals (Sweden)

B. E. Hammer

2011-11-01

Full Text Available We demonstrate magnetic resonance imaging (MRI visualization of a 6 MeV electron beam in ferrous-doped water; a 25 mm penetration depth was measured. Time domain nuclear magnetic resonance was used to investigate the effect of generated free radicals on the free induction decay (FID in nondoped water; no apparent effects to the FID were observed. We show that MRI visualization of charged particle beams used in medical applications will require exogenous agents to provide contrast enhancement.

Electronic structure imperfections and chemical bonding at graphene interfaces

Science.gov (United States)

Schultz, Brian Joseph

nanomaterial with lateral dimensions in the hundreds of microns if not larger, with a corresponding atomic vertical thickness poses significant difficulties. Graphene's unique structure is dominated by surface area or potentially hybridized interfaces; consequently, the true realization of this remarkable nanomaterial in device constructs relies on engineering graphene interfaces at the surface in order to controllably mold the electronic structure. Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy and the transmission mode analogue scanning transmission X-ray microscopy (STXM) are particularly useful tools to study the unoccupied states of graphene and graphene interfaces. In addition, polarized NEXAFS and STXM studies provide information on surface orientation, bond sterics, and the extent of substrate alignment before and after interfacial hybridization. The work presented in this dissertation is fundamentally informed by NEXAFS and STXM measurements on graphene/metal, graphene/dielectric, and graphene/organic interfaces. We start with a general review of the electronic structure of freestanding graphene and graphene interfaces in Chapter 1. In Chapter 2, we investigate freestanding single-layer graphene via STXM and NEXAFS demonstrating that electronic structure heterogeneities from synthesis and processing are ubiquitous in 2-dimensional graphene. We show the mapping of discrete charge transfer regions as a result of doped impurities that decorate the surfaces of graphene and that transfer processing imparts local electronic corrugations or ripples. In corroboration with density functional theory, definitive assignments to the spectral features, global steric orientations of the localized domains, and quantitative charge transfer schemes are evidenced. In the following chapters, we deliberately (Chapter 3) incorporate substitutional nitrogen into reduced graphene oxide to induce C--N charge redistribution and improve global conductivity, (Chapter 4

Climate change under a scenario near 1.5 °C of global warming: monsoon intensification, ocean warming and steric sea level rise

Directory of Open Access Journals (Sweden)

J. Schewe

2011-03-01

Full Text Available We present climatic consequences of the Representative Concentration Pathways (RCPs using the coupled climate model CLIMBER-3α, which contains a statistical-dynamical atmosphere and a three-dimensional ocean model. We compare those with emulations of 19 state-of-the-art atmosphere-ocean general circulation models (AOGCM using MAGICC6. The RCPs are designed as standard scenarios for the forthcoming IPCC Fifth Assessment Report to span the full range of future greenhouse gas (GHG concentrations pathways currently discussed. The lowest of the RCP scenarios, RCP3-PD, is projected in CLIMBER-3α to imply a maximal warming by the middle of the 21st century slightly above 1.5 °C and a slow decline of temperatures thereafter, approaching today's level by 2500. We identify two mechanisms that slow down global cooling after GHG concentrations peak: The known inertia induced by mixing-related oceanic heat uptake; and a change in oceanic convection that enhances ocean heat loss in high latitudes, reducing the surface cooling rate by almost 50%. Steric sea level rise under the RCP3-PD scenario continues for 200 years after the peak in surface air temperatures, stabilizing around 2250 at 30 cm. This contrasts with around 1.3 m of steric sea level rise by 2250, and 2 m by 2500, under the highest scenario, RCP8.5. Maximum oceanic warming at intermediate depth (300–800 m is found to exceed that of the sea surface by the second half of the 21st century under RCP3-PD. This intermediate-depth warming persists for centuries even after surface temperatures have returned to present-day values, with potential consequences for marine ecosystems, oceanic methane hydrates, and ice-shelf stability. Due to an enhanced land-ocean temperature contrast, all scenarios yield an intensification of monsoon rainfall under global warming.

Electronic coarse graining enhances the predictive power of molecular simulation allowing challenges in water physics to be addressed

Energy Technology Data Exchange (ETDEWEB)

Cipcigan, Flaviu S., E-mail: flaviu.cipcigan@ed.ac.uk [School of Physics and Astronomy, University of Edinburgh, Peter Guthrie Tait Road, Edinburgh EH9 3FD (United Kingdom); National Physical Laboratory, Hampton Road, Teddington, Middlesex TW11 0LW (United Kingdom); Sokhan, Vlad P. [National Physical Laboratory, Hampton Road, Teddington, Middlesex TW11 0LW (United Kingdom); Crain, Jason [School of Physics and Astronomy, University of Edinburgh, Peter Guthrie Tait Road, Edinburgh EH9 3FD (United Kingdom); National Physical Laboratory, Hampton Road, Teddington, Middlesex TW11 0LW (United Kingdom); Martyna, Glenn J. [IBM T. J. Watson Research Center, Yorktown Heights, NY 10598 (United States)

2016-12-01

One key factor that limits the predictive power of molecular dynamics simulations is the accuracy and transferability of the input force field. Force fields are challenged by heterogeneous environments, where electronic responses give rise to biologically important forces such as many-body polarisation and dispersion. The importance of polarisation in the condensed phase was recognised early on, as described by Cochran in 1959 [Philosophical Magazine 4 (1959) 1082–1086] [32]. Currently in molecular simulation, dispersion forces are treated at the two-body level and in the dipole limit, although the importance of three-body terms in the condensed phase was demonstrated by Barker in the 1980s [Phys. Rev. Lett. 57 (1986) 230–233] [72]. One approach for treating both polarisation and dispersion on an equal basis is to coarse grain the electrons surrounding a molecular moiety to a single quantum harmonic oscillator (cf. Hirschfelder, Curtiss and Bird 1954 [The Molecular Theory of Gases and Liquids (1954)] [37]). The approach, when solved in strong coupling beyond the dipole limit, gives a description of long-range forces that includes two- and many-body terms to all orders. In the last decade, the tools necessary to implement the strong coupling limit have been developed, culminating in a transferable model of water with excellent predictive power across the phase diagram. Transferability arises since the environment automatically identifies the important long range interactions, rather than the modeler through a limited set of expressions. Here, we discuss the role of electronic coarse-graining in predictive multiscale materials modelling and describe the first implementation of the method in a general purpose molecular dynamics software: QDO-MD. - Highlights: • Electronic coarse graining unites many-body dispersion and polarisation beyond the dipole limit. • It consists of replacing the electrons of a molecule using a quantum harmonic oscillator, called a

Electronic coarse graining enhances the predictive power of molecular simulation allowing challenges in water physics to be addressed

International Nuclear Information System (INIS)

Cipcigan, Flaviu S.; Sokhan, Vlad P.; Crain, Jason; Martyna, Glenn J.

2016-01-01

One key factor that limits the predictive power of molecular dynamics simulations is the accuracy and transferability of the input force field. Force fields are challenged by heterogeneous environments, where electronic responses give rise to biologically important forces such as many-body polarisation and dispersion. The importance of polarisation in the condensed phase was recognised early on, as described by Cochran in 1959 [Philosophical Magazine 4 (1959) 1082–1086] [32]. Currently in molecular simulation, dispersion forces are treated at the two-body level and in the dipole limit, although the importance of three-body terms in the condensed phase was demonstrated by Barker in the 1980s [Phys. Rev. Lett. 57 (1986) 230–233] [72]. One approach for treating both polarisation and dispersion on an equal basis is to coarse grain the electrons surrounding a molecular moiety to a single quantum harmonic oscillator (cf. Hirschfelder, Curtiss and Bird 1954 [The Molecular Theory of Gases and Liquids (1954)] [37]). The approach, when solved in strong coupling beyond the dipole limit, gives a description of long-range forces that includes two- and many-body terms to all orders. In the last decade, the tools necessary to implement the strong coupling limit have been developed, culminating in a transferable model of water with excellent predictive power across the phase diagram. Transferability arises since the environment automatically identifies the important long range interactions, rather than the modeler through a limited set of expressions. Here, we discuss the role of electronic coarse-graining in predictive multiscale materials modelling and describe the first implementation of the method in a general purpose molecular dynamics software: QDO-MD. - Highlights: • Electronic coarse graining unites many-body dispersion and polarisation beyond the dipole limit. • It consists of replacing the electrons of a molecule using a quantum harmonic oscillator, called a

Polyurethane Membranes Modified with Isopropyl Myristate as a Potential Candidate for Encapsulating Electronic Implants: A Study of Biocompatibility and Water Permeability

Directory of Open Access Journals (Sweden)

Deepen Paul

2010-07-01

Full Text Available Medical polyurethanes have shown good bio-stability and mechanical properties and have been used as coating for implantable medical devices. However, despite their excellent properties, they are relatively permeable to liquid water and water vapour which is a drawback for electronic implant encapsulation. In this study polyether polyurethanes with different soft segment molecular weights were modified by incorporating isopropyl myristate (IPM, as a hydrophobic modifying agent, and the effect of IPM on water resistant and biocompatibility of membranes were investigated. IPM changed the surface properties of the polyurethane film and reduced its surface energy. Polyurethane films were found to be stable with IPM concentrations of 1–5 wt% based upon their chemistry; however it leached out in BSA at higher concentrations. Though, low concentrations of IPM reduced both liquid water and water vapour permeability; at higher IPM content liquid permeability did not improved significantly. In general, the polyurethane materials showed much lower water permeability compared with currently used silicone packaging material for electronic implants. In addition, cytotoxicity assessment of IPM containing polyurethanes showed no evidence of cytotoxcity up to 5 wt% IPM.

Reactivity of Hydrated Electron in Finite Size System: Sodium Pickup on Mixed N2O–Water Nanoparticles

Czech Academy of Sciences Publication Activity Database

Šmídová, Daniela; Lengyel, Jozef; Pysanenko, Andriy; Med, J.; Slavíček, P.; Fárník, Michal

2015-01-01

Roč. 6, č. 15 (2015), s. 2865-2869 ISSN 1948-7185 R&D Projects: GA ČR GA14-08937S Institutional support: RVO:61388955 Keywords : solvated electron * water clusters * fragmentation-free mass spectrometry Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.539, year: 2015

Water resistance and surface morphology of synthetic fabrics covered by polysiloxane/acrylate followed by electron beam irradiation

CERN Document Server

El-Naggar, A M; Mohammed, S S; Alam, E A

2003-01-01

Different synthetic fabrics were treated by electron beam surface coating with two formulations based on polydimethylsiloxane (PDMS) and polystyrene (PS) or poly(methyl methacrylate) (PMMA) oligomers. The water resistance properties were investigated in terms of the percentage of water repellency and absorption. Also, the surface coated fabrics were examined by scanning electron microscopy/microscope (SEM) connected to an energy dispersive X-ray (EDX) unit to determine the percentage atomic contents of elements. The results showed that the adhesion of the polysiloxane formulation to the surface depends largely on the kind of acrylate oligomer and textile fabric as indicated by the EDX analysis for silicon. In this regard, PDMS/PS formulation is more compatible with polyester and nylon-6 fabrics than PDMS/PMMA one. However, it was found that PDMS/PMMA formulation is more compatible with cotton/polyester blend than PDMS/PS. The SEM micrographs give further supports to the EDX analysis. On the basis of the perce...

Bibliography of electron and photon cross sections with atoms and molecules published in the 20th century. Water vapour

International Nuclear Information System (INIS)

Hayashi, Makoto

2003-12-01

Bibliographies of original and review reports of experiments or theories of electron and photon cross sections and also electron swarm data are presented for atomic or molecular species with specified targets. These works covered 17 atoms and 51 molecules. The present bibliography is only for water vapour (H 2 O, D 2 O and HDO). About 1200 papers were compiled. A comprehensive author index is included. The bibliography covers the period 1915 through 2000 for H 2 O. Finally, author's comments for electron collision cross sections and photodissociation processes of H 2 O are given. (author)

Dissolution of Monocrystalline Silicon Nanomembranes and Their Use as Encapsulation Layers and Electrical Interfaces in Water-Soluble Electronics.

Science.gov (United States)

Lee, Yoon Kyeung; Yu, Ki Jun; Song, Enming; Barati Farimani, Amir; Vitale, Flavia; Xie, Zhaoqian; Yoon, Younghee; Kim, Yerim; Richardson, Andrew; Luan, Haiwen; Wu, Yixin; Xie, Xu; Lucas, Timothy H; Crawford, Kaitlyn; Mei, Yongfeng; Feng, Xue; Huang, Yonggang; Litt, Brian; Aluru, Narayana R; Yin, Lan; Rogers, John A

2017-12-26

The chemistry that governs the dissolution of device-grade, monocrystalline silicon nanomembranes into benign end products by hydrolysis serves as the foundation for fully eco/biodegradable classes of high-performance electronics. This paper examines these processes in aqueous solutions with chemical compositions relevant to groundwater and biofluids. The results show that the presence of Si(OH) 4 and proteins in these solutions can slow the rates of dissolution and that ion-specific effects associated with Ca 2+ can significantly increase these rates. This information allows for effective use of silicon nanomembranes not only as active layers in eco/biodegradable electronics but also as water barriers capable of providing perfect encapsulation until their disappearance by dissolution. The time scales for this encapsulation can be controlled by introduction of dopants into the Si and by addition of oxide layers on the exposed surfaces.The former possibility also allows the doped silicon to serve as an electrical interface for measuring biopotentials, as demonstrated in fully bioresorbable platforms for in vivo neural recordings. This collection of findings is important for further engineering development of water-soluble classes of silicon electronics.

Energy and angular distribution of electrons ejected from water by the impact of fast O8+ ion beams

Science.gov (United States)

Bhattacharjee, Shamik; Bagdia, Chandan; Chowdhury, Madhusree Roy; Monti, Juan M.; Rivarola, Roberto D.; Tribedi, Lokesh C.

2018-01-01

Double differential cross sections (DDCS) of electrons emitted from vapor water molecules (in vapor phase) by 2.0 MeV/u and 3.75 MeV/u bare oxygen ion impact have been measured by continuum electron spectroscopy technique. The ejected electrons were detected by an electrostatic hemispherical deflection analyzer over an energy range of 1-600 eV and emission angles from 20∘ to 160∘. The DDCS data has been compared with the continuum-distorted-wave-eikonal-initial state (CDW-EIS) approximation and a reasonable agreement was found with both version of the models i.e. post and prior version. By numerical integration of the DDCS data, the single differential cross section (SDCS) and total ionization cross section (TCS) were obtained. The obtained TCS results were compared with other available TCS results for water target within the same energy range. The total ionization cross sections values are seen to saturate as the projectile charge state ( q p ) increases, which is in contrast to the first-Born predicted q p 2 dependence. This is also in contrast to the prediction of the CDW-EIS models.

Corrosion in Electronics

DEFF Research Database (Denmark)

Ambat, Rajan; Gudla, Helene Virginie Conseil; Verdingovas, Vadimas

2017-01-01

Electronic control units, power modules, and consumer electronics are used today in a wide variety of varying climatic conditions. Varying external climatic conditions of temperature and humidity can cause an uncontrolled local climate inside the device enclosure. Uncontrolled humidity together...... and high density packing combined with the use of several materials, which can undergo electrochemical corrosion in the presence of water film formed due to humidity exposure and bias conditions on the PCBA surface. This article provides a short review of the corrosion reliability issues of electronics due...... to the use of electronics under varying humidity conditions. Important PCBA aspects, which are fundamental to the corrosion cell formation under humid conditions, are discussed. Effect of hygroscopic residues from the process and service and their role in assisting water film build up and corrosion...

Mimicking Daphnia magna bioassay performance by an electronic tongue for urban water quality control

Energy Technology Data Exchange (ETDEWEB)

Kirsanov, Dmitry, E-mail: d.kirsanov@gmail.com [Laboratory of Chemical Sensors, St. Petersburg State University, St. Petersburg (Russian Federation); Laboratory of Artificial Sensor Systems, ITMO University, St. Petersburg (Russian Federation); Legin, Evgeny [Laboratory of Artificial Sensor Systems, ITMO University, St. Petersburg (Russian Federation); Sensor Systems LLC, St. Petersburg (Russian Federation); Zagrebin, Anatoly; Ignatieva, Natalia; Rybakin, Vladimir [Institute of Limnology, Russian Academy of Sciences, St. Petersburg (Russian Federation); Legin, Andrey [Laboratory of Chemical Sensors, St. Petersburg State University, St. Petersburg (Russian Federation); Laboratory of Artificial Sensor Systems, ITMO University, St. Petersburg (Russian Federation)

2014-05-01

Highlights: • -Daphnia magna bioassay can be simulated with multisensor system. • Urban water toxicity can be predicted from potentiometric ET data. • Independent test set validation confirms statistical significance of the results. - Abstract: Toxicity is one of the key parameters of water quality in environmental monitoring. However, being evaluated as a response of living beings (as their mobility, fertility, death rate, etc.) to water quality, toxicity can only be assessed with the help of these living beings. This imposes certain restrictions on toxicity bioassay as an analytical method: biotest organisms must be properly bred, fed and kept under strictly regulated conditions and duration of tests can be quite long (up to several days), thus making the whole procedure the prerogative of the limited number of highly specialized laboratories. This report describes an original application of potentiometric multisensor system (electronic tongue) when the set of electrochemical sensors was calibrated against Daphnia magna death rate in order to perform toxicity assessment of urban waters without immediate involvement of living creatures. PRM (partial robust M) and PLS (projections on latent structures) regression models based on the data from this multisensor system allowed for prediction of toxicity of unknown water samples in terms of biotests but in the fast and simple instrumental way. Typical errors of water toxicity predictions were below 20% in terms of Daphnia death rate which can be considered as a good result taking into account the complexity of the task.

15.0 MeV/u He2+ ion-induced low energy electrons from water vapor

International Nuclear Information System (INIS)

Okada, Y.; Sato, Y.; Soga, F.; Ohsawa, D.

2005-01-01

We present the absolute doubly differential cross sections (DDCS) of low-energy electrons and their angular distributions (20deg - 160deg ) produced in the collisions of 15.0 MeV/u He 2+ ions with water vapor. Details of the experiments by 6.0 and 10.0 MeV/u He 2+ ions were already reported in our previous paper, in which the total uncertainty (±13%) was discussed. This paper shows the absolute DDCS data (1 - 100 eV) by 15.0 MeV/u He 2+ ions, in which the cover surrounding the interaction region was changed to μ-metal from Cu, in order to suppress the residual magnetic field for measuring the low-energy electrons effectively. (author)

Rehydrated sterically stabilized phospholipid nanomicelles of budesonide for nebulization: physicochemical characterization and in vitro, in vivo evaluations

Directory of Open Access Journals (Sweden)

Sahib MN

2011-10-01

Full Text Available Mohanad Naji Sahib, Yusrida Darwis, Kok Khiang Peh, Shaymaa Abdalwahed Abdulameer, Yvonne Tze Fung TanSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, Penang, MalaysiaBackground: Inhaled corticosteroids provide unique systems for local treatment of asthma or chronic obstructive pulmonary disease. However, the use of poorly soluble drugs for nebulization has been inadequate, and many patients rely on large doses to achieve optimal control of their disease. Theoretically, nanotechnology with a sustained-release formulation may provide a favorable therapeutic index. The aim of this study was to determine the feasibility of using sterically stabilized phospholipid nanomicelles of budesonide for pulmonary delivery via nebulization.Methods: PEG5000-DSPE polymeric micelles containing budesonide (BUD-SSMs were prepared by the coprecipitation and reconstitution method, and the physicochemical and pharmacodynamic characteristics of BUD-SSMs were investigated.Results: The optimal concentration of solubilized budesonide at 5 mM PEG5000-DSPE was 605.71 ± 6.38 µg/mL, with a single-sized peak population determined by photon correlation spectroscopy and a particle size distribution of 21.51 ± 1.5 nm. The zeta potential of BUD-SSMs was -28.43 ± 1.98 mV. The percent entrapment efficiency, percent yield, and percent drug loading of the lyophilized formulations were 100.13% ± 1.09%, 97.98% ± 1.95%, and 2.01% ± 0.02%, respectively. Budesonide was found to be amorphous by differential scanning calorimetry, and had no chemical interaction with PEGylated polymer according to Fourier transform infrared spectroscopy. Transmission electron microscopic images of BUD-SSMs revealed spherical nanoparticles. BUD-SSMs exhibited prolonged dissolution behavior compared with Pulmicort Respules® (P , 0.05. Aerodynamic characteristics indicated significantly higher deposition in the lungs compared with Pulmicort Respules®. The mass median aerodynamic, geometric

Density functional theory study of silodithiophene thiophenepyrrolopyrroledion-based small molecules: The effect of alkyl side chain length in electron donor materials

Energy Technology Data Exchange (ETDEWEB)

Seo, Dong Kyun; Yeo, Hak; Kwak, Kyung Won [Dept. of Chemistry, Chung-Ang University, Seoul (Korea, Republic of); Yoon, Young Woon; Kim, Bong Soo [Photo-electronic Hybrids Research Center, Korea Institute of Science and Technology, Seoul (Korea, Republic of); Lee, Kyung Koo [Dept. of Chemistry, Kunsan National University, Gunsan (Korea, Republic of)

2015-02-15

Push–pull small molecules are promising electron-donor materials for organic solar cells. Thus, precise prediction of their electronic structures is of paramount importance to control the optical and electrical properties of the solar cells. Various types of alkyl chains are usually introduced to increase solubility and modify the morphology of the resulting molecular films. Here, using density functional theory (DFT) and time-dependent DFT (TD-DFT), we report the precise effect of increasing the length of the alkyl chain on the electronic structure of an electron donor molecule 6,60-((4,4-dialkyl-4H-silolo[3,2-b:4,5-b′]-dithiophene-2,6-diyl) bis(thiophene-5,2-diyl))bis(2,5-alkyl-3-(thiophen-2-yl) -2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (DTS1TDPP). Alkyl groups were attached to the bridging position (silicon atom) of the fused rings and nitrogen atom of the pyrrolopyrroledione groups. We demonstrate that the alkyl groups do not perturb the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels, π-delocalized backbone structure, and UV–Vis absorption spectrum when they are placed at the least steric effect positions.

Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro

KAUST Repository

Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M.; Savoie, Huguette; Flanagan, Keith J.; Sy, Cindy; Sitte, Elisabeth; Telitchko, Maxime; Laquai, Fré dé ric; Boyle, Ross W.; Senge, Mathias O.

2017-01-01

Heavy atom-free BODIPY-anthracene dyads (BADs) generate locally excited triplet states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with the anthracene moiety yielding highly fluorescent species. The steric demand of the alkyl substituents in the BODIPY subunit defines the site of 1O2 addition. Novel bis- and tetraepoxides and bicyclic acetal products, arising from rearrangements of anthracene endoperoxides were isolated and characterized. 1O2 generation by BADs in living cells enables visualization of the dyads distribution, promising new imaging applications.

Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro

KAUST Repository

Filatov, Mikhail A.

2017-04-14

Heavy atom-free BODIPY-anthracene dyads (BADs) generate locally excited triplet states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with the anthracene moiety yielding highly fluorescent species. The steric demand of the alkyl substituents in the BODIPY subunit defines the site of 1O2 addition. Novel bis- and tetraepoxides and bicyclic acetal products, arising from rearrangements of anthracene endoperoxides were isolated and characterized. 1O2 generation by BADs in living cells enables visualization of the dyads distribution, promising new imaging applications.

Electron transparent graphene windows for environmental scanning electron microscopy in liquids and dense gases.

Science.gov (United States)

Stoll, Joshua D; Kolmakov, Andrei

2012-12-21

Due to its ultrahigh electron transmissivity in a wide electron energy range, molecular impermeability, high electrical conductivity and excellent mechanical stiffness, suspended graphene membranes appear to be a nearly ideal window material for in situ (in vivo) environmental electron microscopy of nano- and mesoscopic objects (including bio-medical samples) immersed in liquids and/or in dense gaseous media. In this paper, taking advantage of a small modification of the graphene transfer protocol onto metallic and SiN supporting orifices, reusable environmental cells with exchangeable graphene windows have been designed. Using colloidal gold nanoparticles (50 nm) dispersed in water as model objects for scanning electron microscopy in liquids as proof of concept, different conditions for imaging through the graphene membrane were tested. Limiting factors for electron microscopy in liquids, such as electron beam induced water radiolysis and damage of the graphene membrane at high electron doses, are discussed.

Spacebased Observation of Water Balance Over Global Oceans

Science.gov (United States)

Liu, W.; Xie, X.

2008-12-01

We demonstrated that ocean surface fresh water flux less the water discharge into the ocean from river and ice melt balances the mass loss in the ocean both in magnitude and in the phase of annual variation. The surface water flux was computed from the divergence of the water transport integrated over the depth of the atmosphere. The atmospheric water transport is estimated from the precipitable water measured by Special Sensor Microwave Imager, the surface wind vector by QuikSCAT, and the NOAA cloud drift wind through a statistical model. The transport has been extensively validated using global radiosonde and data and operational numerical weather prediction results. Its divergence has been shown to agree with the difference between evaporation estimated from the Advanced Microwave Scanning Radiometer data and the precipitation measured by Tropical Rain Measuring Mission over the global tropical and subtropical oceans both in magnitude and geographical distribution for temporal scales ranging from intraseasonal to interannual. The water loss rate in the ocean is estimated by two methods, one is from Gravity Recovery and Climate Experiment and the other is by subtracting the climatological steric change from the sea level change measured by radar altimeter on Jason. Only climatological river discharge and ice melt from in situ measurements are available and the lack of temporal variation may contribute to discrepancies in the balance. We have successfully used the spacebased surface fluxes to estimate to climatological mean heat transport in the Atlantic ocean and is attempting to estimate the meridional fresh water (or salt) transport from the surface flux. The approximate closure of the water balance gives a powerful indirect validation of the spacebased products.

Removal of diclofenac from surface water by electron beam irradiation combined with a biological aerated filter

Science.gov (United States)

He, Shijun; Wang, Jianlong; Ye, Longfei; Zhang, Youxue; Yu, Jiang

2014-12-01

The degradation of DCF was investigated in aqueous solution by using electron beam (EB) technology. When the initial concentration was between 10 and 40 mg/L, almost 100% of the DCF was degraded at a dose of 0.5 kGy. However, only about 6.5% of DCF was mineralized even at 2 kGy according to total organic carbon (TOC) measurements. A combined process of EB and biological aerated filter (BAF) was therefore developed to enhance the treatment of DCF contaminated surface water. The effluent quality of combined process was substantially improved by EB pretreatment due to the degradation of DCF and related intermediates. Both irradiation and biological treatment reduced the toxicity of the treated water. The experimental results showed that EB is effective for removing DCF from artificial aqueous solution and real surface water.

Application of steric exclusion chromatography for the separation of degradation products of the solvent used for the reprocessing of the nuclear fuels; Application de la chromatographie d`exclusion sterique a la separation de produits de degradation du solvant du retraitement des combustibles nucleaires

Energy Technology Data Exchange (ETDEWEB)

Pozo, C.

1993-08-01

The solvent, used in France in Purex reprocessing plants at La Hague is tributylphosphate (TBP) diluted to 30% with a mixture of branched alkanes, for which the main component is branched dodecane (70%). In order to minimize volumes of organic wastes, we have to maintain Purex solvent qualities and to get rid of degradation products. The subject of this memoir concerns among all the degradation products the heaviest molecules. The separation and the identification of these products have been carried out by preparative steric exclusion chromatography, followed by the analysis of the samples by various analytical methods. An inactive residue containing heavy degradation products was prepared according to the process used in the UP3 La Hague plant. The Analysis of this residue using steric exclusion chromatography and GPC/MS methods, shows the presence of three families of compounds heavier than TBP: the ``dimers of TBP`` (provided from the addition of two molecules of TBP), the ``TBP-alkanes`` (the main molecule is the result of the addition of dodecane with TBP), and ``the functionalized TBP`` (hydroxyled TBP, nitrous TBP, nitrated TBP). Plutonium (IV) retention tests were made on the various fractions generated by steric chromatography. They showed that ``the dimers of TBP`` and ``the functionalized TBP`` families are responsible for that retention. These results confirm the good efficiency of the solvent distillation system operated in UP3 plant which allow the elimination of heavy degradation products of the solvent with the residue and then restore excellent extracting properties for the recycled solvent. (author). 35 figs., 69 refs., 15 tabs.

Reaction of LiD with water vapor: thermogravimetric and scanning electron microscopy studies

International Nuclear Information System (INIS)

Balooch, M; Dinh, L N; LeMay, J D

2000-01-01

The kinetics of hydroxide film growth on LiD have been studied by the thermogravimetric method in nitrogen saturated with water vapor and by scanning electron microscopy (SEM) of samples that have been exposed to air with 50% relative humidity. The reaction probability is estimated to be 4 x 10 -7 for LiD exposed to ambient air with 50% relative humidity, suggesting that the diffusion through the hydroxide film is not the limiting step on the overall process at high moisture levels. The rate of growth is drastically reduced when the temperature is increased to 60 C

Steric Interference of Adhesion Supports In-Vitro Chondrogenesis of Mesenchymal Stem Cells on Hydrogels for Cartilage Repair.

Science.gov (United States)

Goldshmid, Revital; Cohen, Shlomit; Shachaf, Yonatan; Kupershmit, Ilana; Sarig-Nadir, Offra; Seliktar, Dror; Wechsler, Roni

2015-09-28

Recent studies suggest the presence of cell adhesion motifs found in structural proteins can inhibit chondrogenesis. In this context, the current study aims to determine if a polyethylene glycol (PEG)-modified fibrinogen matrix could support better chondrogenesis of human bone marrow mesenchymal stem cells (BM-MSC) based on steric interference of adhesion, when compared to a natural fibrin matrix. Hydrogels used as substrates for two-dimensional (2D) BM-MSC cultures under chondrogenic conditions were made from cross-linked PEG-fibrinogen (PF) and compared to thrombin-activated fibrin. Cell morphology, protein expression, DNA and sulfated proteoglycan (GAG) content were correlated to substrate properties such as stiffness and adhesiveness. Cell aggregation and chondrogenic markers, including collagen II and aggrecan, were observed on all PF substrates but not on fibrin. Shielding fibrinogen's adhesion domains and increasing stiffness of the material are likely contributing factors that cause the BM-MSCs to display a more chondrogenic phenotype. One composition of PF corresponding to GelrinC™--a product cleared in the EU for cartilage repair--was found to be optimal for supporting chondrogenic differentiation of BM-MSC while minimizing hypertrophy (collagen X). These findings suggest that semi-synthetic biomaterials based on ECM proteins can be designed to favourably affect BM-MSC towards repair processes involving chondrogenesis.

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

Science.gov (United States)

Turi, László

2016-04-01

We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

Energy Technology Data Exchange (ETDEWEB)

Turi, László, E-mail: turi@chem.elte.hu [Department of Physical Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518 Budapest 112 (Hungary)

2016-04-21

We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

Enhancement of the water flow velocity through carbon nanotubes resulting from the radius dependence of the friction due to electron excitations

Science.gov (United States)

Sokoloff, J. B.

2018-03-01

Secchi et al. [Nature (London) 537, 210 (2016), 10.1038/nature19315] observed a large enhancement of the permeability and slip length in carbon nanotubes when the tube radius is of the order of 15 nm, but not in boron nitride nanotubes. It will be pointed out that none of the parameters that appear in the usual molecular dynamics treatments of water flow in carbon nanotubes have a length scale comparable to 15 nm, which could account for the observed flow velocity enhancement. It will be demonstrated here, however, that if the friction force between the water and the tube walls in carbon nanotubes is dominated by friction due to electron excitations in the tube walls, the enhanced flow can be accounted for by a reduction in the contribution to the friction due to electron excitations in the wall, resulting from the dependence of the electron energy band gap on the tube radius.

Changes in activities of both photosystems and the regulatory effect of cyclic electron flow in field-grown cotton (Gossypium hirsutum L) under water deficit.

Science.gov (United States)

Yi, Xiao-Ping; Zhang, Ya-Li; Yao, He-Sheng; Han, Ji-Mei; Chow, Wah Soon; Fan, Da-Yong; Zhang, Wang-Feng

2018-01-01

To clarify the influence of water deficit on the functionality of the photosynthetic apparatus of cotton plants, leaf gas exchange, chlorophyll a fluorescence, and P700 redox state were examined in field-grown cotton Gossypium hirsutum L. cv. Xinluzao 45. In addition, we measured changes in the P515 signal and analyzed the activity of ATP synthase and the trans-thylakoid proton gradient (ΔpH). With increasing water deficit, the net CO 2 assimilation rate (A N ) and stomatal conductance (g s ) significantly decreased, but the maximum quantum efficiency of PSII photochemistry (F v /F m ) did not change. The photochemical activity of photosystem II (PSII) was reflected by the photochemical quenching coefficient (qP), quantum efficiency of photosystem II [Y(II)], and electron transport rate through PSII [ETR(II)], while the activity of photosystem I (PSI) was reflected by the quantum efficiency of photosystem I [Y(I)] and the electron transport rate through PSI [ETR(I)]. Both activities were maintained under mild water deficit, but were slightly decreased under moderate water deficit. Under moderate water deficit, cyclic electron flow (CEF), the fraction of absorbed light dissipated thermally via the ΔpH- and xanthophyll-regulated process [Y(NPQ)], and the fraction of P700 oxidized under a given set of conditions [Y(ND)] increased. Our results suggest that the activities of both photosystems are stable under mild water deficit and decrease only slightly under moderate water deficit. Moderate water deficit stimulates CEF, and the stimulation of CEF is essential for protecting PSI and PSII against photoinhibition. Copyright © 2017 Elsevier GmbH. All rights reserved.

Ultrafast transient-absorption of the solvated electron in water

International Nuclear Information System (INIS)

Kimura, Y.; Alfano, J.C.; Walhout, P.K.; Barbara, P.F.

1994-01-01

Ultrafast near infrared (NIR)-pump/variable wavelength probe transient-absorption spectroscopy has been performed on the aqueous solvated electron. The photodynamics of the solvated electron excited to its p-state are qualitatively similar to previous measurements of the dynamics of photoinjected electrons at high energy. This result confirms the previous interpretation of photoinjected electron dynamics as having a rate-limiting bottleneck at low energies presumably involving the p-state

General and efficient one-pot synthesis of novel sugar/heterocyclic(aryl) 1,2-diketones from sugar terminal alkynes by Sonogashira/tetra-n- butylammonium permanganate oxidation.

Science.gov (United States)

Zhang, Fuyi; Wu, Xiaopei; Wang, Liming; Liu, Hong; Zhao, Yufen

2015-11-19

A new approach for one-pot synthesis of novel sugar/heterocyclic(aryl) 1,2-diketones has been achieved by the reaction of various sugar terminal alkynes with heterocyclic(aryl) iodides at room temperature. This one-pot protocol includes Sonogashira coupling and mild n-Bu4NMnO4 oxidation reaction. This method is mild, general and efficient. Fifty-six examples have been given and the sugar/heterocyclic(aryl) 1,2-diketones were obtained in 71-94% yields. The sugar terminal alkynes include 9 structurally different sugars in pyranose, furanose, and acyclic form which have various protecting groups, sensitive groups, and sterically bulky substituents. The heterocyclic(aryl) iodides include sterically bulky heterocyclic compounds and iodobenzenes with electron-donating, electron-neutral, and electron-withdrawing substituents. Copyright © 2015 Elsevier Ltd. All rights reserved.

Identification of hydrogen and deuterium at the surface of water ice by reflection electron energy loss spectroscopy

International Nuclear Information System (INIS)

Yubero, F.; Toekesi, K.

2009-01-01

Complete text of publication follows. The study of elastically backscattered electrons from surfaces by reflection electron energy loss spectroscopy (REELS) has been recently recommended as an alternative technique to quantify the H content at the surface of a-C:H and polymer samples. This analysis is based on the fact that the energy loss of the incident electrons due to the recoil effect depends on the atomic mass of the particular atom present at the surface. The observed difference in recoil energies between H and O atoms (about 2 eV for 1.5 keV primary electrons) can be easily measured with standard electron spectrometers used in surface analysis. In this paper we go one step forward to explore if, with the same experimental approach, it is possible to differentiate between hydrogen and deuterium (D) in the surface region of a sample. This capability could be important for technological fields such as surface functionalization, where it is desired to distinguish between H and D at surfaces after interaction with labeled compounds. We have chosen normal and deuterated water as test labeled compounds because this polar molecule is of key importance in numerous surface reactions. It has been shown that H and D can be easily distinguished at the surface of water ice [4] using standard REELS measurements with 1000 - 1650 eV primary-electron energies, i.e., a surface analytical technique. Differences in recoil energies of the O - H and O - D atom pairs present in H 2 O and D 2 O have been found to agree with MC simulations (see Fig.1). There are many possible applications of H and D detection by REELS. Among many others, this study opens the possibility of nondestructive studies of deuterium-labeled atoms present or adsorbed on surfaces. For example, studies of H incorporation into a polymer or carbonbased surface after plasma activation with gas mixtures with several labeled molecules containing H atoms. Acknowledgements F.Y. thanks the Spanish Ministry of Science

Diverse and tunable electronic structures of single-layer metal phosphorus trichalcogenides for photocatalytic water splitting

International Nuclear Information System (INIS)

Liu, Jian; Li, Xi-Bo; Wang, Da; Liu, Li-Min; Lau, Woon-Ming; Peng, Ping

2014-01-01

The family of bulk metal phosphorus trichalcogenides (APX 3 , A = M II , M 0.5 I M 0.5 III ; X = S, Se; M I , M II , and M III represent Group-I, Group-II, and Group-III metals, respectively) has attracted great attentions because such materials not only own magnetic and ferroelectric properties, but also exhibit excellent properties in hydrogen storage and lithium battery because of the layered structures. Many layered materials have been exfoliated into two-dimensional (2D) materials, and they show distinct electronic properties compared with their bulks. Here we present a systematical study of single-layer metal phosphorus trichalcogenides by density functional theory calculations. The results show that the single layer metal phosphorus trichalcogenides have very low formation energies, which indicates that the exfoliation of single layer APX 3 should not be difficult. The family of single layer metal phosphorus trichalcogenides exhibits a large range of band gaps from 1.77 to 3.94 eV, and the electronic structures are greatly affected by the metal or the chalcogenide atoms. The calculated band edges of metal phosphorus trichalcogenides further reveal that single-layer ZnPSe 3 , CdPSe 3 , Ag 0.5 Sc 0.5 PSe 3 , and Ag 0.5 In 0.5 PX 3 (X = S and Se) have both suitable band gaps for visible-light driving and sufficient over-potentials for water splitting. More fascinatingly, single-layer Ag 0.5 Sc 0.5 PSe 3 is a direct band gap semiconductor, and the calculated optical absorption further convinces that such materials own outstanding properties for light absorption. Such results demonstrate that the single layer metal phosphorus trichalcogenides own high stability, versatile electronic properties, and high optical absorption, thus such materials have great chances to be high efficient photocatalysts for water-splitting

Poisson-Fermi Formulation of Nonlocal Electrostatics in Electrolyte Solutions

Directory of Open Access Journals (Sweden)

Liu Jinn-Liang

2017-10-01

Full Text Available We present a nonlocal electrostatic formulation of nonuniform ions and water molecules with interstitial voids that uses a Fermi-like distribution to account for steric and correlation efects in electrolyte solutions. The formulation is based on the volume exclusion of hard spheres leading to a steric potential and Maxwell’s displacement field with Yukawa-type interactions resulting in a nonlocal electric potential. The classical Poisson-Boltzmann model fails to describe steric and correlation effects important in a variety of chemical and biological systems, especially in high field or large concentration conditions found in and near binding sites, ion channels, and electrodes. Steric effects and correlations are apparent when we compare nonlocal Poisson-Fermi results to Poisson-Boltzmann calculations in electric double layer and to experimental measurements on the selectivity of potassium channels for K+ over Na+.

Electron spectra and mechanism of complexing of uranyl nitrate in water-acetone solutions

International Nuclear Information System (INIS)

Zazhogin, A.A.; Zazhogin, A.P.; Komyak, A.I.; Serafimovich, A.I.

2003-01-01

Based on the analysis of the luminescence and electronic absorption spectra, the processes of complexing in an aqueous solution of UO 2 (NO 3 ) 2 ·6H 2 O with small additions of acetone have been studied. In a pure aqueous solution, uranyl exists as the complex UO 2 ·5H 2 O. It is shown that the addition of acetone to the solution leads to the displacement of some water molecules out of the first coordination sphere of uranyl and the formation of the uranyl nitrate dihydrate complexes UO 2 (NO 3 ) 2 ·2H 2 O. It has been established that the stability of these complexes is determined by the decrease in the water activity and in the degree of hydration of uranyl and nitrate, which is the result of the local increase in the concentration of acetone molecules (due to their hydrophobicity) in the regions of the solution where uranyl and nitrate ions are found. The experimental facts supported the mechanism proposed are presented. (authors)

Controlling site selectivity in Pd-catalyzed oxidative cross-coupling reactions.

Science.gov (United States)

Lyons, Thomas W; Hull, Kami L; Sanford, Melanie S

2011-03-30

This paper presents a detailed investigation of the factors controlling site selectivity in the Pd-mediated oxidative coupling of 1,3-disubstituted and 1,2,3-trisubstituted arenes (aryl-H) with cyclometalating substrates (L~C-H). The influence of both the concentration and the steric/electronic properties of the quinone promoter are studied in detail. In addition, the effect of steric/electronic modulation of the carboxylate ligand is discussed. Finally, we demonstrate that substitution of the carboxylate for a carbonate X-type ligand leads to a complete reversal in site selectivity for many arene substrates. The origins of these trends in site selectivity are discussed in the context of the mechanism of Pd-catalyzed oxidative cross-coupling.

Contribution to the study of solvated electrons in water and alcohols and of radiolytic processes in organic carbonates by picosecond pulse radiolysis

International Nuclear Information System (INIS)

Torche, Faycal

2012-01-01

This work is part of the study area of the interaction of radiation with polar liquids. Using the picosecond electron accelerator ELYSE, studies were conducted using the techniques of pulse radiolysis combined with absorption spectrophotometry Time-resolved in the field of a picosecond. This work is divided into two separate chapters. The first study addresses the temporal variation of the radiolytic yield of solvated electron in water and simple alcohols. Due to original detection system mounted on the accelerator ELYSE, composed of a flash lamp specifically designed for the detection and a streak-camera used for the first time in absorption spectroscopy, it was possible to record the time-dependent radiolytic yields of the solvated electron from ten picoseconds to a few hundred nanoseconds. The scavenging of the electron solvated by methyl viologen, was utilized to reevaluate the molar extinction coefficient of the absorption spectrum of solvated electron in water and ethanol from isobestic points which corresponds to the intersection of the absorption spectra of solvated electron which disappears and methyl viologen which is formed during the reaction. The second chapter is devoted to the study of liquid organic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and propylene carbonate (PC). This family of carbonate which compose the electrolytes lithium batteries, has never been investigated by pulse radiolysis. The studies were focused on the PC in the light of these physicochemical characteristics, including its very high dielectric constant and its strong dipole moment of 4.9 D. The first results were obtained on aqueous solutions containing propylene carbonate to observe the reactions of reduction and oxidation of PC by radiolytic species of water (solvated electron and OH radicals). Then, after the identification (spectral and kinetic) of the species formed by interaction with the OH radical as the PC* radical resulting from the

UV-Vis, infrared, and mass spectroscopy of electron irradiated frozen oxygen and carbon dioxide mixtures with water

International Nuclear Information System (INIS)

Jones, Brant M.; Kaiser, Ralf I.; Strazzulla, Giovanni

2014-01-01

Ozone has been detected on the surface of Ganymede via observation of the Hartley band through the use of ultraviolet spectroscopy and is largely agreed upon to be formed by radiolytic processing via interaction of magnetospheric energetic ions and/or electrons with oxygen-bearing ices on Ganymede's surface. Interestingly, a clearly distinct band near 300 nm within the shoulder of the UV-Vis spectrum of Ganymede was also observed, but currently lacks an acceptable physical or chemical explanation. Consequently, the primary motivation behind this work was the collection of UV-Vis absorption spectroscopy of ozone formation by energetic electron bombardment of a variety of oxygen-bearing ices (oxygen, carbon dioxide, water) relevant to this moon as well as other solar system. Ozone was indeed synthesized in pure ices of molecular oxygen, carbon dioxide and a mixture of water and oxygen, in agreement with previous studies. The Hartley band of the ozone synthesized in these ice mixtures was observed in the UV-Vis spectra and compared with the spectrum of Ganymede. In addition, a solid state ozone absorption cross section of 6.0 ± 0.6 × 10 –17 cm 2 molecule –1 was obtained from the UV-Vis spectral data. Ozone was not produced in the irradiated carbon dioxide-water mixtures; however, a spectrally 'red' UV continuum is observed and appears to reproduce well what is observed in a large number of icy moons such as Europa.

Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74

Directory of Open Access Journals (Sweden)

Erika M. A. Fuentes-Fernandez

2018-02-01

Full Text Available The confined porous environment of metal organic frameworks (MOFs is an attractive system for studying reaction mechanisms. Compared to flat oxide surfaces, MOFs have the key advantage that they exhibit a well-defined structure and present significantly fewer challenges in experimental characterization. As an example of an important reaction, we study here the dissociation of water—which plays a critical role in biology, chemistry, and materials science—in MOFs and show how the knowledge of the structure in this confined environment allows for an unprecedented level of understanding and control. In particular, combining in-situ infrared spectroscopy and first-principles calculations, we show that the water dissociation reaction can be selectively controlled inside Zn-MOF-74 by alcohol, through both chemical and physical interactions. Methanol is observed to speed up water dissociation by 25% to 100%, depending on the alcohol partial pressure. On the other hand, co-adsorption of isopropanol reduces the speed of the water reaction, due mostly to steric interactions. In addition, we also investigate the stability of the product state after the water dissociation has occurred and find that the presence of additional water significantly stabilizes the dissociated state. Our results show that precise control of reactions within nano-porous materials is possible, opening the way for advances in fields ranging from catalysis to electrochemistry and sensors.

Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

Science.gov (United States)

Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

2015-05-27

The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

Behavioral Reactivity Associated With Electronic Monitoring of Environmental Health Interventions--A Cluster Randomized Trial with Water Filters and Cookstoves.

Science.gov (United States)

Thomas, Evan A; Tellez-Sanchez, Sarita; Wick, Carson; Kirby, Miles; Zambrano, Laura; Abadie Rosa, Ghislaine; Clasen, Thomas F; Nagel, Corey

2016-04-05

Subject reactivity--when research participants change their behavior in response to being observed--has been documented showing the effect of human observers. Electronics sensors are increasingly used to monitor environmental health interventions, but the effect of sensors on behavior has not been assessed. We conducted a cluster randomized controlled trial in Rwanda among 170 households (70 blinded to the presence of the sensor, 100 open) testing whether awareness of an electronic monitor would result in a difference in weekly use of household water filters and improved cookstoves over a four-week surveillance period. A 63% increase in number of uses of the water filter per week between the groups was observed in week 1, an average of 4.4 times in the open group and 2.83 times in the blind group, declining in week 4 to an insignificant 55% difference of 2.82 uses in the open, and 1.93 in the blind. There were no significant differences in the number of stove uses per week between the two groups. For both filters and stoves, use decreased in both groups over four-week installation periods. This study suggests behavioral monitoring should attempt to account for reactivity to awareness of electronic monitors that persists for weeks or more.

Water network-mediated, electron-induced proton transfer in [C{sub 5}H{sub 5}N ⋅ (H{sub 2}O){sub n}]{sup −} clusters

Energy Technology Data Exchange (ETDEWEB)

DeBlase, Andrew F.; Wolke, Conrad T.; Johnson, Mark A., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520 (United States); Weddle, Gary H. [Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520 (United States); Department of Chemistry, Fairfield University, 1073 North Benson Road, Fairfield, Connecticut 06824 (United States); Archer, Kaye A.; Jordan, Kenneth D., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260 (United States); Kelly, John T.; Tschumper, Gregory S.; Hammer, Nathan I., E-mail: jordan@pitt.edu, E-mail: nhammer@olemiss.edu, E-mail: mark.johnson@yale.edu [Department of Chemistry and Biochemistry, University of Mississippi, University, Mississippi 38677 (United States)

2015-10-14

The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ⋅ (H{sub 2}O){sub n=3−5}]{sup −} clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH{sup (0)}, occupying one of the primary solvation sites of the OH{sup −}. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the “solvent coordinate” at the heart of a prototypical proton-coupled electron transfer reaction.

Cross sections of electron loss and capture for beams of O+ in water vapor from the energy range of 0,2 to 1,2 MeV

International Nuclear Information System (INIS)

Oliveira, Vitor Jesus de

2015-01-01

The study of the interactions between atoms and molecules is important for the knowledge of the cross sections of the processes that contribute to the deposition of energy by charged particle beams used in radiotherapy planning and transport particle simulation codes. Heavy ions, such as oxygen, induce many cellular and molecular damages in human cells.as a result of interaction between the projectile and atoms and molecules. The use of proton and carbon as the projectile interacting with water molecules is well characterized, however there are few studies with oxygen ions. In this work we are interested in the study of electron loss (projectile ionization) and electron capture with charge state 1+. The Pelletron accelerator of 1.7 MeV from the Federal University of Rio de Janeiro housed in the Atomic and Molecular collisions Laboratory (LACAM) has been used, which can accelerate atomic and molecular ions up to speeds of the order of hundredths of light speed, and consists of the source of negative ions, the Wien filter, the accelerator itself and the magnet load selector. The detection device used to evaluate the processes of interaction (capture and loss) between the beam of the O + and the water molecule is a Microchannel Plate (MCP) at the position sensitive anode. The collisions of O + beans are being studied in the range of 0.2 to 1.2 MeV with water vapor (Z = 10). Were obtained the respective absolute cross sections for electron loss and electron capture and compared with the cross sections of the molecule methane (CH4 → Z = 10), the isoelectronic water molecule. The experimental results show an agreement between the measurements with water and methane. Comparisons were made with results of theoretical models for electron loss using the 'Free Collision Model' and for capture the Bohr and Lindhard model. The theoretical results for electron loss show an agreement of experimental data with the model used. The model of Bohr and Lindhard describes

6.0-10.0-MeV/u He2+-ion-induced electron emission from water vapor

International Nuclear Information System (INIS)

Ohsawa, D.; Sato, Y.; Soga, F.; Okada, Y.; Shevelko, V. P.

2005-01-01

We discuss absolute doubly differential cross sections (DDCS's) for the energy and angular distributions (20 deg. -160 deg.) of secondary electrons produced in the collisions of 6.0- and 10.0-MeV/u He 2+ ions with water vapor. Details of our experiments were reported in our previous paper [D. Ohsawa et al., Nucl. Instrum. Methods Phys. Res. B 227, 431 (2005)], which mainly considered the total uncertainty (±13%), as well as absolute DDCS data (7-10 000 eV) by 6.0-MeV/u He 2+ ions. All DDCS data, including the newly obtained data (20-12 000 eV) by 10.0-MeV/u He 2+ ions, are compared with classical theories after being corrected for relativistic effects. Based on the Rudd model and the Rutherford cross section, the experimental results are discussed by taking account of the momentum spread of the bound electrons. This paper mainly describes the analysis of low-energy electrons and binary encounter peaks at high energies, as well as details of relativistic corrections

Peptide π-Electron Conjugates: Organic Electronics for Biology?

Science.gov (United States)

Ardoña, Herdeline Ann M; Tovar, John D

2015-12-16

Highly ordered arrays of π-conjugated molecules are often viewed as a prerequisite for effective charge-transporting materials. Studies involving these materials have traditionally focused on organic electronic devices, with more recent emphasis on biological systems. In order to facilitate the transition to biological environments, biomolecules that can promote hierarchical ordering and water solubility are often covalently appended to the π-electron unit. This review highlights recent work on π-conjugated systems bound to peptide moieties that exhibit self-assembly and aims to provide an overview on the development and emerging applications of peptide-based supramolecular π-electron systems.

A highly sensitive and selective fluorescent sensor for detection of sulfide anion based on the steric hindrance effect

Science.gov (United States)

Chen, Guanfan; Tang, Mengzhuo; Fu, Xiufang; Cheng, Fenmin; Zou, Xianghua; Wang, Jingpei; Zeng, Rongjin

2018-01-01

Sulfide anions are not only generated as a byproduct from industrial processes but also as a crucial kind of element in biological systems. Therefore, fluorescent probes for detecting sulfide anion with sensitive and selective characters are highly popular. In this study, we report a highly sensitive and selective fluorescent sensor M1 for detection of sulfide anion based on the steric hindrance effect, where the recognition unit, dinitrobenzenesulfonate ester group is linked to aromatic ortho-position in the porphyrin, and correspondingly the fluorescence of fluorescein is efficiently quenched. Compared with the sensors with recognition unit linked to the other aromatic positions, the fluorescent sensor M1 has a lower fluorescence background. Furthermore, the corresponding fluorescence responses (F/F0) of M1 for mercapto amino-acid GSH, Hcy and Cys, were all far lower than the relative fluorescence ratio F/F0 values for S2-. It means that M1 is sensitive and selective to detection of S2-, and has an anti-disturbance ability to the biologically-relevant thiols, GSH, Hcy and Cys, and has the prospect of application in the exact detection of sulfide anions in living organisms. This approach offers some useful insights for realizing sensitive and selective fluorescent turn-on sensing in the detection assays for other analytes.

Impacts of Continuous Electron Beam Accelerator Facility operations on groundwater and surface water: Appendix 9

International Nuclear Information System (INIS)

Lee, D.W.

1986-04-01

The operation of the proposed Continuous Electron Beam Accelerator Facility (CEBAF) at Newport News, Virginia, is expected to result in the activation and subsequent contamination of water resources in the vicinity of the accelerator. Since the proposed site is located in the headwaters of the watershed supplying Big Bethel Reservoir, concern has been expressed about possible contamination of water resources used for consumption. Data characterizing the surface water and groundwater regime in the site area are limited. A preliminary geotechnical investigation of the site has been completed (LAW 1985). This investigation concluded that groundwater flow is generally towards the southeast at an estimated velocity of 2.5 m/y. This conclusion is based on groundwater and soil boring data and is very preliminary in nature. This analysis makes use of the data and conclusions developed during the preliminary geotechnical investigation to provide an upper-bound assessment of radioactive contamination from CEBAF operations. A site water balance was prepared to describe the behavior of the hydrologic environment that is in close agreement with the observed data. The transport of contamination in the groundwater regime is assessed using a one-dimensional model. The groundwater model includes the mechanisms of groundwater flow, groundwater recharge, radioactive decay, and groundwater activation. The model formulation results in a closed-form, exact, analytic solution of the concentration of contamination in the groundwater. The groundwater solution is used to provide a source term for a surface-water analysis. The surface-water and groundwater models are prepared for steady state conditions such that they represent conservative evaluations of CEBAF operations

Electron emission relevant to inner-shell photoionization of condensed water studied by multi-electron coincidence spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Hikosaka, Y., E-mail: hikosaka@las.u-toyama.ac.jp [Graduate School of Medicine and Pharmaceutical Sciences, University of Toyama, Toyama 930-0194 (Japan); Mashiko, R.; Konosu, Y.; Soejima, K. [Department of Environmental Science, Niigata University, Niigata 950-2181 (Japan); Shigemasa, E. [UVSOR Facility, Institute for Molecular Science, Okazaki 444-8585 (Japan); SOKENDAI, Okazaki 444-8585 (Japan)

2016-11-15

Highlights: • Multi-electron coincidence spectroscopy is applied to the study of electron emissions from condensed H2O molecules. • Coincidence Auger spectra are obtained for different photoelectron energies. • The energy distribution of the slow electrons ejected in the Auger decay is deduced from three-fold coincidences. - Abstract: Multi-electron coincidence spectroscopy using a magnetic-bottle electron spectrometer has been applied to the study of the Auger decay following O1s photoionization of condensed H{sub 2}O molecules. Coincidence Auger spectra are obtained for three different photoelectron energy ranges. In addition, the energy distribution of the slow electrons ejected in the Auger decay of the O1s core hole is deduced from three-fold coincidences.

Dose calculation due to electrons interaction with DNA

Energy Technology Data Exchange (ETDEWEB)

Mark, S; Orion, I; Shani, G [Ben-Gurion Univ. of the Negev, Beersheba (Israel). Dept. of Nuclear Engineering; Laster, B [Brookhaven National Lab., Upton, NY (United States)

1996-12-01

Experiments done with gadolinium loaded V79 Chinese Hamster cells, irradiated with thermal neutrons, showed that cells lethality increased by a factor of 1.8 compared to the case where the Gd atoms were located outside the cell.(l) It was obvious that the dramatic increase in cell lethality is due to the emission of Auger electrons following the {sup 157}Gd(n,{gamma}){sup 158}Gd reaction. Electrons of various energies from about 40 keV (very few) to less than 1 keV, are emitted. In the present work, energy absorbed in DNA was calculated, due to interaction of electron of different energies: 30, 15, 10, 8, 5 and 2 keV. The Monte Carlo code EGS4(2) was used for the calculations. The DNA was modeled as a series of alternative layers of sugar (phosphate - C{sub 5}O{sub 5}H{sub 7}P p=1.39gr cm{sup -1}) and water. The sugar layer thickness was assumed 2.5nm and the water layer thickness 10nm. An isotropic electron source was assumed to be located in a water layer and the electrons interactions (absorption and scattering) were calculated in the forward hemisphere. The energy absorbed in a group of 8 layers, (4 sugar and 4 water) was calculated for each one of the electron energies. An interesting fact found in those calculations; when the source electrons energy is 10 keV or more, most of the electrons are absorbed in the DNA-water system, are at energy about 2keV. There is no good explanation for this phenomenon except for assuming that when the electron`s energy reaches a low point of about 2keV, it cannot escape absorption in the medium. 10% of the 10 keV electrons deposit their entire energy in the 8 layers range (authors).

Novel benzimidazole derivatives as corrosion inhibitors of mild steel in the acidic media. Part II: Theoretical studies

International Nuclear Information System (INIS)

Cao, Ziyi; Tang, Yongming; Cang, Hui; Xu, Jinqiu; Lu, Gang; Jing, Wenheng

2014-01-01

Highlights: • Quantum chemical and MD studies of benzimidazole derivatives inhibitors. • Inhibition effectiveness depends on the ability to accept electrons. • Active sites of adsorption are mainly centralized on imidazole rings. • Steric effect results in the non-planar adsorption of BBIA and TBIA. - Abstract: In this paper, the adsorption behavior and inhibition mechanism of 2-aminomethyl benzimidazole (ABI), bis(2-benzimidazolylmethyl) amine (BBIA) and tri-(2-benzimidazolylmethyl) amine (TBIA) on the surface of mild steel were studied by quantum chemical calculations and molecular dynamics (MD) simulations. It was found that the three molecules show the similar ability to donate electrons while the difference in inhibition performance should mainly be attributed to the difference in accepting electrons. MD simulations show that steric effect between the benzimidazole segments significantly affects the adsorptive configurations of the molecules on Fe (1 0 0) surface

Mass transfer in fuel cells. [electron microscopy of components, thermal decomposition of Teflon, water transport, and surface tension of KOH solutions

Science.gov (United States)

Walker, R. D., Jr.

1973-01-01

Results of experiments on electron microscopy of fuel cell components, thermal decomposition of Teflon by thermogravimetry, surface area and pore size distribution measurements, water transport in fuel cells, and surface tension of KOH solutions are described.

Determination of electron depth-dose curves for water, ICRU tissue, and PMMA and their application to radiation protection dosimetry

International Nuclear Information System (INIS)

Grosswendt, B.

1994-01-01

For monoenergetic electrons in the energy range between 60 keV and 10 MeV, normally incident on water, 4-element ICRU tissue and PMMA phantoms, depth-dose curves have been calculated using the Monte Carlo method. The phantoms' shape was that of a rectangular solid with a square front face of 30 cm x 30 cm and a thickness of 15 cm; it corresponds to that recommended by the ICRU for use in the procedure of calibrating radiation protection dosemeters. The depth-dose curves have been used to determine practical ranges, half-value depths, electron fluence to maximum absorbed dose conversion factors, and conversion factors between electron fluence and absorbed dose at depths d corresponding to 0.007 g.cm -2 , 0.3 g.cm -2 , and 1.0 g.cm -2 . The latter data can be used as fluence to dose equivalent conversion factors for extended parallel electron beams. (Author)

In Vivo Cytogenotoxicity and Oxidative Stress Induced by Electronic Waste Leachate and Contaminated Well Water

Directory of Open Access Journals (Sweden)

Adeyinka M. Gbadebo

2013-07-01

Full Text Available Environmental, plant and animal exposure to hazardous substances from electronic wastes (e-wastes in Nigeria is increasing. In this study, the potential cytogenotoxicity of e-wastes leachate and contaminated well water samples obtained from Alaba International Electronic Market in Lagos, Nigeria, using induction of chromosome and root growth anomalies in Allium cepa, and micronucleus (MN in peripheral erythrocytes of Clarias gariepinus, was evaluated. The possible cause of DNA damage via the assessments of liver malondialdehyde (MDA, catalase (CAT, reduced glutathione (GSH and superoxide dismutase (SOD as indicators of oxidative stress in mice was also investigated. There was significant (p < 0.05 inhibition of root growth and mitosis in A. cepa. Cytological aberrations such as spindle disturbance, C-mitosis and binucleated cells, and morphological alterations like tumor and twisting roots were also induced. There was concentration-dependent, significant (p < 0.05 induction of micronucleated erythrocytes and nuclear abnormalities such as blebbed nuclei and binucleated erythrocytes in C. gariepinus. A significant increase (p < 0.001 in CAT, GSH and MDA with concomitant decrease in SOD concentrations were observed in the treated mice. Pb, As, Cu, Cr, and Cd analyzed in the tested samples contributed significantly to these observations. This shows that the well water samples and leachate contained substances capable of inducing somatic mutation and oxidative stress in living cells; and this is of health importance in countries with risk of e-wastes exposure.

Intercomparison of absorbed dose to water and air-kerma based dosimetry protocols for photon and electron beams

International Nuclear Information System (INIS)

Huq, M.S.

2002-01-01

Full text: During the last three decades the International Atomic Energy Agency (IAEA), the American Association of Physicists in Medicine (AAPM) and organizations from various countries have published Codes of Practice (CoP) and dosimetry protocols for the calibration of high-energy photon and electron beams. They are based on the air-kerma or exposure calibration factor of an ionization chamber in a 60 Co gamma ray beam and formalism for the determination of absorbed dose to water in reference conditions. In recent years, the IAEA (IAEA TRS-398) and the AAPM (AAPM TG-51) have published new external beam dosimetry protocols that are based on the use of an ionization chamber calibrated in terms of absorbed dose to water in a standards laboratory's reference quality beam. These two new protocols follow those by the German Standard DIN, the British IPSM and the IAEA CoP for plane-parallel chambers, which have discussed and implemented the procedures for the determination of absorbed dose-to-water based on standards of absorbed dose-to-water. Since the publication of these protocols and CoPs, many comparisons, theoretical as well as experimental, between them have been published in the literature providing valuable information about the sources of similarities and discrepancies that exist among them. For example, the differences in the basic data for photon and electron beams included in the various IAEA CoPs are very small for the second edition of TRS-277 for photons, TRS-381 for electrons and TRS-398. In these cases the data changes posed by the adoption of TRS-398 are within about ±0.3% for the most commonly used energies. When implementing TRS-398 in these cases, the main difference will arise from the transition from K air to D w standards. For example, experimental comparison of absorbed doses between TRS-398 and TRS-277 for photons show an average difference of about 0.3% for most commonly used energies with a maximum difference of about 1% at a TPR 20

Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies.

Science.gov (United States)

Bardhan, Jaydeep P; Jungwirth, Pavel; Makowski, Lee

2012-09-28

Two mechanisms have been proposed to drive asymmetric solvent response to a solute charge: a static potential contribution similar to the liquid-vapor potential, and a steric contribution associated with a water molecule's structure and charge distribution. In this work, we use free-energy perturbation molecular-dynamics calculations in explicit water to show that these mechanisms act in complementary regimes; the large static potential (∼44 kJ/mol/e) dominates asymmetric response for deeply buried charges, and the steric contribution dominates for charges near the solute-solvent interface. Therefore, both mechanisms must be included in order to fully account for asymmetric solvation in general. Our calculations suggest that the steric contribution leads to a remarkable deviation from the popular "linear response" model in which the reaction potential changes linearly as a function of charge. In fact, the potential varies in a piecewise-linear fashion, i.e., with different proportionality constants depending on the sign of the charge. This discrepancy is significant even when the charge is completely buried, and holds for solutes larger than single atoms. Together, these mechanisms suggest that implicit-solvent models can be improved using a combination of affine response (an offset due to the static potential) and piecewise-linear response (due to the steric contribution).

Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies

Science.gov (United States)

Bardhan, Jaydeep P.; Jungwirth, Pavel; Makowski, Lee

2012-01-01

Two mechanisms have been proposed to drive asymmetric solvent response to a solute charge: a static potential contribution similar to the liquid-vapor potential, and a steric contribution associated with a water molecule's structure and charge distribution. In this work, we use free-energy perturbation molecular-dynamics calculations in explicit water to show that these mechanisms act in complementary regimes; the large static potential (∼44 kJ/mol/e) dominates asymmetric response for deeply buried charges, and the steric contribution dominates for charges near the solute-solvent interface. Therefore, both mechanisms must be included in order to fully account for asymmetric solvation in general. Our calculations suggest that the steric contribution leads to a remarkable deviation from the popular “linear response” model in which the reaction potential changes linearly as a function of charge. In fact, the potential varies in a piecewise-linear fashion, i.e., with different proportionality constants depending on the sign of the charge. This discrepancy is significant even when the charge is completely buried, and holds for solutes larger than single atoms. Together, these mechanisms suggest that implicit-solvent models can be improved using a combination of affine response (an offset due to the static potential) and piecewise-linear response (due to the steric contribution). PMID:23020318

Electronic forces as descriptors of nucleophilic and electrophilic regioselectivity and stereoselectivity.

Science.gov (United States)

Liu, Shubin; Rong, Chunying; Lu, Tian

2017-01-04

One of the main tasks of theoretical chemistry is to rationalize computational results with chemical insights. Key concepts of such nature include nucleophilicity, electrophilicity, regioselectivity, and stereoselectivity. While computational tools are available to predict barrier heights and other reactivity properties with acceptable accuracy, a conceptual framework to appreciate above quantities is still lacking. In this work, we introduce the electronic force as the fundamental driving force of chemical processes to understand and predict molecular reactivity. It has three components but only two are independent. These forces, electrostatic and steric, can be employed as reliable descriptors for nucleophilic and electrophilic regioselectivity and stereoselectivity. The advantages of using these forces to evaluate molecular reactivity are that electrophilic and nucleophilic attacks are featured by distinct characteristics in the electrostatic force and no knowledge of quantum effects included in the kinetic and exchange-correlation energies is required. Examples are provided to highlight the validity and general applicability of these reactivity descriptors. Possible applications in ambident reactivity, σ and π holes, frustrated Lewis pairs, and stereoselective reactions are also included in this work.

Electron beam processing of wastewater in Malaysia

International Nuclear Information System (INIS)

Zulkafli Ghazali; Khairul Zaman Dahlan; Ting Teo Ming; Khomsaton A. Bakar

2006-01-01

Electron beam processing technology started in Malaysia in 1991 when two accelerators were installed through JICA cooperation to perform medical product sterilization project. Since then several private companies have installed electron accelerators to develop in removing volatile organic materials and to demonstrate flue gas treatment. In this country report, effort on electron beam processing of wastewater or contaminated groundwater is presented: After de-coloration tests using gamma rays as function of radiation doses, electron beam treatment of textile industry wastewater as function of beam energy and current intensity as well as with combined treatment such as aeration or biological treatment to examine the effectiveness in color and BOD or COD change has been carried out and the main results are reported. Furthermore, the present technique was examined to apply in river water treatment for use as drinking water. Techno-economic feasibility study for recycling of industrial waste water using electron beam technology is now underway. (S. Ohno)

Refined energetic ordering for sulphate-water (n = 3-6) clusters using high-level electronic structure calculations

Science.gov (United States)

Lambrecht, Daniel S.; McCaslin, Laura; Xantheas, Sotiris S.; Epifanovsky, Evgeny; Head-Gordon, Martin

2012-10-01

This work reports refinements of the energetic ordering of the known low-energy structures of sulphate-water clusters ? (n = 3-6) using high-level electronic structure methods. Coupled cluster singles and doubles with perturbative triples (CCSD(T)) is used in combination with an estimate of basis set effects up to the complete basis set limit using second-order Møller-Plesset theory. Harmonic zero-point energy (ZPE), included at the B3LYP/6-311 + + G(3df,3pd) level, was found to have a significant effect on the energetic ordering. In fact, we show that the energetic ordering is a result of a delicate balance between the electronic and vibrational energies. Limitations of the ZPE calculations, both due to electronic structure errors, and use of the harmonic approximation, probably constitute the largest remaining errors. Due to the often small energy differences between cluster isomers, and the significant role of ZPE, deuteration can alter the relative energies of low-lying structures, and, when it is applied in conjunction with calculated harmonic ZPEs, even alters the global minimum for n = 5. Experiments on deuterated clusters, as well as more sophisticated vibrational calculations, may therefore be quite interesting.

Modeling back-relaxation in ionic polymer metal composites: The role of steric effects and composite layers

Science.gov (United States)

Porfiri, Maurizio; Sharghi, Hesam; Zhang, Peng

2018-01-01

Ionic polymer metal composites (IPMCs) are a new class of active materials that are gaining traction as soft actuators in medical and industrial applications. IPMCs can undergo large deformations under modest voltage inputs, in dry and wet environments. Past studies have demonstrated that physical and geometric properties of all the IPMC constituents (ionomer, electrodes, and counterions) may all influence the time scales of the transient response and severity of the back-relaxation. In this study, we present a detailed mathematical model to investigate how the finite size of the counterions and the presence of metal particles in the vicinity of the electrodes modulate IPMC actuation. We build on previous work by our group on thermodynamically consistent modeling of IPMC mechanics and electrochemistry, which attributes IPMC actuation to the interplay between Maxwell stress and osmotic forces. To gain insight into the role of physical and geometric parameters, the resulting nonlinear partial differential equations are solved semianalytically using the method of matched asymptotic expansions, for the initial transient and the steady-state. A numerical solution in COMSOL Multiphysics® is developed to verify semianalytical findings and further explore IPMC actuation. Our model can successfully predict the entire response of IPMCs, from the initial bending toward the anode to the steady-state toward the cathode. We find that the steric effect can abolish the back-relaxation of IPMCs by restraining the counterions' concentration near the electrodes. We also find that increasing the thickness of the ionomer-metal composite layers may enhance IPMC actuation through increased osmotic forces and Maxwell stress.

Power Electronics Thermal Management | Transportation Research | NREL

Science.gov (United States)

Power Electronics Thermal Management Power Electronics Thermal Management A photo of water boiling in liquid cooling lab equipment. Power electronics thermal management research aims to help lower the investigates and develops thermal management strategies for power electronics systems that use wide-bandgap

Electron-induced chemistry in microhydrated sulfuric acid clusters

Science.gov (United States)

Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

2017-11-01

We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H2SO4)m(H2O)n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4)m(H2O)nHSO4- and (H2O)nH2SO4-. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4- ṡ ṡ ṡ H3O+) formation in the neutral H2SO4(H2O)n clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO4)2(H2O)n this process starts as early as n ≥ 2 water molecules. The (H2SO4)m(H2O)nHSO4- clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4- ṡ ṡ ṡ H3O+) ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2O)nH2SO4- cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

Dynamics of soft Nanomaterials captured by transmission electron microscopy in liquid water

Energy Technology Data Exchange (ETDEWEB)

Proetto, Maria T.; Rush, Anthony M.; Chien, Miao-Ping; Abellan Baeza, Patricia; Patterson, Joseph P.; Thompson, Matthew P.; Olson, Norman H.; Moore, Curtis E.; Rheingold, Arnold L.; Andolina, Christopher; Millstone, Jill; Howell, Stephen B.; Browning, Nigel D.; Evans, James E.; Gianneschi, Nathan C.

2014-01-14

In this paper we present in situ transmission electron microscopy (TEM) of soft, synthetic nanoparticles with a comparative analysis using conventional TEM methods. This comparison is made with the simple aim of describing what is an unprecedented example of in situ imaging by TEM. However, we contend the technique will quickly become essential in the characterization of analogous systems, especially where dynamics are of interest in the solvated state. In this case, particles were studied which were obtained from the direct polymerization of an oxaliplatin analog, designed for an ongoing program in novel chemotherapeutic delivery systems. The resulting nanoparticles provided sufficient contrast for facile imaging in situ, and point toward key design parameters that enable this new characterization approach for organic nanomaterials. We describe the preparation of the synthetic micellar nanoparticles to- gether with their characterization in liquid water.

Excited-State Conformational/Electronic Responses of Saddle-Shaped N,N'-Disubstituted-Dihydrodibenzo[a,c]phenazines: Wide-Tuning Emission from Red to Deep Blue and White Light Combination.

Science.gov (United States)

Zhang, Zhiyun; Wu, Yu-Sin; Tang, Kuo-Chun; Chen, Chi-Lin; Ho, Jr-Wei; Su, Jianhua; Tian, He; Chou, Pi-Tai

2015-07-08

A tailored strategy is utilized to modify 5,10-dimethylphenazine (DMP) to donor-acceptor type N,N'-disubstituted-dihydrodibenzo[a,c]phenazines. The representative compounds DMAC (N,N'-dimethyl), DPAC (N,N'-diphenyl), and FlPAC (N-phenyl-N'-fluorenyl) reveal significant nonplanar distortions (i.e., a saddle shape) and remarkably large Stokes-shifted emission independent of the solvent polarity. For DPAC and FlPAC with higher steric hindrance on the N,N'-substituents, normal Stokes-shifted emission also appears, for which the peak wavelength reveals solvent-polarity dependence. These unique photophysical behaviors are rationalized by electronic configuration coupled conformation changes en route to the geometry planarization in the excited state. This proposed mechanism is different from the symmetry rule imposed to explain the anomalously long-wavelength emission for DMP and is firmly supported by polarity-, viscosity-, and temperature-dependent steady-state and nanosecond time-resolved spectroscopy. Together with femtosecond early dynamics and computational simulation of the reaction energy surfaces, the results lead us to establish a sequential, three-step kinetics. Upon electronic excitation of N,N'-disubstituted-dihydrodibenzo[a,c]phenazines, intramolecular charge-transfer takes place, followed by the combination of polarization stabilization and skeletal motion toward the planarization, i.e., elongation of the π-delocalization over the benzo[a,c]phenazines moiety. Along the planarization, DPAC and FlPAC encounter steric hindrance raised by the N,N'-disubstitutes, resulting in a local minimum state, i.e., the intermediate. The combination of initial charge-transfer state, intermediate, and the final planarization state renders the full spectrum of interest and significance in their anomalous photophysics. Depending on rigidity, the N,N'-disubstituted-dihydrodibenzo[a,c]phenazines exhibit multiple emissions, which can be widely tuned from red to deep blue and

Use of remotely reporting electronic sensors for assessing use of water filters and cookstoves in Rwanda.

Science.gov (United States)

Thomas, Evan A; Barstow, Christina K; Rosa, Ghislaine; Majorin, Fiona; Clasen, Thomas

2013-01-01

Remotely reporting electronic sensors offer the potential to reduce bias in monitoring use of environmental health interventions. In the context of a five-month randomized controlled trial of household water filters and improved cookstoves in rural Rwanda, we collected data from intervention households on product compliance using (i) monthly surveys and direct observations by community health workers and environmental health officers, and (ii) sensor-equipped filters and cookstoves deployed for about two weeks in each household. The adoption rate interpreted by the sensors varied from the household reporting: 90.5% of households reported primarily using the intervention stove, while the sensors interpreted 73.2% use, and 96.5% of households reported using the intervention filter regularly, while the sensors interpreted no more than 90.2%. The sensor-collected data estimated use to be lower than conventionally collected data both for water filters (approximately 36% less water volume per day) and cookstoves (approximately 40% fewer uses per week). An evaluation of intrahousehold consistency in use suggests that households are not using their filters or stoves on an exclusive basis, and may be both drinking untreated water at times and using other stoves ("stove-stacking"). These results provide additional evidence that surveys and direct observation may exaggerate compliance with household-based environmental interventions.

Communication: Microsecond dynamics of the protein and water affect electron transfer in a bacterial bc1 complex

Science.gov (United States)

Martin, Daniel R.; Matyushov, Dmitry V.

2015-04-01

Cross-membrane electron transport between cofactors localized in proteins of mitochondrial respiration and bacterial photosynthesis is the source of all biological energy. The statistics and dynamics of nuclear fluctuations in these protein/membrane/water heterogeneous systems are critical for their energetic efficiency. The results of 13 μs of atomistic molecular dynamics simulations of the membrane-bound bc1 bacterial complex are analyzed here. The reaction is affected by a broad spectrum of nuclear modes, with the slowest dynamics in the range of time-scales ˜0.1-1.6 μs contributing half of the reaction reorganization energy. Two reorganization energies are required to describe protein electron transfer due to dynamical arrest of protein conformations on the observation window. This mechanistic distinction allows significant lowering of activation barriers for reactions in proteins.

Communication: Microsecond dynamics of the protein and water affect electron transfer in a bacterial bc1 complex

International Nuclear Information System (INIS)

Martin, Daniel R.; Matyushov, Dmitry V.

2015-01-01

Cross-membrane electron transport between cofactors localized in proteins of mitochondrial respiration and bacterial photosynthesis is the source of all biological energy. The statistics and dynamics of nuclear fluctuations in these protein/membrane/water heterogeneous systems are critical for their energetic efficiency. The results of 13 μs of atomistic molecular dynamics simulations of the membrane-bound bc 1 bacterial complex are analyzed here. The reaction is affected by a broad spectrum of nuclear modes, with the slowest dynamics in the range of time-scales ∼0.1-1.6 μs contributing half of the reaction reorganization energy. Two reorganization energies are required to describe protein electron transfer due to dynamical arrest of protein conformations on the observation window. This mechanistic distinction allows significant lowering of activation barriers for reactions in proteins

A Monte Carlo Code (PHOEL) for generating initial energies of photoelectrons and compton electrons produced by photons in water

International Nuclear Information System (INIS)

Turner, J.E.; Modolo, J.T.; Sordi, G.M.A.A.; Hamm, R.N.; Wright, H.A.

1979-01-01

PHOEL provides a source term for a Monte Carlo code which calculates the electron transport and energy degradation in liquid water. This code is used to study the relative biological effectiveness (RBE) of low-LET radiation at low doses. The basic numerical data used and their mathematical treatment are described as well as the operation of the code [pt

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

Electron beam treatment of industrial wastewater

International Nuclear Information System (INIS)

Han, Bumsoo; Kim, JinKyu; Kim, Yuri

2004-01-01

For industrial wastewater with low impurity levels such as contaminated ground water, cleaning water and etc., purification only with electron beam is possible, but it should be managed carefully with reducing required irradiation doses as low as possible. Also for industrial wastewater with high impurity levels such as dyeing wastewater, leachate and etc., purification only with electron beam requires high amount of doses and far beyond economies. Electron beam treatment combined with conventional purification methods such as coagulation, biological treatment, etc. is suitable for reduction of non-biodegradable impurities in wastewater and will extend the application area of electron beam. A pilot plant with electron beam for treating 1,000 m 3 /day of wastewater from dyeing industries has constructed and operated continuously since Oct 1998. Electron beam irradiation instead of chemical treatment shows much improvement in removing impurities and increases the efficiency of biological treatment. Actual plant is under consideration based upon the experimental results. (author)

Pressurized waterproof case electronic device

KAUST Repository

Berumen, Michael L.

2013-01-01

A pressurized waterproof case for an electronic device is particularly adapted for fluid-tight containment and operation of a touch-screen electronic device or the like therein at some appreciable water depth. In one example, the case may be formed

Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

Science.gov (United States)

Zhu, Zhengguang; Xu, Na; Yu, Qiuping; Guo, Lei; Cao, Hui; Lu, Xinhua; Cai, Yuanli

2015-08-01

Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron injection dynamics in high-potential porphyrin photoanodes.

Science.gov (United States)

Milot, Rebecca L; Schmuttenmaer, Charles A

2015-05-19

There is a growing need to utilize carbon neutral energy sources, and it is well known that solar energy can easily satisfy all of humanity's requirements. In order to make solar energy a viable alternative to fossil fuels, the problem of intermittency must be solved. Batteries and supercapacitors are an area of active research, but they currently have relatively low energy-to-mass storage capacity. An alternative and very promising possibility is to store energy in chemical bonds, or make a solar fuel. The process of making solar fuel is not new, since photosynthesis has been occurring on earth for about 3 billion years. In order to produce any fuel, protons and electrons must be harvested from a species in its oxidized form. Photosynthesis uses the only viable source of electrons and protons on the scale needed for global energy demands: water. Because artificial photosynthesis is a lofty goal, water oxidation, which is a crucial step in the process, has been the initial focus. This Account provides an overview of how terahertz spectroscopy is used to study electron injection, highlights trends from previously published reports, and concludes with a future outlook. It begins by exploring similarities and differences between dye-sensitized solar cells (DSSCs) for producing electricity and a putative device for splitting water and producing a solar fuel. It then identifies two important problems encountered when adapting DSSC technology to water oxidation-improper energy matching between sensitizer energy levels with the potential for water oxidation and the instability of common anchoring groups in water-and discusses steps to address them. Emphasis is placed on electron injection from sensitizers to metal oxides because this process is the initial step in charge transport. Both the rate and efficiency of electron injection are analyzed on a sub-picosecond time scale using time-resolved terahertz spectroscopy (TRTS). Bio-inspired pentafluorophenyl porphyrins are

Electron-induced chemistry in microhydrated sulfuric acid clusters

Directory of Open Access Journals (Sweden)

J. Lengyel

2017-11-01

Full Text Available We investigate the mixed sulfuric acid–water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT calculations. The microhydration of (H2SO4m(H2On clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4m(H2OnHSO4− and (H2OnH2SO4−. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4−  ⋅  ⋅  ⋅  H3O+ formation in the neutral H2SO4(H2On clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO42(H2On this process starts as early as n ≥ 2 water molecules. The (H2SO4m(H2OnHSO4− clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4−  ⋅  ⋅  ⋅  H3O+ ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2OnH2SO4− cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid–water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid–water aerosols are discussed.

Iron Catalyzed Cycloaddition of Alkynenitriles and Alkynes

Science.gov (United States)

D’Souza, Brendan R.; Lane, Timothy K.

2011-01-01

The combination of Fe(OAc)2 and an electron-donating, sterically-hindered pyridyl bisimine ligand catalyzes the cycloaddition of alkynenitriles and alkynes. A variety of substituted pyridines were obtained in good yields. PMID:21557582

Electron irradiation-induced destruction of carbon nanotubes in electron microscopes

International Nuclear Information System (INIS)

Molhave, Kristian; Gudnason, Sven Bjarke; Pedersen, Anders Tegtmeier; Clausen, Casper Hyttel; Horsewell, Andy; Boggild, Peter

2007-01-01

Observations of carbon nanotubes under exposure to electron beam irradiation in standard transmission electron microscope (TEM) and scanning electron microscope (SEM) systems show that such treatment in some cases can cause severe damage of the nanotube structure, even at electron energies far below the approximate 100 keV threshold for knock-on damage displacing carbon atoms in the graphene structure. We find that the damage we observe in one TEM can be avoided by use of a cold finger. This and the morphology of the damage imply that water vapour, which is present as a background gas in many vacuum chambers, can damage the nanotube structure through electron beam-induced chemical reactions. Though, the dependence on the background gas makes these observations specific for the presently used systems, the results demonstrate the importance of careful assessment of the level of subtle structural damage that the individual electron microscope system can do to nanostructures during standard use

Electron spin-echo envelope modulation (ESEEM) reveals water and phosphate interactions with the KcsA potassium channel.

Science.gov (United States)

Cieslak, John A; Focia, Pamela J; Gross, Adrian

2010-02-23

Electron spin-echo envelope modulation (ESEEM) spectroscopy is a well-established technique for the study of naturally occurring paramagnetic metal centers. The technique has been used to study copper complexes, hemes, enzyme mechanisms, micellar water content, and water permeation profiles in membranes, among other applications. In the present study, we combine ESEEM spectroscopy with site-directed spin labeling (SDSL) and X-ray crystallography in order to evaluate the technique's potential as a structural tool to describe the native environment of membrane proteins. Using the KcsA potassium channel as a model system, we demonstrate that deuterium ESEEM can detect water permeation along the lipid-exposed surface of the KcsA outer helix. We further demonstrate that (31)P ESEEM is able to identify channel residues that interact with the phosphate headgroup of the lipid bilayer. In combination with X-ray crystallography, the (31)P data may be used to define the phosphate interaction surface of the protein. The results presented here establish ESEEM as a highly informative technique for SDSL studies of membrane proteins.

Wettability modification of human tooth surface by water and UV and electron-beam radiation

International Nuclear Information System (INIS)

Tiznado-Orozco, Gaby E.; Reyes-Gasga, José; Elefterie, Florina; Beyens, Christophe; Maschke, Ulrich; Brès, Etienne F.

2015-01-01

The wettability of the human tooth enamel and dentin was analyzed by measuring the contact angles of a drop of distilled water deposited on the surface. The samples were cut along the transverse and longitudinal directions, and their surfaces were subjected to metallographic mirror-finish polishing. Some samples were also acid etched until their microstructure became exposed. Wettability measurements of the samples were done in dry and wet conditions and after ultraviolet (UV) and electron beam (EB) irradiations. The results indicate that water by itself was able to increase the hydrophobicity of these materials. The UV irradiation momentarily reduced the contact angle values, but they recovered after a short time. EB irradiation raised the contact angle and maintained it for a long time. Both enamel and dentin surfaces showed a wide range of contact angles, from approximately 10° (hydrophilic) to 90° (hydrophobic), although the contact angle showed more variability on enamel than on dentin surfaces. Whether the sample's surface had been polished or etched did not influence the contact angle value in wet conditions. - Highlights: • Human tooth surface wettability changes in dry/wet and UV/EB radiation conditions. • More variability in contact angle is observed on enamel than on dentin surfaces. • Water by itself increases the hydrophobicity of the human tooth surface. • UV irradiation reduces momentarily the human tooth surface hydrophobicity. • EB irradiation increases and maintains the hydrophobicity for a long time

Wettability modification of human tooth surface by water and UV and electron-beam radiation

Energy Technology Data Exchange (ETDEWEB)

Tiznado-Orozco, Gaby E., E-mail: gab0409@gmail.com [UMET, Bâtiment C6, Université de Lille 1, Sciences et Technologies, 59650 Villeneuve d' Ascq (France); Unidad Académica de Odontología, Universidad Autónoma de Nayarit, Edificio E7, Ciudad de la Cultura “Amado Nervo”, C.P. 63190 Tepic, Nayarit (Mexico); Reyes-Gasga, José, E-mail: jreyes@fisica.unam.mx [UMET, Bâtiment C6, Université de Lille 1, Sciences et Technologies, 59650 Villeneuve d' Ascq (France); Instituto de Física, UNAM, Circuito de la Investigación s/n, Ciudad Universitaria, 04510 Coyoacan, México, D.F. (Mexico); Elefterie, Florina, E-mail: elefterie_florina@yahoo.com [UMET, Bâtiment C6, Université de Lille 1, Sciences et Technologies, 59650 Villeneuve d' Ascq (France); Beyens, Christophe, E-mail: christophe.beyens@ed.univ-lille1.fr [UMET, Bâtiment C6, Université de Lille 1, Sciences et Technologies, 59650 Villeneuve d' Ascq (France); Maschke, Ulrich, E-mail: Ulrich.Maschke@univ-lille1.fr [UMET, Bâtiment C6, Université de Lille 1, Sciences et Technologies, 59650 Villeneuve d' Ascq (France); Brès, Etienne F., E-mail: etienne.bres@univ-lille1.fr [UMET, Bâtiment C6, Université de Lille 1, Sciences et Technologies, 59650 Villeneuve d' Ascq (France)

2015-12-01

The wettability of the human tooth enamel and dentin was analyzed by measuring the contact angles of a drop of distilled water deposited on the surface. The samples were cut along the transverse and longitudinal directions, and their surfaces were subjected to metallographic mirror-finish polishing. Some samples were also acid etched until their microstructure became exposed. Wettability measurements of the samples were done in dry and wet conditions and after ultraviolet (UV) and electron beam (EB) irradiations. The results indicate that water by itself was able to increase the hydrophobicity of these materials. The UV irradiation momentarily reduced the contact angle values, but they recovered after a short time. EB irradiation raised the contact angle and maintained it for a long time. Both enamel and dentin surfaces showed a wide range of contact angles, from approximately 10° (hydrophilic) to 90° (hydrophobic), although the contact angle showed more variability on enamel than on dentin surfaces. Whether the sample's surface had been polished or etched did not influence the contact angle value in wet conditions. - Highlights: • Human tooth surface wettability changes in dry/wet and UV/EB radiation conditions. • More variability in contact angle is observed on enamel than on dentin surfaces. • Water by itself increases the hydrophobicity of the human tooth surface. • UV irradiation reduces momentarily the human tooth surface hydrophobicity. • EB irradiation increases and maintains the hydrophobicity for a long time.

Quantitative structure-activity relationships of salicylamide neuroleptic agents.

Science.gov (United States)

Gupta, S P; Saha, R N; Singh, P

1990-05-01

The in vitro antidopamine activity of substituted N-[(1-alkyl-2-pyrrolidinyl)methyl]-6-methoxysalicylamides was found to be well correlated with the hydrophobic and electronic nature of substituents at the 3-position, and with the steric nature of groups replacing the hydrogen atom of the salicyl hydroxy group. In contrast, only the hydrophobic and steric characteristics were found to be important in the in vivo activity of these neuroleptics. This difference suggests that different mechanisms are probably involved in their in vitro and in vivo actions, and that the relevant receptors are slightly different in structure. The in vitro results suggest that electron donation by the 3-substituent strengthens the formation of a hydrogen bond between the carbonyl group of the amide moiety and a hydrogen of the receptor.

Electron self-exchange in azurin

DEFF Research Database (Denmark)

Mikkelsen, K V; Skov, L K; Nar, H

1993-01-01

Electronic coupling between the copper atoms in an azurin dimer has been calculated in this conformationally well-defined system by using many-electronic wave functions. When one of the two water molecules forming intermolecular hydrogen bonds between the copper-ligating His-117 of the two azurin...

Communication: Microsecond dynamics of the protein and water affect electron transfer in a bacterial bc{sub 1} complex

Energy Technology Data Exchange (ETDEWEB)

Martin, Daniel R.; Matyushov, Dmitry V., E-mail: dmitrym@asu.edu [Department of Physics and Department of Chemistry and Biochemistry, Arizona State University, P.O. Box 871504, Tempe, Arizona 85287 (United States)

2015-04-28

Cross-membrane electron transport between cofactors localized in proteins of mitochondrial respiration and bacterial photosynthesis is the source of all biological energy. The statistics and dynamics of nuclear fluctuations in these protein/membrane/water heterogeneous systems are critical for their energetic efficiency. The results of 13 μs of atomistic molecular dynamics simulations of the membrane-bound bc{sub 1} bacterial complex are analyzed here. The reaction is affected by a broad spectrum of nuclear modes, with the slowest dynamics in the range of time-scales ∼0.1-1.6 μs contributing half of the reaction reorganization energy. Two reorganization energies are required to describe protein electron transfer due to dynamical arrest of protein conformations on the observation window. This mechanistic distinction allows significant lowering of activation barriers for reactions in proteins.

Physico-Chemical and Structural Interpretation of Discrete Derivative Indices on N-Tuples Atoms

Science.gov (United States)

Martínez-Santiago, Oscar; Marrero-Ponce, Yovani; Barigye, Stephen J.; Le Thi Thu, Huong; Torres, F. Javier; Zambrano, Cesar H.; Muñiz Olite, Jorge L.; Cruz-Monteagudo, Maykel; Vivas-Reyes, Ricardo; Vázquez Infante, Liliana; Artiles Martínez, Luis M.

2016-01-01

This report examines the interpretation of the Graph Derivative Indices (GDIs) from three different perspectives (i.e., in structural, steric and electronic terms). It is found that the individual vertex frequencies may be expressed in terms of the geometrical and electronic reactivity of the atoms and bonds, respectively. On the other hand, it is demonstrated that the GDIs are sensitive to progressive structural modifications in terms of: size, ramifications, electronic richness, conjugation effects and molecular symmetry. Moreover, it is observed that the GDIs quantify the interaction capacity among molecules and codify information on the activation entropy. A structure property relationship study reveals that there exists a direct correspondence between the individual frequencies of atoms and Hückel’s Free Valence, as well as between the atomic GDIs and the chemical shift in NMR, which collectively validates the theory that these indices codify steric and electronic information of the atoms in a molecule. Taking in consideration the regularity and coherence found in experiments performed with the GDIs, it is possible to say that GDIs possess plausible interpretation in structural and physicochemical terms. PMID:27240357

Application of electron beam technology in improving sewage water ...

African Journals Online (AJOL)

user

irradiation sewage water can find its application either in agriculture for irrigation or in industry sector for cooling ... The water samples were collected from sewage water treatment .... to be irrigated, soil conditions and the irrigation system.

Picric acid sensing and capture by a sterically encumbered azo ...

Indian Academy of Sciences (India)

Dhananjayan Kaleeswaran

2018-01-25

Jan 25, 2018 ... above observations in mind, here we demonstrate how the presence of bulky ... can affect the azo-polymerization process, PNACs sens- ing ability and CO2 uptake ... on a JEOL model JSM-7600F electron microscope, operat- ing at the .... i PrTAPB is flanked by two isopropyl groups and hence results in a ...

Electron beam synthesis of silica/nano silver composite and its application in controlling microorganisms in drinking water

International Nuclear Information System (INIS)

Ramnani, S.P.; Biswal, Jayashree; Sabharwal, S.; Rama Rao, K.C.; Sai Prasad, P.

2008-01-01

Silica/nano silver composites were prepared by electron beam (EB) irradiation technique. The solution containing silica nanoparticles and AgNO 3 in various proportion were subjected to EB irradiation. The EB dose delivered was such that all the Ag + is converted into metallic silver. The samples were characterized by XRD, SEM and TEM analysis. The composites were tested for their anti microbial activity in water samples. The results indicated that there is an optimum size of Ag nanoparticles that shows better antimicrobial activity. (author)

Steric control of reactivity: formation of oximes, benzodiazepinone N-oxides and isoxazoloquinolinones

OpenAIRE

Heaney, Frances; Bourke, Sharon; Cunningham, Desmond; McArdle, Patrick

1998-01-01

Reaction of the alkenyl carbonyl compounds 1 with hydroxylamine can lead to the formation of the oximes 2, the benzodiazepinone N-oxides 3 or the isoxazoloquinolinones 5. The product(s) of reaction are shown to depend on the electronic nature of the terminal olefinic substituent R3 and the space filling capacity of the substituents R1, R2 and R4. When the olefinic centre is electron poor (R3 = CO2Et) ketocarbonyls convert exclusively to bicyclic nitrones 3 whereas aldehydes are more sensitive...

Ammonium boranes for the selective complexation of cyanide or fluoride ions in water.

Science.gov (United States)

Hudnall, Todd W; Gabbaï, François P

2007-10-03

With the recognition of aqueous fluoride and cyanide ions as an objective, we have investigated the anion binding properties of two isomeric ammonium boranes, namely [p-(Mes2B)C6H4(NMe3)]+ ([1]+) and [o-(Mes2B)C6H4(NMe3)]+ ([2]+). These cationic boranes, which could be obtained by reaction of the known 4- and 2-dimesitylboryl-N,N-dimethylaniline with MeOTf, have been investigated both experimentally and computationally. They both react with fluoride and cyanide ions in organic solvents to afford the corresponding fluoroborate/ or cyanoborate/ammonium zwitterions 1F, 1CN, 2F, and 2CN. In aqueous solution, however, these cationic boranes behave as remarkably selective receptors. Indeed, [1]+ only complexes cyanide ions while [2]+ only complexes fluoride ions. In H2O/DMSO 60:40 vol (HEPES 6 mM, pH 7), the cyanide binding constant of [1]+ and the fluoride binding constant of [2]+ are respectively equal to 3.9 (+/-0.1) x 108 and 910 (+/-50) M-1. Structural and computational studies indicate that both steric and electronic effects contribute to the unusual selectivity displayed by these cationic boranes. Owing to favorable Coulombic effects, the para-derivative [1]+ has a very high affinity for cyanide; yet these effects are not sufficiently intense to allow complexation of the more efficiently hydrated and less basic fluoride anion. In the case of the ortho-derivative [2]+, the proximity of the ammonium moiety leads to an increase in the Lewis acidity of the boron center thus making fluoride binding possible. However, steric effects prevent cyanide coordination to the boron center of [2]+. Finally, cation [1]+ and [2]+ bind their dedicated anions reversibly and show a negligible response in the presence of other common anions including Cl-, Br-, I-, NO3-, OAc-, H2PO4-, and HSO4-.

The pH dependency of N-converting enzymatic processes, pathways and microbes: effect on net N₂O production

DEFF Research Database (Denmark)

Blum, Jan-Michael; Su, Qingxian; Ma, Yunjie

2018-01-01

causing steric changes in catalytic sites or proton/electron transfer routes that alter the enzymes' overall activity. Augmenting molecular information with, e.g., nitritation or denitrification rates yields explanations of changes in net N2 O production with pH. Ammonia oxidizing bacteria are of highest...... relevance for N2 O production, while heterotrophic denitrifiers are relevant for N2 O consumption at pH > 7.5. Net N2 O production in N-cycling water engineering systems is predicted to display a 'bell-shaped' curve in the range of pH 6.0-9.0 with a maximum at pH 7.0-7.5. Net N2 O production at acidic p...

Non-Fullerene Electron Acceptors for Use in Organic Solar Cells

KAUST Repository

Nielsen, Christian B.

2015-10-27

The active layer in a solution processed organic photovoltaic device comprises a light absorbing electron donor semiconductor, typically a polymer, and an electron accepting fullerene acceptor. Although there has been huge effort targeted to optimize the absorbing, energetic, and transport properties of the donor material, fullerenes remain as the exclusive electron acceptor in all high performance devices. Very recently, some new non-fullerene acceptors have been demonstrated to outperform fullerenes in comparative devices. This Account describes this progress, discussing molecular design considerations and the structure–property relationships that are emerging. The motivation to replace fullerene acceptors stems from their synthetic inflexibility, leading to constraints in manipulating frontier energy levels, as well as poor absorption in the solar spectrum range, and an inherent tendency to undergo postfabrication crystallization, resulting in device instability. New acceptors have to address these limitations, providing tunable absorption with high extinction coefficients, thus contributing to device photocurrent. The ability to vary and optimize the lowest unoccupied molecular orbital (LUMO) energy level for a specific donor polymer is also an important requirement, ensuring minimal energy loss on electron transfer and as high an internal voltage as possible. Initially perylene diimide acceptors were evaluated as promising acceptor materials. These electron deficient aromatic molecules can exhibit good electron transport, facilitated by close packed herringbone crystal motifs, and their energy levels can be synthetically tuned. The principal drawback of this class of materials, their tendency to crystallize on too large a length scale for an optimal heterojunction nanostructure, has been shown to be overcome through introduction of conformation twisting through steric effects. This has been primarily achieved by coupling two units together, forming dimers

Calorimetry at industrial electron accelerators

DEFF Research Database (Denmark)

Miller, Arne; Kovacs, A.

1985-01-01

Calorimetry is a convenient way to measure doses at industrial electron accelerators, where high absorbed doses (1-100 kGy) are delivered at dose rates of 102-105 Gy s-1 or even higher. Water calorimeters have been used for this purpose for several years, but recently other materials such as grap......Calorimetry is a convenient way to measure doses at industrial electron accelerators, where high absorbed doses (1-100 kGy) are delivered at dose rates of 102-105 Gy s-1 or even higher. Water calorimeters have been used for this purpose for several years, but recently other materials...

Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: Acrolein in water

International Nuclear Information System (INIS)

Floris, Franca Maria; Amovilli, Claudio; Filippi, Claudia

2014-01-01

We investigate here the vertical n → π * and π → π * transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π * case and also improve considerably the shift for the π → π * transition

Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: Acrolein in water

Science.gov (United States)

Floris, Franca Maria; Filippi, Claudia; Amovilli, Claudio

2014-01-01

We investigate here the vertical n → π* and π → π* transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π* case and also improve considerably the shift for the π → π* transition.

Tracking the Structural and Electronic Configurations of a Cobalt Proton Reduction Catalyst in Water

Energy Technology Data Exchange (ETDEWEB)

Moonshiram, Dooshaye; Gimbert-Suriñach, Carolina [Institute; Guda, Alexander [International; Picon, Antonio; Lehmann, C. Stefan; Zhang, Xiaoyi; Doumy, Gilles; March, Anne Marie; Benet-Buchholz, Jordi [Institute; Soldatov, Alexander [International; Llobet, Antoni [Institute; Departament; Southworth, Stephen H.

2016-08-09

Time resolved X-ray absorption spectroscopy (X-TAS) has been used to study the light induced hydrogen evolution reaction catalyzed by a highly stable cobalt complex, [Ru(bpy)3]2+ photosensitizer and an equimolar mixture of sodium ascorbate/ascorbic acid electron donor in pure water. XANES and EXAFS analysis of a binary mixture of the octahedral Co(III) pre-catalyst and [Ru(bpy)3]2+ after illumination, revealed in-situ formation of a square pyramidal Co(II) intermediate, with electron transfer kinetics of 51 ns. On the other hand, X-TAS experiments of the complete photocatalytic system in the presence of the electron donor showed the formation of a square planar Co(I) intermediate species within a few nanoseconds followed by its decay in the microsecond timescales. The Co(I) structural assignment is supported by calculations based on density functional theory (DFT). At longer reaction times, we observe the formation of the initial Co(III) species concomitant to the decay of Co(I), thus closing the catalytic cycle. The experimental X-ray absorption spectra of the molecular species formed along the catalytic cycle are modeled using a combination of molecular orbital DFT calculations (DFT-MO) and Finite Difference Method (FDM). These findings allowed us to unequivocally assign the full mechanistic pathway followed by the catalyst as well as to determine the rate limiting step of the process, which consists in the protonation of the Co(I). This study provides a complete kinetics scheme for the hydrogen evolution reaction by a cobalt catalyst, revealing unique information for the development of better catalysts for the reductive side of hydrogen fuel cells.

Ring-opening polymerization of 19-electron [2]cobaltocenophanes: a route to high-molecular-weight, water-soluble polycobaltocenium polyelectrolytes.

Science.gov (United States)

Mayer, Ulrich F J; Gilroy, Joe B; O'Hare, Dermot; Manners, Ian

2009-08-05

Water-soluble, high-molecular-weight polycobaltocenium polyelectrolytes have been prepared by ring-opening polymerization (ROP) techniques. Anionic polymerization of a strained 19-electron dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium chloride resulted in the formation of oligomers with up to nine repeat units. Thermal ROP of dicarba[2]cobaltocenophane followed by oxidation in the presence of ammonium nitrate resulted in the formation of high-molecular-weight polycobaltocenium nitrate, a redox-active cobalt-containing polyelectrolyte.

Antibody-Hapten Recognition at the Surface of Functionalized Liposomes Studied by SPR: Steric Hindrance of Pegylated Phospholipids in Stealth Liposomes Prepared for Targeted Radionuclide Delivery

Directory of Open Access Journals (Sweden)

Eliot. P. Botosoa

2011-01-01

Full Text Available Targeted PEGylated liposomes could increase the amount of drugs or radionuclides delivered to tumor cells. They show favorable stability and pharmacokinetics, but steric hindrance of the PEG chains can block the binding of the targeting moiety. Here, specific interactions between an antihapten antibody (clone 734, specific for the DTPA-indium complex and DTPA-indium-tagged liposomes were characterized by surface plasmon resonance (SPR. Non-PEGylated liposomes fused on CM5 chips whereas PEGylated liposomes did not. By contrast, both PEGylated and non-PEGylated liposomes attached to L1 chips without fusion. SPR binding kinetics showed that, in the absence of PEG, the antibody binds the hapten at the surface of lipid bilayers with the affinity of the soluble hapten. The incorporation of PEGylated lipids hinders antibody binding to extents depending on PEGylated lipid fraction and PEG molecular weight. SPR on immobilized liposomes thus appears as a useful technique to optimize formulations of liposomes for targeted therapy.

Corrosion in electronics: Overview of failures and countermeasures

DEFF Research Database (Denmark)

Jellesen, Morten Stendahl; Verdingovas, Vadimas; Conseil, Helene

2014-01-01

Many field failure returns of electronics are marked as “no failure found”, yet numerous of these failures are likely due to corrosion, since corrosion related failures are not easily detected during subsequent failure analysis. In some cases failures are intermittent and occur because of service...... life conditions (humidity and contamination) where water film formation on the printed circuit board assembly (PCBA) leads to leakage currents resulting in wrong output signal of the electronic device. If the leakage current itself will not result in malfunctioning of the electronics, the formed water...

Radiation sterilization of harmful algae in water

International Nuclear Information System (INIS)

Byung Chull An; Jae-Sung Kim; Seung Sik Lee; Shyamkumar Barampuram; Eun Mi Lee; Byung Yeoup Chung

2007-01-01

Complete text of publication follows. Objective: Drinking water, water used in food production and for irrigation, water for fish farming, waste water, surface water, and recreational water have been recently recognized as a vector for the transmission of harmful micro-organisms. The human and animal harmful algae is a waterborne risk to public health and economy because the algae are ubiquitous and persistent in water and wastewater, not completely removed by physical-chemical treatment processes, and relatively resistant to chemical disinfection. Gamma and electron beam radiation technology is of growing in the water industry since it was demonstrated that gamma and electron beam radiation is very effective against harmful algae. Materials and Methods: Harmful algae (Scenedesmus quadricauda(Turpin) Brebisson 1835 (AG10003), Chlorella vulgaris Beijerinck 1896 (AG30007) and Chlamydomonas sp. (AG10061)) were distributed from Korean collection for type cultures (KCTC). Strains were cultured aerobically in Allen's medium at 25□ and 300 umol/m2s for 1 week using bioreactor. We investigated the disinfection efficiency of harmful algae irradiated with gamma (0.05 to 10 kGy for 30 min) and electron beam (1 to 19 kGy for 5 sec) rays. Results and Conclusion: We investigated the disinfection efficiency of harmful algae irradiated with gamma and electron beam rays of 50 to 19000 Gy. We established the optimum sterilization condition which use the gamma and electron beam radiation. Gamma ray disinfected harmful algae at 400 Gy for 30 min. Also, electron beam disinfected at 1000 Gy for 5 sec. This alternative disinfection practice had powerful disinfection efficiency. Hence, the multi-barrier approach for drinking water treatment in which a combination of various disinfectants and filtration technologies are applied for removal and inactivation of different microbial pathogens will guarantee a lower risk of microbial contamination.

Pressurized waterproof case electronic device

KAUST Repository

Berumen, Michael L.

2013-01-31

A pressurized waterproof case for an electronic device is particularly adapted for fluid-tight containment and operation of a touch-screen electronic device or the like therein at some appreciable water depth. In one example, the case may be formed as an enclosure having an open top panel or face covered by a flexible, transparent membrane or the like for the operation of the touchscreen device within the case. A pressurizing system is provided for the case to pressurize the case and the electronic device therein to slightly greater than ambient in order to prevent the external water pressure from bearing against the transparent membrane and pressing it against the touch screen, thereby precluding operation of the touch screen device within the case. The pressurizing system may include a small gas cartridge or may be provided from an external source.

Development techniques and electron optical studies of high voltage, high current electron guns

International Nuclear Information System (INIS)

Rangarajan, L.M.; Mahadevan, S.; Ramamurthi, S.S.

1992-01-01

The progress of the electron gun design, limiting to axially symmetric geometries is discussed here with a view to utilise such guns for electron accelerators. The mechanical design features leading to the physical configuration of the gun with stringent tolerances are outlined. Vacuum processing is done at pressures of 1.3x10 -5 Pa. The gun employs W-filament emitter or a cathode pellet with bombarder service. A water cooled compact faraday cup is used to measure the electron current. Electron gun geometries have been studied using the computer programme. The preveance of the gun is 0.7x10 -7 A/Vsup(1.5) at 80 kV. Developmental techniques of such pulsed electron guns are described. (author). 7 refs., 5 figs

Strain and water effects on the electronic structure and chemical activity of in-plane graphene/silicene heterostructure

Science.gov (United States)

Kistanov, Andrey A.; Cai, Yongqing; Zhang, Yong-Wei; Dmitriev, Sergey V.; Zhou, Kun

2017-03-01

By using first-principles calculations, the electronic structure of planar and strained in-plane graphene/silicene heterostructure is studied. The heterostructure is found to be metallic in a strain range from  -7% (compression) to  +7% (tension). The effect of compressive/tensile strain on the chemical activity of the in-plane graphene/silicene heterostructure is examined by studying its interaction with the H2O molecule. It shows that compressive/tensile strain is able to increase the binding energy of H2O compared with the adsorption on a planar surface, and the charge transfer between the water molecule and the graphene/silicene sheet can be modulated by strain. Moreover, the presence of the boron-nitride (BN)-substrate significantly influences the chemical activity of the graphene/silicene heterostructure upon its interaction with the H2O molecule and may cause an increase/decrease of the charge transfer between the H2O molecule and the heterostructure. These findings provide insights into the modulation of electronic properties of the in-plane free-standing/substrate-supported graphene/silicene heterostructure, and render possible ways to control its electronic structure, carrier density and redox characteristics, which may be useful for its potential applications in nanoelectronics and gas sensors.

Strain and water effects on the electronic structure and chemical activity of in-plane graphene/silicene heterostructure

International Nuclear Information System (INIS)

Kistanov, Andrey A; Zhou, Kun; Cai, Yongqing; Zhang, Yong-Wei; Dmitriev, Sergey V

2017-01-01

By using first-principles calculations, the electronic structure of planar and strained in-plane graphene/silicene heterostructure is studied. The heterostructure is found to be metallic in a strain range from  −7% (compression) to  +7% (tension). The effect of compressive/tensile strain on the chemical activity of the in-plane graphene/silicene heterostructure is examined by studying its interaction with the H 2 O molecule. It shows that compressive/tensile strain is able to increase the binding energy of H 2 O compared with the adsorption on a planar surface, and the charge transfer between the water molecule and the graphene/silicene sheet can be modulated by strain. Moreover, the presence of the boron-nitride (BN)-substrate significantly influences the chemical activity of the graphene/silicene heterostructure upon its interaction with the H 2 O molecule and may cause an increase/decrease of the charge transfer between the H 2 O molecule and the heterostructure. These findings provide insights into the modulation of electronic properties of the in-plane free-standing/substrate-supported graphene/silicene heterostructure, and render possible ways to control its electronic structure, carrier density and redox characteristics, which may be useful for its potential applications in nanoelectronics and gas sensors. (paper)

Ultrafast electron dynamics at alkali/ice structures adsorbed on a metal surface

International Nuclear Information System (INIS)

Meyer, Michael

2011-01-01

The goal of this work is to study the interaction between excess electrons in water ice structures adsorbed on metal surfaces and other charged or neutral species, like alkali ions, or chemically reactive molecules, like chlorofluorocarbons (CFC), respectively. The excess electrons in the ice can interact with the ions directly or indirectly via the hydrogen bonded water molecules. In both cases the presence of the alkali influences the population, localization, and lifetime of electronic states of excess electrons in the ice adlayer. These properties are of great relevance when considering the highly reactive character of the excess electrons, which can mediate chemical reactions by dissociative electron attachment (DEA). The influence of alkali adsorption on electron solvation and transfer dynamics in ice structures is investigated for two types of adsorption configurations using femtosecond time-resolved two-photon photoelectron spectroscopy. In the first system alkali atoms are coadsorbed on top of a wetting amorphous ice film adsorbed on Cu(111). At temperatures between 60 and 100 K alkali adsorption leads to the formation of positively charged alkali ions at the ice/vacuum interface. The interaction between the alkali ions at the surface and the dipole moments of the surrounding water molecules results in a reorientation of the water molecules. As a consequence new electron trapping sites, i.e. at local potential minima, are formed. Photoinjection of excess electrons into these alkali-ion covered amorphous ice layers, results in the trapping of a solvated electron at an alkali-ion/water complex. In contrast to solvation in pure amorphous ice films, where the electrons are located in the bulk of the ice layer, solvated electrons at alkali-ion/water complexes are located at the ice/vacuum interface. They exhibit lifetimes of several picoseconds and show a fast energetic stabilization. With ongoing solvation, i.e. pump-probe time delay, the electron transfer is

Electronic structures and water reactivity of mixed metal sulfide cluster anions

Energy Technology Data Exchange (ETDEWEB)

Saha, Arjun; Raghavachari, Krishnan [Department of Chemistry, Indiana University, Bloomington, Indiana 47405 (United States)

2014-08-21

The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS{sub 4}{sup −}) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H{sub 2} release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo{sub 2}S{sub 4}{sup −} and W{sub 2}S{sub 4}{sup −}) as well as mixed metal oxides (MoWO{sub 4}{sup −})

Water equivalence of polymer gel dosimeters

International Nuclear Information System (INIS)

Sellakumar, P.; James Jebaseelan Samuel, E.; Supe, Sanjay S.

2007-01-01

To evaluate the water equivalence and radiation transport properties of polymer gel dosimeters over the wide range of photon and electron energies 14 different types of polymer gels were considered. Their water equivalence was evaluated in terms of effective atomic number (Z eff ), electron density (ρ e ), photon mass attenuation coefficient (μ/ρ), photon mass energy absorption coefficient (μ en /ρ) and total stopping power (S/ρ) tot of electrons using the XCOM and the ESTAR database. The study showed that the effective atomic number of polymer gels were very close ( en /ρ for all polymer gels were in close agreement ( tot of electrons in polymer gel dosimeters were within 1% agreement with that of water. From the study we conclude that at lower energy (<80keV) the polymer gel dosimeters cannot be considered water equivalent and study has to be carried out before using the polymer gel for clinical application

The drift velocity of electrons in water vapour at low values of E/N

International Nuclear Information System (INIS)

Cheung, B.; Elford, M.T.

1990-01-01

The drift velocity of electrons in water vapour at 294 K has been measured over the E/N range 1.4 to 40 Td with an error estimated to be 35 Td. The present data show that μN decreases monotonically with decreasing E/N at low E/N values as observed by Wilson et al. (1975) and does not become independent of E/N as indicated by Lowke and Rees (1963). The present values although lower than those of Lowke and Rees, lie within the combined error limits, except for values below 2 Td. The present data suggested that the momentum transfer cross section at low energies is approximately 10% larger than that obtained by Pack et al. (1962) from their drift velocity measurements. 13 refs., 2 tabs., 5 figs

The Manipulation of Hydrophobicity in Catalyst Design for Applications of Aerobic Alcohols Oxidation and Electrocatalytic Water Oxidation

KAUST Repository

Chen, Batian

2016-05-17

Hydrophobicity is the generalized characteristic of non-polar substances that brings about their exclusion from aqueous phases. This property, entropic in its nature, drives key self-assembly and phase separation processes in water. Protein folding, the formation of DNA double helix, the existence of lipid bilayers and the wetting properties of leaf surfaces are all due to hydrophobic interactions. Inspired by Nature, we aimed to use hydrophobicity for creating novel and improved catalytic systems. (I) A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. (II) An enzyme-inspired catalytic system based on a rationally designed multifunctional surfactant was developed. The resulting micelles feature metal-binding sites and stable free radical moieties as well as fluorous pockets that attract and preconcentrate molecular oxygen. In the presence of copper ions, the micelles effect chemoselective aerobic alcohol oxidation under ambient conditions in water, a transformation that is challenging to achieve nonenzymatically. (III) Development of a facile means of photo/electrocatalytic water splitting is one of the main barriers to establishing of a solar hydrogen economy. Of the two half-reactions involved in splitting water into O2 and H2, water oxidation presents the most challenge due to its mechanistic complexity. A practical water oxidation catalyst must be highly active, yet inexpensive and indefinitely stable under harsh oxidative conditions. Here, I shall describe the synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine, (BimH)3. A wide range of catalysts differing in their electronic properties

Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.

Science.gov (United States)

Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R

2003-03-24

Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = 33.781(7) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = 18.540(2) A, b = 8.3443(7) A, c = 8.7795(7) A, beta = 93.039(1)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

Low-energy electron diffraction and induced damage in hydrated DNA

International Nuclear Information System (INIS)

Orlando, Thomas M.; Oh, Doogie; Chen Yanfeng; Aleksandrov, Alexandr B.

2008-01-01

Elastic scattering of 5-30 eV electrons within the B-DNA 5 ' -CCGGCGCCGG-3 ' and A-DNA 5 ' -CGCGAATTCGCG-3 ' DNA sequences is calculated using the separable representation of a free-space electron propagator and a curved wave multiple scattering formalism. The disorder brought about by the surrounding water and helical base stacking leads to a featureless amplitude buildup of elastically scattered electrons on the sugar and phosphate groups for all energies between 5 and 30 eV. However, some constructive interference features arising from diffraction are revealed when examining the structural waters within the major groove. These appear at 5-10, 12-18, and 22-28 eV for the B-DNA target and at 7-11, 12-18, and 18-25 eV for the A-DNA target. Although the diffraction depends on the base-pair sequence, the energy dependent elastic scattering features are primarily associated with the structural water molecules localized within 8-10 A spheres surrounding the bases and/or the sugar-phosphate backbone. The electron density buildup occurs in energy regimes associated with dissociative electron attachment resonances, direct electronic excitation, and dissociative ionization. Since diffraction intensity can be localized on structural water, compound H 2 O:DNA states may contribute to energy dependent low-energy electron induced single and double strand breaks

Methyl Iodide Oxidative Addition to Rhodium(I) Complexes: a DFT ...

African Journals Online (AJOL)

NJD

to the understanding of the role of the steric and electronic prop- erties of the different .... The pure Density Functional Theory (DFT) calculations were carried out using .... Since quantum computational methods are applied for the first time to ...

Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: Acrolein in water

Energy Technology Data Exchange (ETDEWEB)

Floris, Franca Maria, E-mail: floris@dcci.unipi.it; Amovilli, Claudio [Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, 56126 Pisa (Italy); Filippi, Claudia [MESA Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands)

2014-01-21

We investigate here the vertical n → π{sup *} and π → π{sup *} transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π{sup *} case and also improve considerably the shift for the π → π{sup *} transition.

Mass-induced [|#8#|]Sea Level Variations in the Red Sea from Satellite Altimetry and GRACE

Science.gov (United States)

Feng, W.; Lemoine, J.; Zhong, M.; Hsu, H.

2011-12-01

We have analyzed mass-induced sea level variations (SLVs) in the Red Sea from steric-corrected altimetry and GRACE between January 2003 and December 2010. The steric component of SLVs in the Red Sea calculated from climatological temperature and salinity data is relatively small and anti-phase with the mass-induced SLV. The total SLV in the Red Sea is mainly driven by the mass-induced SLV, which increases in winter when the Red Sea gains the water mass from the Gulf of Aden and vice versa in summer. Spatial and temporal patterns of mass-induced SLVs in the Red Sea from steric-corrected altimetry agree very well with GRACE observations. Both of two independent observations show high annual amplitude in the central Red Sea (>20cm). Total mass-induced SLVs in the Red Sea from two independent observations have similar annual amplitude and phase. One main purpose of our work is to see whether GRGS's ten-day GRACE results can observe intra-seasonal mass change in the Red Sea. The wavelet coherence analysis indicates that GRGS's results show the high correlation with the steric-corrected SLVs on intra-seasonal time scale. The agreement is excellent for all the time-span until 1/3 year period and is patchy between 1/3 and 1/16 year period. Furthermore, water flux estimates from current-meter arrays and moorings show mass gain in winter and mass loss in summer, which is also consistent with altimetry and GRACE.

The calculation of relative output factor and depth dose for irregular electron fields in water

International Nuclear Information System (INIS)

Dunscombe, Peter; McGhee, Peter; Chu, Terence

1996-01-01

Purpose: A technique, based on sector integration and interpolation, has been developed for the computation of both relative output factor and depth dose of irregular electron fields in water. The purpose of this study was to determine the minimum experimental data set required for the technique to yield results within accepted dosimetric tolerances. Materials and Methods: PC based software has been written to perform the calculations necessary to dosimetrically characterize irregular shaped electron fields. The field outline is entered via digitiser and the SSD and energy via the keyboard. The irregular field is segmented into sectors of specified angle (2 deg. was used for this study) and the radius of each sector computed. The central ray depth dose is reconstructed by summing the contributions from each sector deduced from calibration depth doses measured for circular fields. Relative output factors and depth doses at SSDs at which calibrations were not performed are found by interpolation. Calibration data were measured for circular fields from 2 to 9 cm diameter at 100, 105, 110, and 115 cm SSD. A clinical cut out can be characterized in less than 2 minutes including entry of the outline using this software. The performance of the technique was evaluated by comparing calculated relative output factors, surface dose and the locations of d 80 , d 50 and d 20 with experimental measurements on a variety of cut out shapes at 9 and 18 MeV. The calibration data set (derived from circular cut outs) was systematically reduced to identify the minimum required to yield an accuracy consistent with current recommendations. Results: The figure illustrates the ability of the technique to calculate the depth dose for an irregular field (shown in the insert). It was found that to achieve an accuracy of 2% in relative output factor and 2% or 2 mm (our criterion) in percentage depth dose, calibration data from five circular fields at the four SSDs spanning the range 100-115 cm

Progress of electron processing system useful for environmental preservation

International Nuclear Information System (INIS)

Hoshi, Yasuhisa

1998-01-01

Electron Processing has been used in the field of industrial application, mainly to process plastics or polymers, which is represented by the cross-linking of Polyethylene to improve heat resistance. On the other hand, there has been many research studies to use Electron Beam for an environmental preservation. Typical examples are Sterilization of Food, Flue Gas Treatment, Sterilization of Waste Water Sludge, Purification of Water, Removal of Volatile Organic Compound (VOC), etc. These research works have been done in the USA, Germany, Austria, Japan, etc. They reported some of the features of electron beam method. In addition, there is an unique report that the combination of Ozone and Electron Beam provides a better efficiency of the purification of the water. Recently, they have started the investigation for the practical use of Electron Beam in the environmental application. Flue gas treatment is a remarkable example of the investigation. They built the demonstration plant last year and they started the operation last fall. Presently, the system is in a demonstrative operation. This paper will report an outline of the R and D works of environmental applications of Electron Beam and also will introduce the latest technologies of Electron Processing Systems which will be available for the environmental preservation. (author)

Low-energy electron microdosimetry of CS-137

International Nuclear Information System (INIS)

Paschoa, A.S.; Wrenn, M.E.

1980-09-01

The mass of tissue irradiated by an internal emitter depends upon the distribution of the radionuclide within the organism and the type of radiation emitted. The range (95% absorption) of low-energy electron effectively defines the sensitive volume in which the energy of the emitted electron is deposited. Accordingly, in the case of Auger electron microdosimetry of internal emitters the correct definition of the sensitive volume is of paramount importance. The amount of energy delivered by the monoenergetic electrons emitted by the decay system 137 Cs → sup(137m)Ba to spherical volumes of water-like tissue media of radii equivalent to the estimated ranges of those electrons in water is calculated and discussed as far as the variations of the estimated ranges of electrons as a function of the initial energy of emission are concerned. Although there are still many uncertainties on the actual ranges of low-energy electrons, one can state confidently that the ranges of the Auger electrons of the decay system 137 Cs → 137 sup(m) Ba → 137 Ba can be considered to be in the same order of magnitude of the diameter of a cell. The energy deposition in spherical volumes of water-like tissue media, considered equivalent to the sensitive volumes for the Auger electrons of the decay system 137 Cs → 137 sub(m) Ba → 137 Ba, range for several orders of magnitude from 10 2 to about 10 10 times higher than the energy deposition in similar media by the internal conversion electrons of this decay system. If equivalent variations of energy deposition per unit mass occur when the masses considered are cellular, and subcellular structures, then the effects into the sensitive volume should be taken into biological consideration as far as the microdosimetry of low-energy electrons (approximately equal to 10 keV) is considered, whenever there is internal localization of Auger emitters. (Author) [pt

Nicotinic Receptor Transduction Zone: Invariant Arginine Couples to Multiple Electron-Rich Residues

Science.gov (United States)

Mukhtasimova, Nuriya; Sine, Steven M.

2013-01-01

Summary Gating of the muscle-type acetylcholine receptor (AChR) channel depends on communication between the ACh-binding site and the remote ion channel. A key region for this communication is located within the structural transition zone between the ligand-binding and pore domains. Here, stemming from β-strand 10 of the binding domain, the invariant αArg209 lodges within the hydrophobic interior of the subunit and is essential for rapid and efficient channel gating. Previous charge-reversal experiments showed that the contribution of αArg209 to channel gating depends strongly on αGlu45, also within this region. Here we determine whether the contribution of αArg209 to channel gating depends on additional anionic or electron-rich residues in this region. Also, to reconcile diverging findings in the literature, we compare the dependence of αArg209 on αGlu45 in AChRs from different species, and compare the full agonist ACh with the weak agonist choline. Our findings reveal that the contribution of αArg209 to channel gating depends on additional nearby electron-rich residues, consistent with both electrostatic and steric contributions. Furthermore, αArg209 and αGlu45 show a strong interdependence in both human and mouse AChRs, whereas the functional consequences of the mutation αE45R depend on the agonist. The emerging picture shows a multifaceted network of interdependent residues that are required for communication between the ligand-binding and pore domains. PMID:23442857

Fulltext PDF

Indian Academy of Sciences (India)

that touch us in every way, in addition to their important role in chemical ... Both steric effects and electronic effects contribute to the stability of free .... Cigarette smoke is known to ... good knowledge of the bond dissociation energies of various.

One-pot, three-component synthesis of highly substituted pyridines ...

Indian Academy of Sciences (India)

Administrator

trile in the presence of nanocrystalline magnesium oxide provides the highly substituted pyridine derivatives in moderate to ..... NAP–MgO (0⋅1 g), ethanol (5 mL) at reflux temperature b ... difference in the electronic and steric properties of.

Electron migration in hydrated biopolymers following pulsed irradiation at low temperatures

International Nuclear Information System (INIS)

Lith, D. van.

1987-01-01

Charge migration in biopolymer-water mixtures and the effect of water concentration on the charge migration is investigated by measuring the electrical conductivity and the light emission with the pulse radiolysis technique. A preliminary account of the microwave conductivity observed in hydrated DNA and collagen at low temperature after pulsed irradiation is given. The results show that when hydrated DNA or collagen are irradiated at low temperatures, conductivity transients with microsecond lifetime are observed. It is tentatively concluded that these transients are due to the highly mobile dry electron. The effect of water concentration on mobility, lifetime and migration distance of the electron is discussed. The effect of additives to the hydrated systems on the behaviour of the electron is described. It is shown that the observed effects of the additives confirm the earlier conclusions that the dry electron is the species responsible for the radiation induced conductivity. The water concentration in the DNA- and collagen-systems could be varied only between zero and approximately fifty percent, due to inhomogeneities which occur at higher water concentrations. Experiments on gelatin, a biopolymer which forms homogeneous samples with levels of hydration varying from almost zero to 100% water (ice) are described. Both the radiation induced and the dark microwave conductivity have been studied as a function of water content. Preliminary results of a study of the light emission from pulse irradiated DNA-water mixtures are reported in an attempt to establish a relation between the observed electron migration and the formation of excited states via charge neutralization. (Auth.)

Transport of secondary electrons and reactive species in ion tracks

Science.gov (United States)

Surdutovich, Eugene; Solov'yov, Andrey V.

2015-08-01

The transport of reactive species brought about by ions traversing tissue-like medium is analysed analytically. Secondary electrons ejected by ions are capable of ionizing other molecules; the transport of these generations of electrons is studied using the random walk approximation until these electrons remain ballistic. Then, the distribution of solvated electrons produced as a result of interaction of low-energy electrons with water molecules is obtained. The radial distribution of energy loss by ions and secondary electrons to the medium yields the initial radial dose distribution, which can be used as initial conditions for the predicted shock waves. The formation, diffusion, and chemical evolution of hydroxyl radicals in liquid water are studied as well. COST Action Nano-IBCT: Nano-scale Processes Behind Ion-Beam Cancer Therapy.

Valence holes observed in nanodiamonds dispersed in water

Science.gov (United States)

Petit, Tristan; Pflüger, Mika; Tolksdorf, Daniel; Xiao, Jie; Aziz, Emad F.

2015-02-01

Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp2-hybridized carbon disappear, and holes in the valence band are observed.Colloidal dispersion is essential for most nanodiamond applications, but its influence on nanodiamond electronic properties remains unknown. Here we have probed the electronic structure of oxidized detonation nanodiamonds dispersed in water by using soft X-ray absorption and emission spectroscopies at the carbon and oxygen K edges. Upon dispersion in water, the π* transitions from sp2-hybridized carbon disappear, and holes in the valence band are observed. Electronic supplementary information (ESI) available: Experimental methods, details on XAS/XES normalization and background correction procedures. See DOI: 10.1039/c4nr06639a

Generating high-brightness and coherent soft x-ray pulses in the water window with a seeded free-electron laser

Directory of Open Access Journals (Sweden)

Kaishang Zhou

2017-01-01

Full Text Available We propose a new scheme to generate high-brightness and temporal coherent soft x-ray radiation in a seeded free-electron laser. The proposed scheme is based on the coherent harmonic generation (CHG and superradiant principles. A CHG scheme is first used to generate a coherent signal at ultrahigh harmonics of the seed. This coherent signal is then amplified by a series of chicane-undulator modules via the fresh bunch and superradiant processes in the following radiator. Using a representative of a realistic set of parameters, three-dimensional simulations have been carried out and the simulations results demonstrated that 10 GW-level ultrashort (∼20  fs coherent radiation pulses in the water window can be achieved by using a 1.6 GeV electron beam based on the proposed technique.

Nanoparticle composites for printed electronics

International Nuclear Information System (INIS)

Männl, U; Van den Berg, C; Magunje, B; Härting, M; Britton, D T; Jones, S; Van Staden, M J; Scriba, M R

2014-01-01

Printed Electronics is a rapidly developing sector in the electronics industry, in which nanostructured materials are playing an increasingly important role. In particular, inks containing dispersions of semiconducting nanoparticles, can form nanocomposite materials with unique electronic properties when cured. In this study we have extended on our previous studies of functional nanoparticle electronic inks, with the development of a solvent-based silicon ink for printed electronics which is compatible with existing silver inks, and with the investigation of other metal nanoparticle based inks. It is shown that both solvent-based and water-based inks can be used for both silver conductors and semiconducting silicon, and that qualitatively there is no difference in the electronic properties of the materials printed with a soluble polymer binder to when an acrylic binder is used. (paper)

A reduced graphene oxide nanofiltration membrane intercalated by well-dispersed carbon nanotubes for drinking water purification

Science.gov (United States)

Chen, Xianfu; Qiu, Minghui; Ding, Hao; Fu, Kaiyun; Fan, Yiqun

2016-03-01

drinking water purification to retain the nanoparticles, dyes, proteins, organophosphates, sugars, and particularly humic acid. Experimentally, it is shown that the rGO-CNT hybrid NF membranes have high retention efficiency, good permeability and good anti-fouling properties. The retention was above 97.3% even for methyl orange (327 Da); for other objects, the retention was above 99%. The membrane's permeability was found to be as high as 20-30 L m-2 h-1 bar-1. Based on these results, we can conclude that (i) the use of BCPs as a surfactant can enhance steric repulsion and thus disperse CNTs effectively; (ii) placing well-dispersed 1D CNTs within 2D graphene sheets allows an uniform network to form, which can provide many mass transfer channels through the continuous 3D nanostructure, resulting in the high permeability and separation performance of the rGO-CNT hybrid NF membranes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08697c

A Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II,Rh(III,Ru(II Photoinitiated Electron Collectors

Directory of Open Access Journals (Sweden)

Shamindri M. Arachchige

2011-12-01

Full Text Available Mixed-metal supramolecular complexes have been designed that photochemically absorb solar light, undergo photoinitiated electron collection and reduce water to produce hydrogen fuel using low energy visible light. This manuscript describes these systems with an analysis of the photophysics of a series of six supramolecular complexes, [{(TL2Ru(dpp}2RhX2](PF65 with TL = bpy, phen or Ph2phen with X = Cl or Br. The process of light conversion to a fuel requires a system to perform a number of complicated steps including the absorption of light, the generation of charge separation on a molecular level, the reduction by one and then two electrons and the interaction with the water substrate to produce hydrogen. The manuscript explores the rate of intramolecular electron transfer, rate of quenching of the supramolecules by the DMA electron donor, rate of reduction of the complex by DMA from the 3MLCT excited state, as well as overall rate of reduction of the complex via visible light excitation. Probing a series of complexes in detail exploring the variation of rates of important reactions as a function of sub-unit modification provides insight into the role of each process in the overall efficiency of water reduction to produce hydrogen. The kinetic analysis shows that the complexes display different rates of excited state reactions that vary with TL and halide. The role of the MLCT excited state is elucidated by this kinetic study which shows that the 3MLCT state and not the 3MMCT is likely that key contributor to the photoreduction of these complexes. The kinetic analysis of the excited state dynamics and reactions of the complexes are important as this class of supramolecules behaves as photoinitiated electron collectors and photocatalysts for the reduction of water to hydrogen.

Autoregulation of transcription of the hupA gene in Escherichia coli: evidence for steric hindrance of the functional promoter domains induced by HU.

Science.gov (United States)

Kohno, K; Yasuzawa, K; Hirose, M; Kano, Y; Goshima, N; Tanaka, H; Imamoto, F

1994-06-01

The molecular mechanism of autoregulation of expression of the hupA gene in Escherichia coli was examined. The promoter of the gene contains a palindromic sequence with the potential to form a cruciform DNA structure in which the -35 sequence lies at the base of the stem and the -10 sequence forms a single-stranded loop. An artificial promoter lacking the palindrome, which was constructed by replacing a 10 nucleotide repeat for the predicted cruciform arm by a sequence in the opposite orientation, was not subject to HU-repression. DNA relaxation induced by deleting HU proteins and/or inhibiting DNA gyrase in cells results in increased expression from the hupA promoter. We propose that initiation of transcription of the hupA gene is negatively regulated by steric hindrance of the functional promoter domains for formation of the cruciform configuration, which is facilitated at least in part by negative supercoiling of the hupA promoter DNA region. The promoter region of the hupB gene also contains a palindromic sequence that can assume a cruciform configuration. Negative regulation of this gene by HU proteins may occur by a mechanism similar to that operating for the hupA gene.

Iodine generator for reclaimed water purification

Science.gov (United States)

Wynveen, R. A.; Powell, J. D.; Schubert, F. H. (Inventor)

1977-01-01

The system disclosed is for controlling the iodine level in a water supply in a spacecraft. It includes an iodine accumulator which stores crystalline iodine, an electrochemical valve to control the input of iodine to the drinking water and an iodine dispenser. A pump dispenses fluid through the iodine dispenser and an iodine sensor to a potable water tank storage. The iodine sensor electronically detects the iodine level in the water, and through electronic means, produces a correction current control. The correction current control operates the electro-chemical iodine valve to release iodine from the iodine accumulator into the iodine dispenser.

How carbo-benzenes fit molecules in their inner core as do biologic ion carriers?

KAUST Repository

Turias, Francesc; Poater, Jordi; Chauvin, Remi; Poater, Albert

2015-01-01

The present computational study complements experimental efforts to describe and characterize carbo-benzene derivatives as paradigms of aromatic carbo-mers. A long-lasting issue has been the possibility of the π-electron crown of the C18 carbo-benzene ring to fit metals or any chemical agents in its core. A systematic screening of candidate inclusion complexes was carried out by density functional theory calculations. Mayer bond order, aromaticity indices, and energy decomposition analyses complete the understanding of the strength of the host-guest interaction. The change in steric and electronic properties induced by the guest agent is investigated by means of steric maps. Substitution of H atoms at the carbo-benzene periphery by electron-withdrawing or electron-donating groups is shown to have a determining influence on the stability of the inclusion complex ions: while electronegative substituents enhance the recognition of cations, electropositive substituents do the same for anions. The results confirm the experimental failure hitherto to evidence a carbo-benzene complex. Nevertheless, the affinity of carbo-benzene for the potassium cation appears promising for the design of planar hydrocarbon analogues of biologic ion carriers. © 2015 Springer Science+Business Media New York.

How carbo-benzenes fit molecules in their inner core as do biologic ion carriers?

KAUST Repository

Turias, Francesc

2015-09-25

The present computational study complements experimental efforts to describe and characterize carbo-benzene derivatives as paradigms of aromatic carbo-mers. A long-lasting issue has been the possibility of the π-electron crown of the C18 carbo-benzene ring to fit metals or any chemical agents in its core. A systematic screening of candidate inclusion complexes was carried out by density functional theory calculations. Mayer bond order, aromaticity indices, and energy decomposition analyses complete the understanding of the strength of the host-guest interaction. The change in steric and electronic properties induced by the guest agent is investigated by means of steric maps. Substitution of H atoms at the carbo-benzene periphery by electron-withdrawing or electron-donating groups is shown to have a determining influence on the stability of the inclusion complex ions: while electronegative substituents enhance the recognition of cations, electropositive substituents do the same for anions. The results confirm the experimental failure hitherto to evidence a carbo-benzene complex. Nevertheless, the affinity of carbo-benzene for the potassium cation appears promising for the design of planar hydrocarbon analogues of biologic ion carriers. © 2015 Springer Science+Business Media New York.

Physico-Chemical and Structural Interpretation of Discrete Derivative Indices on N-Tuples Atoms

Directory of Open Access Journals (Sweden)

Oscar Martínez-Santiago

2016-05-01

Full Text Available This report examines the interpretation of the Graph Derivative Indices (GDIs from three different perspectives (i.e., in structural, steric and electronic terms. It is found that the individual vertex frequencies may be expressed in terms of the geometrical and electronic reactivity of the atoms and bonds, respectively. On the other hand, it is demonstrated that the GDIs are sensitive to progressive structural modifications in terms of: size, ramifications, electronic richness, conjugation effects and molecular symmetry. Moreover, it is observed that the GDIs quantify the interaction capacity among molecules and codify information on the activation entropy. A structure property relationship study reveals that there exists a direct correspondence between the individual frequencies of atoms and Hückel’s Free Valence, as well as between the atomic GDIs and the chemical shift in NMR, which collectively validates the theory that these indices codify steric and electronic information of the atoms in a molecule. Taking in consideration the regularity and coherence found in experiments performed with the GDIs, it is possible to say that GDIs possess plausible interpretation in structural and physicochemical terms.

Hydrogen Transfer from Hantzsch 1,4-Dihydropyridines to Carbon-Carbon Double Bonds under Microwave Irradiation

OpenAIRE

Jean Jacques Vanden Eynde; Didier Barbry; Guy Cordonnier; Séverine Torchy

2002-01-01

1,4-Dihydropyridines (DHPs) have been used in the reduction of carbon-carbon double bonds under microwave irradiation without solvent. The efficiency of the reactions is dramatically dependent on the steric effects in the DHPs and on the electronic effects in the olefins.

Correction: β-Amyrin synthase from Euphorbia tirucalli L. functional analyses of the highly conserved aromatic residues Phe413, Tyr259 and Trp257 disclose the importance of the appropriate steric bulk, and cation-π and CH-π interactions for the efficient catalytic action of the polyolefin cyclization cascade.

Science.gov (United States)

Ito, Ryousuke; Nakada, Chika; Hoshino, Tsutomu

2017-01-18

Correction for 'β-Amyrin synthase from Euphorbia tirucalli L. functional analyses of the highly conserved aromatic residues Phe413, Tyr259 and Trp257 disclose the importance of the appropriate steric bulk, and cation-π and CH-π interactions for the efficient catalytic action of the polyolefin cyclization cascade' by Ryousuke Ito et al., Org. Biomol. Chem., 2017, 15, 177-188.

Mechanism and kinetics of hydrated electron diffusion

International Nuclear Information System (INIS)

Tay, Kafui A.; Coudert, Francois-Xavier; Boutin, Anne

2008-01-01

Molecular dynamics simulations are used to study the mechanism and kinetics of hydrated electron diffusion. The electron center of mass is found to exhibit Brownian-type behavior with a diffusion coefficient considerably greater than that of the solvent. As previously postulated by both experimental and theoretical works, the instantaneous response of the electron to the librational motions of surrounding water molecules constitutes the principal mode of motion. The diffusive mechanism can be understood within the traditional framework of transfer diffusion processes, where the diffusive step is akin to the exchange of an extramolecular electron between neighboring water molecules. This is a second-order process with a computed rate constant of 5.0 ps -1 at 298 K. In agreement with experiment the electron diffusion exhibits Arrhenius behavior over the temperature range of 298-400 K. We compute an activation energy of 8.9 kJ mol -1 . Through analysis of Arrhenius plots and the application of a simple random walk model it is demonstrated that the computed rate constant for exchange of an excess electron is indeed the phenomenological rate constant associated with the diffusive process

Solvation of positive ions in water: the dominant role of water-water interaction

International Nuclear Information System (INIS)

Krekeler, Christian; Site, Luigi Delle

2007-01-01

Local polarization effects, induced by monovalent and divalent positive ions in water, influence (and in turn are influenced by) the large-scale structural properties of the solvent. Experiments can only distinguish this process of interplay in a generic qualitative way. Instead, first-principles calculations can address the question at both the electronic and atomistic scale, accounting for electronic polarization as well as geometrical conformations. For this reason we study the extension of the scales' interconnection by means of first-principle Car-Parrinello molecular dynamics applied to systems of different size. In this way we identify the general aspects dominating the physics of the first solvation shell and their connection to the effects related to the formation of the outer shells and eventually the bulk. We show that while the influence of the ions is extended to the first shell only, the water-water interaction is instead playing a dominant role even within the first shell independently of the size or the charge of the ion. (fast track communication)

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

KAUST Repository

Poater, Albert; Cavallo, Luigi

2015-01-01

During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

KAUST Repository

Poater, Albert

2015-09-29

During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

Characterization of CaSn(OH6 and CaSnO3 Nanostructures Synthesized by a New Precursor

Directory of Open Access Journals (Sweden)

S. Moshtaghi

2015-04-01

Full Text Available In this paper, calcium stannate nanoparticles were synthesized by a fast and simple co-precipitation procedure. For CaSnO3 preparation ammonia was used as precipitation agent. The effect of various surfactants such as cationic, anionic and neutral on the morphology of the products was investigated. By changing in Ca(Sal2 as a new precursor different morphologies were obtained. Ligand as a capping agent with steric hindrance leads to preparation of product with lower particle size. These semiconductor nanostructures have photo-catalyst activities and can degrade organic dyes as water pollution. The synthesized materials were characterized by X-ray diffraction (XRD technique, scanning electron microscopy (SEM Fourier transform infrared (FT-IR and UV-visible spectroscopy.

Nicotinic receptor transduction zone: invariant arginine couples to multiple electron-rich residues.

Science.gov (United States)

Mukhtasimova, Nuriya; Sine, Steven M

2013-01-22

Gating of the muscle-type acetylcholine receptor (AChR) channel depends on communication between the ACh-binding site and the remote ion channel. A key region for this communication is located within the structural transition zone between the ligand-binding and pore domains. Here, stemming from β-strand 10 of the binding domain, the invariant αArg209 lodges within the hydrophobic interior of the subunit and is essential for rapid and efficient channel gating. Previous charge-reversal experiments showed that the contribution of αArg209 to channel gating depends strongly on αGlu45, also within this region. Here we determine whether the contribution of αArg209 to channel gating depends on additional anionic or electron-rich residues in this region. Also, to reconcile diverging findings in the literature, we compare the dependence of αArg209 on αGlu45 in AChRs from different species, and compare the full agonist ACh with the weak agonist choline. Our findings reveal that the contribution of αArg209 to channel gating depends on additional nearby electron-rich residues, consistent with both electrostatic and steric contributions. Furthermore, αArg209 and αGlu45 show a strong interdependence in both human and mouse AChRs, whereas the functional consequences of the mutation αE45R depend on the agonist. The emerging picture shows a multifaceted network of interdependent residues that are required for communication between the ligand-binding and pore domains. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Experimental study of water absorption of electronic components and internal local temperature and humidity into electronic enclosure

DEFF Research Database (Denmark)

Conseil, Helene; Jellesen, Morten Stendahl; Ambat, Rajan

2014-01-01

Corrosion reliability of electronic products is a key factor for electronics industry, and today there is a large demand for performance reliability in large spans of temperature and humidity during day and night shifts. Corrosion failures are still seen due to the effects of temperature, humidity......, differential humidity, and temperature effects simulating day/night, and the use of desiccants....

Phospholipids chiral at phosphorus. Steric course of the reactions catalyzed by phosphatidylserine synthase from Escherichia coli and yeast

International Nuclear Information System (INIS)

Raetz, C.R.H.; Carman, G.M.; Dowhan, W.; Jiang, R.T.; Waszkuc, W.; Loffredo, W.; Tsai, M.D.

1987-01-01

The steric courses of the reactions catalyzed by phosphatidylserine (PS) synthase from Escherichia coli and yeast were elucidated by the following procedure. R/sub P/ and S/sub P/ isomers of 1,2-dipalmitoyl-sn-glycero-3-[ 17 O, 18 O]phosphoethanolamine ([ 17 O, 18 O]DPPE) were synthesized and converted to (R/sub P/)- and (S/sub P/)-1,2-dipalmitoyl-sn-glycero-3-[ 16 O, 17 O, 18 O]DPPA), respectively, by incubating with phospholipase D. Condensation of [ 16 O, 17 O, 18 O]DPPA with cytidine 5'-monophosphomorpholidate in pyridine gave the desired substrate for PS synthase, [ 17 O, 18 O]cytidine 5'-diphospho-1,2-dipalmitoyl-sn-glycerol ([ 17 O, 18 O]CDP-DPG), as a mixture of several isotopic and configurational isomers. Incubation of [ 17 O, 18 O]CDP-DPG), as a mixture of several isotopic and configurational isomers. Incubation of [ 17 O, 18 O] CDP-DPG with a mixture of L-serine, PS synthase and PS decarboxylase gave [ 17 O, 18 O]DPPE. The configuration and isotopic enrichments of the starting [ 17 O, 18 O]DPPE and the product were analyzed by 31 P NMR following trimethylsilylation of the DPPE. The results indicate that the reaction of E. coli PS synthase proceeds with retention of configuration at phosphorus, which suggests a two-step mechanism involving a phosphatidyl-enzyme intermediate, while the yeast PS synthase catalyzes the reaction with inversion of configuration, which suggests a single-displacement mechanism. Such results lend strong support to the ping-pong mechanism proposed for the E. coli enzyme and the sequential Bi-Bi mechanism proposed for the yeast enzyme, both based on previous isotopic exchange experiments

Relation between electron- and photon-caused oxidation in EUVL optics

Science.gov (United States)

Malinowski, Michael E.; Steinhaus, Charles A.; Meeker, Donald E.; Clift, W. Miles; Klebanoff, Leonard E.; Bajt, Sasa

2003-06-01

Extreme ultraviolet (EUV)-induced oxidation of silicon-capped, [Mo/Si] multilayer mirrors in the presence of background levels of water vapor is recognized as one of the most serious threats to multilayer lifetime since oxidation of the top silicon layer is an irreversible process. The current work directly compares the oxidation on a silicon-capped, [Mo/Si] multilayers caused by EUV photons with the oxidation caused by 1 keV electrons in the presence of the same water vapor environment (2 x 10-6 Torr). Similar, 4 nm, silicon-capped, [Mo/Si] multilayer mirror samples were exposed to photons (95.3 eV) + water vapor at the ALS, LBNL, and also to a 1 keV electron beam + water vapor in separate experimental systems. The results of this work showed that the oxidation produced by ~1 µA of e-beam current was found to be equivalent to that produced by ~1 mW of EUV exposure. These results will help allow the use of 1 keV electrons beams, instead of EUV photons, to perform environmental testing of multilayers in a low-pressure water environment and to more accurately determine projected mirror lifetimes based on the electron beam exposures.

Synthesis, photophysical and electrochemical properties of water–soluble phthalocyanines bearing 8-hydroxyquinoline-5-sulfonicacid derivatives

Energy Technology Data Exchange (ETDEWEB)

Günsel, Armağan; Kocabaş, Sibel; Bilgiçli, Ahmet T. [Department of Chemistry, Sakarya University, 54140 Esentepe, Sakarya (Turkey); Güney, Sevgi [Department of Chemistry, Istanbul Technical University, 34469 Maslak, Istanbul (Turkey); Kandaz, Mehmet, E-mail: mkandaz@sakarya.edu.tr [Department of Chemistry, Sakarya University, 54140 Esentepe, Sakarya (Turkey)

2016-08-15

We have presented in this paper, the synthesis, characterization, photophysical properties and electrochemical characterization of water soluble phthalocyanines (Pcs) bearing 8-hydroxyquinoline-5-sulfonicacid conjugates and their cationic quaternized counterpart that play important roles their application in photodynamic therapy (PDT). The periphery and non-periphery substituted phthalocyanines show high solubility and low aggregation tendency due to bulky 8-hydroxyquinoline-5-sulfonicacid steric hindrance moieties and axially bound counter chlorine anion. Singlet oxygen quantum yields, photodegradation quantum yields, photophysical properties and also the nature of the substituent and solvent effect on the photophysical and photochemical parameters of α-ZnPc and β-ZnPc are reported. In electrovalent cobalt (II) and manganese (III) compounds, metal based electron transfer reactions have been observed in addition to the common phthalocyanine ring-based electron transfer processes. The effect of point of substitution on the electrochemical properties of newly synthesized phthalocyanines substituted with 8-hydroxyquinoline-5-sulfonicacid group were evaluated.

Detection of the adsorption of water monolayers through the ion oscillation frequency in the magnesium oxide lattice by means of low energy electron diffraction

Directory of Open Access Journals (Sweden)

M. Guevara-Bertsch

2016-03-01

Full Text Available We investigate the variation of the oscillation frequency of the Mg2+ and O2− ions in the magnesium oxide lattice due to the interactions of the surface with water monolayers by means of Low Energy Electron Diffraction. Our key result is a new technique to determine the adsorbate vibrations produced by the water monolayers on the surface lattice as a consequence of their change in the surface Debye temperature and its chemical shift. The latter was systematically investigated for different annealing times and for a constant external thermal perturbation in the range of 110–300 K in order to accomplish adsorption or desorption of water monolayers in the surface lattice.

Detection of the adsorption of water monolayers through the ion oscillation frequency in the magnesium oxide lattice by means of low energy electron diffraction

Energy Technology Data Exchange (ETDEWEB)

Guevara-Bertsch, M.; Avendaño, E. [Escuela de Física, Universidad de Costa Rica, 2060 San Pedro, San José (Costa Rica); Centro de Investigación en Ciencia e Ingeniería de Materiales, Universidad de Costa Rica, 2060 San Pedro, San José (Costa Rica); Ramírez-Hidalgo, G. [Centro de Investigación en Ciencia e Ingeniería de Materiales, Universidad de Costa Rica, 2060 San Pedro, San José (Costa Rica); Sección de Física Teórica, Universidad de Costa Rica, 2060 San Pedro, San José (Costa Rica); Chavarría-Sibaja, A.; Araya-Pochet, J. A. [Centro de Investigación en Ciencia e Ingeniería de Materiales, Universidad de Costa Rica, 2060 San Pedro, San José (Costa Rica); Herrera-Sancho, O. A., E-mail: oscar-andrey.herrera@uibk.ac.at [Escuela de Física, Universidad de Costa Rica, 2060 San Pedro, San José (Costa Rica); Centro de Investigación en Ciencia e Ingeniería de Materiales, Universidad de Costa Rica, 2060 San Pedro, San José (Costa Rica); Institut für Quantenoptik und Quanteninformation, Österreichische Akademie der Wissenschaften, Technikerstr. 21a, 6020 Innsbruck (Austria)

2016-03-15

We investigate the variation of the oscillation frequency of the Mg{sup 2+} and O{sup 2−} ions in the magnesium oxide lattice due to the interactions of the surface with water monolayers by means of Low Energy Electron Diffraction. Our key result is a new technique to determine the adsorbate vibrations produced by the water monolayers on the surface lattice as a consequence of their change in the surface Debye temperature and its chemical shift. The latter was systematically investigated for different annealing times and for a constant external thermal perturbation in the range of 110–300 K in order to accomplish adsorption or desorption of water monolayers in the surface lattice.

Simultaneous determination of bromide and iodide as acetone derivatives by gas chromatography and electron capture detection in natural waters and biological fluids