Memory, Critical Theory and the Argument from History.

ERIC Educational Resources Information Center

Cox, J. Robert

1990-01-01

Explores the function of memory in critical theory, particularly in the work of Herbert Marcuse, as the basis for a critical argumentation. Argues that Marcuse's view suggests that argument is a "re-membering" of what had been split asunder--reason, imagination, and the capacity of action. Discusses other implications of Marcuse's…

Interactions of NO{sub 2}{sup {minus}} and SO{sub 3}{sup 2{minus}} with organic triplets. Charge transfer versus energy transfer: The role of reorganization energy in triplet-anion interactions and spectroscopic methods for its evaluation

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

Loeff, I.; Treinin, A.; Linschitz, H.

1992-06-25

Charge-transfer (CT) and energy-transfer (NT) interactions of simple anions with organic triplets are reviewed and discussed in connection with new quenching rate constant (K{sub q}) and radical yield measurements for SO{sub 3}{sup 2{minus}} and No{sub 2}{sup {minus}}. In the latter case both processes may occur at high organic triplet energies. Reorganization energies for one-electron oxidations are obtained for several anions, using data on charge-transfer-to-solvent (CTTS) spectra and photoelectron emission thresholds, which like the kinetic parameters of Marcus-Hush theory, also reflect Franck-Condon strains. The results, combined with thermodynamic free energies, give vertical redox potentials which correlate better than do equilibrium potentialsmore » with quenching rates. The theoretical basis for correlation between k{sub q} and Hv{sub CTTS} is discussed in the framework of Marcus rate theory. Assigning the total reorganization energy in the CT quenching reaction to the small anion component of the D-A pair gives reasonable agreement with data on quenching of dye triplets but too slow rates for aryl carbonyl triplets where exciplex formation may possibly occur. The optical reorganization energy for NO{sub 2}{sup {minus}} leads to values of the thermal self-exchange rate agreeing with those computed from the Marcus-Hush cross-relations, which also neglect bonding effects. The mechanism of NO{sub 2}{sup {minus}} interaction with triplets is discussed in detail, including indirect kinetic evidence for quenching of a short-lived exciplex by NO{sub 2}{sup {minus}} without radical formation. The possibility of reduction by triplet NO{sub 2}{sup {minus}} formed by initial NT from the organic triplet is also considered. Finally, a scheme is presented involving an equilibrium between CT and NT states and relating the free energy difference between these states to radical yields. 54 refs., 8 figs., 3 tabs.« less

Groundwork for the Concept of Technique in Education: Herbert Marcuse and Technological Society

ERIC Educational Resources Information Center

Pierce, Clayton

2006-01-01

This article articulates the groundwork for a new understanding of the concept of technique through a critical engagement with Herbert Marcuse's critical theory of technology. To this end, it identifies and engages three expressions of technique in Marcuse's work: mimesis, reified labor, and the happy consciousness. It is argued that this mapping…

Electrochemical reduction of carbon fluorine bond in 4-fluorobenzonitrile Mechanistic analysis employing Marcus Hush quadratic activation-driving force relation

NASA Astrophysics Data System (ADS)

Muthukrishnan, A.; Sangaranarayanan, M. V.

2007-10-01

The reduction of carbon-fluorine bond in 4-fluorobenzonitrile in acetonitrile as the solvent, is analyzed using convolution potential sweep voltammetry and the dependence of the transfer coefficient on potential is investigated within the framework of Marcus-Hush quadratic activation-driving force theory. The validity of stepwise mechanism is inferred from solvent reorganization energy estimates as well as bond length calculations using B3LYP/6-31g(d) method. A novel method of estimating the standard reduction potential of the 4-fluorobenzonitrile in acetonitrile is proposed.

A Short Account of RRKM Theory of Unimolecular Reactions and of Marcus Theory of Electron Transfer in a Historical Perspective

ERIC Educational Resources Information Center

Di Giacomo, Francesco

2015-01-01

The RRKM Theory of Unimolecular Reactions and Marcus Theory of Electron Transfer are here briefly discussed in a historical perspective. In the final section, after a general discussion on the educational usefulness of teaching chemistry in a historical framework, hints are given on how some characteristics of Marcus' work could be introduced in…

Marcus canonical integral for non-Gaussian processes and its computation: pathwise simulation and tau-leaping algorithm.

PubMed

Li, Tiejun; Min, Bin; Wang, Zhiming

2013-03-14

The stochastic integral ensuring the Newton-Leibnitz chain rule is essential in stochastic energetics. Marcus canonical integral has this property and can be understood as the Wong-Zakai type smoothing limit when the driving process is non-Gaussian. However, this important concept seems not well-known for physicists. In this paper, we discuss Marcus integral for non-Gaussian processes and its computation in the context of stochastic energetics. We give a comprehensive introduction to Marcus integral and compare three equivalent definitions in the literature. We introduce the exact pathwise simulation algorithm and give the error analysis. We show how to compute the thermodynamic quantities based on the pathwise simulation algorithm. We highlight the information hidden in the Marcus mapping, which plays the key role in determining thermodynamic quantities. We further propose the tau-leaping algorithm, which advance the process with deterministic time steps when tau-leaping condition is satisfied. The numerical experiments and its efficiency analysis show that it is very promising.

A post Gurney quantum mechanical perspective on the electrolysis of water: ion neutralization in solution

NASA Astrophysics Data System (ADS)

Guo, Enyi; McKenzie, David R.

2017-11-01

Electron fluxes crossing the interface between a metallic conductor and an aqueous environment are important in many fields; hydrogen production, environmental scanning tunnelling microscopy, scanning electrochemical microscopy being some of them. Gurney (Gurney 1931 Proc. R. Soc. Lond. 134, 137 (doi:10.1098/rspa.1931.0187)) provided in 1931 a scheme for tunnelling during electrolysis and outlined conditions for it to occur. We measure the low-voltage current flows between gold electrodes in pure water and use the time-dependent behaviour at voltage switch-on and switch-off to evaluate the relative contribution to the steady current arising from tunnelling of electrons between the electrodes and ions in solution and from the neutralization of ions adsorbed onto the electrode surface. We ascribe the larger current contribution to quantum tunnelling of electrons to and from ions in solution near the electrodes. We refine Gurney's barrier scheme to include solvated electron states and quantify energy differences using updated information. We show that Gurney's conditions would prevent the current flow at low voltages we observe but outline how the ideas of Marcus (Marcus 1956 J. Chem. Phys. 24, 966-978 (doi:10.1063/1.1742723)) concerning solvation fluctuations enable the condition to be relaxed. We derive an average barrier tunnelling model and a multiple pathways tunnelling model and compare predictions with measurements of the steady-state current-voltage relation. The tunnelling barrier was found to be wide and low in agreement with other experimental studies. Applications as a biosensing mechanism are discussed that exploit the fast tunnelling pathways along molecules in solution.

Diffraction Pattern Analysis as an Optical Inspection Technique

DTIC Science & Technology

1991-08-01

BACKGROUND Diameters of fiber samples have commonly been measured manually with an optical microscope. Marcuse and Presby developed an automatic...by analyzing the back-scattered light when a beam of laser light impinged upon the fiber [2]. Presby and Marcuse extended this back-scattering tech...be im- proved further in order to become a feasible method for detecting a small number of blocked openings in CRT screens. 20 REFERENCES 1. Marcuse

Teasing out specific language impairment from an autism spectrum disorder.

PubMed

Tierney, Cheryl D; Gupta, Vidya Bhushan; Angel, Alma Patricia Del; Augustyn, Marilyn

2012-04-01

Marcus is a handsome, sweet, 7½-year-old boy with a significant history of delayed development, specifically in speech and language skills, as well as difficulties with social interactions that have led other specialists to be concerned about a diagnosis of an autism spectrum disorder.He has been seen in our primary care practice since birth. He was born full-term after vaginal delivery weighing 6 pounds, 6 ounces. There were no pregnancy or delivery complications noted. Genetic testing revealed normal chromosomes, fragile X, and microarray testing. Marcus was a picky eater and good sleeper and had delays in toilet training.There is no family history of attention-deficit hyperactivity disorder (ADHD), autism, or substance abuse. Maternal grandmother and mother have a history of learning difficulties, and his father and a paternal uncle have a history of depression and anxiety. Marcus lives in a supportive environment with his mother, father, and sister.Marcus was noted to have significantly delayed language, stuttering, and immediate echolalia as a toddler. Gross and fine motor milestones were met on time, but he did not talk or follow directions until 4 to 5 years old. As a younger child, he would pretend to talk on the phone or mow the grass with a pretend lawn mower, but other household activities were not of interest to Marcus.Currently, he enjoys puzzles, reading, and board games. He likes to play with other children and can interact with familiar adults. Marcus is reported to initiate social interactions, although he has difficulty in understanding personal space. Imaginative play is preferred over other types. He seeks out adult attention and will bring objects over to an adult especially to share his perceived accomplishment. Marcus has difficulty in playing cooperatively with his sister.He is independent with activities of daily living. Marcus is noted to have auditory defensiveness including covering his ears to loud noises and becoming distressed. Parents feel he is immature and inattentive for his age. Marcus responds well when a routine is followed.Previous testing about 2 years ago revealed significant language deficits on the Clinical Evaluation of Language Functioning with average scores on the Woodcock Johnson Achievement Testing and Test of Nonverbal Intelligence Version 3. Marcus was not referred for early intervention and he did not attend preschool. In a regular education Kindergarten, he received speech and occupational therapy along with reading and math support.Comments from teachers or evaluator include the following: Marcus looked to his peers for clues about what he should be doing. Marcus has great difficulty in understanding requests but seems to be interested in pleasing his teacher and others. Marcus' language difficulty makes socialization with his peers problematic; however, he is interested in interacting with them and they seem to accept him willingly. Marcus has intent to communicate with others but relies on visual support to decipher social situations. Marcus has difficulty in attending to details and moves from activity to activity quickly. His short attention span is likely impacting not only learning but also his ability to socially interact with peers.On the day you see him for his 7-year-old checkup, he brought many toys over to show his father and interrupted your conversation to get your attention intermittently throughout the examination. He immediately pointed out a lit ceiling tile with Nemo illuminated to show his father. Marcus does not have any notable or significant repetitive motor mannerisms or stereotypies reported or observed. Marcus' gesture use was appropriate for age and included both symbolic (directing eye gaze and pointing) and concrete (hands up to be picked up and touching an item rather than pointing to it) gestures. Play observed today, although immature for age, was novel, imaginative, and functional. Answers to questions did not always match the question posed. He had a difficult time waiting for his turn before interrupting a conversation. Visual cues were helpful in understanding what was expected of him and what was going on socially.Marcus' speech is notable for persistent stuttering and difficulty in turn-taking in conversation. He gets frustrated easily and has a hard time being understood. He continues to confuse pronouns and makes some grammatical errors. He is able to follow simple directions but has a hard time following complex or multistep directions with accuracy. Nonverbal communication includes pointing to objects of interest in order to share the experience ("Look mom!"). He will point to identify an object and can follow a point across the room. He is able to use his eye contact to direct yours to moderate social interactions.Marcus has a special interest in Thomas the Tank Engine Train and Disney movies but is able to move away from those topics to engage in other play interests. Repetitive behaviors are not noted. Toe walking, hand flapping, or spinning, or unusual hand motions or observation of objects were not observed.Difficulties noted today include delays in his receptive and expressive language, poor intelligibility, dysfluency, and impaired motor planning. He recently underwent an audiogram which was normal. You decide to refer to a specialist for further evaluation.

Theoretical Studies of Low-Loss Optical Fibers.

DTIC Science & Technology

1980-09-15

on the fiber surface. Single-mode fiber operation is of interest in communications. Marcuse has shown that surface imperfections are a strong source...0.01 very small value of a : 8A at X = 1 vim Marcuse single mode 2.7 typical value of a = 1 jim, A : 10.6 vm, af = 37 Pim surface imperfections 55...Braunstein, "Scattering Losses in Single and Polycrystalline Materials for Infrared Fiber Applications," unpublished. 5. D. Marcuse , "Mode Conversion

An experimental comparison of the Marcus-Hush and Butler-Volmer descriptions of electrode kinetics applied to cyclic voltammetry. The one electron reductions of europium (III) and 2-methyl-2-nitropropane studied at a mercury microhemisphere electrode

NASA Astrophysics Data System (ADS)

Henstridge, Martin C.; Wang, Yijun; Limon-Petersen, Juan G.; Laborda, Eduardo; Compton, Richard G.

2011-11-01

We present a comparative experimental evaluation of the Butler-Volmer and Marcus-Hush models using cyclic voltammetry at a microelectrode. Numerical simulations are used to fit experimental voltammetry of the one electron reductions of europium (III) and 2-methyl-2-nitropropane, in water and acetonitrile, respectively, at a mercury microhemisphere electrode. For Eu (III) very accurate fits to experiment were obtained over a wide range of scan rates using Butler-Volmer kinetics, whereas the Marcus-Hush model was less accurate. The reduction of 2-methyl-2-nitropropane was well simulated by both models, however Marcus-Hush required a reorganisation energy lower than expected.

Quenching mechanism of Zn(salicylaldimine) by nitroaromatics.

PubMed

Germain, Meaghan E; Vargo, Thomas R; McClure, Beth Anne; Rack, Jeffrey J; Van Patten, P Gregory; Odoi, Michael; Knapp, Michael J

2008-07-21

Nitroaromatics and nitroalkanes quench the fluorescence of Zn(Salophen) (H2Salophen = N,N'-phenylene-bis-(3,5-di- tert-butylsalicylideneimine); ZnL(R)) complexes. A structurally related family of ZnL(R) complexes (R = OMe, di-tBu, tBu, Cl, NO2) were prepared, and the mechanisms of fluorescence quenching by nitroaromatics were studied by a combined kinetics and spectroscopic approach. The fluorescent quantum yields for ZnL(R) were generally high (Phi approximately 0.3) with sub-nanosecond fluorescence lifetimes. The fluorescence of ZnL(R) was quenched by nitroaromatic compounds by a mixture of static and dynamic pathways, reflecting the ZnL(R) ligand bulk and reduction potential. Steady-state Stern-Volmer plots were curved for ZnL(R) with less-bulky substituents (R = OMe, NO2), suggesting that both static and dynamic pathways were important for quenching. Transient Stern-Volmer data indicated that the dynamic pathway dominated quenching for ZnL(R) with bulky substituents (R = tBu, DtBu). The quenching rate constants with varied nitroaromatics (ArNO2) followed the driving force dependence predicted for bimolecular electron transfer: ZnL* + ArNO2 --> ZnL(+) + ArNO2(-). A treatment of the diffusion-corrected quenching rates with Marcus theory yielded a modest reorganization energy (lambda = 25 kcal/mol), and a small self-exchange reorganization energy for ZnL*/ZnL(+) (ca. 20 kcal/mol) was estimated from the Marcus cross-relation, suggesting that metal phenoxyls may be robust biological redox cofactors. Electronic structure calculations indicated very small changes in bond distances for the ZnL --> ZnL(+) oxidation, suggesting that solvation was the dominant contributor to the observed reorganization energy. These mechanistic insights provide information that will be helpful to further develop ZnL(R) as sensors, as well as for potential photoinduced charge transfer chemistry.

Quantitative weaknesses of the Marcus-Hush theory of electrode kinetics revealed by Reverse Scan Square Wave Voltammetry: The reduction of 2-methyl-2-nitropropane at mercury microelectrodes

NASA Astrophysics Data System (ADS)

Laborda, Eduardo; Wang, Yijun; Henstridge, Martin C.; Martínez-Ortiz, Francisco; Molina, Angela; Compton, Richard G.

2011-08-01

The Marcus-Hush and Butler-Volmer kinetic electrode models are compared experimentally by studying the reduction of 2-methyl-2-nitropropane in acetonitrile at mercury microelectrodes using Reverse Scan Square Wave Voltammetry. This technique is found to be very sensitive to the electrode kinetics and to permit critical comparison of the two models. The Butler-Volmer model satisfactorily fits the experimental data whereas Marcus-Hush does not quantitatively describe this redox system.

Ligand reorganization and activation energies in nonadiabatic electron transfer reactions

NASA Astrophysics Data System (ADS)

Zhu, Jianjun; Wang, Jianji; Stell, George

2006-10-01

The activation energy and ligand reorganization energy for nonadiabatic electron transfer reactions in chemical and biological systems are investigated in this paper. The free energy surfaces and the activation energy are derived exactly in the general case in which the ligand vibration frequencies are not equal. The activation energy is derived by free energy minimization at the transition state. Our formulation leads to the Marcus-Hush [J. Chem. Phys. 24, 979 (1956); 98, 7170 (1994); 28, 962 (1958)] results in the equal-frequency limit and also generalizes the Marcus-Sumi [J. Chem. Phys. 84, 4894 (1986)] model in the context of studying the solvent dynamic effect on electron transfer reactions. It is found that when the ligand vibration frequencies are different, the activation energy derived from the Marcus-Hush formula deviates by 5%-10% from the exact value. If the reduced reorganization energy approximation is introduced in the Marcus-Hush formula, the result is almost exact.

A Simple Geometric Model for the Marcus Theory of Proton Transfer

ERIC Educational Resources Information Center

McLennan, Duncan J.

1976-01-01

Uses the intersecting parabola model to derive an equation that relates the observed free energy of activation for a slow proton transfer to the overall thermodynamic free energy change in the reaction. (MLH)

Predicting Accurate Electronic Excitation Transfer Rates via Marcus Theory with Boys or Edmiston-Ruedenberg Localized Diabatization †

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

Subotnik, Joseph E.; Vura-Weis, Josh; Sodt, Alex J.

We model the triplet-triplet energy-transfer experiments from the Closs group [Closs, G. L.; et al. J. Am. Chem. Soc. 1988, 110, 2652.] using a combination of Marcus theory and either Boys or Edmiston-Ruedenberg localized diabatization, and we show that relative and absolute rates of electronic excitation transfer may be computed successfully. For the case where both the donor and acceptor occupy equatorial positions on a rigid cyclohexane bridge, we find βcalc = 2.8 per C-C bond, compared with the experimental value βexp = 2.6. This work highlights the power of using localized diabatization methods as a tool for modeling nonequilibriummore » processes.« less

Predicting Accurate Electronic Excitation Transfer Rates via Marcus Theory with Boys or Edmiston-Ruedenberg Localized Diabatization

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

Subotnik, Joseph E.; Vura-Weis, Josh; Sodt, Alex J.

We model the triplet-triplet energy-transfer experiments from the Closs group [Closs, G. L.; et al. J. Am. Chem. Soc. 1988, 110, 2652.] using a combination of Marcus theory and either Boys or Edmiston-Ruedenberg localized diabatization, and we show that relative and absolute rates of electronic excitation transfer may be computed successfully. For the case where both the donor and acceptor occupy equatorial positions on a rigid cyclohexane bridge, we find β calc = 2.8 per C-C bond, compared with the experimental value β exp = 2.6. This work highlights the power of using localized diabatization methods as a tool formore » modeling nonequilibrium processes.« less

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

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

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

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

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

DOE PAGES

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

2017-12-24

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

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

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

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

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

The role of fearless dominance in differentiating psychopathy from antisocial personality disorder: comment on Marcus, Fulton, and Edens.

PubMed

Patrick, Christopher J; Venables, Noah C; Drislane, Laura E

2013-01-01

Comments on the original article by Marcus et al. (see record 2011-23134-001). Based on their meta-analytic review of the correlates of the two factors of the Psychopathic Personality Inventory (PPI), Fearless Dominance (FD) and Self-Centered Impulsivity (SCI), Marcus, Fulton, and Edens (this issue, pp. 70-79) raise important questions about the role of FD in diagnostic conceptualizations of psychopathy. In considering their findings, general limitations of metaanalyses (e.g., Ioannidis & Lau, 1999) should be borne in mind, along with specific limitations of their analysis. These limitations are discussed here.

On Marcuse and Caring in Education

ERIC Educational Resources Information Center

Shel, Tammy

2006-01-01

Can caring and standardized testing coincide? Marcuse criticized the misuse of science because it also legitimizes social and economic hierarchy. By the same token, scholars develop standardized testing, claiming these tests are scientific and can measure objectively individuals' learning and intelligence capabilities. However, if inclusive caring…

Ligand reorganization and activation energies in nonadiabatic electron transfer reactions

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

Zhu Jianjun; Wang Jianji; Stell, George

2006-10-28

The activation energy and ligand reorganization energy for nonadiabatic electron transfer reactions in chemical and biological systems are investigated in this paper. The free energy surfaces and the activation energy are derived exactly in the general case in which the ligand vibration frequencies are not equal. The activation energy is derived by free energy minimization at the transition state. Our formulation leads to the Marcus-Hush [J. Chem. Phys. 24, 979 (1956); 98, 7170 (1994); 28, 962 (1958)] results in the equal-frequency limit and also generalizes the Marcus-Sumi [J. Chem. Phys. 84, 4894 (1986)] model in the context of studying themore » solvent dynamic effect on electron transfer reactions. It is found that when the ligand vibration frequencies are different, the activation energy derived from the Marcus-Hush formula deviates by 5%-10% from the exact value. If the reduced reorganization energy approximation is introduced in the Marcus-Hush formula, the result is almost exact.« less

The Secret of the Winning Streak

ERIC Educational Resources Information Center

Woolley, Thomas E.; du Sautoy, Marcus P. F.

2011-01-01

In 2006, Marcus du Sautoy delivered the Royal Institution Christmas Lectures on the subject of mathematics. From this, a workshop was created using ideas illustrated in the programme. A group of mathematical students from the University of Oxford, known as Marcus' Marvellous Mathemagicians, were trained in this workshop and now travel to schools…

One-Dimensionality and Whiteness

ERIC Educational Resources Information Center

Calderon, Dolores

2006-01-01

This article is a theoretical discussion that links Marcuse's concept of one-dimensional society and the Great Refusal with critical race theory in order to achieve a more robust interrogation of whiteness. The author argues that in the context of the United States, the one-dimensionality that Marcuse condemns in "One-Dimensional Man" is best…

Strategy, National Interests, and Means to an End

DTIC Science & Technology

2007-10-01

p. 2. 13. Codevilla and Seabury, p. 251. 22 14. Ibid., pp. 92-94. 15. Ibid. 16. Ibid., pp. 84-85. 17. Ibid., p. 85. 18. Marcus Aurelius ...nor with divergent motives. Marcus Aurelius18 Somalia’s descent into chaos is well-chronicled in several publications, so additional diagnosis of

Marcus-Hush-Chidsey theory of electron transfer to and from species bound at a non-uniform electrode surface: Theory and experiment

NASA Astrophysics Data System (ADS)

Henstridge, Martin C.; Batchelor-McAuley, Christopher; Gusmão, Rui; Compton, Richard G.

2011-11-01

Two simple models of electrode surface inhomogeneity based on Marcus-Hush theory are considered; a distribution in formal potentials and a distribution in electron tunnelling distances. Cyclic voltammetry simulated using these models is compared with that simulated using Marcus-Hush theory for a flat, uniform and homogeneous electrode surface, with the two models of surface inhomogeneity yielding broadened peaks with decreased peak-currents. An edge-plane pyrolytic graphite electrode is covalently modified with ferrocene via 'click' chemistry and the resulting voltammetry compared with each of the three previously considered models. The distribution of formal potentials is seen to fit the experimental data most closely.

Contact/Disability Performance. An Essay Constructed between Petra Kuppers and Neil Marcus

ERIC Educational Resources Information Center

Kuppers, Petra; Marcus, Neil

2009-01-01

This dialogue discusses disability and performance through poetic interrogation, interspersed with segments of Neil Marcus's play "My Sexual History." The authors touch on such topics such as sexuality and representation, dance and theatre, the management of disability staring, speech difference and writing, curiosity and shrouding. (Contains 1…

Marcus Theory: Thermodynamics CAN Control the Kinetics of Electron Transfer Reactions

ERIC Educational Resources Information Center

Silverstein, Todd P.

2012-01-01

Although it is generally true that thermodynamics do not influence kinetics, this is NOT the case for electron transfer reactions in solution. Marcus Theory explains why this is so, using straightforward physical chemical principles such as transition state theory, Arrhenius' Law, and the Franck-Condon Principle. Here the background and…

Critical Social Theory: A Portrait

ERIC Educational Resources Information Center

Torres, Carlos A.

2012-01-01

The term Critical Social Theory is employed in this article following the tradition of the Frankfurt School, and particularly the work of Herbert Marcuse and his interpretation of the political and social philosophy of Hegel and Marx. Discussing the contribution of G.W.F. Hegel to social theory Marcuse argued that: "Hegel's system brings to a…

Rudolph A. Marcus and His Theory of Electron Transfer Reactions

Science.gov Websites

early 1950s and soon discovered ... a strong experimental program at Brookhaven on electron-transfer experimental work provided the first verification of several of the predictions of his theory. This, in turn Marcus theory, namely, experimental evidence for the so-called "inverted region" where rates

Critical Theory and Information Studies: A Marcusean Infusion

ERIC Educational Resources Information Center

Pyati, Ajit K.

2006-01-01

In the field of library and information science, also known as information studies, critical theory is often not included in debates about the discipline's theoretical foundations. This paper argues that the critical theory of Herbert Marcuse, in particular, has a significant contribution to make to the field of information studies. Marcuse's…

Reassessing Subjectivity, Criticality, and Inclusivity: Marcuse's Challenge to Adult Education.

ERIC Educational Resources Information Center

Brookfield, Stephen

2002-01-01

Although Herbert Marcuse did not write as an adult educator, his analysis of subjectivity, criticality, and inclusivity has implications for adult education. He demonstrated how apparently humanistic tolerance for diversity can be manipulated to reinforce dominant ideology, and he made a case for aesthetic education as a site for critical…

Validation of Brain Event-Related Potentials as Indicators of Cognitive Styles, Abilities, and Aptitudes.

DTIC Science & Technology

1983-02-01

1970; Callaway, 1973, 1975; Chalke & Ertl, 1965; Ertl, 1969; Ertl & Schafer, 1969; Galbraith, Gliddon, & Busk , 1970; Gucker, 1973; Marcus, 1970...related to intelligence--although not always (Bigum, Dustman, & Beck, 1970; Galbraith, Gliddon, & Busk , 1970; Perry, McCoy, Cunningham, Falgout...be directly related to intelligence--but not always (Bigum, Dustman, & Beck, 1970; Galbraith, Gliddon, & Busk , 1970; Perry, McCoy, Cunningham, Falgot

Anarchism, Schooling, and Democratic Sensibility

ERIC Educational Resources Information Center

Kennedy, David

2017-01-01

This paper seeks to address the question of schooling for democracy by, first, identifying at least one form of social character, dependent, after Marcuse, on the historical emergence of a "new sensibility." It then explores one pedagogical thread related to the emergence of this form of subjectivity over the course of the last two…

Learning Non-Adjacent Regularities at Age 0 ; 7

ERIC Educational Resources Information Center

Gervain, Judit; Werker, Janet F.

2013-01-01

One important mechanism suggested to underlie the acquisition of grammar is rule learning. Indeed, infants aged 0 ; 7 are able to learn rules based on simple identity relations (adjacent repetitions, ABB: "wo fe fe" and non-adjacent repetitions, ABA: "wo fe wo", respectively; Marcus et al., 1999). One unexplored issue is…

Prevention of Infections Associated With Combat-Related Eye, Maxillofacial, and Neck Injuries

DTIC Science & Technology

2011-08-01

REVIEW ARTICLE Prevention of Infections Associated With Combat-Related Eye, Maxillofacial, and Neck Injuries Kyle Petersen, DO, FACP, FIDSA...Marcus H Colyer, MD, David K. Hayes, MD, FACS, Robert G. Hale, DDS, R. B1yan Bell, DDS, MD, FACS, and the Prevention of Combat-Related Infections ...article reviews recent data from military and civilian studies to support evidence-based recommendations for the prevention of infections associated

Hyperbolic metamaterial nanostructures to tune charge-transfer dynamics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lee, Kwang Jin; Xiao, Yiming; Woo, Jae Heun; Kim, Eun Sun; Kreher, David; Attias, André-Jean; Mathevet, Fabrice; Ribierre, Jean-Charles; Wu, Jeong Weon; André, Pascal

2016-09-01

Charge transfer (CT) is an essential phenomenon relevant to numerous fields including biology, physics and chemistry.1-5 Here, we demonstrate that multi-layered hyperbolic metamaterial (HMM) substrates alter organic semiconductor CT dynamics.6 With triphenylene:perylene diimide dyad supramolecular self-assemblies prepared on HMM substrates, we show that both charge separation (CS) and charge recombination (CR) characteristic times are increased by factors of 2.5 and 1.6, respectively, resulting in longer-lived CT states. We successfully rationalize the experimental data by extending Marcus theory framework with dipole image interactions tuning the driving force. The number of metal-dielectric pairs alters the HMM interfacial effective dielectric constant and becomes a solid analogue to solvent polarizability. Based on the experimental results and extended Marcus theory framework, we find that CS and CR processes are located in normal and inverted regions on Marcus parabola diagram, respectively. The model and further PH3T:PCBM data show that the phenomenon is general and that molecular and substrate engineering offer a wide range of kinetic tailoring opportunities. This work opens the path toward novel artificial substrates designed to control CT dynamics with potential applications in fields including optoelectronics, organic solar cells and chemistry. 1. Marcus, Rev. Mod. Phys., 1993, 65, 599. 2. Marcus, Phys. Chem. Chem. Phys., 2012, 14, 13729. 3. Lambert, et al., Nat. Phys., 2012, 9, 10. 4. C. Clavero, Nat. Photon., 2014, 8, 95. 5. A. Canaguier-Durand, et al., Angew. Chem. Int. Ed., 2013, 52, 10533. 6. K. J. Lee, et al., Submitted, 2015, arxiv.org/abs/1510.08574.

A Dense Corpus Study of Past Tense and Plural Overregularization in English.

ERIC Educational Resources Information Center

Maslen, Robert J.C.; Theakson, Anna L.; Lieven, Elena V.M.; Tomasello, Michael

2004-01-01

In the "blocking-and-retrieval-failure" account of overregularization (OR; G. F. Marcus, 1995; G. F. Marcus et al., 1992), the claim that a symbolic rule generates regular inflection is founded on pervasively low past tense OR rates and the lack of a substantive difference between past tense and plural OR rates. Evidence of extended periods of OR…

Thanatos and Civilization: Lacan, Marcuse, and the Death Drive

ERIC Educational Resources Information Center

Cho, Daniel

2006-01-01

During the 1950s and 1960s two thinkers, Herbert Marcuse and Jacques Lacan, were conducting a "return to Freud" for very similar reasons. If the differences between them are often advertised, their affinities are less so. In this article, I examine how their "return to Freud" and fidelity to psychoanalysis serves as a common ground to read each in…

Electrode redox reactions with polarizable molecules.

PubMed

Matyushov, Dmitry V

2018-04-21

A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

Electrode redox reactions with polarizable molecules

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.

2018-04-01

A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

77 FR 46125 - Sunoco, Inc., R&M, Refining Division, Marcus Hook, PA; Sunoco, Inc., 10 Industrial Hwy., MS4...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-02

... DEPARTMENT OF LABOR Employment and Training Administration [TA-W-81,145; TA-W-81,145A] Sunoco, Inc., R&M, Refining Division, Marcus Hook, PA; Sunoco, Inc., 10 Industrial Hwy., MS4 Building G, Lester, PA; Notice of Negative Determination on Reconsideration On April 30, 2012, the Department of Labor issued an Affirmative Determination Regarding...

77 FR 29362 - Sunoco, Inc., R&M Refining Division, Marcus Hook, PA; Sunoco, Inc., 10 Industrial Hwy, MS4...

Federal Register 2010, 2011, 2012, 2013, 2014

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... DEPARTMENT OF LABOR Employment and Training Administration [TA-W-81,145; TA-W-81,145A] Sunoco, Inc., R&M Refining Division, Marcus Hook, PA; Sunoco, Inc., 10 Industrial Hwy, MS4 Building G, Lester, PA; Notice of Affirmative Determination Regarding Application for Reconsideration By application dated March 26, 2012, the United Steel Workers Union...

Political Authoritarianism and Economic Success in Indonesia and South Korea

DTIC Science & Technology

2017-06-01

ECONOMIC SUCCESS IN INDONESIA AND SOUTH KOREA by Marcus A. Johnson June 2017 Thesis Advisor: Naazneen Barma Second Reader: Robert Weiner THIS PAGE...4. TITLE AND SUBTITLE POLITICAL AUTHORITARIANISM AND ECONOMIC SUCCESS IN INDONESIA AND SOUTH KOREA 5. FUNDING NUMBERS 6. AUTHOR(S) Marcus A...CODE 13. ABSTRACT (maximum 200 words) This thesis researches the features of political authoritarianism that might contribute to economic success

An Assessment of Nonresponse Bias in Mail Surveys of Naval Personnel

DTIC Science & Technology

1976-02-01

Hollowell, Ida Harloff, and Marge Covher. Special thanks are due to Jim Herbert who spent many hours keep- ing track of cases, tabulating, and...volunteering for psychological experiments has revealed that the type of experiment (Martin & Marcuse , 1958), the alterna- tives to participating...M., & Marcuse , F. L. Characteristics of volunteers and nonvol- unteers in psychological experimentation. Journal of Consulting Psychology, 1958

Evaluating Teaching in Higher Education. A Collection of Conference Papers.

ERIC Educational Resources Information Center

London Univ. (England). Inst. of Education.

Some of the difficult problems related to introducing greater accountability for teaching were assessed and tentative policies considered at a British conference on higher education held in April 1975. R.C. Tress, Peter Kennedy, R. Rickett, Tom Driver, Marcus Merriman, and Alastair Stewart are the authors of the first set of papers entitled…

Relative importance of driving force and electrostatic interactions in the reduction of multihaem cytochromes by small molecules.

PubMed

Quintas, Pedro O; Cepeda, Andreia P; Borges, Nuno; Catarino, Teresa; Turner, David L

2013-06-01

Multihaem cytochromes are essential to the energetics of organisms capable of bioremediation and energy production. The haems in several of these cytochromes have been discriminated thermodynamically and their individual rates of reduction by small electron donors were characterized. The kinetic characterization of individual haems used the Marcus theory of electron transfer and assumed that the rates of reduction of each haem by sodium dithionite depend only on the driving force, while electrostatic interactions were neglected. To determine the relative importance of these factors in controlling the rates, we studied the effect of ionic strength on the redox potential and the rate of reduction by dithionite of native Methylophilus methylotrophus cytochrome c″ and three mutants at different pH values. We found that the main factor determining the rate is the driving force and that Marcus theory describes this satisfactorily. This validates the method of the simultaneous fitting of kinetic and thermodynamic data in multihaem cytochromes and opens the way for further investigation into the mechanisms of these proteins. Copyright © 2013 Elsevier B.V. All rights reserved.

Surface hopping with a manifold of electronic states. III. Transients, broadening, and the Marcus picture

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

Dou, Wenjie; Subotnik, Joseph E.; Nitzan, Abraham

2015-06-21

In a previous paper [Dou et al., J. Chem. Phys. 142, 084110 (2015)], we have introduced a surface hopping (SH) approach to deal with the Anderson-Holstein model. Here, we address some interesting aspects that have not been discussed previously, including transient phenomena and extensions to arbitrary impurity-bath couplings. In particular, in this paper we show that the SH approach captures phonon coherence beyond the secular approximation, and that SH rates agree with Marcus theory at steady state. Finally, we show that, in cases where the electronic tunneling rate depends on nuclear position, a straightforward use of Marcus theory rates yieldsmore » a useful starting point for capturing level broadening. For a simple such model, we find I-V curves that exhibit negative differential resistance.« less

Blinking suppression of CdTe quantum dots on epitaxial graphene and the analysis with Marcus electron transfer

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

Hirose, Takuya; Tamai, Naoto, E-mail: tamai@kwansei.ac.jp; Kutsuma, Yasunori

We have prepared epitaxial graphene by a Si sublimation method from 4H-SiC. Single-particle spectroscopy of CdTe quantum dots (QDs) on epitaxial graphene covered with polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) showed the suppression of luminescence blinking and ∼10 times decreased luminescence intensity as compared with those on a glass. The electronic coupling constant, H{sub 01}, between CdTe QDs and graphene was calculated to be (3.3 ± 0.4) × 10{sup 2 }cm{sup −1} in PVP and (3.7 ± 0.8) × 10{sup 2 }cm{sup −1} in PEG based on Marcus theory of electron transfer and Tang-Marcus model of blinking with statistical distribution.

Trait Anxiety and Salivary Cortisol During Free Living and Military Stress

DTIC Science & Technology

2008-02-01

2 x February 2008 129 RESEARCH ARTICLE Trait Anxiety and Salivary Cortisol During Free Living and Military Stress Marcus K. Taylor , Jared P...cortex to produce and re- lease glucocorticoid hormones ( 6 ). The primary glucocorticoid is cortisol, which affects many body tissues, including...publication in November 2007 . Address reprint requests to: Marcus K. Taylor, Ph.D., Naval Health Research Center, Stress Physiology Research Core, Dept

Analysis of S2QA- charge recombination with the Arrhenius, Eyring and Marcus theories.

PubMed

Rantamäki, Susanne; Tyystjärvi, Esa

2011-01-01

The Q band of photosynthetic thermoluminescence, measured in the presence of a herbicide that blocks electron transfer from PSII, is associated with recombination of the S(2)Q(A)(-) charge pair. The same charge recombination reaction can be monitored with chlorophyll fluorescence. It has been shown that the recombination occurs via three competing routes of which one produces luminescence. In the present study, we measured the thermoluminescence Q band and the decay of chlorophyll fluorescence yield after a single turnover flash at different temperatures from spinach thylakoids. The data were analyzed using the commonly used Arrhenius theory, the Eyring rate theory and the Marcus theory of electron transfer. The fitting error was minimized for both thermoluminescence and fluorescence by adjusting the global, phenomenological constants obtained when the reaction rate theories were applied to the multi-step recombination reaction. For chlorophyll fluorescence, all three theories give decent fits. The peak position of the thermoluminescence Q band is correct by all theories but the form of the Q band is somewhat different in curves predicted by the three theories. The Eyring and Marcus theories give good fits for the decreasing part of the thermoluminescence curve and Marcus theory gives the closest fit for the rising part. Copyright © 2011 Elsevier B.V. All rights reserved.

Moral, Ethical, and Psychological Preparation of Soldiers and Units for Combat

DTIC Science & Technology

2011-01-01

Stoic phi los o pher Marcus Aurelius ob served, “Re spect be comes con crete through em pa thy.” Cicero re - minds us that a sol dier’s re spect must...build ing trust with the pop u la tion ought to be M C M A S T E R 1 3 * Marcus Tullius Cicero, On Du ties, ed. and trans. M. T. Grif fin and E. M. Atkins

A new sexual revolution? Critical theory, pornography, and the Internet.

PubMed

Garlick, Steve

2011-08-01

The "sexual revolution" was a central element of North American culture in the 1960s. Today, sex is increasingly central to mainstream culture, in large part due to the Internet, and we might wonder whether we are living through a comparable period of sexual history. In this article, I revisit the work of Herbert Marcuse-the original theorist of the sexual revolution-to ask whether it can contribute to a critical theory of sexuality in the era of digital technology. After outlining Marcuse's theory of the role of Eros in social life, I discuss two pornographic Web sites that combine eroticism and social critique. I argue that Marcuse's work is valuable for its emphasis on the intersection of sex, technology, and capitalist economy, but that it needs to be supplemented by a focus on masculinity and the male body in Internet pornography.

Metal cation exchange reactions of ore minerals in Fe-Mn crusts of the Marcus Wake Rise (Pacific Ocean) in aqueous-salt solutions

NASA Astrophysics Data System (ADS)

Novikov, G. V.; Bogdanova, O. Yu.; Melnikov, M. E.; Drozdova, A. N.; Lobus, N. V.; Shulga, N. A.

2017-12-01

It is shown that the reaction ability of metal cations of ore minerals in Fe-Mn crusts of the Marcus Wake Rise increases in the following manner: (Co2+ < Cu2+ < Ni2+) < (Mg2+ < Mn2+ < K+ ≈ Ca2+ ≈ Na+). The composition of the exchange complex of the ore minerals is constant and includes these metal cations. Ca2+ and Na+ are major contributors to the exchange capacity of the ore minerals. The capacity of the ore minerals by cations of alkali and base metals is 0.43-0.60 and 2.08-2.70 mg-equiv/g, respectively. The exchange capacity of the ore minerals by cations of base metals increases linearly with the increase in the MnO2 content of the crust and does not depend on the geographical locations of the Marcus Wake guyots.

Studies of the Processing of Single Words Using Positron Tomographic Measures of Cerebral Blood Flow Change.

DTIC Science & Technology

1987-01-01

BLOOD FLOW CHANGE Steven E. Petersen, Peter T. Fox, Michael I. Posner, Marcus Raichle McDonnell Center for Studies of Higher Brain Function...Single Words Using Positron Emission Tomographic Measurements of Cerebral Blood Flow Change *= ’I PERSONAL AUTHOR(S) * Petersen, Steven E. 13a. TYPE OF...CHANGE Steven E. Petersen, Peter T. Fox, Michael I. Posner, Marcus E. Raichle INTRODUCTION Language is an essential characteristic of the human

Fatigue Testing of AA7050-T7451 with Various Corrosion Prevention Surface Treatments

DTIC Science & Technology

2013-06-01

UNCLASSIFIED Authors Marcus McDonald Air Vehicles Division Marcus McDonald initially spent 3 years working in the oil & gas, steel and...treatments: caustic degreasing, de-oxidising or anodising. The pits in the anodised coupons were larger than the pits caused by the pre-IVD etching...those fatigue cracks that grew from them spent less time in growing whilst they were small, because the crack started at what was a larger effective

Effects of Strong Local Sporadic E on ELF Propagation.

DTIC Science & Technology

1978-08-15

Huygens diffraction model (e.g., Marcuse , 1972). The model is similar to that used by Crombie. Unlike Crombie’s work however , the Fresnel approximation...40. Marcuse , D., “Light transmission optics ,” Van Nostrand Reinhold Co., New York , 1972. Papper t , R. A. & Moler , W. F., “A theoretica’ study of...ATTN Donald Dubbert O1 CY ATTN Herbert Rend University of IllinoisDepartment of Electrical Engineering Develco Urbana , IL 61803 530 Logue Avenue O2CY

First-principles calculation of photo-induced electron transfer rate constants in phthalocyanine-C60 organic photovoltaic materials: Beyond Marcus theory

NASA Astrophysics Data System (ADS)

Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan

2014-03-01

Classical Marcus theory is commonly adopted in solvent-mediated charge transfer (CT) process to obtain the CT rate constant, but it can become questionable when the intramolecular vibrational modes dominate the CT process as in OPV devices because Marcus theory treats these modes classically and therefore nuclear tunneling is not accounted for. We present a computational scheme to obtain the electron transfer rate constant beyond classical Marcus theory. Within this approach, the nuclear vibrational modes are treated quantum-mechanically and a short-time approximation is avoided. Ab initio calculations are used to obtain the basic parameters needed for calculating the electron transfer rate constant. We apply our methodology to phthalocyanine(H2PC)-C60 organic photovoltaic system where one C60 acceptor and one or two H2PC donors are included to model the donor-acceptor interface configuration. We obtain the electron transfer and recombination rate constants for all accessible charge transfer (CT) states, from which the CT exciton dynamics is determined by employing a master equation. The role of higher lying excited states in CT exciton dynamics is discussed. This work is pursued as part of the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences under 390 Award No. DE-SC0000957.

Tuning the driving force for exciton dissociation in single-walled carbon nanotube heterojunctions

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

Ihly, Rachelle; Mistry, Kevin S.; Ferguson, Andrew J.

2016-04-25

Understanding the kinetics and energetics of interfacial electron transfer in molecular systems is crucial for the development of a broad array of technologies, including photovoltaics, solar fuel systems and energy storage. The Marcus formulation for electron transfer relates the thermodynamic driving force and reorganization energy for charge transfer between a given donor/acceptor pair to the kinetics and yield of electron transfer. Here we investigated the influence of the thermodynamic driving force for photoinduced electron transfer (PET) between single-walled carbon nanotubes (SWCNTs) and fullerene derivatives by employing time-resolved microwave conductivity as a sensitive probe of interfacial exciton dissociation. For the firstmore » time, we observed the Marcus inverted region (in which driving force exceeds reorganization energy) and quantified the reorganization energy for PET for a model SWCNT/acceptor system. The small reorganization energies (about 130 meV, most of which probably arises from the fullerene acceptors) are beneficial in minimizing energy loss in photoconversion schemes.« less

A combined crossed molecular beams and theoretical study of the reaction CN + C2H4

NASA Astrophysics Data System (ADS)

Balucani, Nadia; Leonori, Francesca; Petrucci, Raffaele; Wang, Xingan; Casavecchia, Piergiorgio; Skouteris, Dimitrios; Albernaz, Alessandra F.; Gargano, Ricardo

2015-03-01

The CN + C2H4 reaction has been investigated experimentally, in crossed molecular beam (CMB) experiments at the collision energy of 33.4 kJ/mol, and theoretically, by electronic structure calculations of the relevant potential energy surface and Rice-Ramsperger-Kassel-Marcus (RRKM) estimates of the product branching ratio. Differently from previous CMB experiments at lower collision energies, but similarly to a high energy study, we have some indication that a second reaction channel is open at this collision energy, the characteristics of which are consistent with the channel leading to CH2CHNC + H. The RRKM estimates using M06L electronic structure calculations qualitatively support the experimental observation of C2H3NC formation at this and at the higher collision energy of 42.7 kJ/mol of previous experiments.

76 FR 77782 - Takes of Marine Mammals Incidental to Specified Activities; Marine Geophysical Survey in the...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-14

...) during the study. The shot interval will be relatively short, approximately 15 to 18 seconds (s), for the... than the one provided here. Comments sent via email, including all attachments, must not exceed a 10... 21, 2012. L-DEO plans to use one source vessel, the R/V Marcus G. Langseth (Langseth) and a seismic...

Implications of Marcus-Hush theory for steady-state heterogeneous electron transfer at an inlaid disk electrode.

PubMed

Feldberg, Stephen W

2010-06-15

For an outer-sphere heterogeneous electron transfer, Ox + e = Red, between an electrode and a redox couple, the Butler-Volmer formalism predicts that the operative heterogeneous rate constant, k(red) (cm s(-1)) for reduction (or k(ox) for oxidation) increases without limit as an exponential function of -alpha (E - E(0)) for reduction (or (1 - alpha)(E - E(0)) for oxidation), where E is the applied electrode potential, alpha (~1/2) is the transfer coefficient and E(0) is the formal potential. The Marcus-Hush formalism, as exposited by Chidsey (Chidsey, C. E. D. Science 1991, 215, 919), predicts that the value of k(red) or k(ox) limits at sufficiently large values of -(E - E(0)) or (E - E(0)). The steady-state currents at an inlaid disk electrode obtained for a redox species in solution were computed using both formalisms with the Oldham-Zoski approximation (Oldham, K. B.; Zoski, C. G. J. Electroanal. Chem. 1988, 256, 11). Significant differences are noted for the two formalisms. When k(0)r(0)/D is sufficiently small (k(0) is the standard rate constant, r(0) is the radius of the disk electrode, and D is the diffusion coefficient of the redox species), the Marcus-Hush formalism effects a limiting current that can be significantly smaller than the mass transport limited current. This is easily explained in terms of the limiting values of k(red) and k(ox) predicted by the Marcus-Hush formalism. The experimental conditions that must be met to effect significant differences in behavior are discussed; experimental conditions that effect virtually identical behavior are also discussed. As a caveat for experimentalists, applications of the Butler-Volmer formalism to systems that are more properly described using the Marcus-Hush formalism are shown to yield incorrect values of k(0) and meaningless values of alpha, which serves only as a fitting parameter.

Marcus Bell-Shaped Electron Transfer Kinetics Observed in an Arrhenius Plot.

PubMed

Waskasi, Morteza M; Kodis, Gerdenis; Moore, Ana L; Moore, Thomas A; Gust, Devens; Matyushov, Dmitry V

2016-07-27

The Marcus theory of electron transfer predicts a bell-shaped dependence of the reaction rate on the reaction free energy. The top of the "inverted parabola" corresponds to zero activation barrier when the electron-transfer reorganization energy and the reaction free energy add up to zero. Although this point has traditionally been reached by altering the chemical structures of donors and acceptors, the theory suggests that it can also be reached by varying other parameters of the system including temperature. We find here dramatic evidence of this phenomenon from experiments on a fullerene-porphyrin dyad. Following photoinduced electron transfer, the rate of charge recombination shows a bell-shaped dependence on the inverse temperature, first increasing with cooling and then decreasing at still lower temperatures. This non-Arrhenius rate law is a result of a strong, approximately hyperbolic temperature variation of the reorganization energy and the reaction free energy. Our results provide potentially the cleanest confirmation of the Marcus energy gap law so far since no modification of the chemical structure is involved.

Charge transfer kinetics at the solid-solid interface in porous electrodes

NASA Astrophysics Data System (ADS)

Bai, Peng; Bazant, Martin Z.

2014-04-01

Interfacial charge transfer is widely assumed to obey the Butler-Volmer kinetics. For certain liquid-solid interfaces, the Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report a simple method to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures. The fitted reorganization energy matches the Born solvation energy for electron transfer from carbon to the iron redox site. The kinetics are thus limited by electron transfer at the solid-solid (carbon-LixFePO4) interface rather than by ion transfer at the liquid-solid interface, as previously assumed. The proposed experimental method generalizes Chidsey’s method for phase-transforming particles and porous electrodes, and the results show the need to incorporate Marcus kinetics in modelling batteries and other electrochemical systems.

Access to enhanced differences in Marcus-Hush and Butler-Volmer electron transfer theories by systematic analysis of higher order AC harmonics.

PubMed

Stevenson, Gareth P; Baker, Ruth E; Kennedy, Gareth F; Bond, Alan M; Gavaghan, David J; Gillow, Kathryn

2013-02-14

The potential-dependences of the rate constants associated with heterogeneous electron transfer predicted by the empirically based Butler-Volmer and fundamentally based Marcus-Hush formalisms are well documented for dc cyclic voltammetry. However, differences are often subtle, so, presumably on the basis of simplicity, the Butler-Volmer method is generally employed in theoretical-experimental comparisons. In this study, the ability of Large Amplitude Fourier Transform AC Cyclic Voltammetry to distinguish the difference in behaviour predicted by the two formalisms has been investigated. The focus of this investigation is on the difference in the profiles of the first to sixth harmonics, which are readily accessible when a large amplitude of the applied ac potential is employed. In particular, it is demonstrated that systematic analysis of the higher order harmonic responses in suitable kinetic regimes provides predicted deviations of Marcus-Hush from Butler-Volmer behaviour to be established from a single experiment under conditions where the background charging current is minimal.

Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: the contribution of π-stacking interactions to hydrogen atom transfer rates.

PubMed

D'Alfonso, Claudio; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela

2013-02-01

The kinetics of reactions of the phthalimide N-oxyl radical (PINO) with a series of activated phenols (2,2,5,7,8-pentamethylchroman-6-ol (PMC), 2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols) were investigated by laser flash photolysis in CH(3)CN and PhCl in order to establish if the reactions with PINO can provide a useful tool for evaluating the radical scavenging ability of phenolic antioxidants. On the basis of the small values of deuterium kinetic isotope effects, the relatively high and negative ρ values in the Hammett correlations and the results of theoretical calculations, we suggest that these reactions proceed by a hydrogen atom transfer (HAT) mechanism having a significant degree of charge transfer resulting from a π-stacked conformation between PINO and the aromatic ring of the phenols. Kinetic solvent effects were analyzed in detail for the hydrogen transfer from 2,4,6-trimethylphenol to PINO and the data obtained are in accordance with the Snelgrove-Ingold equation for HAT. Experimental rate constants for the reactions of PINO with activated phenols are in accordance with those predicted by applying the Marcus cross relation.

Charge-transfer mechanism for electrophilic aromatic nitration and nitrosation via the convergence of (ab initio) molecular-orbital and Marcus-Hush theories with experiments.

PubMed

Gwaltney, Steven R; Rosokha, Sergiy V; Head-Gordon, Martin; Kochi, Jay K

2003-03-19

The highly disparate rates of aromatic nitrosation and nitration, despite the very similar (electrophilic) properties of the active species: NO(+) and NO(2)(+) in Chart 1, are quantitatively reconciled. First, the thorough mappings of the potential-energy surfaces by high level (ab initio) molecular-orbital methodologies involving extensive coupled-cluster CCSD(T)/6-31G optimizations establish the intervention of two reactive intermediates in nitration (Figure 8) but only one in nitrosation (Figure 7). Second, the same distinctive topologies involving double and single potential-energy minima (Figures 6 and 5) also emerge from the semiquantitative application of the Marcus-Hush theory to the transient spectral data. Such a striking convergence from quite different theoretical approaches indicates that the molecular-orbital and Marcus-Hush (potential-energy) surfaces are conceptually interchangeable. In the resultant charge-transfer mechanism, the bimolecular interactions of arene donors with both NO(+) and NO(2)(+) spontaneously lead (barrierless) to pi-complexes in which electron transfer is concurrent with complexation. Such a pi-complex in nitration is rapidly converted to the sigma-complex, whereas this Wheland adduct in nitrosation merely represents a high energy (transition-state) structure. Marcus-Hush analysis thus demonstrates how the strongly differentiated (arene) reactivities toward NO(+) and NO(2)(+) can actually be exploited in the quantitative development of a single coherent (electron-transfer) mechanism for both aromatic nitrosation and nitration.

[The doctor and the consul. Relations between Galen and Flavius Boethos under Marcus Aurelius].

PubMed

Gourevitch, Danielle

2012-01-01

The author describes the rich relationship between young Galen, just arrived in Rome from his native Minor Asia, and Flavius Boethos a consul suffectus who was to become the governor of Syria, and asked him to cure his wife and then their son, Cyrillos. Although very famous, Galen who never became a Roman citizen, needed such a friend and social mentor.

On the theory of time dilation in chemical kinetics

NASA Astrophysics Data System (ADS)

Baig, Mirza Wasif

2017-10-01

The rates of chemical reactions are not absolute but their magnitude depends upon the relative speeds of the moving observers. This has been proved by unifying basic theories of chemical kinetics, which are transition state theory, collision theory, RRKM and Marcus theory, with the special theory of relativity. Boltzmann constant and energy spacing between permitted quantum levels of molecules are quantum mechanically proved to be Lorentz variant. The relativistic statistical thermodynamics has been developed to explain quasi-equilibrium existing between reactants and activated complex. The newly formulated Lorentz transformation of the rate constant from Arrhenius equation, of the collision frequency and of the Eyring and Marcus equations renders the rate of reaction to be Lorentz variant. For a moving observer moving at fractions of the speed of light along the reaction coordinate, the transition state possess less kinetic energy to sweep translation over it. This results in the slower transformation of reactants into products and in a stretched time frame for the chemical reaction to complete. Lorentz transformation of the half-life equation explains time dilation of the half-life period of chemical reactions and proves special theory of relativity and presents theory in accord with each other. To demonstrate the effectiveness of the present theory, the enzymatic reaction of methylamine dehydrogenase and radioactive disintegration of Astatine into Bismuth are considered as numerical examples.

Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

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

You, Zhi-Qiang; Herbert, John M., E-mail: herbert@chemistry.ohio-state.edu; Mewes, Jan-Michael

2015-11-28

The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations failsmore » to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents.« less

Marcus Theory of Ion-Pairing

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

Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J.

We present a theory for ion pair dissociation and association, motivated by the concepts of the Marcus theory of electron transfer. Despite the extensive research on ion-pairing in many chemical and biological processes, much can be learned from the exploration of collective reaction coordinates. To this end, we explore two reaction coordinates, ion pair distance and coordination number. The study of the correlation between these reaction coordinates provides a new insight into the mechanism and kinetics of ion pair dissociation and association in water. The potential of mean force on these 2D-surfaces computed from molecular dynamics simulations of different monovalentmore » ion pairs reveal a Marcus-like mechanism for ion-pairing: Water molecules rearrange forming an activated coordination state prior to ion pair dissociation or association, followed by relaxation of the coordination state due to further water rearrangement. Like Marcus theory, we find the existence of an inverted region where the transition rates are slower with increasing exergonicity. This study provides a new perspective for the future investigations of ion-pairing and transport. SR, CJM, and GKS were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS3 (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). The research was performed using PNNL Institutional Computing. PNNL is a multi-program national laboratory operated by Battelle for the U.S. Department of Energy.« less

MD studies of electron transfer at ambient and elevated pressures

NASA Astrophysics Data System (ADS)

Giles, Alex; Spooner, Jacob; Weinberg, Noham

2013-06-01

The effect of pressure on the rate constants of outer-sphere electron transfer reactions has often been described using the Marcus-Hush theory. This theory agrees well with experiment when internal reorganization of the ionic system is negligible, however it does not offer a recipe for calculation of the effects that result from significant solute restructuring. We have recently developed a molecular dynamics technique that accurately describes structural dependence of molecular volumes in non-polar and weakly polar systems. We are now extending this approach to the case of highly polar ionic systems where both solvent and solute restructuring components are important. For this purpose we construct pressure-dependent two-dimensional surfaces for electron transfer reactions in coordinate system composed of interionic distance and Marcus-type solvent polarization coordinate, and use these surfaces to describe pressure effects on reaction kinetics. R.A. Marcus. J. Chem. Phys. 24, 966 (1956); 24, 979 (1956); 26, 867 (1957). Discuss. Faraday Soc. 29, 21 (1960). Faraday Discuss. Chem. Soc. 74, 7 (1982); N.S. Hush. Trans. Faraday Soc. 57, 557 (1961).

SS Edgar M. Queeny collision with the Liberian S/T Corinthos, Marcus Hook, Pennsylvania, 31 January 1975. Marine casualty report

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

Not Available

1977-10-27

At 0029, on January 31, 1975, the U.S. Registered tankship SS EDGAR M. QUEENY, laden with chemical and petroleum products, was maneuvering into Marcus Hook channel of the Delaware River in Pennsylvania, when it collided with the Liberian tanker S/T CORINTHOS which was moored and discharging a bulk cargo of crude oil at the British Petroleum Company dock. The port anchor of the QUEENY slightly penetrated the port side plating of the CORINTHOS at an angle of about 39 deg. into one or more of the wing cargo tanks, which were being pumped and were approximately half full. Almost immediately,more » a series of increasingly intense explosions began in the CORINTHOS, and the vessel was engulfed in flames. Twenty-six persons were killed or are missing and 11 were injured in this accident. The QUEENY suffered minor damage but the CORINTHOS was destroyed. The Delaware River was polluted by oil about Marcus Hook. Property damage was estimated to be $20 million.« less

Communication: Standard surface hopping predicts incorrect scaling for Marcus' golden-rule rate: The decoherence problem cannot be ignored

NASA Astrophysics Data System (ADS)

Landry, Brian R.; Subotnik, Joseph E.

2011-11-01

We evaluate the accuracy of Tully's surface hopping algorithm for the spin-boson model for the case of a small diabatic coupling parameter (V). We calculate the transition rates between diabatic surfaces, and we compare our results to the expected Marcus rates. We show that standard surface hopping yields an incorrect scaling with diabatic coupling (linear in V), which we demonstrate is due to an incorrect treatment of decoherence. By modifying standard surface hopping to include decoherence events, we recover the correct scaling (˜V2).

"Abnormal" salt and solvent effects on anion/cation electron-transfer reactions: an interpretation based on Marcus-Hush treatment.

PubMed

Garcia-Fernandez, E; Prado-Gotor, R; Sanchez, F

2005-08-11

Salt and solvent effects on the kinetics of the reactions [Fe(CN)6]3- + [Ru(NH3)5pz](2+) right arrow over left arrow [Fe(CN)6]4- + [Ru(NH3)5pz]3+ (pz = pyrazine) have been studied through T-jump measurements. The forward and reverse reactions show different behaviors: "abnormal" salt and solvent effects in the first case and normal effects in the second one. These facts imply an asymmetric behavior of anion/cation reactions depending on the charge of the oxidant. The results can be rationalized by using the Marcus-Hush treatment for electron-transfer reactions.

Effect of viscosity on photoinduced electron transfer reaction: An observation of the Marcus inverted region in homogeneous solvents

NASA Astrophysics Data System (ADS)

Saini, Rajesh Kumar; Kuchlyan, Jagannath; Sarkar, Nilmoni

2016-09-01

The viscosity effect of homogeneous solvents on the dynamics of photoinduced electron transfer (PET) reaction among the coumarins and N,N-dimethylaniline (DMA) is investigated using steady-state and time-resolved fluorescence spectroscopy. A bell shape Marcus inversion in the ET rates has been detected in the plot of ET rate constant (kq) with free energy change (ΔG0) in viscous solvents decanol and EG, but it is not observed in DMSO like low viscous solvent. We have also reported that there is no complex formation between the coumarin dye and DMA molecule by using fluorescence correlation spectroscopy.

Thermodynamic and spectroscopic speciation to explain the blackening process of hematite formed by atmospheric SO2 impact: the case of Marcus Lucretius House (Pompeii).

PubMed

Maguregui, Maite; Knuutinen, Ulla; Martínez-Arkarazo, Irantzu; Castro, Kepa; Madariaga, Juan M

2011-05-01

After many decades exposed to a polluted environment, in some areas of Marcus Lucretius House, there are clear signs that plasters and hematite pigments are suffering deterioration. In the exhaustive analysis of the black layer covering the red pigment hematite it was possible to identify magnetite (Fe(3)O(4)) as responsible for the black colour, which always appears in combination with gypsum. Thermodynamic modelling stated that the presence of gypsum as well as the transformation of hematite into magnetite is a consequence of the attack of atmospheric SO(2).

"East side story": on being an epidemiologist in the former USSR: an interview with Marcus Klingberg.

PubMed

Klingberg, Marcus

2006-01-01

Marcus Klingberg was born on 7 October 1918, in Warsaw, Poland, into a Hasidic, rabbinical family. After the Nazi invasion of Poland, he escaped to the USSR where he trained and worked as an epidemiologist from 1939 to 1945. For 35 years after the war, he continued his professional work in Israel. The harsh conditions within the Soviet Union during World War II provided a challenging setting for epidemiologic work-a setting that has remained largely hidden from Western view. In this interview, Klingberg describes his work as an epidemiologist in the USSR and his subsequent encounter with Western epidemiology.

Delaware River water quality Bristol to Marcus Hook, Pennsylvania, August 1949 to December 1963

USGS Publications Warehouse

Keighton, Walter B.

1965-01-01

During the 14-year period from August 1949 to July 1963, the U.S. Geological Survey, in cooperation with the city of Philadelphia, collected samples of river water once each month in the 43-mile reach of the Delaware River from Bristol to Marcus Hook, Pa., and daily at Trenton, 10 miles upstream from Bristol. This part of the Delaware is an estuary into which salt water is brought by tides; fresh water flows into the estuary at Trenton, NJ, and farther downstream from the Schuylkill River and other tributaries of the Delaware. In March, April, and May, when fresh-water flow is high, the average concentration of dissolved solids in the water at Bristol was 76 ppm (parts per million), and at Marcus Hook 112 PPM In August and September, streamflow is lower, and the average concentration of dissolved solids increased to 117 PPM at Bristol and 804 PPM at Marcus Hook. Major salinity invasions of the Delaware River occurred in 1949, 1953, 1954, 1957, and 1963. In each of these years the fresh-water flow into the tidal river at Trenton was low during the period from July to October. The greatest dissolved-solids concentrations in these monthly samples were 160 PPM at Bristol and 4,000 PPM at Marcus Hook. At times the dissolved-oxygen concentration of the river water has become dangerously low, especially in that reach of the river between Wharton Street and League Island. At the Benjamin Franklin Bridge, one-third of the samples of river water were less than 30 percent saturated with oxygen; however, no trend, either for better or for worse, was apparent during the 14-year period. It is useful now to summarize these monthly analyses for the period 1949-63 even though a much more detailed description of water quality in this reach of the estuary will soon become available through the use of recording instrumental conditions. This compendium of water-quality data is useful as an explicit statement of water quality during the 14-year study period and is valuable for directing attention to water-quality problems for selecting instrument sites, and for making comparative studies with the more detailed information which is already being obtained with the aid of recording instruments.

Kinetics of self-decomposition and hydrogen atom transfer reactions of substituted phthalimide N-oxyl radicals in acetic acid.

PubMed

Cai, Yang; Koshino, Nobuyoshi; Saha, Basudeb; Espenson, James H

2005-01-07

Kinetic data have been obtained for three distinct types of reactions of phthalimide N-oxyl radicals (PINO(.)) and N-hydroxyphthalimide (NHPI) derivatives. The first is the self-decomposition of PINO(.) which was found to follow second-order kinetics. In the self-decomposition of 4-methyl-N-hydroxyphthalimide (4-Me-NHPI), H-atom abstraction competes with self-decomposition in the presence of excess 4-Me-NHPI. The second set of reactions studied is hydrogen atom transfer from NHPI to PINO(.), e.g., PINO(.) + 4-Me-NHPI <=> NHPI + 4-Me-PINO(.). The substantial KIE, k(H)/k(D) = 11 for both forward and reverse reactions, supports the assignment of H-atom transfer rather than stepwise electron-proton transfer. These data were correlated with the Marcus cross relation for hydrogen-atom transfer, and good agreement between the experimental and the calculated rate constants was obtained. The third reaction studied is hydrogen abstraction by PINO(.) from p-xylene and toluene. The reaction becomes regularly slower as the ring substituent on PINO(.) is more electron donating. Analysis by the Hammett equation gave rho = 1.1 and 1.8 for the reactions of PINO(.) with p-xylene and toluene, respectively.

Organic magnetoresistance based on hopping theory

NASA Astrophysics Data System (ADS)

Yang, Fu-Jiang; Xie, Shi-Jie

2014-09-01

For the organic magnetoresistance (OMAR) effect, we suggest a spin-related hopping of carriers (polarons) based on Marcus theory. The mobility of polarons is calculated with the master equation (ME) and then the magnetoresistance (MR) is obtained. The theoretical results are consistent with the experimental observation. Especially, the sign inversion of the MR under different driving bias voltages found in the experiment is predicted. Besides, the effects of molecule disorder, hyperfine interaction (HFI), polaron localization, and temperature on the MR are investigated.

Travails of travel. Subtle and obscure causes of illness.

PubMed

Gordon, M E

1988-07-01

Knowledge of patients' travel history is an important facet of diagnosis. Malaria, Chagas' disease, toxoplasmosis, Lyme disease, arboviruses, and many other relatively unusual diseases can be contracted while the patient is traveling, and the symptoms, which may mimic another disease, may not become obvious until the patient returns. The Roman philosopher Marcus Aurelius Antoninus alerts us to easier resolutions of our daily diagnostic dilemmas: "Look within and let neither the peculiar quality of anything nor its value escape thee."

Eros and Thanatos: A Nondualistic Interpretation: The Dynamic of Drives in Personal and Civilizational Development From Freud to Marcuse.

PubMed

Kli, Maria

2018-02-01

The Freudian theory of drives gave prominence to the idea that there is an inherent principle of entropy, a tendency for dissolution of life, referred to as the Death drive, or Thanatos. Freud recognized a counterbalancing tendency for sustaining life, known as the Life drive, or Eros. The psychoanalytical expounding of the struggle of Eros and Thanatos in the context of the civilizational process sparked the philosophical critique of civilization. Although Freud tended to consider repression an indispensable dimension of this process, the author proposes in this paper that Herbert Marcuse's political critique took Freud's metapsychology further philosophically, suggesting a nondualistic interpretation of Freud's position.

Penning ionization and ion fragmentation of formamide HCONH2 by He∗, Ne∗, and Ar∗ in molecular beams

NASA Astrophysics Data System (ADS)

Madison, Tamika A.; Siska, P. E.

2009-10-01

Mass spectra from Penning ionization by metastable atom bombardment (MAB) in the title system at kinetic energies near 1 kcal/mol are reported. The experiments employ a supersonic excited noble gas beam crossing an effusive beam of formamide vapor. Product ions are extracted perpendicular to the plane of the beams, analyzed by a quadrupole mass filter, and counted by a scintillation-type ion counter. Relative to 70 eV electron impact, the He∗ and Ne∗ spectra show more extensive breakage of C-N and C-H bonds despite the smaller available energy, while the Ar∗ spectrum shows only the molecular ion (m /z 45), H atom elimination (44), and the decarbonylation products CO+NH3+ (17). Fragmentation in the latter system has been analyzed using a combination of ab initio calculations and Rice-Ramsperger-Kassel-Marcus theory with tunneling correction; good agreement with the experimental 45/44/17 intensity ratio 100/6.8±0.7/6.2±1.7 is obtained. 15% of m/z 17 and 50% of m /z 44 is attributed to tunneling. The ab initio decarbonylation reaction path yields a hydrogen bonded H2N-HCO+ transition state, which transfers a proton while proceeding downhill to the observed products, while both the path and the energetics support the earlier conclusion that the lowest lying electronically excited state of the ion (2π or 2a″) crosses the ground state early along the reaction path, thereby dominating the dynamics of decarbonylation.

Chemical characteristics of Delaware River water, Trenton, New Jersey, to Marcus Hook, Pennsylvania

USGS Publications Warehouse

Durfor, Charles N.; Keighton, Walter B.

1954-01-01

This progress report gives the results of an investigation of the quality of water in the Delaware River from Trenton, N. J. to Marcus Hook, Pa., for the period August 1949 to December 1952. The Delaware River is the principal source of water for the many industries and municipal water supplies along this reach of the river and both industries and municipalities use it for the disposal of their wastes. Consequently, a study of the quality of the water and variations in the quality caused by changes in streamflow, tidal effects, pollution and other factors is important to the many users. In both New Jersey and Pennsylvania steps are being taken to abate pollution, thus it is of more than passing interest to measure the effects of waste treatment on the quality of the Delaware River water. At average or higher rates of streamflow the mineral content of the water increases slightly from Trenton to Marcus Hook. There is little variation in the concentration of dissolved minerals from bank to bank or from top to bottom of the river. At times of protracted low rates of flow the effect of ocean water mixing with the river water may be noted as far upstream as Philadelphia. At such times the salinity is often greater near the bottom of the river than near the top. The increase in chloride concentration upstream from Philadelphia is small compared to the rapid increase downstream from Philadelphia. Temperatures of offshore water vary with the season, but on a given day are substantially uniform throughout the reach of the river from Trenton to Marcus Hook. The water contains less dissolved oxygen as it flows downstream indicating that oxygen is being consumed by oxidizable matter. From Philadelphia downstream there are periods, especially in late summer, when the dissolved oxygen is barely sufficient to meet the oxygen demands of the pollution load.

Dynamics of a Chlorophyll Dimer in Collective and Local Thermal Environments

DOE PAGES

Merkli, M.; Berman, Gennady Petrovich; Sayre, Richard Thomas; ...

2016-01-30

Here we present a theoretical analysis of exciton transfer and decoherence effects in a photosynthetic dimer interacting with collective (correlated) and local (uncorrelated) protein-solvent environments. Our approach is based on the framework of the spin-boson model. We derive explicitly the thermal relaxation and decoherence rates of the exciton transfer process, valid for arbitrary temperatures and for arbitrary (in particular, large) interaction constants between the dimer and the environments. We establish a generalization of the Marcus formula, giving reaction rates for dimer levels possibly individually and asymmetrically coupled to environments. We identify rigorously parameter regimes for the validity of the generalizedmore » Marcus formula. The existence of long living quantum coherences at ambient temperatures emerges naturally from our approach.« less

Structure and Dynamics of Solvent Landscapes in Charge-Transfer Reactions

NASA Astrophysics Data System (ADS)

Leite, Vitor B. Pereira

The dynamics of solvent polarization plays a major role in the control of charge transfer reactions. The success of Marcus theory describing the solvent influence via a single collective quadratic polarization coordinate has been remarkable. Onuchic and Wolynes have recently proposed (J. Chem Phys 98 (3) 2218, 1993) a simple model demonstrating how a many-dimensional-complex model composed by several dipole moments (representing solvent molecules or polar groups in proteins) can be reduced under the appropriate limits into the Marcus Model. This work presents a dynamical study of the same model, which is characterized by two parameters, an average dipole-dipole interaction as a term associated with the potential energy landscape roughness. It is shown why the effective potential, obtained using a thermodynamic approach, is appropriate for the dynamics of the system. At high temperatures, the system exhibits effective diffusive one-dimensional dynamics, where the Born-Marcus limit is recovered. At low temperatures, a glassy phase appears with a slow non-self-averaging dynamics. At intermediate temperatures, the concept of equivalent diffusion paths and polarization dependence effects are discussed. This approach is extended to treat more realistic solvent models. Real solvents are discussed in terms of simple parameters described above, and an analysis of how different regimes affect the rate of charge transfer is presented. Finally, these ideas are correlated to analogous problems in other areas.

Carrier mobility in double-helix DNA and RNA: A quantum chemistry study with Marcus-Hush theory.

PubMed

Wu, Tao; Sun, Lei; Shi, Qi; Deng, Kaiming; Deng, Weiqiao; Lu, Ruifeng

2016-12-21

Charge mobilities of six DNAs and RNAs have been computed using quantum chemistry calculation combined with the Marcus-Hush theory. Based on this simulation model, we obtained quite reasonable results when compared with the experiment, and the obtained charge mobility strongly depends on the molecular reorganization and electronic coupling. Besides, we find that hole mobilities are larger than electron mobilities no matter in DNAs or in RNAs, and the hole mobility of 2L8I can reach 1.09 × 10 -1 cm 2 V -1 s -1 which can be applied in the molecular wire. The findings also show that our theoretical model can be regarded as a promising candidate for screening DNA- and RNA-based molecular electronic devices.

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

NASA Astrophysics Data System (ADS)

Xu, Weilin; Li, Songtao; Zhou, Xiaochun; Xing, Wei; Huang, Mingyou; Lu, Tianhong; Liu, Changpeng

2006-05-01

In the present work a nonmonotonic dependence of standard rate constant (k0) on reorganization energy (λ) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k0 on λ is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of λ, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the λ dependence of k0 for Process I is monotonic thoroughly, while for Process II on electrode surface the λ dependence of k0 could show a nonmonotonicity.

Carrier mobility in double-helix DNA and RNA: A quantum chemistry study with Marcus-Hush theory

NASA Astrophysics Data System (ADS)

Wu, Tao; Sun, Lei; Shi, Qi; Deng, Kaiming; Deng, Weiqiao; Lu, Ruifeng

2016-12-01

Charge mobilities of six DNAs and RNAs have been computed using quantum chemistry calculation combined with the Marcus-Hush theory. Based on this simulation model, we obtained quite reasonable results when compared with the experiment, and the obtained charge mobility strongly depends on the molecular reorganization and electronic coupling. Besides, we find that hole mobilities are larger than electron mobilities no matter in DNAs or in RNAs, and the hole mobility of 2L8I can reach 1.09 × 10-1 cm2 V-1 s-1 which can be applied in the molecular wire. The findings also show that our theoretical model can be regarded as a promising candidate for screening DNA- and RNA-based molecular electronic devices.

Asymmetric Marcus-Hush theory for voltammetry.

PubMed

Laborda, Eduardo; Henstridge, Martin C; Batchelor-McAuley, Christopher; Compton, Richard G

2013-06-21

The current state-of-the-art in modeling the rate of electron transfer between an electroactive species and an electrode is reviewed. Experimental studies show that neither the ubiquitous Butler-Volmer model nor the more modern symmetric Marcus-Hush model are able to satisfactorily reproduce the experimental voltammetry for both solution-phase and surface-bound redox couples. These experimental deviations indicate the need for revision of the simplifying approximations used in the above models. Within this context, models encompassing asymmetry are considered which include different vibrational and solvation force constants for the electroactive species. The assumption of non-adiabatic electron transfer is also examined. These refinements have provided more satisfactory models of the electron transfer process and they enable us to gain more information about the microscopic characteristics of the system by means of simple electrochemical measurements.

Ab Initio Analysis of Auger-Assisted Electron Transfer.

PubMed

Hyeon-Deuk, Kim; Kim, Joonghan; Prezhdo, Oleg V

2015-01-15

Quantum confinement in nanoscale materials allows Auger-type electron-hole energy exchange. We show by direct time-domain atomistic simulation and analytic theory that Auger processes give rise to a new mechanism of charge transfer (CT) on the nanoscale. Auger-assisted CT eliminates the renown Marcus inverted regime, rationalizing recent experiments on CT from quantum dots to molecular adsorbates. The ab initio simulation reveals a complex interplay of the electron-hole and charge-phonon channels of energy exchange, demonstrating a variety of CT scenarios. The developed Marcus rate theory for Auger-assisted CT describes, without adjustable parameters, the experimental plateau of the CT rate in the region of large donor-acceptor energy gap. The analytic theory and atomistic insights apply broadly to charge and energy transfer in nanoscale systems.

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Fresh-water discharge salinity relations in the tidal Delaware River

USGS Publications Warehouse

Keighton, Walter B.

1966-01-01

Sustained flows of fresh water greater than 3,500, 4,400, and 5,300 cubic feet per second into the Delaware River estuary at Trenton, NJ assure low salinity at League Island, Eddystone, and Marcus Hook, respectively. When the discharge at Trenton is less than these critical values, salinity is very sensitive to change in discharge, so that a relatively small decrease in fresh-water discharge results in a relatively great increase in salinity. Comparison of the discharge-salinity relations observed for the 14-year period August 1949-December 1963 with relations proposed by other workers but based on other time periods indicate that such relations change with time and that salinity is affected not only by discharge but also by dredging; construction of breakwater, dikes, and tidal barriers; changing sea level; tidal elevation; tidal range; and wind intensity and direction.

Impact of Laurel Wilt, Caused by Raffaelea lauricola, on Leaf Gas Exchange and Xylem Sap Flow in Avocado, Persea americana.

PubMed

Ploetz, Randy C; Schaffer, Bruce; Vargas, Ana I; Konkol, Joshua L; Salvatierra, Juanpablo; Wideman, Ronney

2015-04-01

Laurel wilt, caused by Raffaelea lauricola, is a destructive disease of avocado (Persea americana). The susceptibility of different cultivars and races was examined previously but more information is needed on how this host responds to the disease. In the present study, net CO2 assimilation (A), stomatal conductance of H2O (gs), transpiration (E), water use efficiency (WUE), and xylem sap flow rates were assessed in cultivars that differed in susceptibility. After artificial inoculation with R. lauricola, there was a close relationship between symptom development and reductions in A, gs, E, WUE, and mean daily sap flow in the most susceptible cultivar, 'Russell', and significantly greater disease and lower A, gs, E, WUE, and sap flow rates were usually detected after 15 days compared with the more tolerant 'Brogdon' and 'Marcus Pumpkin'. Significant differences in preinoculation A, gs, E, and WUE were generally not detected among the cultivars but preinoculation sap flow rates were greater in Russell than in Brogdon and Marcus Pumpkin. Preinoculation sap flow rates and symptom severity for individual trees were correlated at the end of an experiment (r=0.46), indicating that a plant's susceptibility to laurel wilt was related to its ability to conduct water. The potential management of this disease with clonal rootstocks that reduce sap flow rates is discussed.

Utilizing the R/V Marcus G. Langseth's streamer to measure the acoustic radiation of its seismic source in the shallow waters of New Jersey's continental shelf.

PubMed

Crone, Timothy J; Tolstoy, Maya; Gibson, James C; Mountain, Gregory

2017-01-01

Shallow water marine seismic surveys are necessary to understand a range of Earth processes in coastal environments, including those that represent major hazards to society such as earthquakes, tsunamis, and sea-level rise. Predicting the acoustic radiation of seismic sources in shallow water, which is required for compliance with regulations designed to limit impacts on protected marine species, is a significant challenge in this environment because of variable reflectivity due to local geology, and the susceptibility of relatively small bathymetric features to focus or shadow acoustic energy. We use data from the R/V Marcus G. Langseth's towed hydrophone streamer to estimate the acoustic radiation of the ship's seismic source during a large survey of the shallow shelf off the coast of New Jersey. We use the results to estimate the distances from the source to acoustic levels of regulatory significance, and use bathymetric data from the ship's multibeam system to explore the relationships between seafloor depth and slope and the measured acoustic radiation patterns. We demonstrate that existing models significantly overestimate mitigation radii, but that the variability of received levels in shallow water suggest that in situ real-time measurements would help improve these estimates, and that post-cruise revisions of received levels are valuable in accurately determining the potential acoustic impact of a seismic survey.

A Critical Theory Perspective on Accelerated Learning.

ERIC Educational Resources Information Center

Brookfield, Stephen D.

2003-01-01

Critically analyzes accelerated learning using concepts from Herbert Marcuse (rebellious subjectivity) and Erich Fromm (automaton conformity). Concludes that, by providing distance and separation, accelerated learning has more potential to stimulate critical autonomous thought. (SK)

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

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

Xu Weilin; Li Songtao; Zhou Xiaochun

2006-05-07

In the present work a nonmonotonic dependence of standard rate constant (k{sup 0}) on reorganization energy ({lambda}) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k{sup 0} on {lambda} is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of {lambda}, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the {lambda} dependence of k{sup 0} for Process Imore » is monotonic thoroughly, while for Process II on electrode surface the {lambda} dependence of k{sup 0} could show a nonmonotonicity.« less

[The Antonine plague].

PubMed

Haas, Charles

2006-01-01

During the reign of Marcus Aurelius, the Roman Empire was struck by a long and destructive epidemic. It began in Mesopotamia in late AD 165 or early AD 166 during Verus' Parthian campaign, and quickly spread to Rome. It lasted at least until the death of Marcus Aurelius in AD 180 and likely into the early part of Commodus' reign. Its victims were "innumerable". Galen had first-hand knowledge of the disease. He was in Rome when the plague reached the city in AD 166. He was also present during an outbreak among troops stationed at Aquileia during the winter of AD 168-169. His references to the plague are scattered and brief but enough information is available to firmly identify the plague as smallpox. His description of the exanthema is fairly typical of the smallpox rash, particularly in the hemorrhagic phase of the disease.

[The use of opium in Roman society and the dependence of Princeps Marcus Aurelius].

PubMed

Trancas, Bruno; Borja Santos, Nuno; Patrício, Luís D

2008-01-01

Opium was known and frequently used in Roman society. Medical practice recognized its usefulness as an analgesic, soporific, anti-tussic or anti-diarrheic agent, as well as other currently unsupported uses with quasi-magical properties. It was additionally used as an ingredient in antidotes, panaceas and poisons. The authors present a non-exhaustive compilation of opium use according to medical doctors, writers and encyclopaedists of the time. Mythological and literary representations of the opium poppy reflected its diverse roles, being associated with prosperity and fertility, sleep, death and the underworld and with the art of medicine. Despite its free and routine use, there is no solid evidence of addiction, except the putative case of emperor Marcus Aurelius, consistently reported as one of the most likely cases of addiction to opium.

Photoinduced electron transfer in an imidazolium ionic liquid and in its binary mixtures with water, methanol, and 2-propanol: appearance of Marcus-type of inversion.

PubMed

Sarkar, Souravi; Mandal, Sarthak; Ghatak, Chiranjib; Rao, Vishal Govind; Ghosh, Surajit; Sarkar, Nilmoni

2012-02-02

The photoinduced electron transfer (PET) reaction has been investigated in a room temperature imidazolium ionic liquid (RTIL), 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO(4)]) and also in [Emim][EtSO(4)]-co-solvents mixtures from N,N-dimethyl aniline (DMA) to different Coumarin dyes using steady state and time-resolved fluorescence quenching measurements. We have used water and methanol and 2-propanol as the cosolvents of RTILs for the PET study. On going from neat ionic liquid to the RTIL-co-solvents mixtures the electron transfer rate has been largely enhanced. In neat RTIL as well as in [Emim][EtSO(4)]-co-solvents mixtures, a Marcus type of inversion in the PET rate have been observed.

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

H. Nolen, S. Maxwell, R. Neri, J. Grab

This research effort sought to achieve a solution package that yields energy savings greater than 30 percent over the pre-existing conditions in a minimally intrusive multifamily retrofit project. The Consortium for Advanced Residential Buildings (CARB) partnered with L+M Development Partners, Inc. on a Mitchell-Lama Housing Program project, Marcus Garvey Village, in Brooklyn, NY (Climate Zone 4A). The Mitchell-Lama Housing Program is a form of housing subsidy in the state of New York that provides affordable rental and cooperative housing to moderate- and middle-income families. Marcus Garvey Village was founded in 1975 and contains 625 residential units (ranging from studios tomore » 5-bedroom units) in thirty-two 4-story garden-style apartment structures built with concrete and faced in light brown brick. The single largest challenge for implementation of energy conservation measures at Marcus Garvey was working within occupied spaces. Measures are being implemented in phases to minimize disruption. As of August 2015, the retrofit work is over 50 percent complete. The wall insulation, sealing of the through wall AC vent, and installation of new oil-filled electric baseboards with advanced controls are conducted at one time, limiting disruption to the living room space. In a similar fashion, the kitchen work is done, then the bathroom. The final selection of energy conservation measures is projected to save 26.5 percent in source energy with a cost just under $3.7 million and utility bill savings of nearly $480,000 (of an average $1.8 million annual utility cost for the development).« less

Large impact of reorganization energy on photovoltaic conversion due to interfacial charge-transfer transitions.

PubMed

Fujisawa, Jun-ichi

2015-05-14

Interfacial charge-transfer (ICT) transitions are expected to be a novel charge-separation mechanism for efficient photovoltaic conversion featuring one-step charge separation without energy loss. Photovoltaic conversion due to ICT transitions has been investigated using several TiO2-organic hybrid materials that show organic-to-inorganic ICT transitions in the visible region. In applications of ICT transitions to photovoltaic conversion, there is a significant problem that rapid carrier recombination is caused by organic-inorganic electronic coupling that is necessary for the ICT transitions. In order to solve this problem, in this work, I have theoretically studied light-to-current conversions due to the ICT transitions on the basis of the Marcus theory with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. An apparent correlation between the reported incident photon-to-current conversion efficiencies (IPCE) and calculated reorganization energies was clearly found, in which the IPCE increases with decreasing the reorganization energy consistent with the Marcus theory in the inverted region. This activation-energy dependence was systematically explained by the equation formulated by the Marcus theory based on a simple excited-state kinetic scheme. This result indicates that the reduction of the reorganization energy can suppress the carrier recombination and enhance the IPCE. The reorganization energy is predominantly governed by the structural change in the chemical-adsorption moiety between the ground and ICT excited states. This work provides crucial knowledge for efficient photovoltaic conversion due to ICT transitions.

The First Journalism School.

ERIC Educational Resources Information Center

Boyle, Diane

2000-01-01

Offers a brief look at the life of Marcus Walter Williams: his early life and education, his work life in journalism, and his founding of the first school of Journalism (located at the University of Missouri) in 1906. (SR)

A Faculty Trains Itself to Improve Student Discipline

ERIC Educational Resources Information Center

Grantham, Marvin L.; Harris, Clifton S., Jr.

1976-01-01

The Marcus School staff feels that the best approach to discipline is a preventive one--the provision of a variety of educational and environmental alternatives that will interest, challenge, and motivate the pupil. (Author)

Can we Predict Quantum Yields Using Excited State Density Functional Theory for New Families of Fluorescent Dyes?

NASA Astrophysics Data System (ADS)

Kohn, Alexander W.; Lin, Zhou; Shepherd, James J.; Van Voorhis, Troy

2016-06-01

For a fluorescent dye, the quantum yield characterizes the efficiency of energy transfer from the absorbed light to the emitted fluorescence. In the screening among potential families of dyes, those with higher quantum yields are expected to have more advantages. From the perspective of theoreticians, an efficient prediction of the quantum yield using a universal excited state electronic structure theory is in demand but still challenging. The most representative examples for such excited state theory include time-dependent density functional theory (TDDFT) and restricted open-shell Kohn-Sham (ROKS). In the present study, we explore the possibility of predicting the quantum yields for conventional and new families of organic dyes using a combination of TDDFT and ROKS. We focus on radiative (kr) and nonradiative (knr) rates for the decay of the first singlet excited state (S_1) into the ground state (S_0) in accordance with Kasha's rule. M. Kasha, Discuss. Faraday Soc., 9, 14 (1950). For each dye compound, kr is calculated with the S_1-S_0 energy gap and transition dipole moment obtained using ROKS and TDDFT respectively at the relaxed S_1 geometry. Our predicted kr agrees well with the experimental value, so long as the order of energy levels is correctly predicted. Evaluation of knr is less straightforward as multiple processes are involved. Our study focuses on the S_1-T_1 intersystem crossing (ISC) and the S_1-S_0 internal conversion (IC): we investigate the properties that allow us to model the knr value using a Marcus-like expression, such as the Stokes shift, the reorganization energy, and the S_1-T_1 and S_1-S_0 energy gaps. Taking these factors into consideration, we compare our results with those obtained using the actual Marcus theory and provide explanation for discrepancy. T. Kowalczyk, T. Tsuchimochi, L. Top, P.-T. Chen, and T. Van Voorhis, J. Chem. Phys., 138, 164101 (2013). M. Kasha, Discuss. Faraday Soc., 9, 14 (1950).

78 FR 24798 - Qualification of Drivers; Exemption Applications; Vision

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-26

... exceeded the speed limit by 13 mph. Marcus R. Watkins Mr. Watkins, 50, has had a retinal detachment in his... vision to perform driving tasks required to operate a commercial vehicle.'' Mr. Watkins reported that he...

On the non-Arrhenius temperature dependence of the interwell electron tunneling rate in quasi two dimensional organic quantum wells

NASA Astrophysics Data System (ADS)

Jeong, I. S.; Scott, K.; Donovan, K. J.; Wilson, E. G.

2000-11-01

The tunneling rate of photocreated charge carriers between layers in Langmuir-Blodgett multilayer structures is measured indirectly using the novel technique of bimolecular recombination quenching. The tunneling rate is measured as a function of the applied electrostatic potential difference between the layers as the temperature is varied between 300 and 4 K. This dependence is examined in light of the Marcus theory of charge transfer where the electrostatic potential replaces the chemical potential as the driving potential. The expectations of the Marcus theory are not met and the rate is effectively temperature independent, contrary to expectation. Other mechanisms are explored that may explain the lack of temperature dependence including the role of high frequency vibrations and the role of the zero point energy of those vibrations. The temperature dependence of the exciton dissociation probability is also examined.

Adiabatic elimination for systems with inertia driven by compound Poisson colored noise.

PubMed

Li, Tiejun; Min, Bin; Wang, Zhiming

2014-02-01

We consider the dynamics of systems driven by compound Poisson colored noise in the presence of inertia. We study the limit when the frictional relaxation time and the noise autocorrelation time both tend to zero. We show that the Itô and Marcus stochastic calculuses naturally arise depending on these two time scales, and an extra intermediate type occurs when the two time scales are comparable. This leads to three different limiting regimes which are supported by numerical simulations. Furthermore, we establish that when the resulting compound Poisson process tends to the Wiener process in the frequent jump limit the Itô and Marcus calculuses, respectively, tend to the classical Itô and Stratonovich calculuses for Gaussian white noise, and the crossover type calculus tends to a crossover between the Itô and Stratonovich calculuses. Our results would be very helpful for understanding relevant experiments when jump type noise is involved.

Effects of tunnelling and asymmetry for system-bath models of electron transfer

NASA Astrophysics Data System (ADS)

Mattiat, Johann; Richardson, Jeremy O.

2018-03-01

We apply the newly derived nonadiabatic golden-rule instanton theory to asymmetric models describing electron-transfer in solution. The models go beyond the usual spin-boson description and have anharmonic free-energy surfaces with different values for the reactant and product reorganization energies. The instanton method gives an excellent description of the behaviour of the rate constant with respect to asymmetry for the whole range studied. We derive a general formula for an asymmetric version of the Marcus theory based on the classical limit of the instanton and find that this gives significant corrections to the standard Marcus theory. A scheme is given to compute this rate based only on equilibrium simulations. We also compare the rate constants obtained by the instanton method with its classical limit to study the effect of tunnelling and other quantum nuclear effects. These quantum effects can increase the rate constant by orders of magnitude.

Model of a thin film optical fiber fluorosensor

NASA Technical Reports Server (NTRS)

Egalon, Claudio O.; Rogowski, Robert S.

1991-01-01

The efficiency of core-light injection from sources in the cladding of an optical fiber is modeled analytically by means of the exact field solution of a step-profile fiber. The analysis is based on the techniques by Marcuse (1988) in which the sources are treated as infinitesimal electric currents with random phase and orientation that excite radiation fields and bound modes. Expressions are developed based on an infinite cladding approximation which yield the power efficiency for a fiber coated with fluorescent sources in the core/cladding interface. Marcuse's results are confirmed for the case of a weakly guiding cylindrical fiber with fluorescent sources uniformly distributed in the cladding, and the power efficiency is shown to be practically constant for variable wavelengths and core radii. The most efficient fibers have the thin film located at the core/cladding boundary, and fibers with larger differences in the indices of refraction are shown to be the most efficient.

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

Chęcińska, Agata; Heaney, Libby; Pollock, Felix A.

Motivated by a proposed olfactory mechanism based on a vibrationally activated molecular switch, we study electron transport within a donor-acceptor pair that is coupled to a vibrational mode and embedded in a surrounding environment. We derive a polaron master equation with which we study the dynamics of both the electronic and vibrational degrees of freedom beyond previously employed semiclassical (Marcus-Jortner) rate analyses. We show (i) that in the absence of explicit dissipation of the vibrational mode, the semiclassical approach is generally unable to capture the dynamics predicted by our master equation due to both its assumption of one-way (exponential) electronmore » transfer from donor to acceptor and its neglect of the spectral details of the environment; (ii) that by additionally allowing strong dissipation to act on the odorant vibrational mode, we can recover exponential electron transfer, though typically at a rate that differs from that given by the Marcus-Jortner expression; (iii) that the ability of the molecular switch to discriminate between the presence and absence of the odorant, and its sensitivity to the odorant vibrational frequency, is enhanced significantly in this strong dissipation regime, when compared to the case without mode dissipation; and (iv) that details of the environment absent from previous Marcus-Jortner analyses can also dramatically alter the sensitivity of the molecular switch, in particular, allowing its frequency resolution to be improved. Our results thus demonstrate the constructive role dissipation can play in facilitating sensitive and selective operation in molecular switch devices, as well as the inadequacy of semiclassical rate equations in analysing such behaviour over a wide range of parameters.« less

Retrofitting Garden-Style Apartments in Brooklyn, New York

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

Nolen, Heather; Maxwell, Sean; Neri, Robin

This research effort sought to achieve a solution package that yields energy savings greater than 30% over the pre-existing conditions in a minimally intrusive multifamily retrofit project. The Consortium for Advanced Residential Buildings (CARB) partnered with L+M Development Partners, Inc. on a Mitchell-Lama Housing Program project, Marcus Garvey Village, in Brooklyn, NY (Climate Zone 4A). The Mitchell-Lama Housing Program is a form of housing subsidy in the state of New York that provides affordable rental and cooperative housing to moderate- and middle-income families. Marcus Garvey Village was founded in 1975 and contains 625 residential units (ranging from studios to 5-bedroommore » units) in thirty-two 4-story garden-style apartment structures built with concrete and faced in light brown brick. The single largest challenge for implementation of energy conservation measures at Marcus Garvey was working within occupied spaces. Measures are being implemented in phases to minimize disruption. As of August 2015, the retrofit work is over 50% complete. The wall insulation, sealing of the through wall AC vent, and installation of new oil-filled electric baseboards with advanced controls are conducted at one time, limiting disruption to the living room space. In a similar fashion, the kitchen work is done, then the bathroom. The final selection of energy conservation measures is projected to save 26.5% in source energy with a cost just under $3.7 million and utility bill savings of nearly $480,000 (of an average $1.8 million annual utility cost for the development).« less

Building America Case Study: Retrofitting Garden-Style Apartments, Brooklyn, New York

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

This research effort sought to achieve a solution package that yields energy savings greater than 30 percent over the pre-existing conditions in a minimally intrusive multifamily retrofit project. The Consortium for Advanced Residential Buildings (CARB) partnered with L+M Development Partners, Inc. on a Mitchell-Lama Housing Program project, Marcus Garvey Village, in Brooklyn, NY (Climate Zone 4A). The Mitchell-Lama Housing Program is a form of housing subsidy in the state of New York that provides affordable rental and cooperative housing to moderate- and middle-income families. Marcus Garvey Village was founded in 1975 and contains 625 residential units (ranging from studios tomore » 5-bedroom units) in thirty-two 4-story garden-style apartment structures built with concrete and faced in light brown brick. The single largest challenge for implementation of energy conservation measures at Marcus Garvey was working within occupied spaces. Measures are being implemented in phases to minimize disruption. As of August 2015, the retrofit work is over 50 percent complete. The wall insulation, sealing of the through wall AC vent, and installation of new oil-filled electric baseboards with advanced controls are conducted at one time, limiting disruption to the living room space. In a similar fashion, the kitchen work is done, then the bathroom. The final selection of energy conservation measures is projected to save 26.5 percent in source energy with a cost just under $3.7 million and utility bill savings of nearly $480,000 (of an average $1.8 million annual utility cost for the development).« less

Utilizing the R/V Marcus G. Langseth’s streamer to measure the acoustic radiation of its seismic source in the shallow waters of New Jersey’s continental shelf

PubMed Central

Tolstoy, Maya; Gibson, James C.; Mountain, Gregory

2017-01-01

Shallow water marine seismic surveys are necessary to understand a range of Earth processes in coastal environments, including those that represent major hazards to society such as earthquakes, tsunamis, and sea-level rise. Predicting the acoustic radiation of seismic sources in shallow water, which is required for compliance with regulations designed to limit impacts on protected marine species, is a significant challenge in this environment because of variable reflectivity due to local geology, and the susceptibility of relatively small bathymetric features to focus or shadow acoustic energy. We use data from the R/V Marcus G. Langseth’s towed hydrophone streamer to estimate the acoustic radiation of the ship’s seismic source during a large survey of the shallow shelf off the coast of New Jersey. We use the results to estimate the distances from the source to acoustic levels of regulatory significance, and use bathymetric data from the ship’s multibeam system to explore the relationships between seafloor depth and slope and the measured acoustic radiation patterns. We demonstrate that existing models significantly overestimate mitigation radii, but that the variability of received levels in shallow water suggest that in situ real-time measurements would help improve these estimates, and that post-cruise revisions of received levels are valuable in accurately determining the potential acoustic impact of a seismic survey. PMID:28800634

Racism and Surplus Repression.

ERIC Educational Resources Information Center

Johnson, Howard

1983-01-01

Explores the relationship between Herbert Marcuse's theory of "surplus repression" and Freud's theory of the "unconscious" with respect to latent, hidden, covert, or subliminal aspects of racism in the United States. Argues that unconscious racism, manifested in evasion/avoidance, acting out/projection, and attempted…

Remediation System Evaluation, SMS Instruments Superfund Site

EPA Pesticide Factsheets

The SMS Instruments Superfund Site is located at 120 Marcus Boulevard in Deer Park, Suffolk County,New York. The site consists of a 34,000 square foot building located on a 1.5-acre lot that is surroundedby other light industrial facilities.

Australian DefenceScience. Volume 13, Number 2, Winter

DTIC Science & Technology

2005-01-01

has been marketing the OAVD technology through its Business and Commercialisation Office (BCO). Marcus Belder, Technology Commercialisation Manager...for ADF organisational structures, and training and education initiatives.” The inquiry process As one line of inquiry, the team has been carrying

Tuskegee Institute in the 1920's

ERIC Educational Resources Information Center

Marable, Manning

1977-01-01

During the time of Marcus Garvey, the Harlem Renaissance and Southern black labor militancy, Tuskegee perpetuated a conservative social philosophy. This contradictory legacy set the stage for a confrontation between the black middle class of Tuskegee and a white racist society. (Author/GC)

Ab initio quantum chemical study of electron transfer in carboranes

NASA Astrophysics Data System (ADS)

Pati, Ranjit; Pineda, Andrew C.; Pandey, Ravindra; Karna, Shashi P.

2005-05-01

The electron transfer (ET) properties of 10- and 12-vertex carboranes are investigated by the ab initio Hartree-Fock method within the Marcus-Hush (MH) two-state model and the Koopman theorem (KT) approach. The calculated value of the ET coupling matrix element, VAB, is consistently higher in the KT approach than in the MH two-state model. For the carborane molecules functionalized by -CH 2 groups at C-vertices, VAB strongly depends on the relative orientation of the planes containing the terminal -CH 2 groups. The predicted conformation dependence of VAB offers a molecular mechanism to control ET between two active centers in molecular systems.

Traces and echoes of De Architectura by Marcus Vitruvius Pollio in the work of Xu Guangqi in 17th century China

NASA Astrophysics Data System (ADS)

Cigola, Michela; Fang, Yibing

2016-03-01

This study aims to investigate the role played by Xu Guangqi (1562-1633), minister of the Ming Dynasty, in the development of European scientific and technical knowledge in China between the 16th and 17th centuries by analyzing a book of Western technology that he wrote, namely, Taixi Shuifa ( On Western Hydraulics). Several Western books related to machine knowledge are searched to trace the source of the illustrations in Taixi Shuifa. We found that Archimedes' screw and Ctesibius' machine, which are included in Vitruvius' De Architectura volumes, also appear in the work of Xu Guangqi.

STS-127 Crew Visit to Anne Beers Elementary

NASA Image and Video Library

2009-09-23

Students, including Marcus Pratt, left, and Ajani Young, second from left, pay close attention as the crew from STS-127 makes their presentation during a visit to Anne Beers Elementary school, Thursday, Sept. 24, 2009, in Washington. Photo Credit: (NASA/Paul E. Alers)

Education on Trial. Strategies for the Future.

ERIC Educational Resources Information Center

Johnston, William J., Ed.

Problems and opportunities in educational reform at all educational levels are considered in this collection of 18 articles. Titles and authors are as follows: Introduction (William J. Johnston); "Evidence of Decline in Educational Standards" (Philip N. Marcus); "Standards--by What Criteria?" (Francis Keppel); "Educational…

Firing back: how great leaders rebound after career disasters.

PubMed

Sonnenfeld, Jeffrey A; Ward, Andrew J

2007-01-01

Among the tests of a leader, few are more challenging-and more painful-than recovering from a career catastrophe. Most fallen leaders, in fact, don't recover. Still, two decades of consulting experience, scholarly research, and their own personal experiences have convinced the authors that leaders can triumph over tragedy--if they do so deliberately. Great business leaders have much in common with the great heroes of universal myth, and they can learn to overcome profound setbacks by thinking in heroic terms. First, they must decide whether or not to fight back. Either way, they must recruit others into their battle. They must then take steps to recover their heroic status, in the process proving, both to others and to themselves, that they have the mettle necessary to recover their heroic mission. Bernie Marcus exemplifies this process. Devastated after Sandy Sigoloff ired him from Handy Dan, Marcus decided to forgo the distraction of litigation and instead make the marketplace his batttleground. Drawing from his network of carefully nurtured relationships with both close and more distant acquaintances, Marcus was able to get funding for a new venture. He proved that he had the mettle, and recovered his heroic status, by building Home Depot, whose entrepreneurial spirit embodied his heroic mission. As Bank One's Jamie Dimon, J.Crew's Mickey Drexler, and even Jimmy Carter, Martha Stewart, and Michael Milken have shown, stunning comebacks are possible in all industries and walks of life. Whatever the cause of your predicament, it makes sense to get your story out. The alternative is likely to be long-lasting unemployment. If the facts of your dismissal cannot be made public because they are damning, then show authentic remorse. The public is often enormously forgiving when it sees genuine contrition and atonement.

Dust Acoustic Wave Excitation in a Plasma with Warm Dust

NASA Astrophysics Data System (ADS)

Rosenberg, M.; Thomas, E., Jr.; Marcus, L.; Fisher, R.; Williams, J. D.; Merlino, R. L.

2008-11-01

Measurements of the dust acoustic wave dispersion relation in dusty plasmas formed in glow discharges at the University of Iowa [1] and Auburn University [2] have shown the importance of finite dust temperature effects. The effect of dust grains with large thermal speeds was taken into account using kinetic theory of the ion-dust streaming instability [3]. The results of analytic and numerical calculations of the dispersion relation based on the kinetic theory will be presented and compared with the experimental results. [1] E. Thomas, Jr., R. Fisher, and R. L. Merlino, Phys. Plasmas 14, 123701 (2007). [2] J. D. Williams, E. Thomas Jr., and L. Marcus, Phys. Plasmas 15, 043704 (2008). [3] M. Rosenberg, E. Thomas Jr., and R. L. Merlino, Phys. Plasmas 15, 073701 (2008).

Repressive Tolerance and the Practice of Adult Education

ERIC Educational Resources Information Center

Brookfield, Stephen D.

2014-01-01

Herbert Marcuse's concept of repressive tolerance argues that behind the justification of tolerance lies the possibility of ideological domination. Tolerance allows intolerable practices to go unchallenged and flattens discussion to assume all viewpoints have equal validity. When alternative, dissenting views are inserted into the curriculum…

The Good Fight: from Plessy to Brown.

ERIC Educational Resources Information Center

Quarles, Benjamin

1979-01-01

The work of Black leaders and organizations from 1896 to 1954 is reviewed. Discussed are Booker T. Washington, W.E.B. DuBois, the NAACP, the National Urban League, Marcus Garvey, Arthur A. Schomberg, Carter G. Woodson, Charles S. Johnson, and A. Philip Randolph. (MC)

Chemistry Research of Optical Fibers.

DTIC Science & Technology

1982-09-27

BROADENING IN OPTICAL FIBERS Herbert B. Rosenstock* Naval Research Laboratory Washington, DC 20375 ABSTRACT A light pulse transmitted through a fiber...Marcatili, Marcuse , and Personick, "Dispersion Properties of Fibers" (Ch. 4 in "Optical Fiber Telecommunications," S. E. Miller and A. C. Chynoweth, eds

Broadband calibration of the R/V Marcus G. Langseth four-string seismic sources

NASA Astrophysics Data System (ADS)

Tolstoy, M.; Diebold, J.; Doermann, L.; Nooner, S.; Webb, S. C.; Bohnenstiehl, D. R.; Crone, T. J.; Holmes, R. C.

2009-08-01

The R/V Marcus G. Langseth is the first 3-D seismic vessel operated by the U.S. academic community. With up to a four-string, 36-element source and four 6-km-long solid state hydrophone arrays, this vessel promises significant new insights into Earth science processes. The potential impact of anthropogenic sound sources on marine life is an important topic to the marine seismic community. To ensure that operations fully comply with existing and future marine mammal permitting requirements, a calibration experiment was conducted in the Gulf of Mexico in 2007-2008. Results are presented from deep (˜1.6 km) and shallow (˜50 m) water sites, obtained using the full 36-element (6600 cubic inches) seismic source. This array configuration will require the largest safety radii, and the deep and shallow sites provide two contrasting operational environments. Results show that safety radii and the offset between root-mean-square and sound exposure level measurements were highly dependent on water depth.

Talking Circles Promote Equitable Discourse

ERIC Educational Resources Information Center

Hung, Marcus

2015-01-01

Teachers facilitate math talk in the classroom, but introducing a structured discussion format called the "talking circle" can influence opportunities for equitable student participation. Drawing on his reflections over the 2013-14 academic year and reviewing his detailed teaching notes and lesson plans, Marcus Hung takes a close look at…

Education as Simulation Game: A Critical Hermeneutic.

ERIC Educational Resources Information Center

Palermo, James

1979-01-01

This paper examines a specific educational game called "Popcorn Factory." First, it gives a detailed description of the game, then shifts the description into a critical hermeneutical framework, analyzing the deep structures at work in the "Popcorn Factory" according to the theories of Freud and Marcuse. (Author/SJL)

Innovation and Creativity.

ERIC Educational Resources Information Center

1998

This document contains four papers from a symposium on innovation and creativity and their relationship to human resource development (HRD). "Intrapreneurial Programs and Their Impact on Sales, Profit, and Return to Investors" (Melissa H. Marcus, Dennis G. Tesolowski, Clinton H. Isbell) reports on a study in which 100 of 217 randomly…

Critical Thinking as Cultural-Historical Practice.

ERIC Educational Resources Information Center

Panofsky, Carolyn P.

1999-01-01

Explores critical thinking as it has been constructed in schooling and in dominant traditions of psychological theory, presenting a dialectical view of critical thinking suggested in the social and philosophical writings of critical theorists (e.g., Theodor Adorno and Herbert Marcuse) and supported by the sociohistorical or cultural-historical…

22. Photocopy of architectural drawing. (Original is in the collection ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

22. Photocopy of architectural drawing. (Original is in the collection of Richard F. McCann, Pasadena, CA.) Site Plan (Untitled). Dated May 3, 1934. Race Course for Mr. Joseph Gottstein, Washington Jockey Club. B. Marcus Priteca. - Longacres, 1621 Southwest Sixteenth Street, Renton, King County, WA

2012 ARPA-E Energy Innovation Summit: Profiling Sheetak: Low Cost - Solid State Cooling

ScienceCinema

Pokharna, Himanshu; Ghoshal, Uttam

2018-05-30

The third annual ARPA-E Energy Innovation Summit was held in Washington D.C. in February, 2012. The event brought together key players from across the energy ecosystem - researchers, entrepreneurs, investors, corporate executives, and government officials - to share ideas for developing and deploying the next generation of energy technologies. A few videos were selected for showing during the Summit to attendees. These "performer videos" highlight innovative research that is ongoing and related to the main topics of the Summit's sessions. Featured in this video are David Marcus, Founder of General Compression, and Eric Ingersoll, CEO of General Compression. Himanshu Pokharna, Vice President of Sheetak Uttam Ghoshal, President and CEO of Sheetak.

Regular Morphology and the Lexicon.

ERIC Educational Resources Information Center

Bybee, Joan

1995-01-01

This article compares three models of morphological storage and processing: (1) the dual-processing model of Pinker, Marcus and others; (2) the connectionist model of Marchman, Plunkett, Seidenberg, and others; and (3) the network model of Bybee and Langacker. Type frequency of a morphological pattern is shown to be important in determining…

Stability Analysis of Finite Difference Approximations to Hyperbolic Systems, and Problems in Applied and Computational Matrix Theory

DTIC Science & Technology

1988-07-08

Marcus and C. Baczynski), Computer Science Press, Rockville, Maryland, 1986. 3. An Introduction to Pascal and Precalculus , Computer Science Press...Science Press, Rockville, Maryland, 1986. 35. An Introduction to Pascal and Precalculus , Computer Science Press, Rockville, Maryland, 1986. 36

Understanding the Charter School Special Education Gap: Evidence from Denver, Colorado

ERIC Educational Resources Information Center

Winters, Marcus A.

2014-01-01

Center on Reinventing Public Education (CRPE) commissioned Dr. Marcus Winters to analyze the factors driving the special education gap between Denver's charter and traditional public elementary and middle schools. Using student-level data, Winters shows that Denver's special education enrollment gap starts at roughly 2 percentage points in…

2005 Armaments Technology Seminar and Exhibition

DTIC Science & Technology

2005-06-13

Carolina Sofer •Catina Crismale •Preparedness •Jason Emmel •Andrea Marcus •James Smith •Tim Phelan •Nikiesha Nicholas •Kathy Wioland •Mary Paczkowski • Jamie ...ASSESS PRI CATEGORY HPTs EFFECTS AGENCY ASSET AGENCY ASSET WHEN AGENCY ASSET 1 3 4 5 6 LAWTON Mayor Coop

The Perils of Repressive Tolerance in Music Education Curriculum

ERIC Educational Resources Information Center

Perrine, William M.

2017-01-01

In recent years, philosophers of music education have called for a greater degree of political engagement by music education practitioners. Using Marcuse's discussion of "repressive tolerance" as a conceptual framework, I argue that a politicized curriculum in music education works against the liberal ideas of free speech and a free…

An Archetypal Phenomenology of "Skholé"

ERIC Educational Resources Information Center

Kennedy, David

2017-01-01

In this essay David Kennedy argues that children represent one vanguard of an emergent shift in Western subjectivity, and that adult-child dialogue, especially in the context of schooling, is a key locus for the epistemological change that implies. Following Herbert Marcuse's invocation of a "new sensibility," Kennedy argues that the…

Approval of Alternative Test Method for Puerto Nuevo Wastewater Treatment Plant, San Juan, Puerto Rico Memorandum

EPA Pesticide Factsheets

This December 2008 memorandum is from Conniesue Oldham of the Measurement Technology Group to Marcus E. Kantz in EPA Region 2. This memorandum is regarding a request to use an alternative test method at the Puerto Neuvo wastewater treatment plant

Utopia and Education in Critical Theory

ERIC Educational Resources Information Center

Lewis, Tyson

2006-01-01

In this article the author examines the intimate connections between utopia and education in Frankfurt School critical theory. Although substantial links have been made in the critical pedagogy tradition between education, critique, and utopian dreaming, an in-depth analysis of the utopia-education matrix in the works of Herbert Marcuse, Theodor…

78 FR 49267 - Conflict of Interest Waiver

Federal Register 2010, 2011, 2012, 2013, 2014

2013-08-13

... FEDERAL COMMUNICATIONS COMMISSION Conflict of Interest Waiver AGENCY: Federal Communications Commission. ACTION: Notice of waiver of section 4(b) of the Communications Act of 1934. SUMMARY: Notice is... section 4(b) of the Communications Act of 1924, as amended, 47 U.S.C. 154(b), for Mr. Theodore Marcus...

22. Photocopy of architectural drawing. (Original is in the collection ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

22. Photocopy of architectural drawing. (Original is in the collection of Richard F. McCann, Pasadena, CA.) Grandstand Balcony Plan. Dated June 30, 1933. Race Course for Mr. Joseph Gottstein, Washington Jockey Club. B. Marcus Priteca. - Longacres, Original Grandstand, 1621 Southwest Sixteenth Street, Renton, King County, WA

lcmodels

Cancer.gov

The R package provides individual risks of lung cancer and lung cancer death based on various published papers: Bach et al., 2003; Spitz et al., 2007; Cassidy et al., 2008 (LLP); Hoggart et al., 2012; Tammemagi et al., 2013; Marcus et al., 2015 (LLPi); Wilson and Weissfeld, 2015 (Pittsburgh); Katki et al., 2016 (LCRAT and LCDRAT)

The NMC Horizon Report: 2013 Museum Edition

ERIC Educational Resources Information Center

Johnson, L.; Adams Becker, S.; Freeman, A.

2013-01-01

The "NMC Horizon Report: 2013 Museum Edition," is a co-production with the Marcus Institute for Digital Education in the Arts (MIDEA), and examines six emerging technologies for their potential impact on and use in education and interpretation within the museum environment: BYOD (Bring Your Own Device), crowdsourcing, electronic…

Gifted Sixth-Graders and Primary Source Philosophy.

ERIC Educational Resources Information Center

White, David A.; Schlaggar, Sheila

1993-01-01

A sixth-grade gifted class studied the history of philosophy, including selections from such philosophers as Plato, Confucius, Buddha, Marcus Aurelius, and Moses Maimonides. Readings drew on fundamental features of child experience, such as their sense of justice, concern for moral values, and questions about reality. The paper describes classroom…

Disrupting Myths of Poverty in the Face of Resistance

ERIC Educational Resources Information Center

Pollock, Katina; Lopez, Ann; Joshee, Reva

2013-01-01

This case disrupts some of the prevalent myths about families from low-income and poor households held by educators. Recognizing the inherent tensions, this case demonstrates the importance of creating equitable and inclusive learning environments. We presented some of the challenges faced by Marcus, a progressive principal, as he attempts to…

Re-Imagining Spaces, Collectivity, and the Political Dimension of Contemporary Art

ERIC Educational Resources Information Center

Peters, Clorinde

2015-01-01

In a neoliberal moment of cultural production marked by commodification and the dominance of economic values, it is necessary to investigate the cultural, social, and aesthetic value of art. By examining Herbert Marcuse's aesthetic dimension, this article seeks to locate the political and pedagogic potential both in the aesthetics and in the…

Molecular Dynamics Simulations of the Hydrogen Peroxyl Radical

DTIC Science & Technology

2014-05-01

Pasta , and Ulam10 (FPU) on the equipartion of energy in a one-dimensional anharmonic chain of oscillators yielded results that surprised the...Slater, Proc. Camb. Phil. Soc. 35, 56 (1939). 9 R. A. Marcus, J. Chem. Phys. 20, 359 (1952). 10 E. Fermi, J. R. Pasta , and S. M. Ulam, Los Alamos

The Voice of Authority

ERIC Educational Resources Information Center

Wetterlund, Kris

2012-01-01

In the last part of 2011, conversations swirled around the Internet and print about the assault on museum authority. The Marcus Institute for Digital Education in the Arts (MIDEA) summarized some of the discussion in their blog entry "The Participatory Museum and a New Authority." Other sites joined in the discussion, for example, the Museum Geek…

20 CFR Appendix A to Subpart F of... - U.S. Seaports

Code of Federal Regulations, 2010 CFR

2010-04-01

... Port, LA New Orleans, LA Beaumont, TX Brownsville, TX Corpus Christi, TX Freeport, TX Galveston, TX..., MA Fall River, MA New Bedford, MA Providence, RI Bridgeport, CT New Haven, CT New London, CT Albany, NY New York, NY/NJ Camden, NJ Gloucester City, NJ Paulsboro, NJ Chester, PA Marcus Hook, PA...

Factors Associated with Transitional Shifts in College Students' Physical Activity Behavior

ERIC Educational Resources Information Center

Levy, Susan S.; Cardinal, Bradley J.

2006-01-01

The Transtheoretical Model (Prochaska & Marcus, 1994) has been widely used as a framework for understanding exercise behavior change. The purpose of this study was to clarify equivocal research findings reported for model predictions when examining stage movement over time rather than static stages and to provide some evidence of the construct…

Return on Investment in the Public Sector

DTIC Science & Technology

2004-12-01

of Corporate Finance . 4th Ed. New York: McGraw-Hill/Irwin, 2004. Brook, Douglas A. <dabrook@nps.navy.mil> “CNO Visit.” [E-mail to Larry Jones...Analysis: Concepts and Practice. 10th Ed. Upper Saddle River: Prentice Hall, 1996. Brealey, Richard, Alan J. Marcus, and Stewart C. Myers. Fundamentals

Neoteny, Dialogic Education and an Emergent Psychoculture: Notes on Theory and Practice

ERIC Educational Resources Information Center

Kennedy, David

2014-01-01

This article argues that children represent one vanguard of an emergent shift in Western subjectivity, and that adult-child dialogue, especially in the context of schooling, is a key locus for the epistemological change that implies. Following Herbert Marcuse's invocation of a "new sensibility", the author argues that the…

Charge transfer in model peptides: obtaining Marcus parameters from molecular simulation.

PubMed

Heck, Alexander; Woiczikowski, P Benjamin; Kubař, Tomáš; Giese, Bernd; Elstner, Marcus; Steinbrecher, Thomas B

2012-02-23

Charge transfer within and between biomolecules remains a highly active field of biophysics. Due to the complexities of real systems, model compounds are a useful alternative to study the mechanistic fundamentals of charge transfer. In recent years, such model experiments have been underpinned by molecular simulation methods as well. In this work, we study electron hole transfer in helical model peptides by means of molecular dynamics simulations. A theoretical framework to extract Marcus parameters of charge transfer from simulations is presented. We find that the peptides form stable helical structures with sequence dependent small deviations from ideal PPII helices. We identify direct exposure of charged side chains to solvent as a cause of high reorganization energies, significantly larger than typical for electron transfer in proteins. This, together with small direct couplings, makes long-range superexchange electron transport in this system very slow. In good agreement with experiment, direct transfer between the terminal amino acid side chains can be dicounted in favor of a two-step hopping process if appropriate bridging groups exist. © 2012 American Chemical Society

Marcus Gunn jaw-winking synkinesis: clinical features and management.

PubMed

Demirci, Hakan; Frueh, Bartley R; Nelson, Christine C

2010-07-01

To evaluate the clinical features including eyelid excursion and management of Marcus Gunn jaw-winking synkinesis (MGJWS). Observational case series. Forty-eight consecutive patients with MGJWS. Clinical features and management of 48 patients with MGJWS were reviewed retrospectively. Upper eyelid excursion was measured and graded. Complications of surgical intervention were evaluated. Resolution of MGJWS and symmetry of upper eyelids in primary position. Excursion of the ptotic eyelid with jaw movement in MGJWS was graded as mild (<2 mm) in 16% of patients, moderate (2-4 mm) in 76% of patients, and severe (> or = 5 mm) in 8% of patients. Thirty patients with moderate or severe MGJWS underwent disabling of the involved levator muscle and bilateral or unilateral frontalis suspension and had more than 6 months of follow-up. After a mean follow-up of 62 months, MGJWS resolved in 29 (97%) patients and improved from 6 mm to 2 mm in 1 (3%) patient. Relative upper eyelid height was within 1 mm in 87% of patients in primary position and within 1 mm in 80% of patients in downgaze. Twenty-six patients had bilateral frontalis suspension with disabling of unilateral levator muscle on the involved side. Relative upper eyelid height was within 1 mm in 88% of patients in the primary position and within 1 mm in 88% of patients in downgaze. Four non-amblyopic patients had unilateral frontalis suspension with levator muscle disabling. Relative upper eyelid height was symmetrical in 75% of the patients in primary position and in 25% of patients in downgaze. Complications included eyelash ptosis in 10% of the patients, loss of eyelid crease in 10%, and entropion in 3%. Most of the patients with MGJWS exhibited moderate eyelid excursion. Disabling of the involved levator muscle and bilateral frontalis suspension and, in selected cases, disabling of the involved levator muscle and unilateral frontalis suspension were effective in the treatment of MGJWS. Eyelash ptosis and loss of eyelid crease were the most common complications, each occurring in 10% of the patients. The author(s) have no proprietary or commercial interest in any materials discussed in this article. Copyright 2010 American Academy of Ophthalmology. Published by Elsevier Inc. All rights reserved.

2012 ARPA-E Energy Innovation Summit: Profiling Sheetak: Low Cost - Solid State Cooling

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

Pokharna, Himanshu; Ghoshal, Uttam

The third annual ARPA-E Energy Innovation Summit was held in Washington D.C. in February, 2012. The event brought together key players from across the energy ecosystem - researchers, entrepreneurs, investors, corporate executives, and government officials - to share ideas for developing and deploying the next generation of energy technologies. A few videos were selected for showing during the Summit to attendees. These "performer videos" highlight innovative research that is ongoing and related to the main topics of the Summit's sessions. Featured in this video are David Marcus, Founder of General Compression, and Eric Ingersoll, CEO of General Compression. Himanshu Pokharna,more » Vice President of Sheetak Uttam Ghoshal, President and CEO of Sheetak.« less

The plague under Marcus Aurelius and the decline and fall of the Roman Empire.

PubMed

Fears, J Rufus

2004-03-01

The Roman Empire of the second century was a superpower that, in relative terms, dominated its world as much as the United States does today. In 166 AD, a plague broke out od pandemic proportions. The pandemic ravaged the entire extent of the Roman Empire, from its eastern frontiers in Iraq to its western frontiers on the Rhine River and Gaul, modern France, and western Germany. The disease is identified most often as smallpox, but it may have been anthrax. The study of bacterial DNA may enable identification of this plague that ravaged the Roman Empire at recurrent intervals for more than 100 years and that had a significant role in the decline and fall of this great superpower.

Driving force analysis of proton tunnelling across a reactivity series for an enzyme-substrate complex.

PubMed

Hothi, Parvinder; Hay, Sam; Roujeinikova, Anna; Sutcliffe, Michael J; Lee, Michael; Leys, David; Cullis, Paul M; Scrutton, Nigel S

2008-11-24

Quantitative structure-activity relationships are widely used to probe C-H bond breakage by quinoprotein enzymes. However, we showed recently that p-substituted benzylamines are poor reactivity probes for the quinoprotein aromatic amine dehydrogenase (AADH) because of a requirement for structural change in the enzyme-substrate complex prior to C-H bond breakage. This rearrangement is partially rate limiting, which leads to deflated kinetic isotope effects for p-substituted benzylamines. Here we report reactivity (driving force) studies of AADH with p-substituted phenylethylamines for which the kinetic isotope effect (approximately 16) accompanying C-H/C-(2)H bond breakage is elevated above the semi-classical limit. We show bond breakage occurs by quantum tunnelling and that within the context of the environmentally coupled framework for H-tunnelling the presence of the p-substituent places greater demand on the apparent need for fast promoting motions. The crystal structure of AADH soaked with phenylethylamine or methoxyphenylethylamine indicates that the structural change identified with p-substituted benzylamines should not limit the reaction with p-substituted phenylethylamines. This is consistent with the elevated kinetic isotope effects measured with p-substituted phenylethylamines. We find a good correlation in the rate constant for proton transfer with bond dissociation energy for the reactive C-H bond, consistent with a rate that is limited by a Marcus-like tunnelling mechanism. As the driving force becomes larger, the rate of proton transfer increases while the Marcus activation energy becomes smaller. This is the first experimental report of the driving force perturbation of H-tunnelling in enzymes using a series of related substrates. Our study provides further support for proton tunnelling in AADH.

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

Howell, Matthew D.; McLellan, Jason G.

This report summarizes catch data collected from white sturgeon Acipenser transmontanus in Lake Roosevelt during limited setlining and gill netting activities in the fall of 2003, and documents progress toward development of a U.S. white sturgeon conservation aquaculture program for Lake Roosevelt. From 27-30 October, 42 overnight small mesh gill net sets were made between Marcus and Northport, WA for a total catch of 15 juvenile white sturgeon (275-488 mm FL). All sturgeon captured were of Canadian hatchery origin. These fish had been previously released as sub-yearlings into the Canadian portion (Keenleyside Reach) of the Transboundary Reach of the Columbiamore » River during 2002 and 2003. Most sturgeon (n=14) were caught in the most upstream area sampled (Northport) in low velocity eddy areas. Five fish exhibited pectoral fin deformities (curled or stunted). Growth rates were less than for juvenile sturgeon captured in the Keenleyside Reach but condition factor was similar. Condition factor was also similar to that observed in juvenile sturgeon (ages 1-8) captured in the unimpounded Columbia River below Bonneville Dam between 1987-92. From 10-14 November, 28 overnight setline sets were made in the Roosevelt Reach between the confluence of the Spokane River and Marcus Island for a total catch of 17 white sturgeon (94-213 cm FL). Catch was greatest in the most upstream areas sampled, a distribution similar to that observed during a WDFW setline survey in Lake Roosevelt in 1998. The mean W{sub r} index of 110% for fish captured this year was higher than the mean W{sub r} of 91% for fish captured in 1998. Excellent fish condition hindered surgical examination of gonads as lipid deposits made the ventral body wall very thick and difficult to penetrate with available otoscope specula. Acoustic tags (Vemco model V16 coded pingers, 69 kHz, 48-month life expectancy) were internally applied to 15 fish for subsequent telemetry investigations of seasonal and reproductively motivated movements. In August 2003, three Vemco VR2 fixed station acoustic receivers, supplied by the UCWSRI Transboundary Telemetry Project, were deployed in the vicinities of Kettle Falls Bridge, Marcus Island, and Northport, WA. Data downloaded from these receivers through December 2003 confirmed the findings of a previous telemetry study that the Marcus area is an important overwintering habitat for white sturgeon. On 18 February 2004, juvenile white sturgeon (n=2,000) were transported from Kootenay Sturgeon Hatchery in British Columbia to WDFW Columbia Basin Hatchery (CBH) in Moses Lake, WA. Fish were reared at CBH to approximately 30 g and individually outfitted with PIT tags and scute marked. On 11 May 2004, fish were released into Lake Roosevelt in the vicinities of Kettle Falls Bridge, North Gorge, and Northport.« less

The Tiberias Basin salt deposits and their effects on lake salinity

NASA Astrophysics Data System (ADS)

Inbar, Nimrod; Rosenthal, Eliahu; Möller, Peter; Yellin-Dror, Annat; Guttman, Josef; Siebert, Christian; Magri, Fabien

2015-04-01

Lake Tiberias is situated in one of the pull-apart basins comprising the Dead Sea transform. The Tiberias basin extends along the northern boundary of the Lower Jordan Rift Valley (LJRV) which is known for its massive salt deposits, mostly at its southern end, at the Dead Sea basin. Nevertheless, prior to the drilling of Zemah-1 wildcat, drilled close to the southern shores of Lake Tiberias, the Tiberias Basin was considered rather shallow and free of salt deposits (Starinsky, 1974). In 1983, Zemah-1 wildcat penetrated 2.8 km thick sequence of sedimentary and magmatic rocks of which 980m are salt deposits (Marcus et al., 1984). Recent studies, including the presented geophysical investigations, lay out the mechanisms of salt deposition in the Tiberias basin and estimate its abundance. Supported by seismic data, our interpreted cross-sections display relatively thick salt deposits distributed over the entire basin. Since early days of hydrological research in the area, saline springs are known to exist at Lake Tiberias' surroundings. Water temperatures in some of the springs indicate their origin to be at depths of 2-3 km (Simon and Mero, 1992). In the last decade, several studies suggested that the salinity of springs may be attributed, at least partially, to the Zemah-1 salt deposits. Chemical justification was attributed to post-halite minerals which were thought to be present among those deposits. This hypothesis was never verified. Moreover, Möller et al. (2011) presented a calculation contradicting this theory. In addition to the geophysical investigations, numerical models of thermally driven flow, examine the possible fluid dynamics developing near salt deposits below the lake and their interactions with springs along the lakeshore (Magri et al., 2015). It is shown that leached halite is too heavy to reach the surface. However, salt diffusing from shallow salt crest may locally reach the western side of the lakeshore. References Magri, F., N. Inbar,C. Siebert, E. Rosenthal, J. Guttman and P. Möller (2015) Transient simulations of large-scale hydrogeological processes causing temperature and salinity anomalies in the Tiberias Basin, Journal of Hydrology, Volume 520, Pages 342-355, Marcus, E., Y. Slager, S. Ben-Zaken, and I. Y. Indik (1984), Zemah 1, Geological Complition ReportRep. 84/11, 108 pp, Oil Exploration (Investments) LTD, Tel Aviv. Möller, P., C. Siebert, S. Geyer, N. Inbar, E. Rosenthal, A. Flexer, and M. Zilberbrand (2011), Relationships of Brines in the Kinnarot Basin, Jordan-Dead Sea Rift Valley, Geofluids (doi: 10.1111/j.1468-8123.2011.00353.x). Simon, E., and F. Mero (1992), The salinization mechanism of Lake Kinneret, J. Hydrol., 138, 327-343. Starinsky, A. (1974), Relationship between Ca-Chloride Brines and Sedimentary Rocks in Israel, PhD thesis, 84 pp, Hebrew University, Jerusalem.

Methods for Scaling to Doubly Stochastic Form,

DTIC Science & Technology

1981-06-26

Frobenius -Konig Theorem (MARCUS and MINC [1964],p 97) A nonnegative n xn matrix without support contains an s x t zero subma- trix where: s +t =n + -3...that YA(k) has row sums 1. Then normalize the columns by a diagonal similarity transform defined as follows: Let x = (zx , • z,,) be a left Perron vector

Fostering Persistence: 3D Printing and the Unforeseen Impact on Equity

ERIC Educational Resources Information Center

FitzPatrick, Daniel L.; Dominguez, Victoria S.

2017-01-01

Teaching persistence and problem solving must begin with selecting a problem that can be solved mathematically, that allows for multiple methods of solving, and that generally captures the attention and curiosity of the student (Marcus and Fey 2003; NCTM 1991; Van de Walle 2003). This article shows how a STEM three-dimensional (3D) printing…

Herbert Marcuse's Theory of Play--A Social Philosophical Perspective.

ERIC Educational Resources Information Center

Volkwien, Karin A. E.

Sport has been widely discussed, by conservatives who argue that sport operates within the realm of freedom, and so lies outside the deterministic nexus of capitalist economics and policies, and leftists who argue that sport reproduces the repressive features of capitalism and serves as an ideological tool of the latter. The purpose of this study…

Joint Services Electronics Program (Harvard University. Cambridge, Massachusetts)

DTIC Science & Technology

1988-09-30

34Band Structures of Semimagnetic Compounds," Acta Physica Polonica bf A73 (6), 933-941 (1988). (Partially supported by N00014-86-K-0760). c. Books...Journals K.L. Babcock and R.M. Westervelt, "Dynamics of Simple Electronic neural Net- works," Physica 28D, 305 (1987). C.M. Marcus and R.M. Westervelt

Naive Probability: Model-based Estimates of Unique Events

DTIC Science & Technology

2014-05-04

Gilio & Over, 2012) – a possibility to which we return later. Despite these studies...Barrouillet, Jean-François Bonnefon, Nick Cassimatis, Nick Chater, Ernest Davis, Igor Douven, Angelo Gilio , Adam Harris, Gernot Kleiter, Gary Marcus, Ray...1230-1239. Gilio , A., & Over, D. (2012). The psychology of inferring conditionals from disjunctions: A probabilistic study. Journal of

The Rapid Detection of Single Bacterial Cells by Deep UV Micro Raman Spectroscopy.

DTIC Science & Technology

1992-04-01

Saltzman and C.T. Gregg, Appl. Environ. Microbiol. 44, 1081 (1982). 14. D.’. Mc Greggor, W.K. Grace and G.C. Salzman, in "Rapid Methods and...was used by Dr. Marcus Peter of the Dana -Farber Cancer Institute. During that period he came to our laboratories weekly to study GTP- binding

"Spreading the Love" and Using Performances to Prevent Rape

ERIC Educational Resources Information Center

Murphy, Aurora

2013-01-01

While rape is ordinarily considered an invariable reality, Sharon Marcus argues that it is instead a cultural script, which casts women as victims and men as perpetrators. In imagining rape as a script, it may seem pertinent to suggest that the arts and performance have a role in its prevention. Performances can provide a forum to publicly reflect…

76 FR 26255 - Takes of Marine Mammals Incidental to Specified Activities; Marine Geophysical Survey in the...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-06

..., the R/V Marcus G. Langseth (Langseth) and a seismic airgun array to collect seismic reflection and... possible, depending on logistics and weather. The proposed seismic survey will collect seismic reflection... Shillington, Spahr Webb, and Mladen Nedimovic, all of L-DEO. The vessel will be self-contained, and the crew...

A Navy Escrow Account: Increasing Financial Flexibility

DTIC Science & Technology

2003-06-01

generate cost savings and the means by which those funds could be recapitalized. The creation of an escrow account coincides with the Navy’s Sea...Navy escrow account , as envisioned, would provide financial managers with the incentive to generate cost savings and the means by which those funds...MONTEREY, CALIFORNIA CONRAD ESSAY A Navy Escrow Account : Increasing Financial Flexibility By: Commander Marcus A. Pritchard

Quenching of Emission and of Photochemistry for Aqueous Rh(NH3)5Cl(2+).

DTIC Science & Technology

1979-04-01

Hueneme, CalifornIa 93041 Attn: Dr. R. 3. Marcus 1 Attn: Mr. W. S. Haynes ONR Branch Offi ce Professor 0. Hein7 760 Market Street , Rm. 447...Peebles 1 WashI ngton, D.C. 20380 Directo r, Naval Research Laboratory Offi ce of Naval Researc hWashington, D.C. 20390 Arlington, VIrginia 22217

Electron transfer rate on mixed valence states of Class II/III transition for N, N'-diphenyl-1,4-phenylenediamine structures as a polyaniline unit

NASA Astrophysics Data System (ADS)

Nishiumi, Toyohiko; Nomura, Yasuhiro; Higuchi, Masayoshi; Yamamoto, Kimihisa

2003-08-01

The first example of the determination of the electron transfer rate ( λ, V, Δ G*, kth) for N, N'-diphenyl-1,4-phenylenediamine derivatives using the Marcus-Hush theory is described. These results were in good agreement with the ones obtained using variable-temperature IR spectra measurements.

Theory, Observation, and Validation: Commentary on Almond, Kim, Velasquez, & Shute

ERIC Educational Resources Information Center

Markus, Keith A.

2014-01-01

Keith Marcus congratulates Almond et al. on an interesting article bringing together two topics that are important to the field of testing. He states that some aspects of the exposition came across as not yet fully developed, as if the manuscript had been hurried to press. In this commentary, he attempts to expand aspects of the article, which he…

78 FR 18340 - The Neiman Marcus Group, Inc.; Dr.Jays.com, Inc., Eminent, Inc.; Analysis of Proposed Consent...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-26

... heightened security screening. As a result, we encourage you to submit your comments online. To make sure...'' or ``Eminent, File No. 122 3065'' on your comment and file your comment online at https://ftcpublic... prefer to file your comment on paper, mail or deliver your comment to the following address: Federal...

77 FR 6065 - Takes of Marine Mammals Incidental to Specified Activities; Marine Geophysical Survey in the...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-07

... day public comment period. L-DEO plans to use one source vessel, the R/V Marcus G. Langseth (Langseth... (km) 1,511.9 nautical miles [nmi]) of transect lines (including turns) in the study area. The seismic... involve one source vessel, the Langseth. The Langseth will deploy an array of 36 airguns as an energy...

Sorry Dave, I’m Afraid I Can’t Do That: Explaining Unachievable Robot Tasks using Natural Language

DTIC Science & Technology

2013-06-24

processing components used by Brooks et al. [6]: the Bikel parser [3] combined with the null element (understood subject) restoration of Gabbard et al...Intelligent Robots and Systems (IROS), pages 1988 – 1993, 2010. [12] Ryan Gabbard , Mitch Marcus, and Seth Kulick. Fully parsing the Penn Treebank. In Human

Geometric Computation of Human Gyrification Indexes from Magnetic Resonance Images

DTIC Science & Technology

2009-04-01

GEOMETRIC COMPUTATION OF HUMAN GYRIFICATION INDEXES FROM MAGNETIC RESONANCE IMAGES By Shu Su Tonya White Marcus Schmidt Chiu-Yen Kao and Guillermo...00-2009 to 00-00-2009 4. TITLE AND SUBTITLE Geometric Computation of Human Gyrification Indexes from Magnetic Resonance Images 5a. CONTRACT NUMBER... Geometric Computation of Gyrification Indexes Chiu-Yen Kao 1 Geometric Computation of Human Gyrification

Unclassified Publications of Lincoln Laboratory 1 January - 31 December 1994, Volume 20.

DTIC Science & Technology

1994-12-31

J. Ehrlich, DJ. Hollis, M.A. Kosicki, B.B. Powdrill, T. Beattie, K. Smith, S. Varma, R. Gangadharan, R. Mallik , A. Burke, B.E. Wallace, D...JA-6972, JA-7028 Mallik , A., JA-7164 Manfra, M.J., JA-7027, MS-10604 Mankiewich, P.M., JA-7001 Maragos, P., JA-6764, JA-6888 Marcus, S., JA-6898

Dog Is a Dog Is a Dog: Infant Rule Learning Is Not Specific to Language

ERIC Educational Resources Information Center

Saffran, Jenny R.; Pollak, Seth D.; Seibel, Rebecca L.; Shkolnik, Anna

2007-01-01

Human infants possess powerful learning mechanisms used for the acquisition of language. To what extent are these mechanisms domain specific? One well-known infant language learning mechanism is the ability to detect and generalize rule-like similarity patterns, such as ABA or ABB [Marcus, G. F., Vijayan, S., Rao, S. B., & Vishton, P. M. (1999).…

Marcuse, Bloch and Freire: Reinvigorating a Pedagogy of Hope

ERIC Educational Resources Information Center

Van Heertum, Richard

2006-01-01

Critique of the current order of things is a necessary starting point for any project for radical change. Without an analysis of what is wrong, it is hard to convince anyone that change is necessary. And yet critique alone rarely inspires people to act. We need something to fight for as well as against. The article looks at the centrality of hope…

Toward a Broader Dialectic: Joining Marxism with Mailer to Forge a Multilectics That Advances Teaching and Learning

ERIC Educational Resources Information Center

Fellner, Gene

2014-01-01

I contrast the lenses that Norman Mailer, Herbert Marcuse, and Karl Marx bring to their analyses of social life, exploring the contributions and limits of their respective approaches. I then propose what I call a "multilectical" theoretical lens that encompasses the strengths of all three and leans on the insights of post-Marxist…

Information from Multiple Modalities Helps 5-Month-Olds Learn Abstract Rules

ERIC Educational Resources Information Center

Frank, Michael C.; Slemmer, Jonathan A.; Marcus, Gary F.; Johnson, Scott P.

2009-01-01

By 7 months of age, infants are able to learn rules based on the abstract relationships between stimuli ( Marcus et al., 1999 ), but they are better able to do so when exposed to speech than to some other classes of stimuli. In the current experiments we ask whether multimodal stimulus information will aid younger infants in identifying abstract…

Distal [FeS]-Cluster Coordination in [NiFe]-Hydrogenase Facilitates Intermolecular Electron Transfer

PubMed Central

Petrenko, Alexander; Stein, Matthias

2017-01-01

Biohydrogen is a versatile energy carrier for the generation of electric energy from renewable sources. Hydrogenases can be used in enzymatic fuel cells to oxidize dihydrogen. The rate of electron transfer (ET) at the anodic side between the [NiFe]-hydrogenase enzyme distal iron–sulfur cluster and the electrode surface can be described by the Marcus equation. All parameters for the Marcus equation are accessible from Density Functional Theory (DFT) calculations. The distal cubane FeS-cluster has a three-cysteine and one-histidine coordination [Fe4S4](His)(Cys)3 first ligation sphere. The reorganization energy (inner- and outer-sphere) is almost unchanged upon a histidine-to-cysteine substitution. Differences in rates of electron transfer between the wild-type enzyme and an all-cysteine mutant can be rationalized by a diminished electronic coupling between the donor and acceptor molecules in the [Fe4S4](Cys)4 case. The fast and efficient electron transfer from the distal iron–sulfur cluster is realized by a fine-tuned protein environment, which facilitates the flow of electrons. This study enables the design and control of electron transfer rates and pathways by protein engineering. PMID:28067774

Insights into crustal structure of the Eastern North American Margin from community multichannel seismic and potential field data

NASA Astrophysics Data System (ADS)

Davis, J. K.; Becel, A.; Shillington, D. J.; Buck, W. R.

2017-12-01

In the fall of 2014, the R/V Marcus Langseth collected gravity, magnetic, and reflection seismic data as part of the Eastern North American Margin Community Seismic Experiment. The dataset covers a 500 km wide section of the Mid-Atlantic passive margin offshore North Carolina, which formed after the Mesozoic breakup of the supercontinent Pangaea. Using these seismic and potential field data, we present observations and interpretations along two cross margin and one along-margin profiles. Analyses and interpretations are conducted using pre-stack depth migrated reflection seismic profiles in conjunction with forward modeling of shipboard gravity and magnetic anomalies. Preliminary interpretations of the data reveal variations in basement character and structure across the entire transition between continental and oceanic domains. These interpretations help provide insight into the origin and nature of the prominent East Coast and Blake Spur magnetic anomalies, as well as the Inner Magnetic Quiet Zone which occupies the domain between the anomalies. Collectively, these observations can aid in deciphering the rift-to-drift transition during the breakup of North America and West Africa and formation of the Central Atlantic.

The Mercantile Business Coalition: A Narrative Analysis of a Learning Organization in an African American Community

ERIC Educational Resources Information Center

Harrell, Alma S.

2013-01-01

"A race that is solely dependent upon another for its economic existences sooner or later dies," this quote by Marcus Garvey highlighted the need for African American communities to think about the importance of economic development. This message was also heard by African Americans as early as the 1700s. Not only was the message about…

First Approach of Pneumatic Anthropomorphic Hand

DTIC Science & Technology

2001-10-25

1 o f 3 FIRST APPROACH OF PNEUMATIC ANTHROPOMORPHIC HAND Jiménez, Omar; Leija, Lorenzo; Muñoz, Roberto Centro de Investigación y de Estudios...weight and minimum consumption, minimum control and natural appearance. Keywords- Anthropomorphic, hand, Pneumatic system, Prosthesis 1 . INTRODUCTION...The projects have been guided through an specific line of development. The project MARCUS[ 1 ] includes easiness as the most important aspect what

Toward a Critique of the Information Age: Herbert Marcuse's Contribution to Information Science's Conceptions

ERIC Educational Resources Information Center

Cibangu, Sylvain K.

2013-01-01

Introduction: Just as we have created them, the new social media technologies have shaped every aspect of our societies. Meanwhile, information science has hardly addressed the ways in which these information technologies have shaped humans, and vice-versa. The major reason is the tendency and pressure to adjust (the needs of) humans to the ever…

Sequence to Sequence - Video to Text

DTIC Science & Technology

2015-12-11

Saenko, and S. Guadarrama. Generating natural-language video descriptions using text - mined knowledge. In AAAI, July 2013. 2 [20] P. Kuznetsova, V...Sequence to Sequence – Video to Text Subhashini Venugopalan1 Marcus Rohrbach2,4 Jeff Donahue2 Raymond Mooney1 Trevor Darrell2 Kate Saenko3...1. Introduction Describing visual content with natural language text has recently received increased interest, especially describing images with a

A Comparison of Intranasal and Oral Scopolamine for Motion Sickness Prevention in Military Personnel

DTIC Science & Technology

2008-08-18

Cornum, Caldwell & Cornum, 1997; Cowings et al., 1996; Golding & Stott, 1997; Marcus & Furman, 2006; Putcha, 1999; Wood & Graybiel, 1968). The most...performance effects (Lewandowski, Dietz, & Reeves, 1997; Elsmore, Reeves & Reeves, 2007; Kane , Roebuck-Spenser, Short, Kabat & Wilken, 2007; Wilken...Sullivan, Lewandowski & Kane , 2007). Visual acuity assessment An RAF rule (Neely, 1956) was used to measure visual accommodation (near-focus

An Examination of a Virtual Private Network Implementation to Support a Teleworking Initiative: The Marcus Food Company Inc. Case Study

ERIC Educational Resources Information Center

Ferguson, Jason W.

2010-01-01

In this dissertation, the author examined the capabilities of virtual private networks (VPNs) in supporting teleworking environments for small businesses in the food marketing sector. The goal of this research was to develop an implementation model for small businesses in the food marketing sector that use a VPN solution to support teleworker…

77 FR 4765 - Takes of Marine Mammals Incidental to Specified Activities; Marine Geophysical Survey in the...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-31

... to complete the abbreviated 2010 study. L-DEO plans to use one source vessel, the R/V Marcus G... will serve as a spare and will be turned on in case of failure of one of the other airguns. The... [email protected] . NMFS is not responsible for email comments sent to addresses other than the one...

Learning to Be Precarious--The Transition of Young People from School into Precarious Work in Germany

ERIC Educational Resources Information Center

Eckelt, Marcus; Schmidt, Guido

2015-01-01

The integration of young adults into the labor market is a challenge for every society. Because Germany survived the current crisis quite well and youth unemployment rate is more or less stable, the German apprenticeship-system, Duale Ausbildung, became a kind of new role model in Europe. In this article Marcus Eckelt and Guido Schmidt analyze the…

NEPC Review: "New York Charter Schools Outperform Traditional Selective Public Schools--More Evidence That Cream-Skimming Is Not Driving Charters' Success"

ERIC Educational Resources Information Center

Cordes, Sarah A.

2017-01-01

A common argument leveled against charter schools is that they attract the most motivated and intelligent students from already struggling public schools. Marcus Winters seeks to examine this claim, known as "cream-skimming," by comparing the performance of New York City's (NYC) charter middle schools with a set of traditional selective…

The Limits of Soviet Airpower: The Bear Versus the Mujahideen in Afghanistan, 1979-1989

DTIC Science & Technology

1997-06-01

satellite imagery identified Soviet TMS-65 decontamination vehicles and AGV-3 detox chambers in the vicinity of combat areas. In addition, the...Vladislav Tamarov, Afghanistan: Soviet Vietnam, trans. Naomi Marcus, Marianne Clarke Trangen, and Vladislav Tamarov (San Francisco: Mercury House...Tamarov. San Francisco: Mercury House, 1992. Turbiville, Graham. Ambush! The Road War in Afghanistan. Fort Leavenworth, KS: Soviet Army Studies Office

Scaling Bulk Data Analysis with Mapreduce

DTIC Science & Technology

2017-09-01

Submitted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE IN COMPUTER SCIENCE from the NAVAL POSTGRADUATE SCHOOL September...2017 Approved by: Michael McCarrin Thesis Co-Advisor Marcus S. Stefanou Thesis Co-Advisor Peter J. Denning Chair, Department of Computer Science iii...98 xiii THIS PAGE INTENTIONALLY LEFT BLANK xiv List of Acronyms and Abbreviations CART Computer Analysis and Response Team DELV Distributed Environment

Stochastic Adaptive Estimation and Control.

DTIC Science & Technology

1994-10-26

Marcus, "Language Stability and Stabilizability of Discrete Event Dynamical Systems ," SIAM Journal on Control and Optimization, 31, September 1993...in the hierarchical control of flexible manufacturing systems ; in this problem, the model involves a hybrid process in continuous time whose state is...of the average cost control problem for discrete- time Markov processes. Our exposition covers from finite to Borel state and action spaces and

The galenic plague: a breakdown of the imperial pathocoenosis. Pathocoenosis and longue durée.

PubMed

Gourevitch, Danielle

2005-01-01

Is 'pathocoenosis', a notion conceived and a word coined by Mirko Grmek (1969), useful as far as ancient history is concerned? The author is interested in Galenic pathocoenosis, that of doctor Galen and his Emperor Marcus Aurelius (IInd cent. A.D.), when a new 'pestilence' or 'plague' (smallpox?) devastated the whole empire, from Mesopotamia to the Danube at least.

Evidence of the Ideology of Marcus Fabius Quintilianus in Three Periods of American Educational Thought: 1750-1980

ERIC Educational Resources Information Center

Kasper, Beverly B.

2004-01-01

Nearly two thousand years ago, Quintilian wrote a guide for the education of the ideal citizen which combined theory with educational practice. He believed in the importance of early education, the place of play and joy in learning, the necessity to base education on students' individual patterns of growth and learning, the magnitude of the…

Preventing Point-of-Sale System Intrusions

DTIC Science & Technology

2014-06-01

executives from Target and Nieman Marcus prepared written testimonials in advance of several congressional hearings on retail data breaches the week...of February 05, 2014 (Associated Press, 2014; United States Senate, 2014). While the Target data breach attracted significant national attention due...other parts of the world, and whether Congress should pass a federal data breach notification law that would require businesses to notify customers if

[Marcus Aurelius Antonius (121-180AD), philosopher and Roman emperor, and Galen's plague].

PubMed

Muñoz-Sanz, Agustín

2012-11-01

The study of the aetiologies of diseases in Ancient Times is usually a speculative intellectual exercise. When some authors attribute a specific aetiology to an old disease, there is a great risk of committing a methodological error, known as presentism by the modern historiography. The authority of the investigator, more than the weight of the scientific truth, is usually the reason why the diagnosis has remained over the years. The great epidemic of the years 164-165AD and afterwards, could have been smallpox (haemorrhagic form). Claude Galen, the famous doctor, described the symptoms in several books of his great Opera Omnia. For this reason, it is currently known among the scholars as Galen's plague. The epidemic was described for the first time in Seleucia (Mesopotamia). Until now, the actual geographic origin is unknown. We propose here that the beginning might be the kingdom of the old Han dynasty (now the Chinese Popular Republic). The epidemic swept the Roman Empire, from the east to the west, and from the southern to the northern borders. An immediate consequence of the infection was a high morbidity and mortality. In this sense, Galen's epidemic was one of the many factors that caused the fall and destruction of the Roman Empire. On the other hand, there is a general agreement among historians, biographers and researchers that the philosopher emperor Marcus Aurelius Antoninus (121-180AD was affected by the infection in the epidemic wave of 164-165AD. The death of Marcus Aurelius occurred on March 17 in the year 180AD, in Vindobonne, or perhaps Sirminium (near to Vienna). Many authors propose that the cause of the emperor's death was the same epidemic. We consider that it is not possible to demonstrate any of those speculative diagnoses. Finally, the epidemic of 189-190AD, that we have named of Commodus, was probably a different disease to the Galen's plague. There were several kinds of animals affected (anthropozoonoses). In this sense, this infection resembles more the previous Athens plague (430BC) or the epidemic of Justinian (552AD) than that of Galen's. Copyright © 2012 Elsevier España, S.L. All rights reserved.

Crystal structure and charge transport properties of poly(arylene-ethynylene) derivatives: A DFT approach

NASA Astrophysics Data System (ADS)

Garzón, Andrés; Granadino-Roldán, José M.; García, Gregorio; Moral, Mónica; Fernández-Gómez, Manuel

2013-04-01

In the present study, a series of crystalline poly(arylene-ethynylene) copolymers containing phenylethynylene and 2,5-dialkoxy-phenylethynylene units together with 1,3,4-thiadiazole rings has been modeled by means of periodic calculations. Optimized three-dimensional polymeric structures show interchain distances that are consistent with the experimental values reported for a related polymer. It has also been observed that the presence of pendant alkoxy chains brings on both a further flattening and a separation of the coplanar chains. This fact is linked to a decrease of the interchain cofacial distance. The electron transport character of the polymer crystal structures was assessed through Marcus theory. Electronic coupling between neighboring polymer chains is most influenced by the presence of alkoxy chains giving rise to an expectable enhancement of the electron hopping mobility.

2012 ARPA-E Energy Innovation Summit: Profiling General Compression: A River of Wind

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

Marcus, David; Ingersoll, Eric

The third annual ARPA-E Energy Innovation Summit was held in Washington D.C. in February, 2012. The event brought together key players from across the energy ecosystem - researchers, entrepreneurs, investors, corporate executives, and government officials - to share ideas for developing and deploying the next generation of energy technologies. A few videos were selected for showing during the Summit to attendees. These 'performer videos' highlight innovative research that is ongoing and related to the main topics of the Summit's sessions. Featured in this video are David Marcus, Founder of General Compression, and Eric Ingersoll, CEO of General Compression. General Compression,more » with the help of ARPA-E funding, has created an advanced air compression process which can store and release more than a weeks worth of the energy generated by wind turbines.« less

2012 ARPA-E Energy Innovation Summit: Profiling General Compression: A River of Wind

ScienceCinema

Marcus, David; Ingersoll, Eric

2018-05-30

The third annual ARPA-E Energy Innovation Summit was held in Washington D.C. in February, 2012. The event brought together key players from across the energy ecosystem - researchers, entrepreneurs, investors, corporate executives, and government officials - to share ideas for developing and deploying the next generation of energy technologies. A few videos were selected for showing during the Summit to attendees. These 'performer videos' highlight innovative research that is ongoing and related to the main topics of the Summit's sessions. Featured in this video are David Marcus, Founder of General Compression, and Eric Ingersoll, CEO of General Compression. General Compression, with the help of ARPA-E funding, has created an advanced air compression process which can store and release more than a weeks worth of the energy generated by wind turbines.

Case Report: Rhabdomyolysis in Service Member Following SERE Physical Training

DTIC Science & Technology

2017-09-19

Member following SERE physical training. Sb. GRANT NUMBER Sc. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER Capt Matthew A Pombo Se. TASK...NOTES 14. ABSTRACT Case Report: Rhabdomyolysis in Service Member following SERE physical training. Authors: Matthew A. Pombo, DO (Capt, USAF...in Service Member following SERE physical training. Authors: Matthew A. Pombo, DO (Capt, USAF); Dwaipayan Chakraborti, MD (MAJ, USA); Joseph Marcus

DoD Global, Laboratory-Based, Influenza Surveillance Program, End-of-Year Report, 2014-2015

DTIC Science & Technology

2016-01-01

DeMarcus January 2016 Air Force Research Laboratory 711th Human Performance Wing U.S. Air Force School of Aerospace Medicine ...Public Health and Preventive Medicine Dept 2510 Fifth St. Wright-Patterson AFB, OH 45433-7913 DISTRIBUTION STATEMENT A. Approved for public release...PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) USAF School of Aerospace Medicine Public Health and Preventive Medicine Dept/PHR 2510 Fifth St

Integrated Cognition - A Proposed Definition of Ingredients, A Survey of Systems, and Example Architecture

DTIC Science & Technology

2004-10-01

Information Proc- essing Technology Office (IPTO) for their support of this work. We thank Dr. John Salasin for his vision in conceiving these...ingredients of cognition identified in the INCOG framework presented herein, including: Dr. John R. Anderson, Mr. Albert-Laszlo Barabasi, Dr...Goertzel, Professor Marvin Minsky, Dr. Robert Hecht-Nielsen, Dr. Marcus J. Huber, Dr. John Laird, Professor Pat Langley, Dr. Christian Lebiere, Dr

Ambient Temperature Rechargeable Lithium Cells: State of the Art; Problems and Opportunities.

DTIC Science & Technology

1982-12-01

Brigham Young University Dr. Royce W. Murray Provo, Utah 84602 1 Department of Chemistry University of North Carolina Dr. R. A. Marcus Chapel Hill, North...Chemistry Department Dr. Michael J. Weaver Massachusetts Institute Department of Chemistry of Technology Michigan State University Cambridge...Chudacek McGraw-Edison Company Dr. Janet Osteryoung Edison Battery Division Department of Chemistry Post Office Box 28 State University of Bloomfield

Guest and solvent modulated photo-driven charge separation and triplet generation in a perylene bisimide cyclophane

DOE PAGES

Spenst, Peter; Young, Ryan M.; Wasielewski, Michael R.; ...

2016-05-18

Cofacial positioning of two perylene bisimide (PBI) chromophores at a distance of 6.5 Å in a cyclophane structure prohibits the otherwise common excimer formation and directs photoexcited singlet state relaxation towards intramolecular symmetry-breaking charge separation (τ CS = 161 ± 4 ps) in polar CH 2Cl 2, which is thermodynamically favored with a Gibbs free energy of ΔG CS = –0.32 eV. The charges then recombine slowly in τ CR = 8.90 ± 0.06 ns to form the PBI triplet excited state, which can be used subsequently to generate singlet oxygen in 27% quantum yield. This sequence of events ismore » eliminated by dissolving the PBI cyclophane in non-polar toluene, where only excited singlet state decay occurs. In contrast, complexation of electron-rich aromatic hydrocarbons by the host PBI cyclophane followed by photoexcitation of PBI results in ultrafast electron transfer (<10 ps) from the guest to the PBI in CH 2Cl 2. As a result, the rate constants for charge separation and recombination increase as the guest molecules become easier to oxidize, demonstrating that charge separation occurs close to the peak of the Marcus curve and the recombination lies far into the Marcus inverted region.« less

A hybrid approach to simulation of electron transfer in complex molecular systems

PubMed Central

Kubař, Tomáš; Elstner, Marcus

2013-01-01

Electron transfer (ET) reactions in biomolecular systems represent an important class of processes at the interface of physics, chemistry and biology. The theoretical description of these reactions constitutes a huge challenge because extensive systems require a quantum-mechanical treatment and a broad range of time scales are involved. Thus, only small model systems may be investigated with the modern density functional theory techniques combined with non-adiabatic dynamics algorithms. On the other hand, model calculations based on Marcus's seminal theory describe the ET involving several assumptions that may not always be met. We review a multi-scale method that combines a non-adiabatic propagation scheme and a linear scaling quantum-chemical method with a molecular mechanics force field in such a way that an unbiased description of the dynamics of excess electron is achieved and the number of degrees of freedom is reduced effectively at the same time. ET reactions taking nanoseconds in systems with hundreds of quantum atoms can be simulated, bridging the gap between non-adiabatic ab initio simulations and model approaches such as the Marcus theory. A major recent application is hole transfer in DNA, which represents an archetypal ET reaction in a polarizable medium. Ongoing work focuses on hole transfer in proteins, peptides and organic semi-conductors. PMID:23883952

Calibration of the R/V Marcus G. Langseth Seismic Array in shallow Cascadia waters using the Multi-Channel Streamer

NASA Astrophysics Data System (ADS)

Crone, T. J.; Tolstoy, M.; Carton, H. D.

2013-12-01

In the summer of 2012, two multi-channel seismic (MCS) experiments, Cascadia Open-Access Seismic Transects (COAST) and Ridge2Trench, were conducted in the offshore Cascadia region. An area of growing environmental concern with active source seismic experiments is the potential impact of the received sound on marine mammals, but data relating to this issue is limited. For these surveys sound level 'mitigation radii' are established for the protection of marine mammals, based on direct arrival modeling and previous calibration experiments. Propagation of sound from seismic arrays can be accurately modeled in deep-water environments, but in shallow and sloped environments the complexity of local geology and bathymetry can make it difficult to predict sound levels as a function of distance from the source array. One potential solution to this problem is to measure the received levels in real-time using the ship's streamer (Diebold et al., 2010), which would allow the dynamic determination of suitable mitigation radii. We analyzed R/V Langseth streamer data collected on the shelf and slope off the Washington coast during the COAST experiment to measure received levels in situ up to 8 km away from the ship. Our analysis shows that water depth and bathymetric features can affect received levels in shallow water environments. The establishment of dynamic mitigation radii based on local conditions may help maximize the safety of marine mammals while also maximizing the ability of scientists to conduct seismic research. With increasing scientific and societal focus on subduction zone environments, a better understanding of shallow water sound propagation is essential for allowing seismic exploration of these hazardous environments to continue. Diebold, J. M., M. Tolstoy, L. Doermann, S. Nooner, S. Webb, and T. J. Crone (2010) R/V Marcus G. Langseth Seismic Source: Modeling and Calibration. Geochemistry, Geophysics, Geosystems, 11, Q12012, doi:10.1029/2010GC003216.

Equilibrium fluctuation relations for voltage coupling in membrane proteins.

PubMed

Kim, Ilsoo; Warshel, Arieh

2015-11-01

A general theoretical framework is developed to account for the effects of an external potential on the energetics of membrane proteins. The framework is based on the free energy relation between two (forward/backward) probability densities, which was recently generalized to non-equilibrium processes, culminating in the work-fluctuation theorem. Starting from the probability densities of the conformational states along the "voltage coupling" reaction coordinate, we investigate several interconnected free energy relations between these two conformational states, considering voltage activation of ion channels. The free energy difference between the two conformational states at zero (depolarization) membrane potential (i.e., known as the chemical component of free energy change in ion channels) is shown to be equivalent to the free energy difference between the two "equilibrium" (resting and activated) conformational states along the one-dimensional voltage couplin reaction coordinate. Furthermore, the requirement that the application of linear response approximation to the free energy functionals of voltage coupling should satisfy the general free energy relations, yields a novel closed-form expression for the gating charge in terms of other basic properties of ion channels. This connection is familiar in statistical mechanics, known as the equilibrium fluctuation-response relation. The theory is illustrated by considering the coupling of a unit charge to the external voltage in the two sites near the surface of membrane, representing the activated and resting states. This is done using a coarse-graining (CG) model of membrane proteins, which includes the membrane, the electrolytes and the electrodes. The CG model yields Marcus-type voltage dependent free energy parabolas for the response of the electrostatic environment (electrolytes etc.) to the transition from the initial to the final configuratinal states, leading to equilibrium free energy difference and free energy barrier that follow the trend of the equilibrium fluctuation relation and the Marcus theory of electron transfer. These energetics also allow for a direct estimation of the voltage dependence of channel activation (Q-V curve), offering a quantitative rationale for a correlation between the voltage dependence parabolas and the Q-V curve, upon site-directed mutagenesis or drug binding. Taken together, by introducing the voltage coupling as the energy gap reaction coordinate, our framework brings new perspectives to the thermodynamic models of voltage activation in voltage-sensitive membrane proteins, offering an a framework for a better understating of the structure-function correlations of voltage gating in ion channels as well as electrogenic phenomena in ion pumps and transporters. Significantly, this formulation also provides a powerful bridge between the CG model of voltage coupling and the conventional macroscopic treatments. Copyright © 2015 Elsevier B.V. All rights reserved.

Electron Flow in Multiheme Bacterial Cytochromes is a Balancing Act Between Heme Electronic Interaction and Redox Potentials

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

Breuer, Marian; Rosso, Kevin M.; Blumberger, Jochen

The naturally widespread process of electron transfer from metal reducing bacteria to extracellular solid metal oxides entails unique biomolecular machinery optimized for long-range electron transport. To perform this function efficiently microorganisms have adapted multi-heme c-type cytochromes to arrange heme cofactors into wires that cooperatively span the cellular envelope, transmitting electrons along distances greater than 100 Angstroms. Implications and opportunities for bionanotechnological device design are self-evident. However, at the molecular level how these proteins shuttle electrons along their heme wires, navigating intraprotein intersections and interprotein interfaces effciently, remains a mystery so far inaccessible to experiment. To shed light on this criticalmore » topic, we carried out extensive computer simulations to calculate Marcus theory quantities for electron transfer along the ten heme cofactors in the recently crystallized outer membrane cytochrome MtrF. The combination of electronic coupling matrix elements with free energy calculations of heme redox potentials and reorganization energies for heme-to-heme electron transfer allows the step-wise and overall electron transfer rate to be estimated and understood in terms of structural and dynamical characteristics of the protein. By solving a master equation for electron hopping, we estimate an intrinsic, maximum possible electron flux through solvated MtrF of 104-105 s-1, consistent with recently measured rates for the related MtrCAB protein complex. Intriguingly, this flux must navigate thermodynamically uphill steps past low potential hemes. Our calculations show that the rapid electron transport through MtrF is the result of a clear correlation between heme redox potential and the strength of electronic coupling along the wire: Thermodynamically uphill steps occur only between electronically well connected stacked heme pairs. This suggests that the protein evolved to harbor low potential hemes, presumably necessary for reduction of certain soluble substrates, without slowing down electron ow. These findings are particularly profound in light of the apparently well conserved staggered cross heme wire structural motif in functionally related outer-membrane proteins.« less

Sleep/Wake Patterns and Parental Perceptions of Sleep in Children Born Preterm

PubMed Central

Biggs, Sarah N.; Meltzer, Lisa J.; Tapia, Ignacio E.; Traylor, Joel; Nixon, Gillian M.; Horne, Rosemary S.C.; Doyle, Lex W.; Asztalos, Elizabeth; Mindell, Jodi A.; Marcus, Carole L.

2016-01-01

Study Objectives: To compare sleep/wake patterns in children born preterm in Australia vs Canada and determine cultural differences in the relationship between parental perception of sleep and actual sleep behaviors. Methods: Australian and Canadian children born preterm were recruited from the Caffeine for Apnea of Prematurity trial (n = 188, 5–12 y) and underwent 14 days actigraphy monitoring. Parents completed the National Sleep Foundation 2004 Sleep in America questionnaire. Cross-cultural differences in sleep characteristics assessed by actigraphy and parent-reported questionnaire were examined. Correlational analyses determined the associations between parental perceptions of child sleep need and sleep behavior. Results: Actigraphy showed preterm children obtained, on average, 8 h sleep/night, one hour less than population recommendations for their age. There was no difference in total sleep time (TST) between Australian and Canadian cohorts; however, bed and wake times were earlier in Australian children. Bedtimes and TST varied by 60 minutes from night to night in both cohorts. Parent-reported child TST on the National Sleep Foundation questionnaire was 90 minutes longer than recorded by actigraphy. Both bedtime and TST on weekdays and weekends were related to parental perception of child sleep need in the Australian cohort. Only TST on weekdays was related to parental perception of child sleep need in the Canadian cohort. Conclusions: This study suggests that short sleep duration and irregular sleep schedules are common in children born preterm. Cultural differences in the association between parental perception of child sleep need and actual sleep behaviors provide important targets for future sleep health education. Citation: Biggs SN, Meltzer LJ, Tapia IE, Traylor J, Nixon GM, Horne RS, Doyle LW, Asztalos E, Mindell JA, Marcus CL. Sleep/wake patterns and parental perceptions of sleep in children born preterm. J Clin Sleep Med 2016;12(5):711–717. PMID:26857057

Electrochemical kinetics and dimensional considerations, at the nanoscale

NASA Astrophysics Data System (ADS)

Yamada, H.; Bandaru, P. R.

2016-06-01

It is shown that the consideration of the density of states variation in nanoscale electrochemical systems yields modulations in the rate constant and concomitant electrical currents. The proposed models extend the utility of Marcus-Hush-Chidsey (MHC) kinetics to a larger class of materials and could be used as a test of dimensional character. The implications of the study are of much significance to an understanding and modulation of charge transfer nanostructured electrodes.

Thermal Decomposition of 1,5-Dinitrobiuret (DNB): Direct Dynamics Trajectory Simulations and Statistical Modeling

DTIC Science & Technology

2011-05-03

18 . NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON Dr. Tommy W. Hawkins a. REPORT Unclassified b. ABSTRACT Unclassified c. THIS PAGE...branching using Rice-Ramsperger-Kassel-Marcus (RRKM) theory, 18 and finally to the analysis of inter-conversions of primary decomposition products...theory, 18 was employed to examine the properties of the reactant, intermediate complex and transition states as a function of the total internal energy

RRTMGP: A High-Performance Broadband Radiation Code for the Next Decade

DTIC Science & Technology

2015-09-30

NOAA ), Robin Hogan (ECMWF), a number of colleagues at the Max-Planck Institute, and Will Sawyer and Marcus Wetzstein (Swiss Supercomputer Center...somewhat out of date, so that the accuracy of our simplified algorithms can not be thoroughly evaluated. RRTMGP_LW_v0 has been provided to our NASA ...support, RRTMGP_LW_v0, has been completed and distributed to selected colleagues at modeling centers, including NOAA , NCAR, and CSCS. Our colleagues

State and Local Homeland Security Officials: Who Are They and What Do They Do?

DTIC Science & Technology

2011-09-01

importance of social networking and its direct impact upon the effectiveness of their work during an emergency. (Marcus, 2005, as adapted by Bell...strict constructionists who maintain that homeland security is about terrorism, middle-of-the-road moderates who sense that an all-hazards approach... method . As the interviews were conducted, data was analyzed and patterns emerged, which then provide insight into the population being studied. The

Exploiting Novel Calcium-Mediated Apoptotic Processes for the Treatment of Human Breast Cancers with Elevated Nqo1 Levels

DTIC Science & Technology

2008-03-01

in β-Lapachone-induced programmed necrosis. Biomedical Graduate Student Symposium, Case Western Reserve University, Cleveland, OH April 2002-06.  o...of β- lapachone-induced cell death” October, 2005  o The Vance Lemmon Poster Award, Biomedical Graduate Student Symposium, Case Western Reserve...cell death” April, 2005  o The Marcus Singer Poster Award, Biomedical Graduate Student Symposium, Case Western Reserve University, Cleveland, OH for

Dynamics and Stabilization of Materials Possessing High Energy Content

DTIC Science & Technology

1991-10-31

Barton, Nucl. Acids Res., J2, 2595 (1991). 24. "Diffusion and Percolation of Radical Pairs in Zeolite Media. A Product Analysis Study," J. Am. Chem...Photobiol. A: Chem., i, 35 (1991). 33. "Effect of External Pressure on Photoinduced Electron-Transfer Reactions in the Marcus Inverted Region," W.-S. Chung...duPont (Towanda, PA), Unilever USA Research (Edgewater, NJ), IBM Almaden Research Labs (San Jose, CA), Hoeschst Chemical Company (Frankfurt, Germany

How to Compute Electron Ionization Mass Spectra from First Principles.

PubMed

Bauer, Christoph Alexander; Grimme, Stefan

2016-06-02

The prediction of electron ionization (EI) mass spectra (MS) from first principles has been a major challenge for quantum chemistry (QC). The unimolecular reaction space grows rapidly with increasing molecular size. On the one hand, statistical models like Eyring's quasi-equilibrium theory and Rice-Ramsperger-Kassel-Marcus theory have provided valuable insight, and some predictions and quantitative results can be obtained from such calculations. On the other hand, molecular dynamics-based methods are able to explore automatically the energetically available regions of phase space and thus yield reaction paths in an unbiased way. We describe in this feature article the status of both methodologies in relation to mass spectrometry for small to medium sized molecules. We further present results obtained with the QCEIMS program developed in our laboratory. Our method, which incorporates stochastic and dynamic elements, has been a significant step toward the reliable routine calculation of EI mass spectra.

Role of coherence and delocalization in photo-induced electron transfer at organic interfaces

NASA Astrophysics Data System (ADS)

Abramavicius, V.; Pranculis, V.; Melianas, A.; Inganäs, O.; Gulbinas, V.; Abramavicius, D.

2016-09-01

Photo-induced charge transfer at molecular heterojunctions has gained particular interest due to the development of organic solar cells (OSC) based on blends of electron donating and accepting materials. While charge transfer between donor and acceptor molecules can be described by Marcus theory, additional carrier delocalization and coherent propagation might play the dominant role. Here, we describe ultrafast charge separation at the interface of a conjugated polymer and an aggregate of the fullerene derivative PCBM using the stochastic Schrödinger equation (SSE) and reveal the complex time evolution of electron transfer, mediated by electronic coherence and delocalization. By fitting the model to ultrafast charge separation experiments, we estimate the extent of electron delocalization and establish the transition from coherent electron propagation to incoherent hopping. Our results indicate that even a relatively weak coupling between PCBM molecules is sufficient to facilitate electron delocalization and efficient charge separation at organic interfaces.

Long Range Spoil Disposal Study. Part 3. Sub-Study 2. Nature, Source, and Cause of Shoal

DTIC Science & Technology

1973-09-01

Report) Prepared for public release; distribution unlimited 17. DISTRIBUTION STATEMENT (of the abetract entered In Block 20, if different from Report) IS...SUPPLEMENTARY NOTES 19. KEY WORDS (Continue on reverse side if necseseey and identify by block number) Delaware River River Channel Delaware Estuary...Marcus Hook, Pa. Dredging Hydraulic Dredge Spoil Disposal Sediment transport 2o ABSTRACT r -ciftue a r verse - i- - n a eay amd ideai fy by block

Electrochemistry and Spectroelectrochemistry of Polynuclear Zinc Phthalocyanines: Formation of Mixed Valence Cation Radical Species.

DTIC Science & Technology

1988-02-25

No. No. Copies Cpe Office of Naval Research 2 Dr. David You.)g Attn: Code 1113 Code 334 800 N. Quinc’ Street NORDA Arlington, Virginia 22217-5000 NSTL...Naval Surface Weapons Center Chapel Hill, North Carolina 27514 Silver Spring, Maryland 20910 Or. R. A. Marcus Dr. Michael J. Weaver Department of...Microprocessor model 340 spectrometer. Cyclic and dif, rential pulse voltammetry were performed with a Princeton Applied Research (PARC) model 174A

Computer-Assisted Communication Device for Botulinum-Intoxicated Patients

DTIC Science & Technology

2008-01-01

development of small molecule therapeutics for botulinum neurotoxin and on the development of nerve agent pretreatments and therapies . He has published...Souayah, N., Karim, H., Kamin, S.S., McArdle, J. and Marcus, S. (2006) ‘Severe botulism after focal injection of botulinum toxin’, Neurology , Vol...67, pp.1855–1856. Tacket, C.O., Shandera, W.X., Mann, J.M., Hargrett, N.T. and Blake, P.A. (1984) ‘ Equine antitoxin use and other factors that

Fundamental Noise Limits in Miniature Acoustic and Vibration Sensors

DTIC Science & Technology

1991-12-31

1982) 86 WV " NADC-91113-50 [121 Anderson, Herbert L.. (ed.), A Physicist’s Desk Rcference, AIP, NY (1989) [13] Sears, Francis W. and Gerhard L...Dover, NY (1956) [16] Callen, Herbert B. and Theodore A. Welton, "Irreversibility and generalized noise," Phys. Rev. 83(1), 34-40 (1951) [17] Kittel...34] Misner, Charles W., Kip S. Thorne, and John Archibald Wheeler, Gravitation, W. H. Freeman, NY (1973) 88 NMADC-91113-50 [35] Marcuse , Dietrich

Index to FAA Office of Aerospace Medicine Reports

DTIC Science & Technology

2011-01-01

Development and evaluation of a radar air traffic control research task. AD660198 65-32 Gogel WC, Mertens HW: Problems in depth perception: A method of...and the air traffic control specialist: Some conclusions from a decade of research . ADA093266/5 80-15 Boone JO, Van Buskirk L, Steen JA: The Federal... control applicants. ADA328998 97-18 Marcus JH: A flexible cabin simulator. ADA328996 97-19 Broach D: Designing selection tests for the future National

The Anxious and Ambivalent Partisan: The Effect of Incidental Anxiety on Partisan Motivated Recall and Ambivalence.

PubMed

Groenendyk, Eric

2016-01-01

Affective Intelligence Theory (AIT) asserts that anxiety reduces the effect of party identification on candidate preferences (Marcus, Neuman, and MacKuen 2000), but recent studies have raised doubts about this causal claim. Rather than functioning as a moderator of party identification, perhaps anxiety has a direct effect on preferences, or perhaps the relationship is reversed and preferences drive emotions (Ladd and Lenz 2008). Alternatively, Marcus et al.'s measure of anxiety may simply be capturing partisan ambivalence, so the posited relationship is spurious (Lavine, Johnston, and Steenbergen 2012). This paper addresses each of these questions by examining the effect of experimentally induced emotions on the types of considerations that came to mind when a national sample of adult Americans was asked what they liked and disliked about Barack Obama. By directly manipulating anxiety, this experiment avoids the causal ambiguity plaguing this debate and ascertains the true nature of the relationship between anxiety and ambivalence. Consistent with AIT, anxiety led respondents to recall more contemporary considerations, whereas enthusiasm brought to mind more long-standing considerations. Because the political context at the time of the study (fall 2013) was a very tumultuous time for the Obama administration, the increased accessibility of contemporary considerations led Democratic participants to experience more ambivalence in the anxiety condition. This effect was concentrated among those Democrats who were exposed to the most newspaper coverage.

Electrochemical and spectroscopic effects of mixed substituents in bis(phenolate)–copper(II) galactose oxidase model complexes

PubMed Central

Pratt, Russell C.; Lyons, Christopher T.; Wasinger, Erik C.; Stack, T. Daniel. P.

2012-01-01

Non-symmetric substitution of salen (1R1,R2) and reduced salen (2R1,R2) CuII-phenoxyl complexes with a combination of -tBu, -SiPr, and -OMe substituents leads to dramatic differences in their redox and spectroscopic properties, providing insight into the influence of the cysteine-modified tyrosine cofactor in the enzyme galactose oxidase (GO). Using a modified Marcus-Hush analysis, the oxidized copper complexes are characterized as Class II mixed-valent due to the electronic differentiation between the two substituted phenolates. Sulfur K-edge X-ray absorption spectroscopy (XAS) assesses the degree of radical delocalization onto the single sulfur atom of non-symmetric [1tBu,SMe]+ at 7%, consistent with other spectroscopic and electrochemical results that suggest preferential oxidation of the -SMe bearing phenolate. Estimates of the thermodynamic free-energy difference between the two localized states (ΔG∘) and reorganizational energies (λR1R2) of [1R1,R2]+ and [2R1,R2]+ leads to accurate predictions of the spectroscopically observed IVCT transition energies. Application of the modified Marcus-Hush analysis to GO using parameters determined for [2R1,R2]+ predicts a νmax of ~ 13600 cm−1, well within the energy range of the broad Vis-NIR band displayed by the enzyme. PMID:22471355

[Three Jewish Germans as chief surgeons in the Berlin-Friedrichshain Hospital--a historical reminiscence].

PubMed

Franke, A; Franke, K

2005-10-01

Three jewish Germans were between 1903 and 1933 continuously in charge of a department of surgery at the oldest municipal hospital in Berlin-Friedrichshain (founded 1874). They were A. Neumann (1865-1920), Moritz Katzenstein (1872-1932) and Max Marcus (1892-1983). A. Neumann described in 1907 the so-called omentum-majus-cuff. By this a drain is wrapped up and put into a perforated ulcus pylori, which cannot be treated by another procedure. M. Katzenstein in 1900 was the first in Germany who repaired a torn off meniscus by suture with a good result (The very first was T. Annandale in Edinburgh in 1883). Aside of this procedure, important for prevention of gonarthrosis, M. K. described new methods for repairing torn ligaments of the elbow and the ankle joint. He was a close friend of Albert Einstein during his years in Berlin. Max Marcus was after the death of M. Katzenstein the youngest chief surgeon in Berlin--but only until April 1933. Then he was expelled by the Nazis, because he was a jew. In June 1933 he immigrated to Palestine and became the leading surgeon there in the later Israel. After the end of World War II he refused coming back to Germany, though F. Sauerbruch spoke about him as the "great hope for the German surgery".

The Anxious and Ambivalent Partisan

PubMed Central

Groenendyk, Eric

2016-01-01

Affective Intelligence Theory (AIT) asserts that anxiety reduces the effect of party identification on candidate preferences (Marcus, Neuman, and MacKuen 2000), but recent studies have raised doubts about this causal claim. Rather than functioning as a moderator of party identification, perhaps anxiety has a direct effect on preferences, or perhaps the relationship is reversed and preferences drive emotions (Ladd and Lenz 2008). Alternatively, Marcus et al.’s measure of anxiety may simply be capturing partisan ambivalence, so the posited relationship is spurious (Lavine, Johnston, and Steenbergen 2012). This paper addresses each of these questions by examining the effect of experimentally induced emotions on the types of considerations that came to mind when a national sample of adult Americans was asked what they liked and disliked about Barack Obama. By directly manipulating anxiety, this experiment avoids the causal ambiguity plaguing this debate and ascertains the true nature of the relationship between anxiety and ambivalence. Consistent with AIT, anxiety led respondents to recall more contemporary considerations, whereas enthusiasm brought to mind more long-standing considerations. Because the political context at the time of the study (fall 2013) was a very tumultuous time for the Obama administration, the increased accessibility of contemporary considerations led Democratic participants to experience more ambivalence in the anxiety condition. This effect was concentrated among those Democrats who were exposed to the most newspaper coverage. PMID:27274573

Flipping of the coordinated triazine moiety in Cu(I)-L2 and the small electronic factor, κel, for direct outer-sphere cross reactions: syntheses, crystal structures and redox behaviour of copper(II)/(I)-L2 complexes (L = 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine).

PubMed

Yamada, Atsutoshi; Mabe, Takuya; Yamane, Ryohei; Noda, Kyoko; Wasada, Yuko; Inamo, Masahiko; Ishihara, Koji; Suzuki, Takayoshi; Takagi, Hideo D

2015-08-21

Six-coordinate [Cu(pdt)2(H2O)2](2+) and four-coordinate [Cu(pdt)2](+) complexes were synthesized and the cross redox reactions were studied in acetonitrile (pdt = 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine). Single crystal analyses revealed that [Cu(pdt)2(H2O)2](BF4)2 was of pseudo-D2h symmetry with two axial water molecules and two symmetrically coordinated equatorial pdt ligands, while the coordination structure of [Cu(pdt)2]BF4 was a squashed tetrahedron (dihedral angle = 54.87°) with an asymmetric coordination by two pdt ligands: one pdt ligand was coordinated to Cu(i) through pyridine-N and triazine-N2 while another pdt ligand was coordinated through pyridine-N and triazine-N4, and a stacking interaction between the phenyl ring on one pdt ligand and the triazine ring on another pdt ligand caused the squashed structure and non-equivalent Cu-N bond lengths. The cyclic voltammograms for [Cu(pdt)2(H2O)2](2+) and [Cu(pdt)2](+) in acetonitrile were identical to each other and quasi-reversible. The reduction of [Cu(pdt)2(H2O)2](2+) by decamethylferrocene and the oxidation of [Cu(pdt)2](+) by [Co(2,2'-bipyridine)3](3+) in acetonitrile revealed that both cross reactions were sluggish through a gated process (the structural change took place prior to the electron transfer) accompanied by slow direct electron transfer processes. It was found that the triazine ring of the coordinated pdt ligand rotates around the C-C bond between the triazine and pyridine rings with the kinetic parameters k = 51 ± 5 s(-1) (297.8 K), ΔH(‡) = 6.2 ± 1.1 kJ mol(-1) and ΔS(‡) = -192 ± 4 J mol(-1) K(-1). The electron self-exchange process was directly measured using the line-broadening method: kex = (9.9 ± 0.5) × 10(4) kg mol(-1) s(-1) (297.8 K) with ΔH(‡) = 44 ± 7 kJ mol(-1) and ΔS(‡) = 0.2 ± 2.6 J mol(-1) K(-1). By comparing this rate constant with the self-exchange rate constants estimated from the cross reactions using the Marcus cross relation, the non-adiabaticity (electronic) factors, κel, for the direct electron transfer processes between [Cu(pdt)2](+/2+) and non-copper metal (Fe(2+) and Co(3+)) complexes were estimated as ca. 10(-7), indicating that the electronic coupling between the d orbitals of copper and of non-copper metals is very small.

Genetic Studies of Strabismus, Congenital Cranial Dysinnervation Disorders (CCDDs), and Their Associated Anomalies

ClinicalTrials.gov

2018-03-21

Congenital Fibrosis of Extraocular Muscles; Duane Retraction Syndrome; Duane Radial Ray Syndrome; Mobius Syndrome; Brown Syndrome; Marcus Gunn Syndrome; Strabismus Congenital; Horizontal Gaze Palsy; Horizontal Gaze Palsy With Progressive Scoliosis; Facial Palsy; Facial Paresis, Hereditary, Congenital; Third Nerve Palsy; Fourth Nerve Palsy; Sixth Nerve Palsy; Synkinesis; Ocular Motility Disorders; Levator-Medial Rectus Synkinesis; Athabaskan Brainstem Dysgenesis; Tongue Paralysis; Ninth Nerve Disorder; Fifth Nerve Palsy; Seventh Nerve Palsy; Eleventh Nerve Disorder; Twelfth Nerve Disorder; Vagus Nerve Paralysis; Moebius Sequence

Air Force Civil Engineer, Volume 15, Number 2, 2007

DTIC Science & Technology

2007-01-01

painter wearing this gear in an atmosphere that measures 50 x TLV experiences the same level of exposure as an unprotected painter exposed to the TLV ...It’s a huge challenge, but if anyone was going to be able to do this, or had the experience , it was us. We have the most diversity; we go from...helps clear a path through a minefield near Bagram Airfield. (photo by SSgt Marcus McDonald) their last return date. During May 2006, the Air Force

Decoherence and Noise in Spin-based Solid State Quantum Computers. Approximation-Free Numerical Simulations

DTIC Science & Technology

2007-07-21

the spin coherent states P-representation", Conference on Quantum Computations and Many- Body Systems, February 2006, Key West, FL 9. B. N. Harmon...solid-state spin-based qubit systems was the focus of our project. Since decoherence is a complex many- body non-equilibrium process, and its...representation of the density matrix, see Sec. 3 below). This work prompted J. Taylor from the experimental group of C. Marcus and M. Lukin (funded by

Mechanism of Action of Botulinum Neurotoxin and Overview of Medical Countermeasures for Intoxication

DTIC Science & Technology

2008-01-01

D.F., Kane , C.T., Comille, F., and Hackley, Jr., B.E. 1999a. Evaluation of phosphoramidon and three synthetic phosphonates for inhibition of botulinum...of botulism. Clin. Toxicol. II: 19-25. Chertow, D.S., Tan, E.T., Maslanka, S., Schulte, J., Bresnitz, E.A., Weisman, RS., Bernstein, J., Marcus , S.M...manner in which the toxin of Clostridiumbotulinum act upon the body . II. The effect upon the voluntary nervous system. J. Exp. Med.38:327-346. Dolly, J.O

Proceedings of the International Symposium on Methodologies for Intelligent Systems (Poster Session) (7th) held at Trondheim, Norway, on 15-18 June, 1993

DTIC Science & Technology

1993-06-18

David Hislop (US Army Research Office), Eero Hyvonen (VTT, Finland), Marek Karpinski (Bonn, Germany), Yves Kodratoff (Paris VI, France), Jan...21] M. P. Marcus, A theory of Syntactic Recognition for Natural Language, The MIT Press, Cambridge, Mass., 1980 [221 K.R. McKeown, The TEXT System...H. Simon, The Sciences of the Artificial, The MIT Press, Cambridge, MA, ( 1980 ). 3. M.D. Mesarovich, D. Macko, Y. Takahara Y., Theory of Hierarchical

Integration of Narrative Processing, Data Fusion, and Database Updating Techniques in an Automated System.

DTIC Science & Technology

1981-10-29

are implemented, respectively, in the files "W-Update," "W-combine" and RW-Copy," listed in the appendix. The appendix begins with a typescript of an...the typescript ) and the copying process (steps 45 and 46) are shown as human actions in the typescript , but can be performed easily by a "master...for Natural Language, M. Marcus, MIT Press, 1980. I 29 APPENDIX: DATABASE UPDATING EXPERIMENT 30 CONTENTS Typescript of an experiment in Rosie

Responsiveness and Reliability: A History of the Philadelphia District and the Marine Design Center, U.S. Army Corps of Engineers, 1972-2008

DTIC Science & Technology

2012-01-01

Philadelphia, Pa., to the mouth of the Delaware Bay, with appropriate bend widenings, partial deepening of the Marcus Hook anchorage, and relocation...flyway. • Tasked by the North Atlantic Division to support relocating the Army’s C4ISR electronics research and development program to Aberdeen...bill that, in his words , “would cost billions of dollars and often do more harm than good.” His actions outraged Philadelphia’s Delaware River

Annual Report on Electronics Research at The University of Texas at Austin.

DTIC Science & Technology

1983-05-15

Kathleen A. Thrush, Chemistry David Grant, Physics *Jim Weidner, EE Jessy Grizzle, EE *Evan Westwood, Physics Jim Higdon John E. White, AerospaceJae...129 (1982). M. H . Kelley and M. Fink, "The Temperature Dependence of the Molecular Structure Parameters of SF 6" J. Chem. Phys. 77, pp. 1813-1817 (1982...D. Finello and H . L. Marcus, "Correlation of Electronic State and Fracture Path of Aluminum-Graphite Interfaces," Scripta Met., 16, 855 (1982). M. H

Evaluation of Malware Target Recognition Deployed in a Cloud-Based Fileserver Environment

DTIC Science & Technology

2012-03-01

many of these detection techniques could be evaded with simple obfuscation. Kolter and Maloof extend Schultz’s research in [KM04] and [KM06]. Their...69 [KM04] Jeremy Z. Kolter and Marcus A. Maloof. Learning to detect malicious executables in the wild. In Proceedings of the tenth ACM SIGKDD...international conference on Knowledge discovery and data mining, KDD ’04, pages 470–478, New York, NY, USA, 2004. ACM. [KM06] J.Z. Kolter and M.A. Maloof

Bathymetric and sediment facies maps for China Bend and Marcus Flats, Franklin D. Roosevelt Lake, Washington, 2008 and 2009

USGS Publications Warehouse

Weakland, Rhonda J.; Fosness, Ryan L.; Williams, Marshall L.; Barton, Gary J.

2011-01-01

The U.S. Geological Survey (USGS) created bathymetric and sediment facies maps for portions of two reaches of Lake Roosevelt in support of an interdisciplinary study of white sturgeon (Acipenser transmontanus) and their habitat areas within Franklin D. Roosevelt Lake, Washington. In October 2008, scientists from the USGS used a boat-mounted multibeam echo sounder (MBES) to describe bathymetric data to characterize surface relief at China Bend and Marcus Flats, between Northport and Kettle Falls, Washington. In March 2009, an underwater video camera was used to view and record sediment facies that were then characterized by sediment type, grain size, and areas of sand deposition. Smelter slag has been identified as having the characteristics of sand-sized black particles; the two non-invasive surveys attempted to identify areas containing black-colored particulate matter that may be elements and minerals, organic material, or slag. The white sturgeon population in Lake Roosevelt is threatened by the failure of natural recruitment, resulting in a native population that consists primarily of aging fish and that is gradually declining as fish die and are not replaced by nonhatchery reared juvenile fish. These fish spawn and rear in the riverine and upper reservoir reaches where smelter slag is present in the sediment of the river lake bed. Effects of slag on the white sturgeon population in Lake Roosevelt are largely unknown. Two recent studies demonstrated that copper and other metals are mobilized from slag in aqueous environments with concentrations of copper and zinc in bed sediments reaching levels of 10,000 and 30,000 mg/kg due to the presence of smelter slag. Copper was found to be highly toxic to 30-day-old white sturgeon with 96-h LC50 concentrations ranging from 3 to 5 (u or mu)g copper per liter. Older juvenile and adult sturgeons commonly ingest substantial amounts of sediment while foraging. Future study efforts in Lake Roosevelt should include sampling of bottom material to confirm the presence or absence of slag material indicated on the map. In addition, follow-up acoustic work to determine stream velocities at varying discharges, in conjunction with sediment mapping, would be helpful to more accurately identify areas of scour and areas of sediment deposition where slag deposits may accumulate within the Marcus Flats and China Bend reaches. MBES mapping could also be used to determine changes in bed elevation and sedimentation in the study reaches and could help evaluate annual deposition and provide estimates on fine-sediment thickness.

Metal-metal interactions in tetrakis(diphenylphosphino)benzene-bridged dimetallic complexes and their related coordination polymers

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

Wang, Pei-Wei; Fox, M.A.

1994-06-22

Electrochemical, EPR, and spectroelectrochemical methods have been used to probe electronic coupling through a 1,2,4,5-tetrakis(diphenylphosphino)benzene bridging ligand connecting metal centers in several Ni-, Pd-, and Pt-containing dimetallic complexes. These dimetalated complexes showed weak intervalence charge transfer (IT) bands and slightly shifted redox potentials in comparison with their monometallic models. A Marcus-Hush analysis of the energies of the IT bands for the electrochemically generated mixed-valence heterodimetallic complexes (Ni{sup o}-Pd{sup II} and Ni{sup o}-Pt{sup II}, respectively) established the magnitude of intermetallic electronic coupling. The weak thermal coupling observed in these dimetalated complexes is consistent with the very low conductivities (10{sup {minus}8}-10{sup {minus}10}{omega}{supmore » -1} cm{sup {minus}1}) observed in the polymeric analogs of these complexes, namely, the newly prepared metal coordination polymers (M = Ni{sup II}, Pd{sup II}, Pt{sup II}) with 1,2,4,5-tetrakis(diphenylphosphino)benzene.« less

Crucial role of decoherence for electronic transport in molecular wires: Polyaniline as a case study

NASA Astrophysics Data System (ADS)

Cattena, Carlos J.; Bustos-Marún, Raúl A.; Pastawski, Horacio M.

2010-10-01

In this work we attempt to elucidate the nature of conductivity in polymers by taking the acid-base doped polyaniline (PAni) polymer. We evaluate the PAni conductance by using realistic ab initio parameters and including decoherent processes within the minimal parametrization model of D’Amato-Pastawski. In contrast to general wisdom, which associates the conducting state with coherent propagation in a periodic polaronic lattice, we show that decoherence can account for high conductance in the strongly disordered bipolaronic lattice. Hence, according to our results, there is no need of considering a mix model of “conducting” polaronic lattice islands separated by “insulating” bipolaronic lattice strands as is usually assumed for PAni. We find that without dephasing events, even very short strands of bipolaronic lattices are not able to sustain electronic transport. We also include a discussion of specific mechanisms that should be involved in decoherence rates of PAni and relate them with Marcus-Hush theory of electron transfer.

Electron-transfer quenching vs. exciplex-mediated quenching of the low-lying excited states in phthalocyanines

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

Prasad, D.R.; Ferraudi, G.

1983-05-25

Oxidative electron-transfer quenching of the lowest ligand-centered /sup 3/..pi pi..* of ruthenium (RU) phthalocyanines (pc)L/sub 2/, L = dimethylformamide (dmf) or pyridine (py), by a series of nitroaromatic compounds, viologen salts, and metal complexes has been investigated by laser and conventional flash photolysis. The quenching rate constants, treated according to Marcus-Hush and Rehm-Weller equations, gave self-exchange rate constants, k/sub exch/ approx. 10/sup 7/ M/sup -1/ s/sup -1/, for the electron exchange between the /sup 3/..pi pi..* and the ruthenium(II) ligand radical. The excited states of a number of phthalocyanines, e.g. Ru(pc)(dimethyl sulfoxide(Me/sub 2/SO)/sub 2/), Ru(pc)(dmf)CO, Ru(pc)(py)CO, and Rh(pc)(methanol(CH/sub 3/OH)chloride), undergomore » quenching mediated by exciplex formation. The formation of exciplexes is discussed in terms of the related exciplexes of the porphyrins.« less

Measuring the internal energies of species emitted from hypervelocity nanoprojectile impacts on surfaces using recalibrated benzylpyridinium probe ions

NASA Astrophysics Data System (ADS)

DeBord, J. Daniel; Verkhoturov, Stanislav V.; Perez, Lisa M.; North, Simon W.; Hall, Michael B.; Schweikert, Emile A.

2013-06-01

We present herein a framework for measuring the internal energy distributions of vibrationally excited molecular ions emitted from hypervelocity nanoprojectile impacts on organic surfaces. The experimental portion of this framework is based on the measurement of lifetime distributions of "thermometer" benzylpyridinium ions dissociated within a time of flight mass spectrometer. The theoretical component comprises re-evaluation of the fragmentation energetics of benzylpyridinium ions at the coupled-cluster singles and doubles with perturbative triples level. Vibrational frequencies for the ground and transition states of select molecules are reported, allowing for a full description of vibrational excitations of these molecules via Rice-Ramsperger-Kassel-Marcus unimolecular fragmentation theory. Ultimately, this approach is used to evaluate the internal energy distributions from the measured lifetime distributions. The average internal energies of benzylpyridinium ions measured from 440 keV Au400+4 impacts are found to be relatively low (˜0.24 eV/atom) when compared with keV atomic bombardment of surfaces (1-2 eV/atom).

Use of Direct Dynamics Simulations to Determine Unimolecular Reaction Paths and Arrhenius Parameters for Large Molecules.

PubMed

Yang, Li; Sun, Rui; Hase, William L

2011-11-08

In a previous study (J. Chem. Phys.2008, 129, 094701) it was shown that for a large molecule, with a total energy much greater than its barrier for decomposition and whose vibrational modes are harmonic oscillators, the expressions for the classical Rice-Ramsperger-Kassel-Marcus (RRKM) (i.e., RRK) and classical transition-state theory (TST) rate constants become equivalent. Using this relationship, a molecule's unimolecular rate constants versus temperature may be determined from chemical dynamics simulations of microcanonical ensembles for the molecule at different total energies. The simulation identifies the molecule's unimolecular pathways and their Arrhenius parameters. In the work presented here, this approach is used to study the thermal decomposition of CH3-NH-CH═CH-CH3, an important constituent in the polymer of cross-linked epoxy resins. Direct dynamics simulations, at the MP2/6-31+G* level of theory, were used to investigate the decomposition of microcanonical ensembles for this molecule. The Arrhenius A and Ea parameters determined from the direct dynamics simulation are in very good agreement with the TST Arrhenius parameters for the MP2/6-31+G* potential energy surface. The simulation method applied here may be particularly useful for large molecules with a multitude of decomposition pathways and whose transition states may be difficult to determine and have structures that are not readily obvious.

Unified theory of the exciplex formation/dissipation.

PubMed

Khokhlova, Svetlana S; Burshtein, Anatoly I

2010-11-04

The natural extension and reformulation of the unified theory (UT) proposed here makes it integro-differential and capable of describing the distant quenching of excitation by electron transfer, accompanied with contact but reversible exciplex formation. The numerical solution of the new UT equations allows specifying the kinetics of the fluorescence quenching and exciplex association/dissociation as well as those reactions' quantum yields. It was demonstrated that the distant electron transfer in either the normal or inverted Marcus regions screens the contact reaction of exciplex formation, especially at slow diffusion.

How many molecules are required to measure a cyclic voltammogram?

NASA Astrophysics Data System (ADS)

Cutress, Ian J.; Compton, Richard G.

2011-05-01

The stochastic limit at which fully-reversible cyclic voltammetry can accurately be measured is investigated. Specifically, Monte Carlo GPU simulation is used to study low concentration cyclic voltammetry at a microdisk electrode over a range of scan rates and concentrations, and the results compared to the statistical limit as predicted by finite difference simulation based on Fick's Laws of Diffusion. Both Butler-Volmer and Marcus-Hush electrode kinetics are considered, simulated via random-walk methods, and shown to give identical results in the fast kinetic limit.

Does Marcus-Hush theory really work Optical studies of intervalence transfer in acetylene-bridged biferrocene monocation at infinite dilution and at finite ionic strengths

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

Blackbourn, R.L.; Hupp, J.T.

1990-03-08

Intervalence charge-transfer data for acetylene-bridged biferrocene monocation (Bf{sup +}) have been collected in five solvents in the presence and absence of excess electrolyte and in the limit of infinite chromophore dilution. The study was motivated by earlier work which demonstrated that the intervalence absorption maximum for Bf{sup +} in methylene chloride could vary substantially with both chromophore concentration and added electrolyte concentration. In the present study similar (but smaller) variations are found in other solvents.

Calculation of Kinetic Data for Processes Leading to UV Signatures

DTIC Science & Technology

1989-03-31

Jv we make use of the numerical algorithm developed by Stodden and Micha 17, extending it to the equations of motion in curvilinear coordinates. To be...in the field of the average potential V(Q). The set of equations (4.13’) have been recently derived by Stodden and Michat 5 in a more tedious.way by...B. Bloom, J. Chem. Phys. 83, 5703 (1985) 5 P. K. Swamninathan, C. D. Stodden , and D. A. Micha, J. Chem. Phys., in press (1989). 6 R. A. Marcus, Chem

USSR Report, Political and Sociological Affairs, No. 1434

DTIC Science & Technology

1983-07-25

author loves to make a splash by using slang expressions such as "neulyby" /"frowners^, "nudyagi" /"bores_| y , or "boyaguzy" /cowards/. And he couldn’t...small format. "In the past 5 years four books of large format have been published: selected works of R. Descarte and J.-J. Rousseau, ’The Republic...ligion and Science’ of B. Russell and ’Vocation of Man’ of J. G. Fichte. Books of M. Montaigne, Marcus Aurelius and Epictetus are being prepared for

Approaching Terahertz Range with 3-color Broadband Coherent Raman Micro Spectroscopy

NASA Astrophysics Data System (ADS)

Ujj, Laszlo; Olson, Trevor; Amos, James

The presentation reports the recent progress made on reliable signal recording and processing using 3-color broadband coherent Raman scattering (3C-BCRS). Signals are generated either from nanoparticle structures on surfaces or from bulk samples in transmission and in epi-detected mode. Spectra are recorded with a narrowband (at 532 nm) and a broadband radiation produced by a newly optimized optical parametric oscillator using the signal or idler beams. Vibrational and librational bands are measured over the 0.15-15 THz spectral range from solution and crystalline samples. Volumetric Brag-filter approach is introduced for recording 3C-BCRS spectra at the first time. The technical limitations and advantages of the narrowband filtering relative to the Notch-filter technic is clarified. The signal is proportional to the spectral autocorrelation of the broadband radiation therefore the present scheme gives a better signal-to-noise ratio relative to the traditional multiplex CRS methods. This makes the automation of non-model dependent signal processing more reliable to extract vibrational information which is very crucial in coherent Raman microscopy. Financial support from the Hal Marcus College of Science and Engineering is greatly appreciated.

Structural evolution of preexisting oceanic crust through intraplate igneous activities in the Marcus-Wake seamount chain

NASA Astrophysics Data System (ADS)

Kaneda, Kentaro; Kodaira, Shuichi; Nishizawa, Azusa; Morishita, Taisei; Takahashi, Narumi

2010-10-01

Multichannel seismic reflection studies and seismic refraction surveys with ocean bottom seismographs in the Marcus-Wake seamount chain in the northwestern Pacific Ocean reveal P wave velocity structures of hot spot-origin seamounts and adjacent oceanic crust. Inside the seamounts are central high-velocity (>6.5 km/s) structures extending nearly to the top that may indicate intrusive cores. Thick sediment layers (up to 4 km) with P wave velocities of 4-5 km/s have accumulated on seafloor that predates seamount formation. Downward crustal thickening of up to 2 km was documented beneath a large seamount cluster, but thickening was not confirmed below a small seamount cluster. Volume ratios of an intrusive core to a seamount body are 15-20%, indicating that most of the supplied magma was consumed in forming the thick sedimentary and volcaniclastic layer constituting the seamount flanks. Underplating and downward crustal thickening may tend to occur when second or later intrusive cores are formed in a seamount. P wave velocities in the lowest crust and in the uppermost mantle below the seamount chain are 0.1-0.2 km/s higher and 0.3-0.5 km/s lower, respectively, than velocities below oceanic crust. We explain this difference as a result of sill-like intrusion of magma into the lower crust and uppermost mantle. Reflected waves observed at offsets >200 km are from mantle reflectors at depths of 30-45 km and 55-70 km. The shallower reflectors may indicate structures formed by intraplate igneous activities, and the deeper reflectors may correspond to the lithosphere-asthenosphere boundary.

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electron transfer

NASA Astrophysics Data System (ADS)

Cotton, Stephen J.; Igumenshchev, Kirill; Miller, William H.

2014-08-01

It has recently been shown [S. J. Cotton and W. H. Miller, J. Chem. Phys. 139, 234112 (2013)] that a symmetrical windowing quasi-classical (SQC) approach [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] applied to the Meyer-Miller model [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] for the electronic degrees of freedom in electronically non-adiabatic dynamics is capable of quantitatively reproducing quantum mechanical results for a variety of test applications, including cases where "quantum" coherence effects are significant. Here we apply this same SQC methodology, within a flux-side correlation function framework, to calculate thermal rate constants corresponding to several proposed models of electron transfer processes [P. Huo, T. F. Miller III, and D. F. Coker, J. Chem. Phys. 139, 151103 (2013); A. R. Menzeleev, N. Ananth, and T. F. Miller III, J. Chem. Phys. 135, 074106 (2011)]. Good quantitative agreement with Marcus Theory is obtained over several orders of magnitude variation in non-adiabatic coupling. Moreover, the "inverted regime" in thermal rate constants (with increasing bias) known from Marcus Theory is also reproduced with good accuracy by this very simple classical approach. The SQC treatment is also applied to a recent model of photoinduced proton coupled electron transfer [C. Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, J. Chem. Phys. 131, 154502 (2009)] and population decay of the photoexcited donor state is found to be in reasonable agreement with results calculated via reduced density matrix theory.

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electron transfer

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

Cotton, Stephen J.; Igumenshchev, Kirill; Miller, William H., E-mail: millerwh@berkeley.edu

It has recently been shown [S. J. Cotton and W. H. Miller, J. Chem. Phys. 139, 234112 (2013)] that a symmetrical windowing quasi-classical (SQC) approach [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] applied to the Meyer-Miller model [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] for the electronic degrees of freedom in electronically non-adiabatic dynamics is capable of quantitatively reproducing quantum mechanical results for a variety of test applications, including cases where “quantum” coherence effects are significant. Here we apply this same SQC methodology, within a flux-side correlation functionmore » framework, to calculate thermal rate constants corresponding to several proposed models of electron transfer processes [P. Huo, T. F. Miller III, and D. F. Coker, J. Chem. Phys. 139, 151103 (2013); A. R. Menzeleev, N. Ananth, and T. F. Miller III, J. Chem. Phys. 135, 074106 (2011)]. Good quantitative agreement with Marcus Theory is obtained over several orders of magnitude variation in non-adiabatic coupling. Moreover, the “inverted regime” in thermal rate constants (with increasing bias) known from Marcus Theory is also reproduced with good accuracy by this very simple classical approach. The SQC treatment is also applied to a recent model of photoinduced proton coupled electron transfer [C. Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, J. Chem. Phys. 131, 154502 (2009)] and population decay of the photoexcited donor state is found to be in reasonable agreement with results calculated via reduced density matrix theory.« less

National Guard Posture Statement 2010. America’s Indispensable Force

DTIC Science & Technology

2010-01-01

Michael T. Fuga, AS* SSG Carl R. Fuller, GA SPC Marcus S. Futrell, GA CSM Marilyn L. Gabbard, IA SGT Jerry L. Ganey Jr., GA SGT Seth K. Garceau, IA...Timoteo, NJ SPC Eric L. Toth, KY SSG Robin L. Towns Sr., MD SPC Seth R. Trahan, LA SPC Quoc Binh Tran, CA SSG Philip L. Travis, GA CW4 Chester W. Troxel...SFC Charles H. Warren, GA 1SG William T. Warren, AR SFC Mark C. Warren, OR SPC Glenn J. Watkins , CA MSG Davy N. Weaver, GA SGT Matthew A. Webber, MI SFC

Anomalously large effects of pressure on electron transfer kinetics in solution: The aqueous manganate(VI)-permanganate(VII) system

NASA Astrophysics Data System (ADS)

Swaddle, T. W.; Spiccia, L.

1986-05-01

The classical Stranks-Hush-Marcus theory of pressure effects on the rates of outer-sphere electron transfer reaction rates in solution underestimates |ΔV ∗| specifically, for the MnO 4/MnO 42- (aq) exchange, ΔV ∗=-21.2 (observed) vs. -6.6 cm3mol-1 (calculated). This discrepancy can best be resolved by conceding that the Mn-Mn separation σ in the transition state is variable and pressure-sensitive in the context of non-adiabatic electron transfer within an ellipsoidal cavity with σ ∼ 550 pm.

Psychoanalysis and the community mental health movement.

PubMed

Croghan, L M

1975-01-01

Psychoanalysis and CMHM were once enemies. Psychoanalysis has made noteworthy advances toward the CMHM idea both in technique changes and in community involvement. It is possible that CMHM may finally reject all psychoanalytic contribution and face its future without a theory. If that takes place, the CMHM some day in its future may turn a corner and find itself face to face with the lonely, individual man, conscious of his past and fearful of the unexplained anxiety within him. It is then that the CMHM will find itself once again studying the works of Herbert Marcuse, Erik Erikson, Sigmund Freud, and the psychoanalytic world.

Optimizing Naval Hospital Camp Pendleton’s Primary Care Access by Managing Demand of the Emergency Department through a Health Services Center: A Marcus Welby Care Initiative

DTIC Science & Technology

2006-06-01

10 strep throat . I want to order a throat culture and start you on some antibiotics." As quickly as the doctor appeared, he was gone, moving on to the...TRICARE Prime. She wakes up one morning with an awful sore throat and difficulty swallowing. She tries to contact her Primary Care Manager (PCM) by...next of what seemed a never ending stream of patients. After the throat culture and an additional hour wait at the pharmacy, Mrs. Smith is on her way

Deep Seismic Imaging of the Hellenic Subduction Zone with New MCS Data of the SISMED Project

NASA Astrophysics Data System (ADS)

Becel, A.; Mireille, L.; Hussni, S.; Dessa, J. X.; Schenini, L.; Sachpazi, M.; Vitard, C.

2016-12-01

The southwestern segment of the Hellenic subduction zone has generated a M>8 tsunamigenic earthquake in the past (365 AD), the largest event ever reported in Europe, but fundamental questions remain about the deep geometry and characteristics of the interplate fault and connected splay faults in the overriding plate that might be rooted in the megathrust. In the Fall 2012, the ULYSSE seismic program acquired deep penetration multichannel seismic (MCS) and OBS refraction profiles across a 300-km-wide section of the forearc domain. MCS data were acquired with a 4.5 km-long streamer on board the R/V Le Pourquoi Pas? from the French IFREMER facilities. The two 240 km-long seismic reflection dip profiles reveal a large and rough topography of the top of the forearc crust in both the outer and inner domains, including a several km thick forearc basin. Despite the thick Messinian evaporites at shallow depths, the 11000 cu.in airgun source reveal several discontinuous arcward-dipping reflections at 15 km depth beneath the outer forearc domain that could be related to the top of the subducting oceanic crust. Unfortunately, the 4.5 km-long streamer is too short for improving their lateral continuity and getting more detailed constraints on their geometry. In the Fall 2015, we chartered the R/V Marcus Langseth equipped with unmatched seismic facilities in the European academic fleet by means of a strong mobilization of the French and American involved laboratories (Géoazur, LDEO, ISTEP, ENS-Paris, EOST, LDO, Pau Univ.) and their research agencies (CNRS, NSF, OCA, and UCA). During the SISMED survey (Seismic Imaging inveStigation in MEDiterranean Sea for deep seismogenic faults), we collected with the R/V Marcus Langseth a 210 km-long profile coincident with the eastern ULYSSE transect with the 8 km-long streamer and a 6600 cu.in tuned airgun array shot every 50 meters. The source and the streamer were towed at a depth of 12 m to maximize low frequencies and deep imaging. Here, we will present the preliminary results of the newly acquired high-quality, high-resolution and deep-penetration data and we will provide a comparison of the two datasets collected with different acquisition parameters.

Computer-based three-dimensional reconstruction of the anatomy of Microhedyle remanei (Marcus, 1953), an interstitial acochlidian gastropod from Bermuda.

PubMed

Neusser, Timea P; Hess, Martin; Haszprunar, Gerhard; Schrödl, Michael

2006-02-01

Phylogenetic analysis of the highly enigmatic and aberrant acochlidian opisthobranch gastropods is mainly hindered by the lack of reliable anatomical data. Due to their small size, marine interstitial acochlidian species are not suitable for anatomical investigations by dissecting. The tinyness and complexity of, e.g., opisthobranch central nervous and reproductive systems make data derived from older paraffin-based histology and interpretation by hand-based graphical reconstruction questionable. In a former study, a hermaphroditic member of the basal acochlidian genus Hedylopsis ("Hedylopsacea") has been examined in detail. The present study uses the gonochoric Microhedyle remanei (Microhedylidae) as a model organism of the other traditional major acochlidian subgroup, the "Microhedylacea." More than 20 specimens with up to 2 mm body length were extracted from coarse subtidal sand near Castle Roads, Bermuda Islands. Their central nervous, digestive, circulatory, excretory, and genital systems were reconstructed three-dimensionally from serial semithin histological sections using AMIRA software. The radula was analyzed by SEM. Our specimens closely resemble the original description of M. remanei (Marcus, 1953; as Unela) from Brazil; apparent differences regarding the number of visceral loop ganglia or details of male genitalia are assumed to be due to oversights by the former author or because of different ontogenetic stages. Microhedyle remanei differs from all congeners due to the lack (vs. presence) of eyes; further distinguishing features are discussed. In contrast to members of the hedylopsacean Hedylopsidae, Acochlidiidae, and Tantulidae, M. remanei shows a nervous system with numerous precerebral accessory "ganglia" that are not differentiated into cortex and medulla. While all Microhedylidae previously were thought to lack a heart, M. remanei shows a two-chambered heart, as is usual for opisthobranchs. The oocytes of M. remanei are yolky and large in relation to body size and suggest intracapsular larval development. A comparative microanatomical discussion and the distribution of characters within acochlidian taxa indicate that the current classification of the Acochlidia does not reflect phylogenetic relationships. Detailed structural investigations on further poorly known species are required; the computer-based 3D reconstruction of semithin serial sections with AMIRA is shown to be an ideal tool for efficient analysis and presentation of the microanatomy of small specimens. (c) 2005 Wiley-Liss, Inc.

Use of in situ and confocal Raman spectroscopy to study the nature and distribution of carotenoids in brown patinas from a deteriorated wall painting in Marcus Lucretius House (Pompeii).

PubMed

Maguregui, M; Knuutinen, U; Trebolazabala, J; Morillas, H; Castro, K; Martinez-Arkarazo, I; Madariaga, J M

2012-02-01

Colonisation of wall paintings by microorganisms and other organisms is a well-known problematic phenomenon. Besides taxonomic identification of the biodeteriogen, it is essential to evaluate the consequences of the colonisation, e.g., unsightly coloured patinas. This work proposes new methodology for characterisation of the nature of the main carotenoids and their distribution in brown stains or patinas of a deteriorated wall painting on the north wall of the atrium of Marcus Lucretius House (Pompeii, Italy). Characterisation of the brown patinas and surrounding areas (plaster and polychromy) from the wall painting started with in situ screening using, mainly, a portable Raman instrument with a handheld FTIR (DRIFTS sampling interface) in order to select the sampling areas suitable for further analysis in the laboratory. Two wall painting fragments were then analysed in the laboratory in two steps. First, microscopic observations (SEM and phase-contrast microscopy) were used to determine whether biodeteriogens were present in the samples. In a second step, confocal Raman microscopy (785 and 514 nm excitation lasers) was used to characterise the main biogenic compounds of the brown stains. Because of the resonance Raman effect (514 nm excitation laser), it was possible to obtain reliable Raman features to assign not only the nature of the main biogenic pigments (carotenoids) present in the stains, but also their spatial conformation. Moreover, Raman confocal applications, for example, Raman imaging and depth profiling were also used in a first attempt to determine the distribution of biosynthesised carotenoids in the stains, and to determine the thickness of the brown patinas.

Basic instincts

NASA Astrophysics Data System (ADS)

Hutson, Matthew

2018-05-01

In their adaptability, young children demonstrate common sense, a kind of intelligence that, so far, computer scientists have struggled to reproduce. Gary Marcus, a developmental cognitive scientist at New York University in New York City, believes the field of artificial intelligence (AI) would do well to learn lessons from young thinkers. Researchers in machine learning argue that computers trained on mountains of data can learn just about anything—including common sense—with few, if any, programmed rules. But Marcus says computer scientists are ignoring decades of work in the cognitive sciences and developmental psychology showing that humans have innate abilities—programmed instincts that appear at birth or in early childhood—that help us think abstractly and flexibly. He believes AI researchers ought to include such instincts in their programs. Yet many computer scientists, riding high on the successes of machine learning, are eagerly exploring the limits of what a naïve AI can do. Computer scientists appreciate simplicity and have an aversion to debugging complex code. Furthermore, big companies such as Facebook and Google are pushing AI in this direction. These companies are most interested in narrowly defined, near-term problems, such as web search and facial recognition, in which blank-slate AI systems can be trained on vast data sets and work remarkably well. But in the longer term, computer scientists expect AIs to take on much tougher tasks that require flexibility and common sense. They want to create chatbots that explain the news, autonomous taxis that can handle chaotic city traffic, and robots that nurse the elderly. Some computer scientists are already trying. Such efforts, researchers hope, will result in AIs that sit somewhere between pure machine learning and pure instinct. They will boot up following some embedded rules, but will also learn as they go.

Theoretical study on the charge transport in single crystals of TCNQ, F2-TCNQ and F4-TCNQ.

PubMed

Ji, Li-Fei; Fan, Jian-Xun; Zhang, Shou-Feng; Ren, Ai-Min

2018-01-31

2,5-Difluoro-7,7,8,8-tetracyanoquinodimethane (F 2 -TCNQ) was recently reported to display excellent electron transport properties in single crystal field-effect transistors (FETs). Its carrier mobility can reach 25 cm 2 V -1 s -1 in devices. However, its counterparts TCNQ and F 4 -TCNQ (tetrafluoro-7,7,8,8-tetracyanoquinodimethane) do not exhibit the same highly efficient behavior. To better understand this significant difference in charge carrier mobility, a multiscale approach combining semiclassical Marcus hopping theory, a quantum nuclear enabled hopping model and molecular dynamics simulations was performed to assess the electron mobilities of the F n -TCNQ (n = 0, 2, 4) systems in this work. The results indicated that the outstanding electron transport behavior of F 2 -TCNQ arises from its effective 3D charge carrier percolation network due to its special packing motif and the nuclear tunneling effect. Moreover, the poor transport properties of TCNQ and F 4 -TCNQ stem from their invalid packing and strong thermal disorder. It was found that Marcus theory underestimated the mobilities for all the systems, while the quantum model with the nuclear tunneling effect provided reasonable results compared to experiments. Moreover, the band-like transport behavior of F 2 -TCNQ was well described by the quantum nuclear enabled hopping model. In addition, quantum theory of atoms in molecules (QTAIM) analysis and symmetry-adapted perturbation theory (SAPT) were used to characterize the intermolecular interactions in TCNQ, F 2 -TCNQ and F 4 -TCNQ crystals. A primary understanding of various noncovalent interaction responses for crystal formation is crucial to understand the structure-property relationships in organic molecular materials.

Iron(IV)hydroxide pK(a) and the role of thiolate ligation in C-H bond activation by cytochrome P450.

PubMed

Yosca, Timothy H; Rittle, Jonathan; Krest, Courtney M; Onderko, Elizabeth L; Silakov, Alexey; Calixto, Julio C; Behan, Rachel K; Green, Michael T

2013-11-15

Cytochrome P450 enzymes activate oxygen at heme iron centers to oxidize relatively inert substrate carbon-hydrogen bonds. Cysteine thiolate coordination to iron is posited to increase the pK(a) (where K(a) is the acid dissociation constant) of compound II, an iron(IV)hydroxide complex, correspondingly lowering the one-electron reduction potential of compound I, the active catalytic intermediate, and decreasing the driving force for deleterious auto-oxidation of tyrosine and tryptophan residues in the enzyme's framework. Here, we report on the preparation of an iron(IV)hydroxide complex in a P450 enzyme (CYP158) in ≥90% yield. Using rapid mixing technologies in conjunction with Mössbauer, ultraviolet/visible, and x-ray absorption spectroscopies, we determine a pK(a) value for this compound of 11.9. Marcus theory analysis indicates that this elevated pK(a) results in a >10,000-fold reduction in the rate constant for oxidations of the protein framework, making these processes noncompetitive with substrate oxidation.

Ultrafast photoinduced electron transfer in the micelle and the gel phase of a PEO-PPO-PEO triblock copolymer

NASA Astrophysics Data System (ADS)

Mandal, Ujjwal; Ghosh, Subhadip; Dey, Shantanu; Adhikari, Aniruddha; Bhattacharyya, Kankan

2008-04-01

Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to coumarin dyes is studied in the micelle and the gel phase of a triblock copolymer, (PEO)20-(PPO)70-(PEO)20 (Pluronic P123) by picosecond and femtosecond emission spectroscopies. The rate of PET in a P123 micelle and gel is found to be nonexponential and faster than the slow components of solvation dynamics. In a P123 micelle and gel, PET occurs on multiple time scales ranging from a subpicosecond time scale to a few nanoseconds. In the gel phase, the highest rate constant (9.3×109M-1s-1) of ET for C152 is about two times higher than that (3.8×109M-1s-1) observed in micelle phase. The ultrafast components of electron transfer (ET) exhibits a bell shaped dependence with the free energy change which is similar to the Marcus inversion. Possible reasons for slower PET in P123 micelle compared to other micelles and relative to P123 gel are discussed.

Kinetics of Spontaneous Bimetallization between Silver and Noble Metal Nanoparticles.

PubMed

Hirakawa, Kazutaka; Kaneko, Tetsuya; Toshima, Naoki

2018-06-05

A physical mixture of polymer-protected Ag nanoparticles and Rh, Pd, or Pt nanoparticles spontaneously forms Ag-core bimetallic nanoparticles. The formed nanoparticles were smaller than the parent Ag nanoparticles. In the initial process of this reaction, the surface plasmon absorption of Ag nanoparticles diminished and then almost ceased within one hour. Within several minutes, the decrease in Ag surface plasmon absorption could be analyzed by second-order reaction. This reaction was accelerated with an increase of temperature and the energy gap in the Fermi level between Ag and the other metals. The activation energy (E a ) of this reaction could be determined. An electron transfer reaction from Ag to other metal nanoparticles was proposed as the initial interaction between these metal nanoparticles because the Fermi level of Ag is relatively high, and the electron transfer is possible in terms of energy. The Marcus plot between the rate constant and the driving force, roughly estimated from the work function of metals, and the observed E a values reasonably explained the proposed electron transfer mechanism. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intramolecular singlet-singlet energy transfer in antenna-substituted azoalkanes.

PubMed

Pischel, Uwe; Huang, Fang; Nau, Werner M

2004-03-01

Two novel azoalkane bichromophores and related model compounds have been synthesised and photophysically characterised. Dimethylphenylsiloxy (DPSO) or dimethylnaphthylsiloxy (DNSO) serve as aromatic donor groups (antenna) and the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) as the acceptor. The UV spectral window of DBO (250-300 nm) allows selective excitation of the donor. Intramolecular singlet-singlet energy transfer to DBO is highly efficient and proceeds with quantum yields of 0.76 with DPSO and 0.99 with DNSO. The photophysical and spectral properties of the bichromophoric systems suggest that energy transfer occurs through diffusional approach of the donor and acceptor within a van der Waals contact at which the exchange mechanism is presumed to dominate. Furthermore, akin to the behaviour of electron-transfer systems in the Marcus inverted region, a rate of energy transfer 2.5 times slower was observed for the system with the more favourable energetics, i.e. singlet-singlet energy transfer from DPSO proceeded slower than from DNSO, although the process is more exergonic for DPSO (-142 kJ mol(-1) for DPSO versus-67 kJ mol(-1) for DNSO).

Reaction mechanisms and kinetics of the elimination processes of 2-chloroethylsilane and derivatives: A DFT study using CTST, RRKM, and BET theories

NASA Astrophysics Data System (ADS)

Shiroudi, Abolfazl; Zahedi, Ehsan; Oliaey, Ahmad Reza; Deleuze, Michael S.

2017-03-01

The thermal decomposition kinetics of 2-chloroethylsilane and derivatives in the gas phase has been studied computationally using density functional theory, along with various exchange-correlation functionals (UM06-2x and ωB97XD) and the aug-cc-pVTZ basis set. The calculated energy profile has been supplemented with calculations of kinetic rate constants under atmospheric pressure and in the fall-off regime, using transition state theory (TST) and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Activation energies and rate constants obtained using the UM06-2x/aug-cc-pVTZ approach are in good agreement with the experimental data. The decomposition of 2-chloroethyltriethylsilane species into the related products [C2H4 + Et3SiCl] is characterized by 6 successive structural stability domains associated to the sequence of catastrophes C8H19SiCl: 6-C†FCC†[FF]-0: C6H15SiCl + C2H4. Breaking of Si-C bonds and formation of Si-Cl bonds occur in the vicinity of the transition state.

Photoinduced electron transfer in a room temperature ionic liquid 1-butyl-3-methylimidazolium octyl sulfate micelle: a temperature dependent study.

PubMed

Sarkar, Souravi; Mandal, Sarthak; Pramanik, Rajib; Ghatak, Chiranjib; Rao, Vishal Govind; Sarkar, Nilmoni

2011-05-19

The effect of temperature on the dynamics of photoinduced electron transfer (PET) between different coumarin dyes and N,N-dimethyl aniline in a room temperature ionic liquid 1-butyl-3-methylimidazolium octyl sulfate ([C(4)mim][C(8)SO(4)]) micelle have been investigated using steady-state and time-resolved fluorescence quenching measurements at four different temperatures: 208, 298, 308, and 318 K. The quenching rates (k(q)(TR)) of the PET process in this micellar system are found to be lower than the PET rate in sodium dodecyl sulfate and Triton-X 100 micelle and almost comparable to the dodecyl trimethyl ammonium bromide and cetyl trimethyl ammonium bromide micelle due to larger donor–acceptor separation in the micellar phase. The temperature dependent PET rates are well correlated with the Arrhenius type of correlation for all the coumarin dyes. Marcus type of inversion in PET rates has been observed at relatively lower exergonicity, and the correlation plots gradually move upward with the increase of temperature. © 2011 American Chemical Society

Final Technical Report of the project "Controlling Quantum Information by Quantum Correlations"

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

Girolami, Davide

The report describes hypotheses, aims, methods and results of the project 20170675PRD2, “Controlling Quantum Information by Quantum Correlations”, which has been run from July 31, 2017 to January 7, 2018. The technical work has been performed by Director’s Fellow Davide Girolami of the T-4 Division, Physics of Condensed Matter and Complex Systems, under the supervision of Wojciech Zurek (T-4), Lukasz Cincio (T-4), and Marcus Daniels (CCS-7). The project ended as Davide Girolami has been converted to J. R. Oppenheimer Fellow to work on the project 20180702PRD1, “Optimal Control of Quantum Machines”, started on January 8, 2018.

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

NASA Astrophysics Data System (ADS)

Takagi, Hideo D.; Swaddle, Thomas W.

1996-01-01

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

Regioselective electrochemical reduction of 2,4-dichlorobiphenyl - Distinct standard reduction potentials for carbon-chlorine bonds using convolution potential sweep voltammetry

NASA Astrophysics Data System (ADS)

Muthukrishnan, A.; Sangaranarayanan, M. V.; Boyarskiy, V. P.; Boyarskaya, I. A.

2010-04-01

The reductive cleavage of carbon-chlorine bonds in 2,4-dichlorobiphenyl (PCB-7) is investigated using the convolution potential sweep voltammetry and quantum chemical calculations. The potential dependence of the logarithmic rate constant is non-linear which indicates the validity of Marcus-Hush theory of quadratic activation-driving force relationship. The ortho-chlorine of the 2,4-dichlorobiphenyl gets reduced first as inferred from the quantum chemical calculations and bulk electrolysis. The standard reduction potentials pertaining to the ortho-chlorine of 2,4-dichlorobiphenyl and that corresponding to para chlorine of the 4-chlorobiphenyl have been estimated.

The charger transfer electronic coupling in diabatic perspective: A multi-state density functional theory study

NASA Astrophysics Data System (ADS)

Guo, Xinwei; Qu, Zexing; Gao, Jiali

2018-01-01

The multi-state density functional theory (MSDFT) provides a convenient way to estimate electronic coupling of charge transfer processes based on a diabatic representation. Its performance has been benchmarked against the HAB11 database with a mean unsigned error (MUE) of 17 meV between MSDFT and ab initio methods. The small difference may be attributed to different representations, diabatic from MSDFT and adiabatic from ab initio calculations. In this discussion, we conclude that MSDFT provides a general and efficient way to estimate the electronic coupling for charge-transfer rate calculations based on the Marcus-Hush model.

A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride

NASA Astrophysics Data System (ADS)

Rivero, Uxía; Meuwly, Markus; Willitsch, Stefan

2017-09-01

The neutral and cationic Diels-Alder-type reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride have been computationally explored as the first step of a combined experimental and theoretical study. Density functional theory calculations show that the neutral reaction is concerted while the cationic reaction can be either concerted or stepwise. Further isomerizations of the Diels-Alder products have been studied in order to predict possible fragmentation pathways in gas-phase experiments. Rice-Ramsperger-Kassel-Marcus (RRKM) calculations suggest that under single-collision experimental conditions the neutral product may reform the reactants and the cationic product will most likely eliminate CO2.

Anharmonic Effect in CH3CH2C(=O)OCH2CH3 Decomposition

NASA Astrophysics Data System (ADS)

Ding, Yang; Song, Liguo; Yao, Li; Xia, Wenwen

2017-12-01

In this paper, using the B3LYP functional and CCSD(T) method with 6-311++G** basis set, the harmonic and anharmonic rate constants in the unimolecular dissociation of ethyl propanoate have been calculated using Rice-Ramsperger-Kassel-Marcus theory. The anharmonic rate constants of the title reaction have also been examined, the comparison shows that, the anharmonic effect especially in the case of high total energies and temperature for channels 3 to 6 is significant, so that the anharmonic effect cannot be neglected for unimolecular dissociation reaction of CH3CH2C(=O)OCH2CH3 both in microcanonical and canonical systems.

Communication: Charge-transfer rate constants in zinc-porphyrin-porphyrin-derived dyads: A Fermi golden rule first-principles-based study

NASA Astrophysics Data System (ADS)

Manna, Arun K.; Dunietz, Barry D.

2014-09-01

We investigate photoinduced charge transfer (CT) processes within dyads consisting of porphyrin derivatives in which one ring ligates a Zn metal center and where the rings vary by their degree of conjugation. Using a first-principles approach, we show that molecular-scale means can tune CT rates through stabilization affected by the polar environment. Such means of CT tuning are important for achieving high efficiency optoelectronic applications using organic semiconducting materials. Our fully quantum mechanical scheme is necessary for reliably modeling the CT process across different regimes, in contrast to the pervading semi-classical Marcus picture that grossly underestimates transfer in the far-inverted regime.

Influence of electric field on interwell tunneling rate in quasi two dimensional organic quantum wells

NASA Astrophysics Data System (ADS)

Donovan, K. J.; Elliott, J. E.; Jeong, I. S.; Scott, K.; Wilson, E. G.

2000-11-01

The tunneling rate of photocreated charge carriers between layers in Langmuir-Blodgett multilayer structures is measured indirectly using the novel technique of bimolecular recombination quenching. The tunneling rate is demonstrated to be dependent upon the applied electrostatic potential difference between the layers. This dependence is explored in light of the Marcus theory of charge transfer. That theory was developed to describe redox reactions where the driving force is supplied by a chemical potential difference between two chemically different parts of a more complex system. In the current work the electrostatic potential replaces the chemical potential as the driving potential. The field dependence of the exciton dissociation probability is also determined.

Modeling of hydrogen evolution reaction on the surface of GaInP2

NASA Astrophysics Data System (ADS)

Choi, Woon Ih; Wood, Brandon; Schwegler, Eric; Ogitsu, Tadashi

2012-02-01

GaInP2 is promising candidate material for hydrogen production using sunlight. It reduces solvated proton into hydrogen molecule using light-induced excited electrons in the photoelectrochemical cell. However, it is challenging to model hydrogen evolution reaction (HER) using first-principles molecular dynamics. Instead, we use Anderson-Newns model and generalized solvent coordinate in Marcus-Hush theory to describe adiabatic free energy surface of HER. Model parameters are fitted from the DFT calculations. We model Volmer-Heyrovsky reaction path on the surfaces of CuPt phase of GaInP2. We also discuss effects of surface oxide and catalyst atoms that exist on top of bare surfaces in experimental circumstances.

Kinetics of the reduction of cobalt(III) amine complexes by 1-hydroxy-1-methylethyl radicals

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

Kusaba, K.; Ogino, Hiroshi; Bakac, A.

1989-03-08

In order to better understand the rate constants for the reduction of several cobalt complexes by 1-hydroxy-1-methylene radicals ({sup {sm bullet}}C(CH{sub 3}){sub 2}OH), the reactions of {sup {sm bullet}}(CH{sub 3}){sub 2}OH with several cobalt(III) complexes of bidentate amines have been studied. The Marcus-Hush theory was deemed the most appropriate for analysis of the kinetic data. The correlation between the kinetics of the reduction of the Co(III) amines by C(CH{sub 3}){sub 2}OH and the reduction of the first d-d band for Co(III) complexes is discussed. 21 refs., 2 figs., 1 tab.

Activation Energies of Fragmentations of Disaccharides by Tandem Mass Spectrometry

NASA Astrophysics Data System (ADS)

Kuki, Ákos; Nagy, Lajos; Szabó, Katalin E.; Antal, Borbála; Zsuga, Miklós; Kéki, Sándor

2014-03-01

A simple multiple collision model for collision induced dissociation (CID) in quadrupole was applied for the estimation of the activation energy (Eo) of the fragmentation processes for lithiated and trifluoroacetated disaccharides, such as maltose, cellobiose, isomaltose, gentiobiose, and trehalose. The internal energy-dependent rate constants k(Eint) were calculated using the Rice-Ramsperger-Kassel-Marcus (RRKM) or the Rice-Ramsperger-Kassel (RRK) theory. The Eo values were estimated by fitting the calculated survival yield (SY) curves to the experimental ones. The calculated Eo values of the fragmentation processes for lithiated disaccharides were in the range of 1.4-1.7 eV, and were found to increase in the order trehalose < maltose < isomaltose < cellobiose < gentiobiose.

CN radical reactions with hydrogen cyanide and cyanogen - Comparison of theory and experiment

NASA Technical Reports Server (NTRS)

Yang, D. L.; Yu, T.; Lin, M. C.; Melius, C. F.

1992-01-01

The method of laser photolysis/laser-induced fluorescence is used to obtain absolute rate constants for CN radical reactions with HCN and C2N2. The rate constants were found to be temperature-dependent in the range 300-740 K and pressure independent in the range 100-600 Torr. Rice-Remsperger-Kassel-Marcus theory for both reactions employing the transition state parameters obtained by the BAC-MP4 method are made. These calculations yielded reasonable results for the CN + HCN reaction, predicting both the temperature dependence and pressure independence. No pressure effect was observed in the pressure range 100-1000 Torr at temperatures below 900 K, confirming the experimental results.

A new calibration of the semi-empirical photometric theory for Halley and other comets

NASA Technical Reports Server (NTRS)

Newburn, R. L., Jr.

1984-01-01

The semiempirical photometric theory of gas and dust production in comets (Newburn, 1979, 1981, and 1982) is recalibrated on the basis of the 17-comet compilation of spectrophotometric data of Newburn and Spinrad (1984). The results are presented in graphs and tables, and it is shown that no corrections are required for the constant R and the function delta, but that the mixing ratios (obtained as functions of heliocentric distance) can be improved, with implications for the visual-photometric comet model. Recently calculated light curves for comet Halley are compared, and the use of the nearly identical curves of Bortle and Morris (1984) and Marcus (1983) is recommended.

SU-F-T-171: Manufacturing Cost Effective Heterogeneous Phantoms for Use in Proton Therapy

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

Pruett, J; Chen, Y; Ahmad, S

Purpose: To study the feasibility of 3D printing cost effective heterogeneous phantoms for use in proton therapy treatment planning quality assurance. Methods: A desktop 3D printer was utilized to create a series of 2 cm × 2 cm × 4 cm PLA plastic blocks of varying fill materials and hexagonal fill pattern. The blocks were than tested when filled with air, polyurethane foam, paraffin, silicone, and caulk of calcium carbonate – acrylic polymer blend. The blocks were evaluated with a “GE Lightspeed” 16 slice CT scanner and average CT# of the materials’ centers evaluated. Blocks were then placed into amore » custom aperture fitted to a Mevion Proton system to determine the relative stopping power of each. Scans were performed in water tank with Marcus type parallel plate chamber under a beam with a range of 15 cm and modulation of 2 cm. Shifts in range occurring relative to the 80% distal edge of the open SOBP were evaluated. Results: The CT#s of the blocks were plotted against their measured relative stopping power. This curve was compared to that which is in clinical use. While the trend agrees generally, specific differences between the relative stopping powers were as great as 10%. Conclusion: We have demonstrated that it is possible to utilize different cost effective materials in the manufacturing of phantoms for use in proton therapy. While different materials may provide better agreement to established calibration curves, a custom curve specific to the materials used may be utilized to accurately predict proton treatment dose distributions.« less

A scrutiny of the premise of the Rice-Ramsperger-Kassel-Marcus theory in isomerization reaction of an Ar7-type molecule

NASA Astrophysics Data System (ADS)

Takatsuka, Kazuo; Seko, Chihiro

1996-12-01

The validity of the physical premise of the Rice-Ramsperger-Kassel-Marcus (RRKM) theory is investigated in terms of the classical dynamics of isomerization reaction in Ar7-like molecules (clusters). The passage times of classical trajectories through the potential basins of isomers in the structural transitions are examined. In the high energy region corresponding to the so-called liquidlike phase, remarkable uniformity of the average passage times has been found. That is, the average passage time is characterized only by a basin through which a trajectory is currently passing and, hence, does not depend on the next visiting basins. This behavior is out of accord with the ordinary chemical law in that the ``reaction rates'' do not seem to depend on the height of the individual potential barriers. We ascribe this seemingly strange uniformity to the strong mixing (chaos) lying behind the rate process. That is, as soon as a classical path enters a basin, it gets involved into a chaotic zone in which many paths having different channels are entangled among each other, and effectively (in the statistical sense) loses its memory about which basin it came from and where it should visit next time. This model is verified by confirming that the populations of the lifetime of transition from one basin to others are expressed in exponential functions, which should have very similar exponents to each other in each passing-through basin. The inverse of the exponent is essentially proportional to the average passage time, and consequently brings about the uniformity. These populations set a foundation for the multichannel generalization of the RRKM theory. Two cases of the non-RRKM behaviors have been studied. One is a nonstatistical behavior in the low energy region such as the so-called coexistence phase. The other is the short-time behavior. It is well established [M. Berblinger and C. Schlier, J. Chem. Phys. 101, 4750 (1994)] that in a relatively simple and small system such as H+3, the so-called direct paths, which lead to dissociation before the phase-space mixing is completed, increase the probability of short-time passage. In contrast, we have found in our Ar7-like molecules that trajectories of short passage time are fewer than expected by the statistical theory. It is conceived that somewhat a long time in the initial stage of the isomerization is spent by a trajectory to find its ways out to the next basins.

Ab initio chemical kinetic study on Cl + ClO and related reverse processes.

PubMed

Xu, Z F; Lin, M C

2010-11-04

The reaction of ClO with Cl and its related reverse processes have been studied theoretically by ab initio quantum chemical and statistical mechanical calculations. The geometric parameters of the reactants, products, and transition states are optimized by both UMPW1PW91 and unrestricted coupled-cluster single and double excitation (UCCSD) methods with the 6-311+G(3df) basis set. The potential energy surface has been further refined (with triple excitations, T) at the UCCSD(T)/6-311+G(3df) level of theory. The results show that Cl(2) and O ((3)P) can be produced by chlorine atom abstraction via a tight transition state, while ClOCl ((1)A(1)) and ClClO ((1)A') can be formed by barrierless association processes with exothermicities of 31.8 and 16.0 kcal/mol, respectively. In principle the O ((1)D) atom can be generated with a large endothermicity of 56.9 kcal/mol; on the other hand, its barrierless reaction with Cl(2) can readily form ClClO ((1)A'), which fragments rapidly to give ClO + Cl. The rate constants of both forward and reverse processes have been predicted at 150-2000 K by the microcanonical variational transition state theory (VTST)/Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The predicted rate constants are in good agreement with available experimental data within reported errors.

Charge-transfer dynamics and nonlocal dielectric permittivity tuned with metamaterial structures as solvent analogues

NASA Astrophysics Data System (ADS)

Lee, Kwang Jin; Xiao, Yiming; Woo, Jae Heun; Kim, Eunsun; Kreher, David; Attias, André-Jean; Mathevet, Fabrice; Ribierre, Jean-Charles; Wu, Jeong Weon; André, Pascal

2017-07-01

Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7--that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal-dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.

Length-dependence of intramolecular electron transfer in σ-bonded rigid molecular rods: an ab initio molecular orbital study

NASA Astrophysics Data System (ADS)

Pati, Ranjit; Karna, Shashi P.

2002-01-01

The dependence of electron transfer (ET) coupling element, VAB, on the length of rigid-rod-like systems consisting of bicyclo[1.1.1]pentane (BCP), cubane (CUB), and bicyclo[2.2.2]octane (BCO) monomers, has been investigated with the use of ab initio Hartree-Fock (HF) method employing Marcus-Hush two-state (TS) model. The value of VAB decreases exponentially with increase in the number of the cage units of the σ-bonded molecules. The calculated decay constant, β, shows good agreement with previously reported data. For molecular length⩾15 Å, the value of VAB becomes negligibly small, suggesting complete suppression of the through bond direct tunneling contribution to ET process.

Chain conformations dictate multiscale charge transport phenomena in disordered semiconducting polymers

PubMed Central

Noriega, Rodrigo; Salleo, Alberto; Spakowitz, Andrew J.

2013-01-01

Existing models for the electronic properties of conjugated polymers do not capture the spatial arrangement of the disordered macromolecular chains over which charge transport occurs. Here, we present an analytical and computational description in which the morphology of individual polymer chains is dictated by well-known statistical models and the electronic coupling between units is determined using Marcus theory. The multiscale transport of charges in these materials (high mobility at short length scales, low mobility at long length scales) is naturally described with our framework. Additionally, the dependence of mobility with electric field and temperature is explained in terms of conformational variability and spatial correlation. Our model offers a predictive approach to connecting processing conditions with transport behavior. PMID:24062459

Effect of group electronegativity on electron transfer in bis(hydrazine) radical cations.

PubMed

Qin, Haimei; Zhong, Xinxin; Si, Yubing; Zhang, Weiwei; Zhao, Yi

2011-04-14

The radical cation of 4,10-ditert-butyl-5,9-diisopropyl-4,5,9,10-tetraazatetracyclo[6.2.2.2]-tetradecane (sBI4T(+)), as well as its substituted bis(hydrazine) radical cations, is chosen for the investigation of the electronegativity dependence of its intramolecular electron transfer. To do so, two parameters, reorganization energy and electronic coupling, are calculated with several ab initio approaches. It is found that the electronic couplings decrease with the increase of the group electronegativity while the reorganization energies do not show an explicit dependency. Furthermore, Marcus formula is employed to reveal those effect on the electron transfer rates. The predicted rates of electron transfer generally decrease with increasing group electronegativity, although not monotonically.

Investigation of giant magnetoconductance in organic devices based on hopping mechanism

NASA Astrophysics Data System (ADS)

Yang, F. J.; Qin, W.; Xie, S. J.

2014-04-01

We suggest a spin-dependent hopping mechanism which includes the effect of the external magnetic field as well as hyperfine interaction (HFI) to explain the observed giant magnetoconductance (MC) in non-magnetic organic devices. Based on the extended Marcus theory, we calculate the MC by using the master equation. It is found that a MC value as large as 91% is obtained under a low driving voltage. For suitable parameters, the theoretical results are in good agreement with the experimental data. Influences of the carrier density, HFI, and the carrier localization on the MC value are investigated. Especially, it is found that a low-dimensional structure of the organic materials is favorable to get a large MC value.

Investigation of giant magnetoconductance in organic devices based on hopping mechanism

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

Yang, F. J.; Qin, W.; Xie, S. J., E-mail: xsj@sdu.edu.cn

2014-04-14

We suggest a spin-dependent hopping mechanism which includes the effect of the external magnetic field as well as hyperfine interaction (HFI) to explain the observed giant magnetoconductance (MC) in non-magnetic organic devices. Based on the extended Marcus theory, we calculate the MC by using the master equation. It is found that a MC value as large as 91% is obtained under a low driving voltage. For suitable parameters, the theoretical results are in good agreement with the experimental data. Influences of the carrier density, HFI, and the carrier localization on the MC value are investigated. Especially, it is found thatmore » a low-dimensional structure of the organic materials is favorable to get a large MC value.« less

Chain conformations dictate multiscale charge transport phenomena in disordered semiconducting polymers.

PubMed

Noriega, Rodrigo; Salleo, Alberto; Spakowitz, Andrew J

2013-10-08

Existing models for the electronic properties of conjugated polymers do not capture the spatial arrangement of the disordered macromolecular chains over which charge transport occurs. Here, we present an analytical and computational description in which the morphology of individual polymer chains is dictated by well-known statistical models and the electronic coupling between units is determined using Marcus theory. The multiscale transport of charges in these materials (high mobility at short length scales, low mobility at long length scales) is naturally described with our framework. Additionally, the dependence of mobility with electric field and temperature is explained in terms of conformational variability and spatial correlation. Our model offers a predictive approach to connecting processing conditions with transport behavior.

Theoretical insights into the effect of a conjugated core on the hole transport properties of hole-transporting materials for perovskite solar cells.

PubMed

Zhang, Zemin; Hu, Weixia; Cui, Jianyu; He, Rongxing; Shen, Wei; Li, Ming

2017-09-20

Conjugated bifluorenylidene and naphthalene central cores are introduced into hole-transporting materials DT1 and DT2 to replace the spiro-core of the reported, highly efficient FDT. The effects of the conjugated core on the geometrics, electronic properties and hole transport properties are investigated by using density functional theory coupled with Marcus theory and the Einstein relation. The calculated results show that DT1 (-5.21 eV) and DT2 (-5.23 eV) have lower HOMO levels than FDT (-5.15 eV), which indicates that the perovskite solar cells with conjugated hole-transporting materials can have higher open-circuit voltages. The introduction of the conjugated core is beneficial to the more efficient face-to-face packing pattern of the dimer, resulting in a larger intermolecular electronic coupling. Importantly, it is found that DT1 (1.6 × 10 -3 cm 2 V -1 s -1 ) and DT2 (2.7 × 10 -2 cm 2 V -1 s -1 ) exhibit relatively higher hole mobilities than FDT (1.3 × 10 -4 cm 2 V -1 s -1 ) owing to the larger electronic coupling. Therefore, enhanced hole transport ability can be achieved by switching from the spiro-core to the conjugated core. The present work provides a new strategy to improve the hole transport properties of hole-transporting materials, which will contribute to the development of conjugated small molecules as hole-transporting materials in efficient perovskite solar cells.

The effect of zero-point energy differences on the isotope dependence of the formation of ozone: a classical trajectory study.

PubMed

Schinke, Reinhard; Fleurat-Lessard, Paul

2005-03-01

The effect of zero-point energy differences (DeltaZPE) between the possible fragmentation channels of highly excited O(3) complexes on the isotope dependence of the formation of ozone is investigated by means of classical trajectory calculations and a strong-collision model. DeltaZPE is incorporated in the calculations in a phenomenological way by adjusting the potential energy surface in the product channels so that the correct exothermicities and endothermicities are matched. The model contains two parameters, the frequency of stabilizing collisions omega and an energy dependent parameter Delta(damp), which favors the lower energies in the Maxwell-Boltzmann distribution. The stabilization frequency is used to adjust the pressure dependence of the absolute formation rate while Delta(damp) is utilized to control its isotope dependence. The calculations for several isotope combinations of oxygen atoms show a clear dependence of relative formation rates on DeltaZPE. The results are similar to those of Gao and Marcus [J. Chem. Phys. 116, 137 (2002)] obtained within a statistical model. In particular, like in the statistical approach an ad hoc parameter eta approximately 1.14, which effectively reduces the formation rates of the symmetric ABA ozone molecules, has to be introduced in order to obtain good agreement with the measured relative rates of Janssen et al. [Phys. Chem. Chem. Phys. 3, 4718 (2001)]. The temperature dependence of the recombination rate is also addressed.

Theoretical comparative studies on transport properties of pentacene, pentathienoacene, and 6,13-dichloropentacene.

PubMed

Zhang, Xu; Yang, Xiaodi; Geng, Hua; Nan, Guangjun; Sun, Xingwen; Xi, Jinyang; Xu, Xin

2015-05-05

Pentacene derivative 6,13-dichloropentacene (DCP) is one of the latest additions to the family of organic semiconductors with a great potential for use in transistors. We carry out a detailed theoretical calculation for DCP, with systematical comparison to pentacene, pentathienoacene (PTA, the thiophene equivalent of pentacene), to gain insights in the theoretical design of organic transport materials. The charge transport parameters and carrier mobilities are investigated from the first-principles calculations, based on the widely used Marcus electron transfer theory and quantum nuclear tunneling model, coupled with random walk simulation. Molecular structure and the crystal packing type are essential to understand the differences in their transport behaviors. With the effect of molecule modification, significant one-dimensional π-stacks are found within the molecular layer in PTA and DCP crystals. The charge transport along the a-axis plays a dominant role for the carrier mobilities in the DCP crystal due to the strong transfer integrals within the a-axis. Pentacene shows a relatively large 3D mobility. This is attributed to the relatively uniform electronic couplings, which thus provides more transport pathways. PTA has a much smaller 3D mobility than pentacene and DCP for the obvious increase of the reorganization energy with the introduction of thiophene. It is found that PTA and DCP exhibit lower HOMO (highest occupied molecular orbital) levels and better environmental stability, indicating the potential applications in organic electronics. © 2015 Wiley Periodicals, Inc.

Rolling the dice on the ice; New modes for underway data acquisition in the Arctic Ocean

NASA Astrophysics Data System (ADS)

Coakley, B.; Dove, D.

2012-12-01

Exploration of the Arctic Ocean has always depended on the sea ice. It has been a platform supporting drifting ice stations and an obstacle to be over come by force (icebreakers) or finesse (US Navy fast attack submarines). Reduced seasonal sea ice cover has made it possible to work more freely in the peripheral Arctic Ocean, opening relatively unknown regions to scientific exploration and study. In September 2011, the RV Marcus G. Langseth set sail from Dutch Harbor, Alaska bound through Bering Strait for the Arctic Ocean. This was the first Arctic Ocean trip for MGG data acquisition by a US academic research vessel since 1994, when the RV Maurice Ewing collected a 2-D MCS profile across the Bering Shelf, through the Strait and along the Beaufort Shelf, stopping near Barrow, Alaska. RV Langseth arrived on the mid-Chukchi shelf and streamed gear just south of the "Crackerjack" well, drilled by Shell Exploration in the late eighties. The ship sailed north, crossing the "Popcorn" well and then set a course to the NW, setting the baseline for the survey parallel to the Beaufort Shelf edge. Sailing through almost entirely ice-free waters, approximately 5300 km of multi-channel seismic reflection data were acquired on a NW-SE oriented grid, which straddled the transition from Chukchi Shelf to the Chukchi Borderland. It would not have been possible for Langseth, which is not ice reinforced, to acquire these data prior to 2007. The dramatic expansion of late Summer open water in the western Arctic Ocean made it possible to use this ship effectively across a broad swath of the shelf and the periphery of the deep central basin. While the survey region was almost entirely ice free during this cruise, which straddled the ice minimum for 2011, it was not possible to predict this a priori, despite expectations set by the previous five years of ice edge retreat. For this reason, the Canadian Ice Service was engaged to provide interpreted ice imagery, multiple times per day, substantially improving the ship's ability to operate confidently in this region, particularly at night. As confidence increases about the timing and extent of open water over the shelves and periphery of Arctic Ocean, it is possible to anticipate utilizing other UNOLS vessels and other resources (eg. JOIDES Resolution) in the Arctic. Employing these ships, with appropriate interpretive support, will open a new chapter in the exploration of this relatively unknown ocean basin.

Hydrogen scrambling in ethane induced by intense laser fields: statistical analysis of coincidence events.

PubMed

Kanya, Reika; Kudou, Tatsuya; Schirmel, Nora; Miura, Shun; Weitzel, Karl-Michael; Hoshina, Kennosuke; Yamanouchi, Kaoru

2012-05-28

Two-body Coulomb explosion processes of ethane (CH(3)CH(3)) and its isotopomers (CD(3)CD(3) and CH(3)CD(3)) induced by an intense laser field (800 nm, 1.0 × 10(14) W/cm(2)) with three different pulse durations (40 fs, 80 fs, and 120 fs) are investigated by a coincidence momentum imaging method. On the basis of statistical treatment of the coincidence data, the contributions from false coincidence events are estimated and the relative yields of the decomposition pathways are determined with sufficiently small uncertainties. The branching ratios of the two body decomposition pathways of CH(3)CD(3) from which triatomic hydrogen molecular ions (H(3)(+), H(2)D(+), HD(2)(+), D(3)(+)) are ejected show that protons and deuterons within CH(3)CD(3) are scrambled almost statistically prior to the ejection of a triatomic hydrogen molecular ion. The branching ratios were estimated by statistical Rice-Ramsperger-Kassel-Marcus calculations by assuming a transition state with a hindered-rotation of a diatomic hydrogen moiety. The hydrogen scrambling dynamics followed by the two body decomposition processes are discussed also by using the anisotropies in the ejection directions of the fragment ions and the kinetic energy distribution of the two body decomposition pathways.

Describing long-range charge-separation processes with subsystem density-functional theory

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

Solovyeva, Alisa; Neugebauer, Johannes, E-mail: j.neugebauer@uni-muenster.de; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu

2014-04-28

Long-range charge-transfer processes in extended systems are difficult to describe with quantum chemical methods. In particular, cost-effective (non-hybrid) approximations within time-dependent density functional theory (DFT) are not applicable unless special precautions are taken. Here, we show that the efficient subsystem DFT can be employed as a constrained DFT variant to describe the energetics of long-range charge-separation processes. A formal analysis of the energy components in subsystem DFT for such excitation energies is presented, which demonstrates that both the distance dependence and the long-range limit are correctly described. In addition, electronic couplings for these processes as needed for rate constants inmore » Marcus theory can be obtained from this method. It is shown that the electronic structure of charge-separated states constructed by a positively charged subsystem interacting with a negatively charged one is difficult to converge — charge leaking from the negative subsystem to the positive one can occur. This problem is related to the delocalization error in DFT and can be overcome with asymptotically correct exchange–correlation (XC) potentials or XC potentials including a sufficiently large amount of exact exchange. We also outline an approximate way to obtain charge-transfer couplings between locally excited and charge-separated states.« less

Charge-transfer mobility and electrical conductivity of PANI as conjugated organic semiconductors

NASA Astrophysics Data System (ADS)

Zhang, Yahong; Duan, Yuping; Song, Lulu; Zheng, Daoyuan; Zhang, Mingxing; Zhao, Guangjiu

2017-09-01

The intramolecular charge transfer properties of a phenyl-end-capped aniline tetramer (ANIH) and a chloro-substituted derivative (ANICl) as organic semiconductors were theoretically studied through the first-principles calculation based on the Marcus-Hush theory. The reorganization energies, intermolecular electronic couplings, angular resolution anisotropic mobilities, and density of states of the two crystals were evaluated. The calculated results demonstrate that both ANIH and ANICl crystals show the higher electron transfer mobilities than the hole-transfer mobilities, which means that the two crystals should prefer to function as n-type organic semiconductors. Furthermore, the angle dependence mobilities of the two crystals show remarkable anisotropic character. The maximum mobility μmax of ANIH and ANICl crystals is 1.3893 and 0.0272 cm2 V-1 s-1, which appear at the orientation angles near 176°/356° and 119°/299° of a conducting channel on the a-b reference plane. It is synthetically evaluated that the ANIH crystal possesses relatively lower reorganization energy, higher electronic coupling, and electron transfer mobility, which means that the ANIH crystal may be the more ideal candidate as a high performance n-type organic semiconductor material. The systematic theoretical studies on organic crystals should be conducive to evaluating the charge-transport properties and designing higher performance organic semiconductor materials.

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

NASA Astrophysics Data System (ADS)

Kavner, Abby; Bonet, François; Shahar, Anat; Simon, Justin; Young, Edward

2005-06-01

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from -0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values (relative to IRMM-14) ranging from -0.18(±0.02) to -2.290(±0.006) ‰, and corresponding δ 57Fe values of -0.247(±0.014) and -3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus's theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.

Charge-transfer mobility and electrical conductivity of PANI as conjugated organic semiconductors.

PubMed

Zhang, Yahong; Duan, Yuping; Song, Lulu; Zheng, Daoyuan; Zhang, Mingxing; Zhao, Guangjiu

2017-09-21

The intramolecular charge transfer properties of a phenyl-end-capped aniline tetramer (ANIH) and a chloro-substituted derivative (ANICl) as organic semiconductors were theoretically studied through the first-principles calculation based on the Marcus-Hush theory. The reorganization energies, intermolecular electronic couplings, angular resolution anisotropic mobilities, and density of states of the two crystals were evaluated. The calculated results demonstrate that both ANIH and ANICl crystals show the higher electron transfer mobilities than the hole-transfer mobilities, which means that the two crystals should prefer to function as n-type organic semiconductors. Furthermore, the angle dependence mobilities of the two crystals show remarkable anisotropic character. The maximum mobility μ max of ANIH and ANICl crystals is 1.3893 and 0.0272 cm 2 V -1 s -1 , which appear at the orientation angles near 176°/356° and 119°/299° of a conducting channel on the a-b reference plane. It is synthetically evaluated that the ANIH crystal possesses relatively lower reorganization energy, higher electronic coupling, and electron transfer mobility, which means that the ANIH crystal may be the more ideal candidate as a high performance n-type organic semiconductor material. The systematic theoretical studies on organic crystals should be conducive to evaluating the charge-transport properties and designing higher performance organic semiconductor materials.

On the gas phase fragmentation of protonated uracil: a statistical perspective.

PubMed

Rossich Molina, Estefanía; Salpin, Jean-Yves; Spezia, Riccardo; Martínez-Núñez, Emilio

2016-06-01

The potential energy surface of protonated uracil has been explored by an automated transition state search procedure, resulting in the finding of 1398 stationary points and 751 reactive channels, which can be categorized into isomerizations between pairs of isomers, unimolecular fragmentations and bimolecular reactions. The use of statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory and Kinetic Monte Carlo (KMC) simulations allowed us to determine the relative abundances of each fragmentation channel as a function of the ion's internal energy. The KMC/RRKM product abundances are compared with novel mass spectrometry (MS) experiments in the collision energy range 1-6 eV. To facilitate the comparison between theory and experiments, further dynamics simulations are carried out to determine the fraction of collision energy converted into the ion's internal energy. The KMC simulations show that the major fragmentation channels are isocyanic acid and ammonia losses, in good agreement with experiments. The third predominant channel is water loss according to both theory and experiments, although the abundance obtained in the KMC simulations is very low, suggesting that non-statistical dynamics might play an important role in this channel. Isocyanic acid (HNCOH(+)) is also an important product in the KMC simulations, although its abundance is only significant at internal energies not accessible in the MS experiments.

Cardiomyocytes from human pluripotent stem cells: From laboratory curiosity to industrial biomedical platform.

PubMed

Denning, Chris; Borgdorff, Viola; Crutchley, James; Firth, Karl S A; George, Vinoj; Kalra, Spandan; Kondrashov, Alexander; Hoang, Minh Duc; Mosqueira, Diogo; Patel, Asha; Prodanov, Ljupcho; Rajamohan, Divya; Skarnes, William C; Smith, James G W; Young, Lorraine E

2016-07-01

Cardiomyocytes from human pluripotent stem cells (hPSCs-CMs) could revolutionise biomedicine. Global burden of heart failure will soon reach USD $90bn, while unexpected cardiotoxicity underlies 28% of drug withdrawals. Advances in hPSC isolation, Cas9/CRISPR genome engineering and hPSC-CM differentiation have improved patient care, progressed drugs to clinic and opened a new era in safety pharmacology. Nevertheless, predictive cardiotoxicity using hPSC-CMs contrasts from failure to almost total success. Since this likely relates to cell immaturity, efforts are underway to use biochemical and biophysical cues to improve many of the ~30 structural and functional properties of hPSC-CMs towards those seen in adult CMs. Other developments needed for widespread hPSC-CM utility include subtype specification, cost reduction of large scale differentiation and elimination of the phenotyping bottleneck. This review will consider these factors in the evolution of hPSC-CM technologies, as well as their integration into high content industrial platforms that assess structure, mitochondrial function, electrophysiology, calcium transients and contractility. This article is part of a Special Issue entitled: Cardiomyocyte Biology: Integration of Developmental and Environmental Cues in the Heart edited by Marcus Schaub and Hughes Abriel. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Columnar mesophases of hexabenzocoronene derivatives. II. Charge carrier mobility

NASA Astrophysics Data System (ADS)

Kirkpatrick, James; Marcon, Valentina; Kremer, Kurt; Nelson, Jenny; Andrienko, Denis

2008-09-01

Combining atomistic molecular dynamic simulations, Marcus-Hush theory description of charge transport rates, and master equation description of charge dynamics, we correlate the temperature-driven change of the mesophase structure with the change of charge carrier mobilities in columnar phases of hexabenzocoronene derivatives. The time dependence of fluctuations in transfer integrals shows that static disorder is predominant in determining charge transport characteristics. Both site energies and transfer integrals are distributed because of disorder in the molecular arrangement. It is shown that the contributions to the site energies from polarization and electrostatic effects are of opposite sign for positive charges. We look at three mesophases of hexabenzocoronene: herringbone, discotic, and columnar disordered. All results are compared to time resolved microwave conductivity data and show excellent agreement with no fitting parameters.

Sharpen your bargaining skills.

PubMed

Marcus, L J

1996-10-14

As the health-care revolution continues, bargaining skills have become more crucial for doctors than ever before. If you want your practice to thrive, you must regularly negotiate with colleagues, practice administrators, allied health professionals, managed-care plans, business groups, hospitals, and the government. Yet medical schools and residency programs devote little if any time to negotiating skills. The "golden days," when physicians could afford to be mavericks, are over. Doctors must develop a new collaborative outlook to be successful and happy in their careers, says Leonard J. Marcus, Ph.D., lead author of the book "Renegotiating Health Care: Resolving conflict to Build Collaboration." He and his co-authors often conduct seminars for health professionals on improving bargaining skills. The following excerpt concerns the role of conflict in negotiation, and how to resolve it.

Columnar mesophases of hexabenzocoronene derivatives. II. Charge carrier mobility.

PubMed

Kirkpatrick, James; Marcon, Valentina; Kremer, Kurt; Nelson, Jenny; Andrienko, Denis

2008-09-07

Combining atomistic molecular dynamic simulations, Marcus-Hush theory description of charge transport rates, and master equation description of charge dynamics, we correlate the temperature-driven change of the mesophase structure with the change of charge carrier mobilities in columnar phases of hexabenzocoronene derivatives. The time dependence of fluctuations in transfer integrals shows that static disorder is predominant in determining charge transport characteristics. Both site energies and transfer integrals are distributed because of disorder in the molecular arrangement. It is shown that the contributions to the site energies from polarization and electrostatic effects are of opposite sign for positive charges. We look at three mesophases of hexabenzocoronene: herringbone, discotic, and columnar disordered. All results are compared to time resolved microwave conductivity data and show excellent agreement with no fitting parameters.

Computer-based diagnostic decisionmaking.

PubMed

Miller, R A

1987-12-01

The three decisionmaking aids described by the authors attack the generic problem of "see no evil, hear no evil, speak no evil"--improving the detection, diagnosis, and therapy of psychiatric disorders in the primary care setting. The three systems represent interventions at different steps in the process of providing appropriate care to psychiatric patients. The DSPW system of Robins and Marcus offers the potential of increasing the recognition of psychiatric disease in the physician's office. Politser's IDS program is representative of the sort of sophisticated microcomputer-based decisionmaking support tools that will become available to physicians in the not-too-distant future. Erdman's study of the impact of explanation capabilities on the acceptability of therapy recommending systems points out the need for careful scientific evaluations of features added to diagnostic and therapeutic systems.

The rules of drug taking: wine and poppy derivatives in the Ancient World. VIII. Lack of evidence of opium addiction.

PubMed

Nencini, P

1997-09-01

The widespread therapeutic use of opium and its probable ritual use is faced with the absence of any explicit description of cases of opium dependence. It is possible that this was due to a lack of diagnostic capability. However, even the attempt to uncover cases of opium dependence by systematically analyzing the literary passages in which poppies, opium, and meconium are quoted are unsuccessful. The only two cases of suspected opium addiction that can be selected in this way are those of the Emperor Marcus Aurelius and Ovid. The most parsimonious interpretation is the lack of an hedonic use of poppy derivatives, being that this kind of use is the most frequently connected with the development of addiction.

Galen and his anatomic eponym: vein of Galen.

PubMed

Ustun, Cagatay

2004-09-01

Galen or Galenus was born at Pergamum (now Bergama in Turkey) in 129 A.D., and died in the year 200 A.D. He was a 2nd century Greek philosopher-physician who switched to the medical profession after his father dreamt of this calling for his son. Galen's training and experiences brought him to Alexandria and Rome and he rose quickly to fame with public demonstrations of anatomical and surgical skills. He became physician to emperor Marcus Aurelius and the emperor's ambitious son, Commodus. He wrote prodigiously and was able to preserve his medical research in 22 volumes of printed text, representing half of all Greek medical literature that is available to us today. The structures, the great cerebral vein and the communicating branch of the internal laryngeal nerve, bear his eponym.

Fragment-based Quantum Mechanical/Molecular Mechanical Simulations of Thermodynamic and Kinetic Process of the Ru2+-Ru3+ Self-Exchange Electron Transfer.

PubMed

Zeng, Xiancheng; Hu, Xiangqian; Yang, Weitao

2012-12-11

A fragment-based fractional number of electron (FNE) approach, is developed to study entire electron transfer (ET) processes from the electron donor region to the acceptor region in condensed phase. Both regions are described by the density-fragment interaction (DFI) method while FNE as an efficient ET order parameter is applied to simulate the electron transfer process. In association with the QM/MM energy expression, the DFI-FNE method is demonstrated to describe ET processes robustly with the Ru 2+ -Ru 3+ self-exchange ET as a proof-of-concept example. This method allows for systematic calculations of redox free energies, reorganization energies, and electronic couplings, and the absolute ET rate constants within the Marcus regime.

[The Antonine Plague and the decline of the Roman Empire].

PubMed

Sabbatani, S; Fiorino, S

2009-12-01

The Antonine Plague, which flared up during the reign of Marcus Aurelius from 165 AD and continued under the rule of his son Commodus, played such a major role that the pathocenosis in the Ancient World was changed. The spread of the epidemic was favoured by the occurrence of two military episodes in which Marcus Aurelius himself took part: the Parthian War in Mesopotamia and the wars against the Marcomanni in northeastern Italy, in Noricum and in Pannonia. Accounts of the clinical features of the epidemic are scant and disjointed, with the main source being Galen, who witnessed the plague. Unfortunately, the great physician provides us with only a brief presentation of the disease, his aim being to supply therapeutic approaches, thus passing over the accurate description of the disease symptoms. Although the reports of some clinical cases treated by Galen lead us to think that the Antonine plague was caused by smallpox, palaeopathological confirmation is lacking. Some archaeological evidence (such as terracotta finds) from Italy might reinforce this opinion. In these finds, some details can be observed, suggesting the artist's purpose to represent the classic smallpox pustules, typical signs of the disease. The extent of the epidemic has been extensively debated: the majority of authors agree that the impact of the plague was severe, influencing military conscription, the agricultural and urban economy, and depleting the coffers of the State. The Antonine plague affected ancient Roman traditions, also leaving a mark on artistic expression; a renewal of spirituality and religiousness was recorded. These events created the conditions for the spread of monotheistic religions, such as Mithraism and Christianity. This period, characterized by health, social and economic crises, paved the way for the entry into the Empire of neighbouring barbarian tribes and the recruitment of barbarian troops into the Roman army; these events particularly favoured the cultural and political growth of these populations. The Antonine Plague may well have created the conditions for the decline of the Roman Empire and, afterwards, for its fall in the West in the fifth century AD.

Theoretical analysis of the unusual temperature dependence of the kinetic isotope effect in quinol oxidation.

PubMed

Ludlow, Michelle K; Soudackov, Alexander V; Hammes-Schiffer, Sharon

2009-05-27

In this paper we present theoretical calculations on model biomimetic systems for quinol oxidation. In these model systems, an excited-state [Ru(bpy)(2)(pbim)](+) complex (bpy = 2,2'-dipyridyl, pbim = 2-(2-pyridyl)benzimidazolate) oxidizes a ubiquinol or plastoquinol analogue in acetonitrile. The charge transfer reaction occurs via a proton-coupled electron transfer (PCET) mechanism, in which an electron is transferred from the quinol to the Ru and a proton is transferred from the quinol to the pbim(-) ligand. The experimentally measured average kinetic isotope effects (KIEs) at 296 K are 1.87 and 3.45 for the ubiquinol and plastoquinol analogues, respectively, and the KIE decreases with temperature for plastoquinol but increases with temperature for ubiquinol. The present calculations provide a possible explanation for the differences in magnitudes and temperature dependences of the KIEs for the two systems and, in particular, an explanation for the unusual inverse temperature dependence of the KIE for the ubiquinol analogue. These calculations are based on a general theoretical formulation for PCET reactions that includes quantum mechanical effects of the electrons and transferring proton, as well as the solvent reorganization and proton donor-acceptor motion. The physical properties of the system that enable the inverse temperature dependence of the KIE are a stiff hydrogen bond, which corresponds to a high-frequency proton donor-acceptor motion, and small inner-sphere and solvent reorganization energies. The inverse temperature dependence of the KIE may be observed if the 0/0 pair of reactant/product vibronic states is in the inverted Marcus region, while the 0/1 pair of reactant/product vibronic states is in the normal Marcus region and is the dominant contributor to the overall rate. In this case, the free energy barrier for the dominant transition is lower for deuterium than for hydrogen because of the smaller splittings between the vibronic energy levels for deuterium, and the KIE increases with increasing temperature. The temperature dependence of the KIE is found to be very sensitive to the interplay among the driving force, the reorganization energy, and the vibronic coupling in this regime.

Phytohormone Signaling of the Resistance to Plum pox virus (PPV, Sharka Disease) Induced by Almond (Prunus dulcis (Miller) Webb) Grafting to Peach (P. persica L. Batsch).

PubMed

Dehkordi, Azam Nikbakht; Rubio, Manuel; Babaeian, Nadali; Albacete, Alfonso; Martínez-Gómez, Pedro

2018-05-03

Plum pox virus (PPV, sharka) is a limiting factor for peach production, and no natural sources of resistance have been described. Recent studies, however, have demonstrated that grafting the almond cultivar "Garrigues" onto the "GF305" peach infected with Dideron-type (PPV-D) isolates progressively reduces disease symptoms and virus accumulation. Furthermore, grafting "Garrigues" onto "GF305" prior to PPV-D inoculation has been found to completely prevent virus infection, showing that resistance is constitutive and not induced by the virus. To unravel the phytohormone signaling of this mechanism, we analyzed the following phytohormones belonging to the principal hormone classes: the growth-related phytohormones cytokinin trans-zeatin (tZ) and the gibberellins GA₃ and GA₄; and the stress-related phytohormones ethylene acid precursor 1-aminocyclopropane-1-carboxylic acid (ACC), abscisic acid (ABA), salicylic acid (SA), and jasmonic acid (JA). PPV inoculation produced a significant increase in GA₃ and ABA in peach, and these imbalances were related to the presence of chlorosis symptoms. However, grafting "Garrigues" almond onto the PPV-inoculated "GF305" peach produced the opposite effect, reducing GA₃ and ABA contents in parallel to the elimination of symptoms. Our results showed the significant implication of SA in this induced resistance in peach with an additional effect on tZ and JA concentrations. This SA-induced resistance based in the decrease in symptoms seems to be different from Systemic Acquired Resistance (SAR) and Induced Systemic Resistance (ISR), which are based in other reactions producing necrosis. Further studies are necessary, however, to validate these results against PPV-D isolates in the more aggressive Marcus-type (PPV-M) isolates.

Electron transfer reactivity of the aqueous iron(IV)–oxo complex. Outer-sphere vs proton-coupled electron transfer

DOE PAGES

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

2016-06-18

Here, the kinetics of oxidation of organic and inorganic reductants by aqueous iron(IV) ions, Fe IV(H 2O) 5O 2+ (hereafter Fe IV aqO 2+), are reported. The substrates examined include several water-soluble ferrocenes, hexachloroiridate(III), polypyridyl complexes M(NN) 3 2+ (M = Os, Fe and Ru; NN = phenanthroline, bipyridine and derivatives), HABTS–/ABTS 2–, phenothiazines, Co II(dmgBF 2) 2, macrocyclic nickel(II) complexes, and aqueous cerium(III). Most of the reductants were oxidized cleanly to the corresponding one-electron oxidation products, with the exception of phenothiazines which produced the corresponding oxides in a single-step reaction, and polypyridyl complexes of Fe(II) and Ru(II) that generatedmore » ligand-modified products. Fe IV aqO 2+ oxidizes even Ce(III) (E 0 in 1 M HClO 4 = 1.7 V) with a rate constant greater than 10 4 M –1 s –1. In 0.10 M aqueous HClO 4 at 25 °C, the reactions of Os(phen) 3 2+ (k = 2.5 × 10 5 M –1 s –1), IrCl 6 3– (1.6 × 10 6), ABTS 2– (4.7 × 10 7), and Fe(cp)(C 5H 4CH 2OH) (6.4 × 10 7) appear to take place by outer sphere electron transfer (OSET). The rate constants for the oxidation of Os(phen) 3 2+ and of ferrocenes remained unchanged in the acidity range 0.05 < [H+] < 0.10 M, ruling out prior protonation of Fe IV aqO 2+ and further supporting the OSET assignment. A fit to Marcus cross-relation yielded a composite parameter (log k 22 + E 0 Fe/0.059) = 17.2 ± 0.8, where k 22 and E 0 Fe are the self-exchange rate constant and reduction potential, respectively, for the Fe IV aqO 2+/Fe III aqO + couple. Comparison with literature work suggests k 22 < 10 –5 M –1 s –1 and thus E 0(Fe IV aqO 2+/Fe III aqO +) > 1.3 V. For proton-coupled electron transfer, the reduction potential is estimated at E 0 (Fe IV aqO 2+, H +/Fe III aqOH 2+) ≥ 1.95 V.« less

Graeco-Roman Astro-Architecture: The Temples of Pompeii

NASA Astrophysics Data System (ADS)

Tiede, Vance R.

2014-01-01

Roman architect Marcus Vetruvius Pollio (ca. 75-15 BC) wrote, “[O]ne who professes himself as an architect should be…acquainted with astronomy and the theory of the heavens…. From astronomy we find the east, west, south, and north, as well as the theory of the heavens, the Equinox, Solstice and courses of the Stars.” (De Architectura Libri Decem I:i:3,10). In order to investigate the role of astronomy in temple orientation, the author conducted a preliminary GIS DEM/Satellite Imaging survey of 11 temples at Pompeii, Italy (N 40d 45', E 14d 29'). The GIS survey measured the true azimuth and horizon altitude of each temple’s major axis and was field checked by a Ground Truth survey with theodolite and GPS, 5-18 April 2013. The resulting 3D vector data was analyzed with Program STONEHENGE (Hawkins 1983, 328) to identify the local skyline declinations aligned with the temple major axes. Analysis suggests that the major axes of the temples of Apollo, Jupiter and Venus are equally as likely to have been oriented to Pompeii’s urban grid, itself oriented NW-SE on Mt. Vesuvius’ slope and hydraulic gradient to optimize urban sewer/street drainage (cf. Hodge 1992). However, the remaining nine temples appear to be oriented to astronomical targets on the local horizon associated with Graeco-Roman calendrics and mythology. TEMPLE/ DATE/ MAJOR AXIS ASTRO-TARGET (Skyline Declination in degrees) Public Lares/AD 50/ Cross-Quarter 7 Nov/3 Feb Sun Set, Last Gleam (-16.5) Vespsian/ AD 69-79/ Cross-Quarter 7 Nov/3 Feb Sun Set, LG (-16.2) Fortuna Augusta/ AD 1/ Winter Solstice Sun Set, LG (-22.9) Aesculapius/ 100 BC/ Perseus Rise (β Persei-Algol = +33.0) & Midsummer Moon Major Stand Still Set, LG (-28.1) Isis/ 100 BC/ Midwinter Moon Major Stand Still Rise, Tangent (+28.5) & Equinox Sun Set, Tangent (-0.3) Jupiter/ 150 BC/ Θ Scorpionis-Sargas Rise (-38.0) Apollo/ 550 (rebuilt 70 BC)/ α Columbae-Phact Rise (-37.1) Venus/ 150 BC (rebuilt 70 BC)/ α Columbae-Phact Rise (-37.7) Ceres/ 250 BC/ Midsummer Moon Major Stand Still Set, LG (-27.9) Dioysyus/ 250 BC/ Equinox Sun Set, LG (+0.3) Doric/ 550 BC/ β Orionis-Rigel Rise (-14.6)

Waterborne Transportation Lines of the United States

DTIC Science & Technology

1988-10-01

C. OUPLANTI! ICO. INC. 3P. C. -0,N 725 I CUNA LA 71161 13 ; 1PrKMNAANE COOP. I2001 MARCUS AVE . ILANE SUCCESS 4Y 1114? 29i APRN TINUI% CU. !ATTN? CAIRN...LANE WEALSO 00 9942. tI I TI 333L06ALj o %EWhSLVA LA ?0114As, Ja3ft4iS p,*v 13 I ATTA, toAL. 1P. 0. -01 Isq3 I A4TIM-1 CA 1I.V31 Al’ hA. II * AV , (1 1...0NM .li. :01 IS. 179 XENTOCVT LIII P3CK CO.. I 1.0 9 170 9~~~ 9 439 14411 9 9 I I -MI "SO,09 -I9**i C W. .IS 13 IT.*92 O L* O4 00111 I I AVE . I

Excited-state redox properties of ruthenium(II) phthalocyanine from electron-transfer quenching

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

Prasad, D.R.; Ferraudi, G.

1982-09-30

Electron-transfer reactions between the lowest-lying triplet state, /sup 3/..pi pi../sup */, of ruthenium (phthalocyanine)(pyridine)/sub 2/ and various nitroaromatic compounds have been studied by laser and conventional flash photolysis. Quenching rate constants determined for the oxidation of the excited state have been treated according to the Marcus-Hush theory. A self-exchange rate constant K approx. 10/sup 7/ M/sup -1/ x/sup -1/ was determined for the self-exchange reaction between the /sup 3/..pi pi../sup */ and radical cation, Ru(ph)(py)/sub 2//sup +/. Such a value indicates that the major component to the Franck-Condon reorganizational energy is the outer-sphere contribution. The photochemical properties of the phthalocyaninesmore » are discussed in terms of the redox potentials estimate for various excited states.« less

Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

NASA Technical Reports Server (NTRS)

Benjamin, Ilan; Pohorille, Andrew

1993-01-01

The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

Graded activity: legacy of the sanatorium.

PubMed

Creighton, C

1993-08-01

Occupational therapists in all areas of practice grade therapeutic activities to help patients progress toward their goals. It is proposed in this paper that the concept of graded activity originated in German tuberculosis sanatoria in the late 1800s, when patients were required to walk on graded (sloped) land for exercise. British physician Marcus Paterson included work, as well as walking, in his graduated exercise program for tuberculosis patients and was honored for this innovation at the founding meeting of the National Society for the Promotion of Occupational Therapy (NSPOT). George Barton, Susan Tracy, and Herbert Hall were among the NSPOT members who contributed to the development of graded activity as a principle in occupational therapy intervention. The military rehabilitation programs established during World War I provided additional impetus, and by the mid-1920s, graded activity was recognized as central to the profession.

Heart regeneration.

PubMed

Breckwoldt, Kaja; Weinberger, Florian; Eschenhagen, Thomas

2016-07-01

Regenerating an injured heart holds great promise for millions of patients suffering from heart diseases. Since the human heart has very limited regenerative capacity, this is a challenging task. Numerous strategies aiming to improve heart function have been developed. In this review we focus on approaches intending to replace damaged heart muscle by new cardiomyocytes. Different strategies for the production of cardiomyocytes from human embryonic stem cells or human induced pluripotent stem cells, by direct reprogramming and induction of cardiomyocyte proliferation are discussed regarding their therapeutic potential and respective advantages and disadvantages. Furthermore, different methods for the transplantation of pluripotent stem cell-derived cardiomyocytes are described and their clinical perspectives are discussed. This article is part of a Special Issue entitled: Cardiomyocyte Biology: Integration of Developmental and Environmental Cues in the Heart edited by Marcus Schaub and Hughes Abriel. Copyright © 2015 Elsevier B.V. All rights reserved.

Women of the Manhattan Project

NASA Astrophysics Data System (ADS)

Marshall, Jill

2009-10-01

In the book Their Day in the Sun, Ruth Howes and Caroline Herzenberg documented more than 1000 women who worked on the Manhattan Project, preserving their legacy for generations to come. At the 2009 Chicago meeting, the AAPT Committee on Women in Physics celebrated the accomplishments of these women and the men who worked beside them. Howes presented an overview of the contributions of women to the development of the first nuclear weapon, and the session was honored with talks from two Manhattan project veterans, Ellen Cleminshaw Weaver, who worked at Oak Ridge, and Dorothy Marcus Gans, who worked as a technician in the Metallurgical Laboratory in Chicago. I will present a summary of the session, analyzing the effect of working on the project on the career trajectories of the women involved, and point listeners toward additional documentation of this history.

The luminescence properties of the heteroleptic [Re(CO)3(N∩N)Cl] and [Re(CO)3(N∩N)(CH3CN)](+) complexes in view of the combined Marcus-Jortner and Mulliken-Hush formalism.

PubMed

Woźna, Agnieszka; Kapturkiewicz, Andrzej

2015-11-11

The luminescence properties of the heteroleptic fac-Re(CO)3(+) complexes with α-diimine N∩N ligands, neutral [Re(CO)3(N∩N)Cl] and cationic [Re(CO)3(N∩N)(CH3CN)](+) species, have been studied in acetonitrile solutions at room temperature. The investigated complexes exhibit the metal to ligand charge-transfer (MLCT) phosphorescence with the emission characteristics strongly affected by the nature of coordinated α-diimine N∩N ligands. The observed trends can be quantitatively described by invoking the electronic interactions between (3)*LC and (3)*MLCT states as well as the spin-orbit interactions between (3)*MLCT and (1)*MLCT states, respectively. All quantities necessary for the description can be straightforwardly accounted from analysis of the radiative (1)*MLCT ← S0 and (3)*MLCT → S0 charge transfer processes. It is also demonstrated that the radiative kr and non-radiative knr decay rate constants of the excited (3)*MLCT states can be interpreted within the same set of parameters. As expected from the Mulliken-Hush formalism the both processes are strictly related that allows prediction of the non-radiative knr rate constants using the parameters available from analysis of the radiative (1)*MLCT ← S0 and (3)*MLCT → S0 charge transfer processes.

Electronic communication across diamagnetic metal bridges: a homoleptic gallium(III) complex of a redox-active diarylamido-based ligand and its oxidized derivatives

PubMed Central

Liddle, Brendan J.; Wanniarachchi, Sarath; Hewage, Jeewantha S.; Lindeman, Sergey V.; Bennett, Brian; Gardinier, James R.

2012-01-01

Complexes with cations of the type [Ga(L)2]n+ where L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido and n = 1, 2, 3 have been prepared and structurally characterized. The electronic properties of each were probed by electrochemical and spectroscopic means and were interpreted with the aid of DFT calculations. The dication, best described as [Ga(L−)(L0)]2+, and is a Robin-Day class II mixed-valence species. As such, a broad, weak, solvent-dependent intervalence charge transfer (IVCT) band was found in the NIR spectrum in the range 6390 to 6925 cm−1, depending on solvent. Band shape analyses and the use of Hush and Marcus relations revealed a modest electronic coupling, Hab of about 200 cm−1, and a large rate constant for electron transfer, ket, on the order of 1010 s−1 between redox active ligands. The di-oxidized complex [Ga(L0)2]3+ shows a half-field ΔMs = 2 transition in its solid-state X-Band EPR spectrum at 5 K which indicates that the triplet state is thermally populated. DFT calculations (M06/Def2-SV(P)) suggest that the singlet state is 21.7 cm−1 lower in energy than the triplet state. PMID:23163736

Online Lectures in Undergraduate Medical Education: Scoping Review.

PubMed

Tang, Brandon; Coret, Alon; Qureshi, Aatif; Barron, Henry; Ayala, Ana Patricia; Law, Marcus

2018-04-10

The adoption of the flipped classroom in undergraduate medical education calls on students to learn from various self-paced tools-including online lectures-before attending in-class sessions. Hence, the design of online lectures merits special attention, given that applying multimedia design principles has been shown to enhance learning outcomes. The aim of this study was to understand how online lectures have been integrated into medical school curricula, and whether published literature employs well-accepted principles of multimedia design. This scoping review followed the methodology outlined by Arksey and O'Malley (2005). Databases, including MEDLINE, PsycINFO, Education Source, FRANCIS, ERIC, and ProQuest, were searched to find articles from 2006 to 2016 related to online lecture use in undergraduate medical education. In total, 45 articles met our inclusion criteria. Online lectures were used in preclinical and clinical years, covering basic sciences, clinical medicine, and clinical skills. The use of multimedia design principles was seldom reported. Almost all studies described high student satisfaction and improvement on knowledge tests following online lecture use. Integration of online lectures into undergraduate medical education is well-received by students and appears to improve learning outcomes. Future studies should apply established multimedia design principles to the development of online lectures to maximize their educational potential. ©Brandon Tang, Alon Coret, Aatif Qureshi, Henry Barron, Ana Patricia Ayala, Marcus Law. Originally published in JMIR Medical Education (http://mededu.jmir.org), 10.04.2018.

Pressure and Temperature Dependence of the Reaction of Vinyl Radical with Ethylene

NASA Technical Reports Server (NTRS)

Ismail, Huzeifa; Goldsmith, C. Franklin; Abel, Paul R.; Howe, Pui-Teng; Fahr, Askar; Halpern, Joshua B.; Jusinski, Leonard E.; Georgievskii, Yuri; Taatjes, Craig A.; Green, William H.

2007-01-01

This work reports measurements of absolute rate coefficients and Rice-Ramsperger-Kassel-Marcus (RRKM) master equation simulations of the C2H3 + C2H4 reaction. Direct kinetic studies were performed over a temperature range of 300-700 K and pressures of 20 and 133 mbar. Vinyl radicals (H2C=CH) were generated by laser photolysis of vinyl iodide (C2H31) at 266 nm, and time-resolved absorption spectroscopy was used to probe vinyl radicals through absorption at 423.2 nm. Measurements at 20 mbar are in good agreement with previous determinations at higher temperature. A weighted three-parameter Arrhenius fit to the experimental rate constant at 133 mbar, with the temperature exponent fixed, gives k = (7 +/- 1) x 10(exp -l4) cu cm/molecule/s (T/298 K)(exp 2) exp[-(1430 +/- 70) K/T]. RRKM master equation simulations, based on G3 calculations of stationary points on the C4H7 potential energy surface, were carried out to predict rate coefficients and product branching fractions. The predicted branching to 1-methylallyl product is relatively small under the conditions of the present experiments but increases as the pressure is lowered. Analysis of end products of 248 nm photolysis of vinyl iodide/ethylene mixtures at total pressures between 27 and 933 mbar provides no direct evidence for participation of I -methylallyl.

Trunk Muscle Size and Composition Assessment in Older Adults with Chronic Low Back Pain: An Intra-Examiner and Inter-Examiner Reliability Study.

PubMed

Sions, Jaclyn Megan; Smith, Andrew Craig; Hicks, Gregory Evan; Elliott, James Matthew

2016-08-01

To evaluate intra- and inter-examiner reliability for the assessment of relative cross-sectional area, muscle-to-fat infiltration indices, and relative muscle cross-sectional area, i.e., total cross-sectional area minus intramuscular fat, from T1-weighted magnetic resonance images obtained in older adults with chronic low back pain. Reliability study. n = 13 (69.3 ± 8.2 years old) After lumbar magnetic resonance imaging, two examiners produced relative cross-sectional area measurements of multifidi, erector spinae, psoas, and quadratus lumborum by tracing regions of interest just inside fascial borders. Pixel-intensity summaries were used to determine muscle-to-fat infiltration indices; relative muscle cross-sectional area was calculated. Intraclass correlation coefficients were used to estimate intra- and inter-examiner reliability; standard error of measurement was calculated. Intra-examiner intraclass correlation coefficient point estimates for relative cross-sectional area, muscle-to-fat infiltration indices, and relative muscle cross-sectional area were excellent for multifidi and erector spinae across levels L2-L5 (ICC = 0.77-0.99). At L3, intra-examiner reliability was excellent for relative cross-sectional area, muscle-to-fat infiltration indices, and relative muscle cross-sectional area for both psoas and quadratus lumborum (ICC = 0.81-0.99). Inter-examiner intraclass correlation coefficients ranged from poor to excellent for relative cross-sectional area, muscle-to-fat infiltration indices, and relative muscle cross-sectional area. Assessment of relative cross-sectional area, muscle-to-fat infiltration indices, and relative muscle cross-sectional area in older adults with chronic low back pain can be reliably determined by one examiner from T1-weighted images. Such assessments provide valuable information, as muscle-to-fat infiltration indices and relative muscle cross-sectional area indicate that a substantial amount of relative cross-sectional area may be magnetic resonance-visible intramuscular fat in older adults with chronic low back pain. © 2015 American Academy of Pain Medicine. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Global minimum profile error (GMPE) - a least-squares-based approach for extracting macroscopic rate coefficients for complex gas-phase chemical reactions.

PubMed

Duong, Minh V; Nguyen, Hieu T; Mai, Tam V-T; Huynh, Lam K

2018-01-03

Master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) has shown to be a powerful framework for modeling kinetic and dynamic behaviors of a complex gas-phase chemical system on a complicated multiple-species and multiple-channel potential energy surface (PES) for a wide range of temperatures and pressures. Derived from the ME time-resolved species profiles, the macroscopic or phenomenological rate coefficients are essential for many reaction engineering applications including those in combustion and atmospheric chemistry. Therefore, in this study, a least-squares-based approach named Global Minimum Profile Error (GMPE) was proposed and implemented in the MultiSpecies-MultiChannel (MSMC) code (Int. J. Chem. Kinet., 2015, 47, 564) to extract macroscopic rate coefficients for such a complicated system. The capability and limitations of the new approach were discussed in several well-defined test cases.

Uniqueness of large positive solutions

NASA Astrophysics Data System (ADS)

López-Gómez, Julián; Maire, Luis

2017-08-01

We establish the uniqueness of the positive solution of the singular problem (1.1) through some standard comparison techniques involving the maximum principle. Our proofs do not invoke to the blow-up rates of the solutions, as in most of the specialized literature. We give two different types of results according to the geometrical properties of Ω and the regularity of partial Ω . Even in the autonomous case, our theorems are extremely sharp extensions of all existing results. Precisely, when a(x)≡ 1, it is shown that the monotonicity and superadditivity of f( u) with constant C≥ 0 entail the uniqueness; f is said to be superadditive with constant C≥ 0 if f(a+b) ≥ f(a) + f(b) - C \\quad for all a, b ≥ 0. This condition, introduced by Marcus and Véron (J Evol Equ 3:637-652, 2004), weakens all previous sufficient conditions for uniqueness, as it will become apparent in this paper.

Barcelona conference on epigenetics and cancer 2016 – beyond cancer genomes

PubMed Central

Dumbovic, Gabrijela; Biayna, Josep; Font, Berta; Buschbeck, Marcus; Forcales, Sonia-V.

2017-01-01

ABSTRACT The Barcelona Conference on Epigenetics and Cancer (BCEC) entitled “Beyond Cancer Genomes” took place October 13th and 14th 2016 in Barcelona. The 2016 BCEC was the fourth edition of a series of annual conferences coordinated by Marcus Buschbeck and subsequently organized by leading research centers in Barcelona together with B•DEBATE, a joint initiative of BIOCAT and “La Caixa” Foundation. Salvador Aznar-Benitah, Eduard Batlle, and Raúl Méndez from the Institute for Research in Biomedicine in Barcelona selected the 2016 BCEC panel of speakers. As the title indicates, this year's conference expanded the epigenetic focus to include additional cancer-relevant topics, such as tumor heterogeneity and RNA regulation. Methods to develop therapeutic approaches on the basis of novel insights have been discussed in great detail. The conference has attracted 217 participants from 11 countries. PMID:28121228

Ab initio studies on the photodissociation dynamics of the 1,1-difluoroethyl radical

NASA Astrophysics Data System (ADS)

Fritsche, Lukas; Bach, Andreas; Chen, Peter

2018-02-01

Born-Oppenheimer molecular dynamics trajectory calculations at the HCTH147/6-31G** level of theory simulate the dissociation dynamics of photolytically excited 1,1-difluoroethyl radicals. EOMCCSD/AUG-cc-pVDZ calculations show that an excitation energy of 94.82 kcal/mol is necessary to initiate photodissociation reactions. In contrast to photodissociation dynamics of ethyl radicals where a large discrepancy between actual dissociation rates and rates that are predicted by statistical rate theories, we find reaction rates of 5.1 × 1011 s-1 for the dissociation of an H atom, which is in perfect accord with what is predicted by Rice-Ramsperger-Kassel-Marcus (RRKM) calculations and there is no indication of any nonstatistical effects. However, our trajectory calculations show a much larger fraction of C-C bond breakage reaction of 56% occurring than that expected by RRKM (only 16%).

First Barcelona Conference on Epigenetics and Cancer

PubMed Central

Palau, Anna; Perucho, Manuel; Esteller, Manel; Buschbeck, Marcus

2014-01-01

The Barcelona Conference on Epigenetics and Cancer (BCEC) entitled “Challenges, opportunities and perspectives” took place November 21–22, 2013 in Barcelona. The 2013 BCEC is the first edition of a series of annual conferences jointly organized by five leading research centers in Barcelona. These centers are the Institute of Predictive and Personalized Medicine of Cancer (IMPPC), the Biomedical Campus Bellvitge with its Program of Epigenetics and Cancer Biology (PEBC), the Centre for Genomic Regulation (CRG), the Institute for Biomedical Research (IRB), and the Molecular Biology Institute of Barcelona (IBMB). Manuel Perucho and Marcus Buschbeck from the Institute of Predictive and Personalized Medicine of Cancer put together the scientific program of the first conference broadly covering all aspects of epigenetic research ranging from fundamental molecular research to drug and biomarker development and clinical application. In one and a half days, 23 talks and 50 posters were presented to a completely booked out audience counting 270 participants. PMID:24413145

A transferable model for singlet-fission kinetics.

PubMed

Yost, Shane R; Lee, Jiye; Wilson, Mark W B; Wu, Tony; McMahon, David P; Parkhurst, Rebecca R; Thompson, Nicholas J; Congreve, Daniel N; Rao, Akshay; Johnson, Kerr; Sfeir, Matthew Y; Bawendi, Moungi G; Swager, Timothy M; Friend, Richard H; Baldo, Marc A; Van Voorhis, Troy

2014-06-01

Exciton fission is a process that occurs in certain organic materials whereby one singlet exciton splits into two independent triplets. In photovoltaic devices these two triplet excitons can each generate an electron, producing quantum yields per photon of >100% and potentially enabling single-junction power efficiencies above 40%. Here, we measure fission dynamics using ultrafast photoinduced absorption and present a first-principles expression that successfully reproduces the fission rate in materials with vastly different structures. Fission is non-adiabatic and Marcus-like in weakly interacting systems, becoming adiabatic and coupling-independent at larger interaction strengths. In neat films, we demonstrate fission yields near unity even when monomers are separated by >5 Å. For efficient solar cells, however, we show that fission must outcompete charge generation from the singlet exciton. This work lays the foundation for tailoring molecular properties like solubility and energy level alignment while maintaining the high fission yield required for photovoltaic applications.

Ab initio studies on the photodissociation dynamics of the 1,1-difluoroethyl radical.

PubMed

Fritsche, Lukas; Bach, Andreas; Chen, Peter

2018-02-28

Born-Oppenheimer molecular dynamics trajectory calculations at the HCTH147/6-31G** level of theory simulate the dissociation dynamics of photolytically excited 1,1-difluoroethyl radicals. EOMCCSD/AUG-cc-pVDZ calculations show that an excitation energy of 94.82 kcal/mol is necessary to initiate photodissociation reactions. In contrast to photodissociation dynamics of ethyl radicals where a large discrepancy between actual dissociation rates and rates that are predicted by statistical rate theories, we find reaction rates of 5.1 × 10 11 s -1 for the dissociation of an H atom, which is in perfect accord with what is predicted by Rice-Ramsperger-Kassel-Marcus (RRKM) calculations and there is no indication of any nonstatistical effects. However, our trajectory calculations show a much larger fraction of C-C bond breakage reaction of 56% occurring than that expected by RRKM (only 16%).

Outage management and health physics issue, 2009

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

Agnihotri, Newal

2009-05-15

The focus of the May-June issue is on outage management and health physics. Major articles include the following: Planning and scheduling to minimize refueling outage, by Pat McKenna, AmerenUE; Prioritizing safety, quality and schedule, by Tom Sharkey, Dominion; Benchmarking to high standards, by Margie Jepson, Energy Nuclear; Benchmarking against U.S. standards, by Magnox North, United Kingdom; Enabling suppliers for new build activity, by Marcus Harrington, GE Hitachi Nuclear Energy; Identifying, cultivating and qualifying suppliers, by Thomas E. Silva, AREVA NP; Creating new U.S. jobs, by Francois Martineau, Areva NP. Industry innovation articles include: MSL Acoustic source load reduction, by Amirmore » Shahkarami, Exelon Nuclear; Dual Methodology NDE of CRDM nozzles, by Michael Stark, Dominion Nuclear; and Electronic circuit board testing, by James Amundsen, FirstEnergy Nuclear Operating Company. The plant profile article is titled The future is now, by Julia Milstead, Progress Energy Service Company, LLC.« less

Sunspot Positions and Areas from Observations by Galileo Galilei

NASA Astrophysics Data System (ADS)

Vokhmyanin, M. V.; Zolotova, N. V.

2018-02-01

Sunspot records in the seventeenth century provide important information on the solar activity before the Maunder minimum, yielding reliable sunspot indices and the solar butterfly diagram. Galilei's letters to Cardinal Francesco Barberini and Marcus Welser contain daily solar observations on 3 - 11 May, 2 June - 8 July, and 19 - 21 August 1612. These historical archives do not provide the time of observation, which results in uncertainty in the sunspot coordinates. To obtain them, we present a method that minimizes the discrepancy between the sunspot latitudes. We provide areas and heliographic coordinates of 82 sunspot groups. In contrast to Sheiner's butterfly diagram, we found only one sunspot group near the Equator. This provides a higher reliability of Galilei's drawings. Large sunspot groups are found to emerge at the same longitude in the northern hemisphere from 3 May to 21 August, which indicates an active longitude.

Comparing preference assessments: selection- versus duration-based preference assessment procedures.

PubMed

Kodak, Tiffany; Fisher, Wayne W; Kelley, Michael E; Kisamore, April

2009-01-01

In the current investigation, the results of a selection- and a duration-based preference assessment procedure were compared. A Multiple Stimulus With Replacement (MSW) preference assessment [Windsor, J., Piché, L. M., & Locke, P. A. (1994). Preference testing: A comparison of two presentation methods. Research in Developmental Disabilities, 15, 439-455] and a variation of a Free-Operant (FO) preference assessment procedure [Roane, H. S., Vollmer, T. R., Ringdahl, J. E., & Marcus, B. A. (1998). Evaluation of a brief stimulus preference assessment. Journal of Applied Behavior Analysis, 31, 605-620] were conducted with four participants. A reinforcer assessment was conducted to determine which preference assessment procedure identified the item that produced the highest rates of responding. The items identified as most highly preferred were different across preference assessment procedures for all participants. Results of the reinforcer assessment showed that the MSW identified the item that functioned as the most effective reinforcer for two participants.

Photodissociation dynamics of the 2-propyl radical, C{sub 3}H{sub 7}

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

Noller, Bastian; Fischer, Ingo

2007-04-14

The photodissociation of 2-propyl leading to propene+H was investigated with nanosecond time resolution. A supersonic beam of isolated 2-propyl radicals was produced by pyrolysis of 2-bromopopane. The kinetic energy release of the H-atom photofragment was monitored as a function of excitation wavelength by photofragment Doppler spectroscopy via the Lyman-{alpha} transition. The loss of hydrogen atoms after excitation proceeds in {alpha} position to the radical center with a rate constant of 5.8x10{sup 7} s{sup -1} at 254 nm. Approximately 20% of the excess energy is deposited as translation in the H-atom photofragment. In contrast 1-propyl does not lose H atoms tomore » a significant extent. The experimental results are compared to simple Rice-Ramsperger-Kassel-Marcus calculations. The possible reaction pathways are examined in hybrid density functional theory calculations.« less

A history of erotic philosophy.

PubMed

Soble, Alan

2009-01-01

This essay historically explores philosophical views about the nature and significance of human sexuality, starting with the Ancient Greeks and ending with late 20th-century Western philosophy. Important figures from the history of philosophy (and theology) discussed include Sappho, Plato, Aristotle, St. Augustine, St. Jerome, the Pelagians, St. Thomas Aquinas, Michel de Montaigne, Rene Descartes, Thomas Hobbes, David Hume, Immanuel Kant, Søren Kierkegaard, Arthur Schopenhauer, Jeremy Bentham, John Stuart Mill, Karl Marx, Friedrich Engels, Sigmund Freud, Jean-Paul Sartre, Simone de Beauvoir, Wilhelm Reich, and Herbert Marcuse. Contemporary philosophers whose recent work is discussed include Michel Foucault, Thomas Nagel, Roger Scruton, Karol Wojtyla (Pope John Paul II), Catharine MacKinnon, Richard Posner, and John Finnis. To show the unity of the humanities, the writings of various literary figures are incorporated into this history, including Mark Twain, Arthur Miller, James Thurber, E. B. White, Iris Murdoch, and Philip Roth.

Phonon-electron coupling and tunneling effect on charge transport in organic semi-conductor crystals of Cn-BTBT.

PubMed

Zhou, Yecheng; Deng, Wei-Qiao; Zhang, Hao-Li

2016-09-14

Cn-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) crystals show very high hole mobilities in experiments. These high mobilities are beyond existing theory prediction. Here, we employed different quantum chemistry methods to investigate charge transfer in Cn-BTBT crystals and tried to find out the reasons for the underestimation in the theory. It was found that the hopping rate estimated by the Fermi Golden Rule is higher than that of the Marcus theory due to the high temperature approximation and failure at the classic limit. More importantly, molecular dynamics simulations revealed that the phonon induced fluctuation of electronic transfer integral is much larger than the average of the electronic transfer integral itself. Mobilities become higher if simulations implement the phonon-electron coupling. This conclusion indicates that the phonon-electron coupling promotes charge transfer in organic semi-conductors at room temperature.

Phonon-electron coupling and tunneling effect on charge transport in organic semi-conductor crystals of Cn-BTBT

NASA Astrophysics Data System (ADS)

Zhou, Yecheng; Deng, Wei-Qiao; Zhang, Hao-Li

2016-09-01

Cn-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) crystals show very high hole mobilities in experiments. These high mobilities are beyond existing theory prediction. Here, we employed different quantum chemistry methods to investigate charge transfer in Cn-BTBT crystals and tried to find out the reasons for the underestimation in the theory. It was found that the hopping rate estimated by the Fermi Golden Rule is higher than that of the Marcus theory due to the high temperature approximation and failure at the classic limit. More importantly, molecular dynamics simulations revealed that the phonon induced fluctuation of electronic transfer integral is much larger than the average of the electronic transfer integral itself. Mobilities become higher if simulations implement the phonon-electron coupling. This conclusion indicates that the phonon-electron coupling promotes charge transfer in organic semi-conductors at room temperature.

Information from multiple modalities helps 5-month-olds learn abstract rules.

PubMed

Frank, Michael C; Slemmer, Jonathan A; Marcus, Gary F; Johnson, Scott P

2009-07-01

By 7 months of age, infants are able to learn rules based on the abstract relationships between stimuli (Marcus et al., 1999), but they are better able to do so when exposed to speech than to some other classes of stimuli. In the current experiments we ask whether multimodal stimulus information will aid younger infants in identifying abstract rules. We habituated 5-month-olds to simple abstract patterns (ABA or ABB) instantiated in coordinated looming visual shapes and speech sounds (Experiment 1), shapes alone (Experiment 2), and speech sounds accompanied by uninformative but coordinated shapes (Experiment 3). Infants showed evidence of rule learning only in the presence of the informative multimodal cues. We hypothesize that the additional evidence present in these multimodal displays was responsible for the success of younger infants in learning rules, congruent with both a Bayesian account and with the Intersensory Redundancy Hypothesis.

Vibrational dynamics of aniline (N2)1 clusters in their first excited singlet state

NASA Astrophysics Data System (ADS)

Hineman, M. F.; Kim, S. K.; Bernstein, E. R.; Kelley, D. F.

1992-04-01

The first excited singlet state S1 vibrational dynamics of aniline(N2)1 clusters are studied and compared to previous results on aniline(CH4)1 and aniline(Ar)1. Intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) rates fall between the two extremes of the CH4 (fast IVR, slow VP) and Ar (slow IVR, fast VP) cluster results as is predicted by a serial IVR/VP model using Fermi's golden rule to describe IVR processes and a restricted Rice-Ramsperger-Kassel-Marcus (RRKM) theory to describe unimolecular VP rates. The density of states is the most important factor determining the rates. Two product states, 00 and 10b1, of bare aniline and one intermediate state ˜(00) in the overall IVR/VP process are observed and time resolved measurements are obtained for the 000 and ˜(000) transitions. The results are modeled with the serial mechanism described above.

Periodic Limb Movements and Disrupted Sleep in Children with Sickle Cell Disease

PubMed Central

Rogers, Valerie E.; Marcus, Carole L.; Jawad, Abbas F.; Smith-Whitley, Kim; Ohene-Frempong, Kwaku; Bowdre, Cheryl; Allen, Julian; Arens, Raanan; Mason, Thornton B. A.

2011-01-01

Study Objectives: To describe the rate, distribution and correlates of periodic limb movements in sleep (PLMS) in children with sickle cell disease (SCD). Design: Prospective, cross-sectional. Setting: Hospital-based sleep laboratory. Participants: Sixty-four children aged 2–18 years with SCD, hemoglobin SS-type who had an overnight polysomnogram and a parent-completed Pediatric Sleep Questionnaire. Mean age was 8.4 years (SD 4.8); 50% were male. Interventions: N/A Measurements and Results: The mean PLMS index was 3.7 (6.6) and ranged from 0 to 31.8, with 23.4% of the sample having PLMS ≥ 5/h. Sleep efficiency was decreased (P = 0.03), and the total arousal index (P = 0.003) and PLMS arousal index (P < 0.001) were increased in children with PLMS ≥ 5/h compared to those with PLMS < 5/h. PLMS were most frequent in NREM stage 2 sleep and during the fourth hour of sleep. Inter-movement interval duration peaked at 25–30 s. “Growing pains worst in bed” or “restlessness of the legs”, suggesting restless legs syndrome (RLS), were reported in 12.5% of the total sample and were more common in children with elevated PLMS. A PLMS score for identifying elevated PLMS in children, based on items from the Pediatric Sleep Questionnaire, did not significantly predict PLMS ≥ 5/h. Conclusions: Elevated PLMS are common in children with SCD and are associated with sleep disruption and symptoms of RLS. Future research into the time structure of PLMS, their causes and consequences, and development of a disease-specific sleep disorders screening questionnaire, is needed in children with SCD. Citation: Rogers VE; Marcus CL; Jawad AF; Smith-Whitley K; Ohene-Frempong K; Bowdre C; Allen J; Arens R; Mason TBA. Periodic limb movements and disrupted sleep in children with sickle cell disease. SLEEP 2011;34(7):899-908. PMID:21731140

Depressive and trauma symptoms in expectant, risk-exposed, mothers and fathers: Is mindfulness a buffer?

PubMed

Hicks, Laurel M; Dayton, Carolyn J; Victor, Bryan G

2018-05-31

Perinatal depression is reported in 15-20% of women (Marcus, 2009), 8-16% of men (Paulson and Bazemore, 2010) and low-SES, diverse populations are particularly at risk (Sareen, 2011). Trauma symptoms are commonly comorbid with depression, especially when individuals are exposed to risk factors such as community violence and poverty (Kastello et al., 2015; WenzGross et al., 2016). Parental mental illness places infants at risk for negative outcomes (Junge et al., 2016). Evidence supports that dispositional mindfulness is linked to mental health in many populations, however, a gap lies in the understanding of the relationship between mindfulness, trauma and depression in risk-exposed, pregnant populations, especially with fathers. We hypothesize that dispositional mindfulness is negatively associated with lower depression and trauma symptoms in pregnancy, in mothers and fathers. Dispositional mindfulness, depressive and trauma symptoms were examined in women and men, exposed to adversity who were expecting a baby (N = 102). Independent t-tests, and bivariate correlations examined the relationships between these variables. Hierarchical regression was utilized to understand how mindfulness and trauma symptoms may contribute to antenatal depression symptoms. Significant differences were observed with mindfulness and depressive symptoms, with no differences reported across gender. Mindfulness, depressive and trauma symptoms were associated in the expected directions. Total mindfulness, specifically being non-reactive to one's own thoughts and trauma symptoms predicted depressive symptoms. Limitations include small sample size, cross-sectional data and self-report measures. Mindfulness and trauma symptoms were found to be significant predictors of depressive symptoms in parents-to-be. Those with lower mindfulness exhibited higher levels of depression. These findings may be helpful in disseminated mindfulness-based interventions aimed at treating antenatal depression in both expectant mothers and fathers who are exposed to adversity. Further research is necessary to understand the mechanisms of mindfulness in risk-exposed, expectant parents. Copyright © 2018. Published by Elsevier B.V.

Oxidation Dynamics of Methionine with Singlet Oxygen: Effects of Methionine Ionization and Microsolvation.

PubMed

Liu, Fangwei; Liu, Jianbo

2015-06-25

We report an in-depth study on the gas-phase reactions of singlet O2[a(1)Δg] with methionine (Met) at different ionization and hydration states (including deprotonated [Met - H](-), hydrated deprotonated [Met - H](-)(H2O)1,2, and hydrated protonated MetH(+)(H2O)1,2), using guided-ion-beam scattering mass spectrometry. The measurements include the effects of collision energy (Ecol) on reaction cross sections over a center-of-mass Ecol range from 0.05 to 1.0 eV. The aim of this study is to probe the influences of Met ionization and hydration on its oxidation mechanism and dynamics. Density functional theory calculations, Rice-Ramsperger-Kassel-Marcus modeling, and quasi-classical, direct dynamics trajectory simulations were performed to examine the properties of various complexes and transition states that might be important along reaction coordinates, probe reaction potential energy surfaces, and to establish the atomic-level mechanism for the Met oxidation process. No oxidation products were observed for the reaction of [Met - H](-) with (1)O2 due to the high-energy barriers located in the product channels for this system. However, this nonreactive property was altered by the microsolvation of [Met - H](-); as a result, hydroperoxides were captured as the oxidation products for [Met - H](-)(H2O)1,2 + (1)O2. For the reaction of MetH(+)(H2O)1,2 + (1)O2, besides formation of hydroperoxides, an H2O2 elimination channel was observed. The latter channel is similar to what was found in the reaction of dehydrated MetH(+) with (1)O2 (J. Phys. Chem. B 2011, 115, 2671). The reactions of hydrated protonated and deprotonated Met are all inhibited by Ecol, becoming negligible at Ecol ≥ 0.5 eV. The kinetic and dynamical consequences of microsolvation on Met oxidation and their biological implications are discussed.

Comparison of depth-dose distributions of proton therapeutic beams calculated by means of logical detectors and ionization chamber modeled in Monte Carlo codes

NASA Astrophysics Data System (ADS)

Pietrzak, Robert; Konefał, Adam; Sokół, Maria; Orlef, Andrzej

2016-08-01

The success of proton therapy depends strongly on the precision of treatment planning. Dose distribution in biological tissue may be obtained from Monte Carlo simulations using various scientific codes making it possible to perform very accurate calculations. However, there are many factors affecting the accuracy of modeling. One of them is a structure of objects called bins registering a dose. In this work the influence of bin structure on the dose distributions was examined. The MCNPX code calculations of Bragg curve for the 60 MeV proton beam were done in two ways: using simple logical detectors being the volumes determined in water, and using a precise model of ionization chamber used in clinical dosimetry. The results of the simulations were verified experimentally in the water phantom with Marcus ionization chamber. The average local dose difference between the measured relative doses in the water phantom and those calculated by means of the logical detectors was 1.4% at first 25 mm, whereas in the full depth range this difference was 1.6% for the maximum uncertainty in the calculations less than 2.4% and for the maximum measuring error of 1%. In case of the relative doses calculated with the use of the ionization chamber model this average difference was somewhat greater, being 2.3% at depths up to 25 mm and 2.4% in the full range of depths for the maximum uncertainty in the calculations of 3%. In the dose calculations the ionization chamber model does not offer any additional advantages over the logical detectors. The results provided by both models are similar and in good agreement with the measurements, however, the logical detector approach is a more time-effective method.

Free energy calculations give insight into the stereoselective hydroxylation of α-ionones by engineered cytochrome P450 BM3 mutants.

PubMed

de Beer, Stephanie B A; Venkataraman, Harini; Geerke, Daan P; Oostenbrink, Chris; Vermeulen, Nico P E

2012-08-27

Previously, stereoselective hydroxylation of α-ionone by Cytochrome P450 BM3 mutants M01 A82W and M11 L437N was observed. While both mutants hydroxylate α-ionone in a regioselective manner at the C3 position, M01 A82W catalyzes formation of trans-3-OH-α-ionone products whereas M11 L437N exhibits opposite stereoselectivity, producing trans-(3S,6S)-OH-α-ionone and cis-(3S,6R)-OH-α-ionone. Here, we explore the stereoselective C3 hydroxylation of α-ionone by Cytochrome P450 BM3 mutants M01 A82W and M11 L437N using molecular dynamics-based free energy calculations to study the interaction between the enzyme and both the substrates and the products. The one-step perturbation approach is applied using an optimized reference state for substrates and products. While the free energy differences between the substrates free in solution amount to ~0 kJ mol(-1), the differences in mutant M01 A82W agree with the experimentally obtained dissociation constants K(d). Moreover, a correlation with experimentally observed trends in product formation is found in both mutants. The trans isomers show the most favorable relative binding free energy in the range of all four possible hydroxylated diastereomers for mutant M01 A82W, while the trans product from (6S)-α-ionone and the cis product from (6R)-α-ionone show highest affinity for mutant M11 L437N. Marcus theory is subsequently used to relate the thermodynamic stability to transition state energies and rates of formation.

Development of the relaxation-assisted 2DIR method for accessing structures of molecules and its application for studying the energy transport on a molecular level

NASA Astrophysics Data System (ADS)

Kasyanenko, Valeriy Mitrofanovich

Measuring the three-dimensional structure of molecules, dynamics of structural changes, and energy transport on a molecular scale is important for many areas of natural science. Supplementing the widely used methods of x-ray diffraction, NMR, and optical spectroscopies, a two-dimensional infrared spectroscopy (2DIR) method was introduced about a decade ago. The 2DIR method measures pair-wise interactions between vibrational modes in molecules, thus acquiring molecular structural constraints such as distances between vibrating groups and the angles between their transition dipoles. The 2DIR method has been applied to a variety of molecular systems but in studying larger molecules such as proteins and peptides the method is facing challenges associated with the congestion of their vibrational spectra and delocalized character of their vibrational modes. To help extract structural information from such spectra and make efficient use of vibrational modes separated by large distances, a novel relaxation-assisted 2DIR method (RA 2DIR) has recently been proposed, which exploits the transport of excess vibrational energy from the initially excited mode. With the goal of further development of RA 2DIR, we applied it to a variety of molecular systems, including model compounds, transition-metal complexes, and isomers. The experiments revealed several novel effects which both enhance the power of RA 2DIR and bring a deeper understanding to the fundamental process of energy transport on a molecular level. We demonstrated that RA 2DIR can enhance greatly (27-fold) the cross-peak amplitude among spatially remote modes, which leads to an increase of the range of distances accessible for structural measurements by several fold. We demonstrated that the energy transport time correlates with the intermode distance. This correlation offers a new way for identifying connectivity patterns in molecules. We developed two models of energy transport in molecules. In one, a spatial overlap of vibrational modes determines the rate of energy transfer. Another model uses generalizations of Marcus theory of electron transfer applied to anharmonic vibrational transitions. These theoretical models reproduce well the main features of RA 2DIR measurements in a set of isomers where the energy transport is found to be affected by the three-dimensional structure as well as in transition-metal complexes, where the energy transport has to go through relatively weak coordination bonds and can be different from that occurring via covalent bonds.

Quantitative analysis of intramolecular exciplex and electron transfer in a double-linked zinc porphyrin-fullerene dyad.

PubMed

Al-Subi, Ali Hanoon; Niemi, Marja; Tkachenko, Nikolai V; Lemmetyinen, Helge

2012-10-04

Photoinduced charge transfer in a double-linked zinc porphyrin-fullerene dyad is studied. When the dyad is excited at the absorption band of the charge-transfer complex (780 nm), an intramolecular exciplex is formed, followed by the complete charge separated (CCS) state. By analyzing the results obtained from time-resolved transient absorption and emission decay measurements in a range of solvents with different polarities, we derived a dependence between the observable lifetimes and internal parameters controlling the reaction rate constants based on the semiquantum Marcus electron-transfer theory. The critical value of the solvent polarity was found to be ε(r) ≈ 6.5: in solvents with higher dielectric constants, the energy of the CCS state is lower than that of the exciplex and the relaxation takes place via the CCS state predominantly, whereas in solvents with lower polarities the energy of the CCS state is higher and the exciplex relaxes directly to the ground state. In solvents with moderate polarities the exciplex and the CCS state are in equilibrium and cannot be separated spectroscopically. The degree of the charge shift in the exciplex relative to that in the CCS state was estimated to be 0.55 ± 0.02. The electronic coupling matrix elements for the charge recombination process and for the direct relaxation of the exciplex to the ground state were found to be 0.012 ± 0.001 and 0.245 ± 0.022 eV, respectively.

Fused thiophene and its periphery fluorinated substitution derivatives: a theoretical study for organic semiconductors

NASA Astrophysics Data System (ADS)

Wei, Hui-Ling; Shi, Ya-Rui; Liu, Yu-Fang

2015-06-01

A series of phenyl end-capped derivatives of benzo[d,d‧]thieno[3,2-b4,5- b‧]dithiophene (BTDT) with periphery-fluorinated substitutions (PFS) were systematically investigated by using density functional theory (DFT) combined with the Marcus-Hush electron transfer theory. The substituting effects of PFS were discussed. Compared with the original compounds, (i) the PFS compounds have a relatively higher efficiency of charge transport, lower barriers of electron injection, and larger HOMO-LUMO gaps; (ii) the air-stability and the device performance are enhanced by PFS; and (iii) the HOMO-LUMO transitions in the absorption spectrum of the PFS compounds show an obvious blue-shift trend. The perfluorophenylbisbenzo[d, d‧]thieno[3,2-b4,5-b‧]dithiophene (BpF-BTDT) is found to be the most stable and most effective compound in charge transport among the investigated compounds, and it is suggested as an ambipolar semiconducting material. The results of electronic coupling of the bisbenzo[d, d‧]thieno[3,2-b 4,5- b‧]dithiophene (BBTDT) derivatives show that the orbital interaction is mainly contributed by the neighboring molecule in the two dimensional (2D) layer. The PFS compounds have lower oxidization potential, ionization potential, and electron affinity values than the corresponding original ones, which suggest that fluorination can enhance the performance of the thiophene-based organic solar cells. These findings provide a better understanding of the PFS effects on organic semiconductors and may help to design high-performance semiconductor materials.

Computational Replication of the Abnormal Secondary Kinetic Isotope Effects in a Hydride Transfer Reaction in Solution with a Motion Assisted H-Tunneling Model

PubMed Central

2015-01-01

We recently reported abnormal secondary deuterium kinetic isotope effects (2° KIEs) for hydride transfer reactions from alcohols to carbocations in acetonitrile (Chem. Comm. 2012, 48, 11337). Experimental 2° KIE values were found to be inflated on the 9-C position in the xanthylium cation but deflated on the β-C position in 2-propanol with respect to the values predicted by the semi-classical transition-state theory. No primary (1°) isotope effect on 2° KIEs was observed. Herein, the KIEs were replicated by the Marcus-like H-tunneling model that requires a longer donor–acceptor distance (DAD) in a lighter isotope transfer process. The 2° KIEs for a range of potential tunneling-ready-states (TRSs) of different DADs were calculated and fitted to the experiments to find the TRS structure. The observed no effect of 1° isotope on 2° KIEs is explained in terms of the less sterically hindered TRS structure so that the change in DAD due to the change in 1° isotope does not significantly affect the reorganization of the 2° isotope and hence the 2° KIE. The effect of 1° isotope on 2° KIEs may be expected to be more pronounced and thus observable in reactions occurring in restrictive environments such as the crowded and relatively rigid active site of enzymes. PMID:24498946

Low intensity, continuous wave photodoping of ZnO quantum dots - photon energy and particle size effects.

PubMed

Aguirre, Matías E; Municoy, S; Grela, M A; Colussi, A J

2017-02-08

The unique properties of semiconductor quantum dots (QDs) have found application in the conversion of solar to chemical energy. How the relative rates of the redox processes that control QD photon efficiencies depend on the particle radius (r) and photon energy (E λ ), however, is not fully understood. Here, we address these issues and report the quantum yields (Φs) of interfacial charge transfer and electron doping in ZnO QDs capped with ethylene glycol (EG) as a function of r and E λ in the presence and absence of methyl viologen (MV 2+ ) as an electron acceptor, respectively. We found that Φs for the oxidation of EG are independent of E λ and photon fluence (φ λ ), but markedly increase with r. The independence of Φs on φ λ ensures that QDs are never populated by more than one electron-hole pair, thereby excluding Auger-type terminations. We show that these findings are consistent with the operation of an interfacial redox process that involves thermalized carriers in the Marcus inverted region. In the absence of MV 2+ , QDs accumulate electrons up to limiting volumetric densities ρ e,∞ that depend sigmoidally on excess photon energy E* = E λ - E BG (r), where E BG (r) is the r-dependent bandgap energy. The maximum electron densities: ρ ev,∞ ∼ 4 × 10 20 cm -3 , are reached at E* > 0.5 eV, independent of the particle radius.

Nonparametric evaluation of quantitative traits in population-based association studies when the genetic model is unknown.

PubMed

Konietschke, Frank; Libiger, Ondrej; Hothorn, Ludwig A

2012-01-01

Statistical association between a single nucleotide polymorphism (SNP) genotype and a quantitative trait in genome-wide association studies is usually assessed using a linear regression model, or, in the case of non-normally distributed trait values, using the Kruskal-Wallis test. While linear regression models assume an additive mode of inheritance via equi-distant genotype scores, Kruskal-Wallis test merely tests global differences in trait values associated with the three genotype groups. Both approaches thus exhibit suboptimal power when the underlying inheritance mode is dominant or recessive. Furthermore, these tests do not perform well in the common situations when only a few trait values are available in a rare genotype category (disbalance), or when the values associated with the three genotype categories exhibit unequal variance (variance heterogeneity). We propose a maximum test based on Marcus-type multiple contrast test for relative effect sizes. This test allows model-specific testing of either dominant, additive or recessive mode of inheritance, and it is robust against variance heterogeneity. We show how to obtain mode-specific simultaneous confidence intervals for the relative effect sizes to aid in interpreting the biological relevance of the results. Further, we discuss the use of a related all-pairwise comparisons contrast test with range preserving confidence intervals as an alternative to Kruskal-Wallis heterogeneity test. We applied the proposed maximum test to the Bogalusa Heart Study dataset, and gained a remarkable increase in the power to detect association, particularly for rare genotypes. Our simulation study also demonstrated that the proposed non-parametric tests control family-wise error rate in the presence of non-normality and variance heterogeneity contrary to the standard parametric approaches. We provide a publicly available R library nparcomp that can be used to estimate simultaneous confidence intervals or compatible multiplicity-adjusted p-values associated with the proposed maximum test.

The seismic velocity structure of a foreshock zone on an oceanic transform fault: Imaging a rupture barrier to the 2008 Mw 6.0 earthquake on the Gofar fault, EPR

NASA Astrophysics Data System (ADS)

Roland, E. C.; McGuire, J. J.; Lizarralde, D.; Collins, J. A.

2010-12-01

East Pacific Rise (EPR) oceanic transform faults are known to exhibit a number of unique seismicity characteristics, including abundant seismic swarms, a prevalence of aseismic slip, and high rates of foreshock activity. Until recently the details of how this behavior fits into the seismic cycle of large events that occur periodically on transforms have remained poorly understood. In 2008 the most recent seismic cycle of the western segment (G3) of the Gofar fault (4 degrees South on the EPR) ended with a Mw 6.0 earthquake. Seismicity associated with this event was recorded by a local array of ocean bottom seismometers, and earthquake locations reveal several distinct segments with unique slip behavior on the G3 fault. Preceding the Mw 6.0 event, a significant foreshock sequence was recorded just to the east of the mainshock rupture zone that included more than 20,000 detected earthquakes. This foreshock zone formed the eastern barrier to the mainshock rupture, and following the mainshock, seismicity rates within the foreshock zone remained unchanged. Based on aftershock locations of events following the 2007 Mw 6.0 event that completed the seismic cycle on the eastern end of the G3 fault, it appears that the same foreshock zone may have served as the western rupture barrier for that prior earthquake. Moreover, mainshock rupture associated with each of the last 8 large (~ Mw 6.0) events on the G3 fault seems to terminate at the same foreshock zone. In order to elucidate some of the structural controls on fault slip and earthquake rupture along transform faults, we present a seismic P-wave velocity profile crossing the center of the foreshock zone of the Gofar fault, as well as a profile for comparison across the neighboring Quebrada fault. Although tectonically similar, Quebrada does not sustain large earthquakes and is thought to accommodate slip primarily aseismically and with small magnitude earthquake swarms. Velocity profiles were obtained using data collected from ~100 km refraction profiles crossing the two faults, each using 8 short period ocean bottom seismometers from OBSIP and over 900 shots from the RV Marcus Langseth. These data are modeled using a 2-D tomographic code that allows joint inversion of the Pg, PmP, and Pn arrivals. We resolve a significant low velocity zone associated with the faults, which likely indicates rocks that have undergone intensive brittle deformation. Low velocities may also signify the presence of metamorphic alteration and/or elevated fluid pressures, both of which could have a significant affect on the friction laws that govern fault slip in these regions. A broad low velocity zone is apparent in the shallow crust (< 3km) at both faults, with velocities that are reduced by more than 1 km/s relative to the surrounding oceanic crust. A narrower zone of reduced seismic velocity appears to extend to mantle depths, and particularly on the Gofar fault, this corresponds with the seismogenic zone inferred from located foreshock seismicity, spanning depths of 3-9 km beneath the seafloor.

[Medical history as an academic subject at the Bamberg University].

PubMed

Locher, W

2000-01-01

A full program of medicine was taught at the Catholic University of Bamberg (founded 1648 as the Academia Ottonia) from 1773 through 1803. Within this period of time, the History of Medicine was taught from 1790 through 1795 by Johann Baptist Dominicus Fin(c)k. This paper elucidates how in this instance protestant universities served as models for catholic universities. Interestingly, it was not the medical faculty itself which developed an interest in teaching medical history. Rather, it was Adalbert Friedrich Marcus (1753-1816), physician-in-waiting of the Prince-Bishop Franz Ludwig von Erthal and medical officer in the principality of Bamberg since June 22, 1790, who was charged by the Prince-Bishop with developing guidelines for medical education. The start of the History of Medicine lectures brought with it a heated dispute about an appropriate textbook. The discussion is evidence of a transition from historiography understood as an account of learned doctors of the past to a study of history in a modern sense.

Electron-transfer dynamics in highly reduced states of simple and superstructured metalloporphyrins

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

Anxolabehere, E.; Lexa, D.; Saveant, J.M.

1992-02-06

The standard rate constants of the Fe(I){sup -}/Fe({open_quotes}0{close_quotes}){sup 2-} couple in a series of four simple and basket-handle superstructured porphyrins have been measured by means of fast cyclic voltammetry at mercury and gold ultramicroelectrodes. Analysis of the experimental data by the Marcus-Hush model revealed that the main rate-controlling factor of these very fast electron-transfer reactions is solvent reorganization. The presence of secondary amide groups borne by the basket-handle structure and located in the close vicinity of the metalloporphyrin center largely facilitates the reaction from a thermodynamic viewpoint. This facilitation of the reaction is not counterbalanced by any significant contribution ofmore » the fluctuational reorganization of the NHCO dipoles thanks to their attachment to the basket-handle chains. A few complementary experiments were carried out with zinc and copper porphyrins where the same general trends were observed. 16 refs., 3 figs., 2 tabs.« less

Solvent effects on the oxidation (electron transfer) reaction of [Fe(CN) 6] 4- by [Co(NH 3) 5pz] 3+

NASA Astrophysics Data System (ADS)

Muriel, F.; Jiménez, R.; López, M.; Prado-Gotor, R.; Sánchez, F.

2004-03-01

Solvent effects on the title reaction were studied in different reaction media constituted by water and organic cosolvents (methanol, tert-butyl alcohol, ethyleneglycol and glucose) at 298.2 K. The results are considered in light of the Marcus-Hush approach for electron transfer reactions. Variations of the electron transfer rate constant are shown to be mainly due to changes in the reaction free energy. On the other hand the energies of the MMCT band, corresponding to the optical electron transfer within the ion pair [Fe(CN) 6] 4-/[Co(NH 3) 5pz] 3+, in the different reaction media, have been obtained. The activation free energies of the thermal electron transfer process have been calculated from the band ( Eop) data, and compared with those obtained from the kinetic study. Quantitative agreement is found between the two series of data. This shows the possibility of estimating activation free energies for electron transfer reactions from static (optical) measurements.

Modeling the free energy surfaces of electron transfer in condensed phases

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.; Voth, Gregory A.

2000-10-01

We develop a three-parameter model of electron transfer (ET) in condensed phases based on the Hamiltonian of a two-state solute linearly coupled to a harmonic, classical solvent mode with different force constants in the initial and final states (a classical limit of the quantum Kubo-Toyozawa model). The exact analytical solution for the ET free energy surfaces demonstrates the following features: (i) the range of ET reaction coordinates is limited by a one-sided fluctuation band, (ii) the ET free energies are infinite outside the band, and (iii) the free energy surfaces are parabolic close to their minima and linear far from the minima positions. The model provides an analytical framework to map physical phenomena conflicting with the Marcus-Hush two-parameter model of ET. Nonlinear solvation, ET in polarizable charge-transfer complexes, and configurational flexibility of donor-acceptor complexes are successfully mapped onto the model. The present theory leads to a significant modification of the energy gap law for ET reactions.

Theoretical study on the electronic structures and phosphorescent properties of four Ir(III) complexes with different substituents on the ancillary ligand

NASA Astrophysics Data System (ADS)

Han, Deming; Shang, Xiaohong; Zhang, Gang; Zhao, Lihui

2013-12-01

The geometry structures, electronic structures, absorption and phosphorescent properties of four Ir(III) complexes {[(F2-ppy)2Ir(pta-X)], where F2-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = -CF3; -H; -CH3; -N(CH3)2}, are investigated using the density functional method. The results reveal that the electron-accepting group -CF3 has no obvious effect on absorption and emission properties, while the substitutive group -N(CH3)2 with strong electron-donating ability has obvious effect on the emission properties. The mobility of hole and electron were studied computationally based on the Marcus-Hush theory. Calculations of ionisation potential and electron affinity were used to evaluate the injection abilities of holes and electrons into these complexes. We hope that this theoretical work can provide a suitable guide to the future design and synthesis of novel phosphorescent materials for use in the organic light-emitting diodes.

Does really Born Oppenheimer approximation break down in charge transfer processes? An exactly solvable model

NASA Astrophysics Data System (ADS)

Kuznetsov, Alexander M.; Medvedev, Igor G.

2006-05-01

Effects of deviation from the Born-Oppenheimer approximation (BOA) on the non-adiabatic transition probability for the transfer of a quantum particle in condensed media are studied within an exactly solvable model. The particle and the medium are modeled by a set of harmonic oscillators. The dynamic interaction of the particle with a single local mode is treated explicitly without the use of BOA. Two particular situations (symmetric and non-symmetric systems) are considered. It is shown that the difference between the exact solution and the true BOA is negligibly small at realistic parameters of the model. However, the exact results differ considerably from those of the crude Condon approximation (CCA) which is usually considered in the literature as a reference point for BOA (Marcus-Hush-Dogonadze formula). It is shown that the exact rate constant can be smaller (symmetric system) or larger (non-symmetric one) than that obtained in CCA. The non-Condon effects are also studied.

Different electronic and charge-transport properties of four organic semiconductors Tetraazaperopyrenes derivatives

NASA Astrophysics Data System (ADS)

Shi, Yarui; Wei, Huiling; Liu, Yufang

2015-03-01

Tetraazaperopyrenes (TAPPs) derivatives are high-performance n-type organic semiconductor material families with the remarkable long-term stabilities. The charge carrier mobilities in TAPPs derivatives crystals were calculated by the density functional theory (DFT) method combined with the Marcus-Hush electron-transfer theory. The existence of considerable C-H…F-C bonding defines the conformation of the molecular structure and contributes to its stability. We illustrated how it is possible to control the electronic and charge-transport parameters of TAPPs derivatives as a function of the positions, a type of the substituents. It is found that the core substitution of TAPPs has a drastic influence on the charge-transport mobilities. The maximum electron mobility value of the core-brominated 2,9-bis (perfluoroalkyl)-substituted TAPPs is 0.521 cm2 V-1 s-1, which appear in the orientation angle 95° and 275°. The results demonstrate that the TAPPs with bromine substituents in ortho positions exhibit the best charge-transfer efficiency among the four different TAPP derivatives.

Maturation status of sarcomere structure and function in human iPSC-derived cardiac myocytes.

PubMed

Bedada, Fikru B; Wheelwright, Matthew; Metzger, Joseph M

2016-07-01

Human heart failure due to myocardial infarction is a major health concern. The paucity of organs for transplantation limits curative approaches for the diseased and failing adult heart. Human induced pluripotent stem cell-derived cardiac myocytes (hiPSC-CMs) have the potential to provide a long-term, viable, regenerative-medicine alternative. Significant progress has been made with regard to efficient cardiac myocyte generation from hiPSCs. However, directing hiPSC-CMs to acquire the physiological structure, gene expression profile and function akin to mature cardiac tissue remains a major obstacle. Thus, hiPSC-CMs have several hurdles to overcome before they find their way into translational medicine. In this review, we address the progress that has been made, the void in knowledge and the challenges that remain. This article is part of a Special Issue entitled: Cardiomyocyte Biology: Integration of Developmental and Environmental Cues in the Heart edited by Marcus Schaub and Hughes Abriel. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Restoration of the Apollo 15 Heat Flow Experiment Data from 1975 to 1977

NASA Technical Reports Server (NTRS)

Nagihara, S.; Nakamura, Y.; Taylor, P. T.; Williams, D. R.; Kiefer, W. S.

2017-01-01

The Apollo 15 Heat Flow Experiment (HFE) was conducted from July 1971 through January 1977. Two heat flow probes were deployed roughly 8.5 meters apart. Probe 1 and Probe 2 penetrated to 1.4-meters and 1-meter depths into the lunar regolith, respectively. Temperatures at different depths and the surface were logged with 7.25-minute intervals and transmitted to Earth. At the conclusion of the experiment, only data obtained from July 1971 through December 1974 were processed and archived at the National Space Science Data Center (NSSDC) by the principal investigator of the experiment, Marcus Langseth of Columbia University. Langseth died in 1997. It is not known what happened to the HFE data tapes he used. Current researchers have strong interests in re-examining the HFE data for the full duration of the experiment. We have recovered and processed large portions of the Apollo 15 HFE data from 1975 through 1977 by assembling data and metadata from various sources.

Hydrogen bonding effects on the reorganization energy for photoinduced charge separation reaction between porphyrin and quinone studied by nanosecond laser flash photolysis.

PubMed

Yago, Tomoaki; Gohdo, Masao; Wakasa, Masanobu

2010-02-25

Alcohol concentration dependences of photoinduced charge separation (CS) reaction of zinc tetraphenyl-porphyrin (ZnTPP) and duroquinone (DQ) were investigated in benzonitrile by a nanosecond laser flash photolysis technique. The photoinduced CS reaction was accelerated by the addition of alcohols, whereas the addition of acetonitrile caused little effect on the CS reactions. The simple theory was developed to calculate an increase in reorganization energies induced by the hydrogen bonding interactions between DQ and alcohols using the chemical equilibrium constants for the hydrogen bonding complexes through the concerted pathway and the stepwise one. The experimental results were analyzed by using the Marcus equation where we took into account the hydrogen bonding effects on the reorganization energy and the reaction free energy for the CS reaction. The observed alcohol concentration dependence of the CS reaction rates was well explained by the formation of the hydrogen bonding complexes through the concerted pathway, demonstrating the increase in the reorganization energy by the hydrogen bonding interactions.

Molecular origin of differences in hole and electron mobility in amorphous Alq3--a multiscale simulation study.

PubMed

Fuchs, Andreas; Steinbrecher, Thomas; Mommer, Mario S; Nagata, Yuki; Elstner, Marcus; Lennartz, Christian

2012-03-28

In order to determine the molecular origin of the difference in electron and hole mobilities of amorphous thin films of Alq(3) (meridional Alq(3) (tris(8-hydroxyquinoline) aluminium)) we performed multiscale simulations covering quantum mechanics, molecular mechanics and lattice models. The study includes realistic disordered morphologies, polarized site energies to describe diagonal disorder, quantum chemically calculated transfer integrals for the off-diagonal disorder, inner sphere reorganization energies and an approximative scheme for outer sphere reorganization energies. Intermolecular transfer rates were calculated via Marcus-theory and mobilities were simulated via kinetic Monte Carlo simulations and by a Master Equation approach. The difference in electron and hole mobility originates from the different localization of charge density in the radical anion (more delocalized) compared to the radical cation (more confined). This results in higher diagonal disorder for holes and less favourable overlap properties for the hole transfer integrals leading to an overall higher electron mobility.

Energetics and dynamics through time-resolved measurements in mass spectrometry

NASA Astrophysics Data System (ADS)

Lifshitz, Chava

Results of recent work on time-resolved photoionization and electron ionization mass spectrometry carried out in Jerusalem are reviewed. Time-resolved photoionization mass spectrometry in the vacuum ultraviolet is applied to polycyclic aromatic hydrocarbons, for example naphthalene, pyrene and fluoranthene as well as to some bromo derivatives (bromonaphthalene and bromoanthracene). Time-resolved photoionization efficiency curves are modelled by Rice-Ramsperger-Kassel-Marcus QET rate-energy k ( E ) dependences of the unimolecular dissociative processes and by the rate process infrared radiative relaxation k . Experimental results are augmented by time-resolved photorad dissociation data for the same species, whenever available. Kinetic shifts, conventional and intrinsic (due to competition between dissociative and radiative decay), are evaluated. Activation parameters (activation energies and entropies) are deduced. Thermochemical information is obtained including bond energies and ionic heats of formation. Fullerenes, notably C , are studied by time-resolved electron ionization and a large intrinsic shift, due to competition with black-bodylike radiative decay in the visible is discussed.

A Critical Test of the “Tunneling and Coupled Motion” Concept in Enzymatic Alcohol Oxidation

PubMed Central

Roston, Daniel; Kohen, Amnon

2013-01-01

The physical mechanism of C-H bond activation by enzymes is the subject of intense study and we have tested the predictions of two competing models for C-H activation in the context of alcohol dehydrogenase. The kinetic isotope effects (KIEs) in this enzyme have previously suggested a model of quantum mechanical tunneling and coupled motion of primary (1°) and secondary (2°) hydrogens. Here we measure the 2° H/T KIEs with both and H and D at the 1° position and find that the 2° KIE is significantly deflated with D-transfer, consistent with the predictions of recent Marcus-like models of H-transfer. The results suggest that the fast dynamics of H-tunneling result in a 1° isotope effect on the structure of the tunneling ready state: the trajectory of D-transfer goes through a shorter donor-acceptor distance than that of H-transfer. PMID:24020836

R/V Maurice Ewing retires

NASA Astrophysics Data System (ADS)

Diebold, John

2005-07-01

The R/V Maurice Ewing came into port for the last time on 10 March 2005, tying up at Quonset Point, R.I., astern of the ship slated to be her replacement (Figure 1). M/V Western Legend (Figure 1, left) will, during fall and winter of 2005-2006, be converted as R/V Marcus G. Langseth, and will replace the Maurice Ewing (Figure 1, right) as the primary seismic research vessel within the U.S. academic research vessel fleet.During its distinguished 15-year career, Ewing's operations added fundamentally to the knowledge and understanding of solid Earth dynamics and structure. Ewing began life as the M/V Bernier, and performed seismic offshore exploration for Petro Canada. In an innovative process, which included initialization provided by Columbia University, the U.S. National Science Foundation (NSF) acquired Bernier in 1989, and the ship's title passed to NSF in 1990. Bernier was converted into R/V Ewing for a total expenditure (approximately $12 million) far below the cost of building and outfitting a new seismic research ship.

Electron-Transfer Dynamics for a Donor-Bridge-Acceptor Complex in Ionic Liquids.

PubMed

DeVine, Jessalyn A; Labib, Marena; Harries, Megan E; Rached, Rouba Abdel Malak; Issa, Joseph; Wishart, James F; Castner, Edward W

2015-08-27

Intramolecular photoinduced electron transfer from an N,N-dimethyl-p-phenylenediamine donor bridged by a diproline spacer to a coumarin 343 acceptor was studied using time-resolved fluorescence measurements in three ionic liquids and in acetonitrile. The three ionic liquids have the bis[(trifluoromethyl)sulfonyl]amide anion paired with the tributylmethylammonium, 1-butyl-1-methylpyrrolidinium, and 1-decyl-1-methylpyrrolidinium cations. The dynamics in the two-proline donor-bridge-acceptor complex are compared to those observed for the same donor and acceptor connected by a single proline bridge, studied previously by Lee et al. (J. Phys. Chem. C 2012, 116, 5197). The increased conformational freedom afforded by the second bridging proline resulted in multiple energetically accessible conformations. The multiple conformations have significant variations in donor-acceptor electronic coupling, leading to dynamics that include both adiabatic and nonadiabatic contributions. In common with the single-proline bridged complex, the intramolecular electron transfer in the two-proline system was found to be in the Marcus inverted regime.

Mechanisms of lithium transport in amorphous polyethylene oxide.

PubMed

Duan, Yuhua; Halley, J W; Curtiss, Larry; Redfern, Paul

2005-02-01

We report calculations using a previously reported model of lithium perchlorate in polyethylene oxide in order to understand the mechanism of lithium transport in these systems. Using an algorithm suggested by Voter, we find results for the diffusion rate which are quite close to experimental values. By analysis of the individual events in which large lithium motions occur during short times, we find that no single type of rearrangement of the lithium environment characterizes these events. We estimate the free energies of the lithium ion as a function of position during these events by calculation of potentials of mean force and thus derive an approximate map of the free energy as a function of lithium position during these events. The results are consistent with a Marcus-like picture in which the system slowly climbs a free energy barrier dominated by rearrangement of the polymer around the lithium ions, after which the lithium moves very quickly to a new position. Reducing the torsion forces in the model causes the diffusion rates to increase.

Catalysis-Enhancement via Rotary Fluctuation of F1-ATPase

PubMed Central

Watanabe, Rikiya; Hayashi, Kumiko; Ueno, Hiroshi; Noji, Hiroyuki

2013-01-01

Protein conformational fluctuations modulate the catalytic powers of enzymes. The frequency of conformational fluctuations may modulate the catalytic rate at individual reaction steps. In this study, we modulated the rotary fluctuation frequency of F1-ATPase (F1) by attaching probes with different viscous drag coefficients at the rotary shaft of F1. Individual rotation pauses of F1 between rotary steps correspond to the waiting state of a certain elementary reaction step of ATP hydrolysis. This allows us to investigate the impact of the frequency modulation of the rotary fluctuation on the rate of the individual reaction steps by measuring the duration of rotation pauses. Although phosphate release was significantly decelerated, the ATP-binding and hydrolysis steps were less sensitive or insensitive to the viscous drag coefficient of the probe. Brownian dynamics simulation based on a model similar to the Sumi-Marcus theory reproduced the experimental results, providing a theoretical framework for the role of rotational fluctuation in F1 rate enhancement. PMID:24268150

New insights into thermal decomposition of polycyclic aromatic hydrocarbon oxyradicals.

PubMed

Liu, Peng; Lin, He; Yang, Yang; Shao, Can; Gu, Chen; Huang, Zhen

2014-12-04

Thermal decompositions of polycyclic aromatic hydrocarbon (PAH) oxyradicals on various surface sites including five-membered ring, free-edge, zigzag, and armchair have been systematically investigated by using ab initio density functional theory B3LYP/6-311+G(d,p) basis set. The calculation based on Hückel theory indicates that PAHs (3H-cydopenta[a]anthracene oxyradical) with oxyradicals on a five-membered ring site have high chemical reactivity. The rate coefficients of PAH oxyradical decomposition were evaluated by using Rice-Ramsperger-Kassel-Marcus theory and solving the master equations in the temperature range of 1500-2500 K and the pressure range of 0.1-10 atm. The kinetic calculations revealed that the rate coefficients of PAH oxyradical decomposition are temperature-, pressure-, and surface site-dependent, and the oxyradical on a five-membered ring is easier to decompose than that on a six-membered ring. Four-membered rings were found in decomposition of the five-membered ring, and a new reaction channel of PAH evolution involving four-membered rings is recommended.

Control of a chemical reaction (photodegradation of the p3ht polymer) with nonlocal dielectric environments

PubMed Central

Peters, V. N.; Tumkur, T. U.; Zhu, G.; Noginov, M. A.

2015-01-01

Proximity to metallic surfaces, plasmonic structures, cavities and other inhomogeneous dielectric environments is known to control spontaneous emission, energy transfer, scattering, and many other phenomena of practical importance. The aim of the present study was to demonstrate that, in spirit of the Marcus theory, the rates of chemical reactions can, too, be influenced by nonlocal dielectric environments, such as metallic films and metal/dielectric bilayer or multilayer structures. We have experimentally shown that metallic, composite metal/dielectric substrates can, indeed, control ordering as well as photodegradation of thin poly-3-hexylthiophene (p3ht) films. In many particular experiments, p3ht films were separated from metal by a dielectric spacer, excluding conventional catalysis facilitated by metals and making modification of the nonlocal dielectric environment a plausible explanation for the observed phenomena. This first step toward understanding of a complex relationship between chemical reactions and nonlocal dielectric environments is to be followed by the theory development and a broader scope of thorough experimental studies. PMID:26434679

Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor.

PubMed

Horke, Daniel A; Li, Quansong; Blancafort, Lluís; Verlet, Jan R R

2013-08-01

Quinones feature prominently as electron acceptors in nature. Their electron-transfer reactions are often highly exergonic, for which Marcus theory predicts reduced electron-transfer rates because of a free-energy barrier that occurs in the inverted region. However, the electron-transfer kinetics that involve quinones can appear barrierless. Here, we consider the intrinsic properties of the para-benzoquinone radical anion, which serves as the prototypical electron-transfer reaction product involving a quinone-based acceptor. Using time-resolved photoelectron spectroscopy and ab initio calculations, we show that excitation at 400 and 480 nm yields excited states that are unbound with respect to electron loss. These excited states are shown to decay on a sub-40 fs timescale through a series of conical intersections with lower-lying excited states, ultimately to form the ground anionic state and avoid autodetachment. From an isolated electron-acceptor perspective, this ultrafast stabilization mechanism accounts for the ability of para-benzoquinone to capture and retain electrons.

DETECTION OF IDIOTYPIC CROSS-REACTIONS AMONG STREPTOCOCCAL ANTISERA FROM RELATED RABBITS

PubMed Central

Kindt, Thomas J.; Seide, Rochelle K.; Bokisch, Viktor A.; Krause, Richard M.

1973-01-01

Idiotypic cross-reactions among antibodies to Group C streptococcal carbohydrate were studied using idiotypic antisera prepared in allotypically matched rabbits. Antibodies with idiotypic cross-specificity to one proband antibody were detected in 58% of the antisera from related rabbits, while approximately 1% of nonrelated rabbits produced antibody with this specificity. The cross-specificity was related to the group a (VH) allotype of 133 rabbits tested with only one exception. Studies utilizing antisera against a second proband antibody failed to detect antibodies with idiotypic cross-reactivity among the same group of related rabbits. This result emphasizes the variation in expression of idiotypic determinants of antibodies. It was further shown that the presence of anti-IgG's in the streptococcal antisera interfere with the detection of idiotypic cross-reactions. These anti-IgG's masked the presence of antibodies with idiotypic cross-specificity when inhibition of precipitation tests were used for their detection. PMID:4727913

Measurement of relative cross sections for simultaneous ionization and excitation of the helium 4 2s and 4 2p states

NASA Technical Reports Server (NTRS)

Sutton, J. F.

1972-01-01

The relative cross sections for simultaneous ionization and excitation of helium by 200-eV electrons into the 4 2s and 4 2p states were measured via a fast delayed coincidence technique. Results show good agreement with the relative cross sections for single electron excitation of helium and hydrogen. An application of the results of the measurement to the development of ultraviolet intensity standard is suggested. This technique involves the use of known branching ratios, a visible light flux reference, and the measured relative cross sections.

Reorganization energy upon charging a single molecule on an insulator measured by atomic force microscopy

NASA Astrophysics Data System (ADS)

Fatayer, Shadi; Schuler, Bruno; Steurer, Wolfram; Scivetti, Ivan; Repp, Jascha; Gross, Leo; Persson, Mats; Meyer, Gerhard

2018-05-01

Intermolecular single-electron transfer on electrically insulating films is a key process in molecular electronics1-4 and an important example of a redox reaction5,6. Electron-transfer rates in molecular systems depend on a few fundamental parameters, such as interadsorbate distance, temperature and, in particular, the Marcus reorganization energy7. This crucial parameter is the energy gain that results from the distortion of the equilibrium nuclear geometry in the molecule and its environment on charging8,9. The substrate, especially ionic films10, can have an important influence on the reorganization energy11,12. Reorganization energies are measured in electrochemistry13 as well as with optical14,15 and photoemission spectroscopies16,17, but not at the single-molecule limit and nor on insulating surfaces. Atomic force microscopy (AFM), with single-charge sensitivity18-22, atomic-scale spatial resolution20 and operable on insulating films, overcomes these challenges. Here, we investigate redox reactions of single naphthalocyanine (NPc) molecules on multilayered NaCl films. Employing the atomic force microscope as an ultralow current meter allows us to measure the differential conductance related to transitions between two charge states in both directions. Thereby, the reorganization energy of NPc on NaCl is determined as (0.8 ± 0.2) eV, and density functional theory (DFT) calculations provide the atomistic picture of the nuclear relaxations on charging. Our approach presents a route to perform tunnelling spectroscopy of single adsorbates on insulating substrates and provides insight into single-electron intermolecular transport.

Re-examining the tetraphenyl-arsonium/tetraphenyl-borate (TATB) hypothesis for single-ion solvation free energies

NASA Astrophysics Data System (ADS)

Pollard, Travis P.; Beck, Thomas L.

2018-06-01

Attempts to establish an absolute single-ion hydration free energy scale have followed multiple strategies. Two central themes consist of (1) employing bulk pair thermodynamic data and an underlying interfacial-potential-free model to partition the hydration free energy into individual contributions [Marcus, Latimer, and tetraphenyl-arsonium/tetraphenyl-borate (TATB) methods] or (2) utilizing bulk thermodynamic and cluster data to estimate the free energy to insert a proton into water, including in principle an interfacial potential contribution [the cluster pair approximation (CPA)]. While the results for the hydration free energy of the proton agree remarkably well between the three approaches in the first category, the value differs from the CPA result by roughly +10 kcal/mol, implying a value for the effective electrochemical surface potential of water of -0.4 V. This paper provides a computational re-analysis of the TATB method for single-ion free energies using quasichemical theory. A previous study indicated a significant discrepancy between the free energies of hydration for the TA cation and the TB anion. We show that the main contribution to this large computed difference is an electrostatic artifact arising from modeling interactions in periodic boundaries. No attempt is made here to develop more accurate models for the local ion/solvent interactions that may lead to further small free energy differences between the TA and TB ions, but the results clarify the primary importance of interfacial potential effects for analysis of the various free energy scales. Results are also presented, related to the TATB assumption in the organic solvents dimethyl sulfoxide and 1,2-dichloroethane.

Through-Space Intervalence Charge Transfer as a Mechanism for Charge Delocalisation in Metal-Organic Frameworks.

PubMed

Hua, Carol; Doheny, Patrick William; Ding, Bowen; Chan, Bun; Yu, Michelle; Kepert, Cameron J; D'Alessandro, Deanna M

2018-05-04

Understanding the nature of charge transfer mechanisms in 3-dimensional Metal-Organic Frameworks (MOFs) is an important goal owing to the possibility of harnessing this knowledge to design conductive frameworks. These materials have been implicated as the basis for the next generation of technological devices for applications in energy storage and conversion, including electrochromic devices, electrocatalysts, and battery materials. After nearly two decades of intense research into MOFs, the mechanisms of charge transfer remain relatively poorly understood, and new strategies to achieve charge mobility remain elusive and challenging to experimentally explore, validate and model. We now demonstrate that aromatic stacking interactions in Zn(II) frameworks containing cofacial thiazolo[5,4-d]thiazole units lead to a mixed-valence state upon electrochemical or chemical reduction. This through-space Intervalence Charge Transfer (IVCT) phenomenon represents a new mechanism for charge delocalisation in MOFs. Computational modelling of the optical data combined with application of Marcus-Hush theory to the IVCT bands for the mixed-valence framework has enabled quantification of the degree of delocalisation using both in situ and ex situ electro- and spectro-electrochemical methods. A distance dependence for the through-space electron transfer has also been identified on the basis of experimental studies and computational calculations. This work provides a new window into electron transfer phenomena in 3-dimensional coordination space, of relevance to electroactive MOFs where new mechanisms for charge transfer are highly sought after, and to understanding biological light harvesting systems where through-space mixed-valence interactions are operative.

14 CFR 1266.102 - Cross-waiver of liability for agreements for activities related to the International Space Station.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 14 Aeronautics and Space 5 2013-01-01 2013-01-01 false Cross-waiver of liability for agreements for activities related to the International Space Station. 1266.102 Section 1266.102 Aeronautics and Space NATIONAL AERONAUTICS AND SPACE ADMINISTRATION CROSS-WAIVER OF LIABILITY § 1266.102 Cross-waiver of...

14 CFR 1266.102 - Cross-waiver of liability for agreements for activities related to the International Space Station.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 14 Aeronautics and Space 5 2011-01-01 2010-01-01 true Cross-waiver of liability for agreements for activities related to the International Space Station. 1266.102 Section 1266.102 Aeronautics and Space NATIONAL AERONAUTICS AND SPACE ADMINISTRATION CROSS-WAIVER OF LIABILITY § 1266.102 Cross-waiver of...

14 CFR 1266.102 - Cross-waiver of liability for agreements for activities related to the International Space Station.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 14 Aeronautics and Space 5 2012-01-01 2012-01-01 false Cross-waiver of liability for agreements for activities related to the International Space Station. 1266.102 Section 1266.102 Aeronautics and Space NATIONAL AERONAUTICS AND SPACE ADMINISTRATION CROSS-WAIVER OF LIABILITY § 1266.102 Cross-waiver of...

BACKSCAT Lidar Simulation Version 3.0: Technical Documentation and Users Guide

DTIC Science & Technology

1992-12-03

Raman Cross Section of Some Simple Gases, J. Opt. Soc. Am., 63:73. 20 Penny, C.M., St. Peters, R.L., and Lapp, M., (1974) Absolute Rotational Raman...of the molecule, and the remaining columns list the relative normalized cross sections for the respective excitation wavelength. The absolute Raman...cross section is obtained by simply multiplying the relative normalized cross section for a molecular species of interest by the absolute cross section

Barriers and Bridges to Positive Cross-Ethnic Relations: African American and White Parent Socialization Beliefs and Practices.

ERIC Educational Resources Information Center

Hamm, Jill V.

2001-01-01

Using interviews and focus groups, lower and middle socioeconomic status (SES) African American parents and middle SES white parents discussed their objectives regarding cross-ethnic relations and how they helped their children forge positive cross-ethnic relations. The groups relied on different methods to promote socialization. Parents' efforts…

David Shoenberg and the beauty of quantum oscillations

NASA Astrophysics Data System (ADS)

Pudalov, V. M.

2011-01-01

The quantum oscillation effect was discovered in Leiden in 1930, by W. J. de Haas and P. M. van Alphen when measuring magnetization, and by L. W. Shubnikov and de Haas when measuring magnetoresistance. Studying single crystals of bismuth, they observed oscillatory variations in the magnetization and magnetoresistance with magnetic field. Shoenberg, whose first research in Cambridge had been on bismuth, found that much stronger oscillations are observed when a bismuth sample is cooled to liquid helium temperature rather than liquid hydrogen, which had been used by de Haas. In 1938 Shoenberg went from Cambridge to Moscow to study these oscillations at Kapitza's Institute where liquid helium was available at that time. In 1947, J. Marcus observed similar oscillations in zinc and that persuaded Schoenberg to return to this research. After that, the dHvA effect became one of his main research topics. In particular, he developed techniques for quantitative measurement of this effect in many metals. A theoretical explanation of quantum oscillations was given by L. Onsager in 1952, and an analytical quantitative theory by I. M. Lifshitz and A. M. Kosevich in 1955. These theoretical advances seemed to provide a comprehensive description of the effect. Since then, quantum oscillations have been widely used as a tool for measuring Fermi surface extremal cross-sections and all-angle electron scattering times. In his pioneering experiments of the 1960's, Shoenberg revealed the richness and deep essence of the quantum oscillation effect and showed how the beauty of the effect is disclosed under nonlinear conditions imposed by interactions in the system under study. It was quite surprising that "magnetic interaction" conditions could cause the apparently weak quantum oscillation effect to have such strong consequences as breaking the sample into magnetic (now called "Shoenberg") domains and forming an inhomogeneous magnetic state. With his contributions to the field of quantum oscillations and superconductivity, Shoenberg is undoubtedly one of the 20th century's foremost scientists. We describe experiments to determine the quantitative parameters of electron-electron interactions in line with Shoenberg's idea that quasiparticle interaction parameters can be found by analyzing quantum oscillations as modified by interactions.

14 CFR § 1266.102 - Cross-waiver of liability for agreements for activities related to the International Space Station.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 14 Aeronautics and Space 5 2014-01-01 2014-01-01 false Cross-waiver of liability for agreements for activities related to the International Space Station. § 1266.102 Section § 1266.102 Aeronautics and Space NATIONAL AERONAUTICS AND SPACE ADMINISTRATION CROSS-WAIVER OF LIABILITY § 1266.102 Cross...

Cross-border ties as a source of risk and resilience: Do cross-border ties moderate the relationship between migration-related stress and psychological distress among Latino migrants in the United States?

PubMed Central

Torres, Jacqueline M.; Alcántara, Carmela; Rudolph, Kara E.; Viruell-Fuentes, Edna A.

2017-01-01

Few studies have examined the associations between health and the cross-border ties that migrants maintain with their family members in communities of origin. We draw on theory related to social ties, ethnic identity, and mental health to examine cross-border ties as potential moderators of the association between migration-related stress and psychological distress among Latino migrants. Using data from the National Latino and Asian American Survey, we find that remittance sending is associated with significantly lower levels of psychological distress for Cuban migrants, and difficulty visiting home is associated with significantly greater psychological distress for Puerto Rican migrants. There were significant associations between migration-related stressors and psychological distress, although these associations fell to non-significance after accounting for multiple testing. We found little evidence that cross-border ties either buffer or exacerbate the association between migration-related stressors and psychological distress. We consider the findings within the current political and historical context of cross-border ties and separation. PMID:27803264

Cross-border Ties as Sources of Risk and Resilience: Do Cross-border Ties Moderate the Relationship between Migration-related Stress and Psychological Distress for Latino Migrants in the United States?

PubMed

Torres, Jacqueline M; Alcántara, Carmela; Rudolph, Kara E; Viruell-Fuentes, Edna A

2016-12-01

Few studies have examined the associations between health and the cross-border ties that migrants maintain with their family members in communities of origin. We draw on theory related to social ties, ethnic identity, and mental health to examine cross-border ties as potential moderators of the association between migration-related stress and psychological distress among Latino migrants. Using data from the National Latino and Asian American Survey, we find that remittance sending is associated with significantly lower levels of psychological distress for Cuban migrants, and difficulty visiting home is associated with significantly greater psychological distress for Puerto Rican migrants. There were significant associations between migration-related stressors and psychological distress, although these associations fell to nonsignificance after accounting for multiple testing. We found little evidence that cross-border ties either buffer or exacerbate the association between migration-related stressors and psychological distress. We consider the findings within the current political and historical context of cross-border ties and separation. © American Sociological Association 2016.

The discrepancy in the perception of the public-political speech in Croatia.

PubMed

Tanta, Ivan; Lesinger, Gordana

2014-03-01

Key place in this paper takes the study of political speech in the Republic of Croatia and their impact on voters, or which keywords are in political speeches and public appearances of politicians in Croatia that their voting body wants to hear. Given listed below we will define the research topic in the form of a question - is there a discrepancy in the perception of the public-political speech in Croatia, and which keywords are specific to the two main regions in Croatia and that inhabitant these regions respond. Marcus Tullius Cicero, the most important Roman orator, he used a specific associative mnemonic technique that is called "technique room". He would talk expound on keywords and conceptual terms that he needed for the desired topic and join in these make them, according to the desired order, in a very creative and unique way, the premises of the house or palace, which he knew well. Then, while holding the speech intended to pass through rooms of the house or palace and then put keywords and concepts come to mind, again according to the desired order. Given that this is a specific kind of research political speech that is relatively recent in Croatia, it should be noted that there is still, this kind of political communication is not sufficiently explored. Particularly the emphasis on the impact and use of keywords specific to the Republic of Croatia, in everyday public and political communication. The paper will be analyzed the political, campaign speeches and promises several winning candidates, and now Croatian MEPs, specific keywords related to: economics, culture, science, education and health. The analysis is based on comparison of the survey results on the representation of key words in the speeches of politicians and qualitative analysis of the speeches of politicians on key words during the election campaign.

Delving Into Dissipative Quantum Dynamics: From Approximate to Numerically Exact Approaches

NASA Astrophysics Data System (ADS)

Chen, Hsing-Ta

In this thesis, I explore dissipative quantum dynamics of several prototypical model systems via various approaches, ranging from approximate to numerically exact schemes. In particular, in the realm of the approximate I explore the accuracy of Pade-resummed master equations and the fewest switches surface hopping (FSSH) algorithm for the spin-boson model, and non-crossing approximations (NCA) for the Anderson-Holstein model. Next, I develop new and exact Monte Carlo approaches and test them on the spin-boson model. I propose well-defined criteria for assessing the accuracy of Pade-resummed quantum master equations, which correctly demarcate the regions of parameter space where the Pade approximation is reliable. I continue the investigation of spin-boson dynamics by benchmark comparisons of the semiclassical FSSH algorithm to exact dynamics over a wide range of parameters. Despite small deviations from golden-rule scaling in the Marcus regime, standard surface hopping algorithm is found to be accurate over a large portion of parameter space. The inclusion of decoherence corrections via the augmented FSSH algorithm improves the accuracy of dynamical behavior compared to exact simulations, but the effects are generally not dramatic for the cases I consider. Next, I introduce new methods for numerically exact real-time simulation based on real-time diagrammatic Quantum Monte Carlo (dQMC) and the inchworm algorithm. These methods optimally recycle Monte Carlo information from earlier times to greatly suppress the dynamical sign problem. In the context of the spin-boson model, I formulate the inchworm expansion in two distinct ways: the first with respect to an expansion in the system-bath coupling and the second as an expansion in the diabatic coupling. In addition, a cumulant version of the inchworm Monte Carlo method is motivated by the latter expansion, which allows for further suppression of the growth of the sign error. I provide a comprehensive comparison of the performance of the inchworm Monte Carlo algorithms to other exact methodologies as well as a discussion of the relative advantages and disadvantages of each. Finally, I investigate the dynamical interplay between the electron-electron interaction and the electron-phonon coupling within the Anderson-Holstein model via two complementary NCAs: the first is constructed around the weak-coupling limit and the second around the polaron limit. The influence of phonons on spectral and transport properties is explored in equilibrium, for non-equilibrium steady state and for transient dynamics after a quench. I find the two NCAs disagree in nontrivial ways, indicating that more reliable approaches to the problem are needed. The complementary frameworks used here pave the way for numerically exact methods based on inchworm dQMC algorithms capable of treating open systems simultaneously coupled to multiple fermionic and bosonic baths.

A Bivariate Generalized Linear Item Response Theory Modeling Framework to the Analysis of Responses and Response Times.

PubMed

Molenaar, Dylan; Tuerlinckx, Francis; van der Maas, Han L J

2015-01-01

A generalized linear modeling framework to the analysis of responses and response times is outlined. In this framework, referred to as bivariate generalized linear item response theory (B-GLIRT), separate generalized linear measurement models are specified for the responses and the response times that are subsequently linked by cross-relations. The cross-relations can take various forms. Here, we focus on cross-relations with a linear or interaction term for ability tests, and cross-relations with a curvilinear term for personality tests. In addition, we discuss how popular existing models from the psychometric literature are special cases in the B-GLIRT framework depending on restrictions in the cross-relation. This allows us to compare existing models conceptually and empirically. We discuss various extensions of the traditional models motivated by practical problems. We also illustrate the applicability of our approach using various real data examples, including data on personality and cognitive ability.

Cross-Sectional Analysis of Time-Dependent Data: Mean-Induced Association in Age-Heterogeneous Samples and an Alternative Method Based on Sequential Narrow Age-Cohort Samples

ERIC Educational Resources Information Center

Hofer, Scott M.; Flaherty, Brian P.; Hoffman, Lesa

2006-01-01

The effect of time-related mean differences on estimates of association in cross-sectional studies has not been widely recognized in developmental and aging research. Cross-sectional studies of samples varying in age have found moderate to high levels of shared age-related variance among diverse age-related measures. These findings may be…

Eigenvalue computations with the QUAD4 consistent-mass matrix

NASA Technical Reports Server (NTRS)

Butler, Thomas A.

1990-01-01

The NASTRAN user has the option of using either a lumped-mass matrix or a consistent- (coupled-) mass matrix with the QUAD4 shell finite element. At the Sixteenth NASTRAN Users' Colloquium (1988), Melvyn Marcus and associates of the David Taylor Research Center summarized a study comparing the results of the QUAD4 element with results of other NASTRAN shell elements for a cylindrical-shell modal analysis. Results of this study, in which both the lumped-and consistent-mass matrix formulations were used, implied that the consistent-mass matrix yielded poor results. In an effort to further evaluate the consistent-mass matrix, a study was performed using both a cylindrical-shell geometry and a flat-plate geometry. Modal parameters were extracted for several modes for both geometries leading to some significant conclusions. First, there do not appear to be any fundamental errors associated with the consistent-mass matrix. However, its accuracy is quite different for the two different geometries studied. The consistent-mass matrix yields better results for the flat-plate geometry and the lumped-mass matrix seems to be the better choice for cylindrical-shell geometries.

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

Arlt, T.; Penzkofer H.; Zinth, W.

The energetics of the primary electron donor (the special pair P) in reaction centers from Rhodopseudomonas viridis were modified by site-directed mutagenesis of histidine L168 to phenylalanine. This leads to the loss of a hydrogen bond between the amino acid side chain and the ring I acetyl carbonyl oxygen of the bacteriochlorophyll molecule BChl{sub LP}. As a result of the mutation, a 35 nm blue shift of the Q{sub y} band of the special pair and a decrease of 80 mV in the P/P{sup +} oxidation-reduction potential occur. Femtosecond spectroscopy revealed an acceleration of the first electron transfer step frommore » 3.5 ps in wild type to 1.1 ps in mutant. Analysis of change in the bacteriochlorophyll monomer (B) band of the mutant reaction centers showed strong bleaching. This is direct evidence that bacteriochlorophyll b is real intermediate in electron transfer. The changes in redox potential and time constants allow one to estimate the energetics in the wild-type and mutated reaction centers according to the Marcus electron transfer theory. 32 refs., 6 figs.« less

Non-conjugated, phenyl assisted coupling in through bond electron transfer in a perylenemonoimide-triphenylamine system.

PubMed

Bell, Toby D M; Stefan, Alina; Lemaur, Vincent; Bernhardt, Stefan; Müllen, Klaus; Cornil, Jérôme; Beljonne, David; Hofkens, Johan; Van der Auweraer, Mark; De Schryver, Frans C

2007-04-01

Two donor-bridge-acceptor compounds containing triphenylamine (TPA) donors and perylenemonoimide (PMI) acceptors have been studied by spectroscopic techniques and quantum chemical computation. Both systems have been observed to emit prompt and delayed fluorescence under certain conditions indicating that forward and reverse electron transfer (ET) processes can occur between the locally excited and the charge separated states. The experimental and computational results show that the TPA and PMI chromophores are better coupled by almost 50% in the meta isomers which undergo ET more readily than the para isomers. Quantum chemical calculations indicate that this unexpected situation is the result of a phenyl group on the side of the bridge being advantageously positioned in the meta isomers. This leads to more extensive delocalisation of the TPA HOMO into the bridge enhancing the total through bond electronic coupling between the TPA and PMI chromophores. The calculations also indicate a strong angle dependence of the total coupling in both isomers. The experimental results are discussed in the context of the high temperature limit of Marcus's theory of non-adiabatic ET.

The gatemon: a transmon with a voltage-variable superconductor-semiconductor junction

NASA Astrophysics Data System (ADS)

Petersson, Karl

We have developed a superconducting transmon qubit with a semiconductor-based Josephson junction element. The junction is made from an InAs nanowire with in situ molecular beam epitaxy-grown superconducting Al contacts. This gate-controlled transmon, or gatemon, allows simple tuning of the qubit transition frequency using a gate voltage to vary the density of carriers in the semiconductor region. In the first generations of devices we have measured coherence times up to ~10 μs. These coherence times, combined with stable qubit operation, permit single qubit rotations with fidelities of ~99.5 % for all gates including voltage-controlled Z rotations. Towards multi-qubit operation we have also implemented a two qubit voltage-controlled cPhase gate. In contrast to flux-tuned transmons, voltage-tunable gatemons may simplify the task of scaling to multi-qubit circuits and enable new means of control for many qubit architectures. In collaboration with T.W. Larsen, L. Casparis, M.S. Olsen, F. Kuemmeth, T.S. Jespersen, P. Krogstrup, J. Nygard and C.M. Marcus. Research was supported by Microsoft Project Q, Danish National Research Foundation and a Marie Curie Fellowship.

Functional single-wall carbon nanotube nanohybrids--associating SWNTs with water-soluble enzyme model systems.

PubMed

Guldi, Dirk M; Rahman, G M Aminur; Jux, Norbert; Balbinot, Domenico; Hartnagel, Uwe; Tagmatarchis, Nikos; Prato, Maurizio

2005-07-13

We succeeded in integrating single-wall carbon nanotubes (SWNTs), several water-soluble pyrene derivatives (pyrene(-)), which bear negatively charged ionic headgroups, and a series of water-soluble metalloporphyrins (MP(8+)) into functional nanohybrids through a combination of associative van der Waals and electrostatic interactions. The resulting SWNT/pyrene(-) and SWNT/pyrene(-)/MP(8+) were characterized by spectroscopic and microscopic means and were found to form stable nanohybrid structures in aqueous media. A crucial feature of our SWNT/pyrene(-) and SWNT/pyrene(-)/MP(8)(+) is that an efficient exfoliation of the initial bundles brings about isolated nanohybrid structures. When the nanohybrid systems are photoexcited with visible light, a rapid intrahybrid charge separation causes the reduction of the electron-accepting SWNT and, simultaneously, the oxidation of the electron-donating MP(8)(+). Transient absorption measurements confirm that the radical ion pairs are long-lived, with lifetimes in the microsecond range. Particularly beneficial are charge recombination dynamics that are located deep in the Marcus-inverted region. We include, for the first time, work devoted to exploring and testing FeP(8)(+) and CoP(8)(+) in donor-acceptor nanohybrids.

Molecular aspects of the Eu3+/Eu2+ redox reaction at the interface between a molten salt and a metallic electrode

NASA Astrophysics Data System (ADS)

Pounds, Michael A.; Salanne, Mathieu; Madden, Paul A.

2015-09-01

We perform molecular dynamics simulations of a system consisting of Eu3+ and Eu2+ species dissolved in a high-temperature KCl electrolyte between two metallic electrodes. The interaction potential includes ion polarisation effects, and a constant electric potential is maintained within the electrodes by allowing the atomic charges to fluctuate in response to the environment. This setup allows us to study the electrochemical Eu3+/Eu2+ reaction in the framework of Marcus theory. Numerous studies have pointed to the highly structured nature of ionic liquids and molten salts close to solid surfaces which is not accounted for in the conventional mean-field description of this interface that underpins the theories of electrochemical reaction rates. Here we examine the influence on the kinetics of the charge-transfer event of the electrical potential across the electrode-electrolyte interface and on the effect of the presence of charged surface on the coordination structure and energetics of the ions in the region important for the charge-transfer event.

Mechanistic information from the first volume profile analysis for a reversible intermolecular electron-transfer reaction involving pentaammine(isonicotinamide)ruthenium and cytochrome c

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

Baensch, B.; Meier, M.; Martinez, P.

1994-10-12

The reversible intermolecular electron-transfer reaction between pentaammine(isonicotinamide)ruthenium(II/III) and horse-heart cytochrome c iron(III/II) was subjected to a detailed kinetic and thermodynamic study as a function of temperature and pressure. Theoretical calculations based on the Marcus-Hush theory were employed to predict all rate and equilibrium constants as well as activation parameters. There is an excellent agreement between the kinetically and thermodynamically determined equilibrium constants and associated pressure parameters. These data are used to construct a volume profile for the overall process, from which it follows that the transition state lies halfway between the reactant and product states on a volume basis. Themore » reorganization in the transition state has reached a similar degree in both directions of the electron-transfer process and corresponds to a {lambda}{sup {double_dagger}} value of 0.44 for this reversible reaction. This is the first complete volume profile analysis for a reversible intermolecular electron-transfer reaction.« less

Effect of the phenoxy groups on PDIB and its derivatives

NASA Astrophysics Data System (ADS)

Song, Peng; Guan, Baijie; Zhou, Qiao; Zhao, Meiyu; Huang, Jindou; Ma, Fengcai

2016-10-01

The anisotropic hole and electron mobilities in N,N‧-3,4,9,10-perylenediimide-1,7-phenoxy (PDIB-2OPh) and N,Nʹ-3,4,9,10-perylenediimide (PDIB) were theoretically predicted using the Marcus-Hush theory. The substituent effect of phenoxy on their mobility rates, absorption spectra, electron affinities, and ionization potentials was explored. By comparing the simulated hole mobility in PDIB and PDIB-2OPh, it is found that the phenoxy rings act as spacers between adjacent stacking columns in the phenoxy-substituted derivatives. The increasement of the number of benzene oxygen groups leads to the absorption spectra red-shift of these molecular systems. This coincides with their change tendency of the adiabatic ionization potentials, vertical ionization potentials. However, the calculated adiabatic electron affinities and vertical electron affinities of N,N‧-butyl-3,4,9,10-perylenediimide-1,6,7,12-phenoxy (PDIB-4OPh) are larger than those of PDIB;OPh. The steric effect in PDIB-4OPh is expected to cause space reversal and thus to changes in the properties of the molecule.

Theoretical study of anisotropic mobility in ladder-type molecule organic semiconductors

NASA Astrophysics Data System (ADS)

Wei, Hui-Ling; Liu, Yu-Fang

2014-09-01

The properties of two ladder-type semiconductors {M1: 2,2'-(2,7-dihexy1-4,9-dihydro- s-indaceno[1,2- b:5,6- b']dithiophene-4,9-diylidene) dimalononitrile and M2: 2,7-dihexy1-4,9-dihydro- s-indaceno[1,2- b:5,6- b']dithiophene-4,9-dione} as the n-type and ambipolar organic materials are systematically investigated using the first-principle density functional theory combined with the Marcus-Hush electron transfer theory. It is found that the substitution of M1 induces large changes in its electron-transfer mobility of 1.370 cm2 V-1 s-1. M2 has both large electron- and hole-transfer mobility of 0.420 and 0.288 cm2 V-1 s-1, respectively, which indicates that M2 is potentially a high efficient ambipolar organic semiconducting material. Both the M1 and M2 crystals show remarkable anisotropic behavior. A proper design of the n-type and ambipolar organic electronic materials, which may have high mobility performance, is suggested based on the investigated two molecules.

Mulliken Hush elucidation of the encounter (precursor) complex in intermolecular electron transfer via self-exchange of tetracyanoethylene anion-radical

NASA Astrophysics Data System (ADS)

Rosokha, S. V.; Newton, M. D.; Head-Gordon, M.; Kochi, J. K.

2006-05-01

The paramagnetic [1:1] encounter complex (TCNE)2-rad is established as the important precursor in the kinetics and mechanism of electron-transfer for the self-exchange between tetracyanoethylene acceptor ( TCNE) and its radical-anion as the donor. Spectroscopic observation of the dimeric complex (TCNE)2-rad by its intervalence absorption band at the solvent-dependent wavelength of λIV ˜ 1500 nm facilitates the application of Mulliken-Hush theory which reveals the significant electronic interaction extant between the pair of cofacial TCNE moieties with the sizable coupling of HDA = 1000 cm -1. The transient existence of such an encounter complex provides the critical link in the electron-transfer kinetics by lowering the classical Marcus reorganization barrier by the amount of HDA in this strongly adiabatic system. Ab initio quantum-mechanical methods as applied to independent theoretical computations of both the reorganization energy ( λ) and the electronic coupling element ( HDA) confirm the essential correctness of the Mulliken-Hush formalism for fast electron transfer via strongly coupled donor/acceptor encounter complexes.

Putting together the clues of the everlasting neuro-cardiac liaison.

PubMed

Franzoso, Mauro; Zaglia, Tania; Mongillo, Marco

2016-07-01

Starting from the late embryonic development, the sympathetic nervous system extensively innervates the heart and modulates its activity during the entire lifespan. The distribution of myocardial sympathetic processes is finely regulated by the secretion of limiting amounts of pro-survival neurotrophic factors by cardiac cells. Norepinephrine release by the neurons rapidly modulates myocardial electrophysiology, and increases the rate and force of cardiomyocyte contractions. Sympathetic processes establish direct interaction with cardiomyocytes, characterized by the presence of neurotransmitter vesicles and reduced cell-cell distance. Whether such contacts have a functional role in both neurotrophin- and catecholamine-dependent communication between the two cell types, is poorly understood. In this review we will address the effects of the sympathetic neuron activity on the myocardium and the hypothesis that the direct neuro-cardiac contact might have a key role both in norepinephrine and neurotrophin mediated signaling. This article is part of a Special Issue entitled: Cardiomyocyte Biology: Integration of Developmental and Environmental Cues in the Heart edited by Marcus Schaub and Hughes Abriel. Copyright © 2016 Elsevier B.V. All rights reserved.

Between Marxism and psychoanalysis: antifascism and antihomosexuality in the Frankfurt School.

PubMed

Halle, R

1995-01-01

In their efforts to utilize individualist psychoanalysis as a tool for understanding mass behavior, the social theorists associated with the Frankfurt School increasingly came to rely on a static, essentializing construction of sexuality which ultimately led to an equation of fascism and homosexuality. Heretofore unexamined in studies of the Frankfurt School, this equation will here serve as the starting point for a fundamental critique of the concept of sexuality developed by this influential circle of Marxist thinkers. While directed at the concept of sexuality, such a critique more importantly opens up the underlying understanding of the social and psychological realms advanced by Critical Theory. Attending to the equation of homosexuality and fascism as the central point of concern, this essay will first trace the introduction of psychoanalysis into Critical Theory through Erich Fromm and then investigate the extent of Fromm's influence on the concept of sexuality propounded by his colleagues, especially Max Horkheimer and Theodor W. Adorno. Finally, it will take up a frequently overlooked essay by Herbert Marcuse which promoted a vision of sexuality radically different from that of his associates.

Electronic and structural aspects of p450-mediated drug metabolism.

PubMed

Lewis, David F V; Ito, Yuko; Lake, Brian G

2009-04-01

From a consideration of first principles for enzymes kinetics, we have employed theoretical methods which enable one to analyse the kinetics of cytochrome P450-mediated reactions which have been based on the known physicochemical principles underlying the majority of chemical or enzymatic reactions. A comparison is made between the correlation equations produced from the QSAR analysis of experimental P450 reaction rate data and those obtained from first principles, where there appears to be a generally satisfactory concordance between the two procedures. In this respect, we have developed expressions based on standard reaction kinetics theory which incorporate the Eyring and Marcus relationships. The analysis of P450-catalyzed reaction rates is elaborated to encompass a treatment of metabolic clearance, and satisfactory correlations are obtained with literature values for both intrinsic clearance and whole body clearance in terms of compound lipophilicity derived from log P data, where P is the octanol/water partition coefficient. The importance of ionization potential as a factor in the overall catalytic turnover of P450-mediated reactions is noted, especially in combination with the lipophilicity parameter, log P.

Self-exchange reaction of [Ni(mnt)2](1-,2-) in nonaqueous solutions.

PubMed

Kowert, Bruce A; Fehr, Michael J; Sheaff, Pamela J

2008-07-07

The rate constant, k, for the homogeneous electron transfer (self-exchange) reaction between the diamagnetic bis(maleonitriledithiolato)nickel dianion, [Ni(mnt) 2] (2-), and the paramagnetic monoanion, [Ni(mnt) 2] (1-), has been determined in acetone and nitromethane (CH 3NO 2) using (13)C NMR line widths at 22 degrees C (mnt = 1,2-S 2C 2(CN) 2). The values of k (2.91 x 10 (6) M (-1) s (-1) in acetone, 5.78 x 10 (6) M (-1) s (-1) in CH 3NO 2) are faster than those for the electron transfer reactions of other Ni(III,II) couples; the structures of [Ni(mnt) 2] (1-) and [Ni(mnt) 2] (2-) allow for a favorable overlap that lowers the free energy of activation. The values of k are consistent with the predictions of Marcus theory. In addition to k, the spin-lattice relaxation time, T 1e, of [Ni(mnt) 2] (1-) is obtained from the NMR line width analysis; the values are consistent with those predicted by spin relaxation theory.

Mechanistic and kinetic studies on the OH-initiated atmospheric oxidation of fluoranthene.

PubMed

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Hu, Jingtian; Chen, Jianmin; Wang, Wenxing

2014-08-15

The atmospheric oxidation of polycyclic aromatic hydrocarbons (PAHs) can generate toxic derivatives which contribute to the carcinogenic potential of particulate organic matter. In this work, the mechanism of the OH-initiated atmospheric oxidation of fluoranthene (Flu) was investigated by using high-accuracy molecular orbital calculations. All of the possible oxidation pathways were discussed, and the theoretical results were compared with the available experimental observation. The rate constants of the crucial elementary reactions were evaluated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The main oxidation products are a range of ring-retaining and ring-opening chemicals containing fluoranthols, fluoranthones, fluoranthenequinones, nitro-fluoranthenes, dialdehydes and epoxides. The overall rate constant of the OH addition reaction is 1.72×10(-11) cm(3) molecule(-1) s(-1) at 298 K and 1 atm. The atmospheric lifetime of Flu determined by OH radicals is about 0.69 days. This work provides a comprehensive investigation of the OH-initiated oxidation of Flu and should help to clarify its atmospheric conversion. Copyright © 2014 Elsevier B.V. All rights reserved.

Intrinsic non-radiative voltage losses in fullerene-based organic solar cells

NASA Astrophysics Data System (ADS)

Benduhn, Johannes; Tvingstedt, Kristofer; Piersimoni, Fortunato; Ullbrich, Sascha; Fan, Yeli; Tropiano, Manuel; McGarry, Kathryn A.; Zeika, Olaf; Riede, Moritz K.; Douglas, Christopher J.; Barlow, Stephen; Marder, Seth R.; Neher, Dieter; Spoltore, Donato; Vandewal, Koen

2017-06-01

Organic solar cells demonstrate external quantum efficiencies and fill factors approaching those of conventional photovoltaic technologies. However, as compared with the optical gap of the absorber materials, their open-circuit voltage is much lower, largely due to the presence of significant non-radiative recombination. Here, we study a large data set of published and new material combinations and find that non-radiative voltage losses decrease with increasing charge-transfer-state energies. This observation is explained by considering non-radiative charge-transfer-state decay as electron transfer in the Marcus inverted regime, being facilitated by a common skeletal molecular vibrational mode. Our results suggest an intrinsic link between non-radiative voltage losses and electron-vibration coupling, indicating that these losses are unavoidable. Accordingly, the theoretical upper limit for the power conversion efficiency of single-junction organic solar cells would be reduced to about 25.5% and the optimal optical gap increases to 1.45-1.65 eV, that is, 0.2-0.3 eV higher than for technologies with minimized non-radiative voltage losses.

From computational discovery to experimental characterization of a high hole mobility organic crystal

PubMed Central

Sokolov, Anatoliy N.; Atahan-Evrenk, Sule; Mondal, Rajib; Akkerman, Hylke B.; Sánchez-Carrera, Roel S.; Granados-Focil, Sergio; Schrier, Joshua; Mannsfeld, Stefan C.B.; Zoombelt, Arjan P.; Bao, Zhenan; Aspuru-Guzik, Alán

2011-01-01

For organic semiconductors to find ubiquitous electronics applications, the development of new materials with high mobility and air stability is critical. Despite the versatility of carbon, exploratory chemical synthesis in the vast chemical space can be hindered by synthetic and characterization difficulties. Here we show that in silico screening of novel derivatives of the dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene semiconductor with high hole mobility and air stability can lead to the discovery of a new high-performance semiconductor. On the basis of estimates from the Marcus theory of charge transfer rates, we identified a novel compound expected to demonstrate a theoretic twofold improvement in mobility over the parent molecule. Synthetic and electrical characterization of the compound is reported with single-crystal field-effect transistors, showing a remarkable saturation and linear mobility of 12.3 and 16 cm2 V−1 s−1, respectively. This is one of the very few organic semiconductors with mobility greater than 10 cm2 V−1 s−1 reported to date. PMID:21847111

Noncontact bimolecular photoionization followed by radical-ions separation and their geminate recombination assisted by coherent HFI induced spin-conversion.

PubMed

Dodin, Dmitry V; Ivanov, Anatoly I; Burshtein, Anatoly I

2008-02-07

The Hamiltonian description of the spin-conversion induced by a hyperfine interaction (HFI) in photogenerated radical-ion pairs is substituted for the rate (incoherent) description of the same conversion provided by the widely used earlier elementary spin model. The quantum yields of the free ions as well as the singlet and triplet products of geminate recombination are calculated using distant dependent ionization and recombination rates, instead of their contact analogs. Invoking the simplest models of these rates, we demonstrate with the example of a spin-less system that the diffusional acceleration of radical-ion pair recombination at lower viscosity gives way to its diffusional deceleration (Angulo effect), accomplished with a kinetic plateau inherent with the primitive exponential model. Qualitatively the same behavior is found in real systems, assuming both ionization and recombination is carried out by the Marcus electron-transfer rates. Neglecting the Coulomb interaction between solvated ions, the efficiencies of radical-ion pair recombination to the singlet and triplet products are well fitted to the available experimental data. The magnetic field dependence of these yields is specified.

HiSeasNet: Oceanographic Ships Join the Grid

NASA Astrophysics Data System (ADS)

Berger, Jonathan; Orcutt, John; Foley, Steven; Bohlen, Steven

2006-05-01

HiSeasNet, the communications network providing full-period Internet access for the U.S. academic ocean research fleet, is an enabling technology that is changing the way oceanography is done in the 21st century. With the installation in March 2006 of a system on the research vessel (R/V) Seward Johnson and the planned installation on the R/V Marcus Langseth later this year, all but two of the Universities National Oceanographic Laboratories System (UNOLS) fleet of large/global and intermediate/ocean vessels will be equipped with HiSeasNet capability. HiSeasNet is a full-service Internet Protocol (IP) satellite network utilizing Cisco technology. In addition to the familiar IP services-such as e-mail, telnet, ssh, rlogin, Web traffic, and ftp-HiSeasNet can move real-time audio and video traffic across the satellite links. Phone systems onboard research ships can be connected to their home institutions' phone exchanges. Video teleconferencing with the current 96 kilobits per second circuits supports compressed video frame rates at about 10 frames per second, allowing for effective conversations and demonstrations with ship-to-shore video.

Characterization of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][Tf2N])∕TX-100∕cyclohexane ternary microemulsion: investigation of photoinduced electron transfer in this RTIL containing microemulsion.

PubMed

Sarkar, Souravi; Pramanik, Rajib; Ghatak, Chiranjib; Rao, Vishal Govind; Sarkar, Nilmoni

2011-02-21

In this study we have characterized a ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethyl- sulfonyl)imide containing ternary nonaqueous microemulsion ([Emim][Tf(2)N]∕∕TX-100∕cyclo- hexane). The phase behavior and dynamic light scattering study show that the [Emim][Tf(2)N]∕TX-100∕cyclohexane three component system can form microemulsion with [Emim][Tf(2)N] as polar core at suitable condition. We have investigated photoinduced electron transfer (PET) using dimethyl aniline as electron donor and several Coumarin dyes as electron acceptor molecules at two different R values (R = [ionic liquid]∕[surfactant]) to observe how the dynamics of the PET rate is affected in this type of confined microenvironment compared to that of the PET dynamics in neat ionic liquid and other pure solvent media. The plot of observed k(q) values with the free energy change (ΔG(0)) for electron transfer reaction shows an apparent inversion in the observed rate as predicted by the Marcus theory.

Bottom-up view of water network-mediated CO2 reduction using cryogenic cluster ion spectroscopy and direct dynamics simulations.

PubMed

Breen, Kristin J; DeBlase, Andrew F; Guasco, Timothy L; Voora, Vamsee K; Jordan, Kenneth D; Nagata, Takashi; Johnson, Mark A

2012-01-26

The transition states of a chemical reaction in solution are generally accessed through exchange of thermal energy between the solvent and the reactants. As such, an ensemble of reacting systems approaches the transition state configuration of reactant and surrounding solvent in an incoherent manner that does not lend itself to direct experimental observation. Here we describe how gas-phase cluster chemistry can provide a detailed picture of the microscopic mechanics at play when a network of six water molecules mediates the trapping of a highly reactive "hydrated electron" onto a neutral CO(2) molecule to form a radical anion. The exothermic reaction is triggered from a metastable intermediate by selective excitation of either the reactant CO(2) or the water network, which is evidenced by the evaporative decomposition of the product cluster. Ab initio molecular dynamics simulations of energized CO(2)·(H(2)O)(6)(-) clusters are used to elucidate the nature of the network deformations that mediate intracluster electron capture, thus revealing the detailed solvent fluctuations implicit in the Marcus theory for electron-transfer kinetics in solution.

Values for gender roles and relations among high school and non-high school adolescents in a Maya community in Chiapas, Mexico.

PubMed

Manago, Adriana M

2015-02-01

In the current study, I describe values for gender roles and cross-sex relations among adolescents growing up in a southern Mexican Maya community in which high school was introduced in 1999. A total of 80 adolescent girls and boys, half of whom were attending the new high school, provided their opinions on two ethnographically derived vignettes that depicted changes in gender roles and relations occurring in their community. Systematic coding revealed that adolescents not enrolled in high school tended to prioritise ascribed and complementary gender roles and emphasise the importance of family mediation in cross-sex relations. Adolescents who were enrolled in high school tended to prioritise equivalent and chosen gender roles, and emphasised personal responsibility and personal fulfillment in cross-sex relations. Perceptions of risks and opportunities differed by gender: girls favourably evaluated the expansion of adult female role options, but saw risks in personal negotiations of cross-sex relations; boys emphasised the loss of the female homemaker role, but favourably evaluated new opportunities for intimacy in cross-sex relations. © 2014 International Union of Psychological Science.

Enrichment of Cross-Linked Peptides Using Charge-Based Fractional Diagonal Chromatography (ChaFRADIC).

PubMed

Tinnefeld, Verena; Venne, A Saskia; Sickmann, Albert; Zahedi, René P

2017-02-03

Chemical cross-linking of proteins is an emerging field with huge potential for the structural investigation of proteins and protein complexes. Owing to the often relatively low yield of cross-linking products, their identification in complex samples benefits from enrichment procedures prior to mass spectrometry analysis. So far, this is mainly accomplished by using biotin moieties in specific cross-linkers or by applying strong cation exchange chromatography (SCX) for a relatively crude enrichment. We present a novel workflow to enrich cross-linked peptides by utilizing charge-based fractional diagonal chromatography (ChaFRADIC). On the basis of two-dimensional diagonal SCX separation, we could increase the number of identified cross-linked peptides for samples of different complexity: pure cross-linked BSA, cross-linked BSA spiked into a simple protein mixture, and cross-linked BSA spiked into a HeLa lysate. We also compared XL-ChaFRADIC with size exclusion chromatography-based enrichment of cross-linked peptides. The XL-ChaFRADIC approach is straightforward, reproducible, and independent of the cross-linking chemistry and cross-linker properties.

Co-sensitization and cross-reactivity between related and unrelated food allergens in dogs - a serological study.

PubMed

Bexley, Jennifer; Nuttall, Timothy J; Hammerberg, Bruce; Halliwell, Richard E

2017-02-01

Knowledge of cross-reactivity between foods is useful so that potentially cross-reactive allergens can be avoided in diet trials. To evaluate allergenic cross-reactivity in related foods. Sera from 469 dogs with suspected adverse food reactions. An IgE-based serological assay using 19 food allergens was performed in 469 dogs. Pairwise comparisons were used to calculate the odds ratios (ORs) for each food pair, with significance at P < 0.0002 by Holm-Bonferroni correction, both in all 469 dogs and in the 261 of 469 dogs with at least one positive reaction. One-way ANOVA with Tukey's post hoc tests (significance at P < 0.05) were used to test for differences between mean logE ORs in different food groups. Inhibition enzyme-linked immunosorbent assays (ELISAs) were performed to assess allergenic cross-reactivity between beef, lamb and cow's milk. Significant associations were observed between both related and unrelated food pairs. Associations were, however, more frequent and stronger among related than unrelated foods. In all 469 dogs, 38 of 43 related food pairs were significantly associated [mean (SD) logE OR 3.4 (0.9)] compared with 79 of 128 unrelated pairs [2.7 (1.0)], P < 0.0002. In positive dogs, 32 of 43 related pairs were significantly associated [2.7 [1.0)] compared with 49 of 128 unrelated pairs [1.8 (1.0)], P < 0.0002. Inhibition ELISAs confirmed the presence of cross-reactive IgE-binding epitopes in beef, lamb and cow's milk. The results suggest that related and potentially cross-reactive foods should be avoided in elimination diets. © 2016 ESVD and ACVD.

Relationship between paraspinal muscle cross-sectional area and relative proprioceptive weighting ratio of older persons with lumbar spondylosis.

PubMed

Ito, Tadashi; Sakai, Yoshihito; Nakamura, Eishi; Yamazaki, Kazunori; Yamada, Ayaka; Sato, Noritaka; Morita, Yoshifumi

2015-07-01

[Purpose] The purpose of this study was to examine the relationship between the paraspinal muscle cross-sectional area and the relative proprioceptive weighting ratio during local vibratory stimulation of older persons with lumbar spondylosis in an upright position. [Subjects] In all, 74 older persons hospitalized for lumbar spondylosis were included. [Methods] We measured the relative proprioceptive weighting ratio of postural sway using a Wii board while vibratory stimulations of 30, 60, or 240 Hz were applied to the subjects' paraspinal or gastrocnemius muscles. Back strength, abdominal muscle strength, and erector spinae muscle (L1/L2, L4/L5) and lumbar multifidus (L1/L2, L4/L5) cross-sectional areas were evaluated. [Results] The erector spinae muscle (L1/L2) cross-sectional area was associated with the relative proprioceptive weighting ratio during 60Hz stimulation. [Conclusion] These findings show that the relative proprioceptive weighting ratio compared to the erector spinae muscle (L1/L2) cross-sectional area under 60Hz proprioceptive stimulation might be a good indicator of trunk proprioceptive sensitivity.

Using a modified Marcus model to analyze the Brønsted correlation of gas-phase reactions of the deprotonation of para-substituted toluenes by CH2Cl-, H(O)C-, CH3O-, H(F)N-, NH2C≡C-, and CH3C≡C- anions

NASA Astrophysics Data System (ADS)

Romanskii, I. A.

2017-10-01

Ab initio calculations of the energy parameters for a series of gas-phase reactions of the deprotonation of para-substituted toluenes (OH, CH3, H, Cl, NC, CN, and NO2 substituents) by CH2Cl-, H(O)C-, CH3O-, H(F)N-, NH2C≡C-, and CH3C≡C- anions (the conjugated acids are chloromethane (CH3Cl), formaldehyde (H2CO), methanol (CH3OH), fluoroamine (NH2F), aminoacetylene (NH2C≡CH), and methylacetylene (CH3C≡CH), respectively) is performed using a technique of intramolecular reorganization proposed earlier. The equilibrium ( E a eq) and nonequilibrium ( E a neq ) contributions to energy of activation E a are found for distance Q(C…B) = 3.0 Å (where C and B are the central atoms of the acid and base). At this value of Q, the tunneling mechanism of proton transfer predominates. The results from calculations, together with similar data obtained earlier for reactions of the deprotonation of toluenes by CH2CN- anions, are considered from the viewpoint of the harmonic Marcus model. It is found that in the graph Δ E 0 - E a neq (where Δ E 0 is the internal energy of the reaction (for a collision complex)), the points for five reaction series with C-bases fall on the same quadratic (within the -11 to 12 kcal/mol range of Δ E 0) curve; the second curve, which includes points for the series with N- and O-bases (OCH3 - and H(F)N-) is shifted below the first curve by 1.5 kcal/mol. For most reaction series (except the one with the strongest bases, CH2Cl- and H(O)C-), the curvature and slope of graph Δ E 0 - E a neq are in agreement with the theory. The correlations of energies E a neq , E a eq, E a, and Δ E 0 with the energy of reaction Δ E 00 are satisfactorily described by quadratic equations as well. Differences between the structures of bases are reflected most by energy E a eq and the height of the proton tunneling barrier in the activated complex (AC) E b. For the series of reactions of toluene with a set of bases, graphs Δ E 00 - E a eq and Δ E 0 - E b show good linear correlation between the values (opposite in sign) of departures from straight lines drawn through the points for two C-bases of the same type (CH2Cl- and CH2CN-).

Near-infrared optical-absorption behavior in high-beta nonlinear optical chromophore-polymer guest-host materials. II. Dye spacer length effects in an amorphous polycarbonate copolymer host

NASA Astrophysics Data System (ADS)

Barto, Richard R.; Frank, Curtis W.; Bedworth, Peter V.; Ermer, Susan; Taylor, Rebecca E.

2005-06-01

In the second of a three-part series, spectral absorption behavior of nonlinear optical (NLO) dyes incorporated into amorphous polycarbonate, comprised of a homologous series of dialkyl spacer groups extending from the midsection of the dye molecule, is characterized by UV-Vis and photothermal deflection spectroscopy. The dyes are structural analogs of the NLO dye FTC [2-(3-cyano-4-{2-[5-(2-{4-[ethyl-(2-methoxyethyl)amino]phenyl}vinyl)-3,4-diethylthiophen-2-yl]vinyl}-5,5-dimethyl-5H-furan-2-ylidene)malononitrile]. Previous Monte Carlo calculations [B. H. Robinson and L. R. Dalton, J. Phys. Chem. A 104, 4785 (2000)] predict a strong dependence of the macroscopic nonlinear optical susceptibility on the chromophore waist: length aspect ratio in electric-field-poled films arising from interactions between chromophores. It is expected that these interactions will play a role in the absorption characteristics of unpoled films, as well. The spacer groups range in length from diethyl to dihexyl, and each dye is studied over a wide range of concentrations. Among the four dyes studied, a universal dependence of near-IR loss on inhomogeneous broadening of the dye main absorption peak is found. The inhomogeneous width and its concentration dependence are seen to vary with spacer length in a manner characteristic of the near-IR loss-concentration slope at transmission wavelengths of 1.06 and 1.3μm, but not at 1.55μm. The lower wavelength loss behavior is assigned to purely Gaussian broadening, and is described by classical mixing thermodynamic quantities based on the Marcus theory of inhomogeneous broadening [R. A. Marcus, J. Chem. Phys. 43, 1261 (1965)], modeled as a convolution of dye-dye dipole broadening and dye-polymer van der Waals broadening. The Gaussian dipole interactions follow a Loring dipole-broadening description [R. F. Loring, J. Phys. Chem. 94, 513 (1990)] dominated by the excited-state dipole moment, and have a correlated homogeneous broadening contribution. The long-wavelength loss behavior has a non-Gaussian dye-dye dipole contribution which follows Kador's broadening analysis [L. Kador, J. Chem. Phys. 95, 5574 (1991)], with a net broadening described by a convolution of this term with a Gaussian van der Waals interaction given by Obata et al. [M. Obata, S. Machida, and K. Horie, J. Polym. Sci. B 37, 2173 (1999)], with each term governed by the dye spacer length. A minimum in broadening and loss-concentration slope at a spacer length of four carbons per alkyl at all wavelengths has important consequences for practical waveguide devices, and is of higher aspect ratio than the spherical limit shown by Robinson and Dalton to minimize dipole interactions under a poling field.

Behavioral Engagement and Reading Achievement in Elementary-School-Age Children: A Longitudinal Cross-Lagged Analysis

ERIC Educational Resources Information Center

Guo, Ying; Sun, Shuyan; Breit-Smith, Allison; Morrison, Frederick J.; Connor, Carol McDonald

2015-01-01

Using data from the National Institute of Child Health and Human Development's Study of Early Child Care and Youth Development, this study examined the cross-lagged relations between behavioral engagement and reading achievement in elementary school and whether these cross-lagged relations differed between low-socioeconomic status (SES) and mid-…

"Sex differences in left-handedness: A meta-analysis of 144 studies": Correction to Papadatou-Pastou et al. (2008).

PubMed

2017-10-01

Reports an error in "Sex differences in left-handedness: A meta-analysis of 144 studies" by Marietta Papadatou-Pastou, Maryanne Martin, Marcus R. Munafò and Gregory V. Jones ( Psychological Bulletin , 2008[Sep], Vol 134[5], 677-699). In the article the statistical evidence is weaker than reported for the moderating effect of writing hand compared to all the other instruments (reported finding: Q (1) = 8.36, p = .02; corrected finding: Q (1) = 3.17, p = .075). While the statistical evidence is thus somewhat weaker on this particular point, the broad conclusions of the article remain unchanged. (The following abstract of the original article appeared in record 2008-11487-004.) Human handedness, a marker for language lateralization in the brain, continues to attract great research interest. A widely reported but not universal finding is a greater male tendency toward left-handedness. Here the authors present a meta-analysis of k = 144 studies, totaling N = 1,787,629 participants, the results of which demonstrate that the sex difference is both significant and robust. The overall best estimate for the male to female odds ratio was 1.23 (95% confidence interval = 1.19, 1.27). The widespread observation of this sex difference is consistent with it being related to innate characteristics of sexual differentiation, and its observed magnitude places an important constraint on current theories of handedness. In addition, the size of the sex difference was significantly moderated by the way in which handedness was assessed (by writing hand or by other means), the location of testing, and the year of publication of the study, implicating additional influences on its development. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Estimating the location of baleen whale calls using dual streamers to support mitigation procedures in seismic reflection surveys.

PubMed

Abadi, Shima H; Tolstoy, Maya; Wilcock, William S D

2017-01-01

In order to mitigate against possible impacts of seismic surveys on baleen whales it is important to know as much as possible about the presence of whales within the vicinity of seismic operations. This study expands on previous work that analyzes single seismic streamer data to locate nearby calling baleen whales with a grid search method that utilizes the propagation angles and relative arrival times of received signals along the streamer. Three dimensional seismic reflection surveys use multiple towed hydrophone arrays for imaging the structure beneath the seafloor, providing an opportunity to significantly improve the uncertainty associated with streamer-generated call locations. All seismic surveys utilizing airguns conduct visual marine mammal monitoring surveys concurrent with the experiment, with powering-down of seismic source if a marine mammal is observed within the exposure zone. This study utilizes data from power-down periods of a seismic experiment conducted with two 8-km long seismic hydrophone arrays by the R/V Marcus G. Langseth near Alaska in summer 2011. Simulated and experiment data demonstrate that a single streamer can be utilized to resolve left-right ambiguity because the streamer is rarely perfectly straight in a field setting, but dual streamers provides significantly improved locations. Both methods represent a dramatic improvement over the existing Passive Acoustic Monitoring (PAM) system for detecting low frequency baleen whale calls, with ~60 calls detected utilizing the seismic streamers, zero of which were detected using the current R/V Langseth PAM system. Furthermore, this method has the potential to be utilized not only for improving mitigation processes, but also for studying baleen whale behavior within the vicinity of seismic operations.

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

NASA Astrophysics Data System (ADS)

Mo, Yirong

2007-06-01

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

Charge transport in metal oxides: A theoretical study of hematite α-Fe2O3

NASA Astrophysics Data System (ADS)

Iordanova, N.; Dupuis, M.; Rosso, K. M.

2005-04-01

Transport of conduction electrons and holes through the lattice of α-Fe2O3 (hematite) is modeled as a valence alternation of iron cations using ab initio electronic structure calculations and electron transfer theory. Experimental studies have shown that the conductivity along the (001) basal plane is four orders of magnitude larger than the conductivity along the [001] direction. In the context of the small polaron model, a cluster approach was used to compute quantities controlling the mobility of localized electrons and holes, i.e., the reorganization energy and the electronic coupling matrix element that enter Marcus' theory. The calculation of the electronic coupling followed the generalized Mulliken-Hush approach using the complete active space self-consistent field method. Our findings demonstrate an approximately three orders of magnitude anisotropy in both electron and hole mobility between directions perpendicular and parallel to the c axis, in good accord with experimental data. The anisotropy arises from the slowness of both electron and hole mobilities across basal oxygen planes relative to that within iron bilayers between basal oxygen planes. Interestingly, for elementary reaction steps along either of the directions considered, there is only less than one order of magnitude difference in mobility between electrons and holes, in contrast to accepted classical arguments. Our findings indicate that the most important quantity underlying mobility differences is the electronic coupling, albeit the reorganization energy contributes as well. The large values computed for the electronic coupling suggest that charge transport reactions in hematite are adiabatic in nature. The electronic coupling is found to depend on both the superexchange interaction through the bridging oxygen atoms and the d-shell electron spin coupling within the Fe-Fe donor-acceptor pair, while the reorganization energy is essentially independent of the electron spin coupling.

Estimating the location of baleen whale calls using dual streamers to support mitigation procedures in seismic reflection surveys

PubMed Central

Abadi, Shima H.; Tolstoy, Maya; Wilcock, William S. D.

2017-01-01

In order to mitigate against possible impacts of seismic surveys on baleen whales it is important to know as much as possible about the presence of whales within the vicinity of seismic operations. This study expands on previous work that analyzes single seismic streamer data to locate nearby calling baleen whales with a grid search method that utilizes the propagation angles and relative arrival times of received signals along the streamer. Three dimensional seismic reflection surveys use multiple towed hydrophone arrays for imaging the structure beneath the seafloor, providing an opportunity to significantly improve the uncertainty associated with streamer-generated call locations. All seismic surveys utilizing airguns conduct visual marine mammal monitoring surveys concurrent with the experiment, with powering-down of seismic source if a marine mammal is observed within the exposure zone. This study utilizes data from power-down periods of a seismic experiment conducted with two 8-km long seismic hydrophone arrays by the R/V Marcus G. Langseth near Alaska in summer 2011. Simulated and experiment data demonstrate that a single streamer can be utilized to resolve left-right ambiguity because the streamer is rarely perfectly straight in a field setting, but dual streamers provides significantly improved locations. Both methods represent a dramatic improvement over the existing Passive Acoustic Monitoring (PAM) system for detecting low frequency baleen whale calls, with ~60 calls detected utilizing the seismic streamers, zero of which were detected using the current R/V Langseth PAM system. Furthermore, this method has the potential to be utilized not only for improving mitigation processes, but also for studying baleen whale behavior within the vicinity of seismic operations. PMID:28199400

Investigating Reasons for CPAP Adherence in Adolescents: A Qualitative Approach

PubMed Central

Prashad, Priya S.; Marcus, Carole L.; Maggs, Jill; Stettler, Nicolas; Cornaglia, Mary A.; Costa, Priscilla; Puzino, Kristina; Xanthopoulos, Melissa; Bradford, Ruth; Barg, Frances K.

2013-01-01

Study Objectives: Adolescents with obstructive sleep apnea syndrome (OSAS) represent an important but understudied subgroup of long-term continuous positive airway pressure (CPAP) users. The purpose of this qualitative study was to identify factors related to adherence from the perspective of adolescents and their caregivers. Methods: Individual open-ended, semi-structured interviews were conducted with adolescents (n = 21) and caregivers (n = 20). Objective adherence data from the adolescents' CPAP machines during the previous month was obtained. Adolescents with different adherence levels and their caregivers were asked their views on CPAP. Using a modified grounded theory approach, we identified themes and developed theories that explained the adolescents' adherence patterns. Results: Adolescent participants (n = 21) were aged 12-18 years, predominantly male (n = 15), African American (n = 16), users of CPAP for at least one month. Caregivers were mainly mothers (n = 17). Seven adolescents had high use (mean use 381 ± 80 min per night), 7 had low use (mean use 30 ± 24 min per night), and 7 had no use during the month prior to being interviewed. Degree of structure in the home, social reactions, mode of communication among family members, and perception of benefits were issues that played a role in CPAP adherence. Conclusions: Understanding the adolescent and family experience of using CPAP may be key to increasing adolescent CPAP adherence. As a result of our findings, we speculate that health education, peer support groups, and developmentally appropriate individualized support strategies may be important in promoting adherence. Future studies should examine these theories of CPAP adherence. Citation: Prashad PS; Marcus CL; Maggs J; Stettler N; Cornaglia MA; Costa P; Puzino K; Xanthopoulos M; Bradford R; Barg FK. Investigating reasons for CPAP adherence in adolescents: a qualitative approach. J Clin Sleep Med 2013;9(12):1303-1313. PMID:24340293

Cross-cultural understandings of festival food-related activities for older women in Chiang Mai, Thailand, Eastern Kentucky, USA and Auckland, New Zealand.

PubMed

Wright-St Clair, Valerie A; Pierce, Doris; Bunrayong, Wannipa; Rattakorn, Phuanjai; Vittayakorn, Soisuda; Shordike, Anne; Hocking, Clare

2013-06-01

This cross-country, cross-cultural study explored the meaning of older women's food-related activities for the annual festivals of Songkran (Thai New Year) in Chiang Mai, Thailand; and Christmas in Richmond, Kentucky, USA; and Auckland, New Zealand. A derived etic method was used. The community-dwelling participants were 33 Thai women, aged 60 and older, and 16 New Zealand and 23 eastern Kentucky women, aged 65 and older. This article focuses on the final cross-cultural analysis of the data. Emic, or within-country, findings are presented, followed by the derived etic, or cross-cultural, interpretations for two themes of meaning; older women's 'protecting what matters' and 'leading the way'. Applying derived etic methods helped reveal how, despite the highly different food-related practices, preparing and sharing celebratory foods at Songkran or Christmas held related meanings for older women in Thailand, Kentucky USA, and New Zealand.

Incarceration and Relative Poverty in Cross-National Perspective: The Moderating Roles of Female Employment and the Welfare State

PubMed Central

Gottlieb, Aaron

2017-01-01

A growing body of scholarship explores how incarceration contributes to inequality. The majority of this scholarship focuses on individual-level outcomes or aggregate outcomes within the United States. Despite substantial cross-national variation in incarceration rates, we know little about whether these differences contribute to cross-national variation in inequality outcomes. Using data from the period 1971–2010 from 15 advanced democracies, this study begins to fill this gap by exploring whether cross-national differences in incarceration rates help to explain cross-national differences in relative poverty rates. Although this research finds no average association, this null association obscures the important moderating role of country context. The association between incarceration and relative poverty is contingent upon a country’s female employment rate and welfare state generosity. PMID:29104322

Measurements of absolute absorption cross sections of ozone in the 185- to 254-nm wavelength region and the temperature dependence

NASA Technical Reports Server (NTRS)

Yoshino, K.; Esmond, J. R.; Freeman, D. E.; Parkinson, W. H.

1993-01-01

Laboratory measurements of the relative absorption cross sections of ozone at temperatures 195, 228, and 295 K have been made throughout the 185 to 254 nm wavelength region. The absolute absorption cross sections at the same temperatures have been measured at several discrete wavelengths in the 185 to 250 nm region. The absolute cross sections of ozone have been used to put the relative cross sections on a firm absolute basis throughout the 185 to 255 nm region. These recalibrated cross sections are slightly lower than those of Molina and Molina (1986), but the differences are within a few percent and would not be significant in atmospheric applications.

Cell protein cross-linking by erbstatin and related compounds | Center for Cancer Research

Cancer.gov

The scheme depicts a possible mechanism of cross-linking by erbstatin and related analogues. A mechanism of action is proposed which involves initial oxidation to reactive quinone intermediates that subsequently cross-link protein nucleophiles via multiple 1,4-Michael-type additions. Similar alkylation of protein by protein-tyrosine kinase inhibitors, such as herbimycin A, has

Extending trust to immigrants: Generalized trust, cross-group friendship and anti-immigrant sentiments in 21 European societies

PubMed Central

van der Linden, Meta; Hooghe, Marc; de Vroome, Thomas; Van Laar, Colette

2017-01-01

The aim of this study is twofold. First, we expand on the literature by testing whether generalized trust is negatively related to anti-immigrant sentiments in Europe. Second, we examine to what extent the relation between generalized trust and anti-immigrant sentiments is dependent upon cross-group friendships. We apply multilevel linear regression modeling to representative survey data enriched with levels of ethnic diversity covering 21 European countries. Results show that both generalized trust and cross-group friendship are negatively related to anti-immigrant sentiments. However, there is a negligible positive relation between generalized trust and cross-group friendship (r = .10), and we can clearly observe that they operate independently from one another. Hence, trusting actors are not more likely to form more cross-group friendships, and cross-group friendship do not lead to the development of more generalized trust. Instead, the findings show that generalized trust leads immigrants too to be included in the radius of trusted others and, as a consequence, the benign effects of generalized trust apply to them as well. We conclude that the strength of generalized trust is a form of generalization, beyond the confines of individual variations in intergroup experiences. PMID:28481925

Extending trust to immigrants: Generalized trust, cross-group friendship and anti-immigrant sentiments in 21 European societies.

PubMed

van der Linden, Meta; Hooghe, Marc; de Vroome, Thomas; Van Laar, Colette

2017-01-01

The aim of this study is twofold. First, we expand on the literature by testing whether generalized trust is negatively related to anti-immigrant sentiments in Europe. Second, we examine to what extent the relation between generalized trust and anti-immigrant sentiments is dependent upon cross-group friendships. We apply multilevel linear regression modeling to representative survey data enriched with levels of ethnic diversity covering 21 European countries. Results show that both generalized trust and cross-group friendship are negatively related to anti-immigrant sentiments. However, there is a negligible positive relation between generalized trust and cross-group friendship (r = .10), and we can clearly observe that they operate independently from one another. Hence, trusting actors are not more likely to form more cross-group friendships, and cross-group friendship do not lead to the development of more generalized trust. Instead, the findings show that generalized trust leads immigrants too to be included in the radius of trusted others and, as a consequence, the benign effects of generalized trust apply to them as well. We conclude that the strength of generalized trust is a form of generalization, beyond the confines of individual variations in intergroup experiences.

22 CFR 41.32 - Nonresident alien Mexican border crossing identification cards; combined border crossing...

Code of Federal Regulations, 2014 CFR

2014-04-01

... identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. 41.32 Section 41.32 Foreign Relations DEPARTMENT OF STATE VISAS VISAS: DOCUMENTATION OF NONIMMIGRANTS UNDER THE... crossing identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. (a...

22 CFR 41.32 - Nonresident alien Mexican border crossing identification cards; combined border crossing...

Code of Federal Regulations, 2010 CFR

2010-04-01

... identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. 41.32 Section 41.32 Foreign Relations DEPARTMENT OF STATE VISAS VISAS: DOCUMENTATION OF NONIMMIGRANTS UNDER THE... crossing identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. (a...

22 CFR 41.32 - Nonresident alien Mexican border crossing identification cards; combined border crossing...

Code of Federal Regulations, 2013 CFR

2013-04-01

... identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. 41.32 Section 41.32 Foreign Relations DEPARTMENT OF STATE VISAS VISAS: DOCUMENTATION OF NONIMMIGRANTS UNDER THE... crossing identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. (a...

22 CFR 41.32 - Nonresident alien Mexican border crossing identification cards; combined border crossing...

Code of Federal Regulations, 2011 CFR

2011-04-01

... identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. 41.32 Section 41.32 Foreign Relations DEPARTMENT OF STATE VISAS VISAS: DOCUMENTATION OF NONIMMIGRANTS UNDER THE... crossing identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. (a...

22 CFR 41.32 - Nonresident alien Mexican border crossing identification cards; combined border crossing...

Code of Federal Regulations, 2012 CFR

2012-04-01

... identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. 41.32 Section 41.32 Foreign Relations DEPARTMENT OF STATE VISAS VISAS: DOCUMENTATION OF NONIMMIGRANTS UNDER THE... crossing identification cards; combined border crossing identification cards and B-1/B-2 visitor visas. (a...

Crossed cerebellar diaschisis in patients with acute middle cerebral artery infarction: Occurrence and perfusion characteristics

PubMed Central

Sommer, Wieland H; Bollwein, Christine; Thierfelder, Kolja M; Baumann, Alena; Janssen, Hendrik; Ertl-Wagner, Birgit; Reiser, Maximilian F; Plate, Annika; Straube, Andreas

2015-01-01

We aimed to investigate the overall prevalence and possible factors influencing the occurrence of crossed cerebellar diaschisis after acute middle cerebral artery infarction using whole-brain CT perfusion. A total of 156 patients with unilateral hypoperfusion of the middle cerebral artery territory formed the study cohort; 352 patients without hypoperfusion served as controls. We performed blinded reading of different perfusion maps for the presence of crossed cerebellar diaschisis and determined the relative supratentorial and cerebellar perfusion reduction. Moreover, imaging patterns (location and volume of hypoperfusion) and clinical factors (age, sex, time from symptom onset) resulting in crossed cerebellar diaschisis were analysed. Crossed cerebellar diaschisis was detected in 35.3% of the patients with middle cerebral artery infarction. Crossed cerebellar diaschisis was significantly associated with hypoperfusion involving the left hemisphere, the frontal lobe and the thalamus. The degree of the relative supratentorial perfusion reduction was significantly more pronounced in crossed cerebellar diaschisis-positive patients but did not correlate with the relative cerebellar perfusion reduction. Our data suggest that (i) crossed cerebellar diaschisis is a common feature after middle cerebral artery infarction which can robustly be detected using whole-brain CT perfusion, (ii) its occurrence is influenced by location and degree of the supratentorial perfusion reduction rather than infarct volume (iii) other clinical factors (age, sex and time from symptom onset) did not affect the occurrence of crossed cerebellar diaschisis. PMID:26661242

Sex- and age-related differences in mid-thigh composition and muscle quality determined by computed tomography in middle-aged and elderly Japanese.

PubMed

Kasai, Takehiro; Ishiguro, Naoki; Matsui, Yasumoto; Harada, Atsushi; Takemura, Marie; Yuki, Atsumu; Kato, Yuki; Otsuka, Rei; Ando, Fujiko; Shimokata, Hiroshi

2015-06-01

Sex- and age-related differences in mid-thigh composition and muscle quality remain unclear. The present study aimed to clarify these differences using computed tomography in middle-aged and elderly Japanese. A total of 2310 participants (age 40-89 years), who were randomly selected from the local residents, underwent computed tomography examination of the right mid-thigh. Thigh circumference and cross-sectional areas of the thigh, muscle, quadriceps, non-quadriceps, fat, and bone were measured. Knee extension strength and muscle quality index (knee extension strength/quadriceps cross-sectional area) were also assessed. Sex- and age-related differences in these indices were analyzed. The thigh cross-sectional area in men and women decreased by 0.6% and 0.5%/year, respectively, because of a decrease in muscle cross-sectional area (men 75.2%, women 40.6%), fat cross-sectional area (men 24.4%, women 59.6%) and bone cross-sectional area (men 0.5%, women -0.2%). Muscle cross-sectional area in men and women decreased by 0.6% and 0.4%/year, respectively, because of a decrease in quadriceps cross-sectional area (men 65.6%, women 81.6%) and non-quadriceps cross-sectional area (men 34.4%, women 18.4%). Muscle quality in men and women decreased by 0.4% and 0.3%/year, respectively. Thigh cross-sectional area decreased with age mainly because of a decrease in muscle cross-sectional area in men and fat cross-sectional area in women. The rate of decrease in muscle cross-sectional area was 1.5-fold higher in men than in women. Muscle cross-sectional area decreased with age mainly because of a decrease in quadriceps cross-sectional area, especially in women. Decrease in muscle quality with age was similar in both sexes. © 2014 Japan Geriatrics Society.

Measurements of top quark pair relative differential cross-sections with ATLAS in pp collisions at $$\\sqrt{s} = 7\\ \\mbox{TeV}$$

DOE PAGES

Aad, G.; Abajyan, T.; Abbott, B.; ...

2013-01-15

Measurements are presented of differential cross sections for top quark pair production in pp collisions at √s = 7 TeV relative to the total inclusive top quark pair production cross-section. A data sample of 2.05 fb -1 recorded by the ATLAS detector at the Large Hadron Collider is used. Relative differential cross-sections are derived as a function of the invariant mass, the transverse momentum and the rapidity of the top quark pair system. Events are selected in the lepton (electron or muon) + jets channel. The backgroundsubtracted differential distributions are corrected for detector effects, normalized to the total inclusive topmore » quark pair production cross-section and compared to theoretical predictions. The measurement uncertainties range typically between 10 % and 20 % and are generally dominated by systematic effects. No significant deviations from the Standard Model expectations are observed.« less

49 CFR 236.787 - Protection, cross.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Protection, cross. 236.787 Section 236.787 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION..., or derail as the result of a cross in electrical circuits. Cross Reference: Ramp, see § 236.744. ...

49 CFR 236.384 - Cross protection.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 49 Transportation 4 2010-10-01 2010-10-01 false Cross protection. 236.384 Section 236.384 Transportation Other Regulations Relating to Transportation (Continued) FEDERAL RAILROAD ADMINISTRATION... and Tests § 236.384 Cross protection. Cross protection shall be tested at least once every six months...

Uncertainty quantification in (α,n) neutron source calculations for an oxide matrix

DOE PAGES

Pigni, M. T.; Croft, S.; Gauld, I. C.

2016-04-25

Here we present a methodology to propagate nuclear data covariance information in neutron source calculations from (α,n) reactions. The approach is applied to estimate the uncertainty in the neutron generation rates for uranium oxide fuel types due to uncertainties on 1) 17,18O( α,n) reaction cross sections and 2) uranium and oxygen stopping power cross sections. The procedure to generate reaction cross section covariance information is based on the Bayesian fitting method implemented in the R-matrix SAMMY code. The evaluation methodology uses the Reich-Moore approximation to fit the 17,18O(α,n) reaction cross-sections in order to derive a set of resonance parameters andmore » a related covariance matrix that is then used to calculate the energydependent cross section covariance matrix. The stopping power cross sections and related covariance information for uranium and oxygen were obtained by the fit of stopping power data in the -energy range of 1 keV up to 12 MeV. Cross section perturbation factors based on the covariance information relative to the evaluated 17,18O( α,n) reaction cross sections, as well as uranium and oxygen stopping power cross sections, were used to generate a varied set of nuclear data libraries used in SOURCES4C and ORIGEN for inventory and source term calculations. The set of randomly perturbed output (α,n) source responses, provide the mean values and standard deviations of the calculated responses reflecting the uncertainties in nuclear data used in the calculations. Lastly, the results and related uncertainties are compared with experiment thick target (α,n) yields for uranium oxide.« less

Electron scattering by highly polar molecules. III - CsCl

NASA Technical Reports Server (NTRS)

Vuskovic, L.; Srivastava, S. K.

1981-01-01

Utilizing a crossed electron-beam-molecular-beam scattering geometry, relative values of differential electron scattering cross sections for cesium chloride at 5 and 20 eV electron impact energies and at scattering angles between 10 and 120 deg have been measured. These relative cross sections have been normalized to the cross section at 15 deg scattering angle calculated by the hybrid S-matrix technique. In the angular range between 0 and 10 deg and between 120 and 180 deg extrapolations have been made to obtain integral and momentum transfer cross sections. An energy-loss spectrum is also presented which gives various spectral features lying between the 4 and 10 eV regions in CsCl.

Foreign-born physicians' perceptions of discrimination and stress in Finland: a cross-sectional questionnaire study.

PubMed

Heponiemi, Tarja; Hietapakka, Laura; Lehtoaro, Salla; Aalto, Anna-Mari

2018-06-07

Foreign-born physicians fill in the shortage of physicians in many developed countries. Labour market theory and previous studies suggest that foreign-born physicians may be a disadvantaged group with a higher likelihood of discrimination and less prestigious jobs. The present study examines foreign-born physicians' experiences of discrimination (coming from management, colleagues and patients separately) and patient-related stress and integration-related stress, and it examines how gender, age, employment sector, country of birth, years from getting a practicing license in Finland, language problems, cross-cultural training, cross-cultural empathy, team climate and skill discretion were associated with these factors. The present study was a cross-sectional questionnaire study among 371 foreign-born physicians in Finland, aged between 26 and 65 (65% women). Analyses of covariance and logistic regression analyses were conducted to examine the associations. A good team climate and high cross-cultural empathy were associated with lower likelihoods of discrimination from all sources, patient-related stress and integration-related stress. Skill discretion was associated with lower levels of integration-related stress and discrimination from management and colleagues. Language problems were associated with higher levels of integration-related stress. The biggest sources of discrimination were patients and their relatives. The present study showed the importance of a good team climate, cross-cultural empathy and patience, skill discretion and language skills in regard to the proper integration of foreign-born health care employees into the workplace. Good job resources, such as a good team climate and the possibility to use one's skills, may help foreign-born employees, for instance by giving them support when needed and offering flexibility. Health care organizations should invest in continuous language training for foreign-born employees and also offer support when there are language problems. Moreover, it seems that training increasing cross-cultural empathy and patience might be beneficial.

The role of cross-racial/ethnic friendships in social adjustment.

PubMed

Kawabata, Yoshito; Crick, Nicki R

2008-07-01

The purpose of this study was to examine the frequency and correlates of cross-racial/ethnic friendships. The sample consisted of 509 (188 African American, 135 European American, 106 Asian American, and 80 Latino) children in 4th grade from 39 classrooms in several public elementary schools. The authors hypothesized that (a) the frequency of cross-racial/ethnic friendships would be different across races/ethnicities and (b) these friendships would be uniquely associated with social adjustment (relational inclusion, leadership). Results showed that European American children displayed a higher frequency of cross-racial/ethnic friendships than African American children. Compared with the sample average, Latino children exhibited a lower frequency of these friendships. Further, findings revealed that children who formed cross-racial/ethnic friendships were more likely to be viewed as relationally inclusive and possessing leadership skills by teachers. Overall, the results showed that cross-racial/ethnic friendships were associated with positive developmental outcomes and that future studies that examine how these friendships are formed and maintained, and how these pathways are related to social adjustment, are warranted.

5 CFR 2422.8 - Intervention and cross-petitions.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 5 Administrative Personnel 3 2011-01-01 2011-01-01 false Intervention and cross-petitions. 2422.8... GENERAL COUNSEL OF THE FEDERAL LABOR RELATIONS AUTHORITY REPRESENTATION PROCEEDINGS § 2422.8 Intervention... with this subpart. (b) Intervention requests and cross-petitions. A request to intervene and a cross...

5 CFR 2422.8 - Intervention and cross-petitions.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 5 Administrative Personnel 3 2010-01-01 2010-01-01 false Intervention and cross-petitions. 2422.8... GENERAL COUNSEL OF THE FEDERAL LABOR RELATIONS AUTHORITY REPRESENTATION PROCEEDINGS § 2422.8 Intervention... with this subpart. (b) Intervention requests and cross-petitions. A request to intervene and a cross...

5 CFR 2422.8 - Intervention and cross-petitions.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 5 Administrative Personnel 3 2012-01-01 2012-01-01 false Intervention and cross-petitions. 2422.8... GENERAL COUNSEL OF THE FEDERAL LABOR RELATIONS AUTHORITY REPRESENTATION PROCEEDINGS § 2422.8 Intervention... with this subpart. (b) Intervention requests and cross-petitions. A request to intervene and a cross...

Rail-highway crossing hazard prediction : research results

DOT National Transportation Integrated Search

1979-12-01

This document presents techniques for constructing and evaluating railroad grade : crossing hazard indexes. Hazard indexes are objective formulas for comparing or ranking : crossings according to relative hazard or for calculating absolute hazard (co...

CrossFit Overview: Systematic Review and Meta-analysis.

PubMed

Claudino, João Gustavo; Gabbett, Tim J; Bourgeois, Frank; Souza, Helton de Sá; Miranda, Rafael Chagas; Mezêncio, Bruno; Soncin, Rafael; Cardoso Filho, Carlos Alberto; Bottaro, Martim; Hernandez, Arnaldo Jose; Amadio, Alberto Carlos; Serrão, Julio Cerca

2018-02-26

CrossFit is recognized as one of the fastest growing high-intensity functional training modes in the world. However, scientific data regarding the practice of CrossFit is sparse. Therefore, the objective of this study is to analyze the findings of scientific literature related to CrossFit via systematic review and meta-analysis. Systematic searches of the PubMed, Web of Science, Scopus, Bireme/MedLine, and SciELO online databases were conducted for articles reporting the effects of CrossFit training. The systematic review followed the PRISMA guidelines. The Oxford Levels of Evidence was used for all included articles, and only studies that investigated the effects of CrossFit as a training program were included in the meta-analysis. For the meta-analysis, effect sizes (ESs) with 95% confidence interval (CI) were calculated and heterogeneity was assessed using a random-effects model. Thirty-one articles were included in the systematic review and four were included in the meta-analysis. However, only two studies had a high level of evidence at low risk of bias. Scientific literature related to CrossFit has reported on body composition, psycho-physiological parameters, musculoskeletal injury risk, life and health aspects, and psycho-social behavior. In the meta-analysis, significant results were not found for any variables. The current scientific literature related to CrossFit has few studies with high level of evidence at low risk of bias. However, preliminary data has suggested that CrossFit practice is associated with higher levels of sense of community, satisfaction, and motivation.

Crossed cerebellar diaschisis in patients with acute middle cerebral artery infarction: Occurrence and perfusion characteristics.

PubMed

Sommer, Wieland H; Bollwein, Christine; Thierfelder, Kolja M; Baumann, Alena; Janssen, Hendrik; Ertl-Wagner, Birgit; Reiser, Maximilian F; Plate, Annika; Straube, Andreas; von Baumgarten, Louisa

2016-04-01

We aimed to investigate the overall prevalence and possible factors influencing the occurrence of crossed cerebellar diaschisis after acute middle cerebral artery infarction using whole-brain CT perfusion. A total of 156 patients with unilateral hypoperfusion of the middle cerebral artery territory formed the study cohort; 352 patients without hypoperfusion served as controls. We performed blinded reading of different perfusion maps for the presence of crossed cerebellar diaschisis and determined the relative supratentorial and cerebellar perfusion reduction. Moreover, imaging patterns (location and volume of hypoperfusion) and clinical factors (age, sex, time from symptom onset) resulting in crossed cerebellar diaschisis were analysed. Crossed cerebellar diaschisis was detected in 35.3% of the patients with middle cerebral artery infarction. Crossed cerebellar diaschisis was significantly associated with hypoperfusion involving the left hemisphere, the frontal lobe and the thalamus. The degree of the relative supratentorial perfusion reduction was significantly more pronounced in crossed cerebellar diaschisis-positive patients but did not correlate with the relative cerebellar perfusion reduction. Our data suggest that (i) crossed cerebellar diaschisis is a common feature after middle cerebral artery infarction which can robustly be detected using whole-brain CT perfusion, (ii) its occurrence is influenced by location and degree of the supratentorial perfusion reduction rather than infarct volume (iii) other clinical factors (age, sex and time from symptom onset) did not affect the occurrence of crossed cerebellar diaschisis. © The Author(s) 2015.

Railroad-highway grade crossing handbook

DOT National Transportation Integrated Search

2007-08-01

The purpose of this handbook is to provide a single reference document on prevalent and best practices as well as adopted standards relative to highway-rail grade crossings. The handbook provides general information on highway-rail crossings; charact...

Women's Participation in Higher Education: Cross-National Trends, Antecedents, and Consequences.

ERIC Educational Resources Information Center

Ramirez, Francisco O.

This paper focuses cross-nationally on women's share of higher education relative to that of men. An institutional perspective is developed that leads to three predictions: (1) women's share of higher education will increase worldwide; (2) countries with relatively more women in higher education will also have relatively more women in the labor…

Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor-Bridge-Acceptor Molecules.

PubMed

Waskasi, Morteza M; Newton, Marshall D; Matyushov, Dmitry V

2017-03-30

A combination of experimental data and theoretical analysis provides evidence of a bell-shaped kinetics of electron transfer in the Arrhenius coordinates ln k vs 1/T. This kinetic law is a temperature analogue of the familiar Marcus bell-shaped dependence based on ln k vs the reaction free energy. These results were obtained for reactions of intramolecular charge shift between the donor and acceptor separated by a rigid spacer studied experimentally by Miller and co-workers. The non-Arrhenius kinetic law is a direct consequence of the solvent reorganization energy and reaction driving force changing approximately as hyperbolic functions with temperature. The reorganization energy decreases and the driving force increases when temperature is increased. The point of equality between them marks the maximum of the activationless reaction rate. Reaching the consistency between the kinetic and thermodynamic experimental data requires the non-Gaussian statistics of the donor-acceptor energy gap described by the Q-model of electron transfer. The theoretical formalism combines the vibrational envelope of quantum vibronic transitions with the Q-model describing the classical component of the Franck-Condon factor and a microscopic solvation model of the solvent reorganization energy and the reaction free energy.

Direct measurements of rate coefficients for thermal decomposition of CF3I using shock—tube ARAS technique

NASA Astrophysics Data System (ADS)

Bystrov, N. S.; Emelianov, A. V.; Eremin, A. V.; Yatsenko, P. I.

2018-05-01

The kinetics of the dissociation of CF3I behind shock waves was experimentally investigated. The reaction CF3I  +  Ar  →  CF3  +  I  +  Ar was studied at temperatures between 900 and 1250 K and pressures of 2–3 bar. For this purpose, the time profiles of the concentration of atomic iodine were measured using a highly sensitive atomic resonance absorption spectroscopy method at a wavelength of 183.04 nm. From these data, the experimental value of the dissociation rate constant of CF3I was obtained: . We found that the investigated range of pressures and temperatures for the CF3I dissociation lies in the pressure transition region. Based on the Rice-Ramsperger–Kassel–Marcus theory, the threshold high and low-pressure rate constants ( and k 0) and falloff curves are calculated for the temperatures of 950–1200 K. As a result of this calculation, the threshold rate constants could be evaluated in the forms: and , and the center broadening factor, which takes into account the contribution of strong and weak collisions in the transition region, is .

Electron Transfer Activity of a de Novo Designed Copper Center in a Three-Helix Bundle Fold

PubMed Central

Plegaria, Jefferson S.; Herrero, Christian; Quaranta, Annamaria; Pecoraro, Vincent L.

2017-01-01

In this work, we characterized the intermolecular ET property of a de novo designed metallopeptide using laser-flash photolysis. α3D-CH3 is three-helix bundle peptide that was designed to contain a copper ET site found in the β-barrel fold of native cupredoxins. The ET activity of Cuα3D-CH3 was determined using five different photosensitizers. By exhibiting a complete depletion of the photo-oxidant and the successive formation of a Cu(II) species at 400 nm, the transient and generated spectra demonstrated an ET transfer reaction between the photo-oxidant and Cu(I)α3D-CH3. This observation illustrated our success in integrating an ET center within a de novo designed scaffold. From the kinetic traces at 400 nm, first-order and bimolecular rate constants of 105 s−1 and 108 M−1 s−1 were derived. Moreover, a Marcus equation analysis on the rate versus driving force study produced a reorganization energy of 1.1 eV, demonstrating that the helical fold of α3D requires further structural optimization to efficiently perform ET. PMID:26427552

A computational study of photo-induced electron transfer rate constants in subphthalocyanine/C60 organic photovoltaic materials via Fermi's golden rule

NASA Astrophysics Data System (ADS)

Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan

2014-03-01

We present a methodology to obtain the photo-induced electron transfer rate constant in organic photovoltaic (OPV) materials within the framework of Fermi's golden rule, using inputs obtained from first-principles electronic structure calculation. Within this approach, the nuclear vibrational modes are treated quantum-mechanically and a short-time approximation is avoided in contrast to the classical Marcus theory where these modes are treated classically within the high-temperature and short-time limits. We demonstrate our methodology on boron-subphthalocyanine-chloride/C60 OPV system to determine the rate constants of electron transfer and electron recombination processes upon photo-excitation. We consider two representative donor/acceptor interface configurations to investigate the effect of interface configuration on the charge transfer characteristics of OPV materials. In addition, we determine the time scale of excited states population by employing a master equation after obtaining the rate constants for all accessible electronic transitions. This work is pursued as part of the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences under 390 Award No. DE-SC0000957.

Theoretical investigation of the electron transfer dynamics and photodegradation pathways in a hydrogen-evolving ruthenium-palladium photocatalyst.

PubMed

Staniszewska, Magdalena; Kupfer, Stephan; Guthmuller, Julien

2018-05-16

Time-dependent density functional theory calculations combined with the Marcus theory of electron transfer (ET) were applied on the molecular photocatalyst [(tbbpy)2Ru(tpphz)PdCl2]2+ in order to elucidate the light-induced relaxation pathways populated upon excitation in the longer wavelength range of its absorption spectrum. The computational results show that after the initial excitation, metal (Ru) to ligand (tpphz) charge transfer (MLCT) triplet states are energetically accessible, but that an ET toward the catalytic center (PdCl2) from these states is a slow process, with estimated time constants above 1 ns. Instead, the calculations predict that low-lying Pd-centered states are efficiently populated - associated to an energy transfer toward the catalytic center. Thus, it is postulated that these states lead to the dissociation of a Cl- and are consequently responsible for the experimentally observed degradation of the catalytic center. Following dissociation, it is shown that the ET rates from the MLCT states to the charge separated states are significantly increased (i.e. 10^5-10^6 times larger). This demonstrates that alteration of the catalytic center generates efficient charge separation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Restoration of the Apollo Heat Flow Experiments Metadata

NASA Technical Reports Server (NTRS)

Nagihara, S.; Stephens, M. K.; Taylor, P. T.; Williams, D. R.; Hills, H. K.; Nakamura, Y.

2015-01-01

Geothermal heat flow probes were deployed on the Apollo 15 and 17 missions as part of the Apollo Lunar Surface Experiments Package (ALSEP). At each landing site, the astronauts drilled 2 holes, 10-m apart, and installed a probe in each. The holes were 1- and 1.5-m deep at the Apollo 15 site and 2.5-m deep at the Apollo 17 sites. The probes monitored surface temperature and subsurface temperatures at different depths. At the Apollo 15 site, the monitoring continued from July 1971 to January 1977. At the Apollo 17 site, it did from December 1972 to September 1977. Based on the observations made through December 1974, Marcus Langseth, the principal investigator of the heat flow experiments (HFE), determined the thermal conductivity of the lunar regolith by mathematically modeling how the seasonal temperature fluctuation propagated down through the regolith. He also determined the temperature unaffected by diurnal and seasonal thermal waves of the regolith at different depths, which yielded the geothermal gradient. By multiplying the thermal gradient and the thermal conductivity, Langseth obtained the endogenic heat flow of the Moon as 21 mW/m(exp 2) at Site 15 and 16 mW/m(exp 2) at Site 17.

Kinetics and Quantitative Structure—Activity Relationship Study on the Degradation Reaction from Perfluorooctanoic Acid to Trifluoroacetic Acid

PubMed Central

Gong, Chen; Sun, Xiaomin; Zhang, Chenxi; Zhang, Xue; Niu, Junfeng

2014-01-01

Investigation of the degradation kinetics of perfluorooctanoic acid (PFOA) has been carried out to calculate rate constants of the main elementary reactions using the multichannel Rice-Ramsperger-Kassel-Marcus theory and canonical variational transition state theory with small-curvature tunneling correction over a temperature range of 200~500 K. The Arrhenius equations of rate constants of elementary reactions are fitted. The decarboxylation is role step in the degradation mechanism of PFOA. For the perfluorinated carboxylic acids from perfluorooctanoic acid to trifluoroacetic acid, the quantitative structure–activity relationship of the decarboxylation was analyzed with the genetic function approximation method and the structure–activity model was constructed. The main parameters governing rate constants of the decarboxylation reaction from the eight-carbon chain to the two-carbon chain were obtained. As the structure–activity model shows, the bond length and energy of C1–C2 (RC1–C2 and EC1–C2) are positively correlated to rate constants, while the volume (V), the energy difference between EHOMO and ELUMO (ΔE), and the net atomic charges on atom C2 (QC2) are negatively correlated. PMID:25196516

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

Waskasi, Morteza M.; Newton, Marshall D.; Matyushov, Dmitry V.

A combination of experimental data and theoretical analysis provides evidence of a bell-shaped kinetics of electron transfer in the Arrhenius coordinates ln k vs 1/T . This kinetic law is a temperature analog of the familiar Marcus bell-shaped dependence based on ln k vs the reaction free energy. These results were obtained for reactions of intramolecular charge shift between the donor and acceptor separated by a rigid spacer studied experimentally by Miller and co-workers. The non-Arrhenius kinetic law is a direct consequence of the solvent reorganization energy and reaction driving force changing approximately as hyperbolic functions with temperature. The reorganizationmore » energy decreases and the driving force increases when temperature is increased. The point of equality between them marks the maximum of the activationless reaction rate. Reaching the consistency between the kinetic and thermodynamic experimental data requires the non-Gaussian statistics of the donor-acceptor energy gap described by the Q-model of electron transfer. Furthermore, the theoretical formalism combines the vibrational envelope of quantum vibronic transitions with the Q-model describing the classical component of the Franck-Condon factor and a microscopic solvation model of the solvent reorganization energy and the reaction free energy.« less

Charge carrier mobility in conjugated organic polymers: simulation of an electron mobility in a carbazole-benzothiadiazole-based polymer

NASA Astrophysics Data System (ADS)

Li, Yaping; Lagowski, Jolanta B.

2011-08-01

Inorganic (mostly silicon based) solar cells are important devices that are used to solve the world energy and environmental needs. Now days, organic solar cells are attracting considerable attention in the field of photovoltaic cells because of their low cost and processing flexibility. Often conjugated polymers are used in the construction of the organic solar cells. We study the conjugated polymers' charge transport using computational approach that involves the use of the density functional theory (DFT), semiempirical (ZINDO), and Monte Carlo (MC) theoretical methods in order to determine their transfer integrals, reorganization energies, transfer rates (with the use of Marcus-Hush equation) and mobilities. We employ the experimentally determined three dimensional (3D) structure of poly(9,9'-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) to estimate the electron mobility in a similar co-alternating polymer consisting of carbazole and benzothiadiazole units (C8BT). In agreement with our previous work, we found that including an orientational disorder in the crystal reduces the electron mobility in C8BT. We hope that the proposed computational approach can be used to predict charge mobility in organic materials that are used in solar cells.

Electron transfer and reaction mechanism of laccases.

PubMed

Jones, Stephen M; Solomon, Edward I

2015-03-01

Laccases are part of the family of multicopper oxidases (MCOs), which couple the oxidation of substrates to the four electron reduction of O2 to H2O. MCOs contain a minimum of four Cu's divided into Type 1 (T1), Type 2 (T2), and binuclear Type 3 (T3) Cu sites that are distinguished based on unique spectroscopic features. Substrate oxidation occurs near the T1, and electrons are transferred approximately 13 Å through the protein via the Cys-His pathway to the T2/T3 trinuclear copper cluster (TNC), where dioxygen reduction occurs. This review outlines the electron transfer (ET) process in laccases, and the mechanism of O2 reduction as elucidated through spectroscopic, kinetic, and computational data. Marcus theory is used to describe the relevant factors which impact ET rates including the driving force, reorganization energy, and electronic coupling matrix element. Then, the mechanism of O2 reaction is detailed with particular focus on the intermediates formed during the two 2e(-) reduction steps. The first 2e(-) step forms the peroxide intermediate, followed by the second 2e(-) step to form the native intermediate, which has been shown to be the catalytically relevant fully oxidized form of the enzyme.

First principles study of the structural, electronic, and transport properties of triarylamine-based nanowires

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

Akande, Akinlolu, E-mail: akandea@tcd.ie; Bhattacharya, Sandip; Cathcart, Thomas

2014-02-21

We investigate with state of the art density functional theory the structural, electronic, and transport properties of a class of recently synthesized nanostructures based on triarylamine derivatives. First, we consider the single molecule precursors in the gas phase and calculate their static properties, namely (i) the geometrical structure of the neutral and cationic ions, (ii) the electronic structure of the frontier molecular orbitals, and (iii) the ionization potential, hole extraction potential, and internal reorganization energy. This initial study does not evidence any direct correlation between the properties of the individual molecules and their tendency to self-assembly. Subsequently, we investigate themore » charge transport characteristics of the triarylamine derivatives nanowires, by using Marcus theory. For one derivative we further construct an effective Hamiltonian including intermolecular vibrations and evaluate the mobility from the Kubo formula implemented with Monte Carlo sampling. These two methods, valid respectively in the sequential hopping and polaronic band limit, give us values for the room-temperature mobility in the range 0.1–12 cm{sup 2}/Vs. Such estimate confirms the superior transport properties of triarylamine-based nanowires, and make them an attracting materials platform for organic electronics.« less

Assessing Backwards Integration as a Method of KBO Family Finding

NASA Astrophysics Data System (ADS)

Benfell, Nathan; Ragozzine, Darin

2018-04-01

The age of young asteroid collisional families can sometimes be determined by using backwards n-body integrations of the solar system. This method is not used for discovering young asteroid families and is limited by the unpredictable influence of the Yarkovsky effect on individual specific asteroids over time. Since these limitations are not as important for objects in the Kuiper belt, Marcus et al. 2011 suggested that backwards integration could be used to discover and characterize collisional families in the outer solar system. But various challenges present themselves when running precise and accurate 4+ Gyr integrations of Kuiper Belt objects. We have created simulated families of Kuiper Belt Objects with identical starting locations and velocity distributions, based on the Haumea Family. We then ran several long-term test integrations to observe the effect of various simulation parameters on integration results. These integrations were then used to investigate which parameters are of enough significance to require inclusion in the integration. Thereby we determined how to construct long-term integrations that both yield significant results and require manageable processing power. Additionally, we have tested the use of backwards integration as a method of discovery of potential young families in the Kuiper Belt.

The role of mutations in the SCN5A gene in cardiomyopathies.

PubMed

Zaklyazminskaya, Elena; Dzemeshkevich, Sergei

2016-07-01

The SCN5A gene encodes the alpha-subunit of the Nav1.5 ion channel protein, which is responsible for the sodium inward current (INa). Since 1995 several hundred mutations in this gene have been found to be causative for inherited arrhythmias including Long QT syndrome, Brugada syndrome, cardiac conduction disease, sudden infant death syndrome, etc. As expected these syndromes are primarily electrical heart diseases leading to life-threatening arrhythmias with an "apparently normal heart". In 2003 a new form of dilated cardiomyopathy was identified associated with mutations in the SCN5A gene. Recently mutations have been also found in patients with arrhythmogenic right ventricular cardiomyopathy and atrial standstill. The purpose of this review is to outline and analyze the following four topics: 1) SCN5A genetic variants linked to different cardiomyopathies; 2) clinical manifestations of the known mutations; 3) possible molecular mechanisms of myocardial remodeling; and 4) the potential implications of gene-specific treatment for those disorders. This article is part of a Special Issue entitled: Cardiomyocyte Biology: Integration of Developmental and Environmental Cues in the Heart edited by Marcus Schaub and Hughes Abriel. Copyright © 2016 Elsevier B.V. All rights reserved.

Description of Uncinaria lyonsi n. sp. (Nematoda: Ancylostomatidae) from the California sea lion Zalophus californianus Lesson (Carnivora: Otariidae).

PubMed

Kuzmina, Tetiana A; Kuzmin, Yuriy

2015-02-01

A new species of hookworm, Uncinaria lyonsi n. sp., is described based on morphological studies of the nematodes collected by Dr. E. T. Lyons from the California sea lion Zalophus californianus (Lesson) on San Miguel Island, California, USA. The new species is morphologically similar to three other species of the genus Uncinaria Frölich, 1789 parasitising pinnipeds, U. lucasi Stiles, 1901, U. hamiltoni Baylis, 1933 and U. sanguinis Marcus, Higgins, Šlapeta & Gray, 2014, in the body dimensions, the structure of the buccal capsule, the shape and structure of the male caudal bursa and female genital system. Uncinaria lyonsi n. sp. is differentiated from U. lucasi by having longer spicules and gubernaculum, larger buccal capsule and more slender oesophagus. The new species differs from U. hamiltoni and U. sanguinis in having shorter spicules and narrower buccal capsule. The latter two species also occur in the Southern Hemisphere and are geographically separated from U. lyonsi n. sp. The present study confirms the existence of a host-specific species of Uncinaria in the California sea lion, previously revealed by molecular and biological investigations.

Nontraumatic femur fracture in an oligomenorrheic athlete.

PubMed

Dugowson, C E; Drinkwater, B L; Clark, J M

1991-12-01

Exercise-associated amenorrhea is the cessation of menses in a woman following onset of training or an increase in training intensity. Its physiologic basis is characterized by consistently low levels of gonadotropin and ovarian hormones, but the underlying cause of this phenomenon is unknown. Although osteopenia has been described in amenorrheic women athletes, it has been primarily a laboratory diagnosis. Several recent studies have described a significantly lower bone mineral density (BMD) in the lumbar spine of amenorrheic athletes. Marcus et al. also reported an increased number of metatarsal and tibial stress fractures in a group of amenorrheic women. We report here the first case of a nontraumatic femur fracture in an amenorrheic athlete. A 32-yr-old white female, with four prior fibular stress fractures, suffered a left femoral shaft fracture during the 13th mile of a half-marathon. The fracture was successfully internally fixed. Biochemical studies showed no metabolic abnormality. Bone mineral density of the lumbar spine, femoral neck, tibia, and fibula were below the mean for both eumenorrheic and amenorrheic female athletes. Exercise-associated amenorrhea is a medical problem that may have serious implications for both competitive and high-intensity recreational female athletes.

Electron transfer reaction of oxo(salen)chromium(V) ion with anilines.

PubMed

Premsingh, Sundarsingh; Venkataramanan, Natarajan Sathiyamoorthy; Rajagopal, Seenivasan; Mirza, Shama P; Vairamani, Mariappanadar; Rao, P Sambasiva; Velavan, K

2004-09-06

The kinetics of oxidation of 16 meta-, ortho-, and para-substituted anilines with nine oxo(salen)chromium(V) ions have been studied by spectrophotometric, ESIMS, and EPR techniques. During the course of the reaction, two new peaks with lambda(max) at 470 and 730 nm appear in the absorption spectrum, and these peaks are due to the formation of emeraldine forms of oligomers of aniline supported by the ESIMS peaks with m/z values 274 and 365 (for the trimer and tetramer of aniline). The rate of the reaction is highly sensitive to the change of substituents in the aryl moiety of aniline and in the salen ligand of chromium(V) complexes. Application of the Hammett equation to analyze kinetic data yields a rho value of -3.8 for the substituent variation in aniline and +2.2 for the substituent variation in the salen ligand of the metal complex. On the basis of the spectral, kinetic, and product analysis studies, a mechanism involving an electron transfer from the nitrogen of aniline to the metal complex in the rate controlling step has been proposed. The Marcus equation has been successfully applied to this system, and the calculated values are compliant with the measured values.

Mechanism and kinetic properties for the OH-initiated atmospheric oxidation degradation of 9,10-Dichlorophenanthrene.

PubMed

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Hu, Jingtian; Wang, Wenxing

2015-02-01

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have become a serious environmental concern due to their widespread occurrence and dioxin-like toxicities. In this work, the mechanism of the OH-initiated atmospheric oxidation degradation of 9,10-dichlorophenanthrene (9,10-Cl₂Phe) was investigated by using high-accuracy quantum chemistry calculations. The rate constants of the crucial elementary reactions were determined by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The theoretical results were compared with the available experimental data. The main oxidation products are a group of ring-retaining and ring-opening compounds including chlorophenanthrols, 9,10-dichlorophenanthrene-3,4-dione, dialdehydes, chlorophenanthrenequinones, nitro-9,10-Cl₂Phe and epoxides et al. The overall rate constant of the OH addition reaction is 2.35 × 10(-12)cm(3) molecule(-1)s(-1) at 298 K and 1 atm. The atmospheric lifetime of 9,10-Cl₂Phe determined by OH radicals is about 5.05 days. This study provides a comprehensive investigation of the OH-initiated oxidation degradation of 9,10-Cl₂Phe and should contribute to clarifying its atmospheric fate. Copyright © 2014 Elsevier B.V. All rights reserved.

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

PubMed

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

2013-06-20

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

Women and Men of the Manhattan Project

NASA Astrophysics Data System (ADS)

Marshall, Jill; Herzenberg, Caroline; Howes, Ruth; Weaver, Ellen; Gans, Dorothy

2010-04-01

In the early 1990s Ruth Howes, a nuclear physicist on the faculty at Ball State University, and Caroline Herzenberg, a nuclear physicist at Argonne National Laboratory, were asked to write a chapter on the Manhattan Project for a volume on women working on weapons development for the military. Realizing that they knew very little about the women who had been involved in that effort, they embarked on a mission to find out more. Howes and Herzenberg were able to document the wartime contributions of more than 1000 women in Their Day in the Sun,2 preserving this legacy for generations to come. At the 2009 AAPT Winter Meeting in Chicago, the AAPT Committee on Women in Physics celebrated the accomplishments of these women and the men who worked beside them in a session co-sponsored with the History and Philosophy of Physics and the Concerns of Senior Physicists committees. Howes presented an overview of the contributions of women to the development of the first nuclear weapon, and the session was honored with the presence of Manhattan Project veterans Ellen Cleminshaw Weaver, who worked at Oak Ridge, and Dorothy Marcus Gans, who worked as a technician in the Metallurgical Laboratory in Chicago.

Qualitative analysis of Cohen-Grossberg neural networks with multiple delays

NASA Astrophysics Data System (ADS)

Ye, Hui; Michel, Anthony N.; Wang, Kaining

1995-03-01

It is well known that a class of artificial neural networks with symmetric interconnections and without transmission delays, known as Cohen-Grossberg neural networks, possesses global stability (i.e., all trajectories tend to some equilibrium). We demonstrate in the present paper that many of the qualitative properties of Cohen-Grossberg networks will not be affected by the introduction of sufficiently small delays. Specifically, we establish some bound conditions for the time delays under which a given Cohen-Grossberg network with multiple delays is globally stable and possesses the same asymptotically stable equilibria as the corresponding network without delays. An effective method of determining the asymptotic stability of an equilibrium of a Cohen-Grossberg network with multiple delays is also presented. The present results are motivated by some of the authors earlier work [Phys. Rev. E 50, 4206 (1994)] and by some of the work of Marcus and Westervelt [Phys. Rev. A 39, 347 (1989)]. These works address qualitative analyses of Hopfield neural networks with one time delay. The present work generalizes these results to Cohen-Grossberg neural networks with multiple time delays. Hopfield neural networks constitute special cases of Cohen-Grossberg neural networks.

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

Laskin, Julia

In this work, resonant ejection coupled with surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer is used to examine fragmentation kinetics of two singly protonated hexapeptides, RYGGFL and KYGGFL, containing the basic arginine residue and less basic lysine residue at the N-terminus. The kinetics of individual reaction channels at different collision energies are probed by applying a short ejection pulse (1 ms) in resonance with the cyclotron frequency of a selected fragment ion and varying the delay time between ion-surface collision and resonant ejection while keeping total reaction delay time constant. Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of themore » experimental data provides accurate threshold energies and activation entropies of individual reaction channels. Substitution of arginine with less basic lysine has a pronounced effect on the observed fragmentation kinetics of several pathways, including the b2 ion formation, but has little or no effect on formation of the b5+H2O fragment ion. The combination of resonant ejection SID, time- and collision energy-resolved SID, and RRKM modeling of both types of experimental data provides a detailed mechanistic understanding of the primary dissociation pathways of complex gaseous ions.« less

Transdiagnostic Motivational Enhancement Therapy to Reduce Treatment Attrition: Use in Emerging Adults

PubMed Central

Mistler, Lisa A.; Sheidow, Ashli J.; Davis, Maryann

2017-01-01

Improving outcomes of youth with mental health (MH) needs as they transition into adulthood is of critical public health significance. Effective psychotherapy MH treatment is available, but can be effective only if the emerging adult (EA) attends long enough to benefit. Unfortunately, completion of psychotherapy among EAs is lower than for more mature adults (Edlund et al., 2002; Olfson, Marcus, Druss, & Pincus, 2002). To target the high attrition of EAs in MH treatment, investigators adapted a developmentally appropriate brief intervention aimed at reducing treatment attrition (TA) in psychotherapy and conducted a feasibility study of implementation. The intervention employs motivational interviewing strategies aimed at engaging and retaining EAs in outpatient MH treatment. Motivational enhancement therapy for treatment attrition, or MET-TA, takes only a few sessions at the outset of treatment as an adjunct to usual treatment. Importantly, it can be used for TA with psychotherapy for any MH condition; in other words, it is transdiagnostic. This article presents the first description of MET-TA, along with a case example that demonstrates important characteristics of the approach, and then briefly describes implementation feasibility based on a small pilot randomized controlled trial. PMID:28979088